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1.
Polysiloxane formation in dimethyldiethoxysilane (DMDES)-ethyl alcohol (EtOH(D))-oxalic acid (OA) (DMDES:EtOH(D):OA=1:2:0.5) and DMDES-dimethylsulfoxide (DMSO)-OA (DMDES:DMSO:OA=1:2:0.5) systems was investigated by gas chromatography-mass spectrometry and 29Si-nuclear magnetic resonance. While the DMDES-EtOH(D)-OA system was homogeneous, the DMDES-DMSO-OA system consisted of two immiscible phases. In both systems, ethoxy-terminated linear oligomers ((EtO)Me2SiO(Me2SiO)nSiMe2(OEt); n=0–4, Et = C2H5, Me = CH3) and cyclic tetramer ((Me2SiO)4) were identified. The reaction mechanism for polysiloxane formation is discussed.  相似文献   

2.
Xerogels containing residues of amide derivatives of phosphonic and thiophosphonic acids, ≡Si(CH2)3NHP(S, O)(OC2H5)2 (functional group concentration of 1.3–2.2 mmol/g) have been prepared by a sol-gel method. It has been shown that xerogels having a developed porous structure (with specific surface areas of 240–485 m2/g, pore volumes of 0.20–0.50 cm3/g, and pore diameters of 3.6–6.5 nm) are formed at tetraethoxysilane-to-trifunctional silane ratios of 4: 1 (and above) and 6: 1 (and above) for the derivatives of phosphonic and thiophosphonic acids, respectively. The IR and 13C CP/MAS NMR spectroscopy data have demonstrated that the surface layer of the xerogels contains not only (thio)phosphonic acid residues, but also silanol groups and water molecules participating in hydrogen bonding. The 29Si CP/MAS NMR spectroscopy data have indicated that structural groups are, for the most part, contained in structural units T3 [(≡SiO)3Si(CH2)3NHP(O, S)(OC2H5)2] and T2 [(≡SiO)2Si(OR)[(CH2)3NHP(O, S)(OC2H5)2] (R = H or C2H5).  相似文献   

3.
The relative rate technique has been used to measure the hydroxyl radical (OH) reaction rate constant of +2-butanol (2BU, CH3CH2CH(OH)CH3) and 2-pentanol (2PE, CH3CH2CH2CH(OH)CH3). 2BU and 2PE react with OH yielding bimolecular rate constants of (8.1±2.0)×10−12 cm3molecule−1s−1 and (11.9±3.0)×10−12 cm3molecule−1s−1, respectively, at 297±3 K and 1 atmosphere total pressure. Both 2BU and 2PE OH rate constants reported here are in agreement with previously reported values [1–4]. In order to more clearly define these alcohols' atmospheric reaction mechanisms, an investigation into the OH+alcohol reaction products was also conducted. The OH+2BU reaction products and yields observed were: methyl ethyl ketone (MEK, (60±2)%, CH3CH2C((DOUBLEBOND)O)CH3) and acetaldehyde ((29±4)% HC((DOUBLEBOND)O)CH3). The OH+2PE reaction products and yields observed were: 2-pentanone (2PO, (41±4)%, CH3C((DOUBLEBOND)O)CH2CH2CH3), propionaldehyde ((14±2)% HC((DOUBLEBOND)O)CH2CH3), and acetaldehyde ((40±4)%, HC((DOUBLEBOND)O)CH3). The alcohols' reaction mechanisms are discussed in light of current understanding of oxygenated hydrocarbon atmospheric chemistry. Labeled (18O) 2BU/OH reactions were conducted to investigate 2BU's atmospheric transformation mechanism details. The findings reported here can be related to other structurally similar alcohols and may impact regulatory tools such as ground level ozone-forming potential calculations (incremental reactivity) [5]. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 745–752, 1998  相似文献   

4.
The 1H, 13C and 31P NMR data of several 2-R-2-thiono-1,3-dioxa organophosphorus molecules with 7-membered rings [R = Cl, OC6H5, C6H5, CH3, N(CH3)2] are reported. The conformation of the 7-membered ring is discussed by reference to the 3J(POCH) coupling constants which are compared with those observed in 6-membered 1,3,2-dioxaphosphorinanes. It is shown that caution must be exercised in using the 3J(POCH) angular dependence as a stereochemical tool. The 31P spin lattice relaxation times of some of these 7-membered rings have been measured and the values are discussed.  相似文献   

5.
The consecutive reactions of (CH3)2Si(OC2H5)2 and CH3Si(OC2H5)3 with methoxide ions were investigated in methanol solutions. The reverse transesterification reactions with ethoxide ions could be neglected in both cases since the concentration of ethoxide in methanol solution was assumed to be low due to the fast equilibrium reaction C2H5O? + CH3OH ? C2H5OH + CH3O?. The progress of the reactions was followed by monitoring the formation of ethanol with a Fourier-transform infrared spectrometer. All rate constants were determined at 295 K. The reactions between the dialkoxydimethylsilanes and methoxide ions were assumed to consist of two consecutive steps that can be represented by the net reaction; (CH3)2Si(OC2H5)2 + 2CH3O? → (CH3)2Si(OCH3)2 + 2C2H5O?. The two consecutive rate constants were established as 1.93 ± 0.12M?1s?1 and 1.00 ± 0.12M?1s?1, respectively. The consecutive rate constants for the reactions between the trialkoxymethylsilanes and methoxide ions can be written according to the total reaction; CH3Si(OC2H5)3 + 3CH3O? → CH3Si(OCH3)3 + 3C2H5O?. The three rate constants corresponding to each consecutive step were established as 1.12 ± 0.09 M?1s?1, 0.82 ± 0.10 M?1s?1, and 0.51 ± 0.06 M?1s?1, respectively. © 1995 John Wiley & Sons, Inc.  相似文献   

6.
The sol-gel method with ethanol as a solvent and fluoride ion as a catalyst was used to prepare polysiloxane xerogels containing both 3-mercaptopropyl and n-propyl groups in the surface layer. An increase in the relative amount of n-propyltriethoxysilane in the initial reaction solution was found to result in the formation of xerogels with developed porous structures, which was accompanied by an increase in the specific surface area from 370 to 550 m2/g; simultaneously, other porous structure parameters such as sorption volume and pore size exhibited a tendency to increase. Atomic-force microscopy was used to show that the xerogels synthesized comprised aggregates of mean size 30 nm. An analysis of the IR and 13C cross-polarization magic angle spinning NMR data led us to conclude that the surface layer of bifunctional xerogels contained not only 3-mercaptopropyl and n-propyl groups but also silanol groups, part of nonhydrolyzed alkoxy groups, and H-bonded water molecules. The 29Si cross-polarization magic angle spinning NMR spectra revealed the presence of structural units of the compositions T1 [(≡SiO)Si(OR’)2(CH2CH2CH3) and/or (≡SiO)Si(OR’)2(CH2)3SH, R’ = H, OCH3, or OC2H5], T2 [(≡SiO)2Si(OR’)(CH2CH2CH3) and (≡SiO)2Si(OR’)(CH2)3SH], and T3 [(≡SiO)3SiCH2CH2CH3 and (≡SiO)3Si(CH2)3SH] in the xerogels synthesized.  相似文献   

7.
The preparation and NO-adsorption/desorption behavior of Li, Ca and Ba silicates were investigated aiming at the application to a NOx-absorbent. Li silicate was prepared by reaction of HSi(OC2H5)3 with aqueous lithium silicate solution (LSS). Ca and Ba silicates were prepared from gels obtained using CH3Si(OC2H5)3, Si(OC2H5)4, HSi(OC2H5)3 and alkaline-earth alkoxides. The surface of these silicates indicated the solid basicity of H0 = 9 and adsorbed the acidic gas of NO. FT-IR spectra of the silicates adsorbing NO showed the absorption peaks in the range of 1300–1600 cm– 1 corresponding to ionic and covalent nitrate NO3. The complete desorption of adsorbed NO species occurred above 500°C in the Li silicate, above 500°C in the Ca and Ba silicates prepared using CH3Si(OC2H5)3, and above 700°C in the Ba and Ca silicates prepared using Si(OC2H5)4. Regarding the Ca and Ba silicates, the difference in siloxane structure is thought to cause the difference in adsorption state and desorption behavior of NO.  相似文献   

8.
Preparation and Spectroscopic Investigations of Highly Branched Functional Siloxanes The preparation of the siloxanes [(Me3SiO)3SiO]n(Me3SiO)3?nSiX and (Me3SiO)3Si[OSi(OSiMe3)2]2X (n = 1?3, X = H, Cl, OC2H5, OH) is described. The hydride-siloxanes and the siloxanoles have been investigated by i.r. and 29Si-n.m.r. spectroscopy. The frequencies of the Si? H stretching vibration, the 29Si? 1H coupling constants and the 29Si-chemical shifts of the Si(H) signal for the hydride-siloxanes as well as the frequencies of the (Si)O? H stretching vibration, the relative (Si)O? H acidity, and the 29Si-chemical shifts of the Si(OH) signal for the siloxanoles show a dependence on the number of the (Me3SiO)3SiO groups. The spectroscopic data are discussed with respect to the silicate environment of the Si(H) and Si(OH) atom, respectively. In the siloxanoles intramolecular hydrogen bondings were observed.  相似文献   

9.
Polysiloxane xerogels containing 3-mercaptopropyl and methyl groups in the surface layer were synthesized by the sol-gel method with ethanol used as a solvent and fluoride ion used as a catalyst. It is established that an increase in the relative content of methyltriethoxysilane in the initial reaction mixture results in formation of xerogels with a developed porous structure. The tendency for an increase in other characteristics of porous structure, the sorption volume and pore size, is also observed. The analogous effect is found upon increasing relative content of tetraethoxysilane with a constant ratio between two trifunctional silanes. By means of atomic force microscopy, it is shown that the xerogels are composed of aggregated particles with mean sizes of 35–45 nm. These results correlate with the data of scanning electron microscopy. On the basis of the data of IR spectroscopy and 13C CP/MAS NMR spectroscopy, it is concluded that the surface layers contain not only 3-mercaptopropyl and methyl groups but also silanol groups, a part of the unhydrolyzed alkoxy groups, and water molecules involved in the formation of hydrogen bonds. The results obtained by 29Si CP/MAS NMR spectroscopy testify that, in synthesized xerogels, the structural units of T1 type [(≡SiO)Si(OR′)2CH3 and/or (≡SiO)Si(OR′)2(CH2)3SH, R′ = H, OCH3 or OC2H5] are absent and the structural units of T3 type [(≡SiO)3SiCH3 and (≡SiO)3Si(CH2)3SH] dominate compared to the units of T2 type [(≡SiO)2Si(OR′)CH3 and (≡SiO)2Si(OR′)(CH2)3SH]. These results are an indirect indication of enhanced hydrolytic stability of surface layers in such xerogels.  相似文献   

10.
Partially deuterated Ca3Al2(SiO4)y(OH)12−4y-Al(OH)3 mixtures, prepared by hydration of Ca3Al2O6 (C3A), Ca12Al14O33 (C12A7) and CaAl2O4 (CA) phases in the presence of silica fume, have been characterized by 29Si and 27Al magic-angle spinning-nuclear magnetic resonance (MAS-NMR) spectroscopies. NMR spectroscopy was used to characterize anhydrous and fully hydrated samples. In hydrated compounds, Ca3Al2(OH)12 and Al(OH)3 phases were detected. From the quantitative analysis of 27Al NMR signals, the Al(OH)3/Ca3Al2(OH)12 ratio was deduced. The incorporation of Si into the katoite structure, Ca3Al2(SiO4)3−x(OH)4x, was followed by 27Al and 29Si NMR spectroscopies. Si/OH ratios were determined from the quantitative analysis of 27Al MAS-NMR components associated with Al(OH)6 and Al(OSi)(OH)5 environments. The 29Si NMR spectroscopy was also used to quantify the unreacted silica and amorphous calcium aluminosilicate hydrates formed, C-S-H and C-A-S-H for short. From 29Si NMR spectra, the amount of Si incorporated into different phases was estimated. Si and Al concentrations, deduced by NMR, transmission electron microscopy, energy dispersive spectrometry, and Rietveld analysis of both X-ray and neutron data, indicate that only a part of available Si is incorporated in katoite structures.  相似文献   

11.
Excess molar volumes VmE for binary liquid mixtures of n-alkoxyethanols or polyethers + 2-pyrrolidinone or N-methyl-2-pyrrolidinone have been measured with a continuous dilution dilatometer at 298.15 K and atmospheric pressure as a function of composition. The alkoxyethanols are diethylene glycol monomethylether, 2-(2-methoxyethoxy) ethanol, CH3(OC2H4)2OH; diethylene glycol monoethylether, 2-(2-ethoxyethoxy) ethanol, C2H5(OC2H4)2OH; and diethylene glycol monobutylether, 2-(2-butoxyethoxy) ethanol, C4H9(OC2H4)2OH; whereas the polyethers are diethylene glycol dimethylether, bis(2-methoxyethyl)ether, CH3(OC2H4)2OCH3; diethylene glycol diethylether, bis(2-ethoxyethyl)ether, C2H5(OC2H4)2OC2H5; and diethylene glycol dibutylether, bis(2-butoxyethyl)ether, C4H9(OC2H4)2OC4H9. In all mixtures the excess molar volumes are negative and symmetric across the entire composition range. The excess volumes are fitted to the Redlich–Kister polynomial equation to obtain the binary coefficients and the standard errors. The experimental results have also been discussed on the basis of IR measurements.  相似文献   

12.
29Si NMR peaks due to species with the double four-membered ring siloxane backbone composed of both Si(O)4/2 and CH3Si(O)3/2 units, (CH3) n Si8O 20 – n /(8 – n) – (n=1–3), formed by co-hydrolysis of tetraethoxysilane and methyltriethoxysilane in the presence of tetramethylammonium ions in methanol have been assigned. It has been found that 29Si NMR peaks due to Si(OSi)3(O) units shift to lower frequencies by replacement of the adjacent Si(O)4/2 units by CH3Si(O)3/2 units, in other words, with increasing m value in Si[OSi(O)3]3 – m [OSi(CH3) (O)2] m (O) (m=0–2). Peaks from CH3 Si(OSi)3 units in the species have also appeared as separated due to the kind of neighbor structural units. On the basis of the assignments, positions of CH3Si(O)3/2 units in the cubic octameric siloxane framework of (CH3) n Si8O 20 – n /(8 – n) – (n=2, 3), for both of which three isomers are present, have been estimated.  相似文献   

13.
Organosilicon guanidine derivatives RNHC(=NH)NHCH2CH2CH2Si(OC2H5)3 - n (OH)n [R = H, n = 1; R = (CH2)3Si(OC2H5)3, n = 0] were synthesized by condensation of guanidinium carbonate with (3-aminopropyl)triethoxysilane. The products were brought into ether interchange with thiethanolamine and hydrolytic polycondensation.  相似文献   

14.
The generality of the intramolecular cyclization of suitable nucleophilic sites to a  S+CH2 center created by a sila-Pummerer rearrangement has been investigated. Successful nucleophilic sites included the OH group (in alcohols, carboxylic acids, and hydroxylamines) and the NH group (in amines and carbamates): attempts to produce carbon-based nucleophilic sites were not effective. Successful cyclizations were achieved to produce sulfur heterocycles with 5-, 6-, and 7-membered rings.  相似文献   

15.
Silica gel films were prepared by spin-coating from Si(OC2H5)4-HNO3-H2O-ROH solutions and heated at 200°C where ROH = CH3OH, C2H5OH, CH3OC2H4OH and CH3CH(OH)CH2OH. Striations were observed with an optical microscope, and quantitatively evaluated by surface roughness measurement. A decrease in height and an increase in spacing of the striations were observed when alcohols of high boiling points were used. However, even when the boiling point of the alcohols was high, an evolution of the striations did occur on spin-coating films, which disappeared while keeping the film in the ambient atmosphere. Convections, which might be the source of the striations, were observed in sol layers placed on a stationary substrate irrespective of the boiling point of the alcohols.  相似文献   

16.
Reactions of benzyl potassium species with CO are shown to proceed via transient carbene-like intermediates that can undergo either dimerization or further CO propagation. In a sterically unhindered case, formal dimerization of the carbene is the dominant reaction pathway, as evidenced by the isolation of ((Ph3SiO)(PhCH2)C)2 2 and PhCH2C(O)CH(OH)CH2Ph 3 . Reactions with increasingly sterically encumbered reagents show competitive reaction pathways involving intermolecular dimerization leading to species analogous to 2 and 3 and those containing newly-formed five-membered rings tBu2C6H2(C(OSiR3)C(OSiR3)CH2) (R=Me 6 , Ph 7 ). Even further encumbered reagents proceed to either dimerize or react with additional CO to give a ketene-like intermediates, thus affording a 7-membered tropolone derivative 14 or the dione (3,5-tBu2C6H3)3C6H2CH2C(O))2 15 .  相似文献   

17.
The diphosphazane ligands of the type, (C20H12O2)PN(R)P(E)Y2 (R = CHMe2 or (S)-*CHMePh; E = lone pair or S; Y2 = O2C20H12 or Y = OC6H5 or OC6H4Me-4 or OC6H4OMe-4 or OC6H4But-4 or C6H5) bearing axially chiral 1,1'-binaphthyl-2,2′-dioxy moiety have been synthesised. The structure and absolute configuration of a diastereomeric palladium complex, [PdCl2{ηsu2}-((O2C20H12)PN((S)-*CHMePh)PPh2] has been determined by X-ray crystallography. The reactions of [CpRu(PPh3)2Cl] with various symmetrical and unsymmetrical diphosphazanes of the type, X2PN(R)PYY′ (R = CHMe2 or (S)-*CHMePh; X = C6H5 or X2 = O2C20H12; Y=Y′= C6H5 or Y = C6H5, Y′ = OC6H4Me-4 or OC6H3Me2-3,5 or N2C3HMe2-3,5) yield several diastereomeric neutral or cationic half-sandwich ruthenium complexes which contain a stereogenic metal center. In one case, the absolute configuration of a trichiral ruthenium complex, viz. [Cp*Ruη2-Ph2PN((S)-*CHMePh)*PPh (N2C3HMe2-3,5)Cl] is established by X-ray diffraction. The reactions of Ru3(CO)12 with the diphosphazanes (C20H12O2)PN(R)PY2 (R = CHMe2orMe; Y2=O2C20H12or Y= OC6H5 or OC6H4Me-4 or OC6H4OMe-4 or OC6H4But-4 or C6H5) yield the triruthenium clusters [Ru3(CO)10{η-(O2C20H12)PN(R)PY2}], in which the diphosphazane ligand bridges two metal centres. Palladium allyl chemistry of some of these chiral ligands has been investigated. The structures of isomeric η3-allyl palladium complexes, [Pd(η3-l,3-R′2-C3H3){η2-(rac)-(02C20H12)PN(CHMe2)PY2}](PF6) (R′ = Me or Ph; Y = C6H5 or OC6H5) have been elucidated by high field two-dimensional NMR spectroscopic and X-ray crystallographic studies.  相似文献   

18.
The reactivity of tetraethoxysilane (TEOS) used in many sol-gel syntheses can be increased by prehydrolysis. In contrast to one-step prehydrolysis acidic two-step prehydrolysis causes an increase of the reactivity of the low molecular species provided the total water/TEOS ratios are the same in both cases. By choice of the processing conditions of the hydrolysis—shown on variation of water content, hydrolysis steps and heat treatment—the degree of condensation, the ratio of hydrolyzable (-OC2H5) and hydrolyzed groups (-OH) and the structure of the low molecular species (short chains, 3-membered and 4-membered rings) can be influenced systematically. The development of the building units formed in the early reaction stages is ascertained by molybdate method and 29Si NMR measurements.  相似文献   

19.
The trianionic heptadentate ligand, (Z)-3-(5′-bromosalicylhydrazinocarbonyl) propenoic acid ((Z)-H4bshcpa), has been synthesized in good yield and reacted with FeCl3?·?6H2O to produce [FeIII 6(C12H8N2O5Br)6(H2O)2(CH3OH)4]?·?8H2O?·?8CH3OH. The complex has been characterized by single-crystal X-ray diffraction. In the self-assembly process the ligand was esterified and transferred into (Z)-methyl 3-(5′-bromosalicylhydrazinocarbonyl) propenoate ((Z)-H3mbshcp). In the crystal structure, the neutral Fe(III) complex contains an 18-membered metallacrown ring consisting of six Fe(III) and six trianionic ligands. The 18-membered metallacrown ring is formed by six structural moieties of the type [Fe(III)–N–N]. Due to the meridional coordination of the ligands to Fe3+, the ligands enforce stereochemistry of the Fe3+ ions as a propeller configuration with alternating Λ/Δ forms. The metallacrown can be treated with SnCl2 to obtain purified ester. In addition, we have also obtained reduced esterified ligand, methyl 3-(5′-bromosalicylhydrazinocarbonyl) propanoate (H3mbshcp), with Zn powder as reductant.  相似文献   

20.
Metal atoms were deposited on an Si (111)-7 × 7 surface, and they were adsorbed with alcohol gases (CH3OH/C2H5OH/C3H7OH). Initially, CnH2n+1OH adsorption was simply used as an intermediate layer to prevent the chemical reaction between metal and Si atoms. Through scanning tunneling microscopy (STM) and a mass spectrometer, the CnH2n+1OH dissociation process is further derived as the construction of a surface quasi-potential with horizontal and vertical directions. With the help of three typical metal depositions, the surface characteristics of CH3OH adsorption are more clearly presented in this paper. Adjusting the preheating temperature, the difference of thermal stability between CH3O and H+ could be obviously derived in Au deposition. After a large amount of H+ was separated, the isolation characteristic of CH3O was discussed in the case of Fe deposition. In the process of building a new metal-CH3O-H+ model, the dual characteristics of CH3OH were synthetically verified in Sn deposition. CH3O adsorption is prone to influencing the interaction between the metal deposition and substrate surface in the vertical direction, while H+ adsorption determines the horizontal behavior of metal atoms. These investigations lead one to believe that, to a certain extent, the formation of regular metal atomic structures on the Si (111)-7 × 7-CH3OH surface is promoted, especially according to the dual characteristics and adsorption models we explored.  相似文献   

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