Title: RAFT thermoplastics from glycerol: a biopolymer for development of sustainable wood adhesives
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 glycerol polymers has yet to be realized. In particular, high molecular weight thermoplastics have been especially elusive due to the multifunctional nature of glycerol. This work details the production of glycerol–acrylic biopolymers. By esterifying glycerol with acrylic acid, and subsequent RAFT polymerization to suppress the gelation, we were able to achieve glycerol thermoplastics with high molecular weights (1 MDa). After studying the thermal/mechanical properties of the polymer, it was found that these glycerol polymers had a high degree of tack. When added to wood as an adhesive, it was found that performance was comparable or exceeded standard wood adhesives such as Poly (Methylene diphenyl diisocyanate) (PMDI) and formaldehyde based adhesives. This yields wood adhesives that have less toxicity, lower environmental impact, and higher renewability. more »« less
Synthetic method for developing plant oil-based monomers (POBMs) using direct transesterification reaction of oil triglycerides with N-(Hydroxyethyl) acrylamide was created and widely used by our group. Resulted acrylic monomers undergo free-radical polymerization, including in emulsion process, to yield latex polymers, suitable for application as adhesives.
Synthetic method for developing plant oil-based monomers (POBMs) using direct transesterification reaction of oil triglycerides with N-(Hydroxyethyl) acrylamide was created and widely used by our group. Resulted acrylic monomers undergo free-radical polymerization, including in emulsion process, to yield latex polymers, suitable for application as adhesives.
Arrowood, Anthony; Li, Morris; Nassr, Mostafa; Lynd, Nathaniel A.; Sanoja, Gabriel E.
(, Macromolecular Chemistry and Physics)
Abstract Pressure‐sensitive‐adhesives (PSAs) are pervasive in electronic, automobile, packaging, and biomedical applications due to their ability to stick to numerous surfaces without undergoing chemical reactions. These materials are typically synthesized by the free radical copolymerization of alkyl acrylates and acrylic acid, leading to an ensemble of polymer chains with varying composition and molecular weight. Here, reversible addition−fragmentation chain‐transfer (RAFT) copolymerizations in a semi‐batch reactor are used to tailor the molecular architecture and bulk mechanical properties of acrylic copolymers. In the absence of cross‐links, the localization of acrylic acid toward the chain ends leads to microphase separation, creep resistance, and enhanced tack. However, in the presence of Al(acac)3crosslinker, the creep resistance remains unchanged and mostly the large‐strain mechanical properties are affected. This behavior is attributed to microphase separation, but also to a change in the energy required to break physical associations, and untangle and elongate associative polymers to large deformations.
Tran, Thi M; Read_de_Alaniz, Javier
(, Journal of the American Chemical Society)
Catalyst-free and reversible step-growth Diels–Alder (DA) polymerization has found a wide range of applications in polymer synthesis and is a promising method to fabricate recyclable thermoplastics. The effectiveness of polymerization and de-polymerization relies on the chemical building blocks, often utilizing furan as the diene and maleimide as the dienophile. Compared to the traditional diene–dienophile or two-component approaches that requires perfect stoichiometry, cyclopentadi-ene (Cp) can serve a dual role via self-dimerization. This internally balanced platform offers a route to access high-molecular-weight polymers and a dynamic handle for polymer recycling, which remains unexplored. Herein, through the reactivity in-vestigation of different telechelic Cp derivatives, the uncontrolled cross-linking of Cp was addressed, revealing the first suc-cessful DA homopolymerization. To demonstrate the generality of our methodology, we synthesized and characterized six Cp homopolymers with backbones derived from common thermoplastics, such as polydimethylsiloxane, hydrogenated poly-butadiene, and ethylene phthalate. Among these materials, the hydrogenated polybutadiene-Cp analog can be thermally de-polymerized (Mn = 68 to 23 kDa) and re-polymerized to the parent polymer (Mn = 68 kDa) under solvent- and catalyst-free conditions. This process was repeated over three cycles without intermediate purification, confirming the efficient thermo-selective recyclability. The varied degradable properties of other four Cp-incorporated thermoplastics were also examined. Overall, this work provides a general methodology to access a new class of reversible homopolymers, potentially expanding the designs and construction of sustainable thermoplastics.
To investigate the utility of acrylic monomers from various plant oils in adhesives manufacturing, 25–45 wt. % of high oleic soybean oil-based monomer (HOSBM) was copolymerized in a miniemulsion with commercially applied butyl acrylate (BA), methyl methacrylate (MMA), or styrene (St). The compositions of the resulting ternary latex copolymers were varied in terms of both “soft” (HOSBM, BA) and “rigid” (MMA or St) macromolecular fragments, while total monomer conversion and molecular weight of copolymers were determined after synthesis. For most latexes, results indicated the presence of lower and higher molecular weight fractions, which is beneficial for the material adhesive performance. To correlate surface properties and adhesive performance of HOSBM-based copolymer latexes, contact angle hysteresis (using water as a contact liquid) for each latex-substrate pair was first determined. The data showed that plant oil-based latexes exhibit a clear ability to spread and adhere once applied on the surface of materials differing by polarities, such as semicrystalline polyethylene terephthalate (PET), polypropylene (PP), bleached paperboard (uncoated), and tops coated with a clay mineral paperboard. The effectiveness of plant oil-based ternary latexes as adhesives was demonstrated on PET to PP and coated to uncoated paperboard substrates. As a result, the latexes with high biobased content developed in this study provide promising adhesive performance, causing substrate failure instead of cohesive/adhesive break in many experiments.
Forrester, Michael, Becker, Andrew, Hohmann, Austin, Hernandez, Nacu, Lin, Fang-Yi, Bloome, Nicholas, Johnson, Grant, Dietrich, Hannah, Marcinko, Joe, Williams, R. Chris, and Cochran, Eric. RAFT thermoplastics from glycerol: a biopolymer for development of sustainable wood adhesives. Retrieved from https://par.nsf.gov/biblio/10283386. Green Chemistry 22.18 Web. doi:10.1039/d0gc01831g.
Forrester, Michael, Becker, Andrew, Hohmann, Austin, Hernandez, Nacu, Lin, Fang-Yi, Bloome, Nicholas, Johnson, Grant, Dietrich, Hannah, Marcinko, Joe, Williams, R. Chris, and Cochran, Eric.
"RAFT thermoplastics from glycerol: a biopolymer for development of sustainable wood adhesives". Green Chemistry 22 (18). Country unknown/Code not available. https://doi.org/10.1039/d0gc01831g.https://par.nsf.gov/biblio/10283386.
@article{osti_10283386,
place = {Country unknown/Code not available},
title = {RAFT thermoplastics from glycerol: a biopolymer for development of sustainable wood adhesives},
url = {https://par.nsf.gov/biblio/10283386},
DOI = {10.1039/d0gc01831g},
abstractNote = {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 glycerol polymers has yet to be realized. In particular, high molecular weight thermoplastics have been especially elusive due to the multifunctional nature of glycerol. This work details the production of glycerol–acrylic biopolymers. By esterifying glycerol with acrylic acid, and subsequent RAFT polymerization to suppress the gelation, we were able to achieve glycerol thermoplastics with high molecular weights (1 MDa). After studying the thermal/mechanical properties of the polymer, it was found that these glycerol polymers had a high degree of tack. When added to wood as an adhesive, it was found that performance was comparable or exceeded standard wood adhesives such as Poly (Methylene diphenyl diisocyanate) (PMDI) and formaldehyde based adhesives. This yields wood adhesives that have less toxicity, lower environmental impact, and higher renewability.},
journal = {Green Chemistry},
volume = {22},
number = {18},
author = {Forrester, Michael and Becker, Andrew and Hohmann, Austin and Hernandez, Nacu and Lin, Fang-Yi and Bloome, Nicholas and Johnson, Grant and Dietrich, Hannah and Marcinko, Joe and Williams, R. Chris and Cochran, Eric},
editor = {null}
}
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