High Glass Transition Temperature Renewable Polymers via Biginelli Multicomponent Polymerization

Abstract

A novel and straightforward one-pot multicomponent polycondensation method was established in this work. The Biginelli reaction is a versatile multicomponent reaction of an aldehyde, a β-ketoester (acetoacetate) and urea, which can all be obtained from renewable resources, yielding diversely substituted 3,4-dihydropyrimidin-2(1H)-ones (DHMPs). In this study, renewable diacetoacetate monomers with different spacer chain lengths (C3, C6, C10, C20) were prepared via simple transesterification of renewable diols and commercial acetoacetates. The diacetoacetate monomers were then reacted with renewable dialdehydes, i.e., terephthalaldehyde and divanillin in a Biginelli type step-growth polymerization. The obtained DHMP polymers (polyDHMPs) displayed high molar masses, high glass transition temperatures (Tg) up to 203 °C and good thermal stability (Td5%) of 280 °C. The Tg of the polyDHMPs could be tuned by variation of the structure of the dialdehyde or the diacetoacetate component.

Multicomponent Tandem Polymerization of Aromatic Alkynes, Carbonyl Chloride, and Fischer's Base toward Poly(diene merocyanine)s

“…In the past decade, inspired by the advantages of multicomponent reactions (MCRs) such as high efficiency, mild condition, atom economy, simple reactants, and structural diversity, they were introduced to polymer chemistry and a large number of multicomponent polymerizations (MCPs) were developed which bring new functional polymer structures and materials . Typical MCPs include Ugi four‐component polymerizations, Passerini three‐component polymerizations, A 3 ‐polycouplings of alkynes, aldehydes, and amines, MCPs based on alkynes and sulfonyl azides, catalyst‐free MCPs of elemental sulfur, amine, and alkynes/isocyanides, and many other MCPs . Compared with traditional one‐component or two‐component polymerizations, MCPs enjoy a series of unique advantages such as great structural diversity of polymer products, and high efficiency of chemical conversion, in situ construction of multiple types of covalent bonds from a single polymerization, and so on.…”

Multicomponent Reactions and Multicomponent Cascade Reactions for the Synthesis of Sequence‐Controlled Polymers

“…Moreover, the Hantzsch and Biginelli three‐component reactions have also been introduced into polymer chemistry recently as efficient tools to prepare multifunctional sequence‐controlled polymers . Even so, due to narrow substrate scope or restricted reaction conditions, few multicomponent reactions in the organic chemistry area have been used for polymer science, not to mention about sequence‐controlled polymers.…”

Synthesis of structurally diverse 3,4-dihydropyrimidin-2(1H)-ones via sequential Biginelli and Passerini reactions

“…Generally, one-pot procedures have many advantages compared to multiple-step syntheses [1–3]. One-pot MCRs can shorten reaction times, provide high yields, reduce work-up steps and waste as well as energy consumption and hence lead to more effective and sustainable processes [4–6]. MCRs found numerous applications, i.e., in combinatorial chemistry, target oriented synthesis or polymer science [6–8].…”

“…One-pot MCRs can shorten reaction times, provide high yields, reduce work-up steps and waste as well as energy consumption and hence lead to more effective and sustainable processes [4–6]. MCRs found numerous applications, i.e., in combinatorial chemistry, target oriented synthesis or polymer science [6–8]. The most important MCRs are the Strecker amino acid synthesis (1850), the Hantzsch dihydropyridine synthesis (1882), the Biginelli dihydropyrimidone synthesis (1891), the Mannich reaction (1912), the Passerini three-component reaction (1921) and the Ugi four-component reaction (1959) [9].…”

“…a) Proposed mechanism of the Biginelli reaction according to [6]. b) Proposed mechanism of the Passerini reaction.…”