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.
Mechanochemistry in Block Copolymers: New Scission Site due to Dynamic Phase Separation
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.
more » « less- PAR ID:
- 10477431
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 62
- Issue:
- 52
- ISSN:
- 1433-7851
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract -
Recent reports have shown that ferrocene displays an unexpected combination of force-free stability and mechanochemical activity, as it acts as the preferred site of chain scission along the backbone of highly extended polymer chains. This observation raises the tantalizing question as to whether similar mechanochemical activity might be present in other metallocenes, and, if so, what features of metallocenes dictate their relative ability to act as mechanophores. In this work, we elucidate polymerization methodologies towards main-chain ruthenocene-based polymers and explore the mechanochemistry of ruthenocene. We find that ruthenocene, in analogy to ferrocene, acts as a highly selective site of main chain scission despite the fact that it is even more inert. A comparison of ruthenocene and ferrocene reactivity provides insights as to the possible origins of metallocene mechanochemistry, including the relative importance of structural and thermodynamic parameters such as bond length and bond dissociation energy. These results suggest that metallocenes might be privileged mechanophores through which highly inert coordination complexes can be made dynamic in a stimuli-responsive fashion, offering potential opportunities in dynamic metallo-supramolecular materials and in mechanochemical routes to reactive intermediates that are otherwise difficult to obtain.more » « less
-
Bottlebrush polymers are complex macromolecules with tunable physical properties dependent on the chemistry and architecture of both the side chains and the backbone. Prior work has demonstrated that bottlebrush polymer additives can be used to control the interfacial properties of blends with linear polymers but has not specifically addressed the effects of bottlebrush side chain microstructures. Here, using a combination of experiments and self-consistent field theory (SCFT) simulations, we investigated the effects of side chain microstructures by comparing the segregation of bottlebrush additives having random copolymer side chains with bottlebrush additives having a mixture of two different homopolymer side chain chemistries. Specifically, we synthesized bottlebrush polymers with either poly(styrene- ran -methyl methacrylate) side chains or with a mixture of polystyrene (PS) and poly(methyl methacrylate) (PMMA) side chains. The bottlebrush additives were matched in terms of PS and PMMA compositions, and they were blended with linear PS or PMMA chains that ranged in length from shorter to longer than the bottlebrush side chains. Experiments revealed similar behaviors of the two types of bottlebrushes, with a slight preference for mixed side-chain bottlebrushes at the film surface. SCFT simulations were qualitatively consistent with experimental observations, predicting only slight differences in the segregation of bottlebrush additives driven by side chain microstructures. Specifically, these slight differences were driven by the chemistries of the bottlebrush polymer joints and side chain end-groups, which were entropically repelled and attracted to interfaces, respectively. Using SCFT, we also demonstrated that the interfacial behaviors were dominated by entropic effects with high molecular weight linear polymers, leading to enrichment of bottlebrush near interfaces. Surprisingly, the SCFT simulations showed that the chemistry of the joints connecting the bottlebrush backbones and side chains played a more significant role compared with the side chain end groups in affecting differences in surface excess of bottlebrushes with random and mixed side chains. This work provides new insights into the effects of side chain microstructure on segregation of bottlebrush polymer additives.more » « less
-
null (Ed.)A one pot synthesis is applied to control the chain structure and architecture of multiply dynamic polymers, enabling fine tuning of materials properties by choice of polymer chain length or crosslink density. Macromolecules containing both non-covalent linkers based on quadruple hydrogen-bonded 2-(((6-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)hexyl)carbamoyl)oxy)ethyl methacrylate (UPyMA), and thermoresponsive dynamic covalent furan–maleimide based Diels–Alder linkers are explored. The primary polymer's architecture was controlled by reversible addition-fragmentation chain transfer (RAFT) polymerization, with the dynamic non-covalent (UPyMA) and dynamic covalent furfuryl methacrylate (FMA) units incorporated into the same backbone. The materials are crosslinked, taking advantage of the “click” chemistry properties of the furan–maleimide reaction. The polymer materials showed stimulus-responsive thermomechanical properties with a decrosslinking temperature increasing with the polymer's primary chain length and crosslink density. The polymers had good thermally promoted self-healing properties due to the dynamic covalent Diels–Alder bonds. Besides, the materials had excellent stress relaxation characteristics induced by the exchange of the hydrogen bonds in UPyMA units.more » « less
-
Understanding structure–mechanochemical reactivity relationships is important for informing the rational design of new stimuli-responsive polymers. To this end, establishing accurate reaction kinetics for mechanophore activation is a key objective. Here, we validate an initial rates method that enables the accurate and rapid determination of rate constants for ultrasound-induced mechanochemical transformations. Experimental reaction profiles are well-aligned with theoretical models, which support that the initial rates method effectively deconvolutes the kinetics of specific mechanophore activation from the competitive process of nonspecific chain scission.more » « less
