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A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Polymer Chemistry".

Deadline for manuscript submissions: closed (31 January 2022) | Viewed by 31752

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Dr. Pavel Ivchenko

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Department of Chemistry, Lomonosov Moscow State University, Moscow, Russia
Interests: single-site catalysis in polymerization and transformations of α-olefins; coordination catalysis and organocatalysis for ring-opening polymerization; synthesis of high-margin petrochemical products; biodegradable polymers; DFT modeling of the mechanisms of organic reactions and catalytic processes
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Dear Colleagues,

The challenge of creating advanced materials with given characteristics can be addressed in different ways. The further expansion of the range of polymerization mechanisms enables the creation of polymers with given microstructure and comonomer sequence. Traditionally, the concept of controlled polymerization has referred to the reactions in which the chain termination is suppressed through the introduction of the reagents forming the "dormant sites" with "living" polymer chain. Atom transfer radical polymerization (ATRP), reversible addition/fragmentation chain transfer polymerization (RAFT), and nitroxide-mediated polymerization (NMP) are common examples of free-radical-controlled polymerization processes.

However, it is reasonable to go beyond this conventional meaning: in broad terms, controlled polymerization implies the formulation of the polymer microstructure in a predetermined number and sequence of comonomer units, no matter how it is brought about. The concept of the "control" could be widened—for example, through the mutual comonomer reactivity (sequence-controlled polymerization), or by the use of cross-coupling reactions (the synthesis of conjugated polymers). These represent just two expansions, and two whole types of prospective amphiphilic and photovoltaic materials, illustrating the extensive opportunities available.

This Special Issue focuses on creating a multidisciplinary forum for the discussion of recent advances in the synthesis of the macromolecules with given microstructure and comonomer sequence, using the methods of controlled polymerization in the broad context.

Dr. Pavel Ivchenko
Guest Editor

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Keywords

controlled polymerization
free-radical polymerization
anionic polymerization
cationic polymerization
coordination polymerization
alternating polymerization
ring-opening polymerizations
single-site catalysts
organocatalysts
chain-transfer reagents
ATRP
RAFT

Published Papers (10 papers)

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Research

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22 pages, 5601 KiB

Open AccessArticle

Synthesis and Phase Behavior of a Platform of CO₂-Soluble Functional Gradient Copolymers Bearing Metal-Complexing Units

by Andrea Ruiu, Cécile Bouilhac, Olinda Gimello, Karine Seaudeau-Pirouley, Marin Senila, Thorsten Jänisch and Patrick Lacroix-Desmazes

Polymers 2022, 14(13), 2698; https://0-doi-org.brum.beds.ac.uk/10.3390/polym14132698 - 30 Jun 2022

Cited by 2 | Viewed by 1703

Abstract

The synthesis and characterization of a platform of novel functional fluorinated gradient copolymers soluble in liquid and supercritical CO₂ is reported. These functional copolymers are bearing different types of complexing units (pyridine, triphenylphosphine, acetylacetate, thioacetate, and thiol) which are well-known ligands for various metals. They have been prepared by reversible addition–fragmentation chain-transfer (RAFT) polymerization in order to obtain well-defined gradient copolymers. The copolymers have been characterized by proton nuclear magnetic resonance (¹H-NMR) spectroscopy, matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry, thermal gravimetric analysis (TGA), dynamical scanning calorimetry (DSC) and cloud point measurements in dense CO₂. All the investigated metal-complexing copolymers are soluble in dense CO₂ under mild conditions (pressure lower than 30 MPa up to 65 °C), confirming their potential applications in processes such as metal-catalyzed reactions in dense CO₂, metal impregnation, (e.g., preparation of supported catalysts) or metal extraction from various substrates (solid or liquid effluents). Particularly, it opens the door to greener and less energy-demanding processes for the recovery of metals from spent catalysts compared to more conventional pyro- and hydro-metallurgical methods. Full article

(This article belongs to the Special Issue Controlled Polymerization)

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17 pages, 4904 KiB

Open AccessArticle

Gamma Radiation- and Ultraviolet-Induced Polymerization of Bis(amino acid)fumaramide Gel Assemblies

by Tomislav Gregorić, Janja Makarević, Zoran Štefanić, Mladen Žinić and Leo Frkanec

Polymers 2022, 14(1), 214; https://0-doi-org.brum.beds.ac.uk/10.3390/polym14010214 - 05 Jan 2022

Cited by 3 | Viewed by 2210

Abstract

Controlling the polymerization of supramolecular self-assembly through external stimuli holds great potential for the development of responsive soft materials and manipulation at the nanoscale. Vinyl esters of bis(leu or val)fumaramide (1a and 2a) have been found to be gelators of various organic solvents and were applied in this investigation of the influence of organogelators’ self-assembly on solid-state polymerization induced by gamma and ultraviolet irradiation. Here, we report our investigation into the influences of self-assemblies of bis(amino acid vinyl ester)fumaramides on gamma-ray- and ultraviolet-induced polymerization. The gelator molecules self-assembled by non-covalent interactions, mainly through hydrogen bonds between the amide group (CONH) and the carboxyl group (COO), thus forming a gel network. NMR and FTIR spectroscopy were used to investigate and characterize supramolecular gels. TEM and SEM microscopy were used to investigate the morphology of gels and polymers. Morphology studies showed that the gels contained a filamentous structure of nanometer dimensions that was exhaustive in a three-dimensional network. The prepared derivatives contained reactive alkyl groups suitable for carrying out the polymerization reaction initiated by gamma or ultraviolet radiation in the supramolecular aggregates of selected gels. It was found that the polymerization reaction occurred only in the network of the gel and was dependent on the structure of aggregates or the proximity and orientation of double bonds in the gel network. Polymers were formed by the gels exposure to gamma and ultraviolet radiation in toluene, and water/DMF gels with transcripts of their gel structure into polymers. The polymeric material was able to immobilize various solvents by swelling. Furthermore, methyl esters of bis(leu and val)fumaramide (1b and 2b) were synthesized; these compounds showed no gelling properties, and the crystal structure of the valine derivative 2b was determined. Full article

(This article belongs to the Special Issue Controlled Polymerization)

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19 pages, 2918 KiB

Open AccessArticle

Functionalized Biodegradable Polymers via Termination of Ring-Opening Polymerization by Acyl Chlorides

by Ilya Nifant’ev, Andrey Shlyakhtin, Vladimir Bagrov, Evgeny Shaputkin, Alexander Tavtorkin and Pavel Ivchenko

Polymers 2021, 13(6), 868; https://0-doi-org.brum.beds.ac.uk/10.3390/polym13060868 - 11 Mar 2021

Cited by 3 | Viewed by 2748

Abstract

Aliphatic polyesters are an important class of polymeric materials for biomedical applications due to their versatile and tunable chemistry, biocompatibility and biodegradability. A capability of direct bonding with biomedically significant molecules, provided by the presence of the reactive end functional groups (FGs), is highly desirable for prospective polymers. Among FGs, N-hydroxysuccinimidyl activated ester group (NHS) and maleimide fragment (MI) provide efficient covalent bonding with –NH– and –SH containing compounds. In our study, we found that NHS- and MI-derived acyl chlorides efficiently terminate living ring-opening polymerization of ε-caprolactone, L-lactide, ethyl ethylene phosphonate and ethyl ethylene phosphate, catalyzed by 2,6-di-tert-butyl-4-methylphenoxy magnesium complex, with a formation of NHS- and MI-functionalized polymers at a high yields. Reactivity of these polymers towards amine- and thiol-containing model substrates in organic and aqueous media was also studied. Full article

(This article belongs to the Special Issue Controlled Polymerization)

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11 pages, 923 KiB

Open AccessArticle

Lignin-Based Polyols with Controlled Microstructure by Cationic Ring Opening Polymerization

by Jonatan Perez-Arce, Ander Centeno-Pedrazo, Jalel Labidi, Jose R. Ochoa-Gomez and Eduardo J. Garcia-Suarez

Polymers 2021, 13(4), 651; https://0-doi-org.brum.beds.ac.uk/10.3390/polym13040651 - 22 Feb 2021

Cited by 8 | Viewed by 2383

Abstract

Lignin-based polyols (LBPs) with controlled microstructure were obtained by cationic ring opening polymerization (CROP) of oxiranes in an organosolv lignin (OL) tetrahydrofuran (THF) solution. The control on the microstructure and consequently on the properties of the LBPs such as hydroxyl number, average molecular weight, melting, crystallization and decomposition temperatures, are crucial to determine the performance and application of the derived-products. The influence of key parameters, for example, molar ratio between the oxirane and the hydroxyl groups content in OLO, initial OL concentration in THF, temperature, specific flow rate and oxirane nature has been investigated. LBPs with hydroxyl numbers from 35 to 217 mg KOH/g, apparent average M_w between 5517 and 52,900 g/mol and melting temperatures from −8.4 to 18.4 °C were obtained. The CROP procedure allows obtaining of tailor-made LBPs for specific applications in a very simple way, opening the way to introduce LBPs as a solid alternative to substitute currently used fossil-based polyols. Full article

(This article belongs to the Special Issue Controlled Polymerization)

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23 pages, 4909 KiB

Open AccessArticle

Comparative Experimental and Theoretical Study of Mg, Al and Zn Aryloxy Complexes in Copolymerization of Cyclic Esters: The Role of the Metal Coordination in Formation of Random Copolymers

by Ilya Nifant’ev, Pavel Komarov, Valeriya Ovchinnikova, Artem Kiselev, Mikhail Minyaev and Pavel Ivchenko

Polymers 2020, 12(10), 2273; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12102273 - 02 Oct 2020

Cited by 11 | Viewed by 2886

Abstract

Homogeneity of copolymers is a general problem of catalytic coordination polymerization. In ring-opening polymerization of cyclic esters, the rational design of the catalyst is generally applied to solve this problem by the equalization of the reactivities of comonomers—however, it often leads to a reduction of catalytic activity. In the present paper, we studied the catalytic behavior of BnOH-activated complexes (BHT)Mg(THF)₂ⁿBu (1), (BHT)₂AlMe (2) and [(BHT)ZnEt]₂ (3), based on 2,6-di-tert-butyl-4-methylphenol (BHT-H) in homo- and copolymerization of L-lactide (lLA) and ε-caprolactone (εCL). Even at 1:5 lLA/εCL ratio Mg complex 1 catalyzed homopolymerization of lLA without involving εCL to the formation of the polymer backbone. On the contrary, Zn complex 3 efficiently catalyzed random lLA/εCL copolymerization; the presence of mono-lactate subunits in the copolymer chain clearly pointed to the transesterification mechanism of copolymer formation. Both epimerization and transesterification side processes were analyzed using the density functional theory (DFT) modeling that confirmed the qualitative difference in catalytic behavior of 1 and 3: Mg and Zn complexes demonstrated different types of preferable coordination on the PLA chain (k² and k³, respectively) with the result that complex 3 catalyzed controlled εCL ROP/PLA transesterification, providing the formation of lLA/εCL copolymers that contain mono-lactate fragments separated by short oligo(εCL) chains. The best results in the synthesis of random lLA/εCL copolymers were obtained during experiments on transesterification of commercially available PLLA, the applicability of 3/BnOH catalyst in the synthesis of random copolymers of εCL with methyl glycolide, ethyl ethylene phosphonate and ethyl ethylene phosphate was also demonstrated. Full article

(This article belongs to the Special Issue Controlled Polymerization)

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8 pages, 1508 KiB

Open AccessArticle

Synthesis of Well-Defined Alternating Copolymer Composed of Ethylmaleimide and Hydroxy-Functionalized Vinyl Ether by RAFT Polymerization and Their Thermoresponsive Properties

by Jin Motoyanagi, Ayaha Oguri and Masahiko Minoda

Polymers 2020, 12(10), 2255; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12102255 - 01 Oct 2020

Cited by 5 | Viewed by 2349

Abstract

Here we report the controlled synthesis of alternating copolymers by reversible addition-fragmentation chain transfer (RAFT) polymerization of hydroxy-functionalized vinyl ether (DEGV) and ethylmaleimide (EtMI) using dithiocarbonate derivative (CPDB) as the RAFT reagent. The resulting alternating copolymer poly[ethylmaleimide-alt-(diethylene glycol mono vinyl ether)] (poly(MalMI-alt-DEGV)) had a relatively narrow molecular weight distribution (M_w/M_n < 1.4). These polymers are fully soluble in cold water (5 °C) and an aqueous solution of poly(MalMI-alt-DEGV) became turbid upon heating (using an incident wavelength of 600 nm and 1.0 mg mL⁻¹ (0.1 wt %) polymer concentration), indicating phase separation above the cloud point temperature (T_cp). The T_cp of the polymer solution ranged from 15–35 °C, depending on the molecular weight and molecular weight distribution of the polymer. Full article

(This article belongs to the Special Issue Controlled Polymerization)

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15 pages, 3326 KiB

Open AccessEditor’s ChoiceArticle

Controlled Synthesis of Poly(pentafluorostyrene-ran-methyl methacrylate) Copolymers by Nitroxide Mediated Polymerization and Their Use as Dielectric Layers in Organic Thin-film Transistors

by Alexander J. Peltekoff, Mathieu N. Tousignant, Victoria E. Hiller, Owen A. Melville and Benoît H. Lessard

Polymers 2020, 12(6), 1231; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12061231 - 29 May 2020

Cited by 10 | Viewed by 4127

Abstract

A library of statistically random pentafluorostyrene (PFS) and methyl methacrylate (MMA) copolymers with narrow molecular weight distributions was produced, using nitroxide mediated polymerization (NMP) to study the effect of polymer composition on the performance of bottom-gate top-contact organic thin-film transistors, when utilized as the dielectric medium. Contact angle measurements confirmed the ability to tune the surface properties of copolymer thin films through variation of its PFS/MMA composition, while impedance spectroscopy determined the effect of this variation on dielectric properties. Bottom-gate, top-contact copper phthalocyanine (CuPc) based organic thin-film transistors were fabricated using the random copolymers as a dielectric layer. We found that increasing the PFS content led to increased field-effect mobility, until a point after which the CuPc no longer adhered to the polymer dielectric. Full article

(This article belongs to the Special Issue Controlled Polymerization)

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18 pages, 2183 KiB

Open AccessArticle

Synthesis of Nixantphos Core-Functionalized Amphiphilic Nanoreactors and Application to Rhodium-Catalyzed Aqueous Biphasic 1-Octene Hydroformylation

by Ahmad Joumaa, Florence Gayet, Eduardo J. Garcia-Suarez, Jonas Himmelstrup, Anders Riisager, Rinaldo Poli and Eric Manoury

Polymers 2020, 12(5), 1107; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12051107 - 12 May 2020

Cited by 14 | Viewed by 3514

Abstract

A latex of amphiphilic star polymer particles, functionalized in the hydrophobic core with nixantphos and containing P(MAA-co-PEOMA) linear chains in the hydrophilic shell (nixantphos-functionalized core-crosslinked micelles, or nixantphos@CCM), has been prepared in a one-pot three-step convergent synthesis using reversible addition-fragmentation chain transfer (RAFT) polymerization in water. The synthesis involves polymerization-induced self-assembly (PISA) in the second step and chain crosslinking with di(ethylene glycol) dimethacrylate (DEGDMA) in the final step. The core consists of a functionalized polystyrene, obtained by incorporation of a new nixantphos-functionalized styrene monomer (nixantphos-styrene), which is limited to 1 mol%. The nixantphos-styrene monomer was synthesized in one step by nucleophilic substitution of the chloride of 4-chloromethylstyrene by deprotonated nixantphos in DMF at 60 °C, without interference of either phosphine attack or self-induced styrene polymerization. The polymer particles, after loading with the [Rh(acac)(CO)₂] precatalyst to yield Rh-nixantphos@CCM, function as catalytic nanoreactors under aqueous biphasic conditions for the hydroformylation of 1-octene to yield n-nonanal selectively, with no significant amounts of the branched product 2-methyl-octanal. Full article

(This article belongs to the Special Issue Controlled Polymerization)

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Review

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20 pages, 4227 KiB

Open AccessReview

Overview: Polycarbonates via Ring-Opening Polymerization, Differences between Six- and Five-Membered Cyclic Carbonates: Inspiration for Green Alternatives

by Zaher Abdel Baki, Hanna Dib and Tuba Sahin

Polymers 2022, 14(10), 2031; https://0-doi-org.brum.beds.ac.uk/10.3390/polym14102031 - 16 May 2022

Cited by 14 | Viewed by 4652

Abstract

This review aims to cover the topic of polycarbonate synthesis via ring-opening polymerization (ROP) of cyclic carbonates. We report a wide variety of ROP-initiating systems along with their detailed mechanisms. We focus on the challenges of preparing the polymers; the precise control of the properties of the materials, including molecular weight; the compositions of the copolymers and their structural characteristics. There is no one approach that works for all scales in cyclic carbonates ROP. A green process to produce polycarbonates is a luring challenge in terms of CO₂ utilization and the targeted domains for application. The main resolution seems to be the use of controlled incorporation of functional/reactive groups into polymer chains that can tailor the physicochemical and biological properties of the polymer matrices, producing what appears to be an unlimited field of applications. Glycerol carbonate (GC) is prepared from renewable glycerol and considered as a CO₂ fixation agent resulting in GC compound. This family of five-membered cyclic carbonates has attracted the attention of researchers as potential monomers for the synthesis of polycarbonates (PCs). This cyclic carbonate group presents a strong alternative to Bisphenol A (BPA), which is used mainly as a monomer for the production of polycarbonate and a precursor of epoxy resins. As of December 2016, BPA is listed as a substance of very high concern (SVHC) under the REACH regulation. In 2006, Mouloungui et al. reported the synthesis and oligomerization of GCs. The importance of GCs goes beyond their carbonate ring and their physical properties (high boiling point, high flash point, low volatility, high electrical conductivity) because they also contain a hydroxyl group. The latter offers the possibility of producing oligo and/or polycarbonate compounds that have hydroxyl groups that can potentially lead to different reaction mechanisms and the production of new classes of polycarbonates with a wide range of applications. Full article

(This article belongs to the Special Issue Controlled Polymerization)

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Other

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16 pages, 2589 KiB

Open AccessPerspective

Macromolecular Engineering by Applying Concurrent Reactions with ATRP

by Yu Wang, Mary Nguyen and Amanda J. Gildersleeve

Polymers 2020, 12(8), 1706; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12081706 - 29 Jul 2020

Cited by 6 | Viewed by 4080

Abstract

Modern polymeric material design often involves precise tailoring of molecular/supramolecular structures which is also called macromolecular engineering. The available tools for molecular structure tailoring are controlled/living polymerization methods, click chemistry, supramolecular polymerization, self-assembly, among others. When polymeric materials with complex molecular architectures are targeted, it usually takes several steps of reactions to obtain the aimed product. Concurrent polymerization methods, i.e., two or more reaction mechanisms, steps, or procedures take place simultaneously instead of sequentially, can significantly reduce the complexity of the reaction procedure or provide special molecular architectures that would be otherwise very difficult to synthesize. Atom transfer radical polymerization, ATRP, has been widely applied in concurrent polymerization reactions and resulted in improved efficiency in macromolecular engineering. This perspective summarizes reported studies employing concurrent polymerization methods with ATRP as one of the reaction components and highlights future research directions in this area. Full article

(This article belongs to the Special Issue Controlled Polymerization)

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