Cationic bottlebrush homopolymers are polymerized using a grafting‐through approach by ring‐opening metathesis polymerization (ROMP) to afford well‐defined polymers. Quaternary ammonium macromonomers (MMs) are prepared by quaternizing tertiary amine MMs synthesized by reversible addition‐fragmentation chain transfer (RAFT) polymerization. The quaternary ammonium MMs undergo ROMP to target molecular weights (
- Award ID(s):
- 2104602
- NSF-PAR ID:
- 10420123
- Date Published:
- Journal Name:
- Polymer Chemistry
- Volume:
- 13
- Issue:
- 41
- ISSN:
- 1759-9954
- Page Range / eLocation ID:
- 5841 to 5851
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract M n= 30 000–100 000 g mol−1) and a low dispersity (Đ = 1.10–1.30). Halide‐ligand exchange between the third generation Grubbs catalyst (G3) and halide counter ions (bromide and iodide ions) of MMs changes the catalyst activity throughout ROMP, causing it to deviate from pseudo‐first order kinetic behavior; however, the polymerization still follows controlled behavior without significant catalyst termination. Increasing steric bulk of the MMs decreases the polymerization rate as well. Amphiphilic block copolymers are synthesized by sequential polymerization of quaternary ammonium MMs and polystyrene (PS) MMs. Using a PS macroinitiator affords block copolymers with lowerĐ values as compared to the less active cationic macroinitiator. -
Abstract Mechanochemistry can lead to the degradation of the properties of covalent macromolecules. In recent years, numerous functional materials have been developed based on block copolymers (BCPs), however, like homopolymers, their chains could undergo mechanochemical damage during processing, which could have crucial impact on their performance. To investigate the mechanochemical response of BCPs, multiple polymers comprising different ratios of butyl acrylate and methyl methacrylate were prepared with similar degree of polymerization and stressed in solution via ultrasonication. Interestingly, all BCPs, regardless of the amount of the methacrylate monomer, presented a mechanochemistry rate constant similar to that of the methacrylate homopolymer, while a random copolymer reacted like the acrylate homopolymer. Size‐exclusion chromatography showed that, in addition to the typical main peak shift towards higher retention times, a different daughter fragment was produced indicating a secondary selective scission site, situated around the covalent connection between the two blocks. Molecular dynamics modeling using acrylate and methacrylate oligomers were carried out and indicated that dynamic phase separation occurs even in a good solvent. Such non‐random conformations can explain the faster polymer mechanochemistry. Moreover, the dynamic model for end‐to‐end chain overstretching supports bond scission which is not necessarily chain‐centered.
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Abstract Mechanochemistry can lead to the degradation of the properties of covalent macromolecules. In recent years, numerous functional materials have been developed based on block copolymers (BCPs), however, like homopolymers, their chains could undergo mechanochemical damage during processing, which could have crucial impact on their performance. To investigate the mechanochemical response of BCPs, multiple polymers comprising different ratios of butyl acrylate and methyl methacrylate were prepared with similar degree of polymerization and stressed in solution via ultrasonication. Interestingly, all BCPs, regardless of the amount of the methacrylate monomer, presented a mechanochemistry rate constant similar to that of the methacrylate homopolymer, while a random copolymer reacted like the acrylate homopolymer. Size‐exclusion chromatography showed that, in addition to the typical main peak shift towards higher retention times, a different daughter fragment was produced indicating a secondary selective scission site, situated around the covalent connection between the two blocks. Molecular dynamics modeling using acrylate and methacrylate oligomers were carried out and indicated that dynamic phase separation occurs even in a good solvent. Such non‐random conformations can explain the faster polymer mechanochemistry. Moreover, the dynamic model for end‐to‐end chain overstretching supports bond scission which is not necessarily chain‐centered.
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Catalytic Halogen Exchange in Miniemulsion ARGET ATRP: A Pathway to Well‐Controlled Block Copolymers
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