One‐Pot Two‐Step Synthesis of Hydroxymethylated Unsaturated VHOSO and Its Application to the Synthesis of Biobased Polyurethanes

Abstract

A one-pot two-step procedure is developed to catalytically convert very high-oleic sunflower oil (VHOSO) into hydroxymethylated unsaturated derivatives featuring both primary alcohols and carbon-carbon double bonds. The degree of functionalization in alcohols and C═C double bonds can be accurately controlled affording low and high substituted hydroxymethylated VHOSO. The key point to achieve such control is to partly hydroformylate the C═C bonds at 80°C and to subsequently reduce the reaction temperature to 20°C to selectively reduce the aldehydes, while keeping a high CO/H 2 pressure. Step-growth polymerization of highly substituted hydroxymethylated VHOSO with cyclohexyl isocyanate or 4,4ʹ-methylenebis(cyclohexyl isocyanate) furnishes biobased polyurethanes with improved thermal stability compared to similar polyurethanes synthesized from castor oil. Practical Applications: This study highlights the implementation of triglycerides featuring both C═C double bonds and hydroxymethyl groups. The synthesis proceeds through a one-pot two-steps procedure that consists of a hydroformylation reaction at 80°C followed by a hydrogenation reaction carried out at room temperature. This simple synthetic procedure is of major interest in a context of an industrial-environmental approach. The high reactivity of the obtained primary alcohols allows the synthesis of bio-PUs, displaying untouched C═C double bonds, which could be further functionalized. This finding is of importance as the obtained bio-PUs can be used in many industrial areas such as foams, elastomers, thermoplastics, thermosets, adhesives, coatings, sealants and fibers.

Hydrohydroxymethylation of Ethyl Ricinoleate and Castor Oil

“…This simple Rh/tertiary amine catalytic system has been successfully used to achieve the hydrohydroxymethylation of triglycerides into hydroxylated triglycerides. 16,17 Surprisingly, this one-pot reaction with a single catalyst was never applied to castor oil and its derivatives. Castor and its derived oil, the so-called "castor oil", are known from the ancient times when the oil was used for cosmetics, or as a laxative, or as a fuel in lamps.…”

“…In this way, Rh catalysts associated to tertiary amines are able to hydroformylate CC bonds and to hydrogenate the resulting aldehydes into alcohols. − Contrary to most of the procedures described in the literature, no oxidable phosphane was used to coordinate Rh species, thus giving this strategy an industrial potential. This simple Rh/tertiary amine catalytic system has been successfully used to achieve the hydrohydroxymethylation of triglycerides into hydroxylated triglycerides. , Surprisingly, this one-pot reaction with a single catalyst was never applied to castor oil and its derivatives. Castor and its derived oil, the so-called “castor oil”, are known from the ancient times when the oil was used for cosmetics, or as a laxative, or as a fuel in lamps. − Nowadays, castor oil has a completely renewed interest, not for its direct applications, but owing to various possibilities in chemical modifications.…”

Synthesis of diols from jojoba oil via rhodium-catalyzed reductive hydroformylation: a smart way to access biobased polyurethanes

“…In order to develop a synthesis route of this diol compound more in line with industry requirements (no stoichiometric reagents such as EtAlCl 2 , high reaction selectivity), a catalytic way involving a rhodium/tertiary amine system was used in this study (Scheme 3(b)). Such Rh/tertiary amine catalytic systems have proven to be highly active in the reductive hydroformylation of various oleochemicals, [25][26][27][28] carbohydrates 29 or petroleum based olefins. [30][31][32][33][34][35][36] In this respect, the catalytic system combining Rh(acac) (CO) 2 and triethylamine was evaluated in the HHM of jojoba oil.…”