Polymer backbone/pendent groups

A number of thermally stable polymers have been synthesized, but in general the types of stmctures that impart thermal resistance also result in poor processing characteristics. Attempts to overcome this problem have largely been concentrated on the incorporation of flexible groups into the backbone or the attachment of stable pendent groups. Among the class of polymers claimed to be thermally stable only a few have achieved technological importance, some of which are polyamides, polyimides, polyquin oxalines, polyquinolines, and polybenzimidazoles. Of these, polyimides have been the most widely explored. 

All phosphoms oxides are obtained by direct oxidation of phosphoms, but only phosphoms(V) oxide is produced commercially. This is in part because of the stabiUty of phosphoms pentoxide and the tendency for the intermediate oxidation states to undergo disproportionation to mixtures. Besides the oxides mentioned above, other lower oxides of phosphoms can be formed but which are poorly understood. These are commonly termed lower oxides of phosphoms (LOOPs) and are mixtures of usually water-insoluble, yeUow-to-orange, and poorly characteri2ed polymers (58). LOOPs are often formed as a disproportionation by-product in a number of reactions, eg, in combustion of phosphoms with an inadequate air supply, in hydrolysis of a phosphoms trihahde with less than a stoichiometric amount of water, and in various reactions of phosphoms haUdes or phosphonic acid. LOOPs appear to have a backbone of phosphoms atoms having —OH, =0, and —H pendent groups and is often represented by an approximate formula, (P OH). LOOPs may either hydroly2e slowly, be pyrophoric, or pyroly2e rapidly and yield diphosphine-contaminated phosphine. LOOP can also decompose explosively in the presence of moisture and air near 150° C. 

Attaching the ketone groups to the polymer backbone is more efficient on a chain scission/ketone basis because some of the light energy that the pendent ketone absorbs leads direcdy to chain scission via the Norrish type II mechanism, as well as photooxidation via the Norrish type I mechanism (see... 

Fig. 3. Mechanisms for polymer degradation. The illustration is a schematic representation of three degradation mechanisms I, cleavage of cross-links II, hydrolysis, ionisa tion, or protonation of pendent groups III, backbone cleavage. Actual biodegradation may be a combination of these mechanisms.

In the pendent chain systems, the dmg is chemically bound to a polymer backbone and is released by hydrolytic or enzymatic cleavage of the chemical bond. The dmg may be attached directiy to the polymer or may be linked via a spacer group. The spacer group may be used to affect the rate of dmg release and the hydrophilicity of the system. These systems allow very high dmg loadings (over 80 wt %) (89) which decrease the cost of the polymeric materials used ia the systems. These systems have beea examiaed by many iavestigators (111,112). 

Mohanty et al. were the first to introduce pendent r-butyl groups in die polymer backbones. The resulting material was quite soluble in aprotic dipolar solvents.83 The PEEK precursors were prepared under a mild reaction condition at 170°C. The polymer precursor can be converted to PEEK in die presence of Lewis acid catalyst A1C13 via a retro Friedel-Crafts alkylation. Approximately 50% of die rerr-butyl substitutes were removed due to die insolubility of the product in die solvent used. Later, Risse et al. showed diat complete cleavage of f< rf-butyl substitutes could be achieved using a strong Lewis acid CF3SO3H as both die catalyst and the reaction medium (Scheme 6.15).84... 

A novel polysiloxane, containing the isocyanide group pendent to the backbone, has been synthesized. It is observed to react with the metal vapors of chromium, iron and nickel to afford binary metal complexes of the type M(CN-[P])n, where n = 6, 5, 4 respectively, in which the polymer-attached isocyanide group provides the stabilization for the metal center. The product obtained from the reaction with Fe was found to be photosensitive yielding the Fe2(CN-[P])q species and extensive cross-linking of the polymer. The Cr and Ni products were able to be oxidized on exposure of thin films to the air, or electrochemically in the presence of an electron relay. The availability of different oxidation states for the metals in these new materials gives hope that novel redox-active polymers may be accessible. 

Hydroformylation and subsequent hydrogenation of C=C and -CHO groups of PBD appear to be an appropriate means whereby a pendent hydroxy group can be introduced onto the polymer backbone. A variety of partially hydroformyl ated (2-20%) and hydroxymethy-lated polymers have been synthesized by a two-step catalytic reaction and characterized by I.R. and 1H N.M.R. spectroscopy. As expected, the hydrophilic group, OH, in the polymer resulted in a greater decrease in the intrinsic viscosity as compared to the HPBD. 

A. Polymers Containing Boron Atoms in the Backbone or in Pendent Groups... 

Redox polymers are electroactive polymers for which the redox centers are localized on pendent, covalently attached redox centers. The electrochemical properties of such materials depend not only on both the loading and the nature of the redox-active center but also on the type of polymer backbone. The electroactive groups are typically metal complexes, which are covalently attached to a polymer... 

The example considered is the redox polymer, [Os(bpy)2(PVP)ioCl]Cl, where PVP is poly(4-vinylpyridine) and 10 signifies the ratio of pyridine monomer units to metal centers. Figure 5.66 illustrates the structure of this metallopolymer. As discussed previously in Chapter 4, thin films of this material on electrode surfaces can be prepared by solvent evaporation or spin-coating. The voltammetric properties of the polymer-modified electrodes made by using this material are well-defined and are consistent with electrochemically reversible processes [90,91]. The redox properties of these polymers are based on the presence of the pendent redox-active groups, typically those associated with the Os(n/m) couple, since the polymer backbone is not redox-active. In sensing applications, the redox-active site, the osmium complex in this present example, acts as a mediator between a redox-active substrate in solution and the electrode. In this way, such redox-active layers can be used as electrocatalysts, thus giving them widespread use in biosensors. 

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