Glow discharge polymerization of tetramethylsilane investigated by infrared spectroscopy and ESCA

The influence of operating conditions (W/FM parameter: W input energy of rf power; F flow rate of monomer; M molecular weight of monomer) on glow discharge polymerization of tetramethylsilane (TMS) was investigated by infrared spectroscopy and ESCA. Elemental analyses showed that the compositions of the polymers formed strongly depended on the level of the W/FM parameter, i.e., whether the W/FM value was more or less than 190 MJ/kg. The infrared spectra indicated that these polymers were composed of Si? H, Si? O, Si? C, Si? CH₃, and Si? CH₂ groups, and that there was no significant difference in structural features between polymers prepared at W/FM parameters of more or less than 190 MJ/kg. ESCA spectra (C_1s and Si_2p core-level spectra) showed that the polymers included carbonized carbon, aliphatic carbon Si? C, C? O, Si? O, and SiO₂ species, and that the sum of carbonized and aliphatic carbons reached more than 50%. Raising the W/FM value increased the formation of the carbonized carbon but did not influence the formation of Si units such as Si? C and Si? O groups. From this evidence the rupture of Si? CH₃ bonds in the polymer forming process is emphasized. The magnitude of the W/FM parameter may be related to the detachment of hydrogen from the aliphatic carbon units.     

Plasma polymers from chloromethyltrimethylsilane and their modification with sodium azide

Plasma polymerization of chloromethyltrimethylsilane (CMTMS) was investigated by elemental analysis, infrared spectroscopy, and ESCA, and the modification of Cl substituents in the plasma polymers from CMTMS with sodium azide was discussed. CMTMS was plasma polymerized to yield filmy polymers. The polymer deposition rate was faster than that from tetramethylsilane containing no Cl atom. The plasma polymers from CMTMS were mainly composed of CH₃, CH₂, Si? CH₃, Si? O? Si, and Si? O? C groups with a small amount of C? Cl groups. The Cl substituents incorporated into the plasma polymers were capable of substitution reactions with azide groups to form azide polymers.     

Glow discharge polymerization of tetramethylgermanium

A glow discharge polymerization technique was applied in the preparation of germanium-containing polymers. The colorless and transparent polymer films formed from tetramethylgermanium (TMG) were investigated by elemental analysis, infrared (IR) spectroscopy, and ESCA. The reaction of TMG was accompanied by the rupture of bonds between Ge and CH₃ groups which led to mixtures of polymers that consisted of CH₃, CH₂, Ge? CH₃, Ge? O? C, and Ge? O? Ge groups and germanium metal. Most Ge species present at the outermost layers of the films were oxidized subsequently by air, whereas the Ge species at the inner layers still existed as Ge metal. This film-forming process can be explained by the concept of atomic polymerization proposed by Yasuda.

1 See H. Yasuda, J. Polym. Sci. Macromol. Rev., 16 , 199 (1981).

     

Synthesis of polyphosphazenes bearing alkoxyethoxy and trifluoroethoxy groups

The synthesis of various phosphoranimines including (CH₃OCH₂CH₂O) (CF₃CH₂O)₂P?N? Si(CH₃)₃, (CH₃OCH₂CH₂OCH₂CH₂O) (CF₃CH₂O)₂P?N? Si (CH₃)₃, (CH₃OCH₂CH₂O)₂(CF₃CH₂O) P?N? Si(CH₃)₃, and (CH₃OCH₂CH₂OCH₂CH₂O)(CF₃CH₂O) P?N? Si(CH₃)₃ via the Staudinger reaction of (CH₃)₃SiN₃ with the suitably substituted phosphite is reported. These monomers were polymerized using tetra-n-butylammonium fluoride and N-methylimidazole in various solvents at several temperatures. In situ ³¹P-NMR kinetic studies and M_n versus time studies were also performed for the monomers to understand the propagation mechanism. © 1994 John Wiley & Sons, Inc.     

Radiation effects on silicon-containing polyacetylenes

Si-containing mono- and disubstituted polyacetylenes(? [CMe?C(SiMe₃)] _n? , ? [CH?H(n? C₅H₁₁)SiMe₃]_n? , etc.) underwent degradation in air; many of them exhibited relatively high yields of main-chain scission (G_s > 1). The G_s values for the polymers having a long n-alkyl group were usually large (ca. 2). In contrast, no polymer degradation occurred in vacuum, indicating that oxygen is necessary for the radiolysis. The polymers irradiated in air contained C?O and Si? O groups, and dissolved in polar solvents, which are nonsolvents of the starting polymers. From the radiation sensitivity and thermal degradability of these polymers, it is concluded that disubstituted polymers with high Si contents (? [CMe?C(SiMe₃)]_n? , ? [CMe?C(SiMe₂CH₂SiMe₃)]_n? , etc.) are not only radiation-sensitive but also thermally stable.     

Spektroskopische Untersuchungen an Phenoxydimethylfloursilanen

Spectroscopie Investigations on R? C₆H₄O(CH₃)₂SiF Compounds The i.r. and Raman spectra of a number of R? C₆H₄O(CH₃)₂SiF compounds (R = H, CH₃, CH₃O, Cl, Br, NO₂, NH₂) have been recorded. The intramolecular and intermolecular interactions were discussed by means of ν SiF, ν Si? O? (C), ν C? O? (Si) and ν_s SiC₂ vibrations.     

Ab initio studies of structural features not easily amenable to experiment. 25. Conformational analysis of methyl propanoate and comparison with the methyl ester of glycine

The molecular geometries of three conformations of methyl propanoate (MEP) (C? C? C?O torsions of 0°, 120°, and 180°) and the potential-energy surfaces of MEP (C? C? C?O torsions) and of the methyl ester of glycine (MEG) (N? C? C?O torsions) have been determined by ab initio gradient calculations at the 4-21G level. MEP has conformational energy minima at 0° and 120° of the C? C? C?O torsion, while the 60–90° range and 180° are energy maxima. For MEG there are two minima (at 0° and 180°) and one barrier to N? C? C?O rotation in the 60–90° range. The N? C? C?O barrier height is about twice as high (4 kcal/mol) as the C? C? C?O barrier. The 180° N? C? C?O minimum is characteristically wide and flat allowing for considerable flexibility of the N? C? C?O torsion in the 150–210° range. This flexibility could be of potential importance for polypeptide systems, since the N? C? C?O angles of helical forms are usually found in this region. The molecular structures of the methyl ester group CH₃OC(?O)CHRR′ in several systems are compared and found to be rather constant when R ? H and R′ ? H, CH₃, CH₃CH₂; or when R ? NH₂ and R′ ? H, CH₃, or CH(CH₃)₂.     

Characterization of plasma polymers from tetramethylsilane,octamethylcyclotetrasiloxane, and methyltrimethoxysilane

The products in inductively coupled plasma excited in organosilicic compounds were studied on chemical structures by spectroscopic methods. Plasma-polymerized tetramethylsilane (PA) contains not only Si? CH₃ groups but also Si? H groups on IR and ²⁹Si-NMR analyses. ¹³C-NMR spectrum of PA reveals that the crosslinked structure of PA is mainly constructed of Ch₂ and CH groups. Plasma-polymerized octamethyleyclotetrasiloxane (PD₄) is composed of Si? CH₃ and Si? O groups. ¹³C- and ²⁹Si-NMR spectra of PD₄ point out the highly preservation of the structural units similar to the monomer. These data of PD₄ suggest that PD₄ is formed from the ring-opening polymerization by cleavages of Si? O bonds. ¹³C-NMR spectrum of poly[methyltrimethoxysilane] (PT) indicates the existence of CH₃? O groups, meanwhile its ²⁹Si-NMR analysis concludes that PT is chiefly composed of the structural units similar to the monomer. The surface analyses by XPS of PA, PD₄ and PT suggest that these organosilicic plasma polymers resemble their starting materials.     

Tautomerism of monochalcogenosilanoic acids CH3Si(O)XH (X = S,Se, Te) in the gas phase and in the polar and aprotic solution: An ab initio computational investigation

Computational investigations by an ab initio molecular orbital method (HF and MP2) with the 6‐311+G(d,p) and 6‐311++G(2df, 2pd) basis sets on the tautomerism of three monochalcogenosilanoic acids CH₃Si(?O)XH (X = S, Se, and Te) in the gas phase and a polar and aprotic solution tetrahydrofuran (THF) was undertaken. Calculated results show that the silanol forms CH₃Si(?X)OH are much more stable than the silanone forms CH₃Si(?O)XH in the gas‐phase, which is different from the monochalcogenocarboxylic acids, where the keto forms CH₃C(?O)XH are dominant. This situation may be attributed to the fact that the Si? O and O? H single bonds in the silanol forms are stronger than the Si? X and X? H single bonds in the silanone forms, respectively, even though the Si?X (X = S, Se, and Te) double bonds are much weaker than the Si?O double bond. These results indicate that the stability of the monochalcogenosilanoic acid tautomers is not determined by the double bond energies, contrary to the earlier explanation based on the incorrect assumption that the Si?S double bond is stronger than the S?O double bond for the tautomeric equilibrium of RSi(?O)SH (R?H, F, Cl, CH₃, OH, NH₂) to shift towards the thione forms [RSi(?S)OH]. The binding with CH₃OCH₃ enhances the preference of the silanol form in the tautomeric equilibrium, and meanwhile significantly lowers the tautomeric barriers by more than 34 kJ/mol in THF solution. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

Anionic graft polymerization of ethylene oxide on starch. II. Structure of the graft polymers

Starch–poly(ethylene oxide) graft polymers were prepared in DMSO at various monomer and starch alkoxide concentrations. Complimentary and varied information on the structure of the graft polymers was obtained from NMR and periodic acid oxidation of the polymers. From the NMR spectra of the graft polymers in pyridine containing a trace of HCl, which causes shifting of the resonance of the internal ? CH₂O? protons from the terminal ? CH₂OH protons, the polyethylene oxide content, the DP _n of the grafted side chains, and the efficiency of the alkoxides were calculated. With increase of the alkoxide concentration there was a small decrease in ? DP _n, and in the efficiency of the alkoxides in initiating graft polymerization. With increase of monomer concentration, there was only a small increase in ? DP _n but a large increase in the efficiency, indicating the existence of transfer reactions between the growing anions and the free hydroxyl groups on the starch. The results of he periodic acid oxidation showed that with increase of alkoxide concentration there was no significant change in the per cent oxidation of the graft polymers, but with increase of monomer, there was an increase in the participation of the secondary hydroxyl groups in initiation. This supports the NMR evidence for the existence of transfer reactions leading to ? DP _n values much lower than those calculated from [monomer]/[catalyst] ratios.     

Spektroskopische Untersuchungen an Siliciumverbindungen. XXXI. Schwingungsverhalten von p-substituierten N,N-Bistrimethylsilylanilinen

The following p-substituted N,N-bis-trimethlsilyl anilines p-X? C₆H₄? N[Si(CH₃)₃]₂ are prepared by silylation of free amines: X = H, CH₃, C₂H₅, CH₃O, CH₃CO, F, Cl, Br, J, CN, C₆H_S, (CH₃)₃SiO, and [(CH₃)₃Si]₂N, and the isotopic derivatives C₆H₅? ¹⁵N[Si(CH₃)₃]₂ and C₆D₅N[Si(CH₃)₃]₂. The vibrational spectra are reported and assigned. The molecular symmetry of p-[(CH₃)₃Si]₂N? C₆H₄? N[Si(CH₃)₃]₂ is determined. The influence of the mass of the substituents X on the positions of the ν_sSiNSi vibrational frequencies is discussed.     

Charakterisierung von Organokieselsäurepolymeren durch thermoanalytische Untersuchungen

Four organosilicate polymers synthesized by addition of vinyl- and H-substituted double four-ring silicic acid derivatives were characterized using DSC and simultaneous TG-DTA measurements. Thermooxidative decomposition proceeds in several steps: Oxidation of (Si?H) groups, oxidation of (Si?CH₂?CH₂?Si) bridges, and oxidation of (Si?CH₃) groups, with formation of new (Si?O?Si) bonds.²⁹Si-NMR-spectroscopic measurements confirm this interpretation. Thermoanlytical methods of investigation proved useful to characterize these organosilicate polymers.     

Spektroskopische Untersuchungen an Siliciumverbindungen. XXXII. Substituenteneinflüsse auf die SiNSi-Bindung in p-substituierten N,N-Bistrimethylsilylanilinen

The influence of the substituents X of the compounds p-X–C₆H₄–N[Si(CH₃)₃]₂ on the positions of the v_s SiNSi vibrational frequencies is described by an empirical equation in dependence on mass and electronic properties of X. The bonding properties of the C? H, Si? C, and Si? N? Si bonds of the disilazane group are discussed by means of complementing informations from ¹³CH coupling constants.     

The anomeric effect: Ab-initio studies on molecules of the type X?CH2?O?CH3

The anomeric effect of the functional groups X = C?N, C?CH, COOH, COO^?, O? CH₃, NH₂, and NH⁺₃ has been studied with ab initio techniques. Geometry effects upon rotation around the central C? O bond in X? CH₂? O? CH₃ have been compared in the various compounds. The energy differences between the conformers with a gauche and trans (X? C? O? C) arrangement were calculated at the 6-31G* level in the fully optimized 4-21G geometries. Energy differences calculated at the 4-21G level appeared not to be reliable, especially for the groups X that contain non-sp³ hybridized atoms. The 6-31G* energy differences indicate a normal anomeric effect for X = COO^?, O? CH₃, and NH₂(g⁺) (ca. 13 kJ/mol) and a small anomeric effect for X = COOH, C?N, and C?CH (ca. 6 kJ/mol). For X = NH₂(t) and NH⁺₃ a reverse anomeric effect occurs. These observations are in line with experimental results and evidence is given for a competition among various stereoelectronic interactions that occur at the same anomeric center. Geometry variations can be understood in terms of simple rules associated with anomeric orbital interactions. Trends followed when the group X is varied cannot be related in a straightforward way to the energy differences between the trans and the gauche forms in these compounds. Only the variation in the gauche torsion angle X? C? O? C follows roughly the same trend.     

Synthesis of New Polysiloxane-Immobilized Ligand System Di(amidomethyl)aminetetraacetic Acid

A new chelating porous polysiloxane-immobilized tetraacetic acid ligand system has been prepared. This material was made by chemical modification of the iminodiacetic acid polysiloxane with thionyl chloride and diethyliminodiacetate, respectively. The polysiloxane functionalized with di(amidomethyl)aminetetraacetic acid of the general formula P-(CH ₂ ) ₃ N(CH ₂ C(O)N) ₂ (CH ₂ COOH) ₄ [where P represents the polysiloxane backbones (Si?O?Si) _n ] was characterized by Thermogravimetric Analysis (TGA) and FTIR spectra. The FTIR results proved that tetraacetic acid groups are successfully grafted onto the polysiloxane surface. This ligand system exhibits high potential for extraction of divalent metal ions (Co⁺², Ni⁺², Cu⁺², and Zn⁺²) from aqueous solution.     

Dynamic mechanical and dielectric properties of ORMOCER® incorporating functionalized poly(styrene) latexes

Organically modified aluminosilicate hybrid materials incorporating polystyrene and poly(styrene‐co‐hydroxypropyl acrylate) latexes, (3‐glycidyloxypropyl) trimethoxysilane, and aluminum sec‐butoxide [Al(O^sBu)₃] were synthesized by a sol–gel process. The bulk materials obtained were macroscopically homogeneous dispersions with good mechanical properties. Dynamic mechanical and dielectric analyses of these new hybrid materials as a function of the Al(O^sBu)₃ concentration and copolymer composition revealed a series of transitions that represented relaxation processes of the incorporated polymer (glass transition), ?Al? O? Si?, the ?Si? O? Si? part of the network, and segmental motion of unreacted ?Si? (CH₂)₃OCH₂CHCH₂O chains. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 860–867, 2001     

Trivalent-pentavalente Phosphorverbindungen/Phosphazene. IV. Darstellung und Eigenschaften neuer N-silylierter Diphosphazene

Trivalent-Pentavalent Phosphorus Compounds/Phosphazenes. IV. Preparation and Properties of New N-silylated Diphosphazenes Phosphazeno-phosphanes, R₃P = N? P(OR′) ₂ (R = CH₃, N(CH₃)₂; R′ = CH₂? CF₃) react with trimethylazido silane to give N-silylated diphosphazenes, R₃P = N? P(OR′)₂ = N? Si(CH₃)₃ compounds decompose by atmospherical air to phosphazeno-phosphonamidic acid esters, R₃ P?N? P(O)(O? CH₂? CF₃)(NH₂). Thermolysis of diphosphazene R₃P = N? P(OR′) ₂ = N? Si(CH₃)₃ (R = CH₃, R′ = CH₂? CF₃) produces phosphazenyl-phosphazenes [N?P(N?P(CH₃)₃)OR′] _n. The compounds are characterized by elementary analysis, IR-, ¹H_-, ²⁹Si-, ³¹P-n.m.r., and mass spectroscopy.     

Long‐range π‐type hydrogen bond in dimers CH2?HF,CH2O?H2O,and CH2O?NH3

Using four basis bets, (6‐311G(d,p), 6‐31+G(d,p), 6‐31++G(2d,2p), and 6‐311++G(3df,3pd), the optimized structures with all real frequencies were obtained at the MP2 level for the dimers CH₂O? HF, CH₂O? H₂O, CH₂O? NH₃, and CH₂O? CH₄. The structures of CH₂O? HF, CH₂O? H₂O, and CH₂O? NH₃ are cycle‐shaped, which result from the larger bend of σ‐type hydrogen bonds. The bend of σ‐type H‐bond O…H? Y (Y?F, O, N) is illustrated and interpreted by an attractive interaction of a chemically intuitive π‐type hydrogen bond. The π‐type hydrogen bond is the interaction between one of the H atoms of CH₂O and lone pair(s) on the F atom in HF, the O atom in H₂O, or the N atom in NH₃. In contrast with the above three dimers, for CH₂O? CH₄, because there is not a π‐type hydrogen bond to bend its linear hydrogen bond, the structure of CH₂O? CH₄ is noncyclic shaped. The interaction energy of hydrogen bonds and the π‐type H‐bond are calculated and discussed at the CCSD (T)/6‐311++G(3df,3pd) level. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Applications of ESCA to polymer chemistry. XVII. Systematic investigation of the core levels of simple homopolymers

The core levels of a series of 83 homopolymers have been studied by electron spectroscopy for chemical analysis (ESCA). Comparisons of the experimentally determined core-level binding energies with theoretical calculations using the ground-state potential model in the complete neglect of differential overlap (CNDO/2) self-consistent field molecular orbital (SCF MO) formalism have been made on the C_1s and O_1s core levels for the oxygen-containing polymers in the series. A comparison of the ground-state potential model (GPM) and relaxation potential model (RPM) on a series of six model compounds representative on the series of polymers is given. Compilations are given of binding energies of C_1s, O_1s, N_1s, Cl_2p, S_2p, Si_2p, and Br_3d levels for typical structural features of common occurrence in polymer systems. These data, taken in conjunction with that previously published on fluoropolymers, provide a sound basis for the development of ESCA as a fingerprint tool in the elaboration of features of structure and bonding in polymers in general.