RAFT thermoplastics from glycerol: a biopolymer for development of sustainable wood adhesives

Forrester, Michael; Becker, A.T.; Hohmann, Austin; Hernández, Nacú; Lin, Fang‐Yi; Bloome, Nicholas; Johnson, Grant E.; Dietrich, Hannah; Marcinko, Joe; Williams, Anna; Cochran, Eric W.

doi:10.1039/d0gc01831g

Cited by 19 publications

(9 citation statements)

References 31 publications

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“…When carried forward through (meth)acrylation, the resultant monomer is a mixture of monofunctional ketal (meth)acrylate and multi-substituted glycerol (meth)acrylates. As we reported previously, under RAFT polymerization, these multifunctional monomers form branched chain polymers with very high molecular weight (≫100 kDa) . While these polymers represent the most efficient conversion process, here our motivation is to characterize and understand the basic properties of the linear (meth)acrylate glycerol ketal polymers.…”

Section: Resultsmentioning

confidence: 99%

“…As we reported previously, under RAFT polymerization, these multifunctional monomers form branched chain polymers with very high molecular weight (≫100 kDa). 41 While these polymers represent the most efficient conversion process, here our motivation is to characterize and understand the basic properties of the linear (meth)acrylate glycerol ketal polymers. Hence, we further vacuum distilled the premonomer to reach 99.5% purity per GC−MS prior to solvent-free enzymatic transesterification with methyl (meth)acrylate at 40 °C using 5 Å molecular sieves to remove any methanol generated as depicted by the reaction scheme in Figure 3.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Several advances toward the commercialization of biobased acrylic and methacrylic acid, key precursors, have been reported in recent years. − However, there is a need for new biobased pendant groups to complete the transformation of the (meth)acrylate industry without compromising the utility of the materials it provides. Recently, we reported glycerol as a useful biobased pendant group that yields water-soluble branched chain elastomers suitable for wood composite adhesives . Glycerol ketals provide a means to extend the utility of glycerol as a pendant group by diversifying the range of accessible bio(meth)acrylates to compete with the incumbent petrochemicals.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, we reported glycerol as a useful biobased pendant group that yields water-soluble branched chain elastomers suitable for wood composite adhesives. 41 Glycerol ketals provide a means to extend the utility of glycerol as a pendant group by diversifying the range of accessible bio(meth)acrylates to compete with the incumbent petrochemicals.…”

Section: ■ Introductionmentioning

confidence: 99%

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

Goyal

Lin

Forrester

et al. 2021

ACS Sustainable Chem. Eng.

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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.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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

Goyal

Lin

Forrester

et al. 2021

ACS Sustainable Chem. Eng.

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“…Forrester et al devised a family of hyperbranched thermoplastic acrylic polymers from glycerol multi-acrylate monomers through an esterification process. 61 We were able to synthesize glycerol acrylate monomers through a solvent-free Fisher esterification process by combining crude or analytical grade glycerol with acrylic acid in the presence of a catalyst and a radical inhibitor. The monomer composition consisted of a mixture of mono-, di-and triacrylated glycerol which was highly susceptible to crosslinking and undergoing gelation upon polymerization through the multiple vinyl groups.…”

Section: Introductionmentioning

confidence: 99%

An update on the future prospects of glycerol polymers

Goyal

Hernández

Cochran

2021

Polymer International

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Glycerol, a water-soluble polyol, is currently used in a wide variety of markets, e.g. as a sweetener in drinks, as an additive in the food and cosmetics industry, or as an antifreeze agent, to name a few. The blooming biodiesel production has created an excess supply of glycerol by-product. Researchers all around the world are actively exploring strategies to utilize this cheap and abundantly available biobased molecule. To date, glycerol-based polymers have only been examined extensively for use in biomedical applications; however, the use of biobased crude glycerol is not viable for such applications due to the presence of impurities such as methanol and residual fatty acids from the biodiesel production process. However, the increased volumes of glycerol generated from biodiesel production have stimulated the research on its use in various other industrial applications such as the production of commodity chemicals, polymers etc. In this article, we summarize some of the efforts to valorize glycerol for polymeric applications such as polyurethanes, polyhydroxyalkanoates and adhesives.

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Multifunctional DNA Hydrogel Enhances Stemness of Adipose‐Derived Stem Cells to Activate Immune Pathways for Guidance Burn Wound Regeneration

Zhou

Zeng

Liu

et al. 2022

Adv Funct Materials

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A grade 3 burn is a nonstatic fatal injury, which can lead to complete damage to the skin structure, accompanied by a series of symptoms such as persistent inflammation, pain, pruritus, ulcer, and peripheral neuropathy. Although the primary clinical burn treatment is skin grafting, it cannot comprehensively solve burn symptoms. Here, a multifunctional DNA hydrogel integrated system is conveniently obtained through dynamic cross-linking of the DNA unit, polyacrylamide, and l-ascorbate 2-phosphate (l-A2P) formation of dense hydrogen bonds. The DNA hydrogel is doped with borneol for pain and itch relief. The obtained DNA hydrogel provides a hotbed similar to the extracellular matrix structure in vivo for the growth and development of stem cells, which can regulate cell proliferation, maintain cell viability, and achieve perfect release in a suitable environment. Additionally, the pharmacological wound dressing shell features excellent mechanical behavior, tissue adhesion, and antibacterial properties. Beyond that, the multifunctional DNA hydrogel integrated system can promote macrophage transformation, angiogenesis, and neurogenesis. Notably, the system activates the phosphatidylinositol 3′-kinase (PI3K)-Akt signaling pathway, which helps to promote tissue regeneration. Therefore, the DNA hydrogel integrated system opens the cascade mode of effective integrated treatment of burn wounds, further driving the in-depth study of clinical transformation mechanisms in the future.

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RAFT thermoplastics from glycerol: a biopolymer for development of sustainable wood adhesives

Abstract: The increasing demand for bioderived plastics and rubbers and the large supply of glycerol makes it an excellent starting chemical for the production of biopolymers. Little success in commercially viable...

Cited by 19 publications

References 31 publications

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

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

An update on the future prospects of glycerol polymers

Multifunctional DNA Hydrogel Enhances Stemness of Adipose‐Derived Stem Cells to Activate Immune Pathways for Guidance Burn Wound Regeneration

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