UNSTEADY DIFFUSION KINETICS OF ZIEGLER-NATTA HETEROGENEOUS CATALYST POLYMERIZATION .4. PREDICTION OF EXPERIMENTAL RESULTS OF PROPYLENE ETHYLENE 1-HEXADECENE TERPOLYMERIZATION

The prediction, based on unsteady diffusion kinetics, of the enhancement of reactivity and incorporation of 1-hexadecene in its copolymerization with propylene on adding a small amount of ethylene (increase from 5,2 mol-% to 10,8 mol-% when 2% of ethylene was added, and to 16,1 mol-% when 5% was added) was verified in the terpolymerization of propylene/1-hexadecene/ethylene on a commercial Solvay-type delta-TiCl3 catalyst. The catalyst efficiency was thus also increased. These augmentations originate from the increase in diffusion coefficient of 1-hexadecene at the catalyst surface when the PP crystallinity decreases on introduction of ethylene. Calculation based on unsteady diffusion kinetics showed that the order of diffusion coefficients ethylene > propylene > 1-hexadecene is reversed as the monomer concentration increases when the monomers are not at their equilibrium concentration. Sequence distribution as determined by means of C-13 NMR revealed a tendency of blocky structure rather than a Bernoullian one. The terpolymer compositions obtained by means of an IR method developed in this work conform rather well with the NMR results. Results in this work not only support the unsteady diffusion kinetics but also provide a new route to prepare olefinic copolymer rubbers with heterogeneous titanium catalysts.

SYNTHESIS AND CHARACTERIZATION OF POLY-ORTHO-METHYLANILINE WITH DIFFERENT DEGREES OF OXIDATION

Poly-ortho-methylanilines (POT) in three states fully oxidized, fully reduced and oxidized in varying degrees were synthesized by the reaction of common POT (C-POT) having nearly equal amounts of benzenediamine and quinonediimine units with iodine or phenyl-hydrazine, and the resulting polymers were characterized by IR, C-13-NMR, SEM and elemental analysis. The results showed that the quinonediimine unit in C-POT could be reduced by phenylhydrazine to the benzenediamine unit, forming the polymer with low OD (oxidation degree) or in a fully reduced state and that iodine-oxidation resulted in the increase of quinonediimine unit and decrease of benzenediamine unit. The solubility and flexibility of the formed polymers depend strongly on the amount of quinonediimine unit in it. It is necessary to reduce the content of quinonediimine structure unit in order to improve the solubility of aniline-class polymers.

CHARACTERIZATION, MORPHOLOGY AND THERMAL-PROPERTIES OF ETHYLENE PROPYLENE BLOCK COPOLYMERS

Characterization, morphology and thermal properties of commercial ethylene-propylene block copolymers have been studied by C-13 nuclear magnetic resonance (n.m.r.) spectroscopy, differential scanning calorimetry (d.s.c.), dynamic mechanical analysis (d.m.a.) and scanning electron microscopy (SEM). The results obtained show that there exists some ethylene-propylene random copolymer in the block copolymers extractable by n-heptane. The possibility of forming PP-b-PE diblock copolymer is questionable on the basis of the effects of residual propene and the chain-transfer reaction in the sequential copolymerization. A difference in the thermal properties between commercial ethylene-propylene block copolymers and PP/PE blends was noticed, which cannot be used to identify PP-b-PE diblock copolymer. The multiphase structure has been confirmed by d.m.a. and SEM, with ethylene-propylene random copolymer and polyethylene forming the domains in the matrix of polypropylene.

An acidic polysaccharide with xylose branches from Porphyra yezoensis

An acidic polysaccharide (PY3) was isolated from the hot water extract of the red algae Porphyra yezoensis by successive column chromatographies over DEAE-cellulose and Sephadex G-200. PY3 with an average molecular weight of 1.8x10(5) was demonstrated to be composed of galactose (Gal), 3,6-anhydrogalactose (3,6-AnGal), 6-OSO3-galactose (6-OSO3-Gal) and xylose (Xyl) in an approximate molar ratio of 25 : 15, 10, 1. In view of Smith degradation and methylation and on the basis of spectral evidence including those of IR, GC, GC-MS, and H-1 and C-13 NMR, the most probable repeating unit of PY3 could be proposed as [(1-->3)beta -D-Gal(1 --> 4)alpha -L-3,6-AnGal](3)-[(1 --> 3)beta -D-Gal(1 --> 4)alpha -L-6-OSO3-Gal](2) with a xylose moiety at the C-6 of one of every twenty-five beta -D-Gal residues. To our knowledge, PY3 was shown to be the first porphyran possessing occasional xylose branches.

Preparation and in vitro antioxidant activity of kappa-carrageenan oligosaccharides and their oversulfated, acetylated, and phosphorylated derivatives

In order to study the relationship between chemical structure and properties of modified carrageenans versus antioxidant activity in vitro, K-carrageenan oligosaccharides were prepared through mild hydrochloric acid hydrolysis of the polysaccharide, and these were used as starting materials for the partial synthesis of their oversulfated, acetylated, and phosphorylated derivatives. The structure and substitution pattern of the oligosaccharides and their derivatives were Studied using FTIR and C-13 NMR spectroscopy, and their in vitro antioxidant activities were investigated. Certain derivatives of the carrageenan oligosaccharides exhibited higher antioxidant activity than the polysaccharides and oligosaccharides in certain antioxidant systems. The oversulfated and acetylated derivatives, which scavenge superoxide radicals, the phosphorylated and low-DS acetylated derivatives, which scavenge hydroxyl radicals, and the phosphorylated derivatives, which scavenge DPPH radicals, all exhibited significant antioxidant activities it, the systems examined. The effect of the molecular weight of the carrageenan on antioxidant activities, however, is not obvious from these studies. (c) 2005 Elsevier Ltd. All rights reserved.

Preparation, structural characterization and in vitro antitumor activity of kappa-carrageenan oligosaccharide fraction from Kappaphycus striatum

Oligosaccharides were prepared through mild hydrochloric acid hydrolysis of kappa-carrageenan from Kappaphycus striatum to compare the antitumor activity with carrageenan polysaccharides. Oligosaccharide fractions were isolated by gel permeation chromatography and the structure of fraction 1 (F1) was studied by using negative- ion electrospray ionization-mass spectrometry (ESI-MS), and H-1 and C-13-NMR spectrometry. The in vitro antitumor effects in three human neoplastic cell lines (KB, BGC, and Hela) of polysaccharides and F1 were investigated. The bioassay results showed that F1 exhibited relatively higher antitumor activity against the three cancer cells than polysaccharides.

Antimicrobial activity of hydroxylbenzenesulfonailides derivatives of chitosan, chitosan sulfates and carboxymethyl chitosan

Chitosan, carboxymethyl chitosan (CIVICS) and chitosan sulfates (CSS) with different molecular weight were modified by reacting with 4-hydroxyl-5-chloride-1,3-benzene-disulfo-chloride or 2-hydroxyl-5-chloride-1,3 -benzene-disulfo-chloride to give 12 kinds of new hydroxylbenzenesulfonailides derivatives of them. The preparation conditions of the derivatives were discussed in this paper, and their structures were characterized by FT-IR and C-13 NMR spectroscopy. The solubility of the derivatives was measured in the experiment. In addition, their antimicrobial activities against four bacteria and five crop-threatening pathogenic fungi were tested in the experiment. Besides, the rule and mechanism of their antibacterial activities were discussed in this paper. (C) 2009 Published by Elsevier B.V.

Preparation of high-molecular weight and high-sulfate content chitosans and their potential antioxidant activity in vitro

The influence of molecular weight and substitution degree of sulfated polysaccharides on their biological activity is considered in majority of works involving the anticoagulant or antiviral properties of these substances. Therefore, the present paper describes the effect of preparation conditions of sulfated chitosans on their molecular weight and sulfur content, such as different reaction time, acid solvent and temperature. Foregoing literature expounded the action of dichloroacetic acid (DCAA) as acid solvent in homogeneous reaction. However, DCAA is expensive and noxious, therefore, in the present paper cheap and non-noxious formic acid (88%) was in place of DCAA. Furthermore, during reaction formic acid was not dehydrated. Under formic acid we obtained the satisfying results that was higher yield and equivalent sulfur contents compared to DCAA. IR and C-13 NMR spectrums proved the structure of the resultant obtained under formic acid or DCAA to be same. Now, it has not been reported for formic acid as acid solvent in homogeneous reaction of chitosan sulfatation. In this present paper, we also determined antioxidant activity of high-molecular weight and high-sulfate-content chitosans (HCTS). The results showed that HCTS could scavenge superoxide and hydroxyl radical. Its IC50 is 0.012 and 3.269 mg/mL, respectively. It had obviously reducing power and slight chelating activity. The data obtained in in vitro models clearly establish the antioxidant potency of HCTS. It is a potential antioxidant in vitro. (C) 2005 Elsevier Ltd. All rights reserved.

Preparation of low-molecular-weight and high-sulfate-content chitosans under microwave radiation and their potential antioxidant activity in vitro

In the present paper microwave radiation has been used to introduce N-sulfo and O-sulfo groups into chitosan with a thigh degree of substitution and low-molecular weight. The sulfation of chitosan was performed in microwave ovens. It was found that microwave heating is a convenient way to obtain a wide range of products of different degrees of substitution and molecular weight only by changing reaction time or/and radiation power. Moreover, microwave radiation accelerated the degradation of sulfated chitosan, and the molecular weight of sulfated chitosan was considerably lower than that obtained by traditional heating. There are no differences in the chemical structure of sulfated chitosan obtained by microwave and by conventional technology. FTIR and C-13 NMR spectral analyses demonstrated that a significantly shorter time is required to obtain a satisfactory degree of substitution and molecular weight by microwave radiation than by conventional technology. In this present paper, we also determined antioxidant activity of low-molecular-weight and high-sulfate-content chitosans (LCTS). The results showed LCTS could scavenge superoxide and hydroxyl radical. Its IC50 is 0.025 and 1.32mg/mL, respectively. It is a potential antioxidant in vitro. (C) 2004 Published by Elsevier Ltd.

The antioxidant activity of 2-(4(or 2)-hydroxyl-5-chloride-1,3-benzene-di-sulfanimide)-chitosan

Chitosan (CS) with two different molecular weights was modified by reacting with 4-hydroxyl-5-chloride-1,3-benzene-disulfo-chloride or 2-hydroxyl-5-chloride-1,3-benzene-disulfo-chloride to give new 2-(4(or 2)-hydroxyl-5-chloride-1,3-benzene-di-sulfanimide)-chitosan (2-HCBSAHCS, 2-HCBSALCS, 4-HCBSAHCS, 4-HCBSALCS). The structure of the derivatives was characterized by FT-IR and C-13 NMR spectroscopy. The antioxidant activities of the derivatives were investigated employing various established systems, such as hydroxyl radical ((OH)-O-center dot)/superoxide anion (O-2(radical anion)) scavenging/reducing power and chelating activity. All the derivatives showed stronger scavenging activity on hydroxyl radical than chitosan and ascorbic acid (Vc), and IC50 of 4-HCBSAHCS, 4-HCBSALCS, 2-HCBSAHCS and 2-HCBSALCS was 0.334, 0.302, 0.442, 0.346 mg/mL, respectively. The inhibitory activities of the derivatives toward superoxide radical by the PMS-NADH system were strong. The results showed that the superoxide radical scavenging effect of 2-(4(or 2)-hydroxyl-5-chloride-1,3-benzene-disulfanimide)-chitosan was higher than chitosan. The derivatives had obviously reducing power and slight chelating activity. The data obtained in in vitro models clearly establish the antioxidant potency of 2-(4(or 2)-hydroxyl-5-chloride-1,3-benzene-disulfanimide)-chitosan. (C) 2007 Elsevier Masson SAS. All rights reserved.

A novel silica-based column packing for reversed-phase HPLC of basic compounds

A novel bonded phase for reversed-phase HPLC was synthesized in two steps. Octylamine was first reacted with beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (beta -ECTS) and then the intermediate product was coupled onto porous silica. The prepared packing was characterized by elemental analysis, solid-state C-13 NMR and Fourier transform infrared (FT-IR). Chromatographic evaluations were carried out by using a mixture of organic compounds including acidic, basic and neutral analytes and methanol-water as binary mobile phase. The results showed that the stationary phase has excellent chromatographic properties and is resistant to hydrolysis between pH = 2 similar to 8. It can be used efficiently for the separation of basic compounds.

Dramatic solvent effects on ring-opening metathesis polymerization of cycloalkenes

A series of metathesis polymers and copolymers have been formed and their structures were analysed by C-13 NMR spectroscopy. Noble metal and non-noble metal salt catalysts are distinguished by their behaviour in various solvents. Thus, in phenolic solvents, the former class produce alternating copolymers from cyclopentene and norbornene, while the latter are unaffected and produce random copolymers. In contrast, ether solvents have the effect of markedly increasing the cis content of polymers from the latter catalysts while the former are unaffected.

Characteristics of RuCl2(CHPh)(PCy3)(2) as a catalyst for ring-opening metathesis polymerization

Ring-opened metathesis polymers and copolymers have been formed from norbornene, norbornadiene, a range of their derivatives, and cyclopentene using RuCl2(CHPh)(PCy3)(2), as catalyst. C-13 NMR analysis of the polymers illustrate a rather selective propagation reaction. The catalyst is highly regioselective, and the polymers are generally high trans with a strong isotactic bias. However, polymers from diene monomers tend to be less isotactic than those from the corresponding monoenes, and in the case of 7-methylnorbornadiene the polymer has an overall syndiotactic bias. A rate enhancing effect, noted previously, due to an oxygen atom proximate to the monomer double bond, is less pronounced than with other initiators. Catalyst activity, in the case of certain diene monomers, was shown to be monomer dependent and rate enhancements were also achieved using phenol as solvent. The results are interpreted in terms of the steric and electronic properties of both the catalyst and the monomers.

CO2 Capture in Wet and Dry Superbase Ionic Liquids

The solubility of carbon dioxide in five tetraalkylphosphonium superbase ionic liquids, namely the trihexyltetradecylphoshonium phenoxide, trihexyltetradecylphoshonium benzotriazolide, trihexyltetradecylphoshonium benzimidazolide, trihexyltetradecylphoshonium 1,2,3-triazolide, and trihexyltetradecylphoshonium 1,2,4-triazolide was studied experimentally under dry and wet conditions at 22 A degrees C and at atmospheric pressure, using a gravimetric saturation technique. The effects of anion structure and of the presence or absence of water in the solution on the carbon dioxide solubility were then deduced from the data. H-1 and C-13-NMR spectroscopy and ab initio calculations were also conducted to probe the interactions in these solutions, as carbon dioxide and water can compete in the ionic liquid structure during the absorption process. Additionally, the viscosity of selected superbase ionic liquids was measured under dry and wet conditions, in the presence or absence of CO2, to evaluate their practical application in carbon dioxide capture processes. Finally, the recyclability of the trihexyltetradecylphoshonium 1,2,4-triazolide under dry and wet conditions was determined to probe the ability of selected solvents to solubilize chemically a high concentration of carbon dioxide and then release it in a low energy demand process.

Aza-annulation of enaminones with itaconic anhydride:kinetic preference for exocyclic enamide products

Enaminones react with itaconic anhydride in methylene chloride at room temperature to give exocyclic enamides sis the major products. These can be readily equilibrated to the thermodynamically more stable endocyclic enamides. In substrates where the exocyclic isomer could not be formed only intractable materials were produced from this reaction. An intermediate in this two step process was detected and identified by proton and C-13 NMR spectroscopy. In two cases chiral enaminones were employed and the relative stereochemistry at the new chiral centre in the product was established by a crystal structure of compound 27.