Synthesis of poly(1,2-butylene oxide-stat-tetrahydrofuran) by controllable polymerization over Sc(OTf)3 for use in high-performance lubricating oil

Abstract

Aliphatic polyethers are synthesized byring-opening polymerization (ROP) of the most common epoxide monomers, such as ethylene oxide (EO) and propylene oxide (PO). 1,2-Butylene oxide (BO) and tetrahydrofuran (THF) are potentially extended ROP monomers, which can give polyether unique properties. In this work, a series of poly(1,2-butylene oxide-stat-tetrahydrofuran)s (PBO-stat-PTHFs) with Mn of 900–3700 g·mol−1 were synthesized by cationic ring-opening polymerization (CROP) of BO with THF using strong Lewis acid Rare Earth triflates (RE(OTf)3) as catalysts and diols as an initiator at room temperature. PBO-stat-PTHFs product with yield up to 90 %, narrow polydispersity of Đ <1.30, and molar ratio of PBO to PTHF 1:1 were obtained. The copolymerization process was studied by in-situ IR and 1H NMR spectroscopy analysis, and the results showed that PBO-stat-PTHF is a statistical copolymer. The early stage of the polymerization reaction was dominated by the activated chain end mechanism (ACEM), which incorporates a large amount of THF into the polymer chains. However, the late stage of the polymerization reaction was dominated by the activated monomer mechanism (AMM), which incorporates a large amount of BO into the polymer chains. Most PBO-stat-PTHFs have a suitable Mn range, super high viscosity index (≥198) and low pour point (≤-53 °C), which can be used as a lubricant base oil and additives. In addition, PBO-stat-PTHFs have excellent miscibility with polyalphaolefin (PAO), which could significantly improve the PAO viscosity index. This study provides a mild route to construct high-performance copolyether materials through cationic ring-opening controllable polymerization.