Radical chemistry in polymer science: an overview and recent advances

• Zixiao Wang,
• Feichen Cui,
• Yang Sui and
• Jiajun Yan

Beilstein J. Org. Chem. 2023, 19, 1580–1603, doi:10.3762/bjoc.19.116

• radical species and the dormant chains to achieve controlled polymerization of the monomers, allowing all polymer chains to grow nearly simultaneously. The product of RAFT polymerization has a preserved thiocarbonylthio chain end. The polymerization reaction can be continued by adding more monomers

• acrylates, under milder conditions [37][38][39]. Grimaldi et al. [40] achieved NMP of styrene and n-butyl acrylate using SG1-type nitroxide radical (N-tert-butyl-N-(1-diethylphosphono-2,2-dimethylpropyl)nitroxide). Compared with TEMPO, SG1 was considered that it initiated the truly “living”/controlled

• polymerization at that time and the rate of propagation was much faster than with TEMPO under the same conditions. 1.3.2 Deactivation by atom transfer: Atom transfer radical polymerization (ATRP) was independently reported by the teams of Matyjaszewski [41] and Sawamoto [42] in 1995. The efficient conduct of

Mechanochemical synthesis of poly(trimethylene carbonate)s: an example of rate acceleration

• Sora Park and
• Jeung Gon Kim

Beilstein J. Org. Chem. 2019, 15, 963–970, doi:10.3762/bjoc.15.93

• -milling polymerization did not allow for controlling the molecular weight distribution, resulting in a broad polydispersity (Mw/Mn) of 2.01 (Table 4, entry 5). As mentioned, fast initiation over chain propagation is one of the requirements in a controlled polymerization. While TBD could chemically enhance

One-pot synthesis of block-copolyrotaxanes through controlled rotaxa-polymerization

• Jessica Hilschmann,
• Gerhard Wenz and
• Gergely Kali

Beilstein J. Org. Chem. 2017, 13, 1310–1315, doi:10.3762/bjoc.13.127

• ]. RAFT polymerization is a useful tool to form well-defined block-copolymers starting from a chain transfer agent (CTA) that drastically reduces the actual radical concentration in a fast equilibrium reaction [35][36][37]. This controlled polymerization should be advantageous for this work, compared to

Methylenelactide: vinyl polymerization and spatial reactivity effects

• Judita Britner and
• Helmut Ritter

Beilstein J. Org. Chem. 2016, 12, 2378–2389, doi:10.3762/bjoc.12.232

• further monomers. Finally, this work reports on the first controlled polymerization of methylenelactide and controlled copolymerization with N,N-dimethylacrylamide via RAFT technique. From the above presented results it can be summarized that MLA represents a highly reactive monomer with a potential for

Recent advances in metathesis-derived polymers containing transition metals in the side chain

• Ileana Dragutan,
• Valerian Dragutan,
• Bogdan C. Simionescu,
• Albert Demonceau and
• Helmut Fischer

Beilstein J. Org. Chem. 2015, 11, 2747–2762, doi:10.3762/bjoc.11.296

• norbornene monomers substituted with rhodocenium units and their controlled polymerization, by two parallel routes (ROMP and RAFT), to rhodocenium-containing metallopolymers. ROMP of both triazolyl-rhodocenium monomers, 40 and 42, proceeded productively and in a living fashion to yield amphiphilic

Metal and metal-free photocatalysts: mechanistic approach and application as photoinitiators of photopolymerization

• Jacques Lalevée,
• Sofia Telitel,
• Pu Xiao,
• Marc Lepeltier,
• Frédéric Dumur,
• Fabrice Morlet-Savary,
• Didier Gigmes and
• Jean-Pierre Fouassier

Beilstein J. Org. Chem. 2014, 10, 863–876, doi:10.3762/bjoc.10.83

• system. Reaction mechanisms for the Ru(ligand)32+/Ph2I+/NVK system upon visible lights. Reaction mechanisms for the violanthrone/Ph2I+/TTMSS (R3SiH) system upon red lights. Reaction mechanisms for the Tr-AD/R-Br/MDEA system upon visible lights. The photoredox catalysis for controlled polymerization

Organotellurium-mediated living radical polymerization under photoirradiation by a low-intensity light-emitting diode

• Yasuyuki Nakamura and
• Shigeru Yamago

Beilstein J. Org. Chem. 2013, 9, 1607–1612, doi:10.3762/bjoc.9.183

• as the use of a 10% transmittance ND filter, resulted in improved MWDs (Table 1, runs 12 and 13). The use of the LED was also found to be effective for the efficient and controlled polymerization of other monomers (Table 2). For example, TERP of methyl acrylate (100 equiv) without ditelluride reached

Stability of SG1 nitroxide towards unprotected sugar and lithium salts: a preamble to cellulose modification by nitroxide-mediated graft polymerization

• Guillaume Moreira,
• Laurence Charles,
• Mohamed Major,
• Florence Vacandio,
• Yohann Guillaneuf,
• Catherine Lefay and
• Didier Gigmes

Beilstein J. Org. Chem. 2013, 9, 1589–1600, doi:10.3762/bjoc.9.181

• activation–deactivation equilibrium, all the chains grow at the same rate affording a living/controlled polymerization. Several nitroxides have been synthesized since their first development in the 1980s [11]. In particular, the cyclic nitroxide TEMPO has been intensely studied [21][22] in the polymerization

• carry out a controlled/living polymerization by SG1-based NMP in DMA/LiCl or DMF/LiCl. As expected, with the BlocBuilder MA alkoxyamine as an initiator (Figure 1), the NMP of styrene performed in DMA at 120 °C without LiCl fulfilled the criteria of a controlled polymerization (PDI values < 1.5, linear

Controlled synthesis of poly(3-hexylthiophene) in continuous flow

• Helga Seyler,
• Jegadesan Subbiah,
• David J. Jones,
• Andrew B. Holmes and
• Wallace W. H. Wong

Beilstein J. Org. Chem. 2013, 9, 1492–1500, doi:10.3762/bjoc.9.170

• : conjugated polymers; continuous-flow synthesis; controlled polymerization; flow chemistry; organic solar cell materials; Introduction Poly(3-hexylthiophene), P3HT, is the most investigated material in bulk heterojunction (BHJ) organic solar cells (OSC) [1]. The reasons for its dominance in the field include

• ). On addition of a desired amount of Ni(II) catalyst, the active catalyst species is formed in solution, and polymerization proceeds until all of the reactive Grignard monomer has been consumed. Controlled polymerization and high molecular weights have been demonstrated by many research groups with

• Suzuki–Miyaura and Stille coupling [12]. In this study, the continuous-flow synthesis of P3HT is examined. Distinct from a recent report of P3HT synthesis in a droplet-based microreactor [20], development of the flow synthesis is described in detail and controlled polymerization of P3HT, both in terms of

The synthesis of well-defined poly(vinylbenzyl chloride)-grafted nanoparticles via RAFT polymerization

• John Moraes,
• Kohji Ohno,
• Guillaume Gody,
• Thomas Maschmeyer and
• Sébastien Perrier

Beilstein J. Org. Chem. 2013, 9, 1226–1234, doi:10.3762/bjoc.9.139

• thermal initiation by an azoinitiator to achieve a well-controlled polymerization of the monomer in solution (Scheme 1). We then use the latter approach to form well-defined core–shell nanoparticles wherein the size of the polymer shell can be varied by changing the degree of polymerization of the grafted

• readily available using surface-initiated RAFT of VBC. Conclusion We have demonstrated the controlled polymerization and grafting onto silica nanoparticles of 4-vinylbenzyl chloride using RAFT polymerization. Whilst thermal autoinitiation of VBC does not lead to well-controlled molecular weight at high

Novel multi-responsive P2VP-block-PNIPAAm block copolymers via nitroxide-mediated radical polymerization

• Cathrin Corten,
• Katja Kretschmer and
• Dirk Kuckling

Beilstein J. Org. Chem. 2010, 6, 756–765, doi:10.3762/bjoc.6.89

• has led to a dramatic increase in the development of procedures that combine architectural control with flexibility in the incorporation of functional groups. Thus, there has been a considerable increase in the understanding of a variety of controlled polymerization strategies [14][15][16][17] over

• the last few years. This includes nitroxide-mediated radical polymerization (NMRP) [18], atom transfer radical polymerization (ATRP) [19][20] and radical addition fragmentation chain transfer procedures (RAFT) [21][22]. The controlled polymerization of styrene, and analogous monomers such as 2

• behavior was investigated in solution and on surfaces [23][24]. The synthesis of NIPAAm homopolymers through different controlled polymerization techniques is described in the literature. Using RAFT it was possible to obtain amphiphilic block copolymers of PNIPAAm (hydrophilic) and poly(styrene) (PS) or