New Developments in Ring-Opening Polymerization

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

Deadline for manuscript submissions: closed (20 March 2018)

Special Issue Editor


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Guest Editor
Laboratory of Industrial Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, 15771 Zografou, Greece
Interests: polymer synthesis; polymer characterization; self-assembly of copolymers in selective solvents
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Special Issue Information

Dear Colleagues,

Polymer Chemistry has witnessed a tremendous progress during the last few decades with the development of novel synthetic methodologies, leading to the synthesis of complex macromolecular architectures with controlled molecular and structural characteristics. One of the most traditional, but at the same time ever-growing polymerization methods, is Ring Opening Polymerization (ROP). This method involves the polymerization of cyclic monomers, leading to macromolecular chains containing monomer units, which are acyclic or contain fewer cycles than the monomer.

A huge variety of monomers can be polymerized using this technique, such as epoxides, cyclic olefins, thioethers and amines, lactams, lactones, thiolactones, disulfides, N-carboxy anhydrides, carbonates, siloxanes, phosphazenes, oxazolines, etc., leading to products with diverse properties, e.g., hydrophilic, hydrophobic, amorphous, semicrystalline, biodegradable, biocompatible, etc. The mechanism of polymerization may be cationic, anionic, radical or catalytic. More recently, Ring Opening Metathesis Polymerization (ROMP) has been emerged as a new, powerful and broadly-applicable tool in the field of Polymer Chemistry, involving the use of metal alkylidene complexes.   

This Special Issue is focused on the recent developments in the area of ROP leading to the synthesis of both linear and non-linear homo- and copolymers. Polymerization of new cyclic monomers, kinetics and thermodynamics of polymerization, mechanistic studies, design and synthesis of novel catalytic species able to promote ROP, along with the synthesis of complex macromolecular architectures in combination with other polymerization methodologies, molecular and structural characterization of the polymeric products, preparation of polymer nanocomposites with inorganic materials (silica, alumina, clays, etc.), carbon nanotubes or graphene are among the topics that will be covered. Both original contributions and reviews are welcome.

Prof. Dr. Marinos Pitsikalis
Guest Editor

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Keywords

  • Cyclic monomers
  • Ring Opening Metathesis Polymerization
  • Linear and non-linear homo- and copolymers
  • Polymer nanocomposites by ROP
  • ROP kinetics
  • Thermodynamics of ROP
  • Polymerization mechanism
  • Molecular and structural characterization

Published Papers (3 papers)

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Research

14 pages, 21349 KiB  
Article
Low-Dissipation Thermosets Derived from Oligo(2,6-Dimethyl Phenylene Oxide)-Containing Benzoxazines
by Chien-Han Chen, Kuan-Wei Lee, Ching-Hsuan Lin and Tzong-Yuan Juang
Polymers 2018, 10(4), 411; https://doi.org/10.3390/polym10040411 - 07 Apr 2018
Cited by 17 | Viewed by 6476
Abstract
Poly(2,6-dimethyl phenyl oxide) (PPO) is known for its low dissipation factor. To achieve insulating materials with low dissipation factors for high-frequency communication applications, a telechelic oligomer-type benzoxazine (P-APPO) and a main-chain type benzoxazine polymer (BPA-APPO) were prepared from an amine end-capped oligo (2,6-dimethyl [...] Read more.
Poly(2,6-dimethyl phenyl oxide) (PPO) is known for its low dissipation factor. To achieve insulating materials with low dissipation factors for high-frequency communication applications, a telechelic oligomer-type benzoxazine (P-APPO) and a main-chain type benzoxazine polymer (BPA-APPO) were prepared from an amine end-capped oligo (2,6-dimethyl phenylene oxide) (APPO). The APPO was prepared from a nucleophilic substitution of a phenol-end capped oligo (2,6-dimethyl phenylene oxide) (a commercial product, SA 90) with fluoronitrobenzene, and followed by catalytic hydrogenation. After self-curing or curing with a dicyclopentadiene-phenol epoxy (HP 7200), thermosets with high-Tg and low-dissipation factor can be achieved. Furthermore, the resulting epoxy thermosets show better thermal and dielectric properties than those of epoxy thermoset cured from its precursor SA90, demonstrating it is a successful modification in simultaneously enhancing the thermal and dielectric properties. Full article
(This article belongs to the Special Issue New Developments in Ring-Opening Polymerization)
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26 pages, 38938 KiB  
Article
Biocompatible Nanobioglass Reinforced Poly(ε-Caprolactone) Composites Synthesized via In Situ Ring Opening Polymerization
by Zoi Terzopoulou, Diana Baciu, Eleni Gounari, Theodore Steriotis, Georgia Charalambopoulou and Dimitrios Bikiaris
Polymers 2018, 10(4), 381; https://doi.org/10.3390/polym10040381 - 01 Apr 2018
Cited by 23 | Viewed by 4503
Abstract
Poly(ε-caprolactone) (PCL) is a bioresorbable synthetic polyester widely studied as a biomaterial for tissue engineering and controlled release applications, but its low bioactivity and weak mechanical performance limits its applications. In this work, nanosized bioglasses with two different compositions (SiO2–CaO and [...] Read more.
Poly(ε-caprolactone) (PCL) is a bioresorbable synthetic polyester widely studied as a biomaterial for tissue engineering and controlled release applications, but its low bioactivity and weak mechanical performance limits its applications. In this work, nanosized bioglasses with two different compositions (SiO2–CaO and SiO2–CaO–P2O5) were synthesized with a hydrothermal method, and each one was used as filler in the preparation of PCL nanocomposites via the in situ ring opening polymerization of ε-caprolactone. The effect of the addition of 0.5, 1 and 2.5 wt % of the nanofillers on the molecular weight, structural, mechanical and thermal properties of the polymer nanocomposites, as well as on their enzymatic hydrolysis rate, bioactivity and biocompatibility was systematically investigated. All nanocomposites exhibited higher molecular weight values in comparison with neat PCL, and mechanical properties were enhanced for the 0.5 and 1 wt % filler content, which was attributed to extensive interactions between the filler and the matrix, proving the superiority of in situ polymerization over solution mixing and melt compounding. Both bioglasses accelerated the enzymatic degradation of PCL and induced bioactivity, since apatite was formed on the surface of the nanocomposites after soaking in simulated body fluid. Finally, all samples were biocompatible as Wharton jelly-derived mesenchymal stem cells (WJ-MSCs) attached and proliferated on their surfaces. Full article
(This article belongs to the Special Issue New Developments in Ring-Opening Polymerization)
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11 pages, 2001 KiB  
Article
Catechol End-Functionalized Polylactide by Organocatalyzed Ring-Opening Polymerization
by Naroa Sadaba, Maitane Salsamendi, Nerea Casado, Ester Zuza, Jone Muñoz, Jose-Ramon Sarasua, David Mecerreyes, Daniele Mantione, Christophe Detrembleur and Haritz Sardon
Polymers 2018, 10(2), 155; https://doi.org/10.3390/polym10020155 - 06 Feb 2018
Cited by 13 | Viewed by 5918
Abstract
There is a great interest in incorporating catechol moieties into polymers in a controlled manner due to their interesting properties, such as the promotion of adhesion, redox activity or bioactivity. One possibility is to incorporate the catechol as end-group in a polymer chain [...] Read more.
There is a great interest in incorporating catechol moieties into polymers in a controlled manner due to their interesting properties, such as the promotion of adhesion, redox activity or bioactivity. One possibility is to incorporate the catechol as end-group in a polymer chain using a functional initiator by means of controlled polymerization strategies. Nevertheless, the instability of catechol moieties under oxygen and basic pH requires tedious protection and deprotection steps to perform the polymerization in a controlled fashion. In the present work, we explore the organocatalyzed synthesis of catechol end-functional, semi-telechelic polylactide (PLLA) using non-protected dopamine, catechol molecule containing a primary amine, as initiator. NMR and SEC-IR results showed that in the presence of a weak organic base such as triethylamine, the ring-opening polymerization (ROP) of lactide takes place in a controlled manner without need of protecting the cathechol units. To further confirm the end-group fidelity the catechol containing PLLA was characterized by Cyclic Voltammetry and MALDI-TOF confirming the absence of side reaction during the polymerization. In order to exploit the potential of catechol moieties, catechol end-group of PLLA was oxidized to quinone and further reacted with aliphatic amines. In addition, we also confirmed the ability of catechol functionalized PLLA to reduce metal ions to metal nanoparticles to obtain well distributed silver nanoparticles. It is expected that this new route of preparing catechol-PLLA polymers without protection will increase the accessibility of catechol containing biodegradable polymers by ROP. Full article
(This article belongs to the Special Issue New Developments in Ring-Opening Polymerization)
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