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Polyether based side-chain liquid crystalline (SCLC) copolymers with distinct microstructures were prepared using living anionic polymerization techniques. The composition, end groups, purity, and sequence of the resulting copolymers were elucidated by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) and tandem mass spectrometry (MS/MS). MALDI-MS analysis confirmed the presence of (CH3)3CO– and –H end groups at the initiating (α) and terminating (ω) chain end, respectively, and allowed determination of the molecular weight distribution and comonomer content of the copolymers. The comonomer positions along the polymer chain were identified by MS/MS, from the fragments formed via C–O and C–C bond cleavages in the polyether backbone. Random and block architectures could readily be distinguished by the contiguous fragment series formed in these reactions. Notably, backbone C–C bond scission was promoted by a radical formed via initial C–O bond cleavage in the mesogenic side chain. This result documents the ability of a properly substituted side chain to induce sequence indicative bond cleavages in the polyether backbone.
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Mesoscale modeling of random chain scission in polyethylene melts
Abstract Polyolefins account for more than half of global primary polymer production, however only a small fraction of these polymers are currently being recycled. Fragmentation of polymer chains into shorter chains with a targeted molecular weight distribution with the goal of reusing these fragments in subsequent chemical synthesis can potentially introduce an alternative approach to polyolefins recycling. Herein we develop a mesoscale framework to model degradation of polyethylene melts at a range of high temperatures. We use the dissipative particle dynamics approach with modified segmental repulsive potential to model the process of random scission in melts of linear polymer chains. We characterize the fragmentation process by tracking the time evolution of the distribution of degrees of polymerization of chain fragments. Specifically, we track the weight average and the number average degrees of polymerization and dispersity of polymer fragments as a function of the fraction of bonds broken. Furthermore, we track the number fraction distribution and the weight fraction distribution of polymer fragments with various degrees of polymerization as functions of the fraction of bonds broken for a range of high temperatures. Our results allow one to quantify to what extent the distribution of polymer chain fragments during random scission can be captured by the respective analytical distributions for the range of conversions considered. Understanding the thermal degradation of polyolefins on the mesoscale can result in the development of alternative strategies for recycling a range of thermoplastics.
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- Award ID(s):
- 2134564
- PAR ID:
- 10525010
- Publisher / Repository:
- IOP Publishing
- Date Published:
- Journal Name:
- Journal of Physics: Materials
- Volume:
- 7
- Issue:
- 3
- ISSN:
- 2515-7639
- Format(s):
- Medium: X Size: Article No. 035010
- Size(s):
- Article No. 035010
- Sponsoring Org:
- National Science Foundation
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