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Ring-Opening Polymerization

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A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organic Chemistry".

Deadline for manuscript submissions: closed (28 February 2015) | Viewed by 98760

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Prof. Dr. Atsushi Sudo

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Guest Editor

Department of Applied Chemistry, Faculty of Science and Engineering, Kinki University, Kowakae 3-4-1, Higashi-Osaka, Osaka 577-8502, Japan
Interests: bio-based polymers; polymerization; polymer reaction

Prof. Dr. Takeshi Endo

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Guest Editor

Molecular Engineering Institute, Kindai University, 11‐6 Kayanomori, Iizuka, Fukuoka 820‐8555, Japan
Interests: polymer synthesis; ring-opening polymerization; equilibrium polymerization; networked polymers

Special Issue Information

Dear Colleagues,

Ring-opening polymerization gives us access to various heteroatom-containing polymers with unique properties and functions that are rather difficult to obtain by chain polymerization of vinyl monomers. To date, a wide variety of cyclic monomers have been developed and their efficient ring-opening polymerizations, both ionic ones and radical ones, have been achieved. In addition, recent advance in living/controlled ring-opening polymerizations has enabled us to develop powerful tools for synthesizing well-defined polymers with controlled chain length and terminus, as well as those for constructing various polymer architectures such as block copolymers, graft copolymers, and star-shaped polymers that exhibit intriguing self-assemblies and the consequent micellization and phase separation behaviors. The advantages of ring-opening polymerizations are opening new doors for their applications in the fields of pharmaceutics, biomaterials, electronics, and aerospace materials.

We invite our colleagues to submit research articles and comprehensive reviews addressing the above-mentioned topics, and on recent advances in ring-opening polymerization in general, for publication in this Special Issue.

Prof. Dr. Atsushi Sudo
Prof. Dr. Takeshi Endo
Guest Editors

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Keywords

new cyclic monomers
ionic ring-opening polymerization
radical ring-opening polymerization
living/controlled ring-opening polymerization
polymer architectures
polymer properties
morphology
degradability

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Published Papers (12 papers)

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Editorial

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2 pages, 143 KiB

Open AccessEditorial

Special Issue “Ring-Opening Polymerization”

by Takeshi Endo and Atsushi Sudo

Molecules 2016, 21(12), 1720; https://doi.org/10.3390/molecules21121720 - 14 Dec 2016

Viewed by 4174

Abstract

Ring-opening polymerization (ROP) has gained much attention because of its usefulness to synthesize polymers with main chains inheriting the heteroatoms and functional groups from the corresponding monomers.[...] Full article

(This article belongs to the Special Issue Ring-Opening Polymerization)

Research

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11 pages, 1137 KiB

Open AccessArticle

One-Pot Synthesis of Organic-Sulfur-Zinc Hybrid Materials via Polycondensation of a Zinc Salt and Thiols Generated in Situ from Cyclic Dithiocarbonates

by Bungo Ochiai and Hirohisa Konta

Molecules 2015, 20(8), 15049-15059; https://doi.org/10.3390/molecules200815049 - 17 Aug 2015

Cited by 4 | Viewed by 6890

Abstract

Soluble organic-sulfur-zinc hybrid polymers were prepared via a one-pot reaction consisting of ring-opening addition and subsequent polycondensation. The first reaction is the nucleophilic ring-opening addition of 2-ethylhexylamine to multifunctional cyclic dithiocarbonates giving multiple thiols in situ. The sequential polycondensation of the in situ generated thiols with Zn(OAc)₂ gave the target hybrid polymers. This one-pot method enabled the use of a shorter amine than the previous polycondensation of Zn(OAc)₂ and purified thiols, which required octadecylamine to obtain a soluble product. The obtained hybrid polymers may be cast as composite films with polystyrene and poly(methyl methacrylate). Owing to the shorter alkyl chain, the calculated n_D values of the products (1.60 or 1.61) are higher than that of the previous product bearing octadecyl chains (1.53). Full article

(This article belongs to the Special Issue Ring-Opening Polymerization)

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16 pages, 1556 KiB

Open AccessArticle

Green Polymer Chemistry: Investigating the Mechanism of Radical Ring-Opening Redox Polymerization (R3P) of 3,6-Dioxa-1,8-octanedithiol (DODT)

by Emily Q. Rosenthal-Kim and Judit E. Puskas

Molecules 2015, 20(4), 6504-6519; https://doi.org/10.3390/molecules20046504 - 13 Apr 2015

Cited by 16 | Viewed by 8306

Abstract

The mechanism of the new Radical Ring-opening Redox Polymerization (R3P) of 3,6-dioxa-1,8-octanedithiol (DODT) by triethylamine (TEA) and dilute H₂O₂ was investigated. Scouting studies showed that the formation of high molecular weight polymers required a 1:2 molar ratio of DODT to TEA and of DODT to H₂O₂. Further investigation into the chemical composition of the organic and aqueous phases by ¹H-NMR spectroscopy and mass spectrometry demonstrated that DODT is ionized by two TEA molecules (one for each thiol group) and thus transferred into the aqueous phase. The organic phase was found to have cyclic disulfide dimers, trimers and tetramers. Dissolving DODT and TEA in water before the addition of H₂O₂ yielded a polymer with M_n = 55,000 g/mol, in comparison with M_n = 92,000 g/mol when aqueous H₂O₂ was added to a DODT/TEA mixture. After polymer removal, MALDI-ToF MS analysis of the residual reaction mixtures showed only cyclic oligomers remaining. Below the LCST for TEA in water, 18.7 °C, the system yielded a stable emulsion, and only cyclic oligomers were found. Below DODT/TEA and H₂O₂ 1:2 molar ratio mostly linear oligomers were formed, with <20% cyclic oligomers. The findings support the proposed mechanism of R3P. Full article

(This article belongs to the Special Issue Ring-Opening Polymerization)

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16 pages, 1914 KiB

Open AccessArticle

Copolymers of Vinyl-Containing Benzoxazine with Vinyl Monomers as Precursors for High Performance Thermosets

by Tsutomu Takeichi, Soulideth Thongpradith and Takehiro Kawauchi

Molecules 2015, 20(4), 6488-6503; https://doi.org/10.3390/molecules20046488 - 10 Apr 2015

Cited by 24 | Viewed by 7127

Abstract

A benzoxazine containing a vinyl group (P-4va) was prepared by the reaction of phenol, 4-vinylaniline, and paraformaldehyde. A differential scanning calorimetry (DSC) study revealed that ring-opening polymerization of the benzoxazine and chain polymerization of the vinyl group occurred in the same temperature range. When 2,2'-azobisisobutyronitrile was added as a radical initiator to P-4va, however, only the vinyl groups were polymerized at lower temperature, giving oligo(P-4va) that contains pendent benzoxazine units. Radical copolymerization of P-4va with various vinyl monomers such as styrene, methyl methacrylate (MMA), and n-butyl acrylate (BuA) was examined. The chemical structure of the copolymers was confirmed by FT-IR and ¹H-NMR to be one of polyolefins bearing benzoxazine units as the pendant groups. The weight-average molecular weights of the copolymers determined by size exclusion chromatography were to be in the range of 1900–51,500 depending on the comonomers. DSC of the copolymers showed that the maxima of the exothermic peaks corresponding to the ring-opening polymerization of the pendent benzoxazine units were observed in the temperature range of 229–250 °C. Thermal cure up to 240 °C of the copolymer films afforded homogenous transparent films with improved thermal properties. Tough cured film was obtained by the copolymerization with MMA, while a tough and flexible film was obtained by the copolymerization with BuA. Full article

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15 pages, 2210 KiB

Open AccessArticle

Ring-Opening Graft Polymerization of Propylene Carbonate onto Xylan in an Ionic Liquid

by Xueqin Zhang, Mingjie Chen, Chuanfu Liu, Aiping Zhang and Runcang Sun

Molecules 2015, 20(4), 6033-6047; https://doi.org/10.3390/molecules20046033 - 7 Apr 2015

Cited by 31 | Viewed by 9657

Abstract

The amidine organocatalyst 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) is an effective nucleophilic catalyst. Biocomposites with tuneable properties were successfully synthesized by ring-opening graft polymerization (ROGP) of propylene carbonate (PC) onto xylan using DBU as a catalyst in the ionic liquid (IL) 1-allyl-3-methylimidazolium chloride ([Amim]Cl). The effects of reaction temperature, reaction time and the molar ratio of PC to anhydroxylose units (AXU) in xylan were investigated. The physico-chemical properties of xylan-graft-poly(propylene carbonate) (xylan-g-PPC) copolymers were characterised by FT-IR, NMR, TGA/DTG, AFM and tensile analysis. The FT-IR and NMR results indicated the successful attachment of PPC onto xylan. TGA/DTG suggested the increased thermal stability of xylan after the attachment of PPC side chains. AFM analysis revealed details about the molecular aggregation of xylan-g-PPC films. The results also showed that with the increased DS of xylan-g-PPC copolymers, the tensile strength and Young’s modulus of the films decreased, while the elongation at break increased. Full article

(This article belongs to the Special Issue Ring-Opening Polymerization)

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16 pages, 2855 KiB

Open AccessArticle

Zinc Complexes Containing Coumarin-Derived Anilido-Aldimine Ligands as Catalysts for Ring Opening Polymerization of L-Lactide

by Chi-Tien Chen, Min-Chian Wang and Tzu-Lun Huang

Molecules 2015, 20(4), 5313-5328; https://doi.org/10.3390/molecules20045313 - 24 Mar 2015

Cited by 12 | Viewed by 6634

Abstract

The coumarin-derived ligand precursors L¹H–L⁶H have been prepared. Treatment of these ligand precursors with 1.2 equiv. of ZnEt₂ in toluene affords zinc ethyl complexes (LZnEt) 1–6 (where L = coumarin-derived ligands bearing different functional groups). Reaction of ligand precursor L³H with 1.5 equiv. of Zn[N(SiMe₃)₂]₂ in toluene affords the zinc amide complex, L³ZnN(SiMe₃)₂, 7. All these compounds were characterized by NMR spectroscopy and elemental analysis. The molecular structures are reported for 1 and 7. The catalytic activities of complexes 1–7 towards the ring opening polymerization of l-lactide in the presence of 9-AnOH have been investigated. Full article

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16 pages, 694 KiB

Open AccessArticle

Cyclic Comonomers for the Synthesis of Carboxylic Acid and Amine Functionalized Poly(l-Lactic Acid)

by Markus Heiny and V. Prasad Shastri

Molecules 2015, 20(3), 4764-4779; https://doi.org/10.3390/molecules20034764 - 16 Mar 2015

Cited by 10 | Viewed by 8635

Abstract

Degradable aliphatic polyesters such as poly(lactic acid) are widely used in biomedical applications, however, they lack functional moieties along the polymer backbone that are amenable for functionalization reactions or could be the basis for interactions with biological systems. Here we present a straightforward route for the synthesis of functional α-ω epoxyesters as comonomers for lactide polymerization. Salient features of these highly functionalized epoxides are versatility in functionality and a short synthetic route of less than four steps. The α-ω epoxyesters presented serve as a means to introduce carboxylic acid and amine functional groups into poly(lactic acid) polymers via ring-opening copolymerization. Full article

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11 pages, 1151 KiB

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Ring-Opening Polymerization of ε-Caprolactone Initiated by Ganciclovir (GCV) for the Preparation of GCV-Tagged Polymeric Micelles

by Alicia J. Sawdon and Ching-An Peng

Molecules 2015, 20(2), 2857-2867; https://doi.org/10.3390/molecules20022857 - 10 Feb 2015

Cited by 14 | Viewed by 6886

Abstract

Ganciclovir (GCV) is a nucleoside analogue with antiviral activity against herpes viral infections, and the most widely used antiviral to treat cytomegalovirus infections. However, the low bioavailability and short half-life of GCV necessitate the development of a carrier for sustained delivery. In this study, guanosine-based GCV was used as the initiator directly in ring-opening polymerization of ε-caprolactone (ε-CL) to form hydrophobic GCV-poly(caprolactone) (GCV-PCL) which was then grafted with hydrophilic chitosan to form amphiphilic copolymers for the preparation of stable micellar nanoparticles. Successful synthesis of GCV-PCL and GCV-PCL-chitosan were verified by ¹H-NMR analysis. Self-assembled micellar nanoparticles were characterized by dynamic light scattering and zetasizer with an average size of 117 nm and a positive charge of 24.2 mV. The drug release kinetics of GCV was investigated and cytotoxicity assay demonstrated that GCV-tagged polymeric micelles were non-toxic. Our results showed that GCV could be used directly in the initiation of ring-opening polymerization of ε-CL and non-toxic polymeric micelles for GCV delivery can be formed. Full article

(This article belongs to the Special Issue Ring-Opening Polymerization)

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12 pages, 995 KiB

Open AccessCommunication

Novel Zinc-Catalytic Systems for Ring-Opening Polymerization of ε-Caprolactone

by Karolina Żółtowska, Marcin Sobczak and Ewa Olędzka

Molecules 2015, 20(2), 2816-2827; https://doi.org/10.3390/molecules20022816 - 9 Feb 2015

Cited by 35 | Viewed by 7220

Abstract

Polycaprolactone (PCL) is a biodegradable synthetic polymer that is currently widely used in many pharmaceutical and medical applications. In this paper we describe the coordination ring-opening polymerization of ε-caprolactone in the presence of two newly synthesized catalytic systems: diethylzinc/gallic acid and diethylzinc/propyl gallate. The chemical structures of the obtained PCLs were characterized by ¹H- or ¹³C-NMR, FTIR spectroscopy and MALDI TOF mass spectrometry. The average molecular weight of the resulting polyesters was analysed by gel permeation chromatography and a viscosity method. The effects of temperature, reaction time and type of catalytic system on the polymerization process were examined. Linear PCLs with defined average molecular weight were successfully obtained. Importantly, in some cases the presence of macrocyclic products was not observed during the polymerization process. This study provides an effective method for the synthesis of biodegradable polyesters for medical and pharmaceutical applications due to the fact that gallic acid/propyl gallate are commonly used in the pharmaceutical industry. Full article

(This article belongs to the Special Issue Ring-Opening Polymerization)

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18 pages, 2918 KiB

Open AccessArticle

Post-Polymerization Modification of Poly(L-glutamic acid) with D-(+)-Glucosamine

by Peter Perdih, Sašo Čebašek, Alenka Možir and Ema Žagar

Molecules 2014, 19(12), 19751-19768; https://doi.org/10.3390/molecules191219751 - 27 Nov 2014

Cited by 16 | Viewed by 12055

Abstract

Carboxyl functional groups of poly(L-glutamic acid) (PGlu) were modified with a D-(+)-glucosamine (GlcN) by amidation using 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM) as a coupling reagent. The coupling reaction was performed in aqueous medium without protection of hydroxyl functional groups of D-(+)-glucosamine. Poly(L-glutamic acid) and GlcN functionalized polyglutamates (P(Glu-GlcN)) were thoroughly characterized by 1D and 2D NMR spectroscopy and SEC-MALS to gain detailed information on their structure, composition and molar mass characteristics. The results reveal successful functionalization with GlcN through the amide bond and also to a minor extent through ester bond formation in position 1 of GlcN. In addition, a ratio between the α- and β-form of glucosamine substituent coupled to polyglutamate repeating units as well as the content of residual dimethoxy triazinyl active ester moiety in the samples were evaluated. Full article

(This article belongs to the Special Issue Ring-Opening Polymerization)

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Review

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21 pages, 2276 KiB

Open AccessReview

Recent Developments of Versatile Photoinitiating Systems for Cationic Ring Opening Polymerization Operating at Any Wavelengths and under Low Light Intensity Sources

by Jacques Lalevée, Haifaa Mokbel and Jean-Pierre Fouassier

Molecules 2015, 20(4), 7201-7221; https://doi.org/10.3390/molecules20047201 - 20 Apr 2015

Cited by 86 | Viewed by 9901

Abstract

Photoinitiators (PI) or photoinitiating systems (PIS) usable in light induced cationic polymerization (CP) and free radical promoted cationic polymerization (FRPCP) reactions (more specifically for cationic ring opening polymerization (ROP)) together with the involved mechanisms are briefly reviewed. The recent developments of novel two- and three-component PISs for CP and FRPCP upon exposure to low intensity blue to red lights is emphasized in details. Examples of such reactions under various experimental conditions are provided. Full article

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23 pages, 752 KiB

Open AccessReview

Enzymatic Polymerization of Cyclic Monomers in Ionic Liquids as a Prospective Synthesis Method for Polyesters Used in Drug Delivery Systems

by Urszula Piotrowska and Marcin Sobczak

Molecules 2015, 20(1), 1-23; https://doi.org/10.3390/molecules20010001 - 23 Dec 2014

Cited by 38 | Viewed by 9985

Abstract

Biodegradable or bioresorbable polymers are commonly used in various pharmaceutical fields (e.g., as drug delivery systems, therapeutic systems or macromolecular drug conjugates). Polyesters are an important class of polymers widely utilized in pharmacy due to their biodegradability and biocompatibility features. In recent years, there has been increased interest in enzyme-catalyzed ring-opening polymerization (e-ROP) of cyclic esters as an alternative method of preparation of biodegradable or bioresorbable polymers. Ionic liquids (ILs) have been presented as green solvents in enzymatic ring-opening polymerization. The activity, stability, selectivity of enzymes in ILs and the ability to catalyze polyester synthesis under these conditions are discussed. Overall, the review demonstrates that e-ROP of lactones or lactides could be an effective method for the synthesis of useful biomedical polymers. Full article

(This article belongs to the Special Issue Ring-Opening Polymerization)

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