Glycerol Ketals as Building Blocks for a New Class of Biobased (Meth)acrylate Polymers

Abstract

Here we present an approach for developing the next generation of bio(meth)acrylates using glycerol ketals as a platform for property differentiation. Crude glycerol, a biodiesel byproduct, and ketones, derived from biomass valorization, are the building blocks for these polymeric materials. Biobased materials are witnessing a prominent boom in research and commercialization due to increased awareness about the carbon footprint and depletion of petroleum resources. Biodiesel and biopolymers are major linchpins to improve sustainable energy and material needs of the world in the coming years. Glycerol ketal (meth)acrylate monomers synthesized by the reaction of glycerol and various ketones consist 65-74 wt.% bioderived content. Glycerol ketals from different ketones used in our study (acetone, cyclopentanone and butanone) are the pendant groups on the (meth)acrylate polymer backbone. We studied the effect of various pendant side-chain ketal groups on the thermal and rheological properties of 1 these polymers. The methacrylate polymers had a higher glass transition temperature (T g ) (8-40 • C) while the acrylate derivatives had much lower T g between -11 • C to 2 • C. The side chain group on these polymers offers us a robust knob to tune the thermal properties (e.g. T g ) and rheological properties (e.g. modulus and entanglement behaviour) for varied applications such as hard block polymers and adhesives.

Monomers and Macromolecular Materials from Renewable Resources: State of the Art and Perspectives

“…The synthesis consisted of the reaction of glycerol with acryloyl chloride, followed by the coupling of the ensuing glycerol triacrylate with ethylenediamine, the production of a glycerol-based dendrimer via free radical mini-emulsion polymerization, and film casting [ 115 ]. A new class of (meth)acrylate polymers was designed from glycerol ketals, whose syntheses were carried out with glycerol and ketones of varying specific molecular structures [ 116 ]. A broad study evaluated the cradle-to-gate life cycle assessment of glycerol-based adhesives produced through a reversible addition-fragmentation chain transfer polymerization process, and the results indicated lower environmental impacts with respect to the fossil analogs [ 117 ].…”

Next-Generation High-Performance Bio-Based Naphthalate Polymers Derived from Malic Acid for Sustainable Food Packaging

“…The advent of single-use plastics (SUPs) has heralded an age of convenience featuring easy long-term storage and widespread accessibility to food and drink. , However, the use of nondegradable petroleum-derived plastics has been a plague to the environment. , Poly­(ethylene terephthalate) (PET) is an engineering thermoplastic with excellent thermal and chemical resistance as well as superb mechanical properties; however, the production of PET has a profound impact on the environment. , In 2015 alone, PET production was responsible for 137 million metric tons of greenhouse gas (GHG) emissions, which has resulted in significant consequences on climate and the environment. − Furthermore, PET performs poorly as a thermal and oxygen barrier in applications involving bottle reuse and liquor storage. PET can neither withstand deformation due to hot water cleaning nor impede the penetration of oxygen into the container, which can affect the flavor of the contents. , Consequently, academia and industry alike are seeking to overcome these issues through the development of high-performance biobased plastics from inexpensive and renewable feedstocks .…”

Polymers without Petrochemicals: Sustainable Routes to Conventional Monomers

“…The conversion of glycerol into ketals has been thoroughly reported and these can further be used in the synthesis of different acrylate and methacrylate monomers. Goyal and co-workers combined glycerol from biodiesel with products from the ketonization of pyrolysis oil from biomass, with p -toluene sulfonic acid as the catalyst, to form glycerol ketals . The second step was to form the methacrylate monomers which involved a transesterification of the ketal pre-monomers and methyl methacrylate, catalyzed by lipase enzymes.…”

“…Goyal and co-workers combined glycerol from biodiesel with products from the ketonization of pyrolysis oil from biomass, with p-toluene sulfonic acid as the catalyst, to form glycerol ketals. 370 The second step was to form the methacrylate monomers which involved a transesterification of the ketal pre-monomers and methyl methacrylate, catalyzed by lipase enzymes. The resulting monomers were polymerized via living radical polymerization.…”