Poly aldehyde solubility

Table IV gives an example of our own work on the polymerization of a number of higher aldehydes. Potassium triphenylmethoxide—a soluble initiator—polymerized a number of higher aldehydes to crystalline isotactic poly aldehydes. Table V lists a number of alkali alkoxides and other related compounds used as initiators for the n-butyraldehyde polymerization. Neither the type of the alkoxide nor the cation is of any great importance for the polymerization rate, the polymer yield, and stereoregularity of the resulting polyaldehyde as long as the initiator is adequately soluble in the reaction mixture.

Most isotactic polyaldehydes are insoluble at room temperatures but are soluble at elevated temperatures in some solvents. We have studied the gel point, which is a measure of polymer solubility. A number of poly aldehydes were investigated in tetrahydronaphthalene polyformaldehyde has the highest gel point observed—namely, about 200° C. For the series of unbranched polyaldehydes the gel point decreases with the increasing length of the aliphatic side chain (Table VI) and parallels the melting points of the polymer. 

The following protocols make use of the compounds adipic acid dihydrazide and carbohy-drazide to derivatize molecules containing aldehydes, carboxylates, and alkylphosphates. The protocols are applicable for the modification of proteins, including enzymes, soluble polymers such as dextrans and poly-amino acids, and insoluble polymers used as micro-carriers or chromatographic supports. 

The phosphinated ligands 135 and 136 prepared from poly(acrylic acid) and from poly(ethyleneimine), respectively, gave active hydroformylation catalysts in reaction with [Rh(acac)(CO)2]. Under the conditions of Table 4.6 low conversions were observed in aqueous/organic biphasic systems, due to the low solubility of 1-octene. Addition of a surfactant (SDS) or an organic co-solvent (MeOH) led to dramatic increases in the yield of aldehydes, revealing the high intrinsic activity of the catalyst [120]. 

A Ta vinylalkylidene complex 6, confirmed by a single crystal X-ray analysis, was revealed to polymerize 2-butyne in a manner of living polymerization.The initiation efficiency is quantitative, and the living end can be end-capped with aromatic aldehydes. As polymers from symmetric acetylenes are generally insoluble, soluble poly(2-butyne) is accessible if the degree of polymerization is suppressed below 200. The NMR analysis of living oligomers of 2-butyne clearly indicates that both cis- and 7ra r-structures exist in the main chain. 

It is thus conceivable that the insoluble material obtained by high concentrations of cationic initiator was crosslinked through the pendant aldehyde groups. Indeed, Moyer and Grev (108) obtained soluble poly-... 

In the reaction between an activated diene and a prochiral aldehyde, which is catalyzed by chiral Lewis acids, 5,6-dihydropyranoncs such as 6 are formed enantiomerically enriched. By attachment of a chiral auxiliary (3-heptafluorobutanoyl camphor derivatives such as 7 to a soluble poly-siloxane by hydrosilylation the catalyst should be recyled easily by precipitation or ultrafiltration while the cycloaddition reaction can be performed in homogeneous solution [lOj. 

Recently, rhodium/poly(enolate-co-vinyl alcohol-co-vinyl acetate) catalysts have been developed for the biphasic hydroformylation of aliphatic alkenes and applied to the selective hydroformylation of functionalized alkenes [16], Although the conversions were low (< 25%), excellent selectivities for the hydroformylation of n-bu-tyl vinyl ether and methyl 3,3-dimethylpenten-4-onate can be achieved with such water-soluble polymer-anchored rhodium catalysts. For instance, the hydroformylation of methyl 3,3-dimethylpenten-4-onate gives only the linear aldehyde. 

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