Macromolecular Engineering by Atom Transfer Radical Polymerization

Matyjaszewski, Krzysztof

doi:10.1002/9783527815562.mme0036

Cited by 13 publications

(14 citation statements)

References 362 publications

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“…Reversible-deactivation radical polymerization (RDRP) has been intensively studied for its versatility to precisely control the molecular weight, dispersity, and architectures of polymers. 1,2 The commonly employed RDRP includes atomtransfer radical polymerization (ATRP), 3 nitroxide-mediated polymerization (NMP), 4 and reversible addition−fragmentation chain-transfer (RAFT) 5 polymerization. Furthermore, recent work on photo-induced RDRP (photo-RDRP) 6,7 provides tunable spatial and temporal control of the polymerization under mild reaction conditions.…”

Section: Introductionmentioning

confidence: 99%

Efficient Visible-Light-Driven RAFT Polymerization Mediated by Deep Eutectic Solvents under an Open-to-Air Environment

2021

Macromolecules

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In this work, we investigate the effects of deep eutectic solvents (DESs) on a facile reversible addition− fragmentation chain-transfer (RAFT) polymerization driven by visible light. A DES composed of tetrabutylammonium chloride (TBACl) and ethylene glycol served as a nonvolatile medium for a variety of monomers, including methyl methacrylate, methyl acrylate, dimethylacrylamide, and styrene. We first employed the polymerization-through pathway to overcome oxygen inhibition in an open-to-air environment using methyl methacrylate as the model compound. The photoiniferter polymerization using trithiocarbonates as the chain transfer agent (CTA) in DESs exhibited enhanced polymerization rates and achieved a narrow molecular weight distribution. Interestingly, even dithiobenzoate, the CTA with low efficiency for photoiniferter polymerization, exhibited a nearly 4.5-fold increase in the apparent polymerization rate constants when compared to the reaction in dimethyl sulfoxide. Moreover, the stability of the CTAs was increased in DESs for efficient control of molecular weight distribution and preservation of functional chain ends. We then surveyed photocatalysts for photoelectron/energy transfer (PET) RAFT polymerization and found that eosin Y was compatible with DESs. The PET-RAFT polymerization using dithiobenzoate in DESs showed even higher polymerization rates than the photoiniferter polymerization and enabled the polymerization under natural sunlight. Besides methyl methacrylate, other monomers also exhibited an increased polymerization rate in DESs, comparable to reactions in ionic liquids. These results suggest that DESs are effective and green media to facilitate photo-induced RAFT polymerization without additives or tedious degassing processes.

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Section: Introductionmentioning

confidence: 99%

Efficient Visible-Light-Driven RAFT Polymerization Mediated by Deep Eutectic Solvents under an Open-to-Air Environment

2021

Macromolecules

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“…38 Additionally, CuCl was used instead of CuBr because CuCl typically results in slower polymerization. 39 The utilization of a catalytic system with equimolar amounts of HMTETA to CuCl led to a 56% monomer conversion after 6 h (Table 4, entry A2) with only a slight enhancement of the conductivity of the hybrids. The efficiency improvement of the GO reduction by the addition of an excess of cheap Et 3 N was not successful, and only a slight acceleration of polymerization was obtained (Table 4, entry A3), probably from either allowing more HMTETA to be involved in the ATRP process or using Et 3 N as a reducing agent for the copper catalyst 40 and thus increasing the concentration of growing radicals in the system.…”

Section: Macromoleculesmentioning

confidence: 99%

One-Pot Strategy for the Preparation of Electrically Conductive Composites Using Simultaneous Reduction and Grafting of Graphene Oxide via Atom Transfer Radical Polymerization

et al. 2021

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In this work, a facile "one-pot" approach for the preparation of composites with tunable electrical conductivity and viscoelastic properties is presented. The effect of reaction conditions, such as reaction time and temperature as well as the structure and concentration of the tertiary amine used as a component of the catalytic complex, on the reduction of graphene oxide was investigated. The reaction conditions were optimized for the simultaneous GO reduction during the synthesis of two types of polymers, poly(methyl methacrylate) (PMMA) and poly-(styrene-co-acrylonitrile) (SAN). GO-graf t-poly(methyl methacrylate) (GO-g-PMMA) and GO-graf t-poly(styrene-co-acrylonitrile) (GO-g-SAN) hybrids with electrical conductivity ranging from 10 −8 to 10 0 S cm −1 were prepared using selected tertiary aminebased ligands. Finally, the reaction conditions were adapted for the in situ preparation of GO-g-PMMA/PMMA and GO-g-SAN/ SAN composites with electrical conductivity ranging from 10 −14 to 10 −4 S cm −1 . The mechanical properties of the synthesized composites were compared with composites prepared from GO and commercial PMMA or SAN.

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“…The copolymers were prepared by atom transfer radical polymerization (ATRP) as well as by statistical free radical and colloidal polymerization. 2,3 Their self-healing ability was attributed to van der Waals forces, originating from interdigitated "key-and-lock" interchain interactions, promoted by alternating BA/MMA sequences. Interestingly, the selfhealing behavior was observed for a relatively narrow compositional range of 50:50 to 55:45 BA/MMA units in the final copolymers.…”

Section: Introductionmentioning

confidence: 99%

Distribution of Alternating Sequences in Methyl Methacrylate/n-Butyl Acrylate Copolymers Prepared by Atom Transfer Radical Polymerization

et al. 2021

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Copolymers of n-butyl acrylate/methyl methacrylate (BA/MMA) with certain compositions were recently proposed as self-healing materials due to "key-and-lock" interchain interactions of alternating sequences. This inspired us to analyze by numerical simulations the formation of heterosequences in BA/MMA copolymers prepared by atom transfer radical polymerization (ATRP). Stochastic Monte Carlo and deterministic simulations using numerical integration of differential equations showed that the highest contribution of alternating sequences is present in a statistical copolymer with 1:1 BA/MMA composition. However, batch ATRP of a 1:1 BA/MMA mixture generates a gradient copolymer with a diminished fraction of alternating sequences. Therefore, a method for preparing a statistical BA/MMA copolymer with the highest fraction of alternating sequences is proposed through normal ATRP copolymerization with feeding of MMA. The contribution of heterosequences was analyzed for both batch ATRP systems and in the presence of feeding, to identify the conditions that maximize the amount of alternating sequences in the copolymers.

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Macromolecular Engineering by Atom Transfer Radical Polymerization

Cited by 13 publications

References 362 publications

Efficient Visible-Light-Driven RAFT Polymerization Mediated by Deep Eutectic Solvents under an Open-to-Air Environment

Efficient Visible-Light-Driven RAFT Polymerization Mediated by Deep Eutectic Solvents under an Open-to-Air Environment

One-Pot Strategy for the Preparation of Electrically Conductive Composites Using Simultaneous Reduction and Grafting of Graphene Oxide via Atom Transfer Radical Polymerization

Distribution of Alternating Sequences in Methyl Methacrylate/n-Butyl Acrylate Copolymers Prepared by Atom Transfer Radical Polymerization

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