In the last few years studies concerning liquid crystal polymers have become of increasing interest because of their theoretical and technological aspects'). As starting compounds, mesogenic polymerizable monomers were used which have the typical structure') of conventional liquid crystals. For polymers formed by condensation reactions, e.g. building the low molecular weight mesogenic monomer into the main chain, nematic as well as smectic polymer phases have been described3).Within the scope of vinyl polymers with mesogenic side chains only some enantiotropic liquid crystalline polymers have been obtained4), although numerous experiments have been made. In most cases it was only possible to freeze in the liquid crystalline structure, which was irreversibly lost above the glass transition temperature5).In conventional liquid crystalline phases the motions of a molecule are restricted only by the anisotropic interactions with its neighbours. This leads to the formation of the orientational long range order. If the mesogenic groups are directly fixed like side chains to the main chain, the ability to move and orient is changed drastically. In the liquid state of the polymer, the tendency of statistical chain conformation hinders an orientation of the side chains. If the anisotropic interactions of side chains are strong enough to form the mesophase, a liquid crystalline structure can nevertheless be formed, but only in accordance with the limited motions of the main chain. Previous results show that smectic structures are favored where the side groups are ordered in planes. An example is the polymer of 4-ethoxy-N-(4-methacryloyloxybenzylidene)aniline6). X-ray investigations indicate that the main chain is ordered in planes within the smectic layers.In addition to the mesogenic structure of the side chain, the connection of the polymer main chain to the side chain is also crucial for the existence of the different liquid crystalline polymer phases. For a systematic synthesis of enantiotropic liquid crystalline vinyl polymers we started from the following model considerations:In the liquid state the motions of the polymer main chain have to be decoupled from those of the anisotropically oriented mesogenic side chains. The decoupling should be possible, if flexible spacer groups are inserted between the main chain and the rigid mesogenic side chains. *) Part 13: cf. D. Naegele, H. Ringsdorf, J. Polym. Sci., in press.