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Keywords = cyclopolymerization

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16 pages, 4591 KB  
Article
Iodine and Nickel Ions Adsorption by Conjugated Copolymers Bearing Repeating Units of Dicyclopentapyrenyl and Various Thiophene Derivatives
by Suchetha Shetty, Noorullah Baig, Sk Abdul Wahed, Atikur Hassan, Neeladri Das and Bassam Alameddine
Polymers 2023, 15(20), 4153; https://doi.org/10.3390/polym15204153 - 19 Oct 2023
Cited by 6 | Viewed by 1921
Abstract
The synthesis of three conjugated copolymers TPP1–3 was carried out using a palladium-catalyzed [3+2] cycloaddition polymerization of 1,6-dibromopyrene with various dialkynyl thiophene derivatives 3a–c. The target copolymers were obtained in excellent yields and high purity, as confirmed by instrumental analyses. TPP1–3 were found [...] Read more.
The synthesis of three conjugated copolymers TPP1–3 was carried out using a palladium-catalyzed [3+2] cycloaddition polymerization of 1,6-dibromopyrene with various dialkynyl thiophene derivatives 3a–c. The target copolymers were obtained in excellent yields and high purity, as confirmed by instrumental analyses. TPP1–3 were found to divulge a conspicuous iodine adsorption capacity up to 3900 mg g−1, whereas the adsorption mechanism studies revealed a pseudo-second-order kinetic model. Furthermore, recyclability tests of TPP3, the copolymer which revealed the maximum iodine uptake, disclosed its efficient regeneration even after numerous adsorption-desorption cycles. Interestingly, the target copolymers proved promising nickel ions capture efficiencies from water with a maximum equilibrium adsorption capacity (qe) of 48.5 mg g−1. Full article
(This article belongs to the Special Issue Functional Polymers for Separation and Purification Applications)
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29 pages, 9529 KB  
Review
Ring-Forming Polymerization toward Perfluorocyclobutyl and Ortho-Diynylarene-Derived Materials: From Synthesis to Practical Applications
by Eugene B. Caldona, Ernesto I. Borrego, Ketki E. Shelar, Karl M. Mukeba and Dennis W. Smith
Materials 2021, 14(6), 1486; https://doi.org/10.3390/ma14061486 - 18 Mar 2021
Cited by 22 | Viewed by 3876
Abstract
Many desirable characteristics of polymers arise from the method of polymerization and structural features of their repeat units, which typically are responsible for the polymer’s performance at the cost of processability. While linear alternatives are popular, polymers composed of cyclic repeat units across [...] Read more.
Many desirable characteristics of polymers arise from the method of polymerization and structural features of their repeat units, which typically are responsible for the polymer’s performance at the cost of processability. While linear alternatives are popular, polymers composed of cyclic repeat units across their backbones have generally been shown to exhibit higher optical transparency, lower water absorption, and higher glass transition temperatures. These specifically include polymers built with either substituted alicyclic structures or aromatic rings, or both. In this review article, we highlight two useful ring-forming polymer groups, perfluorocyclobutyl (PFCB) aryl ether polymers and ortho-diynylarene- (ODA) based thermosets, both demonstrating outstanding thermal stability, chemical resistance, mechanical integrity, and improved processability. Different synthetic routes (with emphasis on ring-forming polymerization) and properties for these polymers are discussed, followed by their relevant applications in a wide range of aspects. Full article
(This article belongs to the Special Issue Advances in Thermoset Materials)
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11 pages, 2188 KB  
Article
Metathesis Cyclopolymerization Triggered Self-Assembly of Azobenzene-Containing Nanostructure
by Wei Song, Jiamin Shen, Xiang Li, Jinhui Huang, Liang Ding and Jianhua Wu
Molecules 2020, 25(17), 3767; https://doi.org/10.3390/molecules25173767 - 19 Aug 2020
Cited by 4 | Viewed by 3060
Abstract
Azobenzene (AB) units were successfully introduced into poly(1,6-heptadiyne)s in order to ensure smooth synthesis of double- and single-stranded poly(1,6-heptadiyne)s (P1 and P2) and simultaneously realize the self-assembly by Grubbs-III catalyst-mediated metathesis cyclopolymerization (CP) of AB-functionalized bis(1,6-heptadiyne) and 1,6-heptadiyne monomers (M1 [...] Read more.
Azobenzene (AB) units were successfully introduced into poly(1,6-heptadiyne)s in order to ensure smooth synthesis of double- and single-stranded poly(1,6-heptadiyne)s (P1 and P2) and simultaneously realize the self-assembly by Grubbs-III catalyst-mediated metathesis cyclopolymerization (CP) of AB-functionalized bis(1,6-heptadiyne) and 1,6-heptadiyne monomers (M1 and M2). Monomers and polymers were characterized by 1H NMR, mass spectroscopy, and GPC techniques. The double-stranded poly(1,6-heptadiyne)s exhibited a large scale of ordered ladder nanostructure. This result was attributed to the π−π attractions between end groups along the longitudinal axis of the polymers and van der Waals interactions between the neighboring polymeric backbones. While the Azo chromophore connected in the side chain of P2 induced conformation of micelles nanostructure during the CP process without any post-treatment. Furthermore, the photoisomerization of Azo units had an obviously different regulatory effect on the conjugated degree of the polymer backbone, especially for the single-stranded P2, which was attributed to the structural differences and the interaction between AB chromophores in the polymers. Full article
(This article belongs to the Special Issue Azobenzene and Applications: From Catalysis to Biology)
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10 pages, 2500 KB  
Article
Functional Block Copolymers Carrying One Double-Stranded Ladderphane and One Single-Stranded Block in a Facile Metathesis Cyclopolymerization Procedure
by Wei Song, Yadi Li, Xunhu Liu, Zongyi Xu, Jianhua Wu and Liang Ding
Int. J. Mol. Sci. 2019, 20(20), 5166; https://doi.org/10.3390/ijms20205166 - 18 Oct 2019
Cited by 1 | Viewed by 2199
Abstract
In order to improve the poor film-forming ability of polymeric ladderphane, di-block copolymers containing perylene diimide (PDI)-linked double-stranded poly(1,6–heptadiyne) ladderphane and branched alkyl side chains modified single-stranded poly(1,6–heptadiyne) were synthesized by metathesis cyclopolymerization (MCP) using Grubbs third-generation catalyst (Ru–III) in tetrahydrofuran solvent. The [...] Read more.
In order to improve the poor film-forming ability of polymeric ladderphane, di-block copolymers containing perylene diimide (PDI)-linked double-stranded poly(1,6–heptadiyne) ladderphane and branched alkyl side chains modified single-stranded poly(1,6–heptadiyne) were synthesized by metathesis cyclopolymerization (MCP) using Grubbs third-generation catalyst (Ru–III) in tetrahydrofuran solvent. The first block containing the ladderphane structure leads to higher thermal-stability, wider UV–vis absorption, lower LUMO level and ladderphane-induced rigidity and poor film-forming ability. The second block containing long alkyl chains is crucial for the guarantee of excellent film-forming ability. By comparing the effect of ladderphane structure on the resulted copolymers, single-stranded poly(1,6–heptadiyne) derivatives with PDI pedant were also processed. The structures of copolymers were proved by 1H NMR and gel permeation chromatography, electrochemical, photophysical, and thermal-stability performance were achieved by cyclic voltammetry (CV), UV-visible spectroscopy and thermogravimetric analysis (TGA) measurements. According to the experiment results, both copolymers possessed outstanding film-forming ability, which cannot be realized by small PDI molecules and oligomers. And they can serve as a superior candidate as for n-type materials, especially for their relatively wide range of light absorption (λ = 200~800 nm), and lower LUMO level (−4.3 and −4.0 eV). Full article
(This article belongs to the Section Materials Science)
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28 pages, 4114 KB  
Article
New, Amino Acid Based Zwitterionic Polymers as Promising Corrosion Inhibitors of Mild Steel in 1 M HCl
by Mohammad A. Jafar Mazumder
Coatings 2019, 9(10), 675; https://doi.org/10.3390/coatings9100675 - 17 Oct 2019
Cited by 23 | Viewed by 4760
Abstract
The zwitterionic monomers, N,N’-diallylamino propanephosphonate and amino acid residual N,N’-diallyl-l-methionine hydrochloride were synthesized, with excellent yields. These monomers were utilized in the preparation of zwitterionic homo and co-cyclopolymers 57 in aqueous solution using 2,2′-azobis (2-methylpropionamidine) [...] Read more.
The zwitterionic monomers, N,N’-diallylamino propanephosphonate and amino acid residual N,N’-diallyl-l-methionine hydrochloride were synthesized, with excellent yields. These monomers were utilized in the preparation of zwitterionic homo and co-cyclopolymers 57 in aqueous solution using 2,2′-azobis (2-methylpropionamidine) dihydrochloride as an initiator. The polymers were characterized by FT-IR, NMR, and TGA. The performance of these synthesized polymers on mild steel in acidic solution was investigated by gravimetric method, Tafel extrapolation, linear polarization resistance, and electrochemical impedance spectroscopy. At 313 K, the maximum inhibition efficiencies of corrosion inhibitors 57 at 4.50 × 10−4 mol L−1 were found to be 85.2%, 83.3%, and 99.5%, respectively. The inhibition efficiencies obtained from gravimetric weight loss, potentiodynamic polarization, and electrochemical impedance spectroscopy measurements were in good agreement. Different adsorption isotherms were also explored to find the best fit, and found to obey Langmuir adsorption isotherm. The thermodynamic parameters, such as activation energy (Ea), standard enthalpy of activation (ΔH*), standard entropy of activation (ΔS*), adsorption–desorption equilibrium constant (Kads), and standard free energy of adsorption (ΔGoads), were determined. Electrochemical data indicated that the zwitterionic copolymer 7 acts as a mixed type inhibitor under the influence of anodic control. The surface morphology of mild steel corrosion was evaluated without and with corrosion inhibitors by AFM, SEM-EDX, and XPS, which confirmed the adsorption of inhibitor molecules on the metal surface. Full article
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17 pages, 747 KB  
Article
Synthesis, Cyclopolymerization and Cyclo-Copolymerization of 9-(2-Diallylaminoethyl)adenine and Its Hydrochloride Salt
by Kamal H. Bouhadir, Lara Abramian, Alaa Ezzeddine, Karyn Usher and Nikolay Vladimirov
Molecules 2012, 17(11), 13290-13306; https://doi.org/10.3390/molecules171113290 - 8 Nov 2012
Cited by 7 | Viewed by 6314
Abstract
We report herein the synthesis and characterization of 9-(2-diallylaminoethyl) adenine. We evaluated two different synthetic routes starting with adenine where the optimal route was achieved through coupling of 9-(2-chloroethyl)adenine with diallylamine. The cyclopolymerization and cyclo-copolymerization of 9-(2-diallylaminoethyl)adenine hydrochloride salt resulted in low molecular [...] Read more.
We report herein the synthesis and characterization of 9-(2-diallylaminoethyl) adenine. We evaluated two different synthetic routes starting with adenine where the optimal route was achieved through coupling of 9-(2-chloroethyl)adenine with diallylamine. The cyclopolymerization and cyclo-copolymerization of 9-(2-diallylaminoethyl)adenine hydrochloride salt resulted in low molecular weight oligomers in low yields. In contrast, 9-(2-diallylaminoethyl)adenine failed to cyclopolymerize, however, it formed a copolymer with SO2 in relatively good yields. The molecular weights of the cyclopolymers were around 1,700–6,000 g/mol, as estimated by SEC. The cyclo-copolymer was stable up to 226 °C. To the best of our knowledge, this is the first example of a free-radical cyclo-copolymerization of a neutral alkyldiallylamine derivative with SO2. These polymers represent a novel class of carbocyclic polynucleotides. Full article
(This article belongs to the Section Organic Chemistry)
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