Polyurethanes based on renewable polyols from bioderived lactones

Andavan, Gurusamy Thangavelu Senthil; Emond, Susanna J.; Kulshrestha, Aman; Macosko, Christopher W.; Tolman, William B.; Hoye, Thomas R.

doi:10.1039/c2py20454a

Cited by 42 publications

(45 citation statements)

References 23 publications

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“…4 Cyclic esters (lactones) have been widely used in the synthesis of biodegradable polymers, such as poly-ε-caprolactone (PCL) 5 and polylactide (PLA) and related copolymers [6][7][8][9][10] , which are employed in a number of biomedical and pharmaceutical applications such as in drug delivery and tissue engineering [11][12][13][14] and constitute the major component of many types of polyurethane biopolymers. 15 Other bio-derived monomers of commercial interest are monoterpenoids, which generate polymers such as polymenthide (PM), polydihydrocarvide (PDC) and polycarvomenthide (PCM) and related ABA block copolymers of polylactide-polymenthide-polylactide triblocks (PLA-PM-PLA). These polymers have applications as thermoplastic elastomers and components of pressure sensitive adhesives.…”

Section: Introductionmentioning

confidence: 99%

“…These polymers have applications as thermoplastic elastomers and components of pressure sensitive adhesives. 7,[15][16][17] Hybrid copolymers of PLA -PM-PLA triblocks are useful in pressure-sensitive adhesives formulations, as they have high-performing thermoplastic elastomer properties comparable to styrenic triblock copolymers. [7][8][9]17 Monomeric compounds can be derived from either natural sources, or as reported more recently via metabolic engineering of microorganisms to generate industrially viable biosynthetic routes.…”

Section: Introductionmentioning

confidence: 99%

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Biocatalytic Routes to Lactone Monomers for Polymer Production

et al. 2018

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Monoterpenoids offer potential as biocatalytically derived monomer feedstocks for high-performance renewable polymers. We describe a biocatalytic route to lactone monomers menthide and dihydrocarvide employing Baeyer-Villiger monooxygenases (BVMOs) from Pseudomonas sp. HI-70 (CPDMO) and Rhodococcus sp. Phi1 (CHMO) as an alternative to organic synthesis. The regioselectivity of dihydrocarvide isomer formation was controlled by site-directed mutagenesis of three key active site residues in CHMO. A combination of crystal structure determination, molecular dynamics simulations, and mechanistic modeling using density functional theory on a range of models provides insight into the origins of the discrimination of the wild type and a variant CHMO for producing different regioisomers of the lactone product. Ring-opening polymerizations of the resultant lactones using mild metal-organic catalysts demonstrate their utility in polymer production. This semisynthetic approach utilizing a biocatalytic step, non-petroleum feedstocks, and mild polymerization catalysts allows access to known and also to previously unreported and potentially novel lactone monomers and polymers.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Biocatalytic Routes to Lactone Monomers for Polymer Production

et al. 2018

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“…polymerization and foaming, occur simultaneously. Renewable resources such as vegetable oil are fast replacing the conventional fossil fuel derived oligomers in polyurethane synthesis . Castor oil is a major candidate in these replacement efforts, due to its inherent advantages over other vegetable oils.…”

Section: Introductionmentioning

confidence: 99%

Foam stability and polymer phase morphology of flexible polyurethane foams synthesized from castor oil

Chandan

Kumar

Unni³

et al. 2014

J of Applied Polymer Sci

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Foam stability and segmented polymeric phase morphology of polyurethane foams synthesized partially and completely from castor oil are investigated. Preliminary analysis of the impact of alterations in the polymeric phase on macroscopic stress dissipation in foams is also carried out. The stability and morphology show unique trends depending on the concentration of castor oil used in foam synthesis. While low and intermediate concentrations of castor oil does not significantly affect the foaming process; at high concentrations, the volumetrically expanding liquid matrix remains in a nonequilibrium state during the entire foaming period, resulting in significant foam decay from top. This increases the final foam cell density and decreases the plateau border thickness at bottom. In the polymeric phase of castor oil based foams, the fraction of monodentate urea increases at the cost of non-hydrogen bonded urea. These monodentate urea domains undergo flocculation in foams synthesized completely from castor oil, thus prominently modifying the segmented morphology. The glass transition temperature of soft segments of partially substituted foams shows moderate increase, with indications of phase mixing between the polyether and castor oil generated urethane domains. Foams synthesized entirely from castor oil have significant sol fraction due to unreacted oligomers. The microscopic alterations in polymeric phase reduce the elastic recovery of partially substituted castor oil foams compared to its viscous dissipation under an applied stress. V C 2014Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40668.

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“…In short, this simple way of preparing α,ω-hydroxyl-terminated poly(lactone) shows significant advances over previously reported synthetic methods. 43,44 Synthesis of Carboxy-Telechelic Poly(carvomenthide). The secondary hydroxyl terminal groups of the PCM samples were (Figure 1d).…”

Section: Synthesis Of Prepolymers Synthesis Of Carvomenthidementioning

confidence: 99%

Thermoset Elastomers Derived from Carvomenthide

Yang

Lee

Choi³

et al. 2014

Biomacromolecules

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Renewable thermoset elastomers were prepared using the plant-based monomer carvomenthide. Controlled ring-opening transesterification polymerization of carvomenthide using diethylene glycol as an initiator gave α,ω-dihydroxyl poly(carvomenthide) (HO-PCM-OH), which was subsequently converted to carboxy-telechelic poly(carvomenthide) (HOOC-PCM-COOH) by esterification with excess succinic anhydride through a one-pot, two-step process, leading to no crystallinity, high viscosity, strong thermal resistance, and low glass transition temperature of the resulting functionalized polyester. Thermal curing processes of the resulting 3, 6, and 12 kg mol(-1) prepolymers were achieved with trifunctional aziridine to give cross-linked PCM elastomers. The thermal properties, mechanical behavior, and biocompatibility of the rubbery thermoset products were investigated by differential scanning calorimetry, thermal gravimetric analysis, dynamic mechanical analysis, tensile tests under static and cyclic loads, and cell adherence. These new materials are useful candidates to satisfy the design objective for the engineering of a variety of soft tissues.

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Polyurethanes based on renewable polyols from bioderived lactones

Cited by 42 publications

References 23 publications

Biocatalytic Routes to Lactone Monomers for Polymer Production

Biocatalytic Routes to Lactone Monomers for Polymer Production

Foam stability and polymer phase morphology of flexible polyurethane foams synthesized from castor oil

Thermoset Elastomers Derived from Carvomenthide

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