Degradation manner of polymer grafts chemically attached on thermally stable polymer films: swelling-induced detachment of hydrophilic grafts from hydrophobic polymer substrates in aqueous media

Enomoto, Kazuyuki; Takahashi, Shinji; Iwase, Tamaki; Yamashita, Takashi; Maekawa, Yasunari

doi:10.1039/c0jm04084c

Cited by 44 publications

(60 citation statements)

References 34 publications

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“…Furthermore, the methyl proton ( d 3 ) of the ester, which was not reported in the previous paper, appears as a broad singlet at 3.6 ppm. In the 13 C-NMR spectrum, the methylene (broad singlet, a 1-3 ) and methine (two peaks, [ 20 ] Furthermore, no fl uorine atoms were observed in 19 F-NMR-spectroscopy measurements (see Figure S1, Supporting Information); the opposite might be expected if the decomposed extracts were obtained as a result of degradation of the fl uorinated ETFE substrate. From the above results, the breaking points for the detachment of the sulfonated MA-grafts should be the initiation points of the polymer grafts at the fl uorinated substrates.…”

Section: Retention Time (Min)mentioning

confidence: 90%

“…[ 20 ] Thus, the swelling-induced detachment should be able to be applied to grafted fi lms consisting of hydrophilic polymer grafts chemically attached onto hydrophobic, and thermally and chemically stable, polymer substrates; for example, poly(styrenesulfonic acid), poly(acrylic acid), poly( N -isopropylacrylamide), poly(vinyl pyridinium salt), poly(vinyl pyrrolidone) and hydrophilic/water-soluble polymer-grafted ETFE, cPTFE, FEP and PFA fi lms. As a fundamental approach, the new isolation method should lead to the understanding of the poly merization process and kinetics in free-radical poly merizations involving initiation, propagation, chaintransfer and termination reactions in the solid (fi lm) state.…”

Section: Retention Time (Min)mentioning

confidence: 99%

“…These results were confi rmed by performing UV-vis and NMR spectroscopy. [ 20 ] We have reported previously that graft-type polymerelectrolyte membranes (PEMs) consisting of alkylsulfonic acids were synthesized by the radiation-induced graft polymerization of methyl acrylate (MA) into a poly(ethylene-co -tetrafl uoroethylene) (ETFE) fi lm, …”

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confidence: 99%

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A Novel Characterization Method for Graft‐Polymer Structures Chemically Attached on Thermally Stable Polymer Films

Enomoto

Takahashi

Maekawa

2011

Macro Chemistry & Physics

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Most polymer grafts in grafted polymer fi lms obtained by radiation-induced solid graft polymerization are not analyzed in detail due to diffi culties in isolation of the grafts without structural decomposition. Herein, a novel structural and molecular weight characterization method is reported for polymer grafts that are chemically attached to thermally and chemically stable polymer substrates, based on a swelling-induced graft detachment in hot water. Polymer grafts prepared by the radiation-induced polymerization of alkyl acrylate into poly(ethylene-co -tetrafl uoroethylene) (ETFE) followed by a sulfonation reaction are found to have a ternary copolymer structure whose monomer units contain -COOH or -SO 3 H groups, or both. fuel-cell polymer-electrolyte membranes for mobile power, vehicles and domestic cogeneration systems. [ 2 , 3 , 6-16 ] The analysis of the chemical structures and molecular weights of the grafts in grafted fi lms prepared by radiationinduced graft polymerization and the subsequent solidstate chemical transformations is restricted to degradable or soluble polymer substrates, such as poly(ethylene oxide), poly(butylene oxide) and natural polymers. [17][18][19] However, grafts introduced into practical polymer substrates are generally thermally and chemically stable, and, thus, cannot be isolated from the substrates for detailed analysis. Recently, we found that the poly(styrenesulfonic acid) (PSSA) grafts in fl uorinated polymer substrates can be successfully isolated in water at 85 ° C by the swellinginduced detachment of the hydrophilic grafts from the hydrophobic polymer substrates without decomposition of the side chains and main chains (thus maintaining the molecular weights). These results were confi rmed by performing UV-vis and NMR spectroscopy. [ 20 ] We have reported previously that graft-type polymerelectrolyte membranes (PEMs) consisting of alkylsulfonic acids were synthesized by the radiation-induced graft polymerization of methyl acrylate (MA) into a poly(ethylene-co -tetrafl uoroethylene) (ETFE) fi lm,

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Section: Retention Time (Min)mentioning

confidence: 90%

Section: Retention Time (Min)mentioning

confidence: 99%

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A Novel Characterization Method for Graft‐Polymer Structures Chemically Attached on Thermally Stable Polymer Films

Enomoto

Takahashi

Maekawa

2011

Macro Chemistry & Physics

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“…On the other hand, Maekawa and co-workers reported swelling-induced detachment of grafted hydrophilic PSSA, a strong polyelectrolyte, from hydrophobic polymer substrates in aqueous media [160]. PSSA was grafted on crosslinked poly(tetrafluoroethylene) (cPTFE), poly(ethylene-co-tetrafluoroethylene) (ETFE), and poly(ether ether ketone) (PEEK) substrates by γ-ray irradiation-initiated radical polymerization followed by further functionalization.…”

Section: Charged Polymer Brushesmentioning

confidence: 99%

Molecular Mechanochemistry: Engineering and Implications of Inherently Strained Architectures

Sheiko

2015

Topics in Current Chemistry

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Mechanical activation of chemical bonds is usually achieved by applying external forces. However, nearly all molecules exhibit inherent strain of their chemical bonds and angles as a result of constraints imposed by covalent bonding and interactions with the surrounding environment. Particularly strong deformation of bonds and angles is observed in hyperbranched macromolecules caused by steric repulsion of densely grafted polymer branches. In addition to the tension amplification, macromolecular architecture allows for accurate control of strain distribution, which enables focusing of the internal mechanical tension to specific chemical bonds and angles. As such, chemically identical bonds in self-strained macromolecules become physically distinct because the difference in bond tension leads to the corresponding difference in the electronic structure and chemical reactivity of individual bonds within the same macromolecule. In this review, we outline different approaches to the design of strained macromolecules along with physical principles of tension management, including generation, amplification, and focusing of mechanical tension at specific chemical bonds.

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“…27,29 Although studies regarding swelling-induced detachment of polymer grafts have been reported [30][31][32][33] , the stability and robustness of the surface-grafted pSBMA brushes in this study will not be compromised under the ambient, nonsubmerged conditions in the intended application environment of an artificial turf surface.…”

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confidence: 98%

Addressing skin abrasions on artificial turfs with zwitterionic polymer brushes

et al. 2016

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Degradation manner of polymer grafts chemically attached on thermally stable polymer films: swelling-induced detachment of hydrophilic grafts from hydrophobic polymer substrates in aqueous media

Cited by 44 publications

References 34 publications

A Novel Characterization Method for Graft‐Polymer Structures Chemically Attached on Thermally Stable Polymer Films

A Novel Characterization Method for Graft‐Polymer Structures Chemically Attached on Thermally Stable Polymer Films

Molecular Mechanochemistry: Engineering and Implications of Inherently Strained Architectures

Addressing skin abrasions on artificial turfs with zwitterionic polymer brushes

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