Water redox systems

The main equilibria in the water redox system are the following ... 

Water. Latices should be made with deionized water or condensate water. The resistivity of the water should be at least lO Q. Long-term storage of water should be avoided to prevent bacteria growth. If the ionic nature of the water is poor, problems of poor latex stabiUty and failed redox systems can occur. Antifreeze additives are added to the water when polymerization below 0°C is required (37). Low temperature polymerization is used to limit polymer branching, thereby increasing crystallinity. 

The most common water-soluble initiators are ammonium persulfate, potassium persulfate, and hydrogen peroxide. These can be made to decompose by high temperature or through redox reactions. The latter method offers versatility in choosing the temperature of polymerization with —50 to 70°C possible. A typical redox system combines a persulfate with ferrous ion ... 

Reducing agents are employed to return the Fe to Fe . By starting at a lower temperature, the heat of reaction can be balanced by the sensible heat of the water in the emulsion. Temperature profiles from 20 to 70°C are typical for such systems. Care must be taken when working with redox systems to... 

Emulsion Polymerization. In this method, polymerization is initiated by a water-soluble catalyst, eg, a persulfate or a redox system, within the micelles formed by an emulsifying agent (11). The choice of the emulsifier is important because acrylates are readily hydrolyzed under basic conditions (11). As a consequence, the commonly used salts of fatty acids (soaps) are preferably substituted by salts of long-chain sulfonic acids, since they operate well under neutral and acid conditions (12). After polymerization is complete the excess monomer is steam-stripped, and the polymer is coagulated with a salt solution the cmmbs are washed, dried, and finally baled. 

Organic peroxide-aromatic tertiary amine system is a well-known organic redox system 1]. The typical examples are benzoyl peroxide(BPO)-N,N-dimethylani-line(DMA) and BPO-DMT(N,N-dimethyl-p-toluidine) systems. The binary initiation system has been used in vinyl polymerization in dental acrylic resins and composite resins [2] and in bone cement [3]. Many papers have reported the initiation reaction of these systems for several decades, but the initiation mechanism is still not unified and in controversy [4,5]. Another kind of organic redox system consists of organic hydroperoxide and an aromatic tertiary amine system such as cumene hydroperoxide(CHP)-DMT is used in anaerobic adhesives [6]. Much less attention has been paid to this redox system and its initiation mechanism. A water-soluble peroxide such as persulfate and amine systems have been used in industrial aqueous solution and emulsion polymerization [7-10], yet the initiation mechanism has not been proposed in detail until recently [5]. In order to clarify the structural effect of peroxides and amines including functional monomers containing an amino group, a polymerizable amine, on the redox-initiated polymerization of vinyl monomers and its initiation mechanism, a series of studies have been carried out in our laboratory. 

It is considered useful to include here the potential-pH diagram for some redox systems related to oxygen (Fig. 2.1) [4]. Lines 11 and 33 correspond to the (a) and (b) dashed lines bounding the stability region of water, as depicted in all the subsequent Pourbaix diagrams. 

Hence, in the absence of a redox system in solution the anodic reaction of FeS2 yields iron oxide/hydroxide and water-soluble sulfate ions. The compound does not undergo non-oxidative dissolution. 

PEMFC)/direct methanol fuel cell (DMFC) cathode limit the available sites for reduction of molecular oxygen. Alternatively, at the anode of a PEMFC or DMFC, the oxidation of water is necessary to produce hydroxyl or oxygen species that participate in oxidation of strongly bound carbon monoxide species. Taylor and co-workers [Taylor et ah, 2007b] have recently reported on a systematic study that examined the potential dependence of water redox reactions over a series of different metal electrode surfaces. For comparison purposes, we will start with a brief discussion of electronic structure studies of water activity with consideration of UHV model systems. 

Abe, R., Sayama, K., Domen, K., and Arakawa, H. (2001) A new type of water splitting system composed of two different Ti02 photocatalysts (anatase, rutile) and a IOj"/r shuttle redox mediator. Chemical Physics Letters, 344 (3-4), 339-344. 

In this case, a moderately water-soluble amphiphilic N-vinylcaprolaclam (NVC1) played the role of a fl-unit, and a well-water-compatible N-vinyl-imidazole (NVIAz) served as a P-unil. The polymerization was carried out in a medium of 10% aqueous dimethylsulfoxide (DMSO). The addition of DMSO to the reaction solvent was necessary because of insufficient NVC1 solubility in pure water. It was also shown that in this solvent mixture, the NVCl-homopolymers and NVCl/NVIAz-copolymers retained their LCST-behaviour [26,28]. Hence, the DMSO in the reaction solvent did not significantly suppress the hydrophobic interactions of the NVC1 units. The polymerization was initiated by the redox system (N,N,N, N -tetramethylethylenediamine (TMEDA) + ammonium persulphate (APS)) and was carried out at 65 °C (1st step). This condition was very important, since admittedly the temperature was higher than the phase separation threshold of the reaction bulk when the polymeric products were formed that is, under these thermal conditions, hydrophobically-induced folding as the NVCl-blocks appear was ensured. After completion of the reaction, the... 

A suspension process using redox initiation in a water medium was developed. The redox system is a combination of persulfatesulfite. Often ferrous or cupric salts were added as a catalyst for the redox reaction. Polymerizations were run in water at low temperature (20-25°C) and low pressure (65-85 psi). Monomer to monomer-plus-water weight ratios of 0.20 to 0.25 were used. Good agitation was required to keep an adequate monomer concentration in the aqueous phase. Yields ofup to 100% were obtained with polymer inherent viscosities of0.4 to 1.5 dl/g in C6F5C1. Reactions were run on both a 1-gal and a 100-gal scale. 

W results not only from their redox-active ranging through oxidation states VI-IV, but because the intermediate V valence state is also accessible, they can act as interfaces between one- and two-electron redox systems, which allows them to catalyse hydroxylation of carbon atoms using water as the ultimate source of oxygen, (Figure 17.1) rather than molecular oxygen, as in the flavin-, haem- or Cu-dependent oxygenases, some of which we have encountered previously. For reviews see Hille, 2002 Brondino et al., 2006 Mendel and Bittner, 2006. 

As Fig. 9.2 shows, the Fe(III)/Fe(II) redox couple can adjust with appropriate ligands to any redox potential within the stability of water. The principles exemplified here are of course also applicable to other redox systems. 

As in the respiratory chain (see p. 140), the light reactions cause electrons to pass from one redox system to the next in an electron transport chain. However, the direction of transport is opposite to that found in the respiratory chain. In the respiratory chain, electrons flow from NADH+H to O2, with the production of water and energy. 

Figure 6, Schematic showing energy correlations for photoassisted electrolysis of water using n-type TiOg as a photoanode and a metal cathode. Symbols as in Figures 3, 4, and 5, except Epis Fermi level for metal contact to TiO and E/ is higher Fermi level in metal cathode, polarized by an external source to a potential negative to the semiconductor anode. EF(Hi) and Ep(02) are abbreviated forms for Fermi energies for redox systems of Figure 3 (13j.

The initiators used in emulsion polymerization are water-soluble initiators such as potassium or ammonium persulfate, hydrogen peroxide, and 2,2 -azobis(2-amidinopropane) dihydrochloride. Partially water-soluble peroxides such a succinic acid peroxide and f-butyl hydroperoxide and azo compounds such as 4,4 -azobis(4-cyanopentanoic acid) have also been used. Redox systems such as persulfate with ferrous ion (Eq. 3-38a) are commonly used. Redox systems are advantageous in yielding desirable initiation rates at temperatures below 50°C. Other useful redox systems include cumyl hydroperoxide or hydrogen peroxide with ferrous, sulfite, or bisulfite ion. 

Water-soluble initiators (potassium peroxodisulfate redox systems) are used except for a few special cases. 

These superabsorbents are synthesized via free radical polymerization of acrylic acid or its salts in presence of a crosslinker (crosslinking copolymerization). Initiators are commonly used, water-soluble compounds (e.g., peroxodi-sulfates, redox systems). As crosslinking comonomers bis-methacrylates or N,hT-methylenebis-(acrylamide) are mostly applied. The copolymerization can be carried out in aqueous solution (see Example 5-11 or as dispersion of aqueous drops in a hydrocarbon (inverse emulsion polymerization, see Sect. 2.2.4.2). 

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