Macromolecular Design via the Interchange of Xanthates (MADIX): Polymerization of Styrene with <i>O</i>‐Ethyl Xanthates as Controlling Agents

Destarac, Mathias; Brochon, Cyril; Catala, J.‐M.; Wilczewska, Agnieszka Z.; Zard, Samir Z.

doi:10.1002/macp.200290002

Cited by 126 publications

(149 citation statements)

References 28 publications

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“…Systems studied by mass spectrometry include (polymer/ RAFT agents): PNIPAM/20,22, [78] PNIPAM/39,40, [93] PVAc/49, [48] PS/21, [126] PS/69, [106] PMMA/8,11, [100] PBA/ 57,63, [127] PMA/21,22,24, [81,83] PEA/79, [49] and poly-(acenaphthalene)/81. [128] ESI is a softer ionization technique than MALDI-TOF and is more likely to leave the end groups intact to be observed in the mass spectrum.…”

Section: Evidence In Support Of the Raft Mechanismmentioning

confidence: 99%

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Living Radical Polymerization by the RAFT Process

Moad¹,

Rizzardo²,

Thang³

2005

Aust. J. Chem.

2,133

1,894

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This paper presents a review of living radical polymerization achieved with thiocarbonylthio compounds [ZC( S)SR] by a mechanism of reversible addition-fragmentation chain transfer (RAFT). Since we first introduced the technique in 1998, the number of papers and patents on the RAFT process has increased exponentially as the technique has proved to be one of the most versatile for the provision of polymers of well defined architecture. The factors influencing the effectiveness of RAFT agents and outcome of RAFT polymerization are detailed. With this insight, guidelines are presented on how to conduct RAFT and choose RAFT agents to achieve particular structures. A survey is provided of the current scope and applications of the RAFT process in the synthesis of well defined homo-, gradient, diblock, triblock, and star polymers, as well as more complex architectures including microgels and polymer brushes.

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Section: Evidence In Support Of the Raft Mechanismmentioning

confidence: 99%

“…In these circumstances, Fig. 7 will (S), [46] (S) [9] - [16,[105][106][107] (BA), [38] (S) [9] - [16,49,106,107] AA, [108] (MA), [16] (EA), [16,49] AA-AM, [108] AA-b-AM, [108] AM, [108] VAc, [6,16] (S), [16] (BA) [16] AA-AM-b-AM [108] [106] - [16,106] - [16,106] (EA) [16] - [106] (tBA), [6] (MMA) [38] -…”

mentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process

Moad¹,

Rizzardo²,

Thang³

2005

Aust. J. Chem.

2,133

1,894

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“…O-ethyl-S-(1-ethoxycarbonyl)ethyldithiocarbonate (1) was prepared according to the literature. 19 1-Phenylethyl phenyldithioacetate (2) was prepared according to the literature. 32 Mn 2 (CO) 10 (Aldrich, 98%) and Fe 2 Cp 2 (CO) 4 (Aldrich, 99%) were used as received and handled in unlighted glovebox (VAC Nexus) under a moistureand oxygen-free argon atmosphere (O 2 < 1 ppm).…”

Section: Experimental Materialsmentioning

confidence: 99%

“…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.…”

mentioning

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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“…For MADIX of MAMs, several kinetic studies have been performed with styrene as the monomer. 7,17,19,25,32,34,36,37 For example, Adamy et al 7 investigated the influence of the chemical structure of the initial RAFT agent for MADIX of styrene in toluene and reported that with (O-ethyl xanthate)-2-ethyl propionate (OEXEP) as the initial RAFT agent, a Đ close to 2 (X m = 20%) can merely be obtained. In contrast, by increasing the electron-withdrawing capacity of the Z group by incorporation of fluorinated groups at β-position to the oxygen atom, as for instance in (O-2,2,2-trifluoro ethyl xanthate)-2-ethyl propionate (OtFOX), a lower but still high Đ of 1.6 can be achieved (X m > 20%), in agreement with an earlier experimental study by Destarac et al 36 The latter observation was attributed to an increased reactivity of the SvC bond due to the decreased availability of the oxygen lone pair to conjugate with the thiocarbonyl group.…”

Section: Introductionmentioning

confidence: 99%