Organometallics condensation polymers

One previous synthesis of ferrocene-containing condensation polymers via interfacial methods at room temperature has been reported by Knobloch and Rauscher, who formed low molecular weight polyamides and polyesters by reacting l,l -bis(chloro-formyl)ferrocene with various diamines and diols. Further, Carraher and co-workers have utilized interfacial techniques in the formation of other types of organometallic polymers. 

The advantage of these polymers over poly(vinylferrocenes) or related species with pendent organometallic units is that the condensation polymers have ferrocene units in the main chain where they can exert their maximum influence on polymer thermal stability. The disadvantage of the condensation products is that, except in the last example, the molecular weights are too low to favor fiber or flexible film formation. Nevertheless, this work indicated the potential usefulness of polymers with metallocene units in the main chain. 

Two major approaches to the formation of materials of this type have involved the derivatization of preformed organic polymers with organometallic functions and the synthesis and polymerization of organometallic monomers that contain vinyl substituents For the transition metals, condensation polymerizations have also been investigated. However, the reactions have generally been conducted at elevated temperatures, and the resulting products have often not... 

Research involving condensation organometallic polymers was catalyzed by the observation that many organometallic halides possess a high degree of covalent character within their composite structure and that they can behave as organic acid chlorides in many reactions, such as hydrolysis... 

Materials that are constructed from organic polymers such as polyethylene, polystyrene, polyisoprene (natural rubber and a synthetic elastomer) and poly(vinyl chloride) are common features of our daily lives. Most of these and related organic polymers are generated from acyclic precursors by free radical, anionic, cationic or organometallic polymerisation processes or by condensation reactions. Cyclic precursors are rarely used for the production of organic polymers. 

Higher molecular weight polymers (40,000-50,000) have been reported from condensation reactions between monomer 6.15 and various silanediols, as illustrated in reaction (6).2 Polymer 6.16 can be melt-fabricated into films or fibers, which probably reflects the presence of roughly 100 repeating units per chain. However, the separation of the ferrocenyl units by the organic linker groups reduces the influence of the organometallic component. 

K does not lead to complexation or the formation of any organometallic compounds [73, 75], In the case of PX and Cl-PX such deposition proceeds without polymerization. The co-deposition of CN-PX with Ag is accompanied by the partial polymerization of monomer. The initial condensates at 77 K contain a small amount of Ag nanocrystals which can be revealed and characterized using UV-vis spectroscopy because such crystals (as it has been shown in Subsection 2.1) have the specific absorption band of surface electron plasmons 430 nm [77], UV irradiation of these condensates at 77 K leads to total conversion of monomers to corresponding polymers (PPX, C1PPX, and CNPPX). However, intensity (/)cr), maximum position and half-width... 

The concept of transesterifications was used for polymerization reactions by Hedrick and colleagues [76]. Various biodegradable polyesters were synthesized with the l,3-dimethylimidazol-2-ylidene carbene in THF at 25 °C. Polymers such as poly(e-caprolactone) were obtained with no need of organometallic catalysts, as in classical methods. Poly(ethylene terephthalate) (PET) 97 was synthesized in the ionic liquid 98, which functions as the reaction medium and, at the same time, as a precatalyst that is activated (99) with KOt-Bu. Dimethyl terephthalate (DMT) 100 was condensed with an excess of ethylene glycol 101 to generate 102. The melt condensation of 102 was performed under vacuum using a heating ramp to 280 °C. 

The first reported thermotropic and lyotropic liquid-crystalline poly(aryleneethynylene)s were not parent PPEs, but organometallic derivatives 65 made by the Pd-catalyzed condensation of Vollhardt s diethynyl 64 with diiodobenzenes 46 [45]. The polymers were isolated in good to excellent yields as amorphous tan or red powders with moderate Pn values of... 

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