Multiphase telomerisation of butadiene with phenol: optimisation and scale-up in different reactor types

Abstract

The telomerisation with phenol is an efficient way to convert the well accessible 1,3-butadiene into products of higher value. This article describes the optimisation of this reaction both on a laboratory scale using a novel multiphase semi-batch mode and in a loop reactor as an alternative concept for a continuous operation mode. The optimised parameters are applied in a miniplant offering an interesting salt-free route to octadienylphenols.

Pd-Catalyzed Telomerization of 1,3-Dienes with Multifunctional Renewable Substrates: Versatile Routes for the Valorization of Biomass-Derived Platform Molecules

“…Behr et al [114] investigated the selective formation of octadienyl phenol ethers in a liquid-liquid biphasic loop reactor. Although the Pd/TPPTS system showed good activity and selectivity (86% conversion with 74% selectivity towards the telomer after 5 h) in a lab-scale batch reactor, telomer yields in the loop reactor were insufficient for efficient phase separation.…”

“…The latter step will be slow, but does provide an irreversible thermodynamic sink. Both the ether as well as the alkylated phenol products can serve as the building blocks for various applications including insecticides or pheromones [114]. The C-alkylated products have the advantage that the phenol group is still available for further modification.…”

Neue Trends in der homogenen Übergangsmetallkatalyse

“…In den letzten Jahren ist diese Reaktion weiter untersucht worden. Interessant ist die Umsetzung von Butadien mit Phenol zu Phenoxyethern, die in den Miniplant-Maßstab überführt wurde [154]. Wenn es gelingt, die Ligninkomponente aus der Lignocellulose gezielt in substituierte Phenole abzubauen, könnten diese biobasierten Nucleophile ebenfalls durch Telomerisation in Wertprodukte überführt werden [155].…”

Palladium-Catalyzed Functionalization of Kraft Lignin: Ether Linkages through the Telomerization Reaction

“…[12][13][14] More recently,t he use of catalytic andc lean reactions to allylate the hydroxyl groups in lignins has emerged as an important issue. [19,20] In comparison to other allylation reactions used with lignins, the telomerization reaction allows grafting longerb is-unsaturated aliphatic tails (i.e.,2 ,7-octanienyl chains) according to ah ighly atom-economical reaction. In this context, we show in the present contribution that the 1,3-butadiene telomerization reaction [16] is an efficient method to functionalize phenolic/aliphatich ydroxyl groups of an industrial grade kraft lignin with allylic octadienylc hains (Scheme 1).…”

“…This reactiono f industrial relevance for the productiono f1 -octene from 1,3butadiene has been essentially described so far with small aliphatic alcohols and polyols, [17] carboxylic acids, [18] ands ubstituted phenols. [19,20] In comparison to other allylation reactions used with lignins, the telomerization reaction allows grafting longerb is-unsaturated aliphatic tails (i.e.,2 ,7-octanienyl chains) according to ah ighly atom-economical reaction.…”