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The direct-growth technique was used to synthesize several macromonomers (MMs) employing reversible addition–fragmentation chain transfer (RAFT) polymerization by growing directly from a norbornene-functionalized chain transfer agent (CTA). We aimed to investigate the formation of bisnorbornenyl species resulting from radical termination by combination ( i.e. , coupling) during RAFT polymerization at different monomer conversion values in four types of monomers: styrene, tert -butyl acrylate, methyl methacrylate and N -acryloyl morpholine. Ring-opening metathesis polymerization (ROMP) of these MMs using Grubbs' 3rd generation catalyst (G3) at an MM : G3 ratio of 100 : 1 resulted in the formation of bottlebrush polymers. Analysis by size-exclusion chromatography (SEC) revealed high molar mass shoulders of varying intensities attributed to the incorporation of these bisnorbornenyl species to generate dimeric or higher-order bottlebrush polymer oligomers. The monomer type in the RAFT step heavily influenced the amount of these bottlebrush polymer dimers and oligomers, as did the monomer conversion value in the RAFT step: We found that the ROMP of polystyrene MMs with a target backbone degree of polymerization of 100 produced detectable coupling at ≥20% monomer conversion in the RAFT step, while it took ≥80% monomer conversion to observe coupling in the poly( tert -butyl acrylate) MMs. We did not detect coupling in the poly(methyl methacrylate) MMs, but broadening of the SEC peaks and an increase in dispersity occurred, suggesting the presence of metathesis-active alkene-containing chain ends created by disproportionation. Finally, poly( N -acryloyl morpholine) MMs, even when reaching 90% monomer conversion in the RAFT step, showed no detectable coupling in the bottlebrush polymers. These results highlight the importance of monomer choice and RAFT polymerization conditions in making MMs for ROMP grafting-through to make well-defined bottlebrush polymers.
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Computer Simulation of Surface‐Initiated Controlled Radical Polymerization: Effect of Free‐Monomer Model on Brush Properties
Abstract Monte Carlo simulation is employed using the bond‐fluctuation model (BFM) to explore the role of free‐monomer model on surface‐initiated controlled polymerization from flat substrates. Three free‐monomer models differ in two aspects: 1) their extent of excluded volume interactions between free‐monomer/polymer segments and 2) monomer availability (finite or infinite) during the simulation. In the explicit monomer (EM) model, free‐monomers behave as a single BFM‑type units. In the phantom monomer (PM) model, free‐monomers act analogously to those in the EM model but lack excluded volume interactions with the growing polymers. In the implicit monomer (IM) model, no explicit monomers are included in the simulation box; the polymers can grow as long as space is available near active chain‐ends. It is found that the breadth of the molecular weight distribution of the grown polymers decreases from EM, to PM, to IM models. With the EM model, free‐monomers are excluded from the near‐surface region, while with the PM model they are not. Due to its excluded volume interactions, the EM model tends to compress the brush against the substrate. Finally, the relaxation of the shape of a polydisperse brush after the polymerization reaction ends has been reported.
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- Award ID(s):
- 1725938
- PAR ID:
- 10460230
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Macromolecular Theory and Simulations
- Volume:
- 28
- Issue:
- 5
- ISSN:
- 1022-1344
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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