Structure Formation of Polymeric Building Blocks: Complex Polymer Architectures

Dilute solution structure of bottlebrush polymers

“…31 The large volume of experimental and theoretical work remains rife with conflicting ob-servations. 23,24,[30][31][32]35,[49][50][51][52][53][54]59,61,74,75,85 Many of these issues have been discussed at length in a recent review by Binder et al 86 This is in part due to the idealization required to make progress with theory, which is compounded by the reliance on experimental characterization that does not directly image the bottlebrush chains but instead infers structure from model predictions. Furthermore, efforts to include simulation data have often used similarlyidealized molecular models, that rarely invoke the specific chemistry used in a given bottlebrush in favor of universal statements.…”

Characterization of the Local Volume Probed by the Side-Chain Ends of Poly(oligo(ethylene glycol) 1-Pyrenemethyl ether methacrylate) Bottle Brushes in Solution Using Pyrene Excimer Fluorescence

“…The present study illustrates how the same PEF-based methodology can be applied to predict the conformation of the side chains of another family of multi-ended macromolecules, namely, a series of polymeric bottle brushes (PBBs) belonging to the PEGMA type introduced by the Lutz group due to their interesting thermo-responsive properties. , In solution, PBBs adopt an extended conformation as the main chain becomes more crowded with increasing side chain length. , The topology of the PBBs generates two length scales, one related to the main chain, which is often described by its persistence length ( l p ), and another by the side chains (SC), which is described by their R G,SC or r EE,SC . − Since it is difficult to separate the scattering signal of the main and side chains, the determination of the parameters l p , R G,SC , and r EE,SC , which are typically extracted from scattering data, requires “dividing out” the contribution of the side chains from the overall scattering signal to isolate the signal pertaining to the main chain. In turn, this mathematical process involves making assumptions about the density profiles of the side chains .…”

“…18,19 In solution, PBBs adopt an extended conformation as the main chain becomes more crowded with increasing side chain length. 20,21 The topology of the PBBs generates two length scales, one related to the main chain, which is often described by its persistence length (l p ), and another by the side chains (SC), which is described by their R G,SC or r EE,SC . 22−34 Since it is difficult to separate the scattering signal of the main and side chains, 21 the determination of the parameters l p , R G,SC , and r EE,SC , which are typically extracted from scattering data, requires "dividing out" the contribution of the side chains from the overall scattering signal to isolate the signal pertaining to the main chain.…”

Simultaneous Bottlebrush Polymerization

“…High densities of side chains lead to high steric repulsion, while their covalent bonding to the backbone prohibits detachment. The molecular bottlebrushes are thus confined to a cylindrical volume with an extended, semiflexible backbone and flexible side chains . The persistence length of the backbone is dependent on the side chain length and grafting density, that is, the number of pendant side chains per backbone monomer atom.…”

“…The molecular bottlebrushes are thus confined to a cylindrical volume with an extended, semiflexible backbone and flexible side chains. 1 The persistence length of the backbone is dependent on the side chain length and grafting density, that is, the number of pendant side chains per backbone monomer atom. A high grafting density increases the distance between entanglements, producing materials with low viscosity that are ideal for applications as rheologic modifiers.…”