Synthesis of Amorphous Hydrophobic Telechelic Hydrocarbon Diols via ADMET Polymerization

Abstract

Amorphous, hydrophobic telechelic hydrocarbon diols were synthesized using acyclic diene metathesis (ADMET) polymerization. These diols can be used in hydrolysis and UV resistant polyurethanes. The hydrocarbon backbone is based on a mimic of an ethylene/isobutylene polymer, made by the ADMET polymerization of a gem‐dimethyl substituted α,ω‐diene followed by hydrogenation of the polymer's repeat unit unsaturation. Chain termination reactants (CTR's) having one, three, and nine methylene “spacers,” respectively, between their olefin and alcohol precursor group were used to cap the polymer chain ends to yield 2.0 functional telechelics. Use of the medium length CTR in a polymerization–depolymerization scheme, resulted in amorphous (Tg = −56 °C) telechelic diols with good molecular weight control.magnified image

Post‐Functionalization of Polymers via Orthogonal Ligation Chemistry

“…Furthermore, Wagener et al228 prepared a series of ADMET polyethylene analogues containing randomly placed alcohol and acetate groups. Schwendeman and Wagener229 prepared amorphous, hydrophobic telechelic hydrocarbon diols using ADMET. The hydrocarbon backbone is based on a polymer of a gem ‐dimethyl‐substituted α,ω‐diene followed by hydrogenation of the polymer's repeat unit.…”

Reactive poly(phosphoester)-telechelics

“…Typically, these groups are protected in order to minimize catalyst quenching. [17,22] In general, ADMET polymerization produces linear telechelic materials as they carry two terminal olefinic end groups (if no isomerization takes place during the polymerization [10]). Herein, we investigated the synthesis of several PPE telechelics.…”

“…useful for the straightforward preparation of telechelics. [16,17] A combination of ADMET with the previously mentioned versatility of the phosphorus chemistry results in a highly adaptable and general protocol to design unsaturated biodegradable polyesters. [18] These polymers can be tailored at various positions: i) at the pendant phosphate ester, ii) at the internal double bonds that are inherent to the metathesis process, and iii) on the orthogonal end groups that are introduced by the chain termination agent in quantitative yield.…”

Precision Polymers through ADMET Polymerization

“…Amorphous, hydrophobic telechelic diols that may be used in hydrolysis‐ and UV‐resistant polyurethanes have also been synthesized by ADMET . ADMET polymerization and subsequent hydrogenation of a gem‐dimethyl‐substituted α,ω‐diene produced the hydrocarbon backbone, which was endcapped by alcohol‐containing monoenes having a varied number of methylene units between their olefin and alcohol precursor group.…”