Cation Binding Properties of Poly(vinyl macrocyclic polyethers)

Kopolow, S. L.; Esch, T. E. Hogen; Smid, Johannes

doi:10.1021/ma60021a024

Cited by 121 publications

(69 citation statements)

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“…69 The vinylbenzocrown ether can be polymerized to high molecular weigbt polymers by a radical initiator in the conventional way. 40 Copolymers with styrene were also prepared, the composition being nearly identical to that of the starting monomer feed and independent of conversion, indicating that the two reactivity ratios are close to unity. Living polymers are formed by polymerizing the vinyl monomers in THF with a~methylstyrene tetramer as catalyst as long as the temperature is kept at about -SO"C. Block copolymers can be synthesized by adding monomers such as styrene, ethylene mtide, methylmethacrylate or vinylpyridine to the living crown polymer, or vice versa.…”

Section: Crown Monomers and Polymersmentioning

confidence: 92%

“…The solubility decreases considerably in more polar media, but P18C6 has a remarkable solubility in water (8 g/100 ml), especially at lower temperatures. 40 The intrinsic viscosity of P18C6 in water is low ('II =0.1 for M. = 100,000), and the molecules apparently are highly coiled. This Ieads to some interesting phenomena when this polymer and certain organic compounds are mixed in water (see below).…”

Section: Crown Monomers and Polymersmentioning

confidence: 97%

“…The rilonomers were prepared with cathecol as starting material. 40 This was converted to 3,4 dihydroxyacetophenone via the catecholdiacetate. The ketone was then reacted with Cl(CH2CH20).…”

Section: Crown Monomers and Polymersmentioning

confidence: 99%

“…Several 40 The decrease in A for the polycrown ethers is, of course, much larger due to the low mobility of the polycation and the decrease in the fraction of free counterions contributing to the conductance. The actual value of A is .a complicated function of the fraction, ' Y· of free counterions, the degree of cation binding, q, and polymer-solvent interactions.…”

Section: Conductance Measurementsmentioning

confidence: 99%

“…39 In this paper the behavior of polymers endowed with crown ethers as pendent groups will be discussed. Such polymers, when dissolved in solvents containing complexable cations, behave as typical polyelectrolytes 40 and the ion binding to the macromolecules can be studied by conductance, viscosity, optical spectroscopy and other techniques. The close proximity of the crown moieties affects the cation binding.…”

Section: Introductionmentioning

confidence: 99%

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Solute Binding to Polymers Containing Macroheterocyclic Rings

Smid

1976

Pure and Applied Chemistry

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Abstraet-Interactions of macroheterocycles and polymers endowed with such cation binding ligands as pendant groups, with ions or ion pairs are discussed, emphasis being placed on the binding properties of the macrocyclic polyethers or crown ethers. The use of ßuorenyl and pierate salts permitted a spectrophotometric investigation of Iigand interactions with ion pairs and a determination of ion pair-crown ether structures, which is of importance in the study of ion transport through low polarity media. Conductometric and spectrophotometric studies were carried out to obtain the complex formation constants of bis(crown ethers) (e.g. crown compounds with two crown moieties at opposite ends of a short aliphatic chain) to cations and their pierate tight ion pairs, as a function of the length and structure of the bis(crown ether) chain. Studies of cation binding to homopolymers and styrene copolymers of vinylbenzo-15-crown-5 and of vinylbenzo-18-crown.{i using extraction equilibria, ion transport, conduc(ance and viscosity, demonstrated the formation of 1 : 1 and 2: 1 crown-cation complexes, selectivity of cation binding, the dependence of the complexation constant on the number of cations bound to the chain, and the possibility of intermolecular 2: 1 crown-cation complex formation and crosslinking in copolymers with a low crown content. The polymer poly(vinylbenzo-18-crown-6) exhibits unusually strong binding of organic neutral and anionic solutes in aqueous media. Binding of pierate salts, methyl orange, phenolphtaleine and other solutes were studied spectrophotometrically. The hydrophobic adsorption of organic solutes also causes this polymer to catalyze the decarboxylation of 6-nitrobenzisoxazole-3-carboxylate by dehydrating the anion. The reaction is accelerated in the presence of complexable cations, which are bound to the polycrown ether, thereby further enhancing the adsorption of organic anions by electrostatic interactions. The same polymer was found to precipitate polynucleotides in water in the presence of complexable cations such as K+. It also exerts a strong inh!bitory effect on the polyriboadenylate templated elongation of oligodeoxythymidine catalyzed by murine leukemia virions.

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Section: Crown Monomers and Polymersmentioning

confidence: 92%

Section: Crown Monomers and Polymersmentioning

confidence: 97%

Section: Crown Monomers and Polymersmentioning

confidence: 99%

Section: Conductance Measurementsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Solute Binding to Polymers Containing Macroheterocyclic Rings

Smid

1976

Pure and Applied Chemistry

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Hydrolysis of active esters by polymer-supported oximes: Influence of macromolecular characters

Aiswaryakumari

Sreekumar

1998

J. Appl. Polym. Sci.

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Hydrolysis of p-nitrophenyl acetate by oximino groups anchored onto two types of supports (i.e., polystyrene and polyacrolein) has been studied. Polystyrene and polyacrolein oximes were prepared using divinylbenzene and tetraethyleneglycol diacrylate as crosslinking agents with a varying extent of crosslinking. The rate of the esterolytic reactions was found to depend on the structural characteristics of the polymer support, which include the hydrophobic or hydrophilic nature of the polymer backbone, solvation of the polymer and the attached functional groups, the nature and extent of crosslinking of the polymer matrix, and also the chemical environments of the oximino groups. The effect of the presence of pyridine residues neighboring the acrolein oxime functionality on the hydrolysis reaction was also studied.

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Crown ethers—complexes and selectivity

Vögtle

Weber

1989

PATAI'S Chemistry of Functional Groups

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Cation Binding Properties of Poly(vinyl macrocyclic polyethers)

Cited by 121 publications

References 0 publications

Solute Binding to Polymers Containing Macroheterocyclic Rings

Solute Binding to Polymers Containing Macroheterocyclic Rings

Hydrolysis of active esters by polymer-supported oximes: Influence of macromolecular characters

Crown ethers—complexes and selectivity

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