High‐Performance Polymers from Nature: Catalytic Routes and Processes for Industry

Abstract

It is difficult to imagine life today without polymers. However, most chemicals are almost exclusively synthesized from petroleum. With diminishing oil reserves, establishing an industrial process to transform renewables into high-value chemicals may be more challenging than running a car without gasoline. This is due to the difficulty in setting up processes that are novel, profitable, and environmentally benign at the same time. Additionally, the quest for sustainability of renewable resources should be based on incorporating ethical considerations in the development of plans that utilize feedstocks intended for human nutrition and health. Thus, it is important to use bio-energy containing renewable resources in the most efficient way. This Concept goes beyond the synthesis of monomers and provides insights for establishing an industrial process that transforms renewable resources into high-value chemicals, and it describes careful investigations that are of paramount importance, including evaluations from an economical and an ecological perspective. The synthesis of monomers suitable for polymer production from renewable resources would ideally be accompanied by a reduction in CO2 emission and waste, through the complete molecular utilization of the feedstock. This Concept advocates the drop-in strategy, and is guided by the example of catalytically synthesized dimethyl 1,19-nonadecanedioate and its α,ω-functionalized derivatives. With respect to the Twelve Principles of Green Chemistry, this Concept describes a technological leap forward for a sustainable green chemical industry.

Palladium‐Catalyzed Aminocarbonylation of Aliphatic Alkenes with N,N‐Dimethylformamide as an In Situ Source of CO

“…To the best of our knowledge, it is the first time only two equivalents of the 1,2‐DTBPMB ligand are used in a carbonylation reaction providing such high n : iso ratios. Usually four, five equivalents or more are used …”

“…In our ongoing interest in palladium‐catalyzed carbonylation reactions, especially with the high‐performance ligand involved in the methoxycarbonylation of aliphatic alkenes for the production of linear esters, 1,2‐bis((di‐ tert ‐butylphosphino)methyl)benzene (1,2‐DTBPMB, Figure ), we developed the idea of aminocarbonylation of linear aliphatic 1‐alkenes with formamides using this catalytic system. Based on the reports on the alkoxycarbonylation of alkenes with formates and our latest investigations in aminocarbonylation with CO applying this catalyst system, we herein report the palladium‐catalyzed aminocarbonylation of aliphatic alkenes with DMF as an in situ source of carbon monoxide and dimethylamine.…”

Aprovechamiento de recursos renovables en la obtención de nuevos materiales

“…A partir de monómeros derivados de recursos naturales y mediante síntesis química se pueden convertir en biomateriales [1,2,4,5,[34][35][36][37][38] como los poliésteres y el PLA. Un ejemplo es el enunciado por Dai y Qiu en 2016, en el que, por medio de una policondensación, en dos etapas, sintetizan materiales biodegradables: tres nuevos copoliésteres poli (succinato de butileno-co-succinato de decametileno) (PBDS) y su homopolímero poli (succinato de butileno) (PBS) a partir de monómeros biobasados como el ácido succínico, el 1,4-butanodiol y el 1,10-decanodiol [34].…”

The mission of addition and fission – catalytic functionalization of oleochemicals

“…This developed protocol for isomerizing alkoxycarbonylation proved in many succeeding publications to be a useful tool for the synthesis of linear diesters of different chain length, depending on the applied substrate, as platform chemicals for the production of different polycondensates . As a result of that, subsequent work has been performed towards natural oils as starting material , mechanistic elucidations , and expanding the reaction scope to related transformations, such as alkoxycarbonylation with formates , terpenes as substrates , and aminocarbonylations .…”

“…This initial work was early followed by the discovery, that internal unsaturated esters, such as methyl oleate, could be converted to the corresponding linear dicarboxylic C19 diester under very mild reaction conditions with very high linearity (Scheme 26) [138]. This developed protocol for isomerizing alkoxycarbonylation proved in many succeeding publications to be a useful tool for the synthesis of linear diesters of different chain length, depending on the applied substrate, as platform chemicals for the production of different polycondensates [139][140][141][142][143]. As a result of that, subsequent work has been performed towards natural oils as starting material [144][145][146][147], mechanistic elucidations [148][149][150][151], and expanding the reaction scope to related transformations, such as alkoxycarbonylation with formates [152], terpenes as substrates [153], and aminocarbonylations [154].…”