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Advances in Polycondensate Polymerization Techniques
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Advances in Polycondensate Polymerization Techniques

A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Materials Chemistry".

Deadline for manuscript submissions: closed (20 March 2023) | Viewed by 11946

Special Issue Editor

Prof. Dr. Stamatina N. Vouyiouka

E-Mail Website
Guest Editor
Laboratory of Polymer Technology, School of Chemical Engineering, National Technical University of Athens, Athens, Greece
Interests: solid state polymerization; polyamides; polyesters; biodegradable polymers; bio-based polymers; enzymatic polymerization; encapsulation systems; recycling

Special Issue Information

Dear Colleagues,

This Special Issue will focus on recent developments in applying different polymerization schemes and techniques to construct new and/or conventional polycondensation polymeric repeating units. The articles can cover all possible polymerization routes (e.g., bulk, solution, suspension, and emulsion polymerization), including solid-state polymerization, in situ polymerization, and enzymatic polymerization. Works can describe process rate-controlling steps and parameters, polymerization mechanisms, use of different catalysis systems, etc., correlating them to polymer composition (copolymers, composites, blends) and properties. Emphasis can be also placed on bio-based and/or biodegradable polymers, like PLA, PBS, and PEF, and new classes of polymers/systems, like vitrimers and encapsulation systems.

It is my pleasure to invite you to submit a manuscript for publication in this Special Issue. Full papers, communications, and reviews are all welcome.

Prof. Dr. Stamatina N. Vouyiouka
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Materials is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2600 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • polycondensation
  • polymerization techniques
  • in situ polymerization
  • solid-state polymerization
  • enzymatic polymerization
  • polyamides
  • polyesters
  • copolymers
  • (nano)composites
  • recycling
  • biobased and/or biodegradable polymers
  • catalysts

Published Papers (4 papers)

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Research

22 pages, 7903 KiB  
Article
Enzymatic Catalysis in Favor of Blocky Structure and Higher Crystallinity of Poly(Butylene Succinate)-Co-(Dilinoleic Succinate) (PBS-DLS) Copolymers of Variable Segmental Composition
by Martyna Sokołowska, Jagoda Nowak-Grzebyta, Ewa Stachowska and Miroslawa El Fray
Materials 2022, 15(3), 1132; https://doi.org/10.3390/ma15031132 - 1 Feb 2022
Cited by 8 | Viewed by 1741
Abstract
To systematically investigate the synthesis of poly(butylene succinate)-co-(dilinoleic succinate) (PBS-DLS) copolymers and to enrich the library of polyesters synthesized via a sustainable route, we conducted a two-step polycondensation using fully biobased monomers such as diethyl succinate (DS), 1,4-butanediol (1,4-BD) and dilinoleic diol (DLD) [...] Read more.
To systematically investigate the synthesis of poly(butylene succinate)-co-(dilinoleic succinate) (PBS-DLS) copolymers and to enrich the library of polyesters synthesized via a sustainable route, we conducted a two-step polycondensation using fully biobased monomers such as diethyl succinate (DS), 1,4-butanediol (1,4-BD) and dilinoleic diol (DLD) in diphenyl ether, using Candida Antarctica lipase B (CAL-B) as biocatalyst. A series of PBS-DLS copolyesters with a 90-10, 70-30 and 50-50 wt% of hard (PBS) to soft (DLS) segments ratio were compared to their counterparts, which were synthesized using heterogenous titanium dioxide/silicon dioxide (TiO2/SiO2) catalyst. Chemical structure and molecular characteristics of resulting copolymers were assessed using nuclear magnetic spectroscopy (1H- and 13C-NMR) and gel permeation chromatography (GPC), whereas thermal and thermomechanical properties as well as crystallization behavior were investigated by differential scanning microscopy (DSC), dynamic mechanical thermal analysis (DMTA), digital holographic microscopy (DHM) and X-ray diffraction (XRD). The obtained results showed that, depending on the type of catalyst, we can control parameters related to blockiness and crystallinity of copolymers. Materials synthesized using CAL-B catalysts possess more blocky segmental distribution and higher crystallinity in contrast to materials synthesized using heterogenous catalysts, as revealed by DSC, XRD and DHM measurements. Full article
(This article belongs to the Special Issue Advances in Polycondensate Polymerization Techniques)
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7 pages, 1396 KiB  
Article
Tacky-Free Polyurethanes Pressure-Sensitive Adhesives by Molecular-Weight and HDI Trimer Design
by Ji-Hong Bae, Jong Chan Won, Won Bin Lim, Byeong Joo Kim, Ju Hong Lee, Jin Gyu Min, Min Ji Seo, Young Hyun Mo and PilHo Huh
Materials 2021, 14(9), 2164; https://doi.org/10.3390/ma14092164 - 23 Apr 2021
Cited by 12 | Viewed by 2740
Abstract
Polyurethane pressure-sensitive adhesives (PU-PSAs) with satisfactory tack, cohesion, and removability were newly developed through the synthetic process by reacting methylene diisocyanate, poly(ethylene glycol) (PEG), and a 1,4-butanediol chain extender based on the different HDI/HDI trimer ratios. The sticking properties of PU-PSAs depended on [...] Read more.
Polyurethane pressure-sensitive adhesives (PU-PSAs) with satisfactory tack, cohesion, and removability were newly developed through the synthetic process by reacting methylene diisocyanate, poly(ethylene glycol) (PEG), and a 1,4-butanediol chain extender based on the different HDI/HDI trimer ratios. The sticking properties of PU-PSAs depended on both the HDI/HDI trimer ratio and crosslinking-agent composition in the formulation. The molecular weight (MW) dependence of adhesion in PU-PSA was observed in the range of 1000 < Mn < 3000, suggesting that the increase in MW limits the pressure-sensitive adhesion of these samples. The differences in the crosslinking-density significantly affected the cohesion, adhesion, and tack in PU-PSA. The formulation of 50 wt.% 600PEG and 50 wt.% crosslinking-agent and an HDI/HDI trimer ratio of 1.0 led to the optimal balance between the adhesion and cohesion properties owing to the sufficient tack, high 180-peel strength, and good cohesion. Full article
(This article belongs to the Special Issue Advances in Polycondensate Polymerization Techniques)
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18 pages, 2407 KiB  
Article
Solid-State Polymerization as a Vitrimerization Tool Starting from Available Thermoplastics: The Effect of Reaction Temperature
by Christos Panagiotopoulos, Athanasios Porfyris, Dimitrios Korres and Stamatina Vouyiouka
Materials 2021, 14(1), 9; https://doi.org/10.3390/ma14010009 - 22 Dec 2020
Cited by 6 | Viewed by 3561
Abstract
In the current work, solid-state polymerization (SSP) was studied for the synthesis of poly(butylene terephthalate), PBT-based vitrimers. A two-step process was followed; the first step involved alcoholysis reactions and the incorporation of glycerol in the polymer chains. The second step comprised transesterification reactions [...] Read more.
In the current work, solid-state polymerization (SSP) was studied for the synthesis of poly(butylene terephthalate), PBT-based vitrimers. A two-step process was followed; the first step involved alcoholysis reactions and the incorporation of glycerol in the polymer chains. The second step comprised transesterification reactions in the solid state (SSP) in the presence of zinc(II) catalyst resulting in the formation of a dynamic crosslinked network with glycerol moieties serving as the crosslinkers. The optimum SSP conditions were found to be 3 h at 180 °C under N2 flow (0.5 L/min) to reach high vitrimer insolubility (up to 75%) and melt strength (2.1 times reduction in the melt flow rate) while increasing the crosslinker concentration (from 3.5 to 7 wt.%) improved further the properties. Glass transition temperature (Tg) was almost tripled in vitrimers compared to initial thermoplastic, reaching a maximum of 97 °C, whereas the melting point (Tm) was slightly decreased, due to loss of symmetry perfection under the influence of the crosslinks. Moreover, the effect of the dynamic crosslinked structure on PBT crystallization behavior was investigated in detail by studying the kinetics of non-isothermal crystallization. The calculated effective activation energy using the Kissinger model and the nucleating activity revealed that the higher crosslinker content impeded and slowed down vitrimers melt crystallization, also inducing an alteration in the crystallization mechanism towards sporadic heterogeneous growth. Full article
(This article belongs to the Special Issue Advances in Polycondensate Polymerization Techniques)
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16 pages, 2881 KiB  
Article
Towards High Molecular Weight Furan-Based Polyesters: Solid State Polymerization Study of Bio-Based Poly(Propylene Furanoate) and Poly(Butylene Furanoate)
by Lazaros Papadopoulos, Eleftheria Xanthopoulou, George N. Nikolaidis, Alexandra Zamboulis, Dimitris S. Achilias, George Z. Papageorgiou and Dimitrios N. Bikiaris
Materials 2020, 13(21), 4880; https://doi.org/10.3390/ma13214880 - 30 Oct 2020
Cited by 13 | Viewed by 2958
Abstract
In the era of polymers from renewable resources, polyesters derived from 2,5 furan dicarboxylic acid (FDCA) have received increasing attention due to their outstanding features. To commercialize them, it is necessary to synthesize high molecular weight polymers through efficient and simple methods. In [...] Read more.
In the era of polymers from renewable resources, polyesters derived from 2,5 furan dicarboxylic acid (FDCA) have received increasing attention due to their outstanding features. To commercialize them, it is necessary to synthesize high molecular weight polymers through efficient and simple methods. In this study, two furan-based polyesters, namely poly (propylene furanoate) (PPF) and poly(butylene furanoate) (PBF), were synthesized with the conventional two-step melt polycondensation, followed by solid-state polycondensation (SSP) conducted at different temperatures and reaction times. Molecular weight, structure and thermal properties were measured for all resultant polyesters. As expected, increasing SSP time and temperature results in polymers with increased intrinsic viscosity (IV), increased molecular weight and reduced carboxyl end-group content. Finally, those results were used to generate a simple mathematical model that prognosticates the time evolution of the materials’ IV and end groups concentration during SSP. Full article
(This article belongs to the Special Issue Advances in Polycondensate Polymerization Techniques)
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