Lawrence C. Baldwin

Synthesis, Characterization, and Cure Chemistry of Renewable Bis(cyanate) Esters Derived from 2-Methoxy-4-Methylphenol

A series of renewable bis(cyanate) esters have been prepared from bisphenols synthesized by condensation of 2-methoxy-4-methylphenol (creosol) with formaldehyde, acetaldehyde, and propionaldehyde. The cyanate esters have been fully characterized by infrared spectroscopy, (1)H and (13)C NMR spectroscopy, and single crystal X-ray diffraction. These compounds melt from 88 to 143 °C, while cured resins have glass transition temperatures from 219 to 248 °C, water uptake (96 h, 85 °C immersion) in the range of 2.05-3.21%, and wet glass transition temperatures from 174 to 193 °C. These properties suggest that creosol-derived cyanate esters may be useful for a wide variety of military and commercial applications. The cure chemistry of the cyanate esters has been studied with FTIR spectroscopy and differential scanning calorimetry. The results show that cyanate esters with more sterically demanding bridging groups cure more slowly, but also more completely than those with a bridging methylene group. In addition to the structural differences, the purity of the cyanate esters has a significant effect on both the cure chemistry and final Tg of the materials. In some cases, post-cure of the resins at 350 °C resulted in significant decomposition and off-gassing, but cure protocols that terminated at 250-300 °C generated void-free resin pucks without degradation. Thermogravimetric analysis revealed that cured resins were stable up to 400 °C and then rapidly degraded. TGA/FTIR and mass spectrometry results showed that the resins decomposed to phenols, isocyanic acid, and secondary decomposition products, including CO2. Char yields of cured resins under N2 ranged from 27 to 35%, while char yields in air ranged from 8 to 11%. These data suggest that resins of this type may potentially be recycled to parent phenols, creosol, and other alkylated creosols by pyrolysis in the presence of excess water vapor. The ability to synthesize these high temperature resins from a phenol (creosol) that can be derived from lignin, coupled with the potential to recycle the composites, provides a possible route to the production of sustainable, high-performance, thermosetting resins with reduced environmental impact.

Synthesis of an Isophorone‐Based Nonlinear Optical Chromophore

Abstract The synthesis of a “CLD‐type” nonlinear optical chromophore incorporating the isophorone unit to rigidize the polyene segment is described. The synthesis required seven steps with an overall yield of 17%.

Poly(thiophenylanilino) and poly(furanylanilino) polymers

Novel hybrid polymers with thiophenylanilino and furanylanilino backbones and substituted phenyl side groups are reported. The new monomers bis-(4-heterocyclic-2-yl-phenyl)-aryl-amine (heterocyclic = thiophen with aryl = 4-benzoyl (2a), 4-nitro-phenyl (2b) and furan with aryl = 4-benzoyl-phenyl (3a), 4-nitro-phenyl (3b)) were prepared by monosubstituting triphenylamine under electrophilic aromatic conditions affording 4-nitrotriphenylamine and 4-benzoyltriphenylamine. Di(bromination) of the latter compounds followed by Stille cross-coupling reactions with 2-tributylstannylthiophene or 2-tributylstannylfuran produces the new monomers 2a–b and 3a–b in high yield. The monomers are electrochemically polymerized at relatively low potentials (<0.8 V versus Ag+/AgCl) in acetonitrile electrolytes resulting in electroactive films. All the new polymers can be repeatedly oxidized and reduced with little loss of electrochemical activity. Vibrational spectroscopy reveals that the monomer units are connected predominately via coupling of the thiophenyl or furanyl rings yielding the novel polymers. Single-crystal molecular structure determinations of 4-nitrotriphenylamine and monomer 3b indicate the importance of the electron-withdrawing groups on the pendent phenyl groups in determining the extent of delocalization of the extended multi-ring systems. Molecular orbital calculations suggest that the HOMO of 2b is delocalized about both anilino and thiophenyl portions of the molecule.

Synthesis and Characterization of bis(Tetrahydrofurfuryl) Ether

Abstract Despite the availability of a large number of alkyl tetrahydrofurfuryl ethers that have a wide range of applications, pure bis(tetrahydrofurfuryl) ether (BTHFE) has not been previously synthesized. Here, we report the synthesis of BTHFE (consisting of the RR, SS, and meso stereoisomers) at greater than 99 % purity from tetrahydrofurfuryl alcohol, using (tetrahydrofuran‐2‐yl)methyl methanesulfonate as an intermediate. Additionally, we demonstrate that BTHFE can be used as a non‐volatile solvent in poly(3,4‐propylenedioxythiophene)‐based supercapacitors. Supercapacitor devices employing solutions of the ionic liquid 1‐ethyl‐3‐methyl‐imidizolium bis(trifluoromethylsulfonyl)imide in BTHFE display similar performances to those prepared by using the neat ionic liquid as an electrolyte, although solution‐based devices exhibit a somewhat higher resistance.

AgInS2 quantum dots for the detection of trinitrotoluene.

AgInS2 (AIS) quantum dots (QDs) were synthesized via a thermal decomposition reaction with dodecylamine as the ligand to help stabilize the QDs. This reaction procedure is relatively easy to implement, scalable to large batches (up to hundreds of milligrams of QDs are produced), and a convenient method for the synthesis of chalcogenide QDs. Metal powders of AgNO3 and In(NO3)3, were used as the metal precursors while diethyldithiocarbamate was used as the sulfur source. The AIS QDs were characterized via transmission electron microscopy, atomic force microscopy, and energy dispersive x-ray spectroscopy. As an application for these less toxic nanomaterials, we demonstrate the selective detection of Trinitrotoluene (TNT) at concentrations as low as 6 micromolar (μM) and without the functionalization of a ligand that is specifically designed to interact with TNT molecules. We also demonstrate a simple approach to patterning the AIS QDs onto filter paper, for the detection of TNT molecules by eye. Collectively, the ease of the synthesis of the less toxic AIS QDs, and the ability to detect TNT molecules by eye suggest an attractive route to highly sensitive and portable substrates for environmental monitoring, chemical warfare agent detection, and other applications.

Cover Picture: Synthesis and Characterization of bis(Tetrahydrofurfuryl) Ether (ChemistryOpen 4/2016)

The Front Cover picture shows crude bis(tetrahydrofurfuryl) ether (BTHFE) before the final fractional distillation. This work demonstrates a synthetic method that allows for tetrahydrofurfuryl ethers with bulky substituents to be produced. The chemical and physical properties of BTHFE make it an interesting compound for use in electrochemical energy storage devices. More information can be found in the Communication by P. A. Goodman and co‐workers on page 297 in Issue 4, 2016 (DOI: 10.1002/open.201600013).

Alternative Route to the Diisocyanate Building Block 1,4-Diisocyanato-4-methylpentane (DIMP)

The synthesis of 1,4-diisocyanato-4-methylpentane was accomplished starting from isobutyronitrile in six steps with 53% overall yield. The two isocyanates were installed by a double Curtius rearrangement. The product reacts with alcohol in a regioselective manner.