Sulfur‐Containing Polymers
Authors: Kultys Anna 
Published: September 2010

This review describes methods of synthesis and some more interesting properties of the various new sulfur‐containing polymers, with particular regard to their potential applications. Also, some new or improved methods of synthesizing already known polymers are discussed.

Polysulfides, including poly(monosulfide)s and poly(disulfide)s, are the subject of many detailed studies. During the past years, extensive efforts have been devoted to the synthesis of cyclic oligomers (macrocyclic aromatic sulfides and disulfides) as precursors for the preparation of high molecular weight poly(thioarylene)s by ring‐opening polymerization. The coordination chemistry of macrocyclic polysulfides has also received considerable attention. The thiacrown ether polymer ligands can be used as ion‐exchange resins, metal ion adsorbents, and polymeric phase‐transfer catalysts. Molecular systems in which tetrathiafulvalene is incorporated into macrocycles with supplementary donor atoms are potential electroactive cation sensors. The π‐conjugated polymers have been extensively studied because of their attractive electronic properties.

Polysulfoxides can be used as functional polymers, polymeric oxidizing reagents, compatibilizers, and polymer solvents, and those with chiral sulfonyl groups as stationary phases of chiral HPLC column or as polymeric reagents.

Polysulfonium salts have been extensively studied because of the versatile possibilities of their application. They can be used as ion‐exchange resins, polymer supports in peptide synthesis, polymeric reagents, or conducting and photochemical polymeric materials.

Polymers substituted by sulfo groups have a wide range of applications. Water‐soluble polymers are used as emulsifiers, flocculants, thickeners, tanning agents, and conductive polymers. The sulfonated polyelectrolyte block copolymers were found to be effective stabilizers in emulsion polymerization. Insoluble polymers are used as ion‐exchange resins and they find application as membrane materials. A great demand for chemically stable ion‐exchange membranes for electromembrane processes, such as electrodialysis, polymer electrolyte membrane electrolysis, and polymer electrolyte fuel cells, has in the past years stimulated investigations dealing with the development of the sulfonation process of thermally and chemically stable engineering plastics. Sulfopolymers are used in biomedical systems. Much effort has recently been expended to improve blood‐contacting biomaterials (e.g., segmented polyurethanes) and develop various polysulfates and polysulfonates as antithrombotic or antiviral agents.

Polysulfates are widely studied because of their potential biomedical applications (e.g., as antithrombotic agents). Polysulfates in general and sulfated polysaccharides in particular are active against a wide variety of enveloped viruses. A major commercial sulfated polysaccharide is carrageenan, which is used in ice cream and other food products.

Poly(thioester)s, poly(thiocarbonate)s, as well as poly(thiouretane)s were studied as potential interesting thermoplastics. Thus, biphenyl‐based poly(thioester)s are high thermal stability polymers. Poly(thiocarbonate)s showing a high refractive index are potentially interesting for optical applications. Polymers bearing five‐membered cyclic dithiocarbonate groups in the side chain are potentially the most versatile reactive polymers.

In the last two decades, various new aliphatic‐aromatic polyesters and polyurethanes containing sulfur linkages in the main chain (i.e., thiopolyesters, thiopolyurethanes) were synthesized and characterized. Cross‐linkable diphenylmethane‐based thiopolyesters were utilized to produce novel polyester‐sulfur compositions with increased tensile strength. Segmented thiopolyurethanes based on simple thiodiols as chain extenders are high elasticity thermoplastic elastomers.

The literature search was made up to February 2010.