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dc.contributor.authorBouchekif, Hassen
dc.contributor.authorSulhami, A. I.
dc.contributor.authorAlGhamdi, Rayed D.
dc.contributor.authorGnanou, Yves
dc.contributor.authorHadjichristidis, Nikos
dc.date.accessioned2015-08-03T12:20:22Z
dc.date.available2015-08-03T12:20:22Z
dc.date.issued2015
dc.identifier.issn17599954
dc.identifier.doi10.1039/c4py01728e
dc.identifier.urihttp://hdl.handle.net/10754/563943
dc.description.abstractA series of novel, well-defined triblock (PnBVE-b-PCEVE-b-PSiDEGVE) and pentablock (PSiDEGVE-b-PCEVE-b-PnBVE-b-PCEVE-b-PSiDEGVE) terpolymers of n-butyl vinyl ether (nBVE), 2-chloroethyl vinyl ether (CEVE) and tert-butyldimethylsilyl ethylene glycol vinyl ether (SiEGVE) were synthesized by sequential base-assisted living cationic polymerization. The living character of the homopolymerization of the three VE monomers and the crossover reaction resulting in the formation of well-defined block copolymers were investigated in various solvents (toluene, dichloromethane and n-hexane) using either a monofunctional [nBVE-acetic acid adduct (nBEA), CEVE-acetic acid adduct (CEEA) and SiDEGVE-acetic acid adduct (SiDEGEA)] or a difunctional [1,4-cyclohexane-1,4-diyl bis(2-methoxyethyl acetate) (cHDMEA)] initiator. All initiators are structurally equivalent to the dormant species of the corresponding monomers in order to achieve fast initiation. The optimal conditions of polymerization were achieved in n-hexane at -20 °C, in the presence of 1 M AcOEt (base). Good control over the number average molecular weight (Mn) and the polydispersity index (PDI) was obtained only at [Et3Al2Cl3]0 = [Chain-end]0 ≤ 10 mM. 2,6-Di-tert-butylpyridine (DtBP) was used as a non-nucleophilic proton trap to suppress any protonic initiation from moisture (i.e., Et3Al2Cl3·H2O). Well-defined PnBVEn-b-PCEVEp-b-PSiDEGVEq and PSiDEGVEq-b-PCEVEp-b-PnBVEn-b-PCEVEp-b-PSiDEGVEq terpolymers with a high crossover efficiency, no PCEVE-induced physical gelation, and predictable Mn and PDI < 1.15 were synthesized successfully provided that the targeted DPCEVE/DPnBVE ratio (i.e., p/n) did not exceed 2 and 0.2, respectively. The quantitative desilylation of the PSiEGVE by n-Bu4N+F- in THF at 0 °C led to triblock and pentablock terpolymers in which the PCEVE is the central block and the polyalcohol is the outer block. The thermal properties of the synthesized materials were examined by differential scanning calorimetry. This journal is
dc.description.sponsorshipThis research was financially supported by King Abdullah University of Science and technology.
dc.publisherRoyal Society of Chemistry (RSC)
dc.titleTriblock and pentablock terpolymers by sequential base-assisted living cationic copolymerization of functionalized vinyl ethers
dc.typeArticle
dc.contributor.departmentChemical Science Program
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.contributor.departmentPolymer Synthesis Laboratory
dc.identifier.journalPolym. Chem.
kaust.personBouchekif, Hassen
kaust.personGnanou, Yves
kaust.personHadjichristidis, Nikos
kaust.personSulhami, A. I.
kaust.personAlGhamdi, Rayed D.


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