Carbohydrate-based building blocks and step-growth polymers : synthesis, characterization and structure-properties relations
Driven by the concern about the future petro-chemical feedstock availability, as well as the need for a green and sustainable society, renewable and bio-based materials have become the natural candidates for alternatives to petro-chemicals. As the most abundant biomass feedstock, carbohydrates are attracting significant attention from both academia and industry for the production of chemicals, fuels and energy. However, one major drawback of directly using carbohydrates in industrial processes is their limited thermal stability caused by the existence of multiple functional groups, for instance hydroxyl groups. Consequently, simplified or bi-functional carbohydrate-derived building blocks are often more attractive than the virgin carbohydrates for polymer chemists. In this thesis, we aim to 1) develop a new family of difunctional bio-based building blocks, and 2) utilize these new building blocks as AA monomers to synthesize step-growth polymers, such as polyesters and polyamides. Ideally, the new polymers are expected to be semicrystalline, preferably having high melting (Tm) and high glass transition temperatures (Tg), and can be used as the potential fully or partially bio-based engineering plastics. Isohexides (1,3:4,6-dianhydrohexitols), a group of secondary, rigid diols, as well as their derivatives are interesting carbohydrate-derived building blocks for various types of step-growth polymers, such as polyesters, polyamides and polycarbonates. Due to the intrinsic rigidity of the structures, isohexides are capable of increasing the glass transition temperatures when incorporated into polymers. However, the relatively poor reactivity of the secondary hydroxyl groups of isohexides has been recognized as a main drawback, which often results in low molecular weight or discolored polymers. In order to overcome these problems, as well as utilizing the rigidity of the isohexide skeleton, a new family of 1-carbon extended isohexide-derivatives were designed and synthesized by transforming the less reactive secondary hydroxyl functionalities into more reactive ones. Based on a key dinitrile intermediate, viz. isoididedinitrile (IIDN), the novel isohexide-derived building blocks were obtained. They are: isoidide-2,5-dicarboxylic acid (IIDCA) and its dimethyl ester (IIDMC), isoidide-2,5-dimethanol (IIDML) and isoidide-2,5-dimethyleneamine (IIDMA). After optimization of the respective synthetic routes, these building blocks were obtained at sufficient scales (5–20 g/batch) and high purities (>99.5%) to be suitable for polymerizations. Three series of polyesters based on the novel 1-carbon extended isohexides were synthesized. The first series of polyesters is based on isoidide dicarboxylic acid (IIDCA) and linear alkylene diols. Unexpectedly, they have rather low Tm (60–100 °C) values whereas the recorded low Tg values (-30–18 °C) were approximately expected. The second series of polyesters is fully based on renewable, isohexide-derived monomers. The combination of both isohexide-based AA/BB monomers gave significantly higher Tg values (45–85 °C) than the partially linear aliphatic polyesters of the first series. Importantly, this part of the project revealed the promising characteristics (reactivity, rigidity and thermal stability) of isoidide-2,5-dimethanol (IIDML) for potential applications in performance polymers with high Tg and Tm. Therefore, the third series of polyesters was entirely focused on IIDML-based semi-aromatic systems. The Tg and Tm values of these polyesters were found to exceed even those of the conventional PET and PBT polyesters, confirming our expectation that IIDML is a promising rigid cyclic diol for engineering plastic applications. Two series of semicrystalline (co)polyamides were synthesized from the new isoidide 2,5-dimethyleneamine (IIDMA) or from a mixture of IIDMA and 1,6-hexamethylene diamine with the biobased dicarboxylic acids sebacic acid or brassylic acid. A combination of melt polymerization of nylon salts with solid-state polycondensation (SSPC) processes afforded the desired copolyamides with maximum number average molecular weight (Mn) of 49,000 g/mol. Analysis by temperature dependent soldi state NMR and FT-IR spectroscopies revealed that the new diamine IIDMA exist in both the crystalline and amorphous phases of the copolyamides. Given the sufficiently high Tm values (~200 °C) of the copolyamides containing less than 50% of IIDMA, these bio-based semicrystalline copolyamides can be useful for engineering plastic applications. By comparing the thermal properties of the polymers based on the new isohexide-based building blocks, i.e. IIDCA, IIDML and IIDMA, with relevant reference polymers, systematic structure-thermal properties studies of each series of polymers were conducted. This work objectively evaluated the relative rigidities, reactivities and thermal stabilities of these new building blocks with respect to those of the parent isohexides, as well as with respect to their linear, cyclic aliphatic and aromatic analogues. Both the experimental (i.e., single crystal X-ray diffraction) and computational-aided methods (i.e., Density Functional Theory (DFT)) were employed to elucidate the structural characteristics of the isohexide-based building blocks, as well as to understand the specific thermal properties of the polymers based thereon. Additional efforts were invested to expand the dinitrile platform to the other stereo-isomers. The isomeric isohexide dinitriles were synthesized by base-induced epimerization. The strong non-nucleophilic organic base 1,8-diazabicycloundec-7-ene (DBU) was found to be a suitable catalyst for such type of isomerization. A kinetic study on the epimerization of three dinitrile isomers revealed an equilibrium between the three possible isomers in THF. Single crystal X-ray diffraction studies demonstrated several structural characters of these molecules regarding their symmetry and linearity. Density Functional Theory (DFT) calculations further supported the base-induced epimerization mechanism. This work concerns a pioneering study of deoxy-1-carbon-extended isohexide-based building blocks. All the monomers and polymers synthesized, characterized and evaluated in this thesis are entirely new. Suitable synthetic laboratory-scale protocols were developed for all the monomers and polymers. The reported study of the structure-thermal properties relations, as well as the crystal structure elucidation by single crystal X-ray diffraction and DFT, are also of high importance concerning the field of isohexide-based polymers and will certainly prove to be very useful for drawing conclusions on the industrial feasibility of such bio-based materials.
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