Polysulfones are a family of thermoplastic polymers. These polymers are known for their toughness and stability at high temperatures. They contain the subunit aryl-SO2-aryl, the defining feature of which is the sulfone group. Polysulfones were introduced in 1965 by Union Carbide. Due to the high cost of raw materials and processing, polysulfones are used in specialty applications and often are a superior replacement for polycarbonates.
1 Definition and technically used polysulfones 2 History 3 Production 4 Properties
4.1 Structure-property relationship
5.1 Membranes 5.2 Materials 5.3 Fuel cells
Definition and technically used polysulfones In principle, any polymer containing a sulfonyl group could be called "polysulfone". However, the term "polysulfone" is normally used for polyarylethersulfones (PAES), since only aromatic polysulfones are used in a technical context. Furthermore, since ether groups are always present in the industrially used polysulfones, PAES are also referred to as polyether sulfones (PES), poly(arylene sulfone)s or simply polysulfone (PSU). The three terms (and abbreviations) may therefore be synonyms. As a term for all polysulfones, "poly(aryl ether sulfone)s (PAES)" is preferable because polysulfone (PSU), polyethersulfone (PES) and poly(arylene sulfone) (PAS) are additionally used as a name for individual polymers. These and some other PAES are listed in the chapter Industrially relevant polysulfones (below). History The simplest polysulfone poly(phenylene sulfone) was known als early as 1960. It can be produced in a Friedel-Crafts reaction from benzenesulfonyl chloride:
A r − S
− C l ⟶ − [ − A r − S
+ H C l
displaystyle mathrm Ar-SO_ 2 -Cllongrightarrow -[-Ar-SO_ 2 -]_ n +HCl
Since this polymer has a melting point of over 500 °C, it is on
one side very heat resistant, on the other hand it is very difficult
to process. In addition, its mechanical properties are rather poor.
Therefore, thermoplastic (melt-processable) polysulfones were
researched as an alternative. At that time it was already assumed that
polyarylether sulphones (PAES) would be a suitable alternative.
Appropriate synthetic routes to PAES were developed almost
simultaneously, and yet independently, from 3M Corporation, Union
Carbide Corporation in the United States, and ICI's Plastics
Division in the United Kingdom. The polymers found at that time are
still used today, but produced by a different synthesis process.
The synthesis method used at that time followed an electrophilic
synthesis. Not only para- but also ortho bonds were generated, which
led to cross-linking in some cases and generally to worse mechanical
properties. The syntheses consisted of an electrophilic aromatic
substitution of an aryl ether with a sulfuryl chloride using a
All PAES commercially available nowadays are not synthesized via this route but rather via a nucleophilic synthesis, see chapter Preparation. Production Technically, polyethersulfones are prepared by a polycondensation reaction of the sodium salt of an aromatic diphenol and bis(4-chlorophenyl)sulfone. The sodium salt of the diphenol is formed in situ by reaction with a stoichiometric amount of sodium hydroxide (NaOH). The formed reaction water must be removed with an azeotropic solvent (e.g. methylbenzene or chlorobenzene). The polymerization is carried out at 130–160 °C under inert conditions in a polar, aprotic solvent, e.g. dimethyl sulfoxide, forming a polyether by elimination of sodium chloride::
Also bis(4-fluorophenyl)sulfone can be used, it is more reactive than
the dichloride but too expensive for commercial use. Through chain
terminators (e.g. chloromethane), the chain length can be regulated in
a range that a technical melt processing is possible. However, the
product shown in the reaction equation still has reactive end groups.
To prevent further condensation in the melt, the end groups can be
etherified with chloromethane.
The diphenol is typically bisphenol-A or 1,4-dihydroxybenzene. Such
step polymerizations require highly pure monomer to ensure high
molecular weight products.
Polysulfones are rigid, high-strength and transparent. They are also
characterized by high strength and stiffness, retaining these
properties between −100 °C and 150 °C. The glass
transition temperature of polysulfones is between 190 to
230 °C. They have a high dimensional stability, the size
change when exposed to boiling water or 150 °C air or steam
generally falls below 0.1%.
^ Makromolekulare Chemie : ein Lehrbuch für Chemiker, Physiker, Materialwissenschaftler und Verfahrenstechniker. Lechner, Manfred D., Gehrke, K., Nordmeier, Eckhard. (4., überarb. und erw. Aufl ed.). Basel [u.a.]: Birkhäuser. 2010. p. 134. ISBN 9783764388904. OCLC 643841472. ^ a b GB, H.A. Vogel, "Polyarylsulphone polymers" ^ GB, Alford G. Farnham, Robert N. Johnson, "Polyarylene Polyethers" ^ GB, Barr Dennis Arthur; Rose John Brewster, "Production of Aromatic Polymers and Intermediates therefor" ^ a b Rose, J. B. (July 1974). "Preparation and properties of poly(arylene ether sulphones)". Polymer. 15 (7): 456–465. doi:10.1016/0032-3861(74)90111-6. ^ a b David Parker, Jan Bussink, Hendrik T. van de Grampel, Gary W. Wheatley, Ernst-Ulrich Dorf, Edgar Ostlinning, Klaus Reinking, "Polymers, High-Temperature" in Ullmann's Encyclopedia of Industrial Chemistry 2002, Wiley-VCH: Weinheim. doi:10.1002/14356007.a21_449 ^ (in German) [books.google.de Handbook of Biomaterial Properties], Springer Science & Business Media, 1998, p. 283, ISBN 978-0-412-60330-3, books.google.de ^ Hee-Gweon Woo, Hong Li (2011) (in German), [books.google.de Advanced Functional Materials], Springer Science & Business Media, p. 23, ISBN 978-3-642-19077-3, books.google.de ^ Kunststoff-Handbuch. 3 Technische Thermoplaste 3 Hochleistungs-Kunststoffe. Becker, Gerhard W., Becker, R., Binsack, Rudolf, Bottenbruch, Ludwig, Braun, Dietrich (1. Aufl ed.). München [u.a.]: Hanser. 1994. p. 140. ISBN 3446163700. OCLC 246423844. ^ Michael A. Hickner; Hossein Ghassemi; Yu Seung Kim; Brian R. Einsla; James E. McGrath (2004). "Alternative polymer systems for proton exchange membranes (PEMs)". Chemical Reviews. 104 (10): 4587–4611. doi:10.1021/cr020711a. ^ Borup, Rod (2007). "Scientific aspects of polymer electrolyte fuel cell durability and degradation". Chemical Reviews. 107 (10): 3904–3951. doi:10.1021/cr020711a. ^ Jimmy Lawrence; Takeo Yamaguchi (200). "The degradation mechanism of sulfonated poly(arylene ether sulfone)s in an oxidative environment". Journal of Membrane Science. 325 (2): 633–640. doi:10.1016/j.memsci.2008.08.027.
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