A new xylylehe-like intermediate: 2-allylidene-5-methylene-2,5-dihydrofuran. Synthesis of [6.2], [4.4], and [4.2]furanophanes.

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/22784/1/0000339.pd

Bridged Aromatic Compounds: A Novel Xylylene-like Intermediate For New Furanophanes; Improved Synthesis Of (3.3)paracyclophane.

PhDOrganic chemistryUniversity of Michigan, Horace H. Rackham School of Graduate Studieshttp://deepblue.lib.umich.edu/bitstream/2027.42/180707/2/7627520.pd

The Second Degree Cohomology Of Finite Orthogonal Groups.

PhDMathematicsUniversity of Michigan, Horace H. Rackham School of Graduate Studieshttp://deepblue.lib.umich.edu/bitstream/2027.42/189413/2/7627519.pd

Polymerization of Linseed Oil with Phenolic Resins

In this study, linseed oil was directly polymerized with different oil soluble resoles. p-Ethyl (PEP), p-tertiary butyl (PTB), p-tertiary octyl (PTO), and p-phenyl (PPP) phenols were separately reacted with formaldehyde to give linseed oil soluble resoles. These were then reacted with linseed oil to give transparent rubbery polymers. A model reaction was performed with methyl oleate and PTB phenol resole to clarify the reaction mechanism. Reaction products were characterized with (1)H-NMR and IR techniques. Spectral examination of the model reaction showed that polymerization reaction proceeded via ene reaction of the quinone methide formed at the end group of the resole with the allylic positions of the fatty ester. Rubbery polymers were obtained with linseed oil using 10 to 40% of the different resoles. Hard, load bearing and tough materials were obtained at 40% phenolic resin loading. Mechanical properties of the materials were characterized by dynamic mechanical analyzer (DMA) and stress strain tests. The best mechanical and thermal properties were obtained with PEP resole which showed a storage modulus of 350 MPa and a tan 8 peak at 65 degrees C. Storage moduli of 275, 250, and 30 were obtained for PPP, PTB, and PTO resoles-linseed oil polymers, respectively. At the same phenolic resin loading, elongation at break and swelling ratios in CH(2)Cl(2) increased with the longer alkyl substitution on the resole resins. The highest thermal stability was observed by PEP resole linseed oil polymer which has a 5% weight loss temperature of 340 degrees C as determined by TGA. The lowest thermal stability was observed for PTB resole-linseed oil polymer at 220 degrees C. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 118: 849-856, 201

Thermal and mechanical behavior of unsaturated polyesters filled with phase change material

Samples of commercial unsaturated polyester (UPE) resin, filled with phase-changeable fillers (PCMs), were prepared, and the thermal and mechanical properties of the cured samples were examined. Fillers chosen were paraffin and Wood's metal. Samples were prepared by making dispersions of these fillers in liquid unsaturated polyester followed by curing with methyl ethyl ketone peroxide (MEKP) and conaphtanate and rigid thermoset samples filled with PCM particles were obtained. The thermal and mechanical behaviors of such a filled composite around the melting points of fillers are very interesting. Effects of varying proportions of PCM on mechanical and thermal properties of final products were examined. The samples show thermal melting behavior without undergoing a change in physical state. Decreases in the maximum working temperature from 75 to 53 degrees C for metal-filled samples and from 75 to 43 degrees C for paraffin-filled samples were observed by using dynamic mechanical thermal analysis. Differential scanning calorimetry indicated that heat absorption of paraffin samples were higher than that of metal-filled samples. For paraffin-filled samples, heats of fusion were 3.44 cal/g for 10% filled sample and 6.35 cal/g for 20% filled sample. For Wood's metal-filled samples, heats of fusion were 1.18 cal/g for 10% metal-filled sample and 1.54 cal/g for 20% metal-filled sample. Surface hardness was tested with Shormeter D. Surface hardness of metal-filled composites varied from 86 to 34 shore D at 21 degrees C and 80.6 to 35 shore D at 80 degrees C. For paraffin-filled samples, surface hardness changed from 86 to 42 shore D at 21 degrees C and from 80.6 to 13 shore D. Morphology of the samples was determined by scanning electron microscopy, of the crack surfaces. (c) 2006 Wiley Periodicals, Inc

A Simple One-Step Synthesis and Polymerization of Plant Oil Triglyceride Iodo Isocyanates

In this study a novel and simple route for the synthesis of the iodine isocyanate (INCO) adduct of soybean oil triglycerides is described. Soybean oil iodo isocyanate (ISONCO) was synthesized by the reaction of iodine isocyanate and soybean oil at room temperature. ISONCO was then polymerized With polyols, such as, castor oil, pentamethylene, glycol, and glycerol to give the corresponding polyurethanes and with polyamines, Such as, ethylene diamine, hexamethylene diamine, and triethylene tetramine to give corresponding polyureas. The structures of the monomer and the polymers were determined by FTIR and H-1-NMR analyses. Thermal properties of the polymers were determined by DSC and TGA. Thermal degradation of the polyurethanes started at 150 degrees C. Stability of the polyureas was higher than polyurethanes. Almost all polymers showed a T-g around -50 degrees C. The mechanical properties of the polymers were determined by tensile tests. Among the polymers synthesized, castor oil polyurethane showed the highest elongation at break and the lowest tensile strength of 140 KPa. The highest tensile strength of 900 KPa was observed in the pentamethylene glycol polyurethanes. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 116: 2433-2440, 201

Polymerization of Acrylated Epoxidized Soybean Oil with Phenol Furfural Resins via Repeated Forward and Retro Diels-Alder Reactions

In this work, the Diels-Alder reaction between the acrylate groups of acrylated epoxidized soybean oil and the furan rings of p-tertiary butyl phenol furfural resin (TBPF) is described. The reaction was carried out at 110 degrees C in presence of FeCl3 catalyst, and tough polymers were obtained in 1 h. Surprisingly, samples that were heated and cooled 5, 10, and 20 times to 140 degrees C and room temperature had better mechanical properties than samples that were kept at 140 degrees C for the same total duration. This unexpected behavior is attributed to a series of forward and retro Diels Alder reactions between the functional groups. To prove this hypothesis, a model reaction between TBPF and n-butyl acrylate was studied. At 100 degrees C, H-1-nuclear magnetic resonance signals of the furan ring protons disappeared, only to reappear at 140 degrees C. Thermogravimetric analysis of the adduct showed a weight loss at 140-150 degrees C, which was in quantitative agreement with the amount of butyl acrylate. Infrared analysis showed that furan rings were not completely consumed by extended heating at 110 degrees C. After five heating and cooling cycles of much shorter duration at 140 degrees C, the furan absorption in the infrared disappeared. The storage modulus of acrylated epoxidized soybean oil-TBPF samples after 20 heating cycles was 1.15 GPa. (C) 2010 Wiley Periodicals, Inc. J Appl! Polym Sci 120: 1707-1712, 201

Isothiocyanate Derivatives of Soybean Oil Triglycerides: Synthesis, Characterization, and Polymerization with Polyols and Polyamines

In this article, a novel two step synthesis of soy oil based isothiocyanate is described. Allylicaly brominated soybean oil (ABSO) was reacted first with ammonium thiocyanate in tetrahydro furan to form allylic thiocyanates. These compounds were then converted to isothiocyanated soybean oil (ITSO) by a thermal rearrangement. Conversion was found to be 70%. The structure of the ITSO was characterized by IR and H-1-NMR techniques. Then ITSO was reacted with ethylene glycol, glycerol, and castor oil to produce polythiourethanes and ethylene diamine and triethylene tetra amine to produce polythioureas. Thermal properties of the products were determined by DSC and TGA techniques. DSC traces showed 7(g)'s for ethylene glycol polythiourethane at -39 and 58 degrees C, for glycerol polythiourethane at -39 and 126 degrees C, for castor oil polythiourethane at -38 degrees C and -17 degrees C, for ethylene diamine polythiourea at -45 degrees C, and for triethylene tetra amine poly thiourea at -39 degrees C. Additionally, DSC analysis of polythioureas showed an endotherm at around 100 degrees C. All of the polymers started to decompose around 200 degrees C. Tensile properties of the polymers were determined. Polythiourethanes showed higher tensile strength and lower elongation when compared with their urea analogs. Stress at break values of the polymers were 1.2 MPa for glycerol polythiourethane, 0.6 MPa for ethylene glycol polythiourethane, 0.5 MPa for ethylene diamine polythiourea, and 0.9 MPa for triethylene tetra amine polythiourea polymers. Unfortunately, polymers synthesized showed poor solvent resistance. All polymers swelled and disintegrated in CH2Cl2 in 5 h. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 116: 125-131, 201

Renewable Polymeric Nanocomposite Synthesis Using Renewable Functionalized Soybean-Oil-Based Intercalant and Matrix

Completely bio-based and renewable polymeric nanocomposites have been prepared using an in situ polymerization technique in the presence of organically-modified montmorillonite (MMT) clays in different loading degrees. Acrylated epoxidized soybean oil (AESO) and styrene have been used as matrices, whereas modification of MMT has been clone by using a new renewable soybean-oil-based intercalant. quarternized functionalized acrylated epoxidized soybean oil, which is the first renewable intercalant described in the literature. It was found that the above-mentioned intercalant could be successfully intercalated between the interlayer galleries of montmorillonite which is confirmed by X-ray diffraction (XRD) data and atomic force microscopy (AFM). The nanocomposite formation Studies examined by both XRD and AFM showed that the desired exfoliated nanocomposite structures can be achieved with all nanofiller loadings. The resultant exfoliated nanocomposites were found to have significantly improved thermal stability and dynamic mechanical performance at very low loadings. The nanocomposites from both renewable intercalant and matrix offer a significant potential for new high-volume. low-cost application,,. (C) Koninklijke Brill NV, Leiden, 200

Long-Range Neuronal Circuits Underlying the Interaction between Sensory and Motor Cortex

SummaryIn the rodent vibrissal system, active sensation and sensorimotor integration are mediated in part by connections between barrel cortex and vibrissal motor cortex. Little is known about how these structures interact at the level of neurons. We used Channelrhodopsin-2 (ChR2) expression, combined with anterograde and retrograde labeling, to map connections between barrel cortex and pyramidal neurons in mouse motor cortex. Barrel cortex axons preferentially targeted upper layer (L2/3, L5A) neurons in motor cortex; input to neurons projecting back to barrel cortex was particularly strong. Barrel cortex input to deeper layers (L5B, L6) of motor cortex, including neurons projecting to the brainstem, was weak, despite pronounced geometric overlap of dendrites with axons from barrel cortex. Neurons in different layers received barrel cortex input within stereotyped dendritic domains. The cortico-cortical neurons in superficial layers of motor cortex thus couple motor and sensory signals and might mediate sensorimotor integration and motor learning