Near-monodisperse,n-alkyl, end-functionalized poly(methyl vinyl ether)s: Synthesis by living cationic polymerization and solution characterization

Abstract

Water‐soluble amphiphilic diblock copolymers were synthesized by the living cationic polymerization of methyl vinyl ether (hydrophilic block) and its subsequent termination with n‐alcohols of chain lengths varying from one to eight, and three n‐alkyl carboxylic acids with 10, 12, and 18 carbon atoms. Additionally, water and ethylene glycol were tested as terminating agents. The extent of the functionalization was determined using 1H NMR spectroscopy. The cloud points of 1% w/w aqueous solutions of the polymers as determined by turbidimetry decreased from 32 to 21°C as the number of carbon atoms of the terminating agent increased. Aqueous GPC revealed micellization of the stearic acid‐terminated block copolymer, while the other block copolymers existed mainly as unimers. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2547–2554, 1998

Functionalized Thermo‐Responsive Poly(vinyl ether) by Living Cationic Random Copolymerization of Methyl Vinyl Ether and 2‐Chloroethyl Vinyl Ether

“…The experimental data summarized in Table 4 clearly indicate a well-controlled copolymerization process with narrow PDI (1.03-1. 16) and a good agreement between the M n;theoretical and the M n;NMR . SEC analysis [ Figure 4(a)] shows a unimodal distribution, no 'tailing' to low molecular weight and the absence of any homo-PMVE or homo-PCEVE in the final products.…”

“…The thermo-responsive PMVE, widely studied by ourselves [3,15] and others, [16][17][18] features not only excellent thermo-responsive properties but has also a predetermined structure with a control over molecular weight and narrow polydispersity. The cationic polymerization of alkyl vinyl ethers (VEs) has been known for a long time, [19] and several polymers are or have been produced.…”

Block Copolymers of Methyl Vinyl Ether and Isobutyl Vinyl Ether With Thermo‐Adjustable Amphiphilic Properties

“…Inversely, it was expected that the opposite monomer addition sequence (living PMVE þ IBVE) would result in an unacceptably fast second-stage polymerization of IBVE as the ZnI 2 concentration, necessary for the polymerization of MVE, is 20 times higher than that normally used for the IBVE (homo)polymerization. However, the results in Table 2 demonstrate that this was not the [14,15] (taking into account the hydrodynamic differences between the polystyrene calibration standards and PMVE) cannot be used for the determination of the exact molecular weight of the PMVE-PIBVE block copolymers. e) M n (NMR) ¼ calculated from the ratio of the MVE/IBVE groups to the initiator and/or acetal end groups.…”

“…b) M n (SEC, PMVE) ¼ the molecular weight of PMVE homopolymers, taking into account the hydrodynamic differences between the polystyrene calibration standards and PMVE, which leads to an overestimation of PMVE molecular weight by a factor of 2. [14,15] c) Additional amount of ZnI 2 added during polymerization of the second PIBVE block;/means that no ZnI 2 has been added. d) The correction factor 0.5 can not be used for the determination of the exact molecular weight of the PMVE-PIBVE block copolymers.…”

Association behavior of thermo-responsive block copolymers based on poly(vinyl ethers)

“…These observations are consistent with the results of Faust [24] and Armes [25] for other PMVE-based block copolymers. In order to investigate the micellization behavior of these block copolymers in water, we selected for this study highly asymmetric AB and ABA block copolymers with a major PMVE block.…”