Low ceiling temperature, thermodynamically unstable polymers have been troublesome to synthesize and keep stable during storage. In this study, stable poly(phthalaldehyde) has been synthesized with BF 3 -OEt 2 catalyst. The role of BF 3 in the polymerization is described. The interaction of BF 3 with the monomer is described and used to maximize the yield and molecular weight of poly(phthalaldehyde). Various Lewis acids were used to investigate the effect of catalyst acidity on poly(phthalaldehyde) chain growth. In situ nuclear magnetic resonance was used to identify possible interactions formed between BF 3 and phthalaldehyde monomer and polymer. The

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Knowledge of the ceiling temperature and thermodynamic variables for low ceiling temperature polymers is critical to understanding the material's synthesis and use. Synthesis of the polymer below its ceiling temperature is the routine polymerization route. In situ 1H NMR of the equilibrium polymerization reaction can provide critical information for determining the enthalpy and entropy of polymer formation. Three polyaldehydes were synthesized with in situ 1H NMR, and their energies of formation were determined for the linear region of ceiling temperature. Insights into the mechanism of polymerization were also found using this method. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 221–228

The study and development of transient devices is an emerging field where the disposal of a device after use is desired to avoid reverse engineering and minimize the environmental impact. Polyaldehydes with phototriggers have been investigated because the radiation wavelength can be adjusted to meet the transient application. Polynuclear aromatic hydrocarbons (PAHs) were used as the optical sensitizer for photoacid generators (PAGs). Photoinduced electron transfer (PET) with an iodonium-based PAG was used to expand the spectral sensitivity range. Anthracene, tetracene, and pentacene derivatives were synthesized with appended phenylethynyl groups to improve the solubility of the sensitizer and adjust the absorption wavelength. Sensitization of the iodonium-based PAG with the PAH derivatives was found to have thermodynamically favorable PET reactions for depolymerization of poly(propylene carbonate) and poly(phthalaldehyde) (PPHA). The Rehm-Weller equation and Stern-Volmer analysis were used to study the electron transfer and the fluorescence quenching rates of the PAHs with the iodonium salts, respectively. The photosensitivity, efficiency, and byproducts of the PET reactions in the decomposable polymer films are reported. A rapid photoreaction is reported for the depolymerization of PPHA exposed to a sunlight dose of <6 J cm −2 (i.e., 1 min of direct sunlight) with a pentacene-based sensitizer.

Polymers can be used as temporary place holders in the fabrication of embedded air gaps in a variety of electronic devices. Embedded air cavities can provide the lowest dielectric constant and loss for electrical insulation, mechanical compliance in devices where low-force deformations are desirable, and can temporarily protect movable parts during processing. Several families of polymers have been used as sacrificial, templating polymers including polycarbonates, polynorbornenes (PNBs), and polyaldehydes. The families can be distinguished by chemical structure and decomposition temperature. The decomposition temperature ranges from over 400 °C to below room temperature in the case of low ceiling temperature polymers. Overcoat materials include silicon dioxide, polyimides, epoxy, and bis-benzocyclobutene (BCB). The methods of air-gap fabrication are discussed. Finally, the use of photoactive compounds in the patterning of the sacrificial polymers is reviewed.