In: Angewandte Chemie International Edition, 2018, vol. 57, no. 4, p. 914–917
Heterotelechelic polymers were synthesized by a kinetic telechelic ring-opening metathesis polymerization method relying on the regioselective cross-metathesis of the propagating Grubbs’ first-generation catalyst with cinnamyl alcohol derivatives. This procedure allowed the synthesis of hetero-bis-end-functional polymers in a one- pot setup. The molecular weight of the polymers could be...
|
In: Macromolecules, 2017, vol. 50, no. 23, p. 9307–9314
Herein we report the facile synthesis of an amphiphilic rod–coil block copolymer obtained by the coupling of an amine-terminated poly(dimethylpropylamine norbornene imide) (PDMAPNI) and a pentafluorophenol ester-terminated poly(dimethoxybenzyl p-aminobenzoate) (PAram). Postpolymerization amide N- deprotection of the block copolymer yielded a strongly aggregating water-soluble rod– coil...
|
In: Macromolecules, 2017, vol. 50, no. 11, p. 4188–4197
The polymerization of aromatic para-amino acid ester derivatives was studied using model compounds. Mechanistic and kinetic experiments led to the discovery of some side reactions. Finally, high molecular weight poly(p-benzamide)s were synthesized and characterized. The use of highly reactive pentafluorophenol ester lead to polymers up to molecular weights of around 50 000 Da....
|
In: Journal of Polymer Science Part A: Polymer Chemistry, 2017, vol. 55, no. 18, p. 2983–2990
Functional enolethers have previously been used to introduce functional end groups at the chain end of ruthenium carbene complex initiated living ring opening metathesis polymers. Here, we investigated whether the weaker π-donating enolesters could equally be used in regio selective reactions with ruthenium carbene complexes and thus as polymer end-functionalization reagents. Enolesters such as...
|
In: CHIMIA, 2017, p. 195-198
|
In: Angewandte Chemie International Edition, 2016, vol. 55, no. 40, p. 12343–12346
Use of a tandem ring-opening–ring-closing metathesis (RORCM) strategy for the synthesis of functional metathesis catalysts is reported. Ring opening of 7-substituted norbornenes and subsequent ring-closing metathesis forming a thermodynamically stable 6-membered ring lead to a very efficient synthesis of new catalysts from commercially available Grubbs’ catalysts. Hydroxy functionalized...
|
In: Physical Chemistry Chemical Physics, 2016, vol. 18, no. 45, p. 31202–31210
Cis-to-trans isomerization of carbon–carbon double bonds can be induced by the application of mechanical force. Using single molecule force spectroscopy by means of atomic force microscopy (AFM) we pulled polymer molecules which contained cis double bonds in the backbone. In the force versus extension profiles of these polymers, a sudden extension increase is observed which is due to the...
|
In: Journal of Polymer Science Part A: Polymer Chemistry, 2016, vol. 54, no. 9, p. 1236–1242
In an attempt to introduce monomer sequence control in a growing polynorbornene via ring-opening metathesis polymerization, we employ dioxepins to efficiently determine the location of the monomers on the macromolecule backbone. Owing to the acid-labile acetal group, dioxepins allow scission of the polymer at the point of the dioxepin insertion and thus provide an indirect way to determine...
|
In: Macromolecular Rapid Communications, 2016, vol. 37, no. 6, p. 532–538
Today's olefin metathesis catalysts show high reactivity, selectivity, and functional group tolerance and allow the design of new syntheses of precisely functionalized polymers. Here the synthesis of a new end-capping reagent is investigated allowing the introduction of a highly reactive activated ester end-group at the polymer chain end as well as its prefunctionalization to directly...
|
In: Macromolecules, 2016, vol. 49, no. 5, p. 1630–1636
The ultrasound-induced cleavage of macromolecules has become a routine experiment in the emerging field of polymer mechanochemistry. To date, it has not been conclusively proven whether the molecular weight of a polymer or its contour length is the determining factor for chain scission upon ultrasonication. Here we report comparative experiments that confirm unequivocally that the contour length...
|
