Isoquinoline-mediated 5-vinylation and N-vinylation of benzo[d]oxazole-2-thiol and benzo[d]thiazole-2-thiol

An effective route to 5-vinylated and N-vinylated benzo[d]oxazole-2（3H）-thiones and benzo[d]thiazole-2（3H）-thiones is described via reaction of acetylenic esters and benzo[d]oxazole-2-thiol and benzo[d]thiazole-2-thiol in the presence of 15 mol%of isoquinoline.

Synthesis and evaluation of poly(N-vinyl caprolactam)-co-tert-butyl acrylate as kinetic hydrate inhibitor

Low dosage kinetic hydrate inhibitors(KHIs)are a kind of alternative chemical additives to high dosage thermodynamic inhibitors for preventing gas hydrate formation in oil&gas production wells and transportation pipelines.In this paper,a new KHI,poly(N-vinyl caprolactam)-co-tert-butyl acrylate(PVCapco-TBA),was successfully synthesized with N-vinyl caprolactam(NVCap)and tert-butyl acrylate.The kinetic inhibition performances of PVCap-co-TBA on the formations of both structureⅠmethane hydrate and structureⅡnatural gas hydrate were investigated by measuring the onset times of hydrate formation under different conditions and compared with commercial KHIs such as PVP,PVCap and inhibex 501.The results indicated that PVCap-co-TBA outperformed these widely applied inhibitors for both structureⅠand structureⅡhydrates.At the same dosage of KHI,the maximum tolerable degree of subcooling under which the onset time of hydrate formation exceeded 24 hours for structureⅠhydrate was much lower than that for structureⅡhydrate.The inhibition strength increased with the increasing dosage of PVCap-co-TBA;The maximum tolerable degree of subcooling for the natural gas hydrate is more than10 K when the dosage was higher than 0.5%(mass)while it achieved 12 K when that dosage rose to0.75%(mass).Additionally,we found polypropylene glycol could be used as synergist at the dosage of 1.0%(mass)or so,under which the kinetic inhibition performance of PVCap-co-TBA could be improved significantly.All evaluation results demonstrated that PVCap-co-TBA was a very promising KHI and a competitive alternative to the existing commercial KHIs.

Absorption Capability Comparison of Two Kinds of Super Absorbent Resins from Carboxymethyl Cellulose

The two kinds of super absorbent resins from carboxymethyl cellulose were synthesized with the potassium persulphate and methylenebisacrylamide as initiator and cross linker respectively by radical polymerization in aqueous solution. Thestructures of the two resins were characterized with Fourier transform infrared spectroscopy FTIR, scanning electron miscroscopy （SEM）, and environment scanning electron miscroscopy （ESEM）, the results indicate that the fibriform of the carboxymethyl cellulose （CMC） is disappeared and the crusslink networks in eopolymer of carboxymethyl cellulose-graft-polyacrylic acid（CMC-g-PAA） are denser than that of eopolymer of carboxymethyl cellulose-graft-poly （acrylic acid-co-N-vinyl Pyrrolidone） （CMC-g- PAA-co-PVP）. The comparison between the two resins in absorption capacities is that CMC-g-PAA is better in the water-keep capability being heated, while CMC-g-PAA-co-PVP is better in the water absorbency and salt resistance.

Synthesis, Characterization and in vitro Degradation Properties of Poly(Propylene Fumarate-co-Propylene Sebacate) Networks

Poly（propylene fumarate-co-propylene sebacate） （P（PF-co-PS）） was crosslinked with Nvinyl pyrrolidone （N-VP） to form networks. It was investigated as biodegradable bone cement. In this paper, P（PF-co-PS） was synthesized and characterized by ^1H-NMR, FTIR and GPC. The effects of the amount of sebacate segments in P（PF-co-PS） main chains and the quantity of N-vinyl pyrrolidone on the in vitro degradation of the polymer networks were examined. Cylindrical specimens were submerged in phosphate buffered saline （PBS） at 37 ℃ and the pH value of PBS is 7.4 for 10 weeks. The gravimetry and compressive mechanical properties were tested over the degradation period. Networks formed by P（PF-oo-PS）8020/N-VP exhibited higher weight loss and better mechanical properties when compared with poly（propylene fumarate）/N-VP networks. The mechanical properties of P（PF-co-PS）/N-VP can be maintained for a very long time, even for 70 days, the yield strength, fracture strength and compressive modulus are （51.78 ± 2.01） MPa, （52.331 ± 1.84） MPa and （957.78 ± 24.40） MPa, respectively. The results demonstrate that the compressive mechanical properties and degradation velocity can be modulated by the amount of crosslinking agents and sebacate segments along the main chains of copolymers.

Photorefractive Effect in an Azobenzene Chromophore Side Groups Polymer

We have analyzed the photorefractive（PR） effect of a polymer composite was reported which combines a novel bi-functional poly（N-vinyl）-3-[p-nitrophenylazo]carbazolyl（PVNPAK） and 2,4,7-trinitro-9-fluorenone（TNF）. PVNPAK was synthesized by a post-azo-coupling reaction, with an azo derivative as the electrooptic chromophore and carbazolyl as photoconductive moiety. The asymmetric two-beam coupling gain of 13.9 cm-1 and diffraction efficiency of 1.2% for poled polymer film fabricated using a corona poling are obtained at the wavelength of 647.1 nm, confirming photorefractivity. We interpreted this result as the orientational enhancement, in which the spatial charge field may enhance the modulated orientation of the azobenzen chromophore. It is unexpected that the photorefractive gain of 9.5 cm-1 for the unpoled polymer film also was observed without external field in two-beam coupling（TBC） experiment. This phenomenon is attributed to a light-induced orientational grating when the azobenzene groups are illuminated by polarized light.

Palladium-catalyzed vinylation of indoles with vinyl ethers via deoxygenative coupling

Indole is a promising heteroarene in many natural products and pharmaceuticals;therefore, various synthetic methods for indole functionalizations have arisen in recent years. Herein, we report a Pd-catalyzed deoxygenative coupling for the N-vinylation of indoles by employing vinyl ethers. The vinylated indoles could be readily prepared in good to excellent yields with N1-regioselectivity regardless of the electronic characteristics and substitution patterns of indole substrates. Some indole-based pharmaceutical molecules, such as gramine, evodiamine, rutaecarpine, and melatonine, are also successfully vinylated. Moreover, carbazoles and indazoles are shown to participate. Additionally, vinylated indole can readily transform into structurally interesting indole derivatives.