Biosourced phenols derived triphenylphosphates: A type of versatile additive covering iron, chromium and molybdenum catalyzed 1,2-insertion polymerization of 1,3-butadiene

Exploration of a versatile additive applicable to various metal catalysts for polymerization of 1,3-diene, unfortunately, has been unsuccessful due to the distinctive nature of metal centre. A novel class of phosphates derived from biosourced Guaiacol, p-Eugenol, Vanillin and Mequinol have been designed and synthesized in this work. These compounds can work well with iron, chromium and molybdenum catalysts as additive to actively catalyse butadiene polymerization. It has been revealed that the use of them is critically important to induce 1,2 enriched insertion along with a syndiotactic mode throughout the polymerization. An array of polybutadienes differs in not only the 1,2 incorporation, tacticity, but molecular weight, thus materials spanning from soft viscoelastic to tough elastomers and rigid plastics, have been obtained. It is rare that introduction of additive confers the catalysts so impressive performances simultaneously, including wider metal adaptability, high catalytic activity, mainly 1,2 regio- and tunable stereoselectivity, and strong thermal tolerance. DFT calculation is also carried out to shed light on the role of the ortho-positioned methoxyl moiety.