Polymeric Sulfonic Acids Research Articles

New sulfonate-containing network polymers based on immobilized cis-metacyclophane-3,5,10,12,17,19,24,26-octols

Polymeric metacyclophaneoctol-based sulfonic acids have been synthesized, and their ion-exchange properties have been studied. New polymeric sulfonic acids have been obtained through the sulfonation of network polymers based on immobilized cis-metacyclophane-3,5,10,12,17,19,24,26-octols. The structure of the polymers has been investigated by means of IR spectroscopy, potentiometric titration, and elemental analysis. The polymers thus obtained possess a high ion-exchange capacity with respect to Na+, Cu2+, [Pd(NH3)4]2+, and In3+ cations in a wide pH range. Selectivity coefficients of Na+-H+, Cu2+-H+, and In3+-H+ ion exchange have been estimated.

Highly Active and Selective Palladium Catalyst for Hydroesterification of Styrene and Vinyl Acetate Promoted by Polymeric Sulfonic Acids.

Highly efficient, selective and recyclable palladium catalyst systems for hydroesterification of styrene and vinyl acetate were realized by using 1,2-bis(di-tert-butylphosphinomethyl)benzene as ligand and polymeric sulfonic acids of limited SO3H loadings as promoter.

Highly active and selective palladium catalyst for hydroesterification of styrene and vinyl acetate promoted by polymeric sulfonic acids

Highly efficient, selective and recyclable palladium catalyst systems for hydroesterification of styrene and vinyl acetate were realized by using 1,2-bis(di-tert-butylphosphinomethyl)benzene as ligand and polymeric sulfonic acids of limited SO(3)H loadings as promoter.

Catalytic membranes: alkene dimerisation by means of acidic porous thin-film composite membranes

Dimerisation of isobutene is of increasing interest to substitute oxygenated products such as MTBE or the like as fuel additives. Catalysts applied in commercial alkylation plants, e.g., hydrofluoric and sulfuric acid may be replaced by less harmful solid catalysts, for example by solid heteropolyacids (“super” acids) or polymeric sulfonic acids. To overcome decrease in catalyst performance by time and to increase product selectivity a membrane reactor approach is suggested and first successful results are presented.

New Ionic Polymer: Synthesis and Properties of “Zinc Sulfonated Natural Rubber”

Zinc sulfonated natural rubbers having different sulfonate contents were synthesized by the reaction of natural rubber with acetyl sulfate, followed by the neutralization of the resultant polymeric sulfonic acid with zinc acetate. The sample notation used for the ionomer is x y M-SNR, where x y is the degree of sulfonation expressed as meq/100 gm rubber, M is the neutralizing metal ion and SNR shows sulfonated natural rubber [Weiss, R.A., Fitzgerald, J.J. and Kim, D. (1991). Macromolecules, 1064: 24]. The modified samples of natural rubber were characterized using spectroscopic techniques such as X-ray Fluorescence Spectroscopy (XRFS), Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICPAES), Fourier Transform Infrared Spectroscopy (FTIR), Fourier Transform Nuclear Magnetic Resonance Spectroscopy (FTNMR), and by the evaluation of mechanical properties. The results show that the incorporation of sulfonate groups into NR improved its physical properties drastically. At a sulfonate level of 24.6 meq/100 g rubber, the tensile strength of the modified rubber incredibly increased to 13 MPa compared to the tensile strength of 0.36 MPa shown by unvulcanized base natural rubber. The Zn-SNR thus synthesized could be reprocessed at 150 C without sacrificing much of its tensile strength.

TGA/FTIR studies on the thermal degradation of some polymeric sulfonic and phosphonic acids and their sodium salts

The thermal degradation of poly(vinyl sulfonic acid) and its sodium salt, poly(4-styrenesulfonic acid) and its sodium salt, and poly(vinylphosphonic acid) was studied by a combination of techniques, including TGA/FTIR, to identify the volatile products which were evolved during the degradation as well as analysis of the residues which were obtained in order to propose a mechanism for the degradation. The motivation for the work was to attempt to identify new monomers which could be graft copolymerized onto a polymer in order to improve the thermal stability of that polymer.

ChemInform Abstract: ETHYL METHACRYLATE FROM METHYL METHACRYLATE BY TRANSESTERIFICATION USING SIMPLE AND POLYMERIC SULFONIC ACIDS AS CATALYSTS

Chemischer InformationsdienstVolume 8, Issue 37 Preparative Organic Chemistry ChemInform Abstract: ETHYL METHACRYLATE FROM METHYL METHACRYLATE BY TRANSESTERIFICATION USING SIMPLE AND POLYMERIC SULFONIC ACIDS AS CATALYSTS A. B. MOUSTAFA, A. B. MOUSTAFASearch for more papers by this authorR. M. MOHSEN, R. M. MOHSENSearch for more papers by this author A. B. MOUSTAFA, A. B. MOUSTAFASearch for more papers by this authorR. M. MOHSEN, R. M. MOHSENSearch for more papers by this author First published: September 13, 1977 https://doi.org/10.1002/chin.197737126Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume8, Issue37September 13, 1977 RelatedInformation

種々の高分子スルホン酸触媒による酢酸-<I>n</I>-ブチルの加水分解

種々の高分子スルホン酸触媒による酢酸-<I>n</I>-ブチルの加水分解

〔80〕高分子スルホン酸触媒による高分子エステルの加水分解

〔80〕高分子スルホン酸触媒による高分子エステルの加水分解

〔87〕 高分子スルホン酸触媒による高分子エステルの加水分解

〔87〕 高分子スルホン酸触媒による高分子エステルの加水分解

Specific Effects in Acid Catalysis by Polymeric Sulfonic Acids in the Hydrolysis of the Amino Ester and Related Compounds

Abstract The amino ester hydrolysis by polymeric sulfonic acids increased as the concentration ratio, Cester/Cacid, was lowered, and a maximum in the plot of the rate constant, k, against the Cester/Cacid ratio was attained near the ratio=0.4 in the case of the β-alanine methyl ester as well as in the case of γ-methyl l-glutamate. At this optimum concentration, the catalytic effect of polyvinylsulfonic acid (A), for example, in the hydrolysis of the β-alanine methyl ester was 16 times greater than that of hydrochloric acid, while the effect of polystyrenesulfonic acid was about 7 times greater. The catalytic effects of hydrochloric acid and ethanesulfonic acid were the same in all cases, and there was no such specific behavior as in the former. Furthermore, the catalytic efficiency of polyvinylsulfonic acid in amino ester hydrolysis increased with an increase in the polymer molecular weight, in contrast with the case of the carboxylic ester, while no such correlation was found in the polystyrenesulfonic acid. Besides, the catalytic effect of partially-neutralized polymeric sulfonic acid, polyvinylsulfonic acid especially, decreased remarkably with the degree of neutralization. These different kinds of behavior can be interpreted as being due to the difference in the expansion in solutions and in the geometrical distances between nearest-neighboring sulfonic acid groups on the polymer chain.

Specific Effects in Acid Catalysis by Polymeric Sulfonic Acids in the Hydrolysis of Some Carboxylic Esters

Abstract The catalytic effects of polymeric sulfonic acids in ester hydrolysis in aqueous acetone were inferior to that of hydrochloric acid. However, the hydrolysis rate was accelerated by increasing the water content of acetone-water mixtures, and, in a water solution, polymeric sulfonic acids were much more effective catalysts. Furthermore, the catalytic efficiency of polymeric sulfonic acid in ester hydrolysis in water increased with the length of the ester molecule. The polymeric sulfonic acid with a strong hydrophobic character was more effective; 69% sulfonated polystyrene-sulfonic acid, for example, hydrolyzed methyl hydrogen azelate in water over five times more rapidly than hydrochloric acid. The specificity thus obtained suggests that, in the hydrolysis of electrically-neutral esters in water, ester molecules are concentrated in the neighborhood of the polymer by the hydrophobic interaction between catalyst and substrate. Besides, in the hydrolysis of aliphatic esters catalyzed by polyvinylsulfonic acid in 50% aqueous acetone, there was a linear relationship between the reciprocal of the rate constant and the intrinsic viscosity of the polymer, while in the case of polystyrenesulfonic acid hardly such any relationship was found. These remarkably different behaviors of the two kinds of polymer catalysts should be attributed to the difference in the expansion of the polymer chain in solutions.

Homogeneous hydrolysis of esters with polymer sulfonic acids

AbstractStudies on homogeneous hydrolysis were carried out of low molecular esters with polymeric sulfonic acids such as polyvinylsulfonic acid, copolymers of vinyl sulfonic acid and styrene, sulfonated polystyrenes, etc.In an aqueous solution of polymeric sulfonic acid, hydrogen ions, which contribute to the hydrolysis, are found only in the neighborhood of polymer molecule, and in dilute solution there is a region where no hydrogen ion being able to contribute to the hydrolysis exists; as a result, the hydrolysis takes place only in the neighborhood of polymer molecule. When longer alkyl ester such as butyl acetate is hydrolysed with partially sulfonated polystyrenes, the ester molecules are bound by hydrophobic interaction between a benzene ring and the alkyl group to result in a higher concentration of ester in the neighborhood of polymer molecule. In such a case, the rate of hydrolysis by a polymeric sulfonic acid is for example more than ten times greater than that of hydrolysis with hydrochloric acid. When no concentration of ester around polymer catalyst occurs, there is apparently no difference between the rates of hydrolysis by polymer catalyst and hydrochloric acid.It was further shown that esters which contain an amino group are hydrolysed with polystyrenesulfonic acid with a much higher rate than with hydrochloric acid due to its electrostatic interaction with the polymeric sulfonic acid.

高分子スルホン酸触媒による高分子エステルの加水分解

分枝ポリビニルアルコール (PVA)(分枝単位: 1.3個以下/100基本分子), ビニルアルコール-アリルアルコール共重合物 (アリルアルコール含量: 22モル%以下), ビニルアルコール-イソプロペニルアルコール共重合物 (イソプロペニルアルコール含量: 18モル%以下) の部分アセチル化物を, ポリスチレンスルホン酸, 部分スルホン化ポリスチレン, ドデシルベンゼンスルホン酸などを触媒に用いて水溶液中でケン化し, 反応の速度定数 (ks) を塩酸触媒の場合のそれ (kHCl) と比較した。これらの改質PVAの部分アセチル化物に対するγ=ks/kHClの値は, 一般に直鎖状の非改質PVAの部分アセチル化物に対する値に近かった。部分アセチル化デンプンの加水分解も検討したが, γ値はアセチル化PVAの場合よりもずっと小さく (平均値2), 部分アセチル化アミロースのほうが部分アセチル化アミロペクチンよりやや大きかった。これらの結果について少し考察した。

高分子スルホン酸触媒による高分子エステルの加水分解

高分子スルホン酸触媒による高分子エステルの加水分解