Polymacromonomers consisting of oligostyrene side chains (700 ≤ M n ≤ 5000 g/mol) and of a high molar mass polymethacrylate main chain are shown to exhibit a bottlebrush structure in that the PMA main chain adopts an extremely stiff conformation (i.e., a Kuhn statistical segment length of up to l k = 2000 Å) which is surrounded by the expanded but still flexible polystyrene side chains.

The polymerization of macromonomers (that is, end-functionalized oligomers. Scheme 1) has been a matter of extensive research in order to prepare well-defined comblike polymers. ['] 10-50 for most of the samples, and accordingly, such polymers should form liquid-crystalline phases.Here we report on X-ray scattering measurements of the polymacromonomers in toluene performed at the synchroton source in Tsukuba, Japan. which indeed show the formation of lyotropic phases, probably nematic, in semi-concentrated solution. The investigated polymacromonomer sample had a molar mass of M , = (2.2.10') gmol-' corresponding to a contour length L, = 1400 8,. The polydispersity index determined by gel permeation chromatography (GPC) was M,/M, z 1.5, and the ' the scattering angle) for polyinacromonomer concentrations 0.2 2 c 2 30% (w/w). In the dilute regime c < 0.5 YO the form factor P(4) of a single chain is measured: the intensity is seen to decrease monotonically with increasing 4. However, the qScheme 1. Reaction scheme for the preparation of the macromonomers.However, the homopolymerization of macromonomers did not yield degrees of polymerization significantly exceeding the length of a macromonomer itself, unless copolymerized with conventional small monomers. A major breakthrough was achieved by Tsukahara et al., who in a radical mechanism homopolymerized anionically prepared oligostyrenes with molar masses between lo3 and lo4 gmol-' that were end-functionalized with methacryloyl groups and obtained degrees of polymerization (weight average) P, of up to 1000.[21 Recent structure characterization of such long-chain polymacromonomers revealed that the main chain exhibits an almost rodlike conformation as measured by the Kuhn statistical segment length ofApparently. the extended structure of the polymethacrylate (PMA) main chain is caused by the strong overcrowding of the oligostyrene side chains, which are only separated by a contour distance 1 = 2.5 8, at the polymer backbone.Also, because of the length of the side chains, the diameter or cross-section of this curved cylindrical macromolecule or "bot- Particularly at the highest measured concentration of 31.5 %, the width of the scattering peak narrows drastically. The scattering peaks observed at higher concentrations cannot be explained by single-particle scattering but rather reflect the interparticle structure factor S(4) originating from the intermolecular order of the molecules.On application of Bragg's relation, a mean distance dB between the scattering planes (100) of hexagonal order is obtained from the scattering peak at q,,, [Eq. (a)]. The mean par-ticle distance d2 is then derived from Equation(b). In order to

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Maltopentaose-carrying polystyrene was synthesized by the homopolymerization of vinylbenzyl maltopentaose amide. Resulted amphiphilc polymacromonomer was dissolved in 0.1 M urea aqueous solution, and its structure was characterized by small-angle X-ray scattering and molecular modeling. Maltopentaose-carrying polystyrene polymacromonomer was found to be represented by a molecular bottlebrush, composed of a large helix of polystyrene backbone and maltopentaose brushes. The molecular bottlebrush seems to be distributed randomly or many even be broken once or twice in segments with no apparent intersegmental spatial correlation. A large helix of polystyrene backbone is formed by a random sequence of TT, TG, and/or TTGG.