Acetal metathesis polymerization (AMP): A method for synthesizing biorenewable polyacetals

Pemba, Alexander G.; Flores, Jeniree A.; Miller, Stephen A.

doi:10.1039/c2gc36588j

Cited by 53 publications

(51 citation statements)

References 20 publications

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“…6 Simultaneously, such huge consumptions bring inevitable environmental pollutions. polyolefins, 30 polyesters, 31 polyethers, 32 polyamides, 33 epoxy 34 and polyurethane resins, 35 and others 36 ). 7 In brief, urgent actions are necessitated to make plastics renewable via using naturally-occurring raw materials and to take advantage of the synthetic potential of nature.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and properties of polyesters derived from renewable eugenol and α,ω-diols via a continuous overheating method

Zhao

et al. 2015

Polym. Chem.

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Two eugenol-based aromatic dimethyl terephthalate (DMT)-like monomers were prepared via thiol-ene click reaction and subsequent nucleophilic substitution reactions with methyl chloroacetate or 1,4-dibromobutane. Two series of thermoplastic polyesters derived from renewable eugenol and linear aliphatic α,ω-diols HO-(CH2)n-OH (n = 2, 3, 4, 6, 10, 12) were successfully synthesized. These prepared polyesters have weight-average molecular weights in the range of 18500-90500 g mol -1 , and polydispersities (PDI) between 1.8 and 2.2. Their chemical structures were all accurately characterized by 1 H NMR, 13 C NMR and FTIR. The random microstructures of synthetic polyesters were also explored by 13 C NMR. The obtained polyesters all exhibit thermal stability above 330°C. More importantly, the thermal stability, the maximum degradation rate and residue weight are intimately associated with the length of the linear aliphatic α,ω-diol. Their thermo-mechanical properties were studied by the differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The length of linear aliphatic α,ω-diol shows crucial influence on the glass transition temperature (Tg). With the gradually increase of the α,ω-diol length, the Tg of the synthesized polyester uniformly exhibits a tendency of decreasing. The polyesters are all amorphous materials at room temperature, whose Tg values range from -28.4 to 7.6°C. The incorporation of aromatic eugenol into the polyester chains reduces the crystallinity obviously, as well as the mechanical properties compared with conventional PET or PBT. The Young's modulus and ultimate strength are just in the range of 1.2-6.9 MPa and 0.96-3.37 MPa, respectively. On the contrary, the elongation at break reaches up to 840-1000%, indicating the excellent viscosity properties for such unmanageable viscous materials.

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Section: Introductionmentioning

confidence: 99%

Synthesis and properties of polyesters derived from renewable eugenol and α,ω-diols via a continuous overheating method

Zhao

et al. 2015

Polym. Chem.

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“…For example, 13 C NMR spectra of the products do not show acetal carbon peak around 90 ppm (see supporting information). FT‐IR spectroscopy provides additional information regarding to the formation of ester carbonyl functionality in the copolymer backbone (see supporting information). The stretching vibration band of the ester carbonyl group of the copolymers appeared around 1740 cm −1 proving the formation of glycolic acid repeat units.…”

Section: Resultsmentioning

confidence: 99%

“…For example, 13 C NMR spectra of the products do not show acetal carbon peak around 90 ppm (see supporting information). 22 FT-IR spectroscopy provides additional information regarding to the formation of ester carbonyl functionality in the copolymer backbone (see We propose the polymerization mechanism as depicted in Figure 7. propagate the copolymerization.…”

Section: Various Reaction Conditions Including Different Epoxide Weigmentioning

confidence: 99%

Polyglycolic acid copolymers from one‐step cationic polymerization of formaldehyde, carbon monoxide, and epoxides derived from PEG

Reyhanoglu

Göktürk

2019

Polymers for Advanced Techs

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Biodegradable polyglycolic acid (PGA) is conventionally produced via the ring‐opening polymerization of glycolide, the cyclic dimer form of glycolic acid, in the presence of mostly tin‐based catalyst initiators which are rather known to be cytotoxic materials. Our previous studies revealed an alternative method for the synthesis of PGA from the perfectly alternating copolymerization of formaldehyde (from trioxane) and carbon monoxide (CO) under BrØnsted acidic conditions. The poor physical properties of PGA (insolubility in many organic solvents, brown color, etc.) limit its use in other marketing applications in the industry. To improve on the physical properties of PGA, such as solubility and appearance, copolymerization of trioxane, CO, and a minor amount of epoxides derived from polyethylene glycol (PEG) were performed under the same reaction conditions for PGA synthesis (in DCM, at 800 psi CO pressure, with triflic acid catalyst, reaction duration of 72 hours). The results have shown that the addition of minor quantities of epoxide comonomers vastly improves the appearance of the obtained PGA copolymers and allows for the control of the polymeric properties, such as solubility and melting temperature.

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“…Although ROP offers greater control over molecular weight and dispersity, step‐growth polymerization can be used with a wider variety of monomers, which can lead to more diverse polymer architectures. For example, Miller and coworkers prepared biorenewable polyalkylene acetals via acetal metathesis polymerization of α,ω‐diols . This research team also synthesized a variety of polycycloacetals incorporating bioaromatic backbone structures through polycondensation of tetraols and aromatic dialdehydes, with number averaged molecular weights ( M n ) reaching 27,100 g/mol .…”

Section: Introductionmentioning

confidence: 99%

“…For example, Miller and coworkers prepared biorenewable polyalkylene acetals via acetal metathesis polymerization of α,ω-diols. 8 This research team also synthesized a variety of polycycloacetals incorporating bioaromatic backbone structures through polycondensation of tetraols and aromatic dialdehydes, with number averaged molecular weights (M n ) reaching 27,100 g/mol. 9 Isosorbide is another intriguing monomer for synthesis of polyacetals, and the resulting polymers displayed degradation rates that correlated with the length of the aliphatic spacer between acetal linkages.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and material properties of elastomeric high molecular weight polycycloacetals derived from diglycerol and meso‐erythritol

Law

Stankowski

Bomann

et al. 2019

J of Applied Polymer Sci

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Copolymerizing glutaraldehyde with tetraols such as diglycerol, meso‐erythritol, and pentaerythritol is particularly effective for forming very high molecular weight polycycloacetals (Mn up to 65,000 g/mol) with elastomeric properties and up to 70% biorenewable content by weight. Altering the tetraol monomer feed ratio provides control over the polycycloacetal's tensile properties. The polymerizations are high‐yielding, readily scalable, and employ commercially available starting materials that are used without further purification. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48780.

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Acetal metathesis polymerization (AMP): A method for synthesizing biorenewable polyacetals

Cited by 53 publications

References 20 publications

Synthesis and properties of polyesters derived from renewable eugenol and α,ω-diols via a continuous overheating method

Synthesis and properties of polyesters derived from renewable eugenol and α,ω-diols via a continuous overheating method

Polyglycolic acid copolymers from one‐step cationic polymerization of formaldehyde, carbon monoxide, and epoxides derived from PEG

Synthesis and material properties of elastomeric high molecular weight polycycloacetals derived from diglycerol and meso‐erythritol

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