Ring-Opening Metathesis Polymerization for the Synthesis of Terpenoid-Based Pressure-Sensitive Adhesives

Abstract

Pressure-sensitive adhesives (PSAs) made from norbornene-functionalized terpenoid-based monomers are reported as a possible alternative to the conventional petrochemically based PSAs. For this, tetrahydrogeranyl, menthyl, and isobornyl norbornenate monomers, with a renewable carbon content up to 72%, are synthesized and copolymerized via ring-opening metathesis polymerization (ROMP) with cyclooctadiene and 5norbornene-2-carboxylic acid. ROMP enables a much faster and controlled polymerization process in comparison to free radical polymerization techniques when targeting high molecular weights and therefore unlocks a potential to design a unique class of PSA materials. The moduli at bonding and debonding frequencies of the obtained PSAs are plotted in the Chang classification system and are used to predict their adhesive performance. Tack and peel measurements indicate that the terpenoid-based norbornenate formulations show similar adhesive properties in comparison to the previously investigated acrylic counterparts.

Partially Biobased Block Copolymers Derived from Phenol and Butanol for High-Performance Elastomers and Pressure-Sensitive Adhesives

“…This window encompasses storage and loss moduli at 0.01 and 100 rad/s, forming the vertices of a rectangle (Figure b), as per Chang’s criteria . The storage and shear moduli of the majority of PSAs typically range between 10 3 and 10 6 Pa. − It should be noted that in our case, we plotted the window at 0.1–100 rad/s for practical applications in which bonding (adhesion, ≈0.1 rad/s) and debonding (peel, ≈100 rad/s) frequencies are significant. Remarkably, both P8 and P9 encompass the general PSA, high shear PSA, and removal PSA categories within the viscoelastic window.…”

Vanillin-Based Polymers via Ring-Opening Metathesis Polymerization

“…Synthesis of BCOct. 42 In a Schlenk flask, 5-norbornene-2carboxylic acid (21.71 mmol, 1.00 equiv, 3.00 g), 3,7-dimethyl-1octanol (26.06 mmol, 1.2 equiv, 4.12 g), N,N′-dicyclohexylcarbodiimide (23.88 mmol, 1.1 equiv, 4.93 g), and 4-dimethylaminopyridine (2.17 mmol, 0.10 equiv, 265.27 mg) were dissolved in 40 mL of DCM. The reaction mixture was stirred at room temperature for 20 h. The reaction mixture was then filtered by using a Buchner funnel.…”

Modular Approach to Bio-Based Poly(enol ether)s with Tunable Thermal Properties and Degradability

“…18−30 Among those polymerization techniques, ROMP has received an increasing interest in producing biobased polymers due to its excellent functional group compatibility and high tolerance to air and water. 31 To date, a variety of biomass-derived feedstocks, including apopinene, 18 δ-pinene, 20,21 terpenoid, 19 rosin, 22 lignin, 23 fatty acid, 24 levoglucosenone, 25,29 sinapic acids, 27 itaconic anhydride, 26 vanillin, 28 and D-glucose, 30 have been transformed into synthetic polymers by the ROMP method. Despite the significant progress in ROMP synthesis of biomass-derived polymers, most of those polymers have nondegradable allcarbon backbones, which raises concerns about their long-term environmental impacts.…”

“…The recent applications of controlled polymerization techniques in biomass resources have unlocked the access to a library of well-defined biomass-derived polymers with novel structures, predetermined molecular weights, and desired properties. , In this emerging direction, biomass-derived small molecules are incorporated with a polymerizable functionality that allows them to polymerize via a specific controlled polymerization mechanism such as reversible-deactivation radical polymerization, − cationic ring-opening polymerization, − and ring-opening metathesis polymerization (ROMP). − Among those polymerization techniques, ROMP has received an increasing interest in producing biobased polymers due to its excellent functional group compatibility and high tolerance to air and water . To date, a variety of biomass-derived feedstocks, including apopinene, δ-pinene, , terpenoid, rosin, lignin, fatty acid, levoglucosenone, , sinapic acids, itaconic anhydride, vanillin, and d -glucose, have been transformed into synthetic polymers by the ROMP method. Despite the significant progress in ROMP synthesis of biomass-derived polymers, most of those polymers have nondegradable all-carbon backbones, which raises concerns about their long-term environmental impacts.…”