Poly 2-vinylpyridine

Peak Notation Assignment of Main Peaks Molecular Weight Retention Index Relative Intensity 

4 -(but-3-ene-1,3-diyl)dipyridine (dimer) b (Z)-4,4-(penta-2,4-diene-1,3-diyl)dipyridine 

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Strauss and Williamst have studied coil dimensions of derivatives of poly(4-vinylpyridine) by light-scattering and viscosity measurements. The derivatives studied were poly(pyridinium) ions quaternized y% with n-dodecyl groups and (1 - y)% with ethyl groups. Experimental coil dimensions extrapolated to 0 conditions and expressed relative to the length of a freely rotating repeat unit are presented here for the molecules in two different environments ... 

Poly(4-vinylpyridine) [25232-41-1] M (105.1)n. Purified by repeated pptn from solns in EtOH and dioxane, and then EtOH and ethyl acetate. Finally, freeze-dried from rcrt-butanol. 

The Zincke reaction has also been adapted for the solid phase. Dupas et al. prepared NADH-model precursors 58, immobilized on silica, by reaction of bound amino functions 57 with Zincke salt 8 (Scheme 8.4.19) for subsequent reduction to the 1,4-dihydropyridines with sodium dithionite. Earlier, Ise and co-workers utilized the Zincke reaction to prepare catalytic polyelectrolytes, starting from poly(4-vinylpyridine). Formation of Zincke salts at pyridine positions within the polymer was achieved by reaction with 2,4-dinitrochlorobenzene, and these sites were then functionalized with various amines. The resulting polymers showed catalytic activity in ester hydrolysis. ... 

Pyridinium ylide is considered to be the adduct car-bene to the lone pair of nitrogen in pyridine. The validity of this assumption was confirmed by Tozume et al. [12J. They obtained pyridinium bis-(methoxycarbonyl) meth-ylide by the photolysis of dimethyl diazomalonate in pyridine. Matsuyama et al. [13] reported that the pyridinium ylide was produced quantitatively by the transylidalion of sulfonium ylide with pyridine in the presence of some sulfides. However, in their method it was not easy to separate the end products. Kondo and his coworkers [14] noticed that this disadvantage was overcome by the use of carbon disulfide as a catalyst. Therefore, they used this reaction to prepare poly[4-vinylpyridinium bis-(methoxycarbonyl) methylide (Scheme 12) by stirring a solution of poly(4-vinylpyridine), methylphenylsulfo-nium bis-(methoxycarbonyl)methylide, and carbon disulfide in chloroform for 2 days at room temperature. 

On the other hand, poly(ethoxycarbonylimino-4-vi-nylpyridinium ylide) (Scheme 13) was prepared essentially by the same method from 1-ethoxycarbonylimino-pyridinium ylide, as described by Hafner [15] from the reaction of poly (4-vinylpyridine) with nitrene, generated from the pyrolysis of ethyl azidoformate. 

The structures of these ylide polymers were determined and confirmed by IR and NMR spectra. These were the first stable sulfonium ylide polymers reported in the literature. They are very important for such industrial uses as ion-exchange resins, polymer supports, peptide synthesis, polymeric reagent, and polyelectrolytes. Also in 1977, Hass and Moreau [60] found that when poly(4-vinylpyridine) was quaternized with bromomalonamide, two polymeric quaternary salts resulted. These polyelectrolyte products were subjected to thermal decyana-tion at 7200°C to give isocyanic acid or its isomer, cyanic acid. The addition of base to the solution of polyelectro-lyte in water gave a yellow polymeric ylide. 

Nucleic acids are anionic under the neutral conditions. Thus, the syntheses of model compounds of the opposite charge are interesting for the discussion of electrostatic contributions in specific interactions of nucleic acids. We have tried to synthesize cationic models by the Menschutkin reaction of poly-4-vinylpyridine with 9-(2-chlo-roethyl)adenine, l-(2-chloroethyl)thymine, and 7-(2-chloroethyl)theophylline15,16 The obtained polymers are poly l-[2-(adenin-9-yl)ethyl]-4-pyridinioethylene chloride 7(APVP), poly l-[2-(thymin-l-yl)ethyl]-4-pyridinioethylene chloride 8 (TPVP), and poly l-[2-(theophyllin-7-yl)ethyl]-4-pyridiniothylene chloride 9 (THPVP), respectively. 

UPEI), and poly[l-(uridin-5 -yl)-iminoethylene halide], 13 (UPEI ). They were obtained by quaternization of poly-4-vinylpyridine or polyethylenimine with ehlo-roethylated, ehloropropylated, or ehlorated nucleic acid bases. 

Cordes et al995 carried out alkaline hydrolyses of p-nitrophenylhexanoate 55 (PNPH) in the presence of poly-4-vinylpyridine partially quaternized with dodecyl-bromide and ethylbromide (QPVP). They also found that the polyelectrolytes are increasingly effective as catalysts with an increasing ratio of dodecyl to ethyl groups, and the hydrophobic interactions are important in determining the catalytic efficiency. They observed the inhibitory effects of several gegen-anions fluoride ions are the weakest inhibitor, and nitrate is the strongest (F- < Cl < S04 [Pg.159]

Recently, the quaternized poly-4-vinylpyridine, 50-54 (QPVP) was found to be an electron acceptor in the charge-transfer interactions 104 Ishiwatari et al.105) studied alkaline hydrolyses of p-nitrophenyl-3-indoleacetate 58 (p-NPIA) and N-(indole-3-acryloyl) imidazole 59 (IAI) (electron donor) in the presence of QPVP. The fcobs vs. polyelectrolyte concentration plots are shown in Fig. 12. As is seen in... 

Pyridine groups show the nucleophilic catalytic activity. Letsinger and Saveride122 hydrolyzed 2,4-dinitrophenyl-acetate, 72 (DNPA) and 3-nitro-4-acetoxybenzene-sulfonate, 66 (NABS) with partially quaternized poly-4-vinylpyridine (QPVP). 

We discussed more quantitatively the correlation of the adsorption with catalytic activity in the heterogeneous systems using poly(4-vinylpyridine-co-divinylbenzene) quaternized with alkylhalide [e. g. 88 (RC16PVP)] as a catalyst and p-nitrophenyl-valerate (PNPV) as a substrate147. ... 

A great variety of suitable polymers is accessible by polymerization of vinylic monomers, or by reaction of alcohols or amines with functionalized polymers such as chloromethylat polystyrene or methacryloylchloride. The functionality in the polymer may also a ligand which can bind transition metal complexes. Examples are poly-4-vinylpyridine and triphenylphosphine modified polymers. In all cases of reactively functionalized polymers, the loading with redox active species may also occur after film formation on the electrode surface but it was recognized that such a procedure may lead to inhomogeneous distribution of redox centers in the film... 

The results of osmotic pressure measurements are shown in Fig. 145 for poly-(4-vinyl-N-butylpyridinium bromide) in alcohol, and for the parent uncharged polymer, poly-(4-vinylpyridine), likewise in alcohol. The value of /c for the former (note difference in scales) is much larger than for the latter, and it increases with dilution. The... 

Fig. 145.—Osmotic pressure-concentration ratios ( in g./cm and c in g./lOO ml.) for poly-(4-vinylpyridine) in alcohol, O, coordinates left and below poly-(N-butyl-4-vinylpyridinium bromide) in alcohol, coordinates right and above and the same polymer in alcoholic 0.61 N lithium bromide, 3 coordinates left and below. °> ...

Wang, Z., Masuo, S., Machida, S. and Itaya, A. (2005) Application of dopant-induced laser ablation to site-selective modification of sea-island structures of polystyrene-fclock-poly(4-vinylpyridine) films. Jpn. J. Appl. Phys., 44, L402-L404. 

These results were compared to those obtained with pyridine 1-oxide (9) and poly(4-vinylpyridine 1-oxide) (8) as catalysts. 

Poly(2-vinylpyridine), with Mv=36,000, was purchased from Aldrich Chemical Co. and purified by two precipitations from ethanol into deionized water. CuC12-2H20 (ACS purity) and poly(4-vinylpyridine) from Mallinckrodt and Polysciences Inc. respectively, were used as received. Complexes with different ratios of Cu to pyridine moiety were formed in solution (95% methanol, 5%H20). Due to decreasing solubility of the complex with increasing copper concentration, the concentration of reagents was varied as shown in Table I. 

The cobalt(II)15 and zinc(II)16 complexes of phthalocyanine(Pc), octcyano-Pc, and tetrasulfon-ato-Pc incorporated in poly(4-vinylpyridine-co-styrene) or Nafion films coated on graphite have also been examined as catalytic devices for dihydrogen electrogeneration in phosphate buffer. These catalytic systems were strongly suggested to be dominated by the electron transfer within the polymer matrix. The best catalytic film is that constituted of the nonsubstituted Con-Pc complex in poly(4-vinylpyridine-co-styrene), giving a turnover number of 2 x 10s h-1 at an applied potential of —0.90 V vs. Ag Ag Cl. 

Films of [Osn(bpy)2(pvp)i0Cl]Cl348 and [Run(bpy)2(pvp)i0Cl]Cl349 (pvp = poly(4-vinylpyridine)] have been shown active for reductive and oxidative detection of nitrite, respectively. 

Following these early solid-state investigations, 1,907 nm EFISHG studies by Tam and co-workers on several complexes [W(CO)5L] (L = py or a 4-substituted py) quote (3 values similar to that of 4-nitroaniline (ca. 10 x 10-30 esu) and sensitive to the nature of the pyridyl substituent.67-69 These results were quickly followed by ZINDO/SCI-SOS calculations on the same series of complexes by Kanis et al.70 the first time that MO theory had been used to describe the quadratic NLO responses of metal complexes. The results of these calculations agree reasonably well with the EFISHG data, and indicate that the modest (3 responses can be traced to relatively small Ap12 values.70 Lacroix et al. obtained low 1,064 nm SHG activities by corona poling films of poly (4-vinylpyridine) and of two other related polymers functionalized with W(CO)5 centers.71... 

Partial hydrogenation of acetylenic compounds bearing a functional group such as a double bond has also been studied in relation to the preparation of important vitamins and fragrances. For example, selective hydrogenation of the triple bond of acetylenic alcohols and the double bond of olefin alcohols (linalol, isophytol) was performed with Pd colloids, as well as with bimetallic nanoparticles Pd/Au, Pd/Pt or Pd/Zn stabilized by a block copolymer (polystyrene-poly-4-vinylpyridine) (Scheme 9.8). The best activity (TOF 49.2 s 1) and selectivity (>99.5%) were obtained in toluene with Pd/Pt bimetallic catalyst due to the influence of the modifying metal [87, 88]. 

Colloidal catalysts in alkyne hydrogenation are widely used in conventional solvents, but their reactivity and high efficiency were very attractive for application in scC02. This method, which is based on colloidal catalyst dispersed in scC02, yields products of high purity at very high reactions rates. Bimetallic Pd/Au nanoparticles (Pd exclusively at the surface, while Au forms the cores) embedded in block copolymer micelles of polystyrene-block-poly-4-vinylpyridine... 

Mdleleni and coworkers137 anchored RhCl3 onto several porous aminated polymers. As displayed in Table 43, the best polymer support was found to be poly (4-vinylpyridine). Conditions T = 100 °C Pco = 0.9 atm RhCl3 3H20 = 5 x 10 5 mol solvent/H20 = 4/1 v/v. 

PDMS nanocomposites with layered mica-type silicates were also reported.374 A two-step sol-gel process of the in situ precipitation of silica led to the development of siloxane-based nanocomposites with particularly high transparencies.3 5 Some unusual nanocomposites prepared by threading polymer chains through zeolites, mesoporous silica, or silica nanotubes were reviewed.3 6 Poly(4-vinylpyridine) nanocross-linked by octa(propylglycidyl ether) polyhedral oligomeric silsesquioxane was reported.377... 

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