Thermal stabilities of end groups in hydroxyalkyl terminated polydimethylsiloxane oligomers

TLDR: In this paper, the authors studied the thermal stabilities of α,ω-hydroxyhexyl terminated polydimethylsiloxane (PDMS) oligomers and showed that the loss of functional end groups is due to the back biting of the terminal silicon in the PDMS by the primary hydroxyl oxygen.

Abstract: Thermal stabilities of α,ω-hydroxypropyl, α,ω-hydroxybutyl, α,ω-2-hydroxypentyl and α,ω-hydroxyhexyl terminated polydimethylsiloxane (PDMS) oligomers were studied. Hydroxypropyl and hydroxybutyl terminated polydimethylsiloxane oligomers showed degradation upon heating, through the loss of functional end groups as determined by FT-IR spectroscopy and gel permeation chromatography. α,ω-Hydroxyhexyl and α,ω-2-hydroxypentyl terminated polydimethylsiloxane oligomers were stable under similar conditions. Instability of the end groups is due to the back biting of the terminal silicon in the PDMS by the primary hydroxyl oxygen, leading to the formation of 5 and 6 membered, stable, heterocylic compounds. Loss of end groups also resulted in a dramatic increase in the molecular weights of the oligomers produced, as determined by gel permeation chromatography.