Normal-phase (temperature gradient) interaction chromatography – A powerful tool for the characterisation of high molecular weight chain-end functionalised polymers

Abstract

(2015) 'Normal-phase (temperature gradient) interaction chromatography A powerful tool for the characterisation of high molecular weight chain-end functionalised polymers.', European polymer journal., 73 . pp. 105-115. Further information on publisher's website: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. is all the more remarkable that complete (baseline) resolution can be achieved for two polymers with an identical molar mass (< 200,000 gmol -1 ), which differ only in that one sample is functionalised with a single primary alcohol group.

End‐Functionalized Chains via Anionic Polymerization: Can the Problems with Using Diphenylethylene Derivatives be Solved by using Bisphenol F?

“…Following deprotection, a significant decrease in the intensity of the peak at ≈2 mL can be seen, accompanied by a new peak at 3.9 mL, which can be ascribed to the deprotected polymer. This is consistent with the stronger interaction between the OH groups and the polar column, compared to the interaction between the protected OH groups and the same polar column—moreover, this has been previously reported . Analysis of the area under the peak indicates that the deprotected, functionalized polymer represents about 65% of the total mass of sample.…”

“…The synthesis of linear polybutadiene arms, with a molecular weight of about 40 000 g mol −1 (PB40‐Br), was performed in benzene using sec ‐BuLi as initiator and the chain‐end functionality was introduced via an end‐capping reaction of the living polymer with ethylene oxide, as described elsewhere . In a typical reaction, PB40‐Br (1.78 g, 0.044 mmol), deprotected end‐capped polystyrene ePS‐OH (0.20 g, 0.017 mmol), and cesium carbonate (Cs 2 CO 3 ) (0.11 g, 0.35 mmol) were dissolved in 10 mL of dry THF under an inert atmosphere of nitrogen.…”

“…Reversed phase (RP) TGIC resolves polymer samples based on molecular weight, not hydrodynamic volume, and thus is a powerful tool for studying the structural heterogeneity of branched polymers, a field that has been recently reviewed . Normal phase (NP) TGIC has only been applied in a few cases, for the resolution of polymers in terms of functionality and molecular weight, with polymer separation achieved by partition between a polar stationary phase (bare silica or diol bonded silica) and a less polar mobile phase . Most recently it has been shown that end‐functionalized polymers can be resolved from unfunctionalized polymers of identical molar mass, for polymers with molecular weights up to 200 000 g mol −1 —at such molecular weights any attempt to analyse the extent of end‐functionalization by NMR or MALDI‐ToF MS would be an exercise in futility.…”

Temperature Gradient Interaction Chromatography: A Perspective

“…The NP-TGIC separation of homopolymers with different functional groups has been successfully achieved by our group [38,39], showing that it is possible to follow chain end functional group transformations and to obtain successful separation of chains with a molar mass of up to 200,000 g mol −1 which differ only by the presence of a single primary alcohol functionality at the chainend [39]. At such molar masses, any attempt to identify the presence of, or to attempt to quantify the extent of end-functionalization by NMR or MALDI-ToF MS would be an act of futility.…”