Exploring the long-term hydrolytic behavior of zwitterionic polymethacrylates and polymethacrylamides

  • The hydrolytic stability of polymers to be used for coatings in aqueous environments, for example, to confer anti-fouling properties, is crucial. However, long-term exposure studies on such polymers are virtually missing. In this context, we synthesized a set of nine polymers that are typically used for low-fouling coatings, comprising the well-established poly(oligoethylene glycol methylether methacrylate), poly(3-(N-2-methacryloylethyl-N,N-dimethyl) ammoniopropanesulfonate) (sulfobetaine methacrylate), and poly(3-(N-3-methacryamidopropyl-N,N-dimethyl)ammoniopropanesulfonate) (sulfobetaine methacrylamide) as well as a series of hitherto rarely studied polysulfabetaines, which had been suggested to be particularly hydrolysis-stable. Hydrolysis resistance upon extended storage in aqueous solution is followed by H-1 NMR at ambient temperature in various pH regimes. Whereas the monomers suffered slow (in PBS) to very fast hydrolysis (in 1 M NaOH), the polymers, including the polymethacrylates, proved to be highly stable. No degradationThe hydrolytic stability of polymers to be used for coatings in aqueous environments, for example, to confer anti-fouling properties, is crucial. However, long-term exposure studies on such polymers are virtually missing. In this context, we synthesized a set of nine polymers that are typically used for low-fouling coatings, comprising the well-established poly(oligoethylene glycol methylether methacrylate), poly(3-(N-2-methacryloylethyl-N,N-dimethyl) ammoniopropanesulfonate) (sulfobetaine methacrylate), and poly(3-(N-3-methacryamidopropyl-N,N-dimethyl)ammoniopropanesulfonate) (sulfobetaine methacrylamide) as well as a series of hitherto rarely studied polysulfabetaines, which had been suggested to be particularly hydrolysis-stable. Hydrolysis resistance upon extended storage in aqueous solution is followed by H-1 NMR at ambient temperature in various pH regimes. Whereas the monomers suffered slow (in PBS) to very fast hydrolysis (in 1 M NaOH), the polymers, including the polymethacrylates, proved to be highly stable. No degradation of the carboxyl ester or amide was observed after one year in PBS, 1 M HCl, or in sodium carbonate buffer of pH 10. This demonstrates their basic suitability for anti-fouling applications. Poly(sulfobetaine methacrylamide) proved even to be stable for one year in 1 M NaOH without any signs of degradation. The stability is ascribed to a steric shielding effect. The hemisulfate group in the polysulfabetaines, however, was found to be partially labile.show moreshow less

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Metadaten
Author details:Eric Schönemann, Andre LaschewskyORCiDGND, Axel RosenhahnORCiDGND
DOI:https://doi.org/10.3390/polym10060639
ISSN:2073-4360
Pubmed ID:http://www.ncbi.nlm.nih.gov/pubmed?term=30966673
Title of parent work (English):Polymers
Publisher:MDPI
Place of publishing:Basel
Publication type:Article
Language:English
Year of first publication:2018
Completion year:2018
Release date:2021/11/25
Tag:anti-fouling materials; hydrolysis; polymer degradation; polysulfabetaine; polysulfobetaine; polyzwitterions; stability
Volume:10
Issue:6
Number of pages:23
Funding institution:Deutsche Forschungsgemeinschaft (DFG)German Research Foundation (DFG) [LA 611/14-1, RO 2524/4-1]
Organizational units:Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie
Peer review:Referiert
Publishing method:Open Access / Gold Open-Access
DOAJ gelistet
License (German):License LogoCC BY - Namensnennung, 4.0 International
External remark:Zweitveröffentlichung in der Schriftenreihe Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe ; 1091