Thermal behavior and molecular packing of alkylated poly(ethylene- alt- maleic anhydride) and poly(styrene-alt-maleic anhydride) were studied by means of differential scanning calorimetry, thermogravimetry, polarizing optical microscopy, and X-ray diffraction. Effects of the length and graft density of alkyl side chains and backbone rigidity on the thermal behavior and on the structure of the mesophases are discussed.

Thermal behavior and molecular packing of a series of £\-helical poly(L-glutamates), with n-alkyl side chain of various lengths (m(number of carbons in the alkyl group) = 1, 2, 6, 12,18), were studied by means of differential scanning calorimetry, polarizing light microscopy and X-ray diffraction. For polymers of m = 1 and 2, There is a pseudohexagonal structure below ca. 130 oC and above this temperature the stable phase is the hexagonal columnar phase. There exists a layered structure in the polymer of m = 6, as well as a solvent induced hexagonal columnar structure which formed during solution casting process. In the polymer of m = 12, a layered structure was formed in the temperature range between 20 to 255 oC. However, for longer side chain, m = 18, tendency of crystallization of alkyl long side chain forced the backbone to pack into layer structure. There are two distinct melting temperature at ca. 60 oC, and the enthalpy are ca. 53 and 19 J/g, which corresponding to the melting of hexagonal and monoclinic side chain crystallines. The polymers with longer side chain (m = 6, 12 and 18) tend to be lyotropic liquid crystalline phase within lamellar inter-rod distance of 1.25 nm in solution state, and the structure will remain after drying. However, the inter-rod distance will collapse at the temperature above ca. 200 ¢J and will not recover after cooling.