Polymerization of isoprene in n-heptane with triethylaluminum–titanium tetrachloride catalyst. I. Effect of Al/Ti ratio on stereoregularity,conversion, molecular weight,and molecular weight distribution

The influence of the Al/Ti ratio of the heterogeneous Ziegler–Natta catalyst system AlEt₃–TiCl₄ on the isoprene polymerization in n-heptane at 30°C in a bench scale reactor was investigated. Each batch run consisted of 50 mL isoprene, 200 mL n-heptane with 0.45 and 0.5g catalyst. Conversion of isoprene and molecular weights of polyisoprene increased with increasing Al/Ti ratio, reaching their maxima values at 1.0 and 1.2, respectively. Conversion and molecular weights decreased remarkably at a higher ratio of Al/Ti. As this ratio decreases from the value of 1.2 to 0.4, the cis1,4 content in polyisoprene decreased from 97 to 25%. When the ratio of Al/Ti increased from 1.2 to 2.2 the cis-1,4 structure of polyisoprene decreased from 97 to 85%.     

PHOTOCATALYTIC OXIDATION OF ALDEHYDES/PCE USING POROUS ANATASE TITANIA AND VISIBLE-LIGHT-RESPONSIVE BROOKITE TITANIA

We have synthesized an annealed porous aerogel titania (LUAG2), which demonstrates a very high photocatalytic activity for aldehydes and perchloroethylene (PCE) photocatalytic oxidation (PCO) in gas phase under blacklight and fluorescent light irradiation. LUAG2 has a BET surface area of 237 m²/g and a porosity of 0.31 (volume fraction). X-ray diffraction (XRD) analysis shows LUAG2 is nearly pure anatase. It has improved the destruction of PCE and aldehydes as a group by 10-34% with black light compared to Degussa P-25. The optimum water vapor to butyraldehyde molar ratio is around 1/3. LUAG2 also shows better mineralization to CO₂ than Degussa P-25 TiO₂ does. Under irradiation of a 4 W fluorescent lamp LUAG2 gives a consistently higher conversion than that of Degussa P-25. The highly active photocatalyst indicates potential applications in indoor and outdoor environmental pollution control. A visible-light-responsive TiO₂, NTB 200, is also investigated for comparison purposes.     

Grafting of poly(ethylene terephthalate) fibers with methacrylic acid using benzoyl peroxide

The graft copolymerization of methacrylic acid onto poly(ethylene terephthalate) fibers, by the aid of benzoyl peroxide, have been investigated. The graft yield increased up to 85°C, and then decreased with the further increase in temperature. The maximum graft yield was obtained at benzoyl peroxide concentration of 4.0 × 10^?3 mol/L. The increase in the concentration of monomer was found to increase the graft yield. The change in the graft yield was followed by the experiments carried out using different water/solvent mixtures. Also, the change in the properties of polye (thylene terephthalate) fibers grafted with methacrylic acid such as moisture regain, density, and diameter were investigated.     

Quantitative preparation of long chain thioethers from an oxo-trans-2-enoic ester and a 9,12-dioxo-trans-10-enoic acid

Branched-chain thioethers have been prepared from methyl 4-oxo-trans-2-hexadecenoate and 9,12-dioxo-trans-10-octadecenoic acid. The reagents involved in these preparations were mercaptoacetic and mercaptopropionic acids. The yields of these thioethers are almost quantitative.     

Role of sand on curing of partex surface by UV radiation

A partex surface was modified by a UV‐curing system with epoxy acrylate (EB‐600). A set of formulations was prepared with oligomer and the trifunctional monomer trimethylol propane triacrylate in different combinations of percentages (1–5%) of sand to study the role of sand in various physical properties of UV‐cured thin films, as well as partex surfaces. Increased pendulum hardness (PH), gloss, adhesion, and abrasion values were obtained by the addition of sand into the partex surfaces. The best results were obtained with the formulation containing 3% sand. An enhanced PH and a decreased percentage of gel content of the UV‐cured film was observed with an increase of the sand concentration. A simulated weathering test was performed with partex surfaces cured by a formulation containing 3% sand in the base coat. The losses of the physical properties were found to be lower over the surface treated with the formulation containing sand. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2385–2392, 2002     

Synthesis of tetrazole from α, β—Unsaturated carbonyl fatty acid

Methyl 4-oxo-trans-2-octadecenoate (II), when treated with excess hydrazoic acid in the presence of BF₃-etherate, produced 66% methyl 5-aza-nonadec-trans-2-enoate (4,5-d)-tetrazole (III), 10% methyl 5-aza-nonadec-4-oxo-trans-2-enoate (IV) and 7% pentadecamide (V). Individual products were characterized by spectral and elemental methods.     

Synthesis and characterization of hydroxyl terminated poly(butadiene)-g-poly(glycidyl azide) copolymer as a new energetic propellant binder

Summary Poly(glycidyl azide), PGA, was grafted onto Hydroxyl Terminated Poly(butadiene), HTPB, via free radical mechanism. PGA-macro azoinitator and HTPB polymer mixture was casted from solution and the polymer film was kept at 90°C for 4 hours. The grafted polymer was isolated from the product by fractional precipitation and characterized by NMR and FT-IR spectroscopy. Graft copolymer structure was also confirmed that volume ratio of nonsolvent to the solution of the graft copolymer was between those of corresponding homopolymers. TGA traces of the block polymers were containing two different maxima at 253°C (for PGA units) and 469°C (for HTPB units). Because of the incompatibility of the blocks, DSC curve showed two T_g's which belong to the related segments.     

Surface modification of polyester and polyamide fabrics by low frequency plasma polymerization of acrylic acid

In this study, the surface characteristics of polyester and polyamide fabrics were changed by plasma polymerization technique utilizing acrylic acid as precursor. This monomer was used to produce hydrophilic materials with extended absorbency. The hydrophilicity, total wrinkle recovery angle (WRA°) and breaking strength of the fabrics were determined prior and after plasma polymerization treatment. The modification of surfaces was carried out at low pressure (<100 Pa) and low temperature (<50°C) plasma conditions. The effects of exposure time and discharge power parameters were optimized by comparing properties of the fabrics before and after plasma polymerization treatments. It was shown that two sides of polyester fabric samples were treated equally and homogeneously in plasma reactor. For polyester fabrics, the minimum wetting time, 0.5 s, was observed at two plasma processing parameters of 10 W–45 min and 10 W–20 min, where untreated fabric has a wetting time of 6 s. For polyester fabrics, the maximum value was obtained at 60 W–5 min with the wrinkle recovery angle of 306° where the untreated fabric has 290°. The optimum plasma conditions for polyamide fabrics were determined as 30 W–45 min where 2 s wetting time was observed. Wrinkle recovery angle of untreated polyamide fabric was 264°. In this study, after plasma polymerization of acrylic acid, wrinkle recovery angle values were increased by 13%. No significant change was observed in breaking strength of both fabrics after plasma treatment. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2318–2322, 2007     

Exhaust Emissions from an Engine Fueled with Biodiesel from High-Oleic Soybeans

Biodiesel is a fuel comprising mono-alkyl esters of medium to long-chain fatty acids derived from vegetable oils or animal fats. Typically, engines operated on soybean-based biodiesel exhibit higher emissions of oxides of nitrogen (NOx) compared with petroleum diesel. The increase in NOx emissions might be an inherent characteristic of soybean oil’s polyunsaturation, because the level of saturation is known to affect the biodiesel’s cetane number, which can affect NOx. A feedstock that is mostly monounsaturated (i.e. oleate) helps to balance the tradeoff between cold flow and oxidative stability. Genetic modification has produced a soybean event, designated 335-13, with a fatty acid profile high in oleic acid (>85%) and with reduced palmitic acid (<4%). This high-oleic soybean oil was converted to biodiesel and run in a John Deere 4045T 4.5-L four-stroke, four-cylinder, turbocharged direct-injection diesel engine. The exhaust emissions were compared with those from conventional soybean oil biodiesel and commercial No. 2 diesel fuel. There was a significant reduction in NOx emissions (α = 0.05) using the high-oleic soybean biodiesel compared with regular soybean oil biodiesel. No significant differences were found between the regular and high-oleic biodiesel for unburned hydrocarbon and smoke emissions.     

Fatty acids of the seeds of <Emphasis Type="Italic">Origanum onites</Emphasis> L. and <Emphasis Type="Italic">O. vulgare</Emphasis> L.

Seed oils of Origanum onites L. from the Antalya and Mugla regions and O. vulgare L. from the Kirklareli region of Turkey were extracted with hexane in a Soxhlet apparatus. The oil yields were 14.1–20.0 and 18.5%, respectively. FA compositions of the seed oils were determined by GC and GC/MS. Twenty FA were identified in both O. onites and O. vulgare seeds. The major FA of both species were linolenic (56.3–57.0%; 61.8%), linoleic (21.5–21.7%; 18.8%), oleic (8.7–8.9%; 5.9%), palmitic (5.9–6.5%; 5.5%), stearic (2.1–2.4%; 2.1%), and (Z)-11-octadecenoic (0.6–0.8%; 0.5%), respectively.