Orientational birefringence of uniaxially compressed PMMA networks in the unswollen state

Swollen PMMA networks show significant deviations from the theory of rubber elasticity. The unusual mechanical, optical and swelling properties have been explained by the existence of associations, well known for PMMA solutions.Unswollen PMMA networks show stress optical properties which are very similar to the networks swollen in carbon tetrachloride which is known as a strong complexing solvent. This indicates that associations exist in the bulk material. Swelling in carbon tetrachloride does not change the content of associations, only the glass transition temperature is reduced.Increasing the amount of crosslinking agent proves that the stress optical coefficient depends on the crosslinking density. This is contrary to the theoretical predictions. An explanation given by the effect of short network chains is not satisfactory. However, the consideration of a crosslinking chain instead of a crosslinking point gives a sufficient explanation. An oriented crosslinking chain gives a positive contribution to the total optical anisotropy while a PMMA chain shows a change from negative values (hindered rotation) to positive values (free rotation).Part I in Colloid & Polym Sci 262:182 (1984)Deceased Sept. 4, 1984