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

Kwak, Yungwan; Matyjaszewski, Krzysztof

doi:10.1021/ma801231r

Cited by 66 publications

(53 citation statements)

References 76 publications

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“…Immediately after mixing, aliquots (0.7 mL each) of the solution were distributed via a syringe into baked glass tubes, which were then sealed by flame under nitrogen atmosphere. The tubes were immersed in thermostatic water bath at 40 C under the 27 W fluorescent light with diffuser [3M Filter Light ( > 400 nm)]. 33 In predetermined intervals, the polymerization was terminated by cooling the reaction mixture to À78 C. Monomer conversion was determined from the concentration of residual monomer measured by gas chromatography with n-octane as an internal standard (118 h, 90.3%).…”

Section: Polymerizationmentioning

confidence: 99%

Mn2(CO)10-Induced RAFT Polymerization of Vinyl Acetate, Methyl Acrylate, and Styrene

2009

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A dinuclear manganese complex [Mn 2 (CO) 10 ] induced the controlled/living radical polymerization of various conjugated and unconjugated vinyl monomers including vinyl acetate, methyl acrylate, and styrene in conjunction with dithiocarbonyl compounds [R-SC(S)Z] under weak visible light at 40 C. The obtained polymers had controlled molecular weights, narrow molecular weight distributions, and well-defined chain-end groups originating from R-SC(S)Z, as indicated by SEC, 1 H NMR, and MALDI-TOF-MS analyses. The polymerization most probably proceeds via the reversible activation of the C-SC(S)Z bond by Á Mn(CO) 5 via the metal-catalyzed process and/or by the carbon-centered radical species via the additionfragmentation chain transfer (RAFT) process.KEY WORDS: Vinyl Acetate / Acrylate / Styrene / Living Radical Polymerization / RAFT Polymerization / Manganese Complex / Various aspects of the controlled/living radical polymerization have been significantly developed in this decade, including a variety of initiating systems, controllable monomers, polymer structures, fusion with other substances, and applications to functional materials. Among the numerous initiating systems, there are now three representatives in terms of wide applicability and good controllability; i.e., the nitroxide-mediated radical polymerization (NMP), 1,2 metal-catalyzed living radical polymerization or atom transfer radical polymerization (ATRP), [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] and reversible addition-fragmentation chain transfer (RAFT) 18 polymerization or macromolecular design via interchange of xanthate (MADIX). 19 Although the components and the mechanisms are different, they are all based on the reversible transient activation of the dormant covalent species into the growing radical species. However, each system has its own characteristics or features due to the differences, which suggests that the choice of initiating systems is important depending on the monomers, conditions, purposes, etc.The metal-catalyzed living radical polymerization or ATRP is one of the best methods in terms of the well-defined architecture of the polymers from a variety of conjugated monomers, such as methacrylates, acrylates, acrylamides, acrylonitrile, and styrenes. This polymerization is generally initiated by the carbon radical generated from the alkyl halide upon the activation of the carbon-halogen bond by the transition metal catalyst, and then proceeds via the metalcatalyzed reversible activation of the carbon-halogen terminal into the growing radical species. One growing polymer chain end is thus generated from one carbon-halogen bond, which can permit the well-defined polymer synthesis. Although various transition metals, such as ruthenium, 3 20 The choice of the metal complexes including metals and ligands as well as the halides is important for the precise control of the polymerizations depending on the monomers.In contrast, the RAFT/MADIX system with the dithiocarbonyl compounds [R-SC(S)Z] is one of the most widely applica...

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Section: Polymerizationmentioning

confidence: 99%

Mn2(CO)10-Induced RAFT Polymerization of Vinyl Acetate, Methyl Acrylate, and Styrene

2009

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“…Less effective RAFT agents for a given monomer can thus be employed as pseudo-halide initiators for ATRP. Kwak et al [17] investigated the effects of initiator and catalysts ligand structures on the ATRP of Sty and methyl methacrylate (MMA) initiated by dithiocarbamates. Well-controlled polymerizations with resulting polydispersities ,1.1 (Sty) and ,1.2 (MMA) were obtained.…”

Section: Overview Of Reactions Of Thiocarbonylthio End-groups Radicalmentioning

confidence: 99%

End Group Reactions of RAFT-Prepared (Co)Polymers

et al. 2011

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“…There have been many studies on the effect of different kinds of initiators on the molecular weight of the polymer and it has been reported that its concentration influences the molecular weight of the polymer [15,16]. Alkyl halides are the common initiators for ATRP [3,6], and halides such as Br and Cl should move between the growing polymer chain and the transition metal for precisely controlled polymerization.…”

Section: Introductionmentioning

confidence: 99%

Effects of dual initiators and catalytic additives on atom transfer radical polymerization of styrene

Park

2011

Res Chem Intermed

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The effect of two initiators, so-called dual initiators system on atom radical transfer polymerization (ATRP), were studied with dimethyl-2,6-dibromohepanedioate (DMDBHD) and ethyl-2-bromoisobutyrate (EBIB). Cu(I)Br as catalyst and N,N,N 0 ,N 0 ,N 0 -pentamethyl-diethylenetriamine as ligand were employed for styrene ATRP. Interestingly, bimodal MWD were shown for the dual initiator system, and one of the peaks had higher molecular weight (MW) and the other had lower MW compared to a one-initiator system. The lower MW peak in bimodal peaks seemed to be mainly resulting from EBIB and the higher MW peak from DMDBHD. Furthermore, methylaluminoxane (MAO) was fed into the ATRP reaction to observe the effect of it on ATRP. As the MAO/CuBr molar ratio in feed increased from 0 to 1, the molecular weight and conversion increased without a notable change in PDI and curve shape of GPC. The conversion in the presence of MAO was also increased with the increase in MAO/CuBr molar ratio. The effect of Cp * TiCl 3 on the ATRP was opposite to that of MAO. As the Cp * TiCl 3 /CuBr molar ratio increased from 0 to 1, the conversion of polymerization was down from 56 to 35%. Furthermore, the molecular weight was drastically decreased from 10,000 to 5,500, but their PDI did not show a significant change. These results can elucidated by the retarding effect of Cp * TiCl 3 on the propagation of polymerization.

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

Cited by 66 publications

References 76 publications

Mn2(CO)10-Induced RAFT Polymerization of Vinyl Acetate, Methyl Acrylate, and Styrene

Mn2(CO)10-Induced RAFT Polymerization of Vinyl Acetate, Methyl Acrylate, and Styrene

End Group Reactions of RAFT-Prepared (Co)Polymers

Effects of dual initiators and catalytic additives on atom transfer radical polymerization of styrene

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