The main use of polymeric polyols is as reactants to make other polymers, They can be reacted with isocyanates to make polyurethanes, and this use consumes most polyether polyols These material are ultimately used to make elastomeric shoe soles, fibers (Spandex for example), foam insulation for appliances (refrigerators and freezers), adhesives, mattresses, automotive seats and so on.
Monomeric polyols such as pentaerythritol, ethylene glycol and glycerin often serve as the starting point for polymeric polyols. Naturally occurring polyols like castor oil and sucrose can also be used to make synthetic polymeric polyols. These materials are often referred to as the "initiators" for the polymeric polyols, but they should not be confused with free radical "initiators" used to promote other polymerization reactions. The functional group used as the starting point for a polymeric polyol need not be a hydroxyl group; there are a number of important polyols which are built up from amines. A primary amino group (-NH2) often functions as the starting point for two polymeric chains, especially in the case of polyether polyols.
The polymeric chains built out from the initiator are usually polyesters or polyethers. Polyether polyols are made by reacting epoxides like ethylene oxide or propylene oxide with the multifunctional initiator in the presence of a catalyst, often a strong base such as potassium hydroxide or more exotic metal cyanides. Common polyether diols are polyethylene glycol, polypropylene glycol, and poly(tetramethylene ether) glycol. The examples shown below are fairly low molecular weight triols based on glycerin (a triol) being reacted with propylene oxide, ethylene oxide or a combination of the two. In reality, the chains would not be of equal length in any one molecule and there would be a distribution of molecular weight polyols within the material. Polyether polyols account for about 90% of the polymeric polyols used industrially; the balance is polyester polyols.
Another class of polymeric polyols is the polyesters. Polyesters are formed by condensation or step-growth polymerization of diols and dicarboxylic acids (or their derivatives), for example diethylene glycol reacting with phthalic acid. Alternatively, the hydroxyl group and the carboxylic acid (or their derivatives) may be within the same molecule, as in the case of caprolactone. The example below is an idealized structure that could be obtained by reacting pentaerythritol (a tetrol) with gamma-butyrolactone.