Diamines for Polymer Materials via Direct Amination of Lipid‐ and Lignocellulose‐based Alcohols with NH₃

Abstract

Via an all‐catalytic route, long‐chain diamines were prepared by the catalytic direct amination of long‐chain diols, derived from plant oils. High conversion was achieved with good selectivity, with the amount of nitrile impurities formed suppressed to a low level. From the lignocellulose‐based 5‐hydroxymethylfurfural (5‐HMF), or from bis(hydroxymethyl)furan, 2,5‐bis(aminomethyl)furan (BAMF) was generated. 5‐HMF was converted in a one‐pot, one‐step direct amination and reductive amination using ammonia. In both cases, the reaction proceeded very efficiently. In the combined amination and reductive amination, the H2 concentration is a rate‐limiting factor. Reducing the partial pressure of H2 also shortened the reaction time required significantly. Polycondensation of the long‐chain diamines with long‐chain diacids led to higher molecular weight polyamides, illustrating the quality of the diamines obtained by this synthetic approach as monomers.

Sustainable access to renewable N-containing chemicals from reductive amination of biomass-derived platform compounds

“…In addition to monoamines, diamines can also be synthesized from the reductive amination of HMF. For example, 2,5-bis(aminomethyl)furan, a versatile feedstock for the production of polymer materials, was successfully produced from the reductive amination of HMF with ammonia in the presence of a Ru-complex catalyst as shown in Scheme 5b [95]. Approximate 65% yield of 2,5-bis(aminomethyl)furan was obtained at 150 °C after 4 h with 0.25 MPa of H 2 .…”

“…Scheme 5 (a) Reductive amination of HMF with aniline to yield N-phenyl-5-(hydroxymethyl)-2-furfuryl amine [93], (b) Reductive amination of HMFwith ammonia to yield 2,5-bis(aminomethyl)furan[95], (c) Reductive amination of HMF with n-heptylamine to yield bis(hydroxylmethylfurfuryl)amine[96] …”

Polyethylene-like materials from plant oils

“…[12,13] The (ultra)long-chain ,-dicarboxylates can be reduced to the corresponding diols cleanly, most elegantly by catalytic reduction with dihydrogen. [8] These diols in turn can be converted to long-chain ,-diamines, by catalytic reaction with ammonia, [14,15] in a purity suited for polycondensation to long-chain polyamides. [15] Figure 4.…”

“…[8] These diols in turn can be converted to long-chain ,-diamines, by catalytic reaction with ammonia, [14,15] in a purity suited for polycondensation to long-chain polyamides. [15] Figure 4. 'Chain doubling' approach, illustrated for oleate as a starting material.…”

“…to long-chain α,ω-diamines, by catalytic reaction with ammonia, [14,15] in a purity suited for polycondensation to long-chain polyamides [15].…”