Recent developments in living cationic polymerization

Nuyken, Oskar; Kröner, Hubertus; Rieß, Gisbert; Oh, Saehoon; Ingrisch, Stefan

doi:10.1002/masy.19961010106

Cited by 4 publications

(1 citation statement)

References 29 publications

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“…It is no doubt the consequence of these difficulties that while the literature on the cationic polymerization of IBVE is abundant, that of MeVE is rather scarce. The living polymerization of MeVE by the (1-iodoethoxy)ethane/I 2 initiating system in toluene or toluene/ CCl 4 (1/1 v/v) at -35 and -15 °C was first reported by Miyamoto et al 14 Amphiphilic block copolymers of MeVE and RVE, where R is hexadecyl (CVE), octadecyl (ODVE), 15 and isobutyl (IBVE) or chloroethyl (CEVE), 16 prepared by sequential monomer addition have also been reported. Interestingly, methanol solutions of (MeVE) 120 -(CVE) 20 diblock copolymers remained cloudy up to 75 °C.…”

Section: Introductionmentioning

confidence: 99%

Amphiphilic Block Copolymers by Sequential Living Cationic Polymerization: Synthesis and Characterization of Poly(isobutylene-b-methyl vinyl ether)

Hadjikyriacou

Faust

1996

Macromolecules

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The living polymerization of methyl vinyl ether (MeVE) was achieved using initiators obtained by capping 2,4,4-trimethyl-2-chloropentane (TMPCl) with 1,1-diphenylethylene (DPE), or 1,1-ditolylethylene (DTE) in conjunction with TiCl n (OEt)4 - n (n = 2−2.4) coinitiator in CH2Cl2/hexanes (60/40 v/v) solvent mixture at 0 °C. Sequential block copolymerization of isobutylene (IB) with MeVE has also been accomplished. Well-defined living poly(isobutylene) (PIB) was first prepared at −80 °C in the presence of TiCl4, followed by capping with DPE or DTE. Then, Ti(OEt)4 was added to reduce the Lewis acidity followed by the addition of MeVE, and the temperature was raised to 0 °C. Well-defined PIB-PMeVE diblock copolymers with controlled molecular weight and narrow molecular weight distribution (M w/M n < 1.1) have been obtained, with the virtual absence of homopolymer contaminants. According to differential scanning calorimetry, the diblock copolymers exhibit two T gs, suggesting microphase separation. PIB-PMeVE diblock copolymers with ∼50/50 w/w composition were insoluble in water but soluble in methanol. The diblock copolymer with 80 wt % PMeVE content was soluble in water, exhibited excellent surfactant properties (critical micelle concentration = 2.3 × 10-5 M), and produced stable emulsions of oil in water (average particle size ∼200 nm).

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Section: Introductionmentioning

confidence: 99%

Amphiphilic Block Copolymers by Sequential Living Cationic Polymerization: Synthesis and Characterization of Poly(isobutylene-b-methyl vinyl ether)

Hadjikyriacou

Faust

1996

Macromolecules

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The possibility of living or long‐lived cationic polymerization in the butyl vinyl ether/iodine/liquid sulfur dioxide system

Oliveria

Moreira

Brandão

et al. 1997

Macro Chemistry & Physics

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The polymerization of butyl vinyl ether (nBuVE) initiated by iodine in the presence of liquid sulfur dioxide has been investigated. The number-average molecular weight increased with monomer concentration and after the addition of a fresh feed of the monomer at the end of the first polymerization step. This behavior has been observed in media of different polarity, that is, S02/toluene = 80 : 10 or 50 : 40 vlv and S02/CH2C12 = 20 : 70 v/v. 'H NMR spectroscopy revealed the presence of aldehyde terminal group derived from acetal end group, indicating the presence of living or long-lived propagating species. The average number of polymer chains carrying aldehyde end groups is higher than the initial iodine concentration, suggesting that an additional initiation process by hydrogen iodide is taking place.

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