Preparation of a mercaptopropyl bonded silica intermediate in supercritical carbon dioxide: synthesis, characterisation and chromatography of a quinine based chiral stationary phase

This research examines the preparation of a mercaptopropyl bonded silica intermediate in supercritical carbon dioxide (sc-CO(2)) and the subsequent conversion in sc-CO(2) to a quinine derived chiral stationary phase (CSP). The effects of reaction temperature, pressure and time on the surface coverage of the silica intermediate were investigated when porous silica particles (Exsil-Avanti, 3microm) were reacted with 3-trimethoxymercaptopropylsilane in sc-CO(2). We present results which demonstrate that a stable mercaptopropyl bonded silica intermediate can be successfully prepared under supercritical conditions of 40 degrees C, 483bar, in a substantially reduced reaction time of 1h with superior surface coverages compared to organic solvent based methods. The further utility of this supercritical fluid technology was demonstrated by the free radical addition of a quinine derived chiral selector onto a mercaptopropyl bonded silica intermediate in sc-CO(2). This supercritical fluid generated chiral stationary phase (CSP) was utilised for the direct LC enantioseparation of a series of 3,5-dinitrobenzoyl (DNB) amino acids. Bonded silica samples were characterised using elemental analysis, diffuse reflectance infrared fourier transform (DRIFT) spectroscopy, solid state (13)C and (29)Si CP-MAS NMR spectroscopy, and thermogravimetric analysis (TGA). This supercritical fluid functionalisation approach offers an efficient and cleaner alternative to existing organic solvent based approaches for the preparation of bonded silica phases.     

Analysis of silica hydride and surface hydrosilation reactions by solid-state NMR in the preparation of<Emphasis Type="Italic"> p</Emphasis>-chlorobenzamide bonded silica phase

²⁹Si and ¹³C CP-MAS NMR spectroscopy was used to follow the conversion of native silica to a p-chlorobenzamide bonded silica material. The benzamide bonded phase was prepared via a hydrosilation reaction of a hydride silica intermediate with p-chloro-N-allylbenzamide. Solid-state NMR was used to show the disappearance of reactive surface hydride species (M_H) and to identify newly formed bonded chemical species on the silica surface. DRIFT spectroscopy, elemental analysis, and specific surface-area determinations (BET) of the prepared phases are also reported.     

On-line liquid-chromatography-nuclear magnetic resonance spectroscopy-mass spectrometry coupling for the separation and characterization of secoisolariciresinol diglucoside isomers in flaxseed

The effect of endcapping on an octdecyl bonded phase synthesized by the silanization/hydrosilation method is investigated. The endcapping reagent is a 1:1 molar ratio of trimethylchlorosilane (TMCS) and hexamethyldisilizane (HMDS). Two approaches for endcapping are possible for this synthetic method that produces a silica hydride intermediate: bonding of TMCS-HMDS after silanization (on the hydride intermediate) or after hydrosilation (on the C18 product stationary phase). The use of TMCS-HMDS is designed to eliminate the few remaining silanols on the silica hydride intermediate. The endcapping process is characterized spectroscopically by diffuse reflectance infrared Fourier transform (DRIFT), 29Si cross polarization magic angle spinning nuclear magnetic resonance spectroscopy (CP-MAS-NMR) and 13-C-CP-MAS-NMR. The octadecyl bonded phases are characterized chromatographically by measuring the capacity factors of several hydrophobic and basic test solutes as well as the separation factors among various solute pairs. Finally, long-term stability tests are done on both products at high and low pH.     

Synthesis and characterization of a novel hydroxypolyether blocked polydimethylsiloxane PEO-b-PDMS-b-PEO

A novel hydroxypolyether blocked polydimethylsiloxane, poly（ethylene oxide） propyl-b-polydimethylsiloxane-b-propyl poly（ethylene oxide） （PEO-b-PDMS-b-PEO） was synthesized by simple hydrosilation reaction of poly（ethylene glycol） monoallyl ether with α,ω-dihydrogen terminated PDMS （HPDMS）. Fourier transform infrared spectroscopy （FTIR） and IH NMR were used to identify the structure of PEO-b-PDMS-b-PEO and intermediate product HPDMS. Based on the effect investigations of temperature, reactant molar ratio, catalyst and time on the hydrosilation, it was found that the conversion of Si-H bond to SiC bond increased with the increase of catalyst and time, and the reaction completed when the content of catalyst was 22μg/g and the time was 5 h, respectively. Urethane reaction of OH and NCO group confirms that PEO-b-PDMS-b-PEO is more reactive toward to diisocyanate than α,ω-dihydroxylbutyl terminated PDMS.     

超临界二氧化碳中无水相涂料的合成与表征

为了减小传统纸张涂布中涂料水分对涂布能耗、涂布质量以及对涂布原纸质量的影响,研究了以超临界二氧化碳为反应介质,制备聚甲基丙烯酸甲酯(PMMA)和碳酸钙颜料混合的粉末涂料粒子.通过FTIR、GPC-十八角度激光光散射联用技术对PMMA组成结构进行了表征,考察了反应体系中引发剂浓度、单体浓度、稳定剂浓度、反应温度和反应时间对聚合反应的转化率和聚合产物的分子量的影响.实验表明,当反应条件为反应压力10MPa,反应温度75℃,反应时间8h,单体浓度0.10g/mL,引发剂浓度0.10×10-2g/mL,稳定剂浓度0.06×10-2g/mL时,其聚合反应的转化率较高,同时PMMA的分子量适中,分子量分布窄.SEM观察到混合涂料粒子颗粒均匀,表明颜料在粉末涂料体系中分散性良好.     

Analysis of organic pollutants in sewage by supercritical fluid extraction

Summary Analytical methods have been developed for the determination of organic pollutants of intermediate polarity in sewage. Water samples are first passed through a solid phase adsorption cartridge. The analytes are then extracted from the absorbent with supercritical CO₂ into a small volume of trapping solvent. Finally, the extracts are analyzed directly by capillary gas chromatography and gas chromatography-mass spectrometer. The various parameters (pressure, temperature, type and concentration of modifiers, trapping solvent, flow rate and volume of supercritical fluid and equilibrium time) influencing the efficiency of extraction were studied. Extraction efficiencies for the test compounds are >70%, and relative standard deviations are <4.6% (n=3). The methods established were applied to the analysis of sewage at the Lanzhou Wastewater Treatment Plant, China. 66 organic pollutants were detected, of which 15 compounds appeared in the list of priority pollutants suggested by the US EPA.     

Mechanism for reduction catalysis by metal oxo: hydrosilation of organic carbonyl groups catalyzed by a rhenium(V) oxo complex

The rhenium oxo complex [Re(O)(hoz)2][TFPB], 1 (where hoz = 2-(2'-hydroxyphenyl)-2-oxazoline(-) and TFPB = tetrakis(pentafluorophenyl)borate) catalyzes the hydrosilation of aldehydes and ketones under ambient temperature and atmosphere. The major organic product is the protected alcohol as silyl ether. Isolated yields range from 86 to 57%. The reaction requires low catalyst loading (0.1 mol %) and proceeds smoothly in CH2Cl2 as well as neat without solvent. In the latter condition, the catalyst precipitates at the end of reaction, allowing easy separation and catalyst recycling. Re(O)(hoz)(H), 3, was prepared, and its involvement in an ionic hydrosilation mechanism was evaluated. Complex 3 was found to be less hydridic than Et3SiH, refuting its participation in catalysis. A viable mechanism that is consistent with experimental findings, rate measurements, and kinetic isotope effects (Et3SiH/Et3SiD = 1.3 and benzaldehyde-H/benzaldehyde-D = 1.0) is proposed. Organosilane is activated via eta2-coordination to rhenium, and the organic carbonyl adds across the coordinated Si-H bond [2 + 2] to afford the organic reduction product.     

Ring-opening polymerization of L-lactide and preparation of its microsphere in supercritical fluids

The ring-opening polymerization of L-lactide initiated by stannous octoate was carried out in supercritical chlorodifluoromethane (scR22) at various reaction conditions (time and temperature) and reactant concentrations (initiator, monomer, and solvent). The monomer conversion increased to ca. 70% on increasing the reaction time to 1 h. The molecular weight of the poly(L-lactide) (PLLA) product also increased to ca. 160,000 g x mol(-1) over the same period. Increasing reaction temperature from 90 to 130 degrees C resulted in increased monomer conversion and PLLA molecular weight. A series of polymerizations conducted at various 1-dodecanol and stannous octoate concentrations suggested that stannous octoate does not act as an initiator by itself, and that the tin-alkoxide formed from 1-dodecanol and stannous octoate serves as the initiating species in scR22. While enhancements of the monomer conversion and PLLA molecular weight were observed with increasing monomer concentration, the chlorodifluoromethane concentration had the opposite on both. After the polymerization, PLLA microspheres were prepared in situ by using a continuous supercritical antisolvent process without residual organic solvent and monomer to yield highly purified microspheres for environmental and biomedical applications.     

Synthesis and Studies on Surface Active Water Soluble Derivatives of Siloxane Oligomers

Abstract

We report the synthesis of cationic water-soluble siloxanes by reacting aminosiloxanes with dimethyl, n-dodecyl 3-chloro-2-hy-droxypropyl quaternary ammonium iodide (DDCQA). Tetramethyl disiloxane on hydrosilation with allyl amine in the presence of hex-achloroplatinic acid/IPA gave bis(3-aminopropyl) octamethyltetra-siloxane. In addition, formation of Si-H containing oligomeric siloxanes were detected during this reaction and the extent of formation of the oligomers was found to depend upon the concentration of platinum. The oligomerization reaction was explained by dehydrogenative coupling of Si-H groups in the presence of platinum catalyst. A plausible mechanism for formation of aminosiloxane and the Si-H oligomers were proposed. Alternatively, cyclic Si -H containing siloxanes on polymerization using butyl lithium gave oligomeric Si-H containing siloxanes, which were hydrosilated to give aminosiloxanes. The quaternary aminosiloxanes synthesized showed lowering in surface tension of water to 26 mN/m.     

Nonclassical titanocene silyl hydrides

The titanocene silyl hydride complexes [Ti(Cp)2(PMe3)(H)(SiR3)] [SiR3=SiMePhCl (6), SiPh2Cl (7), SiMeCl2 (8), SiCl3 (9)] were prepared by HSiR3 addition to [Ti(Cp)2(PMe3)2] and were studied by NMR and IR spectroscopy, X-ray diffraction (for 6, 8, and 9), and DFT calculations. Spectroscopic and structural data established that these complexes exhibit nonclassical Ti-H-Si-Cl interligand hypervalent interactions. In particular, the observation of silicon-hydride coupling constants J(Si,H) in 6-9 in the range 22-40 Hz, the signs of which we found to be negative for 8 and 9, is conclusive evidence of the presence of a direct Si-H bond. The analogous reaction of [Ti(Cp)2(PMe3)2] with HSi(OEt)3 does not afford the expected classical silyl hydride complex [Ti(Cp)2(PMe3)(H)[Si(OEt)3]], and instead NMR-silent titanium (apparently TiIII) complex(es) and the silane redistribution product Si(OEt)4 are formed. The structural data and DFT calculations for the compounds [Ti(Cp)2(PMe3)(H)(SiR3)] show that the strength of interligand hypervalent interactions in the chlorosilyl complexes decreases as the number of chloro groups on silicon increases. However, in the absence of an Si-bound electron-withdrawing group trans to the Si-H moiety, a silane sigma complex is formed, characterized by a long Ti-Si bond of 2.658 A and short Si-H contact of 1.840 A in the model complex [Ti(Cp)2(PMe3)(H)(SiMe3)]. Both the silane sigma complexes and silyl hydride complexes with interligand hypervalent interactions exhibit bond paths between the silicon and hydride atoms in Atoms in Molecules (AIM) studies. To date a classical titanocene phosphane silyl hydride complex without any Si-H interaction has not been observed, and therefore titanocene silyl hydrides are, depending on the nature of the R groups on Si, either silane sigma complexes or compounds with an interligand hypervalent interaction.     

Kinetic studies of photopolymerization using real time FT-IR spectroscopy

The real time FT-IR (RT/FT-IR) technique has been recognized as a very vital tool to quantitatively study the curing parameters such as the effects of initiator (or catalyst) type and concentration, accelerator, stabilizer, irradiation wavelength, temperature, and curing environments. Herein, our results in studies of photoinduced polymerizations for adhesive and coating applications are reported. The photoinduced polymerizations studied included anionic and hydrosilation (a polyaddition polymerization) reactions. In photoinduced anionic polymerization our studies for ethyl cyanoacrylate polymerization are described. The effect of the concentration of photoinitiator and inhibitor on the ethyl cyanoacrylate polymerization kinetic rate will be discussed. In photoinduced catalytic hydrosilation reaction studies, the effects of the catalyst concentration and staging irradiation are disclosed. The hydrosilation reaction was monitored using a Si? H silicone hydride stretching band located at 2169 cm^?1. The cyanoacrylate polymerization was monitored using the C?C stretching band occurring at 1617 cm^?1. The hydrosilation conversion was completed with an appropriate formulation. For monofunctional cyanoacrylate monomer, the photoinduced conversion to straight chain polymer was approximately 85% for a 60 s period. The intrinsic rates of the reactions were calculated for kinetic comparisons. For very fast cyanoacrylate polymerization studies, new FT-IR kinetic software was used to collect 204 spectra/min. Some detailed experimental techniques and polymerization reaction mechanisms are also discussed. © 1993 John Wiley & Sons, Inc.     

溶胶-凝胶法制备Ni-SiO2催化剂的表征与性能

以正硅酸乙酯和硝酸镍为原料,采用溶胶-凝胶法,将硝酸镍分别溶于水和乙醇制得凝胶,分别经超临界干燥和常规干燥制备了一系列Ni-SiO2气凝胶和干凝胶催化剂,运用BET、XRD、TPR、IR、H2-TPD和活性评价等方法对催化剂的物理化学性质和催化间二硝基苯加氢性能进行研究.结果表明,Ni-SiO2气凝胶催化剂均具有较高的比表面积,但由于金属镍烧结导致活性比表面积较小,加氢性能较差;以乙醇为溶剂制备的干凝胶催化剂的镍物种分散度较高,但镍与载体之间的相互作用过强,致使催化剂的还原度降低,活性组分利用率下降;以水为溶剂制备的干凝胶催化剂具有较高的活性比表面积,表现出很高的催化活性和选择性.     

Analysis of an unprecedented mechanism for the catalytic hydrosilylation of carbonyl compounds

This work details an in-depth evaluation of an unprecedented mechanism for the hydrosilylation of carbonyl compounds catalyzed by (PPh3)2Re(O)2I. The proposed mechanism involves addition of a silane Si-H bond across one of the rhenium-oxo bonds to form siloxyrhenium hydride intermediate 2 that reacts with a carbonyl substrate to generate siloxyrhenium alkoxide 4, which, in turn, affords the silyl ether product. Compelling evidence for the operation of this pathway includes the following: (a) isolation and structural characterization by X-ray diffraction of siloxyrhenium hydride intermediate 2, (b) demonstration of the catalytic competence of intermediate 2 in the hydrosilylation reaction, (c) 1H and 31P{1H} NMR and ESI-MS evidence for single-turnover conversion of 2 into 1, (d) observation of intermediate 2 in the working catalyst system, and (e) kinetic analysis of the catalytic hydrosilylation of carbonyl compounds by 1.     

Synthesis and evaluation of silica hydride‐based fluorinated stationary phases

Two novel silica hydride‐based fluorinated bonded phases have been synthesized using a hydrosilation procedure to test combined fluorine and hydride selectivity. The bonded moieties were characterized by elemental and spectral analysis. Chromatographic testing was done using hydrophilic analytes in the aqueous normal phase mode. At higher amounts of the nonpolar solvent in the mobile phase, there should be increased retention for solutes such as acids, bases and other polar compounds, whereas nonpolar solutes can be retained when water is increased as in RP chromatography. The synergistic effects of the fluorinated phase selectivity and aqueous normal phase retention on a hydride surface have been explored for small polar molecules. The stability and repeatability of the hydride‐based fluorinated stationary phases were evaluated. The use of acetone as the organic component in the mobile phase was also tested.     

Synthesis and Reactivity of Hydroxypoly(ethylene oxide) propyl–b–polydimethylsiloxane–b–propyl hydroxypoly(ethylene oxide)

A series of α, ω–bishydroxyl terminated PDMS, hydroxypoly(ethylene oxide) propyl–b–polydimethylsiloxane–b–propyl hydroxypoly(ethylene oxide) (HPEO–PDMS–HPEO) was prepared by a hydrosilation reaction of monoallyloxy substituted poly(ethylene oxide) with α,ω–bishydrogen terminated PDMS (HPDMS) that obtained via acid–catalyzed ring–opening polymerization of octamethylcyclotetrasiloxane with 1,1,3,3–tetramethyldisiloxane. Chloroplatinic acid was employed as the catalyst of hydrosilation. The molecular weight of HPEO–PDMS–HPEO could be controlled easily by varying the chain length of HPDMS. FTIR and ¹H–NMR spectroscopy were used to identify the structure of HPEO–PDMS–HPEO and HPDMS. The conversion of Si–H bond to Si–C bond was affected by the catalyst amount, reaction time and temperature. It was found that the optimum condition of hydrosilation reaction was the catalyst amount of 22 μg/g and 5 h time at 100°C. Synthesized HPEO–PDMS–HPEO showed good storage stability at ambient temperature. Urethane reaction of OH and NCO group revealed that HPEO–PDMS–HPEO was more reactive toward to diisocyanate than α, ω –bishydroxylbutyl terminated PDMS.     

Hydrosilation in Supercritical CO2: Synthesis of Fluorinated Polysiloxanes

Hydrosilation of poly(methylhydrosiloxane) with a fluorinated olefin in supercritical CO₂ (scCO₂) using Karstedt's Pt catalyst has been successfully demonstrated; results were compared with those obtained in a subcritical conventional solvent, i.e. toluene. Rates of hydrosilation were found to be dependent on solvent, reactant concentration, and reaction temperature. Levels of hydrosilation were 40–50%, depending on reaction conditions. Gel formation, which was not observed under any conditions in subcritical toluene, occurred in all reactions done in scCO₂ and accounted for up to 20 wt.‐% of the final product mix.     

Synthesis and hydrosilation of multi-vinyl branched siloxane for self-healing system

In this work, the preparation of α,ω-dichloride-terminated multi-vinyl branched siloxane 1 （yield： 57.1%） used for self-healing polymer composites were synthesized via ring-opening of 1,3,5,7-tetravinyl-1,3,5,7-tetramethyl-cyclotetrasiloxane （D4^vi） in the presence of vinylmethydichlorosilane （VM-32）. 1 was hydrogenated by aluminum lithium hydride （LiAlH4） to get self-healing monomer 2 （yield： 79.8%） which contained both Si-H bonds and Si-vinyl bonds. Then hydrosilation occurred between these two bands and finally silicone 3 was obtained, showing the potential of self-healing.     

Comparative studies on exchange reactions of hexafluoroacetylacetonate in bis(hexafluoroacetylacetonato)(dimethyl sulfoxide)dioxouranium(VI) in nonaqueous solvent and supercritical CO(2)

Exchange reactions of hexafluoroacetylacetonate (hfacac) in UO2(hfacac)2DMSO (DMSO = dimethyl sulfoxide) in o-C6D4Cl2 and supercritical CO2 (sc-CO2) have been studied using the NMR line-broadening method to compare reactivity in a nonaqueous solvent with that in sc-CO2. It was found that the exchange rates of hfacac in both systems are dependent on the concentration of the enol isomer ([Henol]) of hexafluoroacetylacetone and become slow with an increase in the concentration of free DMSO ([DMSO]). The exchange reaction between free and coordinated DMSO in UO2(hfacac)2DMSO has been also examined in o-C6D4Cl2 and sc-CO2. As a result, the exchange rate of DMSO was found to depend on [DMSO]. From these results, the hfacac exchange reactions in UO2(hfacac)2DMSO in o-C6D4Cl2 and sc-CO2 were proposed to proceed through the mechanism that the ring-opening for one of two coordinated hfacac in UO2(hfacac)2DMSO is the rate-determining step, and the resulting vacant site is coordinated by the incoming Henol, followed by the proton transfer from Henol to hfacac and the ring closure of unidentate hfacac. The rate constants at 60 degrees C and the activation parameters (DeltaH and DeltaS) for the ring-opening path are 35.8 +/- 3.2 s(-1), 57.8 +/- 2.7 kJ.mol(-1), and -42.9 +/- 7.7 J.mol(-1).K(-1) for the o-C6D4Cl2 system, and 518 +/- 50 s(-1), 18.9 +/- 1.8 kJ.mol(-1), and -138 +/- 5 J.mol(-1).K(-1) for the sc-CO2 system, respectively. Differences in kinetic parameters between sc-CO2 and o-C6D4Cl2 systems were proposed to be attributed to the solute-solvent interactions such as Lewis acid-Lewis base interactions and hydrogen bondings between sc-CO2 and beta-diketones.     

Off-line SFE-CGC-ECD analysis of 2,4-D and Dicamba residues in real sugar cane,rice and corn samples

Determination of 2,4-D (2,4-dichlorophenoxyacetic acid) and Dicamba (2-methoxy-3,6-dichlorobenzoic acid) residues in sugar cane, rice, and corn was carried out both by solid liquid extraction (SLE), as already described in the literature, and by a supercritical fluid extraction (SFE) method developed in our laboratory. The extracts were esterified and cleaned-up by passing through a Florisil column. Extracts were analyzed by high resolution gas chromatography, with electron capture detection. The tested methods presented good recoveries (above 90%); the SFE CO₂/acetone method showed better extraction efficiencies (extracted 30 % more herbicide in real samples), shorter extraction time and lower organic solvent consumption than the SLE method.     

Hypervalent hydridosilicates: synthesis, structure and hydride bridging

A range of hydridosilicate anions has been prepared and characterised by spectroscopic, structural and computational methods. The general approach involved reaction of KH with a neutral silane precursor in the presence of [18]crown-6. In this manner, [K([18]crown-6)]+ salts of [Ph3SiH2](-) (1), [Ph3SiF2](-) (9), and [(p-FC6H4)3SiHF](-)/[(p-FC6H4)3SiH2](-) (12) were stabilised and characterized by NMR spectroscopy and X-ray diffraction. In each case, the anion adopts a trigonal bipyramidal (TBP) geometry with three equatorial phenyl groups eclipsing the axial Si-H/Si-F bonds. The Si-H[dot dot dot]K distances, along with DFT calculations on 1, indicate an electrostatic interaction that does not dictate the geometry adopted by the anion. A [H2SiOiPr3](-) salt (7) has also been crystallised in the same way; X-ray diffraction shows in this case a distorted TBP array with axial hydride ligands, and both Si-H[...]K and Si-O[...]K interactions. 1H NMR exchange experiments show 1 to undergo facile hydride exchange with Ph3SiH. Compound 1 acts as a good hydride transfer reagent to a variety of substrates, but its high reactivity often results in redistribution and other side reactions.