Reversible complexation mediated polymerization: an emerging type of organocatalytically controlled radical polymerization

Abstract

As a newly-developed approach of controlled radical polymerization (CRP), reversible complexation mediated polymerization (RCMP) was established in 2011 by Goto et al., using iodine as a capping agent and organic...

Hydrogen Bond Effects: A Strategy for Improving Controllability in Organocatalytic Photoinduced Controlled Radical Polymerization Targeting High Molecular Weight

“…Further increasing DP target to 5000 and I 2 dosage ( n (I 2 )/ n (catalyst) = 0.075), the polymerization reaction is still fast and well controlled, affording 99% conversion in 39 h as well as a high M n of 497 kg/mol, very close to the theoretical value and a relatively narrow Đ of 1.49 (run 11). These results are very remarkable, as to the best of our knowledge, organocatalytic photo-CRP has rarely been reported to achieve PMMA with such high and controlled molecular weights, which is very challenging especially for organocatalytic photo-ATRP and photo-RCMP . By contrast, the polymerization targeting DP as 5000 by Cat.3 without hydroxyl group gives a molecular weight severely deviating from the theoretical value with a broad M w distribution ( Đ = 1.70, run 12).…”

“…. This is the activation process that is widely recognized. − ,, Notably, under our experimental conditions, the radical trap experiments show that CPI could dissociate to produce radicals without the catalyst (Figure S4). In addition, the oligomer of MMA is produced (run 5, Table ) in the absence of the catalyst, suggesting the direct photoexcitation of R–I (initiator/polymer–I).…”

“…These results are very remarkable, as to the best of our knowledge, organocatalytic photo-CRP has rarely been reported to achieve PMMA with such high and controlled molecular weights, 16 which is very challenging especially for organocatalytic photo-ATRP 17 and photo-RCMP. 48 By contrast, the polymerization targeting DP as 5000 by Cat.3 without hydroxyl group gives a molecular weight severely deviating from the theoretical value with a broad M w distribution (Đ = 1.70, run 12). The polymerization with a DP target of 5000 by Cat.4 obtains a much lower conversion of 67% and very poor control over the molecular weight (Đ = 2.48, run 13).…”

Well-defined amine-reactive polymethacrylates through organocatalyzed controlled radical polymerization

“…To avoid the ω-iodide elimination, the RCMP process of mPEGMA could be improved by either using a thermal radical initiator and iodine (I 2 ) at 60 °C or by photopolymerization. 19,21,29 Nevertheless, the addition of co-initiators/I 2 can lead to uncontrolled polymer chains and high polymer dispersity values. Therefore, the photopolymerization of mPEGMA using I-Azl as an initiator was considered in this study to synthesize well-defined α-azlactone-functionalized poly(mPEGMA).…”

“…Among them, the reversible complexation-mediated polymerization (RCMP) has emerged as a powerful organocatalyzed technique for synthesizing polymethacrylates with a well-defined structure. 18–21 RCMP is known as a simple and versatile process that can be performed under thermal or photo-irradiation without the addition of a radical initiator. In this context, this contribution focuses on the use of RCMP to synthesize well-defined α-azlactone-terminated polymethacrylates.…”