Water soluble polymeric nanogels by xanthate-mediated radical crosslinking copolymerisation

Taton, Daniel; Baussard, Jean‐François; Dupayage, Ludovic; Poly, Julien; Gnanou, Yves; Ponsinet, Virginie; Destarac, Mathias; Mignaud, Catherine; Pitois, Claire

doi:10.1039/b601456a

Cited by 55 publications

(84 citation statements)

References 17 publications

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“…29,34 It is perhaps noteworthy that this monomer concentration is significantly higher than that employed in many RAFT syntheses. 15,19,22 An M n versus conversion plot proved to be linear for PMMA 50 homopolymer, as expected. (See Figure 1.) A relatively narrow polydispersity (M w /M n < 1.25) was indicated by GPC analysis after 20 h, see entry 1 in Table 1.…”

Section: Resultssupporting

confidence: 56%

Synthesis of Highly Branched Methacrylic Copolymers: Observation of Near-Ideal Behavior using RAFT Polymerization

Rosselgong

Armes

Barton³

et al. 2009

Macromolecules

105

153

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We report the synthesis of model highly branched methacrylic copolymers by copolymerizing methyl methacrylate (MMA) with a disulfide-based dimethacrylate (DSDMA) branching comonomer via reversible addition-fragmentation chain transfer (RAFT) in toluene at 90°C using 1,1 0 -azobiscyclohexanecarbonitrile initiator and a cumyl dithiobenzoate (CDB) chain transfer agent. Selective cleavage of the disulfide bonds in the DSDMA branching comonomer using tributylphosphine leads to the formation of low polydispersity primary chains, as judged by gel permeation chromatography. The molecular weight distribution of these degraded chains is comparable to a RAFT-synthesized linear poly(methyl methacrylate) homopolymer prepared in the absence of any DSDMA brancher. This confirms that good control over the RAFT copolymerization is achieved under branching conditions and that the polydisperse highly branched chains simply comprise randomly coupled near-monodisperse primary chains, as expected. Moreover, HPLC analysis of the copolymerizing solution confirms that the consumption of DSDMA comonomer is close to that expected for a statistical copolymerization. The CDB efficiency is estimated to be 90% by GPC and 1 H NMR spectroscopy. Taking this into account and allowing for the incomplete comonomer conversions (typically 96-97%), our systematic variation of the proportion of DSDMA per primary chain indicates that this RAFT formulation conforms closely to classical Flory-Stockmayer theory. This near-ideal behavior is in marked contrast with earlier literature reports of strongly nonideal behavior, presumably because of significant levels of intramolecular cyclization. Our hypothesis is that this unwanted side reaction, which consumes the DSDMA brancher without leading to intermolecular branching, is suppressed in the present study because of the relatively high comonomer concentration (50% w/w) used in our RAFT syntheses.

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Section: Resultssupporting

confidence: 56%

Synthesis of Highly Branched Methacrylic Copolymers: Observation of Near-Ideal Behavior using RAFT Polymerization

Rosselgong

Armes

Barton³

et al. 2009

Macromolecules

105

153

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show abstract

“…A method generally employed for synthesizing microgels is the radical cross-linking copolymerization of a vinylic monomer with a cross-linker, using one of the three following processes: highly diluted solution, emulsion and precipitation/dispersion polymerizations. We recently reported the one-pot batch solution RCC of AA in the presence of MBA and xanthate X 0 [105,111]. Highly branched and soluble copolymers referred to as polymeric nanogels were obtained under such conditions.…”

Section: Polymeric Nanogelsmentioning

confidence: 99%

Macromolecular Design by Interchange of Xanthates: Background, Design, Scope and Applications

Taton

Destarac

Zard

2008

Handbook of RAFT Polymerization

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“…11 Free radical cross-linking copolymerization (RCC) of a vinyl monomer with a divinyl monomer (cross-linker) is another important and popular strategy to prepare chemical gels. 12 However, in case of RCC method intra-molecular cross-linking predominates at the early stages polymerization and generates highly heterogeneous gels with irregularly distributed branching points. Whereas, cross-linked gels prepared by controlled radical polymerization (CRP) of a vinyl monomer in the presence of a divinyl cross-linker resulted well structured and homogeneous gels.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of amino acid based covalently cross-linked polymeric gels using tetrakis(hydroxymethyl) phosphonium chloride as a cross-linker

Vaish

Roy

2015

Polymer

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Water soluble polymeric nanogels by xanthate-mediated radical crosslinking copolymerisation

Abstract: Branched water-soluble copolymers were obtained by direct radical crosslinking copolymerisation of acrylic acid or acrylamide and N,N'-methylenebisacrylamide at high solid content in the presence of an O-ethylxanthate as a reversible chain transfer agent.

Cited by 55 publications

References 17 publications

Synthesis of Highly Branched Methacrylic Copolymers: Observation of Near-Ideal Behavior using RAFT Polymerization

Synthesis of Highly Branched Methacrylic Copolymers: Observation of Near-Ideal Behavior using RAFT Polymerization

Macromolecular Design by Interchange of Xanthates: Background, Design, Scope and Applications

Synthesis of amino acid based covalently cross-linked polymeric gels using tetrakis(hydroxymethyl) phosphonium chloride as a cross-linker

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