Aqueous Cationic Polymerization of<i>p</i>‐Methoxystyrene Using Hydrophilic Phenylphosphonic Acids

Storey, Robson F.; Scheuer, Adam D.

doi:10.1081/ma-120028205

Cited by 21 publications

(13 citation statements)

References 10 publications

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“…Basically, at this stage of the reaction only short chains were formed by interfacial polymerization (DP ≈ 8−10). However, in contrast to all previously described systems, ,− ,− the polymerization of p -methoxystyrene can proceed further inside the monomer droplet in a controlled fashion by the reactivation of hydroxyl-terminated chains in the organic core of the droplet. Such a striking event was made possible by the entry inside the particles and polymerization catalysis of B(C 6 F 5 ) 3 , presumably in the form of its complex with acetonitrile, which is less hydrophilic than while complexed with water .…”

Section: Fifth Generation: Aromatic Borane-based Cocatalystsmentioning

confidence: 85%

“…In a recent work, Storey at al . reported on the polymerization of p MOS using phosphonic acid initiators [(HO) 2 P(O)R, R = Ph or Ph- o , m , p- NO 2 ] and Yb(OTf) 3 as co-initiator in conditions similar to those proposed by Sawamoto’s team.…”

Section: Second Generation: Lanthanide Triflate Cocatalystsmentioning

confidence: 97%

“…The analysis of poly( p -methoxystyrene)s chain-ends by 1 H NMR spectroscopy was at first revealing the presence of −CH(C 6 H 4 OCH 3 )−Cl ω-terminal group (F n (Cl) ≈ 0.3−0.5). ,, Later, Sawamoto et al and other research teams ,− showed unambiguously that almost all polymer chains were terminated by hydroxyl groups, originating from chain transfer via water. The low stability of terminal −CH(C 6 H 4 OCH 3 )−Cl groups, even in organic solvents, was also observed by Faust et al Originally, it was proposed ,− that the polymerization proceeds inside monomer/organic solvent droplets via carbocationic species generated from initiator located in organic phase through its reversible activation by Yb(OTf) 3 .…”

Section: Second Generation: Lanthanide Triflate Cocatalystsmentioning

confidence: 99%

“…reported on the polymerization of p MOS using phosphonic acid initiators [(HO) 2 P(O)R, R = Ph or Ph- o , m , p- NO 2 ] and Yb(OTf) 3 as co-initiator in conditions similar to those proposed by Sawamoto’s team. It was claimed that polymerization proceeds at the aqueous/organic interface and is not controlled since changing the concentration of initiator did not influence the M n evolution with conversion . The main feature of this initiating system is the possibility to generate poly( p -methoxystyrene)s with high molecular weight ( M n ≤ 20 000 g/mol).…”

Section: Second Generation: Lanthanide Triflate Cocatalystsmentioning

confidence: 99%

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Cationic Polymerization of Vinyl Monomers in Aqueous Media: From Monofunctional Oligomers to Long-Lived Polymer Chains

Kostjuk

Ganachaud

2009

Acc. Chem. Res.

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Polymer latexes are easily prepared on a multimillion ton scale in industry using free radical initiated emulsion and suspension polymerizations in water, a cheap, nonviscous, heat-controlling, and environmentally benign solvent. Until recently, researchers had done little investigation into ionic polymerization because even a small amount of water would easily deactivate the conventional catalysts used in these processes. In the last decade, however, cationic polymerization in aqueous media has emerged as a new and attractive method for controlling the polymerization reactions using mild experimental conditions. This Account reviews the current science of and future outlook for cationic polymerization of vinyl monomers in aqueous media. We particularly emphasize the design and evolution of catalytic systems and the precision synthesis of functional polymers. Early work to tailor the suspension and emulsion cationic polymerizations of reactive monomers such as p-methoxystyrene and vinyl ethers used long-chain strong acids, called INISURF for their dual roles as initiators and surfactants, and lanthanide triflates. These polymerization processes shared two main features: (i) all reactions (initiation, propagation, and termination) occurred at the particle interface; (ii) synthesized polymers have limits on their molecular weight, attributed to the "critical DP" effect, related to the entry of oligomers inside the particles as they become increasingly hydrophobic. The next generation of catalysts, named "Lewis acid-surfactant combined catalysts" (LASC), shifted the polymerization locus from the interface to the inside of the monomer droplets, allowing for the production of long polymer chains. Recently, catalytic systems based on boranes, (BF(3)OEt(2), B(C(6)F(5))(3), (C(6)F(4)-1,2-[B(C(6)F(5))(2)]), and (C(6)F(4)-1,2-[B(C(12)F(8))](2))), have shown great potential in controlling the cationic polymerization in "wet" solution, containing an excess of water relative to Lewis acid, or aqueous media of such industrially important monomers as styrene, cyclopentadiene, and even isobutylene.

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Section: Fifth Generation: Aromatic Borane-based Cocatalystsmentioning

confidence: 85%

Section: Second Generation: Lanthanide Triflate Cocatalystsmentioning

confidence: 97%

Section: Second Generation: Lanthanide Triflate Cocatalystsmentioning

confidence: 99%

Section: Second Generation: Lanthanide Triflate Cocatalystsmentioning

confidence: 99%

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Cationic Polymerization of Vinyl Monomers in Aqueous Media: From Monofunctional Oligomers to Long-Lived Polymer Chains

Kostjuk

Ganachaud

2009

Acc. Chem. Res.

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“…Subsequent work by French scientists15, 16 on aqueous emulsion polymerization of PMOS using the strongly acidic surfactant dodecylbenzenesulfonic acid by itself or in conjunction with Yb(OTf) 3 exhibited analogous behavior indicating that these polymerizations might involve proton mediated initiation and chain transfer processes 9. Medium MW polyPMOS was produced in aqueous media by inclusion of a hydrocarbon soluble BA (i.e., pentachlorophenol)17 or a phosphonic acid18 initiator in conjunction with Yb(OTf) 3 .…”

Section: Introductionmentioning

confidence: 99%

Robotic surgery helps preserve speech after head and neck cancer surgery

Printz¹

2011

Cancer

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Tris(pentafluorophenyl)gallium (3) and aluminum (7) are active coinitiators for the production of medium‐high molecular weight (MW) polymers of styrene and isobutene (IB) under aqueous reaction conditions. Strong Brønsted acids formed in situ by reaction of these coinitiators with background moisture present in the monomer droplet (5 and 8, respectively) are believed to be responsible for inducing cationic polymerization of these monomers. Of the two, 7 is the most active for IB polymerization in both aqueous media and anhydrous aliphatic solvents. These results are in contradistinction to tris(pentafluorophenyl)boron (2), which is incapable of polymerizing IB in aqueous or aliphatic media. The MWs of the polyisobutenes (PIBs) produced under aqueous conditions by either coinitiator greatly exceed those formed under similar reaction conditions by the strongly acidic chelating diborane (1,2‐C6F4[B(C6F5)2]2, 1) or diborole (1,2‐C6F4[9‐BC12F8]2, 6). Both 3 and 7 are readily synthesized from the corresponding Group 13 halide compounds in conjunction with bis(pentafluorophenyl)zinc (4). Aqueous polymerization of IB dissolved in aliphatic solvents with 3 or 7 can yield PIBs with relatively narrow polydispersities. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

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Carbocationic Polymerization*This chapter has already been published in: Matyjaszewski, K., Müller, A. H. E., Controlled and Living Polymerizations, 2009. Copyright Wiley‐VCH Verlag GmbH & Co. KGaA. Reproduced with kind permission of the authors.

Faust

2012

Materials Science and Technology

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The sections in this article are Introduction Mechanistic and Kinetic Details of Living Cationic Polymerization Living Cationic Polymerization Monomers and Initiating Systems Additives in Living Cationic Polymerization Living Cationic Polymerization: Isobutylene ( IB ) β‐Pinene Styrene ( St ) p ‐Methylstyrene ( p ‐ Me St ) p ‐Chlorostyrene ( p ‐ Cl St ) 2,4,6‐Trimethylstyrene ( TMe St ) p ‐Methoxystyrene ( p ‐ Me OSt ) α‐Methylstyrene (α Me St ) Indene N ‐Vinylcarbazol Vinyl Ethers Functional Polymers by Living Cationic Polymerization Functional Initiator Method Functional Terminator Method Telechelic Polymers Macromonomers Synthesis using a Functional Initiator Synthesis using a Functional Capping Agent Chain‐End Modification Block Copolymers Linear Diblock Copolymers Linear Triblock Copolymers Synthesis using Difunctional Initiators Synthesis Using Coupling Agents Block Copolymers with Nonlinear Architecture Synthesis of A n B n Hetero‐Arm Star‐Block Copolymers Synthesis of AA ′ B , ABB ′, and ABC Asymmetric Star‐Block Copolymers using Furan Derivatives Block Copolymers Prepared by the Combination of Different Polymerization Mechanisms Combination of Cationic and Anionic Polymerization Combination of Living Cationic and Anionic Ring‐Opening Polymerization Combination of Living Cationic and Radical Polymerization Branched and Hyperbranched Polymers Surface Initiated Polymerization — Polymer Brushes Conclusions

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Aqueous Cationic Polymerization ofp‐Methoxystyrene Using Hydrophilic Phenylphosphonic Acids

Cited by 21 publications

References 10 publications

Cationic Polymerization of Vinyl Monomers in Aqueous Media: From Monofunctional Oligomers to Long-Lived Polymer Chains

Cationic Polymerization of Vinyl Monomers in Aqueous Media: From Monofunctional Oligomers to Long-Lived Polymer Chains

Robotic surgery helps preserve speech after head and neck cancer surgery

Carbocationic Polymerization*This chapter has already been published in: Matyjaszewski, K., Müller, A. H. E., Controlled and Living Polymerizations, 2009. Copyright Wiley‐VCH Verlag GmbH & Co. KGaA. Reproduced with kind permission of the authors.

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