Poly transport

About half of the wodd production comes from methanol carbonylation and about one-third from acetaldehyde oxidation. Another tenth of the wodd capacity can be attributed to butane—naphtha Hquid-phase oxidation. Appreciable quantities of acetic acid are recovered from reactions involving peracetic acid. Precise statistics on acetic acid production are compHcated by recycling of acid from cellulose acetate and poly(vinyl alcohol) production. Acetic acid that is by-product from peracetic acid [79-21-0] is normally designated as virgin acid, yet acid from hydrolysis of cellulose acetate or poly(vinyl acetate) is designated recycle acid. Indeterrninate quantities of acetic acid are coproduced with acetic anhydride from coal-based carbon monoxide and unknown amounts are bartered or exchanged between corporations as a device to lessen transport costs. 

Membranes and Osmosis. Membranes based on PEI can be used for the dehydration of organic solvents such as 2-propanol, methyl ethyl ketone, and toluene (451), and for concentrating seawater (452—454). On exposure to ultrasound waves, aqueous PEI salt solutions and brominated poly(2,6-dimethylphenylene oxide) form stable emulsions from which it is possible to cast membranes in which submicrometer capsules of the salt solution ate embedded (455). The rate of release of the salt solution can be altered by surface—active substances. In membranes, PEI can act as a proton source in the generation of a photocurrent (456). The formation of a PEI coating on ion-exchange membranes modifies the transport properties and results in permanent selectivity of the membrane (457). The electrochemical testing of salts (458) is another possible appHcation of PEI. 

Figure 4c illustrates interfacial polymerisation encapsulation processes in which the reactant(s) that polymerise to form the capsule shell is transported exclusively from the continuous phase of the system to the dispersed phase—continuous phase interface where polymerisation occurs and a capsule shell is produced. This type of encapsulation process has been carried out at Hquid—Hquid and soHd—Hquid interfaces. An example of the Hquid—Hquid case is the spontaneous polymerisation reaction of cyanoacrylate monomers at the water—solvent interface formed by dispersing water in a continuous solvent phase (14). The poly(alkyl cyanoacrylate) produced by this spontaneous reaction encapsulates the dispersed water droplets. An example of the soHd—Hquid process is where a core material is dispersed in aqueous media that contains a water-immiscible surfactant along with a controUed amount of surfactant. A water-immiscible monomer that polymerises by free-radical polymerisation is added to the system and free-radical polymerisation localised at the core material—aqueous phase interface is initiated thereby generating a capsule sheU (15). 

Figure 4c also describes the spontaneous polymerisation ofpara- s.yX en.e diradicals on the surface of soHd particles dispersed in a gas phase that contains this reactive monomer (16) (see XylylenePOLYMERS). The poly -xylylene) polymer produced forms a continuous capsule sheU that is highly impermeable to transport of many penetrants including water. This is an expensive encapsulation process, but it has produced capsules with impressive barrier properties. This process is a Type B encapsulation process, but is included here for the sake of completeness. 

Another biomedical appHcation of mictocapsules is the encapsulation of Hve mammalian ceUs for transplantation into humans. The purpose of encapsulation is to protect the transplanted ceUs or organisms from rejection by the host. The capsule sheU must prevent entrance of harmful agents into the capsule, aUow free transport of nutrients necessary for ceU functioning into the capsule, and aUow desirable ceUular products to freely escape from the capsule. This type of encapsulation has been carried out with a number of different types of Hve ceUs, but studies with encapsulated pancreatic islets or islets of Langerhans ate most common. The alginate—poly(L-lysine) encapsulation process originally developed in 1981 (54) catalyzed much of the ceU encapsulation work carried out since. A discussion of the obstacles to the appHcation of microencapsulation in islet transplantation reviewed much of the mote recent work done in this area (55). Animal ceU encapsulation has also been researched (56). 

Poly(ethylene oxide) associates in solution with certain electrolytes (48—52). For example, high molecular weight species of poly(ethylene oxide) readily dissolve in methanol that contains 0.5 wt % KI, although the resin does not remain in methanol solution at room temperature. This salting-in effect has been attributed to ion binding, which prevents coagulation in the nonsolvent. Complexes with electrolytes, in particular lithium salts, have received widespread attention on account of the potential for using these materials in a polymeric battery. The performance of soHd electrolytes based on poly(ethylene oxide) in terms of ion transport and conductivity has been discussed (53—58). The use of complexes of poly(ethylene oxide) in analytical chemistry has also been reviewed (59). 

Other electron-deficient heterocyclic systems have also been investigated as electron-transporting materials. In particular, devices employing poly(phenyl qui-noxaline) 43 as an ECHB layer have shown improvements in device efficiency when used in conjunction with an emissive PPV layer [75]. 

Electron-Deficient Polymers - Luminescent Transport Layers 16 Other Electron-Deficient PPV Derivatives 19 Electron-Deficient Aromatic Systems 19 Full Color Displays - The Search for Blue Emitters 21 Isolated Chromophores - Towards Blue Emission 21 Comb Polymers with Chromophores on the Side-Chain 22 Chiral PPV - Polarized Emission 23 Poly(thienylene vinylene)s —... 

Karigl [71] defined a format diffusion coefficient for bromine transport through a poly thy lene separator of a zinc-flow battery by considering the separator a diffusion layer. A value of Dsep(Br3 ) = 2.77 10 10 m2 s l was obtained. 

The huge literature on the electronic conductivity of dry conducting polymer samples will not be considered here because it has limited relevance to their electrochemistry. On the other hand, in situ methods, in which the polymer is immersed in an electrolyte solution under potential control, provide valuable insights into electron transport during electrochemical processes. It should be noted that in situ and dry conductivities of conducting polymers are not directly comparable, since concentration polarization can reduce the conductivity of electrolyte-wetted films considerably.139 Thus in situ conductivities reported for polypyrrole,140,141 poly thiophene,37 and poly aniline37 are orders of magnitude lower than dry conductivities.15... 

Theoretical aspects of mediation and electrocatalysis by polymer-coated electrodes have most recently been reviewed by Lyons.12 In order for electrochemistry of the solution species (substrate) to occur, it must either diffuse through the polymer film to the underlying electrode, or there must be some mechanism for electron transport across the film (Fig. 20). Depending on the relative rates of these processes, the mediated reaction can occur at the polymer/electrode interface (a), at the poly-mer/solution interface (b), or in a zone within the polymer film (c). The equations governing the reaction depend on its location,12 which is therefore an important issue. Studies of mediation also provide information on the rate and mechanism of electron transport in the film, and on its permeability. 

The classical example of a soUd organic polymer electrolyte and the first one found is the poly(ethylene oxide) (PEO)/salt system [593]. It has been studied extensively as an ionically conducting material and the PEO/hthium salt complexes are considered as reference polymer electrolytes. However, their ambient temperature ionic conductivity is poor, on the order of 10 S cm, due to the presence of crystalUne domains in the polymer which, by restricting polymer chain motions, inhibit the transport of ions. Consequently, they must be heated above about 80 °C to obtain isotropic molten polymers and a significant increase in ionic conductivity. 

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