Sulfonated repeat unit

A polysulfone is characterized by the presence of the sulfone group as part of its repeating unit. Polysulfones may be aUphatic or aromatic. AUphatic polysulfones (R and are alkyl groups) were synthesized by radical-induced copolymerization of olefins and sulfur dioxide and characterized many years ago. However, they never demonstrated significant practical utiUty due to their relatively unattractive physical properties, not withstanding the low cost of their raw materials (1,2). The polysulfones discussed in this article are those based on an aromatic backbone stmcture. The term polysulfones is used almost exclusively to denote aromatic polysulfones. 

The single-monomer route (eq. 5) is preferred as it proves to give more linear and para-linked repeat unit stmctures than the two-monomer route. Other sulfone-based polymers can be similarly produced from sulfonyl haUdes with aromatic hydrocarbons. The key step in these polymerisations is the formation of the carbon—sulfur bond. High polymers are achievable via this synthesis route although the resulting polymers are not always completely linear. 

Since poly(oxy-2,6-dimethy1-1,4-phenylene) has exhibited a high tendency to undergo cleavage, rearrangements and to crosslink in the presence of electrophilic reagents,21 our attention has been focused on modification of poly(arylene ether sulfone), 1, and phenoxy resin,4 The active sites in these polymers are the 3-positions of the bisphenol-A repeating units. We will report the extent of... 

The most interesting aminomethyl derivative of condensation polymers that we have prepared to date Is derived from direct reduction of poly(2-cyano-l,3-phenylene arylene ether), 20. Enchainment of benzonitrile repeat units Is accomplished by coupling 2,6-dichlorobenzonitrile with the potassium salt of bisphenol-A copolymers with lower nitrile contents can be produced by copolycondensation of bisphenol-A, 2,6-dichlorobenzonitrile and 4,4 -dichlorodiphenyl sulfone.21 The pendent nitrile function provides an active site for further elaboration. 

A prominent class of poly(aryl ethers) is the sulfone-containing poly(aryl ethers) that is, poly(arylene ether sulfones), or polysulfones (PSF), and their sulfonated derivatives. The structure of a typical sulfonated polysulfone (SPSF) repeat unit is... 

Solutions of poly(l,4-phenylene-2,6-benzobisthiazole), PBT, exhibit an isotropic to nematic phase transition in a variety of solvents including methane sulfonic acid, MSA, chlorosulfonic acid, CSA, and poly phosphoric acid, PPA (1-4). In the latter case the transition occurs over a range of water -P2O5 compositions. In these acids the polymer, with repeating unit... 

The commercial products contain one chlorine atom per 2-3 repeat units and about one chlorosulfonyl group per 70 repeat units. The chlorosulfonyl groups allow the elastomer to be vulcanized with metal oxides such as lead or magnesium oxide by the formation of metal sulfonate linkages ... 

Kwon and coworkers described solid polyelectrolyte complex systems which dissolve rapidly in response to small electric currents. The solid doses were based on poly(ethyl oxazoline) and poly(methacrylic acid) with a repeating unit stoichiometry of 1 1. Insulin was released in response to slight electric currents due to electrically induced polymer dissolution [380]. In similar work Kwon and coworkers [381] studied release of edrophonium chloride and hydrocortisone from poly(2-acrylamido-2-methylpropane sulfonate-co-n-butyl methacrylate). An on/oflf mechanism of the edrophonium chloride release was observed and was attributed to ion exchange of solute and hydroxonium ion. The cationic solute release was assisted by electrostatic forces, whereas release of the neutral hydrocortisone solute was only affected by swelling and deswelling. 

Nylon, polyacetal, polycarbonates, poly(2,6-dimethyl)phenylene oxide (PPO), polyimides, polyphenylene sulfide (PPS), polyphenylene sulfones, polyaryl sulfones, polyalkylene phthalates, and polyarylether ketones (PEEK) are stiff high-melting polymers which are classified as engineering plastics. The formulas for the repeating units of some of these engineering plastics are shown in Figure 1.15. 

Most polyaryl sulfones have the following repeating unit ... 

In addition to sulfone, phenyl units, and ether moieties, the main backbone of polysulfones can contain a number of other connecting units. The most notable such connecting group is the isopropylidene linkage which is part of the repeat unit of the well-known bisphenol A-based polysulfone. It is difficult to clearly describe the chemical makeup of polysulfones without reference to the chemistry used to synthesize them. There are several routes for the synthesis of polysulfones, but the one which has proved to be most practical and versatile over the years is by aromatic nucleophilic substitution. This polycondensation route is based on reaction of essentially equimolar quantities of 4,4,-dihalodiphenylsulfone (usually dichlorodiphenylsulfone (DCDPS)) with a bisphenol in the presence of base thereby forming the aromatic ether bonds and eliminating an alkali salt as a by-product. This route is employed almost exclusively for the manufacture of polysulfones on a commercial scale. 

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