Low‐Temperature Restructuring Processes in Polyhydrosilanes

Summary: This paper presents the structural influence of the Si H functionality on the physicochemical properties of polysilanes. New low‐temperature restructuring processes were discovered using thermal analysis (TGA, DSC). Photoluminescent (FL) and X‐ray photoelectron spectroscopy (XPS) measurements revealed the optoelectronic properties‐chemical structure relationship of the synthesized polymers.

Highly reactive Si H groups lead to restructuring of the main polysilane chain.     

Synthesis of hydrothioxanthenes. I

It is shown that methylene dieyclohexanone reacts with phosphorus sulfides to give a mixture of tricyclic 6-membered ring sulfides: perhydrothioxanthene, 1, 2, 3, 4, 5, 6, 7, 8-octahydrothioxanthene, and thioxanthene. The behaviors of perhydroxanthene and sym-octahy-droxanthene toward oxidation, mercuric chloride, and dehydrogenation are investigated.     

Densely crosslinked polycarbosiloxanes. I. Synthesis

Novel densely crosslinked polycarbosiloxanes were obtained by using functional branched prepolymers. Two types of soluble prepolymers were prepared from di- and trifunctional alkoxysilane monomers via cohydrolysis/condensation and for both final crosslinking occurred via hydrosilylation. The prepolymers having only vinyl functionalities (poly[phenylmethylvinyl]siloxanes, system A) were crosslinked by using a crosslinking agent with reactive silicon–hydrogen bonds. In the prepolymers having both silicon–vinyl and silicon–hydrogen functionalities (poly[phenylmethyl-vinylhydro]siloxanes, system B) crosslinking took place intermolecularly. For the characterization of the prepolymers ¹H-NMR, ²⁹Si–NMR, FT–IR spectroscopy, analytical SEC and VPO were employed. The prepolymers were fractionated with preparative SEC and the fractions analyzed with ¹H-NMR and analytical SEC. The crosslinking reaction was followed by FT–IR spectroscopy. The polymer networks were fully transparent homogeneous materials and are promising for future optical applications. © 1997 John Wiley & Sons, Inc.     

5-vinyl pyrimidines. I. Synthesis

A total synthesis of 5-vinyl pyrimidine and some of its substituted derivatives is described. The following vinyl pyrimidines have been prepared: 5-vinyl pyrimidine, 5-vinyl-4,6-dimethoxy pyrimidine, 5-(α-bromo) vinyl-4,6-dimethoxy pyrimidine.     

Aromatic annelation. I. Synthesis of pyridines.

The preparation of substituted pyridines from cycloalkanones by elaboration of an aromatic ring is described.     

Cyclolinear polysiloxanes. I. Synthesis and characterization

The synthesis and characterization of two novel cyclic siloxanes, diacetoxydiethyltetramethylcyclotetrasiloxane and diacetoxytriethylpentamethylcyclopentasiloxane, and cyclolinear polymers synthesized from these monomers are presented. The cyclic siloxanes were synthesized from tetramethylcyclotetrasiloxane and pentamethylcyclopentasiloxane, respectively, by acetylation followed by ethylation. The cyclic monomers were characterized with ¹H NMR spectroscopy. Subsequently, the cyclic siloxanes were self‐condensed into cyclolinear polysiloxanes and cocondensed (extended) with silanol‐terminated polydimethylsiloxane into high‐molecular‐weight polymers containing cyclic units withlinearpolydimethylsiloxane spacers (extended cyclolinear polysiloxanes). The molecular weights of both the cyclolinear polysiloxanes and extended cyclolinear polysiloxanes were determined. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4039?4052, 2006     

Polyether azomethines. I. Synthesis and characterization

Six new polyether azomethines were synthesized by melt and solution polycondensation of six different diamines with 4,4′-[1,4-phenylene bis(oxy)] bisbenzaldehyde. The polymers synthesized by solution method are yellow to white in color and had inherent viscosities up to 0.59 dL/g in concentrated H₂SO₄. The polymers obtained by melt condensation show higher viscosity. Except polymer IV , others are insoluble in common organic solvents. The polymers were characterized by IR, x-ray, elemental analysis, and DSC study. The thermal stability of the polymers was evaluated by TGA and IGA study. Polymers I-III are highly thermally and thermooxidatively stable and exhibit no appreciable decomposition up to 420°C both in air and nitrogen atmosphere. It was shown that the curing of the polyazo-methines takes place by opening up of the ? CH?N? linkages at higher temperature. The electrical conductivities of the virgin and iodine doped polymers were as high as 10^?11?10^?16 and 10^?6?10^?8S cm^?1, respectively, at 30°C. Electronic spectra of the undoped polymers ( I-III ) indicated a large bathochromic shift of the ? – ?^* absorptions band (376 nm) due to ? C?N? bonds of the model compound. This can be attributed to extensive delocalization of the electrons along the polymer chain. © 1995 John Wiley & Sons, Inc.     

Polyurethane-polyacrylamide IPNs. I. Synthesis and characterization

Hydrophobic-hydrophilic interpenetrating polymer networks (IPNs) of polyurethane and polyacrylamide have been synthesized. The IPNs have been characterized by IR, thermal, and mechanical studies. SEM studies indicate phase mixing of some IPNs. Solvent resistance and surface hydrophilicity as evidenced by contact angle measurements suggest that these IPNs could be used for biomedical applications.     

Enantioselective Synthesis of Pseudomonic Acids. I. Synthesis of Key Intermediates

An enantioselective synthesis of key intermediates for the synthesis of the anti-microbially active pseudomonic acids A ( 1 ), B ( 2 ) and C ( 3 ) is described. D -Ribose ( 4 ) was used as starting material.     

Nonionic reactive surfactants. I. Synthesis and characterization

A procedure to prepare nonionic reactive surfactants with different polymerizable groups is described. The synthesis involves the initiation of living anionic ring-opening polymerization of ethylene oxide and propylene oxide (for the hydrophilic part and the hydrophobic part, respectively) by a potassium salt prepared from the stoichiometric reaction of potassium hydride and diethylene glycol monomethyl ether. The resulting anion is reacted with chloride compounds (methacryloyl, allyl, vinylacetoyl) and maleic anhydride, as well as with isobutanoyl chloride, leading to a nonpolymerizable compound having a similar structure. Then, it was possible to produce a range of reactive surfactants more or less reactive with the monomers. These surfactants are expected to be used further in emulsion polymerization processes (styrene and butyl acrylate). This procedure gives good control of both hydrophobic and hydrophilic parts, and the end reaction for the different functionality of surfmers is quite quantitative. All the surfactants were characterized by size-exclusion chromatography and ¹H NMR. Physicochemical properties, such as the critical micellar concentration and the specific area, were also measured.     

Aromatic-aliphatic copolyesters—I. Synthesis and characterization

Copolyesters have been synthesized by interfacial polycondensation of 2,2-bis(4-hydroxyphenyl)-propane or phenolphthalein as aromatic diol and ethylene glycol or polyethylene glycol as aliphatic diol in various mole ratios with terephthaloyl or isophthaloyl chloride. Chemical compositions, dilute solution viscosities and solubility behaviours of these polymers have been investigated. The introduction of aliphatic diol in aromatic polyesters influences T_g, softening point, chemical resistance and thermal stability.     

Synthesis and thermal characteristics of bisimides. I

Ten structurally different bisimide resins were prepared by reacting maleic anhydride/citraconic anhydride and benzophenone tetracarboxylic dianhydride with aromatic diamines and fused aromatic structures or heterocyclic groups. The amines included were 1,5-diaminonaphthalene, 2,5-bis(p-aminophenyl)1,3,4-oxadiazole, 3,3-bis(p-aminophenyl)phthalide, 9,9-bis(p-aminophenyl)fluorene. and 10,10-bis(p-aminophenyl)anthrone. These monomers were characterized by infrared (IR). ¹H-NMR, mass spectroscopy, and elemental analysis. Thermal polymerization of these monomers was investigated by differential scanning calorimetry. Broad exothermic peaks were observed for a temperature range of 225–380°C. Temperature of exothermic peak position was influenced by the presence of substituents at the olefinic bond, and in biscitraconimides it was 40–50°C lower than in the corresponding bismaleimides. Anaerobic char yields of cured bisimide resins ranged from 44 to 64%. Oxadiazole-containing bisimides had low thermal stability. Increase in formula weight between the imide groups did not influence the char yields in a systematic manner. Graphite cloth laminates with two of these bisimide resins were fabricated and tested for a number of physical properties. Their limiting oxygen index was 70–72%.     

Poly(methyl methacrylate-g-urethane). I. Synthesis

Poly(methyl methacrylate-g-urethane) was prepared by coupling between poly(methyl methacrylate-co-2-hydroxyethyl methacrylate) and polyurethane. The polyurethane was obtained by bulk polycondensation of tolylene diisocyanate and polypropylene glycol. The two polymeric species were synthesized and characterized separately, and the composition of the grafted products varied only by the spacing of the grafted segments. Grafted copolymers with 5, 10, 20, 25, 40, 50, 70, and 90% of incorporated polyurethane have been prepared.     

Polysiloxane zwitterionomers and related model compounds. I. Synthesis

Polymers containing zwitterions were prepared by reacting γ-propanesultone with polydimethylsiloxane-co-(4,7-diazaheptylmethylsiloxane), which generated substituted di(ammonium-3-propane-sulfonate) groups pendant from the siloxane chain. Their concentration in the polymers varied from 0.5 to 10 mole %. Two model compounds were also prepared in order to (1) characterize the reaction leading to the formation of these zwitterions and (2) characterize the ionic forces in solutions (tetrahydrofuran and benzene were used as solvents). The degree of aggregation of these model compounds was higher in tetrahydrofuran and increased in both solutions with the concentration. No rearrangements of siloxane bonds were observed in the presence of these zwitterions or γ-propanesultone.     

Flavinyl peptides. I. Synthesis of flavinyl-aromatic amino acids

The syntheses of flavinyl peptides, in which L-tryptophan, L-tyrosine, or L-phenylalanine are attached via peptide linkage to the isoalloxazine system with ω-carboxyalkyl groups in position 3 or 10, are described. Lumiflavin was carboxymethylated by known methods to yield N-3-carboxymethyllumiflavin. Oxidation of 10-ω-hydroxyhexyl-, 10-ω-hydroxypentyl-, 10-ω-hydroxybutyl-, and 10-formylmethylflavins gave the corresponding 10-ω-carboxyalkylflavins. The 10-ω-carboxyethylflavin was obtained by condensation of 2-amino-4,5-dimethyl-N-ω-carboxyethylaniline with alloxan. Activations of the carboxyl group of the flavins were achieved with N,N′-carbonyldiimidazole and p-nitrophenyltrifluoroacetate to form the corresponding acyl imidazoles and p-nitrophenyl esters. 10-Carboxymethylflavin was hydrogenated to form 10-carboxymethyldihydroflavin and activated by carbodiimide. Reaction of the carboxy-activated flavins with the appropriate amino acid methyl esters, followed by air oxidation in the case of dihydroflavin, gave the corresponding flavinyl peptides. Interaction of the flavin with aromatic amino acids results in a broadening of the visible flavin absorption towards the green, without the appearance of discrete new maxima, and in quenching of the flavin fluorescence. The fluorescence efficiency increases with increasing numbers of methylene groups in the flavin side chain. The nonlinear dependency of fluorescence quenching versus number of methylene groups indicates that different types of intramolecular interactions are involved.