Single electron transfer–degenerative chain transfer mediated living radical polymerization (SET–DTLRP) of vinyl chloride initiated with methylene iodide and catalyzed by sodium dithionite

Percéc, Virgil; Popov, Anatoliy V.; Ramirez‐Castillo, Ernesto; Coelho, Jorge F. J.

doi:10.1002/pola.20543

Cited by 43 publications

(27 citation statements)

References 9 publications

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“…However, the living character was not claimed and demonstrated. Nevertheless, ITP (also called degenerative transfer) enables controlling the polymerization of different monomers, that is, acrylic,40–53 methacrylic,54, 55 styrenic,40, 56, 57 vinyl chloride,42, 44, 45, 47, 48, 53, 58–65 and also, fluorinated olefins 25, 66–68. The synthesis of different commercially available products such as thermoplastic elastomers (TPEs) pioneered by the Daikin Company in 197969 (which nowadays produces Daiel® TPE),70 then studied by DuPont (now Dupont Performance Elastomers),71–73 and developed later by Ausimont (now Solvay Solexis) under the Tecnoflon® trade name74–76 has been reported.…”

Section: Introductionmentioning

confidence: 99%

Iodine transfer copolymerization of vinylidene fluoride and α‐trifluoromethacrylic acid in emulsion process without any surfactants

Boyer

Améduri

2009

J. Polym. Sci. A Polym. Chem.

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The synthesis of poly(VDF-co-TFMA) copolymers (where VDF and TFMA stand for vinylidene fluoride and a-trifluoromethacrylic acid, respectively) by iodine transfer polymerization without any surfactant is presented. First, the synthesis and the control of the copolymerization of VDF and TFMA were investigated in the presence of two chain transfer agents, 1-perfluorohexyl iodide (C 6 F 13 I) and 1,4-diodoperfluorobutane (IC 4 F 8 I). TFMA monomer was incorporated in the copolymer in good yields. Moreover, the molecular weights of the resulting poly(VDF-co-TFMA) copolymers were in good agreement with the theoretical values for feed of TFMA/VDF ratios that ranged from 50/50 to 0/100 mol %, showing that TFMA does not disturb the controlled radical polymerization of VDF. The microstructures of the produced copolymers were characterized by 1 H and 19 F NMR to assess the amount of each comonomer, and the molecular weights and the end-groups of the copolymers. The results on the control of the copolymerization were compared to those obtained with and without the presences of TFMA and surfactant. The addition of a low amount of TFMA improved the control of the polymerization of VDF without using any surfactant. Also, the size of particles, assessed by light scattering, was smaller than 200 nm. The addition of TFMA in low proportions, that is, 5 to 10 mol %, enabled us to stabilize the particle size and to decrease the size by one order of magnitude. The emulsifying behavior of TFMA (in low amount in the copolymer, that is, \10 mol %) was similar to those achieved when a surfactant was added. Indeed, neither sedimentation nor destabilization was observed after several days. The reactivity ratios for r TFMA and r VDF were 0 and 1.6 at 80 C, respectively. V V C 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: [4710][4711][4712][4713][4714][4715][4716][4717][4718][4719][4720][4721][4722] 2009

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Section: Introductionmentioning

confidence: 99%

Iodine transfer copolymerization of vinylidene fluoride and α‐trifluoromethacrylic acid in emulsion process without any surfactants

Boyer

Améduri

2009

J. Polym. Sci. A Polym. Chem.

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“…For example, in the case of RAFT polymerization, the active radicals tend to add to the thiocarbonylthio group of dithioester or trithiocarbonate and are reluctant to fragment from it, thus leading to a retarded or completely inhibited polymerization. Situation has been improved these years and LRP of typical unconjugated monomers such as VAc,12–19 VC,20–27 and NVP28–33 are now available. Among the techniques developed for unconjugated monomers, RAFT/MADIX is the most frequently used process, some ATRP processes have also been developed, and the newly developed organotellurium‐mediated radical polymerization (TERP),34–36 organostibine‐mediated radical polymerization (SBRP),37, 38 and organobismuthine‐mediated radical polymerization (BIRP)39 techniques have been proved effective for both conjugated and unconjugated monomers, including NVP 40.…”

Section: Introductionmentioning

confidence: 99%

Controlled radical polymerization of N‐vinylcaprolactam mediated by xanthate or dithiocarbamate

Wan¹,

Zhou²,

Pu³

et al. 2008

J. Polym. Sci. A Polym. Chem.

111

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Controlled radical polymerization of N‐vinylcaprolactam (NVCL) via reversible addition‐fragmentation chain transfer (RAFT) polymerization or macromolecular design via the interchange of xanthate (MADIX) was described, employing 2‐diphenylthiocarbamoylsulfanyl‐2‐methyl‐propionic acid (CTA1), ((O‐ethylxanthyl)methyl)benzene (CTA2) and (1‐(O‐ethylxanthyl)ethyl)benzene (CTA3) as chain transfer agents (CTA). It was found that all the CTAs led to controlled radical polymerization of NVCL, with the molecular weight increased along with the conversion of monomer and a relatively narrow molecular weight distribution could be obtained, as determined with matrix‐assisted laser desorption and ionization time‐of‐flight (MALDI‐TOF) and gel permeation chromatography (GPC), the polydispersity indices, as determined by MALDI‐TOF, were typically on the order of 1.24, but the polymerization did not proceed in a strictly living manner. The chain transfer ability of these CTAs was in the following order: CTA1 ≈ CTA2 < CTA3. MALTI‐TOF measurement showed that the major population of polymer retained the chain‐end functional group, but minor population deactivated by radical coupling. In preparation of the block copolymer of NVCL and vinyl acetate (VAc) by sequential polymerization, the sequence of monomer addition was important. Using VAc as the first monomer could lead to a block copolymer presenting a unimodal GPC trace and a narrow PDI index, and if NVCL was used as the first monomer, the polymerization was less well controlled. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3756–3765, 2008

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“…At 130 °C in o ‐dichlorobenzene, the LRP of VC initiated by iodide‐containing molecules could be achieved up to ∼20% conversion through single‐electron transfer (SET) activation and degenerative chain‐transfer (DT), the combination of which was subsequently termed single‐electron transfer degenerative transfer/living radical polymerization (SET‐DTLRP). Later, nonmetallic SET activators such as SO

_{2}^{•−}

derived from the aqueous phase decomposition of sodium diothionite5–7 or thiourea/octyl viologen8 were determined to mediate effective aqueous SET‐DTLRP of VC initiated by iodoform or methylene iodide9 at ambient temperatures. Application of this technique allowed for the synthesis of ultrahigh molecular weight PVC free of structural defects and that exhibited a high degree of syndiotacticity and commensurately elevated T g 10.…”

Section: Introductionmentioning

confidence: 99%

Effects of hydrophobic interaction on rheological behavior and microstructure of carboxylated core‐shell latex suspension

Nakamura

Tachi

2006

J of Applied Polymer Sci

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ABSTRACT:We have investigated the effects of hydrophobic interactions on the rheological behavior and microstructure of suspension of carboxylated core-shell latex particles with changing hydrophobicity of shell polymer and suspending medium. The carboxylated core-shell latex particles formed lattice-like microstructures in aqueous suspension with dissociation of carboxyl groups. With increasing hydrophobicity of the shell polymer, the interparticle distance in the microstructure decreased. However, increased with increasing hydrophobicity of the suspending medium. The effect of hydrophobic interaction on was explained by the steric stabilization theory for particles with grafted polymer on the surface. As the carboxylated coreshell latex particles overlapped each other in the microstructure, an attractive force was generated between the particles in aqueous suspension. With increasing hydrophobicity of the shell, the attractive force increased, but with increasing hydrophobicity of the suspending medium, the attractive force decreased.

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Single electron transfer–degenerative chain transfer mediated living radical polymerization (SET–DTLRP) of vinyl chloride initiated with methylene iodide and catalyzed by sodium dithionite

Cited by 43 publications

References 9 publications

Iodine transfer copolymerization of vinylidene fluoride and α‐trifluoromethacrylic acid in emulsion process without any surfactants

Iodine transfer copolymerization of vinylidene fluoride and α‐trifluoromethacrylic acid in emulsion process without any surfactants

Controlled radical polymerization of N‐vinylcaprolactam mediated by xanthate or dithiocarbamate

Effects of hydrophobic interaction on rheological behavior and microstructure of carboxylated core‐shell latex suspension

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