Styrenesulfonate polymerization

Cydodextrins can catalyze certain chemical reactions. Styrenesulfonate polymerization was accelerated in the presence of cyclodextrin, and the polymers had a higher molecular weight.109 Platinum-catalyzed hydroxylation reactions were accelerated in the presence of cyclodextrin.110... 

Fig. 2 Schematic of sodium styrenesulfonate polymerization by the different catalysts. HRP horseradish peroxidase 2,4-PD 2,4-pentanedione H2O2 hydrogen peroxide...

Some polymers from styrene derivatives seem to meet specific market demands and to have the potential to become commercially significant materials. For example, monomeric chlorostyrene is useful in glass-reinforced polyester recipes because it polymerizes several times as fast as styrene (61). Poly(sodium styrenesulfonate) [9003-59-2] a versatile water-soluble polymer, is used in water-poUution control and as a general flocculant (see Water, INDUSTRIAL WATER TREATMENT FLOCCULATING AGENTs) (63,64). Poly(vinylhenzyl ammonium chloride) [70304-37-9] h.a.s been useful as an electroconductive resin (see Electrically conductive polya rs) (65). 

The monomer 4-styrenesulfonic acid was prepared by dehydrohalogenation of -bromoethjibenzene—sulfonyl chloride. The potassium salt can be polymerized in aqueous solution (222). The sulfonation of cross-linked polystyrene beads is being carried out in industry with concentrated sulfuric acid. 

Polymerization and Spinning Solvent. Dimethyl sulfoxide is used as a solvent for the polymerization of acrylonitrile and other vinyl monomers, eg, methyl methacrylate and styrene (82,83). The low incidence of transfer from the growing chain to DMSO leads to high molecular weights. Copolymerization reactions of acrylonitrile with other vinyl monomers are also mn in DMSO. Monomer mixtures of acrylonitrile, styrene, vinyUdene chloride, methallylsulfonic acid, styrenesulfonic acid, etc, are polymerized in DMSO—water (84). In some cases, the fibers are spun from the reaction solutions into DMSO—water baths. 

Radical copolymerization is used in the manufacturing of random copolymers of acrylamide with vinyl monomers. Anionic copolymers are obtained by copolymerization of acrylamide with acrylic, methacrylic, maleic, fu-maric, styrenesulfonic, 2-acrylamide-2-methylpro-panesulfonic acids and its salts, etc., as well as by hydrolysis and sulfomethylation of polyacrylamide Cationic copolymers are obtained by copolymerization of acrylamide with jV-dialkylaminoalkyl acrylates and methacrylates, l,2-dimethyl-5-vinylpyridinum sulfate, etc. or by postreactions of polyacrylamide (the Mannich reaction and Hofmann degradation). Nonionic copolymers are obtained by copolymerization of acrylamide with acrylates, methacrylates, styrene derivatives, acrylonitrile, etc. Copolymerization methods are the same as the polymerization of acrylamide. 

Recently, Kong et al. [159] functionalized MWNT with polyacrylic acid (PAA) and poly(sodium 4-styrenesulfonate) (PSS) by surface-initiating ATRP (atom transfer radical polymerization) following the Schemes 1 and 2 ... 

The living radical polymerization process is also valid for the polymerization of water-soluble monomers. The polymerization of sodium styrenesulfonate in aqueous ethylene glycol (80%) in the presence of TEMPO using potassium per-sulfate/sodium bisulfite as the initiator at 125 °C gave a water-soluble polymer with well-controlled molecular weight and its distribution [207]. 

Materials PSS-Na (20) was prepared by the radical polymerization of p-styrenesulfonate. PVPA was obtained by the hydrolysis of poly-bis-(g-chloroethyl) vinylphosphonate and was concluded to have a following formula (23) ... 

Many ionogenic monomers containing a polymerizable carbon double bond have been reported in the literature, and therefore a wide variety of anionic, cationic, and amphophilic polyelectrolytes may be synthesized using free radical polymerizations. Examples of anionic ionogenic monomers which have been used to synthesize anionic polyelectrolytes include acrylic acid [4-10], methac-rylic acid [6-8,11,12], sodium styrenesulfonate [7,13,14], p-styrene carboxylic... 

The complexing ability of iminodiacetic acid type chelating agents, e.g. benzyl-aminediacetic acid (BDA) (8), was found to be enhanced considerably in aqueous solution by the use of a polymeric analogue such as (vinylbenzylamine diacetic acid)-co-(sodium styrenesulfonate) (PBDA) (9) 23). The chelate formation constants for... 

The polyelectrolytes used in this study are displayed in Table 1. Hydrophobic flexible polyelectrolyte molecules of poly(methacryloyloxyethyl dimethylbenzylammonium chloride) (PMBQ) with a molecular weight of 4.2 Mio g/mol was synthesized by free radical polymerization in water solution as described elsewhere [18,19], Poly(so-dium styrenesulfonate) (PSS) with molecular weight of 70 000 g/mol was purchased from Aldrich and was used without further purification. Water purified and deionized (reverse osmosis followed by ion exchange and filtration) by means of Milli-RO 5Plus and Milli-Q Plus systems (Millipore GmbH, Germany) was used as a solvent. 

In the methodology developed by us [24], the incompatibility of the two polymers was exploited in a positive way. The composites were obtained using a two-step method. In the first step, hydrophilic (hydrophobic) polymer latex particles were prepared using the concentrated emulsion method. The monomer-precursor of the continuous phase of the composite or water, when that monomer was hydrophilic, was selected as the continuous phase of the emulsion. In the second step, the emulsion whose dispersed phase was polymerized was dispersed in the continuous-phase monomer of the composite or its solution in water when the monomer was hydrophilic, after a suitable initiator was introduced in the continuous phase. The submicrometer size hydrophilic (hydrophobic) latexes were thus dispersed in the hydrophobic (hydrophilic) continuous phase without the addition of a dispersant. The experimental observations indicated that the above colloidal dispersions remained stable. The stability is due to both the dispersant introduced in the first step and the presence of the films of the continuous phase of the concentrated emulsion around the latex particles. These films consist of either the monomer-precursor of the continuous phase of the composite or water when the monomer-precursor is hydrophilic. This ensured the compatibility of the particles with the continuous phase. The preparation of poly(styrenesulfonic acid) salt latexes dispersed in cross-linked polystyrene matrices as well as of polystyrene latexes dispersed in crosslinked polyacrylamide matrices is described below. The two-step method is compared to the single-step ones based on concentrated emulsions or microemulsions. 

Polydispersity of the copolymer is still narrow (Mw/Mn = 1.36) whereas it increases to 4.21 in the absence of Tempo, leading to a bimodal molecular weight distribution. Such a process is also applied in aqueous medium [70] for the polymerization of styrenesulfonic acid sodium salt with narrow molecular weight distribution (Mw/Mn as low as 1.18). 

High polymer/surfactant weight ratios (up to about 15 1) of polystyrene microlatexes [73] have been produced in microemulsions stabihzed by polymerizable nonionic surfactant by the semi-continuous process. The copolymerization of styrene with the surfactant ensures the long-term stabihty of the latexes. Nanosized PS microlatexes with polymer content (<25 wt%) were also obtained from an emulsifier-free process [74] by the polymerization of styrene with ionic monomer (sodium styrenesulfonate, NaSS), nonionic comonomer (2-hydroxyethylmethacryalte, HEM A), or both. The surfaces of the latex particles were significantly enriched in NaSS and HEMA, providing better stabilization. 

It has been attempted to perform template polymer syntheses without using biological sources. Concepts focus on the formation of a complex between monomer molecules and a present macromolecule [4,480], This way the monomer will get preorganized and the polymerization is supposed to follow a zip mechanism controlled by the length and the configuration of the template polymer, offering replication of the molecular weight and control of the stereo structure. Polymerization of acrylic acid in the presence of poly(ethyleneimine), N-vinylimidazole/ poly(methacrylic acid) or acrylonitrile with poly(vinylacetate) have been described [469,470,471,472,473]. Recently the preparation of solid polyelectrolyte complexes from chitosan and sodium-styrenesulfonate has been reported [481]. 

It was, therefore, predicted (26) that this reaction should be much faster in polymeric acid solutions than in solutions of monobasic acids at the same pH. Experiments confirmed this expectation with rates more than 100 times faster in 0.01 N poly(styrenesulfonic acid) than in benzenesulfonic acid solutions of a similar concentration (27). In an analogous fashion, the Cannizaro reaction of glyoxal, which involves two hydroxyl ions,... 

An alternative approach is the use of a PS support bearing sulfonate pendant groups. For this, a quaternary ammonium salt of styrenesulfonic acid was copolymerized with a N-(p-styrenesulfonyl)-l,2-diphenylethylenediamine monomer. The polymeric chiral Ru complex was prepared from 177 and [RuCl2(p-cymene)]2 and applied to the asymmetric transfer hydrogenation of aromatic ketones in water (Scheme 3.55) [114]. The polymeric chiral complex was evenly suspended in water and the reaction proceeded smoothly to produce the alcohol in quantitative yield and with high enantioselectivity. For several of the aromatic ketones tested, higher... 

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