High molecular weight and low dispersity polyacrylonitrile by low temperature RAFT polymerization

Moskowitz, Jeremy D.; Abel, Brooks A.; McCormick, Charles L.; Wiggins, Jeffrey S.

doi:10.1002/pola.27806

Cited by 36 publications

(25 citation statements)

References 38 publications

(71 reference statements)

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“…However, control over the polymerisation was lost with increasing conversion and degree of polymerisation, possibly as a result of degradation of the RAFT agent through intramolecular nucleophilic attack. This degradation has been reported in the RAFT polymerisation of other acrylamide derivatives, 24,25 including closely related methacryloyl hydrazide, 26 with better control reported when the polymerisation is carried out at low temperatures. 25,27 This sidereaction is often overlooked in the polymerisation of primary and secondary acryl-and methacrylamides, and makes synthesising highly functional polymers from this type of monomers inherently challenging.…”

Section: Introductionsupporting

confidence: 55%

Poly(Boc-acryloyl hydrazide): the importance of temperature and RAFT agent degradation on its preparation

Creese

Adoni

et al. 2019

Polym. Chem.

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Section: Introductionsupporting

confidence: 55%

Poly(Boc-acryloyl hydrazide): the importance of temperature and RAFT agent degradation on its preparation

Creese

Adoni

et al. 2019

Polym. Chem.

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“…However, control over the polymerisation was lost with increasing conversion and degree of polymerisation, possibly as a result of degradation of the RAFT agent through intramolecular nucleophilic attack. This degradation has been reported in the RAFT polymerisation of other acrylamide derivatives, 24,25 including closely related methacryloyl hydrazide, 26 with better control reported when the polymerisation is carried out at low temperatures. 25,27 This sidereaction is often overlooked in the polymerization of primary and secondary acryl-and methacrylamides, and makes synthesising highly functional polymers from this type of monomers inherently challenging.…”

supporting

confidence: 55%

Poly(Boc-acryloyl hydrazide): The importance of temperature and RAFT agent degradation on its preparation

Creese¹,

Adoni²,

Su³

et al. 2019

Preprint

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Poly(acryloyl hydrazide) is a versatile polymer scaffold readily functionalised through post-polymerisation modification with aldehydes to yield polymers for biological applications. However, its polymerisation is affected by nucleophilic degradation of the RAFT agent that leads to early termination, an issue often overlooked in the polymerisation of primary acrylamides. Here we report the effect of temperature on the RAFT polymerisation of N’-(tert-butoxycarbonyl)acryloyl hydrazide (1) and demonstrate that by carefully selecting this polymerisation temperature, a balance between rate of polymerisation and rate of degradation of the RAFT agent can be achieved. This way a greater control over the polymerisation process is achieved, allowing the synthesis of Boc-protected poly(acryloyl hydrazide) with higher degrees of polymerisation than those achieved previously, while still maintaining low dispersities. We believe our results should be of importance to those working on the RAFT polymerization of primary and secondary (meth)acrylamides and monomers with nucleophilic moieties.

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“…PAN synthesized by FRP typically has a high molecular weight (MW > 150,000), but there is little control over the MW and the molecular weight distribution (MWD). With the introduction of reversible‐deactivation radical polymerization (RDRP) techniques, such as atom transfer radical polymerization (ATRP) and reversible‐addition fragmentation transfer (RAFT) polymerization, PAN with predefined MW, narrow MWD, and complex architectures can be synthesized …”

Section: Introductionmentioning

confidence: 99%

Synthesis of well-defined polyacrylonitrile by ICARATRP with low concentrations of catalyst

Lamson

Kopeć

Ding

et al. 2016

J. Polym. Sci. Part A: Polym. Chem.

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Acrylonitrile (AN) was polymerized by initiators for continuous activator regeneration (ICAR) atom transfer radical polymerization (ATRP). The effect of the ligand, tris(2‐pyridylmethyl)amine (TPMA) and N,N,N',N'‐tetrakis(2‐pyridylmethyl)ethylenediamine (TPEN), in the Cu‐based catalyst, the amount of catalyst, several alkyl halide initiators, targeted degree of polymerization, and amount of azobisisobutyronitrile (AIBN) added were studied. It was determined that the best conditions utilized 50 ppm of CuBr2/TPMA as the catalyst and 2‐bromopropionitrile (BPN) as the initiator. This combination resulted in 46% conversion in 10 h and polyacrylonitrile (PAN) with the narrowest molecular weight distribution (Mw/Mn = 1.11–1.21). Excellent control was maintained after lowering the catalyst loading to 10 ppm, with 56% conversion in 10 h, experimental molecular weight closely matching the theoretical value, and low dispersity (Mw/Mn < 1.30). Catalyst loadings as low as 1 ppm still provided well‐controlled polymerizations of AN by ICAR ATRP, with 65% conversion in 10 h and PAN with relatively low dispersity (Mw/Mn = 1.41). High chain end functionality (CEF) was confirmed via 1H NMR analysis, for short PAN chains, and via clean chain extensions with n‐butyl acrylate (BA). © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 1961–1968

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High molecular weight and low dispersity polyacrylonitrile by low temperature RAFT polymerization

Cited by 36 publications

References 38 publications

Poly(Boc-acryloyl hydrazide): the importance of temperature and RAFT agent degradation on its preparation

Poly(Boc-acryloyl hydrazide): the importance of temperature and RAFT agent degradation on its preparation

Poly(Boc-acryloyl hydrazide): The importance of temperature and RAFT agent degradation on its preparation

Synthesis of well-defined polyacrylonitrile by ICARATRP with low concentrations of catalyst

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