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Polymers
Special Issues
Polymerizations Promoted by Metal Complexes
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Polymerizations Promoted by Metal Complexes

A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Polymer Chemistry".

Deadline for manuscript submissions: closed (30 June 2020) | Viewed by 45448

Special Issue Editors

Prof. Dr. Marinos Pitsikalis

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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
Special Issues, Collections and Topics in MDPI journals
Dr. Ioannis Choinopoulos

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Co-Guest Editor
Laboratory of Industrial Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, Zografou 15771, Greece
Interests: polymer synthesis; polymer characterization; chiral polymers; coordination polymerization; organometallic synthesis

Special Issue Information

Dear Colleagues,

The main effort in polymer chemistry is the development of new synthetic methods leading to products with well-defined molecular and structural characteristics. In this respect, metal-complex-mediated polymerization is now considered one of the most important research frontiers in polymer chemistry and technology.

Transition metal chemistry has witnessed spectacular growth in the past decades. The design and application of transition metal complexes either as catalysts or as initiators has been recognized as a powerful tool for the polymerization of a variety of monomers.

This Special Issue is focused on the recent developments in the synthesis of linear polymers, as well as more complex macromolecular architectures, promoted by metal complexes. The polymerization of new monomers, synthesis of novel metal complexes able to promote polymerization, kinetics of polymerization, mechanistic studies, synthesis of complex macromolecular architectures in combination with other polymerization techniques, molecular and structural characterization of the polymeric products, are among the topics that will be covered. The metal complexes include Ziegler–Natta catalysts, metallocene and half-metallocene complexes of the 3rd, 4th, and 5th groups of the periodic table, non-metallocene complexes bearing diamido, alkylthio, amine-phenolate etc. ligands, late transition metal complexes, complexes for ring opening metathesis polymerization reactions of cycloolefins and alkynes.

Prof. Marinos Pitsikalis
Dr. Ioannis Choinopoulos
Guest Editors

Keywords

  • Catalytic polymerization
  • Coordination polymerization
  • Ziegler–Natta catalysts
  • (Half)-Metallocene complexes
  • Non-metallocene complexes
  • Late transition metal complexes
  • Ring opening metathesis polymerization catalysts
  • Linear and non-linear homo- and copolymers
  • Polymerization kinetics
  • Polymerization mechanisms

Published Papers (10 papers)

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Research

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12 pages, 1786 KiB  
Article
Synthesis of Poly(2-Acrylamido-2-Methylpropane Sulfonic Acid) and its Block Copolymers with Methyl Methacrylate and 2-Hydroxyethyl Methacrylate by Quasiliving Radical Polymerization Catalyzed by a Cyclometalated Ruthenium(II) Complex
by Vanessa Martínez-Cornejo, Joaquin Velázquez-Roblero, Veronica Rosiles-González, Monica Correa-Duran, Alejandro Avila-Ortega, Emanuel Hernández-Núñez, Ronan Le Lagadec and Maria Ortencia González-Díaz
Polymers 2020, 12(8), 1663; https://doi.org/10.3390/polym12081663 - 27 Jul 2020
Cited by 11 | Viewed by 5030
Abstract
The first example of quasiliving radical polymerization and copolymerization of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) without previous protection of its strong acid groups catalyzed by [Ru(o-C6H4-2-py)(phen)(MeCN)2]PF6 complex is reported. Nuclear magnetic resonance (RMN) and gel [...] Read more.
The first example of quasiliving radical polymerization and copolymerization of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) without previous protection of its strong acid groups catalyzed by [Ru(o-C6H4-2-py)(phen)(MeCN)2]PF6 complex is reported. Nuclear magnetic resonance (RMN) and gel permeation chromatography (GPC) confirmed the diblock structure of the sulfonated copolymers. The poly(2-acryloamido-2-methylpropanesulfonic acid)-b-poly(methyl methacrylate) (PAMPS-b-PMMA) and poly(2-acryloamido-2-methylpropanesulfonic acid)-b-poly(2-hydroxyethylmethacrylate) (PAMPS-b-PHEMA) copolymers obtained are highly soluble in organic solvents and present good film-forming ability. The ion exchange capacity (IEC) of the copolymer membranes is reported. PAMPS-b-PHEMA presents the highest IEC value (3.35 mmol H+/g), but previous crosslinking of the membrane was necessary to prevent it from dissolving in aqueous solution. PAMPS-b-PMMA exhibited IEC values in the range of 0.58–1.21 mmol H+/g and it was soluble in methanol and dichloromethane and insoluble in water. These results are well correlated with both the increase in molar composition of PAMPS and the second block included in the copolymer. Thus, the proper combination of PAMPS block copolymer with hydrophilic or hydrophobic monomers will allow fine-tuning of the physical properties of the materials and may lead to many potential applications, such as polyelectrolyte membrane fuel cells or catalytic membranes for biodiesel production. Full article
(This article belongs to the Special Issue Polymerizations Promoted by Metal Complexes)
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18 pages, 4166 KiB  
Article
Macromolecular Brushes Based on Poly(L-Lactide) and Poly(ε-Caprolactone) Single and Double Macromonomers via ROMP. Synthesis, Characterization and Thermal Properties
by Christiana Nikovia, Eleftheria Sougioltzoupoulou, Vyron Rigas and Marinos Pitsikalis
Polymers 2019, 11(10), 1606; https://doi.org/10.3390/polym11101606 - 01 Oct 2019
Cited by 6 | Viewed by 2988
Abstract
Single and double poly(L-lactide) (PLLA) and poly(ε-caprolactone) (PCL) macromonomers having a norbornenyl polymerizable group were prepared by conventional Ring Opening Polymerization (ROP). These macromonomers were further subjected to ring opening metathesis polymerization (ROMP) reactions in order to produce double polymer brushes consisting of [...] Read more.
Single and double poly(L-lactide) (PLLA) and poly(ε-caprolactone) (PCL) macromonomers having a norbornenyl polymerizable group were prepared by conventional Ring Opening Polymerization (ROP). These macromonomers were further subjected to ring opening metathesis polymerization (ROMP) reactions in order to produce double polymer brushes consisting of PLLA or PCL side chains on a polynorbornene (PNBE) backbone. Statistical or block ring opening metathesis copolymerization of the PLLA and PCL macromonomers afforded the corresponding random and block double brushes. Sequential ROMP of the single PLLA, PCL and PLLA macromonomers resulted in the synthesis of the corresponding triblock copolymer brush. The molecular characteristics of the macromolecular brushes were obtained by 1H-NMR spectroscopy and Size Exclusion Chromatography. The thermal properties of the samples were studied by thermogravimetric analysis, TGA, Differential Thermogravimetry, DTG and Differential Scanning Calorimetry, DSC. Full article
(This article belongs to the Special Issue Polymerizations Promoted by Metal Complexes)
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23 pages, 2602 KiB  
Article
Statistical Copolymers of n-Butyl Vinyl Ether and 2-Chloroethyl Vinyl Ether via Metallocene-Mediated Cationic Polymerization. A Scaffold for the Synthesis of Graft Copolymers
by Stavros Zouganelis, Ioannis Choinopoulos, Ioannis Goulas and Marinos Pitsikalis
Polymers 2019, 11(9), 1510; https://doi.org/10.3390/polym11091510 - 16 Sep 2019
Cited by 6 | Viewed by 4770
Abstract
The cationic statistical copolymerization of n-butyl (be) and 2-chloroethyl vinyl ether (CEVE), is efficiently conducted using bis(η5-cyclopentadienyl)dimethyl zirconium (Cp2ZrMe2) in combination with tetrakis(pentafluorophenyl)borate dimethylanilinum salt [B(C6F5)4]–[Me2NHPh] [...] Read more.
The cationic statistical copolymerization of n-butyl (be) and 2-chloroethyl vinyl ether (CEVE), is efficiently conducted using bis(η5-cyclopentadienyl)dimethyl zirconium (Cp2ZrMe2) in combination with tetrakis(pentafluorophenyl)borate dimethylanilinum salt [B(C6F5)4]–[Me2NHPh]+, as an initiation system. The reactivity ratios are calculated using both linear graphical and non-linear methods. Structural parameters of the copolymers are obtained by calculating the dyad sequence fractions and the mean sequence length, which are derived using the monomer reactivity ratios. The glass transition temperatures (Tg) of the copolymers are measured by Differential Scanning Calorimetry (DSC), and the results are compared with predictions based on several theoretical models. The statistical copolymers are further employed as scaffolds for the synthesis of graft copolymers having poly(vinyl ether)s as a backbone and either poly(ε-caprolactone) (PCL) or poly(l-lactide) (PLLA) as side chains. Both the grafting “onto” and the grafting “from” methodologies are employed. The reaction sequence is monitored by Size Exclusion Chromatography (SEC), NMR and IR spectroscopies. The advantages and limitations of each approach are thoroughly examined. Full article
(This article belongs to the Special Issue Polymerizations Promoted by Metal Complexes)
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20 pages, 4636 KiB  
Article
FeNxC Based Catalysts Prepared by the Calcination of Iron-Ethylenediamine@Polyaniline as the Cathode-Catalyst of Proton Exchange Membrane Fuel Cell
by Yen-Zen Wang, Wen-Yao Huang, Tar-Hwa Hsieh, Li-Cheng Jheng, Ko-Shan Ho, Sin-Wei Huang and Liang Chao
Polymers 2019, 11(8), 1368; https://doi.org/10.3390/polym11081368 - 19 Aug 2019
Cited by 11 | Viewed by 3837
Abstract
Calcinated tris(ethylenediamine)iron(III) chloride was used as a non-precious metal catalyst (NPMCs) for a proton exchanged membrane fuel cell (PEMFC) under the protection of polyaniline (PANI), which behaves as both nitrogen source and carbon supporter. The optimal ratio of FeCl3/EDA was found [...] Read more.
Calcinated tris(ethylenediamine)iron(III) chloride was used as a non-precious metal catalyst (NPMCs) for a proton exchanged membrane fuel cell (PEMFC) under the protection of polyaniline (PANI), which behaves as both nitrogen source and carbon supporter. The optimal ratio of FeCl3/EDA was found to be close to 1/3 under the consideration of the electrocatalytic performance, such as better oxygen reduction reaction (ORR) and higher power density. Two-stage calcination, one at 900 °C in N2 and the other at 800 °C in mixed gases of N2 and NH3, result in an FeNxC catalyst (FeNC-900-800-A) with pretty high specific surface area of 1098 m2·g−1 covered with both micro- and mesopores. The ORR active sites focused mainly on Fe–Nx bonding made of various pyridinic, pyrrolic, and graphitic N-s after calcination. The max. power density reaches 140 mW·cm−2 for FeNC-900-800-A, which is superior to other FeNxC catalysts, experiencing only one-stage calcination in N2. The FeNxC demonstrates only 10 mV half-wave-voltage (HWV) loss at 1600 rpm after 1000 redox cycles, as compared to be 27 mV for commercial Pt/C catalyst in the durability test. Full article
(This article belongs to the Special Issue Polymerizations Promoted by Metal Complexes)
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11 pages, 2572 KiB  
Article
Influence of Co-Catalysts and Polymerization Conditions on Properties of Poly(anhydride-alt-epoxide)s from ROCOP Using Salen Complexes with Different Metals
by Matteo Proverbio, Nella Galotto Galotto, Simona Losio, Incoronata Tritto and Laura Boggioni
Polymers 2019, 11(7), 1222; https://doi.org/10.3390/polym11071222 - 22 Jul 2019
Cited by 17 | Viewed by 4106
Abstract
Cyclohexene oxide (CHO) and phthalic anhydride (PA) have been reacted in the presence of commercial salen–type complexes with different metals Cr (1), Al (2), and Mn (3) in combination with 4-(dimethylamino) pyridine (DMAP), bis-(triphenylphosphorydine) ammonium chloride (PPNCl) [...] Read more.
Cyclohexene oxide (CHO) and phthalic anhydride (PA) have been reacted in the presence of commercial salen–type complexes with different metals Cr (1), Al (2), and Mn (3) in combination with 4-(dimethylamino) pyridine (DMAP), bis-(triphenylphosphorydine) ammonium chloride (PPNCl) and bis-(triphenylphosphoranylidene)ammonium azide (PPNN3) as co-catalysts to obtain alternating poly(PA-alt-CHO)s by ring-opening copolymerization (ROCOP). The effect of different reaction conditions (pre-contact between catalyst and co-catalyst, polymerization time) on the productivity, molecular weight and glass transition temperature has been evaluated. By using a 24 h pre-contact, the aliphatic polyesters obtained were characterized by high molecular weight (Mn > 15 kg/mol) and glass transition temperature (Tg) up to 146 °C; the more sustainable metals Al and Mn in the presence of PPNCl give comparable results to Cr. Moreover, biodegradability data of these polyesters and the study of the microstructure reveal that the biodegradability is influenced more by the type of chain linkages rather than by the molecular weight of the polyesters. Full article
(This article belongs to the Special Issue Polymerizations Promoted by Metal Complexes)
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17 pages, 3062 KiB  
Article
Preparation of Butadiene-Isoprene Copolymer with High Vinyl Contents by Al(OPhCH3)(i-Bu)2/MoO2Cl2∙TNPP
by Peipei Li, Kai Liu, Zhe Fu, Yongliang Yu, Zhaobo Wang and Jing Hua
Polymers 2019, 11(3), 527; https://doi.org/10.3390/polym11030527 - 20 Mar 2019
Cited by 3 | Viewed by 3304
Abstract
In this study, a butadiene-isoprene coordination polymerization was initiated by a binary molybdenum (Mo)-based catalytic system consisting of modified MoO2Cl2 as the primary catalyst, triethyl aluminum substituted by m-cresol as the co-catalyst and tris(nonyl phenyl) phosphate (TNPP) as the ligand. [...] Read more.
In this study, a butadiene-isoprene coordination polymerization was initiated by a binary molybdenum (Mo)-based catalytic system consisting of modified MoO2Cl2 as the primary catalyst, triethyl aluminum substituted by m-cresol as the co-catalyst and tris(nonyl phenyl) phosphate (TNPP) as the ligand. The effects of the amount of catalyst and type of co-catalyst were investigated in detail. Experimental results indicated that when the butadiene-isoprene coordination polymerization was initiated by the binary Mo-based catalytic system, the monomer conversion could reach 90%. The resulting butadiene units were primarily based on 1,2-structures, and the reactivity ratios of butadiene and isoprene were 1.13 and 0.31, respectively. The reaction in the catalytic system was attributed to the non-ideal and non-constant ratio copolymerization. When the addition of isoprene monomers was relatively low, the isoprene units on the butadiene-isoprene copolymers were primarily based on the 1,2- and 3,4-structures. Moreover, the orientation of active centers to 1,2- and 3,4-structures gradually decreased with an increase in the addition of isoprene monomers, which resulted in the generation of high vinyl butadiene-isoprene copolymers. Full article
(This article belongs to the Special Issue Polymerizations Promoted by Metal Complexes)
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16 pages, 4264 KiB  
Article
Chiral MnIII (Salen) Immobilized on Organic Polymer/Inorganic Zirconium Hydrogen Phosphate Functionalized with 3-Aminopropyltrimethoxysilane as an Efficient and Recyclable Catalyst for Enantioselective Epoxidation of Styrene
by Xiaochuan Zou, Yue Wang, Cun Wang, Kaiyun Shi, Yanrong Ren and Xin Zhao
Polymers 2019, 11(2), 212; https://doi.org/10.3390/polym11020212 - 26 Jan 2019
Cited by 8 | Viewed by 3184
Abstract
Organic polymers/inorganic zirconium hydrogen phosphate (ZSPP, ZPS-IPPA, and ZPS-PVPA) functionalized with 3-aminopropyltrimethoxysilane were prepared and used to support chiral MnIII (salen) complexes (Jacobsen’s catalyst). Different characterization methods demonstrated that the chiral MnIII (salen) complexes was successfully supported on the surface of [...] Read more.
Organic polymers/inorganic zirconium hydrogen phosphate (ZSPP, ZPS-IPPA, and ZPS-PVPA) functionalized with 3-aminopropyltrimethoxysilane were prepared and used to support chiral MnIII (salen) complexes (Jacobsen’s catalyst). Different characterization methods demonstrated that the chiral MnIII (salen) complexes was successfully supported on the surface of the carrier (ZSPP, ZPS-IPPA, or ZPS-PVPA) through a 3-aminopropyltrimethoxysilane group spacer. The supported catalysts effectively catalyzed epoxidation of styrene with m-chloroperbenzoic acid (m-CPBA) as an oxidant in the presence of N-methylmorpholine N-oxide (NMO) as an axial base. These results (ee%, 53.3–63.9) were significantly better than those achieved under a homogeneous counterpart (ee%, 46.2). Moreover, it is obvious that there was no significant decrease in catalytic activity after the catalyst 3 was recycled four times (cons%: from 95.0 to 92.6; ee%: from 64.7 to 60.1). Further recycles of catalyst 3 resulted in poor conversions, although the enantioselectivity obtained was still higher than that of corresponding homogeneous catalyst even after eight times. After the end of the eighth reaction, the solid catalyst was allowed to stand in 2 mol/L of dilute hydrochloric acid overnight, prompting an unexpected discovery that the catalytic activity of the catalyst was recovered again at the 9th and 10th cycles of the catalyst. Full article
(This article belongs to the Special Issue Polymerizations Promoted by Metal Complexes)
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11 pages, 1937 KiB  
Article
Cobalt-Mediated Radical Copolymerization of Chlorotrifluoroethylene and Vinyl Acetate
by Pucheng Wang, Hu Wang, Qibao Dong and Ruke Bai
Polymers 2019, 11(1), 101; https://doi.org/10.3390/polym11010101 - 09 Jan 2019
Cited by 11 | Viewed by 4148
Abstract
Controlled radical copolymerization of chlorotrifluoroethylene (CTFE) and vinyl acetate (VAc) was successfully achieved in the presence of bis(acetylacetonato)cobalt(II) (Co(acac)2) as a mediated agent and 2,2′-azo-bis-isobutyronitrile (AIBN) as initiator. Both the molar mass and the fluorinated unit content of the copolymer could [...] Read more.
Controlled radical copolymerization of chlorotrifluoroethylene (CTFE) and vinyl acetate (VAc) was successfully achieved in the presence of bis(acetylacetonato)cobalt(II) (Co(acac)2) as a mediated agent and 2,2′-azo-bis-isobutyronitrile (AIBN) as initiator. Both the molar mass and the fluorinated unit content of the copolymer could be controlled, and the chain extension polymerization of the obtained fluorinated copolymer was also achieved. Full article
(This article belongs to the Special Issue Polymerizations Promoted by Metal Complexes)
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Review

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31 pages, 2775 KiB  
Review
Grubbs’ and Schrock’s Catalysts, Ring Opening Metathesis Polymerization and Molecular Brushes—Synthesis, Characterization, Properties and Applications
by Ioannis Choinopoulos
Polymers 2019, 11(2), 298; https://doi.org/10.3390/polym11020298 - 11 Feb 2019
Cited by 55 | Viewed by 10929
Abstract
In this review, molecular brushes and other macromolecular architectures bearing a bottlebrush segment where the main chain is synthesized by ring opening metathesis polymerization (ROMP) mediated by Mo or Ru metal complexes are considered. A brief review of metathesis and ROMP is presented [...] Read more.
In this review, molecular brushes and other macromolecular architectures bearing a bottlebrush segment where the main chain is synthesized by ring opening metathesis polymerization (ROMP) mediated by Mo or Ru metal complexes are considered. A brief review of metathesis and ROMP is presented in order to understand the problems and the solutions provided through the years. The synthetic strategies towards bottlebrush copolymers are demonstrated and each one discussed separately. The initiators/catalysts for the synthesis of the backbone with ROMP are discussed. Syntheses of molecular brushes are presented. The most interesting properties of the bottlebrushes are detailed. Finally, the applications studied by different groups are presented. Full article
(This article belongs to the Special Issue Polymerizations Promoted by Metal Complexes)
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Other

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14 pages, 7098 KiB  
Brief Report
Induction of Polyacetylene to a Chiral Smectic Liquid Crystal–Chiral Direct Conversion
by Akiko Yatsu, Takuya Yonehara and Hiromasa Goto
Polymers 2020, 12(7), 1547; https://doi.org/10.3390/polym12071547 - 13 Jul 2020
Cited by 1 | Viewed by 2507
Abstract
The synthesis of polyacetylene-bearing pyrimidine-type three-ringed mesogenic core exhibiting smectic C (SmC) characteristics was conducted. Gas-phase iodine doping of the polymer provided evidence of chemical interaction between the polyene and iodine, which acted as an electron acceptor. The side-chain fluorine atom tilted the [...] Read more.
The synthesis of polyacetylene-bearing pyrimidine-type three-ringed mesogenic core exhibiting smectic C (SmC) characteristics was conducted. Gas-phase iodine doping of the polymer provided evidence of chemical interaction between the polyene and iodine, which acted as an electron acceptor. The side-chain fluorine atom tilted the mesogen moiety to form SmC as a tilted liquid crystal. The addition of a small amount of chiral inducer yielded SmC* of the polymer as the chiral version of SmC. The liquid crystallinity and electronic properties of the π-conjugated chiral liquid crystal polymer with a helical structure were evaluated. Full article
(This article belongs to the Special Issue Polymerizations Promoted by Metal Complexes)
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