Can Hyperbranched Polymers Entangle? Effect of Hydrogen Bonding on Entanglement Transition and Thermorheological Properties of Hyperbranched Polyglycerol Melts

Melt rheology and thermal phase transition of a series of hyperbranched polyglycerol samples (hbPG) (DB ≈ 60%) in a broad molecular weight range (Mn = 600–440 000 g/mol) were investigated and correlated to both molecular weight and nature of the end group (hydroxyl vs permethylated and trimethylsilylated). The well-characterized and defined flexible polyethers are particularly suitable to shed light on the linear viscoelastic behavior with respect to (i) hyperbranched topology and (ii) hydrogen bond interactions, particularly in comparison to the perfectly linear polyglycerol counterparts studied recently [Osterwinter, C.; Macromolecules 2015, 48, 119−130]. We present a detailed examination…

Systematic Variation of the Degree of Branching (DB) of Polyglycerol via Oxyanionic Copolymerization of Glycidol with a Protected Glycidyl Ether and Its Impact on Rheological Properties

Rheological Consequences of Hydrogen Bonding: Linear Viscoelastic Response of Linear Polyglycerol and Its Permethylated Analogues as a General Model for Hydroxyl-Functional Polymers

Viscoelastic properties of linear, hydroxyl-functional polymers are only little understood with respect to the effect of functional group interactions. Melt rheology and thermal phase transitions of linear polyethers (polyglycerol, linPG-OH) and their methylated analogues (linPG-OMe) in a broad molecular weight range (Mn = 1–100 kg/mol) with low polydispersities (PDI) have been investigated as a general model for hydroxyl-functional polymers with respect to their functionality and hydrogen bond interactions. We provide detailed insight into the rheodynamics of nonentangled and well-entangled polyethers bearing one functional group per monomer unit. Booij–Palmen plots (BBP) revealed failure …

Synthesis of linear polyglycerols with tailored degree of methylation by copolymerization and the effect on thermorheological behavior

Abstract We introduce a two-step strategy for the synthesis of linear polyglycerols (linPG-OHx/OMey) with an adjustable degree of methylation ( y = D M 100 ). Ethoxy ethyl glycidyl ether (EEGE) and glycidyl methyl ether (GME) were copolymerized via the “activated monomer” polymerization technique, using tetraoctylammonium bromide (NOct4Br) as an initiator and triisobutylaluminum (i-Bu3Al) as a catalyst under mild conditions. Subsequent acidic cleavage of the acetal protective groups generates linear polyglycerols with different degree of methylation (DM) by varying the GME comonomer content between 10 and 91%. Size exclusion chromatography (SEC) evidenced good control over molecular weight …