Biobased Polyamides: Recent Advances in Basic and Applied Research

Abstract

Polyamides represent a very important class of polymers for a wide range of applications. After establishing in the 1930s with Nylon and Perlon, their impact on many branches has been continuously growing. In the context of developing sustainable polymers from renewable resources, many polyamides have meanwhile been described, which are based on natural building blocks. In addition to their sustainability, these biobased starting materials can provide special structural features to the resulting polymers and their properties, e.g., side groups, functionalities, or stereoinformation. While some biopolyamides are known for decades and well established (e.g., PA-11, Rilsan), many other promising candidates have been described in fundamental research studies, which have high potential but whose capability-especially for large scale and/or high-performance materials-will have to be proved in the future. Other candidates are very interesting from a scientific point of view, but with less potential for a market establishment due to price and/or feasibility reasons. This article aims at collating the recent developments in the field of biopolyamides and elucidating their properties and potential for different applications.

New Bio‐Polyamides from Terpenes: α‐Pinene and (+)‐3‐Carene as Valuable Resources for Lactam Production

“…Monoterpenes provide a variety of structural elements such as bicyclic motifs, olefins, alcohols, or ketones that enable the production of monomers that would be challenging to synthesize from fossil oil. From these monomers, polyolefins, polyesters, polycarbonates, and PAs have been prepared …”

“…Due to its high impact strength, mechanical resistance, and superior thermal properties, PA is probably the most used semicrystalline technical thermoplastic, with applications in commodities, automotive, medicine, and aviation . An example for the industrial demand of bio‐based PAs is PA11, which is obtained from ricinoelic acid derived from castor beans and commercialized by Arkema under the trade name Rilsan…”

Pinenes: Abundant and Renewable Building Blocks for a Variety of Sustainable Polymers

“…[1][2][3][4][5][6][7][8][9][10][11] Along with their sustainability and renewability,w hich is av ery important task in term of green chemistry in general, [12][13][14][15] these natural feedstock can provide special structural features to the resulting polymers,for example,side groups,s tereocenters,a nd/or functionalities. [1][2][3][4][5][6][7][8][9][10][11] Along with their sustainability and renewability,w hich is av ery important task in term of green chemistry in general, [12][13][14][15] these natural feedstock can provide special structural features to the resulting polymers,for example,side groups,s tereocenters,a nd/or functionalities.…”

“…In this case,t he same Lewis acid may act as aw eak acid when the monomeric counteranion arises,but as strong acid in the conditions when it forms dimers or dimeric counterions.T his can explain the higher MW as compared to polymerizations where only AlCl 3 is applied as co-initiator.T he generation (in situ) of aweakly nucleophilic counterion through the interaction of AlCl 3 OH À with diphenyl ether that results in as uppression of chain transfer reactions could be another explanation for the higher M n values under these conditions.Furthermore,itwas shown that the nature of the electron donor used for the complex generation (AlCl 3 ED,ED= Ph 2 O, Bu 2 Oand EtOAc) has also as trong influence on the M n values.Avery efficient method for the polymerization of b-pinene into moderate-molecularweight poly-b-pinene using the Lewis acid catalysts EtAlCl 2 and Et 1.5 AlCl 1.5 at À78 8 8C, followed by hydrogenation, was also reported. Then, ad ifunctional halide,d icumyl chloride (2). Thep olymers had M n values of about 20 000 and showed ah igh T g (130 8 8C) and degradation temperature (10 %l oss at > 400 8 8C).…”

Pinene: reichlich vorhandene und erneuerbare Bausteine für eine Vielzahl an nachhaltigen Polymeren

“…[1][2][3][4][5][6][7][8][9][10][11] Zusätzlich zur Nachhaltigkeit und Erneuerbarkeit -s ehr wichtigen Faktoren in Bezug auf Grüne Chemie im Allgemeinen [12][13][14][15] -k çnnen diese natürlichen Bausteine spezielle strukturelle Eigenschaften in die resultierenden Polymere "hineinbringen", z. [1][2][3][4][5][6][7][8][9][10][11] Zusätzlich zur Nachhaltigkeit und Erneuerbarkeit -s ehr wichtigen Faktoren in Bezug auf Grüne Chemie im Allgemeinen [12][13][14][15] -k çnnen diese natürlichen Bausteine spezielle strukturelle Eigenschaften in die resultierenden Polymere "hineinbringen", z.…”