The intermolecular forces for polymers are the same as for small molecules. Because polymer molecules are so large, though, the magnitude of their intermolecular forces can vastly exceed those between small molecules. The presence of strong intermolecular forces is one of the main factors leading to the unique physical properties of polymers.
Dispersion forces are due to instantaneous dipoles that form as the charge clouds in the molecules fluctuate. Dispersion forces, the weakest of the intermolecular forces, are present in all polymers. They are the only forces possible for nonpolar polymers such as polyethylene.
Dispersion forces depend on the polarizability of a molecule. Larger molecules generally are more polarizable, so large polymers with high molecular weights can have significant dispersion forces. Ultra high molecular weight polyethylene (UHMWPE), which has a molecular weight in excess of 3,000,000 g/mole, is used to make bulletproof vests.
Dipole-dipole forces result from the attraction between polar groups, such as those in polyesters and vinyl polymers with chlorine pendant groups.
Hydrogen bonding can take place when the polymer molecule contains -OH or -NH groups. Hydrogen bonding is the strongest of the intermolecular forces. Polymers such as poly(vinyl alcohol) and polyamides are hydrogen bonded.
Contributors and Attributions
David Whisnant (Wofford College). Partial support for this work was provided by the National Science Foundation's Division of Undergraduate Education through grants DUE #9950809 and DUE #9950296. Additional support was provided by the Camille and Henry Dreyfus Foundation.