Degree of branching of highly branched polyurethanes synthesized via the Oligomeric A2 Plus B3 methodology

Ann R. Fornof; Thomas E. Glass; Timothy Edward Long

doi:10.1002/macp.200600096

Degree of branching of highly branched polyurethanes synthesized via the Oligomeric A₂ Plus B₃ methodology

Ann R. Fornof, Thomas E. Glass, Timothy Edward Long^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

43 Citations (Scopus)

Abstract

The oligomeric A₂ plus monomeric B₃ synthetic methodology provided highly branched, poly(ether urethane)s based on IMP (B ₃) and isocyanate endcapped polyethers. ¹³C NMR spectroscopic assignments for the branched polyurethanes were verified using model urethane-containing compounds based on TMP and a monofunctional isocyanate (either cyclohexyl or phenyl isocyanate (PI)). Derivatization of hydroxyl endgroups with trifluoroacetic anhydride enhanced the ¹³C NMR resolution in spectra for branched polyurethanes. The ¹³C NMR resonance for the linear unit exhibited a broad shoulder due to quaternary carbons that were attributed to cyclic species in the highly branched polyurethanes. The classical DB calculation revealed the efficiency of the 83 monomer for branching; however, an equation that incorporated the linear contribution of the A₂ oligomer provided a more accurate DB for highly branched polyurethanes.

Original language	English
Pages (from-to)	1197-1206
Number of pages	10
Journal	Macromolecular Chemistry and Physics
Volume	207
Issue number	14
DOIs	https://doi.org/10.1002/macp.200600096
Publication status	Published - 2006 Jul 24
Externally published	Yes

Keywords

C NMR spectroscopy
Degree of branching
Highly branched
Hyperbranched
Polyurethanes

ASJC Scopus subject areas

Condensed Matter Physics
Physical and Theoretical Chemistry
Polymers and Plastics
Organic Chemistry
Materials Chemistry

Access to Document

10.1002/macp.200600096

Cite this

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title = "Degree of branching of highly branched polyurethanes synthesized via the Oligomeric A2 Plus B3 methodology",

abstract = "The oligomeric A2 plus monomeric B3 synthetic methodology provided highly branched, poly(ether urethane)s based on IMP (B 3) and isocyanate endcapped polyethers. 13C NMR spectroscopic assignments for the branched polyurethanes were verified using model urethane-containing compounds based on TMP and a monofunctional isocyanate (either cyclohexyl or phenyl isocyanate (PI)). Derivatization of hydroxyl endgroups with trifluoroacetic anhydride enhanced the 13C NMR resolution in spectra for branched polyurethanes. The 13C NMR resonance for the linear unit exhibited a broad shoulder due to quaternary carbons that were attributed to cyclic species in the highly branched polyurethanes. The classical DB calculation revealed the efficiency of the 83 monomer for branching; however, an equation that incorporated the linear contribution of the A2 oligomer provided a more accurate DB for highly branched polyurethanes.",

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AU - Glass, Thomas E.

AU - Long, Timothy Edward

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AB - The oligomeric A2 plus monomeric B3 synthetic methodology provided highly branched, poly(ether urethane)s based on IMP (B 3) and isocyanate endcapped polyethers. 13C NMR spectroscopic assignments for the branched polyurethanes were verified using model urethane-containing compounds based on TMP and a monofunctional isocyanate (either cyclohexyl or phenyl isocyanate (PI)). Derivatization of hydroxyl endgroups with trifluoroacetic anhydride enhanced the 13C NMR resolution in spectra for branched polyurethanes. The 13C NMR resonance for the linear unit exhibited a broad shoulder due to quaternary carbons that were attributed to cyclic species in the highly branched polyurethanes. The classical DB calculation revealed the efficiency of the 83 monomer for branching; however, an equation that incorporated the linear contribution of the A2 oligomer provided a more accurate DB for highly branched polyurethanes.

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