Atom Transfer Radical Polymerization of Styrene Using Multifunctional Iniferter Reagents as Initiators

Zhang, Wei; Wang, Chengchao; Li, Daoguang; Song, Qing; Cheng, Zhenping; Zhu, Xiulin

doi:10.1002/masy.200850104

Cited by 9 publications

(3 citation statements)

References 24 publications

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“…44,45 Also, when normal ATRP of MMA and styrene (St) was initiated by ethyl 2-N,N-(diethylamino)dithiocarbamoylbutyrate and (1-naphthyl)-methyl N,N-diethyldithiocarbamate, low initiation efficiency and relatively low molecular weight PMMA and polystyrene (PSt) were formed. [46][47][48][49] In the current study, we focused on synthesis and systematic kinetic studies of several new iniferter initiators as well as reactivity of various Cu complexes. This study generated a more comprehensive structure-reactivity correlation and provided new guidelines for selection of the efficient catalysts and initiators to generate well-defined low-polydispersity PSt and PMMA.…”

Section: Introductionmentioning

confidence: 99%

“…Some improvements in iniferter polymerization were made in the presence of copper catalyst. When the reverse ATRP of methyl methacrylate (MMA) was carried out in the presence of copper(II) N , N -diethyldithiocarbamate, poly(methyl methacrylate) (PMMA) with relatively narrow molecular weight distribution was obtained, but the initiation efficiency was low and a large amount of radical initiator was used, resulting in a high level of chain termination. , Also, when normal ATRP of MMA and styrene (St) was initiated by ethyl 2- N , N -(diethylamino)dithiocarbamoylbutyrate and (1-naphthyl)-methyl N,N -diethyldithiocarbamate, low initiation efficiency and relatively low molecular weight PMMA and polystyrene (PSt) were formed. − …”

Section: Introductionmentioning

confidence: 99%

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Effect of Initiator and Ligand Structures on ATRP of Styrene and Methyl Methacrylate Initiated by Alkyl Dithiocarbamate

Kwak

Matyjaszewski

2008

Macromolecules

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Atom transfer radical polymerization (ATRP) of styrene (St) and methyl methacrylate (MMA) initiated by various alkyl diethyldithiocarbamate (DC) initiators was successfully carried out in the presence of copper catalysts with nitrogen-based ligands. Well-controlled polymerizations with narrow molecular weight distribution (M w/M n < 1.1 (St) and M w/M n < 1.2 (MMA)) were achieved in both polymerizations. The polymerization rate followed first-order kinetics with respect to monomer conversion, and the molecular weight of the polymers increased linearly up to high conversion. Initiation efficiency of both polymerizations was strongly dependent on the structure of a DC. The results of 1H NMR analysis of low-mass model compounds and chain extension confirmed that well-defined polystyrene bearing a DC group as the active chain end was obtained via ATRP of St with a DC initiator. Ligand structure and ligand/copper ratio also strongly affected the degree of control attained in the polymerization. Activation rate constants and equilibrium constants of ATRP with DC initiators and copper complexes were determined. The results of cyclic voltammetry with the CuIIDC2 complex indicated that it has more negative reduction potential and, consequently, higher (pseudo)halidophilicity than those of CuIIBr2 or CuIICl2 with the same ligand Me6TREN.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Effect of Initiator and Ligand Structures on ATRP of Styrene and Methyl Methacrylate Initiated by Alkyl Dithiocarbamate

Kwak

Matyjaszewski

2008

Macromolecules

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“…ATRP can be widely conducted in solution, bulk,10 dispersion,11 and emulsion12 polymerization systems. Last decade has witnessed the great progress including new initiation‐catalyst systems,13, 14new monomers,15 and new routes16 in conducting ATRP. Considering the success of emulsion in industrial processes, people naturally began to take ATRP into emulsion polymerization.…”

Section: Introductionmentioning

confidence: 99%

Emulsion copolymerization of styrene and butyl acrylate by reverse atom transfer radical polymerization

Wu¹,

Guo-liang²,

Xu³

et al. 2012

J of Applied Polymer Sci

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Reverse atom transfer radical copolymerization of styrene (St) and butyl acrylate was carried out in emulsion under normal emulsion conditions, using CuBr 2 / bpy complex as catalyst. The effects of surfactant type, initiator type and concentration, and CuBr 2 addition on the system livingness, polymer molecular weight control, and latex stability were examined in detail. It was found that the Polysorbate 80 (Tween 80) and azodiisobutyronitrile gave the best exhibition in this system, polymer samples were got with narrow molecular-weight dispersity (M w /M n ¼ 1.1-1.2) and linear relationships of molecular weight versus monomer conversion, as well as a relatively low polydispersity index (<0.1). Through the GPC and SEM analysis, the polymerization processes under these conditions showed good living/control characteristics relative to the processes under normal emulsion polymerization, although the latex stability was susceptible to the CuBr 2 catalyst.

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ATRP with Alkyl Pseudohalides Acting as Initiators and Chain Transfer Agents: When ATRP and RAFT Polymerization Become One

Nicolaÿ

Kwak²

2012

Israel Journal of Chemistry

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ATRP requires an alkyl halide or pseudohalide [17] (RÀX) as an initiator and a transition-metal complex (e.g., Cu, [10,18] Ru, [9,19] Fe, [20] Os, [21] Mo, [22] Ni, [23] Re, [24] etc. [2,25] ) as a catalyst. The most common catalysts for ATRP are complexes based on copper(I) halide and nitrogen-based ligands. [2,25] ATRP involves the homolytic cleavage of the RÀX bond by a transition-metal complex activator, Mt m -Y/ Ligand, that reversibly generates an alkyl radical, P n * , and the corresponding higher oxidation state metal halide deactivator, X-Mt m + 1 -Y/Ligand (Scheme 2). P n * can then propagate with a vinyl monomer (M), be deactivated by X-Mt m + 1 -Y/Ligand, or terminate with another P n * , at which point two equivalents of deactivator accumulate as persistent radicals. Radical termination is diminished in controlled polymerizations obeying the persistent radical effect (PRE) [26] as the equilibrium becomes strongly shifted toward the dormant species.The PRE is a particular kinetic feature that provides a self-regulating mechanism in radical reactions. According to the PRE, when two radicals are generated at the same rate (for example from the same source, RÀY) and one of them is persistent (e.g., Y) while the other is transient (R * ), the persistent radical eventually becomes the dominating species in solution due to the self-termination of R * . This has the effect of steering the system toward the cross-termination of the two radicals (i.e., formation of RÀY), strongly inhibiting the self-termination of transient radicals. Therefore, the PRE is a key feature of all CRP techniques based on an activation/deactivation process.Polymerization kinetics and degree of control in ATRP largely depend on the appropriate equilibrium between the activation process (generation of radicals, k act ) and the deactivation process (formation of alkyl halides, k deact ). [25] The rate constants and their ratio (K ATRP = k act /

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Atom Transfer Radical Polymerization of Styrene Using Multifunctional Iniferter Reagents as Initiators

Cited by 9 publications

References 24 publications

Effect of Initiator and Ligand Structures on ATRP of Styrene and Methyl Methacrylate Initiated by Alkyl Dithiocarbamate

Effect of Initiator and Ligand Structures on ATRP of Styrene and Methyl Methacrylate Initiated by Alkyl Dithiocarbamate

Emulsion copolymerization of styrene and butyl acrylate by reverse atom transfer radical polymerization

ATRP with Alkyl Pseudohalides Acting as Initiators and Chain Transfer Agents: When ATRP and RAFT Polymerization Become One

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