Importing self-repair or self-healing features into inert materials is of great relevance to material scientists, since it is expected to eliminate the necessity of replenishing a damaged material. Be it material chemistry or more specifically polymer chemistry, such materials have attracted the imagination of both material scientists and chemists. A stroll down the memory lane 70 years back, this might have sounded utopian. However with the current progress in supramolecular chemistry and the emergence of dynamic covalent and non-covalent chemistries, novel perspectives have been opened up to materials science towards the development of dynamic materials (DYNAMATS) and in particular dynamic polymers (DYNAMERS), with the ability to produce such species by custom made designs. Chemistry took giant strides to gain control over the structure and features of materials and, besides basic progress, to apply it for tailor-making matter for applications in our daily life. In that applied perspective, materials science plays a paramount role in shaping our present and in contributing to a sustainable future. The goal is to develop materials, which would be dynamic enough to carry out certain functions as effectively as in biological systems with, however, the freedom to recruit the powers of chemistry on a wider scale, without the limitation imposed by life. Material scientists and in particular polymer chemists may build on chemistry, physics and biology for bridging the gap to develop dynamic materials presenting a wide range of novel functionalities and to convert dreams into reality. In this current review we will focus on developments in the area of dynamic polymers, as a class of dynamic materials presenting self-healing features and, more generally, the ability to undergo adaptation under the effect of physical and/or chemical agents, and thus function as adaptive polymers or ADAPTAMERS.

Summary: Hyperbranched polyesters with controlled molecular weights and properties have been prepared by an A2 + B3 approach by reacting glycerol and adipic acid without any solvents in the presence of tin catalysts. The hyperbranched polyesters have been evaluated by size exclusion chromatography (SEC) analysis and NMR spectroscopy in order to determine molecular weights and degrees of branching.

The highly reactive [4,4′-bi­(1,3-dioxolane)]-2,2′-dione (BDC), also being referred to as erythritol dicarbonate and butadiene dicarbonate, enables the facile isocyanate-free tailoring and melt-processing of bio-based polyhydroxy­urethane (PHU) materials. Both the direct carbonation of erythritol and the chemical fixation of CO2 with 2,2′-bioxirane, obtained by epoxidation of bioethanol-derived butadiene, afford high purity BDC in high yields. According to the FTIR spectroscopic model study BDC reacts with primary alkylamines at room temperature even in the absence of catalysts. High BDC reactivity is essential for producing high molar mass linear PHU thermoplastics via melt-phase polyaddtition with aliphatic diamines. Opposite to conventional isoycanate-mediated polyurethane syntheses erythritol units are incorporated into the polyurethane backbone without requiring the use of protective groups. As a function of the diamine structures and copolymer compositions the PHU properties vary from hard to soft and elastomeric. Typically isophorone diamine (IPDA) and trimethyl­hexamethylene­diamine (TMHMDA) serve as building blocks for hard segments whereas highly flexible diamines such dimer fatty acid-derived diamidoamines render PHU soft and elastomeric. This study elucidates how copolymer composition and reaction parameters such as temperature, catalyst, and stabilizer addition influences PHU molar masses as well as mechanical and thermal properties. For the first time, owing to extraodinary BDC reactivity, melt-phase BDC polyaddition with diamines is competitive with conventional reactive processing of polyurethane thermoplastics using isocyanates. Moreover this versatile isocyanate-free synthetic route offers a great variety of options for fabricating unconventional bio-based PHUs and carbohydrate urethanes unparalleled by conventional polyurethanes.

Hyperbranched aromatic and aliphatic poly(urea‐urethane)s were prepared by the one‐pot method using 2,4‐toluylene diisocyanate (TDI), isophorone diisocyanate, and 2(3‐isocyanatopropyl)cyclohexyl isocyanate as AA* monomers and diethanol amine and diisopropanol amine as B2B* monomers. The characteristics of the resulting polymers were very sensitive to slight changes in the reaction conditions, such as temperature, concentration, and type of catalyst used, as can be seen from the results of gel permeation chromatography and differential scanning calorimetry. The structures were analyzed in detail using 1H and 13C NMR spectroscopy. By using model compounds, the different isomeric structures of the TDI polymers were deduced, their percentages of their linear, terminal, and dendritic subunits were calculated, and their degree of branching (DB) was determined. DB values up to 70% were reached depending on the reaction conditions and stoichiometry of the monomers. The number of terminal groups decreased significantly when dibutylamine was used to stop the reaction instead of B2B*, indicating the presence of a significant number of unreacted isocyanate groups in the hyperbranched product when the polyaddition reaction was stopped. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3062–3081, 2004