Living radical polymerization of methyl methacrylate catalyzed by cuprous <i>N</i>,<i>N</i>‐diethyldithiocarbamate

Qiu, Kun-Yuan

doi:10.1002/pola.10309

Cited by 33 publications

(30 citation statements)

References 28 publications

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“…First-order kinetic plots were obtained when the AIBN-initiated polymerization was catalyzed with Cu(S 2 CNEt 2 )Cl. Similarly to previous work, [6][7][8] the S 2 CNEt 2 moiety preferentially underwent transfer reactions, as the Cu-S bond is weaker than the Cu-Cl bond. The photo-labile end-capping group may function as an iniferter, allowing chain extension and the production of block copolymers.…”

Section: Introductionmentioning

confidence: 82%

Cu(S₂CNEt₂)Cl‐Catalyzed Reverse Atom‐Transfer Radical Polymerization of Vinyl Monomers

Qiu

2002

Macromol. Rapid Commun.

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A new copper catalyst containing chlorine and a photo‐labile diethylthiocarbamoylthiyl group was successfully employed in the reverse ATRP of methyl methacrylate (MMA). The polymeric chains were end‐capped with S2CNEt2, due to pseudo‐halogen atom‐transfer reaction between active and dormant species. Photopolymerization of this PMMA in the presence of fresh MMA and styrene monomers at ambient temperature yielded chain‐extended PMMA and MMA/styrene block copolymers, respectively. GPC traces of (A) PMMA end‐capped with a photo‐labile group (pre‐PMMA), (B) chain‐extended PMMA (post‐PMMA), and (C) PMMA/styrene block copolymer (PMMA‐b‐PSt).magnified imageGPC traces of (A) PMMA end‐capped with a photo‐labile group (pre‐PMMA), (B) chain‐extended PMMA (post‐PMMA), and (C) PMMA/styrene block copolymer (PMMA‐b‐PSt).

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Section: Introductionmentioning

confidence: 82%

Cu(S₂CNEt₂)Cl‐Catalyzed Reverse Atom‐Transfer Radical Polymerization of Vinyl Monomers

Qiu

2002

Macromol. Rapid Commun.

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“…[32] Nishimura et al reported that a living polymerization of styrene with halogen-free initiating system that consist of a transition metal dithiocarbanate Mt{SC(S)NR 2 } n (Mt ¼ Fe(III), Ru(III), Cu(II); R ¼ ethyl or benzyl; n ¼ 2 or 3) and AIBN. [33] Li and Qiu reported that the living radical polymerizations of methyl methacrylate with p-TsCl/Cu(I)(SC-(S)NEt 2 )/bpy, [34] BPO/Cu(I)(SC(S)NEt 2 )/bpy, [35] BPO/ Cu(II)(SC(S)NEt 2 )Cl/bpy [36] and AIBN/Cu(II)(SC(S)-NEt 2 )Cl/bpy [37] as initiating systems, the polymerization was well controlled in all cases. The polymer chain was capped with an ultraviolet light sensitive group was confirmed by chain extension reactions.…”

Section: Introductionmentioning

confidence: 99%

Reverse Atom Transfer Radical Polymerization of Methyl Methacrylate using a New Catalyst, Copper(II) N,N′‐Butyldithiocarbamate

Zhang

Zhu²,

Zhu

et al. 2004

Macro Chemistry & Physics

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Summary: The homogeneous bulk reverse ATRP using AIBN/Cu(SC(S)N(C4H9)2)2/bpy as the initiating system has been successfully carried out for methyl methacrylate. Well‐controlled polymerizations with low polydispersities ($\overline M _{\rm w} /\overline M _{\rm n}$ = 1.10–1.30) have been achieved. The revised number‐average molecular weights ($\overline M _{{\rm n}({\rm rev})}$'s) increased linearly with monomer conversion and were close to the $\overline M _{{\rm n}({\rm th})}$ values. The polymerization rate followed the first‐order kinetics in monomer, while it is about 2.0 order in initiator concentration and 1.15 order in Cu(II) concentration. The k values for the homogeneous bulk reverse ATRP of MMA initiated by AIBN/Cu(SC(S)N(C4H9)2)2/bpy (1:2:6) at 80, 90, 100 and 110 °C were 0.402 × 10−4, 1.021 × 10−4, 2.952 × 10−4, and 3.687 × 10−4 (s−1), respectively. On the basis of the Arrhenius plot, the apparent activation energy was calculated to be ΔE = 87.1 kJ/mol. The obtained PMMA was functionalized with an ultraviolet light sensitive ω‐SC(S)N(C4H9)2 group characterized by means of 1H NMR spectroscopy, and which was also proved by its chain extension with fresh MMA under UV‐light irradiation at room temperature. A polymerization mechanism for this novel initiation system is proposed.Dependence of $\overline M _{{\rm n}({\rm rev})}$ and $\overline M _{\rm w} /\overline M _{\rm n}$ on the monomer conversion for the homogeneous bulk reverse ATRP of MMA at different concentration of catalyst.magnified imageDependence of $\overline M _{{\rm n}({\rm rev})}$ and $\overline M _{\rm w} /\overline M _{\rm n}$ on the monomer conversion for the homogeneous bulk reverse ATRP of MMA at different concentration of catalyst.

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“…26,27 The living system only requires the absence of any chain-breaking reaction. To obtain a polymer with a narrow molar mass distribution, it is necessary to fulfil various requirements that are specific for each polymerization system.…”

Section: Resultsmentioning

confidence: 99%

“…The other compounds were ordered from Sigma-Aldrich and used as received. 27.75 mmol). The tube was closed, frozen in MeOH/dry ice and degassed through the plunger valve by applying cycles of reduced pressure followed by filling the tube with inert gas for 20 times at À40 8C.…”

Section: Experimental Materialsmentioning

confidence: 99%

Synthesis of poly(ethyl acrylate) by single electron transfer‐degenerative chain transfer living radical polymerization in water catalyzed by Na₂S₂O₄

Coelho

Carvalho

Marques

et al. 2007

J. Polym. Sci. A Polym. Chem.

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Living radical polymerization of ethyl acrylate was achieved by single-electron-transfer/degenerative-chain transfer mediated living radical polymerization in water catalyzed by sodium dithionite. The plots of number-average molecular weight versus conversion and ln[M] 0 /[M] versus time are linear, indicating a controlled polymerization. This method leads to the preparation of a,x-di(iodo)poly(ethyl acrylate) (a,x-di(iodo)PEtA) macroinitiator that can be further functionalized. The molecular weight distributions were determined using a combination of three detectors (TriSEC): right-angle light scattering, a differential viscometer and refractive index. The method studied in this work represents a possible route to prepare well-tailored macromolecules made of ethyl acrylate in environmental friendly reaction medium. To the best of our knowledge there is no previous report dealing with the synthesis of PEtA by any LRP approach in aqueous medium. Furthermore, the method described in this article was successfully applied in pilot scale reactions under industrial production conditions.

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Living radical polymerization of methyl methacrylate catalyzed by cuprous N,N‐diethyldithiocarbamate

Cited by 33 publications

References 28 publications

Cu(S₂CNEt₂)Cl‐Catalyzed Reverse Atom‐Transfer Radical Polymerization of Vinyl Monomers

Cu(S₂CNEt₂)Cl‐Catalyzed Reverse Atom‐Transfer Radical Polymerization of Vinyl Monomers

Reverse Atom Transfer Radical Polymerization of Methyl Methacrylate using a New Catalyst, Copper(II) N,N′‐Butyldithiocarbamate

Synthesis of poly(ethyl acrylate) by single electron transfer‐degenerative chain transfer living radical polymerization in water catalyzed by Na₂S₂O₄

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Living radical polymerization of methyl methacrylate catalyzed by cuprous N,N‐diethyldithiocarbamate

Cited by 33 publications

References 28 publications

Cu(S2CNEt2)Cl‐Catalyzed Reverse Atom‐Transfer Radical Polymerization of Vinyl Monomers

Cu(S2CNEt2)Cl‐Catalyzed Reverse Atom‐Transfer Radical Polymerization of Vinyl Monomers

Reverse Atom Transfer Radical Polymerization of Methyl Methacrylate using a New Catalyst, Copper(II) N,N′‐Butyldithiocarbamate

Synthesis of poly(ethyl acrylate) by single electron transfer‐degenerative chain transfer living radical polymerization in water catalyzed by Na2S2O4

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Cu(S₂CNEt₂)Cl‐Catalyzed Reverse Atom‐Transfer Radical Polymerization of Vinyl Monomers

Cu(S₂CNEt₂)Cl‐Catalyzed Reverse Atom‐Transfer Radical Polymerization of Vinyl Monomers

Synthesis of poly(ethyl acrylate) by single electron transfer‐degenerative chain transfer living radical polymerization in water catalyzed by Na₂S₂O₄