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Catalytic Oxyfunctionalization of Methyl 10‐undecenoate for the Synthesis of Step‐Growth Polymers
Author(s) -
Czapiewski Marc,
Meier Michael A. R.
Publication year - 2017
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.201700153
Subject(s) - transesterification , chemistry , polyester , catalysis , monomer , polymer chemistry , organic chemistry , polyamide , polymer
An efficient synthesis strategy for the preparation of two renewable polyesters and one renewable polyamide via catalytic oxyfunctionalization of methyl 10‐undecenoate, a castor oil derived platform chemical, is described. The keto‐fatty acid methyl ester (keto‐FAME) is synthesized applying a cocatalyst‐free Wacker oxidation process using a high‐pressure reactor system. For this purpose, catalytic amounts of palladium chloride are used in the presence of a dimethylacetamide/water mixture and molecular oxygen as sole reoxidant. The thus derived AB monomers (hydroxy‐esters, amine‐ester) are synthesized from the obtained keto‐FAME through Baeyer–Villiger oxidation and subsequent transesterification, reduction, or reductive amination, respectively. The resulting AB step‐growth monomers are then studied in homopolymerizations using 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene, DBU, and titanium(IV) isopropoxide as transesterification catalyst, yielding polymers with molecular weights ( M n ) up to 15 kDa. The polyesters and the polyamide are carefully characterized by FTIR, SEC, 1 H‐NMR spectroscopy, and differential scanning calorimetry analysis.