Rapid approach to biobased telechelics through two one-pot thiol-ene click reactions.
The application of environmentally friendly thiol-ene chemistry to the preparation of biobased telechelics is presented in this work. This methodology is based on two one-pot photoinitiated thiol-ene click processes: step-growth polymerization using a 3,6-dioxa-1,8-octanedithiol and end-group postpolymerization modification with three functional thiols: 2-mercaptoethanol, 3-mercaptopropionic acid, and 3-mercaptopropyltrimethoxysilane. We applied this approach to a potentially 100% biomass-derived monomer, allyl ester of 10-undecenoic acid (UDA). To show the generality and scope of this methodology, a series of well-defined telechelics with molecular weight ranging from 1000-3000 g/mol and hydroxyl, carboxyl, or trimethoxysilyl groups at the polymer terminus were prepared. An exhaustive (1)H NMR and MALDI-TOF MS analyses demonstrates the highly end-group fidelity of this methodology being an interesting procedure for the accelerated preparation of telechelics derived from divinyl monomers. UDA-based thelechelic diol prepared using this methodology was reacted with 4,4'-methylenebis(phenylisocyanate) and 1,4-butanediol as the chain extender to obtain multiblock poly(ester urethane).
Lluch
Cristina
C
Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili, C/Marcel.li Domingo s/n, 43007 Tarragona, Spain.
Ronda
Joan C
JC
Galià
Marina
M
Lligadas
Gerard
G
Cádiz
Virginia
V
D000498:Allyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D002368:Castor Oil / Q000737:chemistry*; D005229:Fatty Acids, Monounsaturated / Q000737:chemistry* / Q000302:isolation & purification; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D008970:Molecular Weight; D011091:Polyesters / Q000138:chemical synthesis* / Q000737:chemistry; D011140:Polyurethanes / Q000138:chemical synthesis* / Q000737:chemistry; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D014476:Undecylenic Acids
D000498:Allyl Compounds; D005229:Fatty Acids, Monounsaturated; D011091:Polyesters; D011140:Polyurethanes; D013438:Sulfhydryl Compounds; D014476:Undecylenic Acids; C081821:microthane foam; D002368:Castor Oil; C538763:undecylenic acid