Design and Synthesis of Polymers

A topical collection in Polymers (ISSN 2073-4360). This collection belongs to the section "Polymer Chemistry".

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Editor


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Collection Editor
Department of Materials Science and Chemistry, University of Hyogo, Shosha, Himeji 2167, Hyogo, Japan
Interests: controlled/living radical polymerization; RAFT; TERP; water-soluble polymer; self-organization; polymer micelle; bioconjugate polymer
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Topical Collection Information

Dear Colleagues,

It is well-known that polymer functions strongly depend on their design and structure. The design and synthesis of polymers are very important for desired properties. Commonly, most polymers are synthesized by the following methods: radical, anionic, cationic, condensation, ring opening, and coordination polymerizations. Unfortunately, these synthetic polymer structures are not well-controlled compared with biopolymers, such as polypeptide, DNA, RNA, and so on. We cannot precisely control molecular weight, molecular weight distribution, monomer sequence, and tacticity. Recently, controlled polymerization methods have been developed to achieve well-controlled structured polymers with defined molecular weight and narrow molecular weight distribution. However, this is unsatisfactory compared with biopolymers. Especially, monomer sequence and tacticity controls constitute difficult challenges. Additionally, there are various design of polymers, such as linear polymer, random copolymer, alternative copolymer, block copolymer, branched polymer, graft copolymer, star-shape copolymer, mikto−arm copolymer, dendrimer, and so on. These designs are the key points of the functions.

This collection is concerned with the design and synthesis of polymers. We hope to share new concept designs of polymers, polymer synthesis methods, and analysis of polymerization mechanisms. Both original contributions and reviews are welcome.

Prof. Shin-ichi Yusa
Collection Editor

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Keywords

  • Linear polymer
  • Random copolymer
  • Alternative copolymer
  • Branched polymer
  • Block copolymer
  • Conjugated polymer
  • Graft copolymer
  • Star-shaped polymer
  • Dendrimer
  • Radical polymerization
  • Anionic polymerization
  • Cationic polymerization
  • Condensation polymerization
  • Ring opening polymerization
  • Coordination polymerization
  • Polyaddition
  • Addition condensation
  • Living polymerization
  • Polymerization mechanism
  • Monomer sequence control
  • Tactility
  • Copolymerization
  • Photo-polymerization
  • New concept of polymerization

Published Papers (41 papers)

2024

Jump to: 2023, 2022, 2021, 2020, 2019

8 pages, 1636 KiB  
Communication
Synthesis and Oxidative Degradation of Leucine-Based Poly(diacylhydrazine)
by Kanda Wongwailikhit, Ratha Suwannakeeree and Nobuhiro Kihara
Polymers 2024, 16(9), 1222; https://doi.org/10.3390/polym16091222 - 27 Apr 2024
Viewed by 514
Abstract
Diacylhydrazine is thermally and chemically stable, and it remains inert to oxygen even at high temperatures. However, it is rapidly oxidized by sodium hypochlorite, leading to its decomposition into carboxylic acid and nitrogen gas. In the synthesis of a novel poly(diacylhydrazine) as an [...] Read more.
Diacylhydrazine is thermally and chemically stable, and it remains inert to oxygen even at high temperatures. However, it is rapidly oxidized by sodium hypochlorite, leading to its decomposition into carboxylic acid and nitrogen gas. In the synthesis of a novel poly(diacylhydrazine) as an oxidatively degradable polymer, L-leucine methyl ester is acylated by terephthaloyl chloride. Subsequent hydrazination yields a bishydrazide monomer. The oxidative coupling polymerization of this monomer produces poly(diacylhydrazine). The molecular structures of the products are confirmed by an 1H NMR analysis. A polymodal molecular weight distribution and a large polydispersity index are observed by GPC in all cases. A 10% weight loss temperature is noted at 286 °C in air by TGA. The obtained polymer is not oxidized by oxygen. No glass transition is observed below the decomposition temperature. Upon the treatment of the poly(diacylhydrazine) with sodium hypochlorite solution, decomposition occurs rapidly, resulting in monomeric carboxylic acid and nitrogen gas. The L-leucine-based poly(diacylhydrazine) serves as a novel on-demand degradable polymer with high levels of thermal and chemical stability during usage. Full article
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16 pages, 3860 KiB  
Review
Recent Advances in Polymers Bearing Activated Esters for the Synthesis of Glycopolymers by Postpolymerization Modification
by Tomonari Tanaka
Polymers 2024, 16(8), 1100; https://doi.org/10.3390/polym16081100 - 15 Apr 2024
Viewed by 840
Abstract
Glycopolymers are functional polymers with saccharide moieties on their side chains and are attractive candidates for biomaterials. Postpolymerization modification can be employed for the synthesis of glycopolymers. Activated esters are useful in various fields, including polymer chemistry and biochemistry, because of their high [...] Read more.
Glycopolymers are functional polymers with saccharide moieties on their side chains and are attractive candidates for biomaterials. Postpolymerization modification can be employed for the synthesis of glycopolymers. Activated esters are useful in various fields, including polymer chemistry and biochemistry, because of their high reactivity and ease of reaction. In particular, the formation of amide bonds caused by the reaction of activated esters with amino groups is of high synthetic chemical value owing to its high selectivity. It has been employed in the synthesis of various functional polymers, including glycopolymers. This paper reviews the recent advances in polymers bearing activated esters for the synthesis of glycopolymers by postpolymerization modification. The development of polymers bearing hydrophobic and hydrophilic activated esters is described. Although water-soluble activated esters are generally unstable and hydrolyzed in water, novel polymer backbones bearing water-soluble activated esters are stable and useful for postpolymerization modification for synthesizing glycopolymers in water. Dual postpolymerization modification can be employed to modify polymer side chains using two different molecules. Thiolactone and glycine propargyl esters on the polymer backbone are described as activated esters for dual postpolymerization modification. Full article
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2023

Jump to: 2024, 2022, 2021, 2020, 2019

17 pages, 4333 KiB  
Article
Novel Chain-End Modification of Polymer Iodides via Reversible Complexation-Mediated Polymerization with Functionalized Radical Generation Agents
by Kazuya Ohtani, Kanta Shimizu, Tatsuhiro Takahashi and Masumi Takamura
Polymers 2023, 15(12), 2667; https://doi.org/10.3390/polym15122667 - 13 Jun 2023
Viewed by 1409
Abstract
The modification of polymer chain ends is important in order to produce highly functional polymers. A novel chain-end modification of polymer iodides (Polymer-I) via reversible complexation-mediated polymerization (RCMP) with different functionalized radical generation agents, such as azo compounds and organic peroxides, was developed. [...] Read more.
The modification of polymer chain ends is important in order to produce highly functional polymers. A novel chain-end modification of polymer iodides (Polymer-I) via reversible complexation-mediated polymerization (RCMP) with different functionalized radical generation agents, such as azo compounds and organic peroxides, was developed. This reaction was comprehensively studied for three different polymers, i.e., poly (methyl methacrylate), polystyrene and poly (n-butyl acrylate) (PBA), two different functional azo compounds with aliphatic alkyl and carboxy groups, three different functional diacyl peroxides with aliphatic alkyl, aromatic, and carboxy groups, and one peroxydicarbonate with an aliphatic alkyl group. The reaction mechanism was probed using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The combination of PBA-I, iodine abstraction catalyst and different functional diacyl peroxides enabled higher chain-end modification to desired moieties from the diacyl peroxide. The dominant key factors for efficiency in this chain-end modification mechanism were the combination rate constant and the amount of radicals generated per unit of time. Full article
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12 pages, 4694 KiB  
Article
Solid State Polymerization of Biodegradable Poly(butylene sebacate-co-terephthalate): A Rapid, Facile Method for Property Enhancement
by Daegyu Lim and Su-il Park
Polymers 2023, 15(5), 1133; https://doi.org/10.3390/polym15051133 - 24 Feb 2023
Viewed by 1840
Abstract
Poly(butylene sebacate-co-terephthalate) (PBSeT) has generated attention as a promising biopolymer for preparing bioplastics. However, there are limited studies on the synthesis of PBSeT, impeding its commercialization. Herein, with a view to addressing this challenge, biodegradable PBSeT was modified using solid state polymerization (SSP) [...] Read more.
Poly(butylene sebacate-co-terephthalate) (PBSeT) has generated attention as a promising biopolymer for preparing bioplastics. However, there are limited studies on the synthesis of PBSeT, impeding its commercialization. Herein, with a view to addressing this challenge, biodegradable PBSeT was modified using solid state polymerization (SSP) with various ranges of time and temperature. The SSP used three different temperatures below the melting temperature of PBSeT. The polymerization degree of SSP was investigated using Fourier-transform infrared spectroscopy. The changes in the rheological properties of PBSeT after SSP were investigated using a rheometer and an Ubbelodhe viscometer. Differential scanning calorimetry and X-ray diffraction showed that the crystallinity of PBSeT was higher after SSP. The investigation revealed that after SSP for 40 min at 90 °C, PBSeT exhibited higher intrinsic viscosity (increased from 0.47 to 0.53 dL/g), crystallinity, and complex viscosity than PBSeT polymerized at other temperatures. However, a high SSP processing time resulted in a decrease in these values. In this experiment, SSP was most effectively performed in the temperature range closest to the melting temperature of PBSeT. This indicates that SSP could be a facile and rapid method for improving the crystallinity and thermal stability of synthesized PBSeT. Full article
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2022

Jump to: 2024, 2023, 2021, 2020, 2019

14 pages, 5193 KiB  
Article
Novel Mesogenic Vinyl Ketone Monomers and Their Based Polymers
by Yaroslav I. Derikov, Daniil R. Belousov, Alexander V. Finko, Georgii A. Shandryuk, Nina M. Kuz’menok, Sergei G. Mikhalyonok, Vladimir S. Bezborodov, Elena V. Chernikova and Raisa V. Talroze
Polymers 2023, 15(1), 5; https://doi.org/10.3390/polym15010005 - 20 Dec 2022
Cited by 3 | Viewed by 1734
Abstract
In the present research, we have synthesized new vinyl ketone monomers with mesogenic substituents, namely, 8-(3′-chloro-4′-pentyl-[1,1′-biphenyl-4-oxy)oct-1-en-3-one (BVK) and 8-[2′-chloro-4‴-octyl-[1,1′:4′,1″:4″,1‴-quaterphenyl-4-oxy]oct-1-en-3-one (QVK). The comparison of BVK, QVK, and previously synthesized 8-((4″-((1R,4S)-4-butylcyclohexyl)-2′-chloro-[1,1′,4′,1″-terphenyl]-4-yl)oxy)oct-1-en-3-one (TVK) has revealed that [...] Read more.
In the present research, we have synthesized new vinyl ketone monomers with mesogenic substituents, namely, 8-(3′-chloro-4′-pentyl-[1,1′-biphenyl-4-oxy)oct-1-en-3-one (BVK) and 8-[2′-chloro-4‴-octyl-[1,1′:4′,1″:4″,1‴-quaterphenyl-4-oxy]oct-1-en-3-one (QVK). The comparison of BVK, QVK, and previously synthesized 8-((4″-((1R,4S)-4-butylcyclohexyl)-2′-chloro-[1,1′,4′,1″-terphenyl]-4-yl)oxy)oct-1-en-3-one (TVK) has revealed that all of them are able to form crystals, while their ability to exhibit liquid crystalline behavior depends on the number of phenyl substituents attached to the para-position of the phenoxy group and is observed for TVK and QVK only. All of the monomers are able to achieve self-polymerization upon heating and free radical polymerization in bulk or in solution under the action of the common radical initiator AIBN. We have also succeeded in the RAFT polymerization of the synthesized vinyl ketones BVK and TVK using asymmetrical trithiocarbonates. The synthesized poly(vinyl ketones) exhibit LC behavior and are able to undergo photodegradation upon UV irradiation. Full article
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11 pages, 4716 KiB  
Article
Phase Diagrams of Polymerization-Induced Self-Assembly Are Largely Determined by Polymer Recombination
by Artem Petrov, Alexander V. Chertovich and Alexey A. Gavrilov
Polymers 2022, 14(23), 5331; https://doi.org/10.3390/polym14235331 - 6 Dec 2022
Cited by 3 | Viewed by 1440
Abstract
In the current work, atom transfer radical polymerization-induced self-assembly (ATRP PISA) phase diagrams were obtained by the means of dissipative particle dynamics simulations. A fast algorithm for determining the equilibrium morphology of block copolymer aggregates was developed. Our goal was to assess how [...] Read more.
In the current work, atom transfer radical polymerization-induced self-assembly (ATRP PISA) phase diagrams were obtained by the means of dissipative particle dynamics simulations. A fast algorithm for determining the equilibrium morphology of block copolymer aggregates was developed. Our goal was to assess how the chemical nature of ATRP affects the self-assembly of diblock copolymers in the course of PISA. We discovered that the chain growth termination via recombination played a key role in determining the ATRP PISA phase diagrams. In particular, ATRP with turned off recombination yielded a PISA phase diagram very similar to that obtained for a simple ideal living polymerization process. However, an increase in the recombination probability led to a significant change of the phase diagram: the transition between cylindrical micelles and vesicles was strongly shifted, and a dependence of the aggregate morphology on the concentration was observed. We speculate that this effect occurred due to the simultaneous action of two factors: the triblock copolymer architecture of the terminated chains and the dispersity of the solvophobic blocks. We showed that these two factors affected the phase diagram weakly if they acted separately; however, their combination, which naturally occurs during ATRP, affected the ATRP PISA phase diagram strongly. We suggest that the recombination reaction is a key factor leading to the complexity of experimental PISA phase diagrams. Full article
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25 pages, 5793 KiB  
Review
Polymerization in the Borstar Polypropylene Hybrid Process: Combining Technology and Catalyst for Optimized Product Performance
by Michiel F. Bergstra, Peter Denifl, Markus Gahleitner, Dusan Jeremic, Vasileios Kanellopoulos, Daniela Mileva, Pavel Shutov, Vasileios Touloupidis and Cornelia Tranninger
Polymers 2022, 14(21), 4763; https://doi.org/10.3390/polym14214763 - 7 Nov 2022
Cited by 2 | Viewed by 6144
Abstract
Producing isotactic polypropylene (iPP) homo- and copolymers in a wide composition and property range according to customer demand requires perfect alignment between the process technology, catalyst system and polymer structure. The present review shows this for the Borstar® PP process, a hybrid [...] Read more.
Producing isotactic polypropylene (iPP) homo- and copolymers in a wide composition and property range according to customer demand requires perfect alignment between the process technology, catalyst system and polymer structure. The present review shows this for the Borstar® PP process, a hybrid process employing liquid bulk and gas phase stages, in an exemplary way. It starts with the process design and continues through two generations of Ziegler–Natta catalyst development history to the design of advanced multimodal random and multiphase copolymers. Essential elements of each of the three areas contributing to performance range are highlighted, and an outlook to future development is given. Full article
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14 pages, 2919 KiB  
Article
Thermo-Responsive Polyion Complex of Polysulfobetaine and a Cationic Surfactant in Water
by Thu Thao Pham and Shin-ichi Yusa
Polymers 2022, 14(15), 3171; https://doi.org/10.3390/polym14153171 - 3 Aug 2022
Viewed by 1464
Abstract
Poly(4-((3-methacrylamidopropyl)dimethylammonium)butane-1-sulfonate) (PSBP) was prepared via controlled radical polymerization. PSBP showed upper critical solution temperature (UCST) behavior in aqueous solutions, which could be controlled by adjusting the polymer and NaCl concentrations. Owing to its pendant sulfonate anions, PSBP exhibited a negative zeta potential of [...] Read more.
Poly(4-((3-methacrylamidopropyl)dimethylammonium)butane-1-sulfonate) (PSBP) was prepared via controlled radical polymerization. PSBP showed upper critical solution temperature (UCST) behavior in aqueous solutions, which could be controlled by adjusting the polymer and NaCl concentrations. Owing to its pendant sulfonate anions, PSBP exhibited a negative zeta potential of −7.99 mV and formed a water-soluble ion complex with the cationic surfactant cetyltrimethylammonium bromide (CTAB) via attractive electrostatic interaction. A neutral PSBP/CTAB complex was formed under equimolar concentrations of the pendant sulfonate group in PSBP and the quaternary ammonium group in CTAB. Transmittance electron microscopic images revealed the spherical shape of the complex. The stoichiometrically neutral-charge PSBP/CTAB complex exhibited UCST behavior in aqueous solutions. Similar to PSBP, the phase transition temperature of the PSBP/CTAB complex could be tuned by modifying the polymer and NaCl concentrations. In 0.1 M aqueous solution, the PSBP/CTAB complex showed UCST behavior at a low complex concentration of 0.084 g/L, whereas PSBP did not exhibit UCST behavior at concentrations below 1.0 g/L. This observation suggests that the interaction between PSBP and CTAB in the complex was stronger than the interpolymer interaction of PSBP. Full article
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13 pages, 1828 KiB  
Article
Highly Active Heterogeneous Double Metal Cyanide Catalysts for Ring-Opening Polymerization of Cyclic Monomers
by Chinh-Hoang Tran, Min-Woong Lee, Soo-Jeong Lee, Jin-Hyeok Choi, Eun-Gyeong Lee, Ha-Kyung Choi and Il Kim
Polymers 2022, 14(12), 2507; https://doi.org/10.3390/polym14122507 - 20 Jun 2022
Cited by 10 | Viewed by 3066
Abstract
A series of heterogeneous Zn-Co double metal cyanide (DMC) catalysts were investigated for ring-opening polymerization (ROP) of various cyclic monomers. Notably, inexpensive and commonly used organic solvents such as acetone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, nitromethane, and 1-methylpyrrolidin-2-one [...] Read more.
A series of heterogeneous Zn-Co double metal cyanide (DMC) catalysts were investigated for ring-opening polymerization (ROP) of various cyclic monomers. Notably, inexpensive and commonly used organic solvents such as acetone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, nitromethane, and 1-methylpyrrolidin-2-one were very effective complexing agents for the preparation of DMC catalysts, showing high catalytic activity for the ROP of propylene oxide, ε-caprolactone, and δ-valerolactone. The chemical structures and compositions of the resultant catalysts were determined using various techniques such as FT-IR, X-ray photoelectron spectroscopy, powder X-ray diffraction, and elemental analysis. α,ω-Hydroxyl-functionalized polyether and polyester polyols with high yields and tunable molecular weights were synthesized in the presence of various initiators to control functionality. Kinetic studies of the ROP of δ-valerolactone were also performed to confirm the reaction mechanism. Full article
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11 pages, 1475 KiB  
Article
Association Behavior of Amphiphilic ABA Triblock Copolymer Composed of Poly(2-methoxyethyl acrylate) (A) and Poly(ethylene oxide) (B) in Aqueous Solution
by Yoko Mizoue, Ema Onodera, Kazutoshi Haraguchi and Shin-ichi Yusa
Polymers 2022, 14(9), 1678; https://doi.org/10.3390/polym14091678 - 20 Apr 2022
Cited by 2 | Viewed by 2180
Abstract
Poly(2-methoxyethyl acrylate) (PMEA) and poly(ethylene oxide) (PEO) have protein-antifouling properties and blood compatibility. ABA triblock copolymers (PMEAl-PEO11340-PMEAm (MEOMn; n is average value of l and m)) were prepared using single-electron transfer-living radical polymerization (SET-LRP) using [...] Read more.
Poly(2-methoxyethyl acrylate) (PMEA) and poly(ethylene oxide) (PEO) have protein-antifouling properties and blood compatibility. ABA triblock copolymers (PMEAl-PEO11340-PMEAm (MEOMn; n is average value of l and m)) were prepared using single-electron transfer-living radical polymerization (SET-LRP) using a bifunctional PEO macroinitiator. Two types of MEOMn composed of PMEA blocks with degrees of polymerization (DP = n) of 85 and 777 were prepared using the same PEO macroinitiator. MEOMn formed flower micelles with a hydrophobic PMEA (A) core and hydrophilic PEO (B) loop shells in diluted water with a similar appearance to petals. The hydrodynamic radii of MEOM85 and MEOM777 were 151 and 108 nm, respectively. The PMEA block with a large DP formed a tightly packed core. The aggregation number (Nagg) of the PMEA block in a single flower micelle for MEOM85 and MEOM777 was 156 and 164, respectively, which were estimated using a light scattering technique. The critical micelle concentrations (CMCs) for MEOM85 and MEOM777 were 0.01 and 0.002 g/L, respectively, as determined by the light scattering intensity and fluorescence probe techniques. The size, Nagg, and CMC for MEOM85 and MEOM777 were almost the same independent of hydrophobic DP of the PMEA block. Full article
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16 pages, 2916 KiB  
Article
pH- and Thermo-Responsive Water-Soluble Smart Polyion Complex (PIC) Vesicle with Polyampholyte Shells
by Thu Thao Pham, Tien Duc Pham and Shin-ichi Yusa
Polymers 2022, 14(9), 1659; https://doi.org/10.3390/polym14091659 - 20 Apr 2022
Cited by 4 | Viewed by 2411
Abstract
A diblock copolymer (P(VBTAC/NaSS)17-b-PAPTAC50; P(VS)17A50) composed of amphoteric random copolymer, poly(vinylbenzyl trimethylammonium chloride-co-sodium p-styrensunfonate) (P(VBTAC/NaSS); P(VS)) and cationic poly(3-(acrylamidopropyl) trimethylammonium chloride) (PAPTAC; A) block, and poly(acrylic acid) (PAAc49) [...] Read more.
A diblock copolymer (P(VBTAC/NaSS)17-b-PAPTAC50; P(VS)17A50) composed of amphoteric random copolymer, poly(vinylbenzyl trimethylammonium chloride-co-sodium p-styrensunfonate) (P(VBTAC/NaSS); P(VS)) and cationic poly(3-(acrylamidopropyl) trimethylammonium chloride) (PAPTAC; A) block, and poly(acrylic acid) (PAAc49) were prepared via a reversible addition−fragmentation chain transfer radical polymerization. Scrips V, S, and A represent VBTAC, NaSS, and PAPTAC blocks, respectively. Water-soluble polyion complex (PIC) vesicles were formed by mixing P(VS)17A50 and PAAc49 in water under basic conditions through electrostatic interactions between the cationic PAPTAC block and PAAc49 with the deprotonated pendant carboxylate anions. The PIC vesicle collapsed under an acidic medium because the pendant carboxylate anions in PAAc49 were protonated to delete the anionic charges. The PIC vesicle comprises an ionic PAPTAC/PAAc membrane coated with amphoteric random copolymer P(VS)17 shells. The PIC vesicle showed upper critical solution temperature (UCST) behavior in aqueous solutions because of the P(VS)17 shells. The pH- and thermo-responsive behavior of the PIC vesicle were studied using 1H NMR, static and dynamic light scattering, and percent transmittance measurements. When the ratio of the oppositely charged polymers in PAPTAC/PAAc was equal, the size and light scattering intensity of the PIC vesicle reached maximum values. The hydrophilic guest molecules can be encapsulated into the PIC vesicle at the base medium and released under acidic conditions. It is expected that the PIC vesicles will be applied as a smart drug delivery system. Full article
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35 pages, 10095 KiB  
Review
A Review on Current Strategies for the Modulation of Thermomechanical, Barrier, and Biodegradation Properties of Poly (Butylene Succinate) (PBS) and Its Random Copolymers
by Mario Iván Peñas, Ricardo Arpad Pérez-Camargo, Rebeca Hernández and Alejandro J. Müller
Polymers 2022, 14(5), 1025; https://doi.org/10.3390/polym14051025 - 3 Mar 2022
Cited by 33 | Viewed by 4959
Abstract
The impact of plastics on the environment can be mitigated by employing biobased and/or biodegradable materials (i.e., bioplastics) instead of the traditional “commodities”. In this context, poly (butylene succinate) (PBS) emerges as one of the most promising alternatives due to its good mechanical, [...] Read more.
The impact of plastics on the environment can be mitigated by employing biobased and/or biodegradable materials (i.e., bioplastics) instead of the traditional “commodities”. In this context, poly (butylene succinate) (PBS) emerges as one of the most promising alternatives due to its good mechanical, thermal, and barrier properties, making it suitable for use in a wide range of applications. Still, the PBS has some drawbacks, such as its high crystallinity, which must be overcome to position it as a real and viable alternative to “commodities”. This contribution covers the actual state-of-the-art of the PBS through different sections. The first section reviews the different synthesis routes, providing a complete picture regarding the obtained molecular weights and the greener alternatives. Afterward, we examine how different strategies such as random copolymerization and the incorporation of fillers can effectively modulate PBS properties to satisfy the needs for different applications. The impact of these strategies is evaluated in the crystallization behavior, crystallinity, mechanical and barrier properties, and biodegradation. The biodegradation is carefully analyzed, highlighting the wide variety of methodologies existing in the literature to measure PBS degradation through different routes (hydrolytic, enzymatic, and soil). Full article
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94 pages, 21201 KiB  
Review
Recent Advances in the Synthesis of Complex Macromolecular Architectures Based on Poly(N-vinyl pyrrolidone) and the RAFT Polymerization Technique
by Nikoletta Roka, Olga Kokkorogianni, Philippos Kontoes-Georgoudakis, Ioannis Choinopoulos and Marinos Pitsikalis
Polymers 2022, 14(4), 701; https://doi.org/10.3390/polym14040701 - 11 Feb 2022
Cited by 12 | Viewed by 4835
Abstract
Recent advances in the controlled RAFT polymerization of complex macromolecular architectures based on poly(N-vinyl pyrrolidone), PNVP, are summarized in this review article. Special interest is given to the synthesis of statistical copolymers, block copolymers, and star polymers and copolymers, along with graft copolymers [...] Read more.
Recent advances in the controlled RAFT polymerization of complex macromolecular architectures based on poly(N-vinyl pyrrolidone), PNVP, are summarized in this review article. Special interest is given to the synthesis of statistical copolymers, block copolymers, and star polymers and copolymers, along with graft copolymers and more complex architectures. In all cases, PNVP is produced via RAFT techniques, whereas other polymerization methods can be employed in combination with RAFT to provide the desired final products. The advantages and limitations of the synthetic methodologies are discussed in detail. Full article
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13 pages, 4210 KiB  
Article
Designing Phenyl Porous Organic Polymers with High-Efficiency Tetracycline Adsorption Capacity and Wide pH Adaptability
by Wenjie Nie, Jiao Liu, Xue Bai, Zefeng Xing and Ying Gao
Polymers 2022, 14(1), 203; https://doi.org/10.3390/polym14010203 - 5 Jan 2022
Cited by 3 | Viewed by 1808
Abstract
Adsorption is an effective method to remove tetracycline (TC) from water, and developing efficient and environment-friendly adsorbents is an interesting topic. Herein, a series of novel phenyl porous organic polymers (P-POPs), synthesized by one-pot polymerization of different ratios of biphenyl and triphenylbenzene under [...] Read more.
Adsorption is an effective method to remove tetracycline (TC) from water, and developing efficient and environment-friendly adsorbents is an interesting topic. Herein, a series of novel phenyl porous organic polymers (P-POPs), synthesized by one-pot polymerization of different ratios of biphenyl and triphenylbenzene under AlCl3 catalysis in CH2Cl2, was studied as a highly efficient adsorbent to removal of TC in water. Notably, the obtained POPs possessed abundant phenyl-containing functional groups, large specific surface area (1098 m2/g) with abundant microporous structure, high pore volume (0.579 cm3/g), favoring the removal of TC molecules. The maximum adsorption capacity (fitted by the Sips model) could achieve 581 mg/g, and the adsorption equilibrium is completed quickly within 1 h while obtaining excellent removal efficiency (98%). The TC adsorption process obeyed pseudo-second-order kinetics and fitted the Sips adsorption model well. Moreover, the adsorption of POPs to TC exhibited a wide range of pH (2–10) adaptability and outstanding reusability, which could be reused at least 5 times without significant changes in structure and efficiency. These results lay a theoretical foundation for the application of porous organic polymer adsorbents in antibiotic wastewater treatment. Full article
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2021

Jump to: 2024, 2023, 2022, 2020, 2019

11 pages, 3083 KiB  
Article
Cyclic Methacrylate Tetrahydropyrimidinones: Synthesis, Properties, (Co)Polymerization
by Victor A. Gerasin, Marina V. Zhurina, Natalia A. Kleshcheva, Nikolai A. Sivov and Dmitry I. Mendeleev
Polymers 2022, 14(1), 107; https://doi.org/10.3390/polym14010107 - 29 Dec 2021
Cited by 1 | Viewed by 1576
Abstract
During radical polymerization of novel biocidal methacrylate guanidine monomers, a cyclic byproduct was discovered and identified as 2-imino-5-methyltetrahydropyrimidin-4(1H)-one (THP). Its methacrylate salt (MTHP) was synthesized and characterized via 1H and 13C NMR and pyrolysis chromatography. Synthesis conditions of both THP and [...] Read more.
During radical polymerization of novel biocidal methacrylate guanidine monomers, a cyclic byproduct was discovered and identified as 2-imino-5-methyltetrahydropyrimidin-4(1H)-one (THP). Its methacrylate salt (MTHP) was synthesized and characterized via 1H and 13C NMR and pyrolysis chromatography. Synthesis conditions of both THP and MTHP were optimized to high yields, and both MTHP homopolymerization (in aqua) and copolymerization with diallyldimethylammonium chloride (in aqua in salt form) were successfully carried out with middle to high yields, providing a promising platform for potential tailored biocide polymers. Full article
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23 pages, 4301 KiB  
Article
RAFT Emulsion Polymerization of Styrene Using a Poly((N,N-dimethyl acrylamide)-co-(N-isopropyl acrylamide)) mCTA: Synthesis and Thermosensitivity
by Katharina Nieswandt, Prokopios Georgopanos, Martin Held, Evgeni Sperling and Volker Abetz
Polymers 2022, 14(1), 62; https://doi.org/10.3390/polym14010062 - 24 Dec 2021
Cited by 14 | Viewed by 4657
Abstract
Thermoresponsive poly((N,N-dimethyl acrylamide)-co-(N-isopropyl acrylamide)) (P(DMA-co-NIPAM)) copolymers were synthesized via reversible addition−fragmentation chain transfer (RAFT) polymerization. The monomer reactivity ratios were determined by the Kelen–Tüdős method to be rNIPAM = 0.83 and rDMA = [...] Read more.
Thermoresponsive poly((N,N-dimethyl acrylamide)-co-(N-isopropyl acrylamide)) (P(DMA-co-NIPAM)) copolymers were synthesized via reversible addition−fragmentation chain transfer (RAFT) polymerization. The monomer reactivity ratios were determined by the Kelen–Tüdős method to be rNIPAM = 0.83 and rDMA = 1.10. The thermoresponsive properties of these copo-lymers with varying molecular weights were characterized by visual turbidimetry and dynamic light scattering (DLS). The copolymers showed a lower critical solution temperature (LCST) in water with a dependence on the molar fraction of DMA in the copolymer. Chaotropic and kosmotropic salt anions of the Hofmeister series, known to affect the LCST of thermoresponsive polymers, were used as additives in the aqueous copolymer solutions and their influence on the LCST was demonstrated. Further on, in order to investigate the thermoresponsive behavior of P(DMA-co-NIPAM) in a confined state, P(DMA-co-NIPAM)-b-PS diblock copolymers were prepared via polymerization induced self-assembly (PISA) through surfactant-free RAFT mediated emulsion polymerization of styrene using P(DMA-co-NIPAM) as the macromolecular chain transfer agent (mCTA) of the polymerization. As confirmed by cryogenic transmission electron microscopy (cryoTEM), this approach yielded stabilized spherical micelles in aqueous dispersions where the PS block formed the hydrophobic core and the P(DMA-co-NIPAM) block formed the hydrophilic corona of the spherical micelle. The temperature-dependent behavior of the LCST-type diblock copolymers was further studied by examining the collapse of the P(DMA-co-NIPAM) minor block of the P(DMA-co-NIPAM)-b-PS diblock copolymers as a function of temperature in aqueous solution. The nanospheres were found to be thermosensitive by changing their hydrodynamic radii almost linearly as a function of temperature between 25 °C and 45 °C. The addition of kosmotropic salt anions, as a potentially useful tuning feature of micellar assemblies, was found to increase the hydrodynamic radius of the micelles and resulted in a faster collapse of the micelle corona upon heating. Full article
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14 pages, 4336 KiB  
Article
Biodegradable PCL-b-PLA Microspheres with Nanopores Prepared via RAFT Polymerization and UV Photodegradation of Poly(Methyl Vinyl Ketone) Blocks
by Taeyoon Kim, Sorim Lee, Soo-Yong Park and Ildoo Chung
Polymers 2021, 13(22), 3964; https://doi.org/10.3390/polym13223964 - 16 Nov 2021
Cited by 7 | Viewed by 3364
Abstract
Biodegradable triblock copolymers based on poly(ε-caprolactone) (PCL) and poly(lactic acid) (PLA) were synthesized via ring-opening polymerization of L-lactide followed by reversible addition–fragmentation chain-transfer (RAFT) polymerization of poly(methyl vinyl ketone) (PMVK) as a photodegradable block, and characterized by FT-IR and 1H NMR spectroscopy [...] Read more.
Biodegradable triblock copolymers based on poly(ε-caprolactone) (PCL) and poly(lactic acid) (PLA) were synthesized via ring-opening polymerization of L-lactide followed by reversible addition–fragmentation chain-transfer (RAFT) polymerization of poly(methyl vinyl ketone) (PMVK) as a photodegradable block, and characterized by FT-IR and 1H NMR spectroscopy for structural analyses, and by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) for their thermal properties. Porous, biodegradable PCL-b-PLA microspheres were fabricated via the oil/water (O/W) emulsion evaporation method, followed by photodegradation of PMVK blocks by UV irradiation. The macro-chain transfer agent (CTA) synthesized by reacting a carboxylic-acid-terminated CTA—S-1-dodecyl-S′-(a,a′-dimethyl-a′′-acetic acid)trithiocarbonate (DDMAT)—with a hydroxyl-terminated PCL-b-PLA block copolymer was used to synthesize well-defined triblock copolymers with methyl vinyl ketone via RAFT polymerization with controlled molecular weights and narrow polydispersity. Gel permeation chromatography traces indicated that the molecular weight of the triblock copolymer decreased with UV irradiation time because of the photodegradation of the PMVK blocks. The morphology of the microspheres before and after UV irradiation was investigated using SEM and videos of three-dimensional confocal laser microscopy, showing a change in their surface texture from smooth to rough, with high porosity owing to the photodegradation of the PMVK blocks to become porous templates. Full article
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20 pages, 6220 KiB  
Article
New Aspects on the Direct Solid State Polycondensation (DSSP) of Aliphatic Nylon Salts: The Case of Hexamethylene Diammonium Dodecanoate
by Angeliki D. Mytara, Athanasios D. Porfyris, Stamatina N. Vouyiouka and Constantine D. Papaspyrides
Polymers 2021, 13(16), 2625; https://doi.org/10.3390/polym13162625 - 6 Aug 2021
Cited by 1 | Viewed by 2378
Abstract
The direct solid state polymerization (DSSP) of hexamethylene diammonium dodecanoate (PA 612 salt) was investigated for two different salt grades, fossil-based and bio-based. Aliphatic polyamide salts (such as PA 612 salt) are highly susceptible to solid melt transition (SMT) phenomena, which restrain the [...] Read more.
The direct solid state polymerization (DSSP) of hexamethylene diammonium dodecanoate (PA 612 salt) was investigated for two different salt grades, fossil-based and bio-based. Aliphatic polyamide salts (such as PA 612 salt) are highly susceptible to solid melt transition (SMT) phenomena, which restrain the industrial application of DSSP. To that end, emphasis was given on reactor design, being the critical parameter influencing byproduct diffusion, amine loss and inherent DSSP kinetics. Experiments took place both at the microscale and the laboratory scale, in which two different reactors were tested in terms of bypassing SMT phenomena. The new reactor designed here proved quite successful in maintaining the solid state during the reaction. Scouting experiments were conducted in order to assess the effect of critical parameters and determine appropriate reaction conditions. Fossil-based PA 612 products proved to have a better end-group imbalance in comparison to bio-based ones, which is critical in terms of achieving high molecular weight. Finally, a real DSSP process was demonstrated, starting from PA 612 salt crystals and ending with PA 612 particles. Full article
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11 pages, 1428 KiB  
Communication
A Facile Strategy for the High Yielding, Quantitative Conversion of Polyglycol End-Groups to Amines
by Jie Yan, Paula Facal Marina and Anton Blencowe
Polymers 2021, 13(9), 1403; https://doi.org/10.3390/polym13091403 - 26 Apr 2021
Cited by 4 | Viewed by 3665
Abstract
Amino end-group functionalised polyglycols are important intermediates in the synthesis of sophisticated polymeric architectures and biomaterials. Herein, we report a facile strategy for the end-group conversion of hydroxyl-terminated polyglycols to amino-terminated polyglycols in high isolated yields and with excellent end-group fidelity. Following traditional [...] Read more.
Amino end-group functionalised polyglycols are important intermediates in the synthesis of sophisticated polymeric architectures and biomaterials. Herein, we report a facile strategy for the end-group conversion of hydroxyl-terminated polyglycols to amino-terminated polyglycols in high isolated yields and with excellent end-group fidelity. Following traditional conversion of polyglycol hydroxyl end-groups to azides via the corresponding mesylate, reduction with zinc in the presence of ammonium chloride afforded a range of amino end-group functionalised poly(ethylene glycol) and poly(propylene glycol) homopolymers and copolymers with isolated yields of 82–99% and end-group conversions of >99% as determined by NMR spectroscopy and MALDI ToF MS. Furthermore, this process is applicable to a sequential reagent addition approach without intermediate polymer isolation steps with only a slight reduction in yield and end-group conversion (95%). Importantly, a simple work-up procedure provides access to high purity polyglycols without contamination from other reagents. Full article
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32 pages, 6016 KiB  
Review
Expanding Monomers as Anti-Shrinkage Additives
by Philipp Marx and Frank Wiesbrock
Polymers 2021, 13(5), 806; https://doi.org/10.3390/polym13050806 - 6 Mar 2021
Cited by 23 | Viewed by 5112
Abstract
Commonly, volumetric shrinkage occurs during polymerizations due to the shortening of the equilibrium Van der Waals distance of two molecules to the length of a (significantly shorter) covalent bond. This volumetric shrinkage can have severe influence on the materials’ properties. One strategy to [...] Read more.
Commonly, volumetric shrinkage occurs during polymerizations due to the shortening of the equilibrium Van der Waals distance of two molecules to the length of a (significantly shorter) covalent bond. This volumetric shrinkage can have severe influence on the materials’ properties. One strategy to overcome this volumetric shrinkage is the use of expanding monomers that show volumetric expansion during polymerization reactions. Such monomers exhibit cyclic or even oligocyclic structural motifs with a correspondingly dense atomic packing. During the ring-opening reaction of such monomers, linear structures with atomic packing of lower density are formed, which results in volumetric expansion or at least reduced volumetric shrinkage. This review provides a concise overview of expanding monomers with a focus on the elucidation of structure-property relationships. Preceded by a brief introduction of measuring techniques for the quantification of volumetric changes, the most prominent classes of expanding monomers will be presented and discussed, namely cycloalkanes and cycloalkenes, oxacycles, benzoxazines, as well as thiocyclic compounds. Spiroorthoesters, spiroorthocarbonates, cyclic carbonates, and benzoxazines are particularly highlighted. Full article
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23 pages, 6359 KiB  
Article
Cross-Linking Strategies for Fluorine-Containing Polymer Coatings for Durable Resistant Water- and Oil-Repellency
by Julia Kredel, Deborah Schmitt, Jan-Lukas Schäfer, Markus Biesalski and Markus Gallei
Polymers 2021, 13(5), 723; https://doi.org/10.3390/polym13050723 - 27 Feb 2021
Cited by 8 | Viewed by 3494
Abstract
Functional coatings for application on surfaces are of growing interest. Especially in the textile industry, durable water and oil repellent finishes are of special demand for implementation in the outdoor sector, but also as safety-protection clothes against oil or chemicals. Such oil and [...] Read more.
Functional coatings for application on surfaces are of growing interest. Especially in the textile industry, durable water and oil repellent finishes are of special demand for implementation in the outdoor sector, but also as safety-protection clothes against oil or chemicals. Such oil and chemical repellent textiles can be achieved by coating surfaces with fluoropolymers. As many concerns exist regarding (per)fluorinated polymers due to their high persistence and accumulation capacity in the environment, a durable and resistant coating is essential also during the washing processes of textiles. Within the present study, different strategies are examined for a durable resistant cross-linking of a novel fluoropolymer on the surface of fibers. The monomer 2-((1,1,2-trifluoro-2-(perfluoropropoxy)ethyl)thio)ethyl acrylate, whose fluorinated side-chain is degradable by treatment with ozone, was used for this purpose. The polymers were synthesized via free radical polymerization in emulsion, and different amounts of cross-linking reagents were copolymerized. The final polymer dispersions were applied to cellulose fibers and the cross-linking was induced thermally or by irradiation with UV-light. In order to investigate the cross-linking efficiency, tensile elongation studies were carried out. In addition, multiple washing processes of the fibers were performed and the polymer loss during washing, as well as the effects on oil and water repellency were investigated. The cross-linking strategy paves the way to a durable fluoropolymer-based functional coating and the polymers are expected to provide a promising and sustainable alternative to functional coatings. Full article
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10 pages, 8642 KiB  
Article
New Pure Organic and Peroxide-Free Redox Initiating Systems for Polymerization in Mild Conditions
by Ahmad Arar, Lilian Wisson and Jacques Lalevée
Polymers 2021, 13(2), 301; https://doi.org/10.3390/polym13020301 - 19 Jan 2021
Cited by 3 | Viewed by 2613
Abstract
Redox initiating systems (RISs) are highly worthwhile for polymerization in mild conditions (at room temperature—RT) without external thermal or light activation. With high performance redox initiating systems RIS, the free radical polymerization FRP can even be carried out under air and without inhibitors/stabilizers [...] Read more.
Redox initiating systems (RISs) are highly worthwhile for polymerization in mild conditions (at room temperature—RT) without external thermal or light activation. With high performance redox initiating systems RIS, the free radical polymerization FRP can even be carried out under air and without inhibitors/stabilizers removal from the monomers/resins. However, efficient RISs are still based on peroxides or metal complexes. In this work, a pure organic and peroxide-free RIS is presented based on the interaction of a well-selected triarylamine derivative (T4epa) with iodonium salt used as reducing and oxidizing agents, respectively. The redox polymerization (Redox FRP) was followed through pyrometry and thermal imaging experiments. Remarkably, a full control of the work time as well as a high reactivity is observed for mild conditions. Full article
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2020

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18 pages, 3134 KiB  
Article
Synthesis of Phosphazene-Containing, Bisphenol A-Based Benzoxazines and Properties of Corresponding Polybenzoxazines
by Igor S. Sirotin, Igor A. Sarychev, Viktoria V. Vorobyeva, Anastasia A. Kuzmich, Natalia V. Bornosuz, Denis V. Onuchin, Irina Yu. Gorbunova and Vyacheslav V. Kireev
Polymers 2020, 12(6), 1225; https://doi.org/10.3390/polym12061225 - 28 May 2020
Cited by 19 | Viewed by 4520
Abstract
With the aim of obtaining halogen-free polybenzoxazazines with reduced flammability, phosphazene-containing benzoxazines (PhBZ) were synthesized in a two-stage method. In the first stage of the reaction of hexachlorocycotriphosphazene with bisphenol A at molar ratios of 1:12, 1:16, and 1:24, respectively, mixtures of bisphenol [...] Read more.
With the aim of obtaining halogen-free polybenzoxazazines with reduced flammability, phosphazene-containing benzoxazines (PhBZ) were synthesized in a two-stage method. In the first stage of the reaction of hexachlorocycotriphosphazene with bisphenol A at molar ratios of 1:12, 1:16, and 1:24, respectively, mixtures of bisphenol and hydroxyaryloxycyclotriphosphazenes were obtained, which mainly contained P3N3[OC6H4C(CH3)3C6H4OH]6. In the second stage, when these mixtures interacted with aniline and an excess of paraformaldehyde in toluene at 80–90 °C, PhBZ containing 20–50% of the phosphazene component with Mw 1200–5800 were formed. According to 1H and 13C NMR spectroscopy, PhBZ contain a small amount of oligomeric compounds with Mannich aminomethylene bridges. With an increase of the content of the phosphazene component, the curing temperature of PhBZ decreases from 242 °C to 215 °C. Cured PhBZ samples with a phosphorus content of more than 1.5% have increased flammability resistance according to UL-94. Full article
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12 pages, 2729 KiB  
Article
Star-Shaped Crosslinker for Multifunctional Shape Memory Polyurethane
by Xiuhuan Song, Hong Chi, Zibiao Li, Tianduo Li and FuKe Wang
Polymers 2020, 12(4), 740; https://doi.org/10.3390/polym12040740 - 26 Mar 2020
Cited by 11 | Viewed by 3602
Abstract
Star-shaped cyclophosphazene (ACP) was employed as covalent crosslinker to form a rigid segment in polyurethanes network, to enhance the mechanical performance and to add extra flame retardant property. The effects of different ACP contents on the shape memory ability and fire resistance performance [...] Read more.
Star-shaped cyclophosphazene (ACP) was employed as covalent crosslinker to form a rigid segment in polyurethanes network, to enhance the mechanical performance and to add extra flame retardant property. The effects of different ACP contents on the shape memory ability and fire resistance performance of polyurethane (PU) were studied. Tensile tests suggested high flexibility of the PUs with the maximum elongation-at-break of 161.59%. Dynamic mechanical analysis (DMA) indicated good shape recovery ratio of 72.58% after more than three repeated cycles. Under thermal treatment, the temporary shape could recover to its original state in 10 s. The peak heat release rate (pHRR), total heat released (THR) and temperature at pHRR (Tp) of flame-retardant shape memory polyurethane (FSPU) by micro-combustion calorimeter (MCC) was as low as 183.2 W/g, 21.4 KJ/g, 330.8 °C respectively, suggesting good inherent fire-resistant performance. As amine-containing crosslinkers are one of the most common building units in thermosetting polymers, we anticipate that our finding will have significant benefits beyond shape memory and fire-resistance. Full article
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11 pages, 3153 KiB  
Article
pH-Dependent Foam Formation Using Amphoteric Colloidal Polymer Particles
by Sayaka Fukui, Tomoyasu Hirai, Yoshinobu Nakamura and Syuji Fujii
Polymers 2020, 12(3), 511; https://doi.org/10.3390/polym12030511 - 27 Feb 2020
Cited by 7 | Viewed by 2946
Abstract
Near-monodispersed micrometer-sized polystyrene (PS) particles carrying amidino and carboxyl groups on their surfaces were synthesized by soap-free emulsion polymerization using an amphoteric free radical initiator. The resulting amphoteric PS particles were characterized in terms of diameter, morphology, disperibility in aqueous media and surface [...] Read more.
Near-monodispersed micrometer-sized polystyrene (PS) particles carrying amidino and carboxyl groups on their surfaces were synthesized by soap-free emulsion polymerization using an amphoteric free radical initiator. The resulting amphoteric PS particles were characterized in terms of diameter, morphology, disperibility in aqueous media and surface charge using scanning electron microscopy (SEM), optical microscopy (OM), sedimentation rate and electrophoretic measurements. At pH 2.0, where the amidino groups are protonated (positively charged), and at pH 11.0, where the carboxyl groups are deprotonated (negatively charged), the PS particles were well dispersed in aqueous media via electrostatic repulsion. At pH 4.8, where the surface charges are neutral, the PS particles were weakly aggregated. Furthermore, it was confirmed that the PS particles can function as a pH-sensitive foam stabilizer: foamability and foam stability were higher at pH 2.0 and 4.8, where the PS particles can be adsorbed to the air–water interface, and lower at pH 11.0, where the PS particles tend to disperse in bulk aqueous medium. SEM and OM studies indicated that hexagonally close-packed arrays of PS particles were formed on the bubble surfaces and moiré patterns were observed on the dried foams. Moreover, the fragments of dried foams showed iridescent character under white light. Full article
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19 pages, 2789 KiB  
Article
Thermoresponsive Poly(ε-Caprolactone)-Poly(Ethylene/Propylene Glycol) Copolymers as Injectable Hydrogels for Cell Therapies
by Kyle Brewer, Batjargal Gundsambuu, Paula Facal Marina, Simon C. Barry and Anton Blencowe
Polymers 2020, 12(2), 367; https://doi.org/10.3390/polym12020367 - 7 Feb 2020
Cited by 20 | Viewed by 4777
Abstract
Injectable, thermoresponsive hydrogels are promising candidates for the delivery, maintenance and controlled release of adoptive cell therapies. Therefore, there is significant interest in the development of cytocompatible and biodegradable thermoresponsive hydrogels with appropriate gelling characteristics. Towards this end, a series of thermoresponsive copolymers [...] Read more.
Injectable, thermoresponsive hydrogels are promising candidates for the delivery, maintenance and controlled release of adoptive cell therapies. Therefore, there is significant interest in the development of cytocompatible and biodegradable thermoresponsive hydrogels with appropriate gelling characteristics. Towards this end, a series of thermoresponsive copolymers consisting of poly(caprolactone) (PCL), poly(ethylene glycol) (PEG) and poly(propylene glycol) (PPG) segments, with various PEG:PPG ratios, were synthesised via ring-opening polymerisation (ROP) of ε-caprolactone and epoxy-functionalised PEG and PPG derivatives. The resultant PCL–PEG–PPG copolymers were characterised via proton nuclear magnetic resonance (1H NMR) spectroscopy, gel permeation chromatography (GPC) and differential scanning calorimetry (DSC). The thermoresponsive characteristics of the aqueous copolymer solutions at various concentrations was investigated using the inversion method. Whilst all of the copolymers displayed thermoresponsive properties, the copolymer with a ratio of 1:2 PEG:PPG exhibited an appropriate sol–gel transition (28 °C) at a relatively low concentration (10 wt%), and remained a gel at 37 °C. Furthermore, the copolymers were shown to be enzymatically degradable in the presence of lipases and could be used for the encapsulation of CD4+ T-cell lymphocytes. These results demonstrate that the thermoresponsive PCL–PEG–PPG hydrogels may be suitable for use as an adoptive cell therapy (ACT) delivery vehicle. Full article
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15 pages, 3256 KiB  
Article
Fabrication of Cellulose Nanocrystal-g-Poly(Acrylic Acid-Co-Acrylamide) Aerogels for Efficient Pb(II) Removal
by Yifan Chen, Qian Li, Yujie Li, Qijun Zhang, Jingda Huang, Qiang Wu and Siqun Wang
Polymers 2020, 12(2), 333; https://doi.org/10.3390/polym12020333 - 5 Feb 2020
Cited by 34 | Viewed by 5109
Abstract
In this work, cellulose nanocrystals (CNCs) obtained by the acid hydrolysis of waste bamboo powder were used to synthesize cellulose nanocrystal-g-poly(acrylic acid-co-acrylamide) (CNC-g-P(AA/AM)) aerogels via graft copolymerization followed by freeze-drying. The structure and morphology of the resulting aerogels were characterized by Fourier transform [...] Read more.
In this work, cellulose nanocrystals (CNCs) obtained by the acid hydrolysis of waste bamboo powder were used to synthesize cellulose nanocrystal-g-poly(acrylic acid-co-acrylamide) (CNC-g-P(AA/AM)) aerogels via graft copolymerization followed by freeze-drying. The structure and morphology of the resulting aerogels were characterized by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM), and the CNC-g-P(AA/AM) aerogels exhibited excellent absorbent properties and adsorption capacities. Subsequent Pb(II) adsorption studies showed that the kinetic data followed the pseudo-second-order equation, while the adsorption isotherms were best described using the Langmuir model. The maximum Pb(II) adsorption capacity calculated by the Langmuir model reached up to 366.3 mg/g, which is a capacity that outperformed that of the pure CNC aerogel. The CNC-g-P (AA/AM) aerogels become structurally stable through chemical cross-linking, which enabled them to be easily regenerated in HCl solution and retain the adsorption capacity after repeated use. The aerogels were found to maintain 81.3% removal efficiency after five consecutive adsorption–desorption cycles. Therefore, this study demonstrated an effective method for the fabrication of an aerogel adsorbent with an excellent reusability in the effective removal of Pb(II) from aqueous solutions. Full article
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2019

Jump to: 2024, 2023, 2022, 2021, 2020

21 pages, 6342 KiB  
Review
Advances in the Phototriggered Synthesis of Single-Chain Polymer Nanoparticles
by Ester Verde-Sesto, Agustín Blázquez-Martín and José A. Pomposo
Polymers 2019, 11(11), 1903; https://doi.org/10.3390/polym11111903 - 18 Nov 2019
Cited by 12 | Viewed by 4367
Abstract
Clean use of photons from light to activate chemical reactions offers many possibilities in different fields, from chemistry and biology to materials science and medicine. This review article describes the advances carried out in last decades toward the phototriggered synthesis of single-chain polymer [...] Read more.
Clean use of photons from light to activate chemical reactions offers many possibilities in different fields, from chemistry and biology to materials science and medicine. This review article describes the advances carried out in last decades toward the phototriggered synthesis of single-chain polymer nanoparticles (SCNPs) as soft nanomaterials with promising applications in enzyme-mimicking catalysis and nanomedicine, among other different uses. First, we summarize some different strategies developed to synthesize SCNPs based on photoactivated intrachain homocoupling, phototriggered intrachain heterocoupling and photogenerated collapse induced by an external cross-linker. Next, we comprehensively review the emergent topic of photoactivated multifolding applied to SCNP construction. Finally, we conclude by summarizing recent strategies towards phototriggered disassembly of SCNPs. Full article
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13 pages, 1818 KiB  
Article
A New Strategy for the Synthesis of Fluorinated Polyurethane
by Pu-Cheng Wang, Dan Lu, Hu Wang and Ru-Ke Bai
Polymers 2019, 11(9), 1440; https://doi.org/10.3390/polym11091440 - 2 Sep 2019
Cited by 5 | Viewed by 4131
Abstract
An alternating fluorinated copolymer based on chlorotrifluoroethylene (CTFE) and butyl vinyl ether (BVE) was synthesized by RAFT/MADIX living/controlled polymerization in the presence of S-benzyl O-ethyl dithiocarbonate (BEDTC). Then, using the obtained poly(CTFE-alt-BVE) as a macro chain transfer agent (macro-CTA), a block copolymer was [...] Read more.
An alternating fluorinated copolymer based on chlorotrifluoroethylene (CTFE) and butyl vinyl ether (BVE) was synthesized by RAFT/MADIX living/controlled polymerization in the presence of S-benzyl O-ethyl dithiocarbonate (BEDTC). Then, using the obtained poly(CTFE-alt-BVE) as a macro chain transfer agent (macro-CTA), a block copolymer was prepared by chain extension polymerization of vinyl acetate (VAc). After a basic methanolysis process, the poly(vinyl acetate) (PVAc) block was transferred into poly(vinyl alcohol) (PVA). Finally, a novel fluorinated polyurethane with good surface properties due to the mobility of the flexible fluorinated polymer chains linked to the network was obtained via reaction of the copolymer bearing the blocks of PVA with isophorone diisocyanate (IPDI) as a cross-linking agent. Full article
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21 pages, 5082 KiB  
Article
In Situ Modification of Polyisoprene by Organo-Nanoclay during Emulsion Polymerization for Reinforcing Natural Rubber Thin Films
by Jadsadaporn Chouytan, Ekwipoo Kalkornsurapranee, Christopher M. Fellows and Wisut Kaewsakul
Polymers 2019, 11(8), 1338; https://doi.org/10.3390/polym11081338 - 12 Aug 2019
Cited by 6 | Viewed by 4467
Abstract
Nanoclay-modified polyisoprene latexes were prepared and then used as a reinforcing component in natural rubber (NR) thin films. Starve-fed emulsion (SFE) polymerization gives a higher conversion than the batch emulsion (BE), while the gel and coagulation contents from both systems are comparable. This [...] Read more.
Nanoclay-modified polyisoprene latexes were prepared and then used as a reinforcing component in natural rubber (NR) thin films. Starve-fed emulsion (SFE) polymerization gives a higher conversion than the batch emulsion (BE), while the gel and coagulation contents from both systems are comparable. This is attributed to the SFE that provides a smaller average polymer particle size which in turn results in a greater polymerization locus, promoting the reaction rate. The addition of organo-nanoclay during synthesizing polyisoprene significantly lessens the polymerization efficiency because the nanoclay has a potential to suppress nucleation process of the reaction. It also intervenes the stabilizing efficiency of the surfactant—SDS or sodium dodecyl sulfate, giving enlarged average sizes of the polymer particles suspended in the latexes. TEM images show that nanoclay particles are attached on and/or inserted in the polymer particles. XRD and thermal (differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA)) analyses were employed to assess the d-spacing of nanoclay structure in NR nanocomposite films, respectively. Based on the overall results, 5 wt% of nanoclay relative to the monomer content utilized to alter the polyisoprene during emulsion polymerization is an optimum amount since the silicate plates of nanoclay in the composite exhibit the largest d-spacing which maximizes the extent of immobilized polymer constituent, giving the highest mechanical properties to the films. The excessive amounts of nanoclay used, i.e., 7 and 10 wt% relative to the monomer content, reduce the reinforcing power because of the re-agglomeration effect. Full article
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12 pages, 2480 KiB  
Article
Excellent Toughening of 2,6-Diaminopyridine Derived Poly (Urethane Urea) via Dynamic Cross-Linkages and Interfering with Hydrogen Bonding of Urea Groups from Partially Coordinated Ligands
by Ailing Sun, Wenjuan Guo, Jinping Zhang, Wenjuan Li, Xin Liu, Hao Zhu, Yuhan Li and Liuhe Wei
Polymers 2019, 11(8), 1320; https://doi.org/10.3390/polym11081320 - 7 Aug 2019
Cited by 9 | Viewed by 3760
Abstract
Conventional approaches to synthesize thermoplastic polyurethane (TPU) with excellent robustness are limited by a competing relationship between soft and hard segments for tuning mechanical properties in terms of chain flexibility and micro-phase separation. Herein, we present a facile and effective way of simultaneously [...] Read more.
Conventional approaches to synthesize thermoplastic polyurethane (TPU) with excellent robustness are limited by a competing relationship between soft and hard segments for tuning mechanical properties in terms of chain flexibility and micro-phase separation. Herein, we present a facile and effective way of simultaneously improving the tensile strength, elongation, and toughness by constructing dynamic cross-linkages from metal-ligand interaction between Zn2+ and pyridine moiety in backbone of poly(urethane urea) (PUU) derived from 2,6-diaminopyridine and poly(propylene glycol). It was found that a Zn2+/pyridine ratio of 1:4 is the most effective for improving robustness. Specifically, tensile strength, elongation, and toughness could be remarkably increased to 16.0 MPa, 1286%, and 89.3 MJ/m3 with 226%, 29%, and 185% increments compared to uncomplexed PUU, respectively. Results from UV-vis, Fourier transform infrared spectroscopy (FTIR), cyclic tensile tests, and stress relaxation reveal that metal-ligand interaction significantly interferes with the hydrogen bonding of urea groups, thus leading to weakening of stiffness. Furthermore, half of vacant ligands enable dynamic complexation during stretching, which consequently ensures constant noncovalent cross-linkages for constraining mutual chain sliding, contributing to simultaneous improvement of tensile strength, elongation, and toughness. This work provides a promising approach for designing TPU with excellent robustness. Full article
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17 pages, 6995 KiB  
Article
A Novel Synthetic Strategy for Preparing Polyamide 6 (PA6)-Based Polymer with Transesterification
by Shengming Zhang, Jingchun Zhang, Lian Tang, Jiapeng Huang, Yunhua Fang, Peng Ji, Chaosheng Wang and Huaping Wang
Polymers 2019, 11(6), 978; https://doi.org/10.3390/polym11060978 - 3 Jun 2019
Cited by 25 | Viewed by 5804
Abstract
In the polymerization of caprolactam, the stoichiometry of carboxyl groups and amine groups in the process of melt polycondensation needs to be balanced, which greatly limits the copolymerization modification of polyamide 6. In this paper, by combining the characteristics of the polyester polymerization [...] Read more.
In the polymerization of caprolactam, the stoichiometry of carboxyl groups and amine groups in the process of melt polycondensation needs to be balanced, which greatly limits the copolymerization modification of polyamide 6. In this paper, by combining the characteristics of the polyester polymerization process, a simple and flexible synthetic route is proposed. A polyamide 6-based polymer can be prepared by combining caprolactam hydrolysis polymerization with transesterification. First, a carboxyl-terminated polyamide 6-based prepolymer is obtained by a caprolactam hydrolysis polymerization process using a dibasic acid as a blocking agent. Subsequently, ethylene glycol is added for esterification to form a glycol-terminated polyamide 6-based prepolymer. Finally, a transesterification reaction is carried out to prepare a polyamide 6-based polymer. In this paper, a series of polyamide 6-based polymers with different molecular weight blocks were prepared by adjusting the amount and type of dibasic acid added, and the effects of different control methods on the structural properties of the final product are analyzed. The results showed that compared with the traditional polymerization method of polyamide 6, the novel synthetic strategy developed in this paper can flexibly design prepolymers with different molecular weights and end groups to meet different application requirements. In addition, the polyamide 6-based polymer maintains excellent mechanical and hygroscopic properties. Furthermore, the molecular weight increase in the polyamide 6 polymer is no longer dependent on the metering balance of the end groups, providing a new synthetic route for the copolymerization of polyamide 6 copolymer. Full article
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23 pages, 4340 KiB  
Article
Control of Gelation and Properties of Reversible Diels–Alder Networks: Design of a Self-Healing Network
by Beata Strachota, Adama Morand, Jiří Dybal and Libor Matějka
Polymers 2019, 11(6), 930; https://doi.org/10.3390/polym11060930 - 28 May 2019
Cited by 19 | Viewed by 4657
Abstract
Reversible Diels–Alder (DA) type networks were prepared from furan and maleimide monomers of different structure and functionality. The factors controlling the dynamic network formation and their properties were discussed. Evolution of structure during both dynamic nonequilibrium and isothermal equilibrium network formation/breaking was followed [...] Read more.
Reversible Diels–Alder (DA) type networks were prepared from furan and maleimide monomers of different structure and functionality. The factors controlling the dynamic network formation and their properties were discussed. Evolution of structure during both dynamic nonequilibrium and isothermal equilibrium network formation/breaking was followed by monitoring the modulus and conversion of the monomer. The gelation, postgel growth, and properties of the thermoreversible networks from tetrafunctional furan (F4) and different bismaleimides (M2) were controlled by the structure of the maleimide monomer. The substitution of maleimides with alkyl (hexamethylene bismaleimide), aromatic (diphenyl bismaleimide), and polyether substituents affects differently the kinetics and thermodynamics of the thermoreversible DA reaction, and thereby the formation of dynamic networks. The gel-point temperature was tuned in the range Tgel = 97–122 °C in the networks of the same functionality (F4-M2) with different maleimide structure. Theory of branching processes was used to predict the structure development during formation of the dynamic networks and the reasonable agreement with the experiment was achieved. The experimentally inaccessible information on the sol fraction in the reversible network was received by applying the theory. Based on the acquired results, the proper structure of a self-healing network was designed. Full article
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10 pages, 4320 KiB  
Article
An Important Factor Affecting the UV Aging Resistance of PBO Fiber Foped with Nano-TiO2: The Number of Amorphous Regions
by Jiping Liu, Xiaobo Liu, Dong Wang and Hu Wang
Polymers 2019, 11(5), 869; https://doi.org/10.3390/polym11050869 - 13 May 2019
Cited by 5 | Viewed by 3879
Abstract
Modified nano-TiO2 was prepared by using triethanolamine and tetraisopropyl di (dioctylphosphate) titanate, respectively. Then the poly(p-phenylene benzobisoxazole) (PBO) fibers doped with different additions of modified nano-TiO2 particles were prepared by preparing PBO polymer solution and dry-jet wet spinning technique. Thermogravimetric and [...] Read more.
Modified nano-TiO2 was prepared by using triethanolamine and tetraisopropyl di (dioctylphosphate) titanate, respectively. Then the poly(p-phenylene benzobisoxazole) (PBO) fibers doped with different additions of modified nano-TiO2 particles were prepared by preparing PBO polymer solution and dry-jet wet spinning technique. Thermogravimetric and derivative thermogravimetry results showed that the addition of nano-TiO2 could improve the crystallinity and maximum thermal decomposition rate temperature of PBO fibers. Tensile strength results showed that nano-TiO2 addition did not affect the tensile properties of PBO fibers before ultraviolet (UV) aging began, and nano-TiO2 with addition values lower than 3% could improve the UV aging resistance performance of PBO fibers, while the aging resistance would be seriously reduced if values were over 5%. The size and quantity of the amorphous regions have a more important influence on the aging resistance of PBO fibers. Full article
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19 pages, 2085 KiB  
Article
Unprecedentedly High Activity and/or High Regio-/Stereoselectivity of Fluorenyl-Based CGC Allyl-Type η31-tert-Butyl(dimethylfluorenylsilyl)amido Ligated Rare Earth Metal Monoalkyl Complexes in Olefin Polymerization
by Ge Guo, Xiaolu Wu, Xiangqian Yan, Li Yan, Xiaofang Li, Shaowen Zhang and Nannan Qiu
Polymers 2019, 11(5), 836; https://doi.org/10.3390/polym11050836 - 8 May 2019
Cited by 7 | Viewed by 3398
Abstract
A series of fluorenyl-based constrained-geometry-configuration (CGC) allyl-type rare earth metal monoalkyl complexes bearing the divalent anionic η31-tert-butyl(dimethylfluorenylsilyl)amido (η31-FluSiMe2NtBu) ligand (η31-FluSiMe2NtBu)Ln(CH2 [...] Read more.
A series of fluorenyl-based constrained-geometry-configuration (CGC) allyl-type rare earth metal monoalkyl complexes bearing the divalent anionic η31-tert-butyl(dimethylfluorenylsilyl)amido (η31-FluSiMe2NtBu) ligand (η31-FluSiMe2NtBu)Ln(CH2SiMe3)(THF)2 (13) have been synthesized via the alkane elimination reaction between the FluHSiMe2NHtBu ligand and rare earth metal tri(trimethylsilylmethyl) complexes Ln(CH2SiMe3)3(THF)n. Their structures are characterized by means of NMR spectrum, elemental analyses, and X-ray diffraction. These complexes 13 are isostructural and isomorphous, and each of them adopts a distorted-trigonal-bipyramidal configuration containing one η31-FluSiMe2NtBu ligand, one CH2SiMe3 ligand, and two THF molecules. Unlike traditional CGC allyl-type rare earth metal complexes showing no or low activity and regio-/stereoselectivity in styrene or MMA polymerization, these complexes 13 exhibit high catalytic activities and/or high regio-/stereoselectivities in the cis-1,4-polymerization of isoprene and myrcene or in the syndiotactic polymerization of styrene under the aid of different activators (borate or borane) and AlR3. The in situ 1H NMR spectra suggest that the exchanges of chelating ligands such as alkyl groups and divalent anionic η31-FluSiMe2NtBu ligands between rare earth metal centers and Al centers result in the formation of a heterobimetallic tetraalkylaluminate complex R2Al(μ-R)2Ln(R)(μ-R)2AlR2, which is activated by activators to form a divalent cationic species [Ln(μ-R)2AlR2]2+ as a catalytically active species in the coordination–insertion polymerization of olefins. Full article
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13 pages, 2161 KiB  
Article
Synthesis and Photoinduced Anisotropy of Polymers Containing Nunchaku-Like Unit with an Azobenzene and a Mesogen
by Lingling Wang, Yingchuan Zhang, Chenhao Zhan, Yong You, Hongxing Zhang, Jinyi Ma, Zhiyuan Xiong, Xiaobo Liu and Renbo Wei
Polymers 2019, 11(4), 600; https://doi.org/10.3390/polym11040600 - 2 Apr 2019
Cited by 8 | Viewed by 3310
Abstract
A series of polymers containing nunchaku-like unit with an azo chromophore and a mesogen group was successfully prepared and photoinduced anisotropy of the obtained polymers was minutely investigated. Firstly, monomers containing nunchaku-like unit with an azo chromophore and a mesogen group linked by [...] Read more.
A series of polymers containing nunchaku-like unit with an azo chromophore and a mesogen group was successfully prepared and photoinduced anisotropy of the obtained polymers was minutely investigated. Firstly, monomers containing nunchaku-like unit with an azo chromophore and a mesogen group linked by flexible group were synthesized. The structure of the monomers was confirmed via NMR COSY spectra. Subsequently, the obtained monomers were polymerized into corresponding polymers through RAFT polymerization. The prepared polymer samples were characterized through NMR, FTIR, gel permeation chromatography (GPC), and UV-vis testing while the thermal properties of the samples were investigated through differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA) measurements. The photoinduced isomerization of the polymers, which was researched in situ via measuring UV-vis spectra of the polymer solutions and spin-coated films under irradiation with 450 nm light or putting in darkness, demonstrated the rapid trans-cis-trans isomerization of the polymers. When irradiated with a linearly polarized light, significant photoinduced birefringence and dichroism were observed, suggesting photoinduced isomerization of azobenzene can drive orientation of mesogen in the system. This study blazes a way to design the optical materials with light-controllable birefringence and dichroism. Full article
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14 pages, 1558 KiB  
Article
Characteristics and Mechanism of Vinyl Ether Cationic Polymerization in Aqueous Media Initiated by Alcohol/B(C6F5)3/Et2O
by Jinghan Zhang, Yibo Wu, Kaixuan Chen, Min Zhang, Liangfa Gong, Dan Yang, Shuxin Li and Wenli Guo
Polymers 2019, 11(3), 500; https://doi.org/10.3390/polym11030500 - 14 Mar 2019
Cited by 11 | Viewed by 6058
Abstract
Aqueous cationic polymerizations of vinyl ethers (isobutyl vinyl ether (IBVE), 2-chloroethyl vinyl ether (CEVE), and n-butyl vinyl ether (n-BVE)) were performed for the first time by a CumOH/B(C6F5)3/Et2O initiating system in an [...] Read more.
Aqueous cationic polymerizations of vinyl ethers (isobutyl vinyl ether (IBVE), 2-chloroethyl vinyl ether (CEVE), and n-butyl vinyl ether (n-BVE)) were performed for the first time by a CumOH/B(C6F5)3/Et2O initiating system in an air atmosphere. The polymerization proceeded in a reproducible manner through the careful design of experimental conditions (adding initiator, co-solvents, and surfactant or decreasing the reaction temperature), and the polymerization characteristics were systematically tested and compared in the suspension and emulsion. The significant difference with traditional cationic polymerization is that the polymerization rate in aqueous media using B(C6F5)3/Et2O as a co-initiator decreases when the temperature is lowered. The polymerization sites are located on the monomer/water surface. Density functional theory (DFT) was applied to investigate the competition between H2O and alcohol combined with B(C6F5)3 for providing a theoretical basis. The effectiveness of the proposed mechanism for the aqueous cationic polymerization of vinyl ethers using CumOH/B(C6F5)3/Et2O was confirmed. Full article
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15 pages, 3682 KiB  
Article
Effects of End-Caps on the Atropisomerization, Polymerization, and the Thermal Properties of ortho-Imide Functional Benzoxazines
by Kan Zhang, Yuqi Liu, Zhikun Shang, Corey J. Evans and Shengfu Yang
Polymers 2019, 11(3), 399; https://doi.org/10.3390/polym11030399 - 1 Mar 2019
Cited by 9 | Viewed by 4176
Abstract
A new type of atropisomerism has recently been discovered in 1,3-benzoxazines, where the intramolecular repulsion between negatively charged oxygen atoms on the imide and the oxazine ring hinders the rotation about the C–N bond. The imide group offers a high degree of flexibility [...] Read more.
A new type of atropisomerism has recently been discovered in 1,3-benzoxazines, where the intramolecular repulsion between negatively charged oxygen atoms on the imide and the oxazine ring hinders the rotation about the C–N bond. The imide group offers a high degree of flexibility for functionalization, allowing a variety of functional groups to be attached, and producing different types of end-caps. In this work, the effects of end-caps on the atropisomerism, thermally activated polymerization of ortho-imide functional benzoxazines, and the associated properties of polybenzoxazines have been systematically investigated. Several end-caps, with different electronic characteristics and rigidities, were designed. 1H and 13C nuclear magnetic resonance (NMR) spectroscopy and density functional theory (DFT) calculations were employed to obtain structural information, and differential scanning calorimetry (DSC) and in situ Fourier transform infrared (FT-IR) spectroscopy were also performed to study the thermally activated polymerization process of benzoxazine monomers. We demonstrated that the atropisomerization can be switched on/off by the manipulation of the steric structure of the end-caps, and polymerization behaviors can be well-controlled by the electronic properties of the end-caps. Moreover, a trade-off effect were found between the thermal properties and the rigidity of the end-caps in polybenzoxazines. Full article
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12 pages, 5910 KiB  
Communication
Synthesis of Polyazobenzenes Exhibiting Photoisomerization and Liquid Crystallinity
by Masashi Otaki, Reiji Kumai, Hajime Sagayama and Hiromasa Goto
Polymers 2019, 11(2), 348; https://doi.org/10.3390/polym11020348 - 17 Feb 2019
Cited by 4 | Viewed by 3788
Abstract
While only a few studies have investigated the synthesis of main chain-type polyazobenzenes, they continue to draw an increasing amount of attention owing to their industrial applications in holography, dyes, and functional adhesives. In this study, dibromoazobenzene was prepared as a monomer for [...] Read more.
While only a few studies have investigated the synthesis of main chain-type polyazobenzenes, they continue to draw an increasing amount of attention owing to their industrial applications in holography, dyes, and functional adhesives. In this study, dibromoazobenzene was prepared as a monomer for constructing azo-based π-conjugated polymers. Miyaura–Suzuki cross-coupling polymerization was conducted to develop copolymers containing an azobenzene unit as a photoisomerization block and a pyrimidine-based liquid crystal generator block. The prepared polymers exhibited thermotropic liquid crystallinity and underwent cis and trans photoisomerization upon irradiation with ultraviolet and visible light. Furthermore, the photoisomerization behavior was examined using optical absorption spectroscopy and synchrotron X-ray diffraction spectrometry. Full article
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13 pages, 2017 KiB  
Article
Hyperbranched Polycaprolactone through RAFT Polymerization of 2-Methylene-1,3-dioxepane
by Ping Xu, Xiaofei Huang, Xiangqiang Pan, Na Li, Jian Zhu and Xiulin Zhu
Polymers 2019, 11(2), 318; https://doi.org/10.3390/polym11020318 - 13 Feb 2019
Cited by 21 | Viewed by 5339
Abstract
Hyperbranched polycaprolactone with controlled structure was synthesized by reversible addition-fragmentation chain transfer radical ring-opening polymerization along with self-condensed vinyl polymerization (SCVP) of 2-methylene-1,3-dioxepane (MDO). Vinyl 2-[(ethoxycarbonothioyl) sulfanyl] propanoate (ECTVP) was used as polymerizable chain transfer agent. Living polymerization behavior was proved via pseudo [...] Read more.
Hyperbranched polycaprolactone with controlled structure was synthesized by reversible addition-fragmentation chain transfer radical ring-opening polymerization along with self-condensed vinyl polymerization (SCVP) of 2-methylene-1,3-dioxepane (MDO). Vinyl 2-[(ethoxycarbonothioyl) sulfanyl] propanoate (ECTVP) was used as polymerizable chain transfer agent. Living polymerization behavior was proved via pseudo linear kinetics, the molecular weight of polymers increasing with conversion and successful chain extension. The structure of polymers was characterized by 1H NMR spectroscopy, tripe detection gel permeation chromatography, and differential scanning calorimetry. The polymer composition was shown to be able to tune to vary the amount of ester repeat units in the polymer backbone, and hence determine the degree of branching. As expected, the degree of crystallinity was lower and the rate of degradation was faster in cases of increasing the number of branches. Full article
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11 pages, 2710 KiB  
Article
Design and Synthesis of a Cyclic Double-Grafted Polymer Using Active Ester Chemistry and Click Chemistry via A “Grafting onto” Method
by Meng Liu, Lu Yin, Shuangshuang Zhang, Zhengbiao Zhang, Wei Zhang and Xiulin Zhu
Polymers 2019, 11(2), 240; https://doi.org/10.3390/polym11020240 - 1 Feb 2019
Cited by 8 | Viewed by 3977
Abstract
Combing active ester chemistry and click chemistry, a cyclic double-grafted polymer was successfully demonstrated via a “grafting onto” method. Using active ester chemistry as post-functionalized modification approach, cyclic backbone (c-P2) was synthesized by reacting propargyl amine with cyclic precursor (poly(pentafluorophenyl 4-vinylbenzoate), [...] Read more.
Combing active ester chemistry and click chemistry, a cyclic double-grafted polymer was successfully demonstrated via a “grafting onto” method. Using active ester chemistry as post-functionalized modification approach, cyclic backbone (c-P2) was synthesized by reacting propargyl amine with cyclic precursor (poly(pentafluorophenyl 4-vinylbenzoate), c-PPF4VB6.5k). Hydroxyl-containing polymer double-chain (l-PS-PhOH) was prepared by reacting azide-functionalized polystyrene (l-PSN3) with 3,5-bis(propynyloxy)phenyl methanol, and further modified by azide group to generate azide-containing polymer double-chain (l-PS-PhN3). The cyclic backbone (c-P2) was then coupled with azide-containing polymer double-chain (l-PS-PhN3) via CuAAC reaction to construct a novel cyclic double-grafted polymer (c-P2-g-Ph-PS). This research realized diversity and complexity of side chains on cyclic-grafted polymers, and this cyclic double-grafted polymer (c-P2-g-Ph-PS) still exhibited narrow molecular weight distribution (Mw/Mn < 1.10). Full article
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