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Themed Issue Dedicated to Prof. Bernard Boutevin

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

Deadline for manuscript submissions: closed (30 April 2024) | Viewed by 19626

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Dr. Benoit Briou

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Guest Editor

ICGM, Univ Montpellier, CNRS, ENSCM, 34095 Montpellier, France
Interests: bio-based material; CNSL; thermoset resin; plasticizer; surfactant

Dr. Bruno Ameduri

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Guest Editor

Ingénierie et Architectures Macromoléculaires, Institut Charles Gerhardt, Ecole Nationale Supérieure de Chimie de Montpellier (UMR5253-CNRS), 8, rue de l’Ecole Normale, 34296 Montpellier, CEDEX 1, France
Interests: fluorinated polymers; radical polymerization; RDRP (co)polymerization; telomerization

Prof. Dr. Cyrille Boyer

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School of Chemical Engineering, University of New South Wales (UNSW), Sydney, NSW 2052, Australia
Interests: photoredox chemistry; photopolymerization; functional polymers; nanomedicine
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Special Issue Information

Dear Colleagues,

Professor Dr. Bernard Boutevin, born in 1948, received his PhD degree in 1974 from the University of Montpellier, France, and joined the French National Centre for Scientific Research (CNRS). Subsequently, he established a Polymer Laboratory in Montpellier in 1985. Then, he was the director of several research units with more than 100 researchers. He was appointed a full professor in 1999. Pr. Boutevin is a member of the American Chemical Society and Groupe Français d’Etudes et d’Applications des Polymères (GFP).

The topics of his research first concerned the telomerization of a wide variety of monomers including fluoroalkenes but also styrenics and acrylics: kinetics, chemical modifications, and their use in architectured polymers (block and grafted copolymers). The concept was first applied to fluorinated monomers, representing almost half of his scientific articles. His research was then directed toward telechelic oligomers, and all the methods of controlled radical polymerization (or RDRP). In the last decade, he has been quite interested in the synthesis and use of new biobased building blocks and polymers.

Pr. Bernard Boutevin has received many awards (especially from the GFP) and has had a long, distinguished teaching and research career. He has authored more than 600 research publications and been the inventor of more than 100 patents. He has mentored >200 graduate students and postdocs. He is now Professor Emeritus and continues his dedication to scientific research.

Molecules is pleased to announce this Special Issue to celebrate Prof. Bernard Boutevin’s 73rd birthday and his enormous contributions in the field of polymer chemistry. This special issue is dedicated to all aspects of Polymer Chemistry, in particular, following Prof. Bernard Boutevin’s interests.

It is a pleasure to invite you to submit a manuscript to this Special Issue. Regular articles, communications, and reviews about polymers are all welcome.

Dr. Benoit Briou
Dr. Bruno Ameduri
Prof. Dr. Cyrille Boyer
Guest Editors

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. Molecules 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 2700 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

Telomerisation
Radical polymerisation
Biobased

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Published Papers (11 papers)

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11 pages, 2461 KiB

Open AccessArticle

The Development of Visible-Light Organic Photocatalysts for Atom Transfer Radical Polymerization via Conjugation Extension

by Hui Shao, Runzhi Long, Hui Xu, Pan Sun, Guangrong Wang, Yuanming Li and Saihu Liao

Molecules 2024, 29(12), 2763; https://doi.org/10.3390/molecules29122763 - 11 Jun 2024

Viewed by 896

Abstract

This work aimed to develop organic photocatalysts (PCs) that could mediate organocatalytic atom transfer radical polymerization (O-ATRP) under visible light. Through the core-modification of known chromophoric structures and ring-locking to reach a conjugation extension, annulated N-aryl benzo[kl]acridines were identified as effective visible light-responsive photocatalysts. The corresponding selenium-doped structure showed excellent performance in the O-ATRP of methacrylates, which could afford polymer products with controlled molecular weights and low dispersities under the irradiation of visible light at a 100 ppm catalyst loading. Full article

(This article belongs to the Special Issue Themed Issue Dedicated to Prof. Bernard Boutevin)

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15 pages, 2271 KiB

Open AccessArticle

Pushing the Limit of Photo-Controlled Polymerization: Hyperchromic and Bathochromic Effects

by Zhilei Wang, Zipeng Zhang, Chenyu Wu, Zikuan Wang and Wenjian Liu

Molecules 2024, 29(10), 2377; https://doi.org/10.3390/molecules29102377 - 18 May 2024

Viewed by 975

Abstract

The photocatalyst (PC) zinc tetraphenylporphyrin (ZnTPP) is highly efficient for photoinduced electron/energy transfer reversible addition-fragmentation chain transfer (PET-RAFT) polymerization. However, ZnTPP suffers from poor absorbance of orange light by the so-called Q-band of the absorption spectrum (maximum absorption wavelength

λ_{\max}

= 600 [...] Read more.

λ_{\max}

= 600 nm, at which molar extinction coefficient

ε_{\max}

1.0 \times 10^{4}

L/(mol·cm)), hindering photo-curing applications that entail long light penetration paths. Over the past decade, there has not been any competing candidate in terms of efficiency, despite a myriad of efforts in PC design. By theoretical evaluation, here we rationally introduce a peripheral benzo moiety on each of the pyrrole rings of ZnTPP, giving zinc tetraphenyl tetrabenzoporphyrin (ZnTPTBP). This modification not only enlarges the conjugation length of the system, but also alters the

a_{1 u}

occupied

π

molecular orbital energy level and breaks the accidental degeneracy between the

a_{1 u}

and

a_{2 u}

orbitals, which is responsible for the low absorption intensity of the Q-band. As a consequence, not only is there a pronounced hyperchromic and bathochromic effect (

λ_{\max}

= 655 nm and

ε_{\max}

5.2 \times 10^{4}

L/(mol·cm)) of the Q-band, but the hyperchromic effect is achieved without increasing the intensity of the less useful, low wavelength absorption peaks of the PC. Remarkably, this strong 655 nm absorption takes advantage of deep-red (650–700 nm) light, a major component of solar light exhibiting good atmosphere penetration, exploited by the natural PC chlorophyll a as well. Compared with ZnTPP, ZnTPTBP displayed a 49% increase in PET-RAFT polymerization rate with good control, marking a significant leap in the area of photo-controlled polymerization. Full article

(This article belongs to the Special Issue Themed Issue Dedicated to Prof. Bernard Boutevin)

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11 pages, 2645 KiB

Open AccessArticle

α-Amido Trifluoromethyl Xanthates: A New Class of RAFT/MADIX Agents

by Mathias Destarac, Juliette Ruchmann-Sternchuss, Eric Van Gramberen, Xavier Vila and Samir Z. Zard

Molecules 2024, 29(10), 2174; https://doi.org/10.3390/molecules29102174 - 7 May 2024

Viewed by 775

Abstract

Xanthates have long been described as poor RAFT/MADIX agents for styrene polymerization. Through the determination of chain transfer constants to xanthates, this work demonstrated beneficial capto-dative substituent effects for the leaving group of a new series of α-amido trifluoromethyl xanthates, with the best effect observed with trifluoroacetyl group. The previously observed Z-group activation with a O-trifluoroethyl group compared to the O-ethyl counterpart was quantitatively established with C_ex = 2.7 (3–4 fold increase) using the SEC peak resolution method. This study further confirmed the advantageous incorporation of trifluoromethyl substituents to activate xanthates in radical chain transfer processes and contributed to identify the most reactive xanthate reported to date for RAFT/MADIX polymerization of styrene. Full article

(This article belongs to the Special Issue Themed Issue Dedicated to Prof. Bernard Boutevin)

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10 pages, 1584 KiB

Open AccessArticle

Temperature Dependence of the Number of Defect-Structures in Poly(vinylidene fluoride)

by Jan Schwaderer, Marco Drache and Sabine Beuermann

Molecules 2024, 29(7), 1551; https://doi.org/10.3390/molecules29071551 - 29 Mar 2024

Cited by 3 | Viewed by 986

Abstract

Poly(vinylidene fluoride) (PVDF) is predominantly characterized by alternating CH₂ and CF₂ units in a polymer backbone, originating from the head-to-tail addition of monomers or regular propagation. Due, to a small extent, to inverse monomer addition, so-called defect structures occur which influence the macroscopic properties of PVDF significantly. The amount of defect structures in the material is determined by the polymerization conditions. Here, the temperature dependence of the fraction of defect structures in PVDF obtained from polymerizations between 45 and 90 °C is reported. We utilized ¹⁹F-NMR spectroscopy to determine the fraction of defect structures as a function of temperature. To derive kinetic data, the polymerization of VDF is considered a quasi-copolymerization described by the Terminal Model involving four different propagation reactions. Based on the experimentally determined temperature-dependent fractions of defect structures, the known overall propagation rate coefficient, and taking into account the self-healing behavior of the macroradical, the Arrhenius parameters of the individual propagation rate coefficients were determined using the Monte Carlo methods. Full article

(This article belongs to the Special Issue Themed Issue Dedicated to Prof. Bernard Boutevin)

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10 pages, 2010 KiB

Open AccessArticle

Nitroxide-Mediated Controlled Radical Copolymerization of α-Trifluoromethylstyrenes with Styrenes

by Tadashi Kanbara, Yuriko Ito, Airi Yamaguchi and Tomoko Yajima

Molecules 2024, 29(6), 1214; https://doi.org/10.3390/molecules29061214 - 8 Mar 2024

Viewed by 1326

Abstract

Fluorinated polymers are important materials in everyday life; however, most monomers of widely used fluoropolymers are gaseous, and their polymerization is difficult in an ordinary laboratory. Therefore, partially fluorinated polymers have recently been reported. As an easy-to-handle fluorine-containing monomer, α-trifluoromethylstyrene (TFMST) can be used to produce partially fluorinated polymers with trifluoromethyl groups in the main chain; however, TFMST does not homopolymerize, and there are limited reports on its copolymerization with styrene (ST). In this study, we applied the controlled radical polymerization method, which is effective for the polymerization of ST, to the copolymerization of TFMST and ST. We also showed that nitroxide-mediated polymerization is effective. The content ratio of TFMST in the TFMST–ST copolymer can be controlled between 10% and 40% by changing its monomer ratio. Additionally, the polymerization of TFMST and ST with substituents was performed to increase structural variations. The thermal stability as well as water and oil repellency of the synthesized polymers with different composition ratios and substituents were also evaluated. Full article

(This article belongs to the Special Issue Themed Issue Dedicated to Prof. Bernard Boutevin)

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13 pages, 2401 KiB

Open AccessArticle

Incorporation of Aramids into Polybenzimidazoles to Achieve Ultra-High Thermoresistance and Toughening Effects

by Xianzhu Zhong, Aniruddha Nag, Kenji Takada, Akinori Nakajima and Tatsuo Kaneko

Molecules 2024, 29(5), 1058; https://doi.org/10.3390/molecules29051058 - 28 Feb 2024

Viewed by 1064

Abstract

Polybenzimidazoles (PBIs) are recognized for their remarkable thermal stability due to their unique molecular structure, which is characterized by aromaticity and rigidity. Despite their remarkable thermal attributes, their tensile properties limit their application. To improve the mechanical performance of PBIs, we made a vital modification to their molecular backbone to improve their structural flexibility. Non-π-conjugated components were introduced into PBIs by grafting meta-polyamide (MA) and para-polyamide (PA) onto PBI backbones to form the copolymers PBI-co-MA and PBI-co-PA. The results indicated that the cooperation between MA and PA significantly enhanced mechanical strain and overall toughness. Furthermore, the appropriate incorporation of aromatic polyamide components (20 mol% for MA and 15% for PA) improved thermal degradation temperatures by more than 30 °C. By investigating the copolymerization of PBIs with MA and PA, we unraveled the intricate relationships between composition, molecular structure, and material performance. These findings advance copolymer design strategies and deepen the understanding of polymer materials, offering tailored solutions that address thermal and mechanical demands across applications. Full article

(This article belongs to the Special Issue Themed Issue Dedicated to Prof. Bernard Boutevin)

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15 pages, 3257 KiB

Open AccessArticle

A One-Step Approach for a Durable and Highly Hydrophobic Coating for Flax Fabrics for Self-Cleaning Application

by Antoine Ishak, Rodolphe Sonnier, Belkacem Otazaghine and Claire Longuet

Molecules 2024, 29(4), 829; https://doi.org/10.3390/molecules29040829 - 13 Feb 2024

Cited by 2 | Viewed by 1562

Abstract

Highly hydrophobic flax fabrics with durable properties were prepared using the “dip-coating” method for self-cleaning application. Flax fabrics were coated with a polysiloxane coating via a hydrosilylation reaction with a Karstedt catalyst at room temperature. The coated fabrics displayed highly and durable hydrophobic properties (contact angle and sliding angle of about 145° and 23°, respectively) with good self-cleaning ability for certain pollutants and excellent durability. Moreover, the influence of the coating process on the mechanical properties of fabrics was investigated. A decrease in E modulus and an increase in tensile stress at maximum force and elongation at maximum force has been observed. Furthermore, this influence of the coating process can be easily controlled by adjusting the proportion of curing agent in the treatment solution. Full article

(This article belongs to the Special Issue Themed Issue Dedicated to Prof. Bernard Boutevin)

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19 pages, 4562 KiB

Open AccessArticle

The Effect of Block Ratio and Structure on the Thermosensitivity of Double and Triple Betaine Block Copolymers

by Jongmin Lim, Hideki Matsuoka, Yusuke Kinoshita, Shin-ichi Yusa and Yoshiyuki Saruwatari

Molecules 2024, 29(2), 390; https://doi.org/10.3390/molecules29020390 - 12 Jan 2024

Viewed by 1158

Abstract

AB-type and BAB-type betaine block copolymers composed of a carboxybetaine methacrylate and a sulfobetaine methacrylate, PGLBT-b-PSPE and PSPE-b-PGLBT-b-PSPE, respectively, were synthesized by one-pot RAFT polymerization. By optimizing the concentration of the monomer, initiator, and chain transfer agent, block extension with precise ratio control was enabled and a full conversion (~99%) of betaine monomers was achieved at each step. Two sets (total degree of polymerization: ~300 and ~600) of diblock copolymers having four different PGLBT:PSPE ratios were prepared to compare the influence of block ratio and molecular weight on the temperature-responsive behavior in aqueous solution. A turbidimetry and dynamic light scattering study revealed a shift to higher temperatures of the cloud point and micelle formation by increasing the ratio of PSPE, which exhibit upper critical solution temperature (UCST) behavior. PSPE-dominant diblocks created spherical micelles stabilized by PGLBT motifs, and the transition behavior diminished by decreasing the PSPE ratio. No particular change was found in the diblocks that had an identical AB ratio. This trend reappeared in the other set whose entire molecular weight approximately doubled, and each transition point was not recognizably impacted by the total molecular weight. For triblocks, the PSPE double ends provided a higher probability of interchain attractions and resulted in a more turbid solution at higher temperatures, compared to the diblocks which had similar block ratios and molecular weights. The intermediates assumed as network-like soft aggregates eventually rearranged to monodisperse flowerlike micelles. It is expected that the method for obtaining well-defined betaine block copolymers, as well as the relationship of the block ratio and the chain conformation to the temperature-responsive behavior, will be helpful for designing betaine-based polymeric applications. Full article

(This article belongs to the Special Issue Themed Issue Dedicated to Prof. Bernard Boutevin)

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15 pages, 2883 KiB

Open AccessFeature PaperArticle

Original Fluorinated Non-Isocyanate Polyhydroxyurethanes

by Lolwa Haydar, Wassim El Malti, Vincent Ladmiral, Ali Alaaeddine and Bruno Ameduri

Molecules 2023, 28(4), 1795; https://doi.org/10.3390/molecules28041795 - 14 Feb 2023

Cited by 2 | Viewed by 1962

Abstract

New fluorinated polyhydroxyurethanes (FPHUs) with various molar weights were synthesized via the polyaddition reaction of a fluorinated telechelic bis(cyclocarbonate) (bis-CC) with a diamine. The fluorinated bis-CC was initially synthesized by carbonylation of a fluorinated diepoxide, 1,4-bis(2′,3′-epoxypropyl)perfluorobutane, in the presence of LiBr catalyst, in high yield. Then, several reaction conditions were optimized through the model reactions of the fluorinated bis-CC with hexylamine. Subsequently, fluorinated polymers bearing hydroxyurethane moieties (FPHUs) were prepared by reacting the bis-CC with different hexamethylenediamine amounts in bulk at 80 °C and the presence of a catalyst. The chemoselective polymerization reaction yielded three isomers bearing primary and secondary hydroxyl groups in 61–82% yield. The synthesized fluorinated CCs and the corresponding FPHUs were characterized by ¹H, ¹⁹F, and ¹³C NMR spectroscopy. They were compared to their hydrogenated homologues synthesized in similar conditions. The gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) data of the FPHUs revealed a higher molar mass and a slight increase in glass transition and decomposition temperatures compared to those of the PHUs. Full article

(This article belongs to the Special Issue Themed Issue Dedicated to Prof. Bernard Boutevin)

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9 pages, 618 KiB

Open AccessArticle

Using Triethylborane to Manipulate Reactivity Ratios in Epoxide-Anhydride Copolymerization: Application to the Synthesis of Polyethers with Degradable Ester Functions

by Vamshi K. Chidara, Yves Gnanou and Xiaoshuang Feng

Molecules 2022, 27(2), 466; https://doi.org/10.3390/molecules27020466 - 11 Jan 2022

Cited by 10 | Viewed by 3117

Abstract

The anionic ring-opening copolymerization (ROCOP) of epoxides, namely of ethylene oxide (EO), with anhydrides (AH) generally produces strictly alternating copolymers. With triethylborane (TEB)-assisted ROCOP of EO with AH, statistical copolymers of high molar mass including ether and ester units could be obtained. In the presence of TEB, the reactivity ratio of EO (r_EO), which is normally equal to 0 in its absence, could be progressively raised to values lower than 1 or higher than 1. Conditions were even found to obtain r_EO equal or close to 1. Samples of P(EO-co-ester) with minimal compositional drift could be synthesized; upon basic degradation of their ester linkages, these samples afforded poly(ethylene oxide) (PEO) diol samples of narrow molar mass distribution. In other cases where r_EO were lower or higher than 1, the PEO diol samples eventually isolated after degradation exhibited a broader distribution of molar masses because of the compositional drift of initial P(EO-co-ester) samples. Full article

(This article belongs to the Special Issue Themed Issue Dedicated to Prof. Bernard Boutevin)

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26 pages, 5758 KiB

Open AccessFeature PaperReview

Monomers and Macromolecular Materials from Renewable Resources: State of the Art and Perspectives

by Alessandro Gandini and Talita M. Lacerda

Molecules 2022, 27(1), 159; https://doi.org/10.3390/molecules27010159 - 28 Dec 2021

Cited by 29 | Viewed by 4184

Abstract

A progressively increasing concern about the environmental impacts of the whole polymer industry has boosted the design of less aggressive technologies that allow for the maximum use of carbon atoms, and reduced dependence on the fossil platform. Progresses related to the former approach are mostly based on the concept of the circular economy, which aims at a thorough use of raw materials, from production to disposal. The latter, however, has been considered a priority nowadays, as short-term biological processes can efficiently provide a myriad of chemicals for the polymer industry. Polymers from renewable resources are widely established in research and technology facilities from all over the world, and a broader consolidation of such materials is expected in a near future. Herein, an up-to-date overview of the most recent and relevant contributions dedicated to the production of monomers and polymers from biomass is presented. We provide some basic issues related to the preparation of polymers from renewable resources to discuss ongoing strategies that can be used to achieve original polymers and systems thereof. Full article

(This article belongs to the Special Issue Themed Issue Dedicated to Prof. Bernard Boutevin)

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