Nitrogen‐Containing Polymers Derived from Terpenes: Possibilities and Limitations

Abstract

Nitrogen-containing polymers are widely applied materials, including polyamides, polyurethanes, and polyureas as well as epoxy thermosets. Their indispensability and the urgent need to replace fossil-based polymers considering more sustainable alternatives lead to significant efforts in exploring renewable feedstock as potential new building blocks. Being obtained from non-edible plant parts and often occurring as waste products, terpenes represent a promising group of renewable compounds that are of possible interest in the synthesis of nitrogen-containing polymers. The structural diversity of terpenes in combination with the mechanical properties that nitrogen-containing moieties bring into polymers can give rise to novel biobased materials that outstand mechanical and thermal properties of conventional fossil-based counterparts. In this review, an overview of the use of terpene compounds in the synthesis of nitrogen-containing polymers is given, covering different approaches to make use of terpenes as a valuable pool of renewable monomers.

Polyamides Derived from Terpenes: Advances in Their Synthesis, Characterization and Applications

“…[ 106–108 ] This interesting compound can meanwhile be considered to be a platform chemical for a variety of biobased N ‐containing polymers including, for example, polyamides (epoxy/amine resins are other examples, where this compound can thus be used as a curing agent) ( Scheme A). [ 28,109 ] Also many similar amine‐containing building blocks can be prepared from Limonene and polymerized, which thus makes a wide variety of interesting polymers accessible. [ 28 ] Furthermore, Polyamides (and also polyurethanes) from limonene can be prepared, for example, via polycondensation of Limonene‐derived diesters and diamines (Meier et al.).…”

“…[ 28,109 ] Also many similar amine‐containing building blocks can be prepared from Limonene and polymerized, which thus makes a wide variety of interesting polymers accessible. [ 28 ] Furthermore, Polyamides (and also polyurethanes) from limonene can be prepared, for example, via polycondensation of Limonene‐derived diesters and diamines (Meier et al.). [ 110 ] Through different combinations, limonene, fatty acid, as well as Nylon 6,6 copolymers were thus prepared, and the relationships between structures and thermal properties were analyzed (Scheme 2B).…”

“…This fact is important for natural polymers (e.g., cellulose [ 23 ] or polyhydroxyalkanoates (PHAs) [ 24 ] and lignin [ 25 ] ), and also for various natural monomeric building blocks, which results mainly in the classification concept of polymer approaches versus molecular approaches. [ 26–31 ]…”

“…It is important to emphasize that other N ‐containing polymers as, for example, polyurethanes (PUs) are also very important, especially with regards to their biobased and sustainable representatives. [ 104 ] Although they are sometimes mentioned herein at appropriate passages in this text, their comprehensive elucidation would be beyond the scope of this article—similar polymers have been reviewed and described in other articles much more detailed, [ 28,105 ] The importance of this review and the difference to the previous reviews about biobased PAs is the uptake of some very recent information and studies about this topic, as well as the structuring regarding the different polymerization mechanisms in this context. Furthermore, the fact that the focus herein is defined especially regarding the Terpene‐based building blocks is important.…”

Antibacterial Properties of Polyurethane Foams Additivated with Terpenes from a Bio-Based Polyol

“…Currently, several industrially relevant polymerization processes are known which take advantage of widely abundant terpenes, e.g., the cationic polymerization of α-pinene for adhesives, coatings, and inks [ 37 ]. Very recently, the Meier group illustrated the research and development of nitrogen-containing polymers such polyamides, polyurethanes (and their non-isocyanate counterparts), polyureas, and epoxy resins, using terpenes and their derivatives as monomers [ 38 ]. Terpene-modified polysiloxane-based polyurethane was also developed to improve mechanical properties of waterborne polyurethane [ 39 ].…”