Synthesis of regular polyampholytes by copolymerization of maleic acid with allyl and diallyl amine derivatives

Abstract

Radical copolymerization of maleic acid with allyl amine or diallyl amine derivatives results in regular polyampholytes which are completely or to high extent soluble in water. With equimolar amounts of both comonomers the rate of the alternating copolymerization runs through a minimum. The copolymers are thermally relatively stable and can be changed to water insoluble products by tempering.

New Regular, Amphiphilic Poly(ampholyte)s: Synthesis and Characterization

“…But above 165 8C, the intensity of the vibration band at 1 730 cm À1 attributed to -COOH vibrations decreases, whereas the intensities of two new bands around 1 780 and 1 850 cm À1 increase. In agreement with similar observations in the literature, [10] the appearance of these two new bands can be attributed to cyclic anhydride groups which are formed between two neighboring carboxylic acids, under the elimination of water. If the temperature is further increased from 200 to 300 8C, the solubility of the polymers in a polar solvent (ethanol þ 1 equivalent of nitric acid per repeat unit) decreases, indicating that cross-linking between the chains occurs.…”

“…The alternating copolymerization of diallylamines 1a-c with maleic acid agrees well with the reported behavior of the diallylamine and N-methyldiallylamine, [6,10] i.e., the alkyl chains and the surfactant character of 1a-c do not interfere with the ''natural'' reactivity of the polymerizable groups. The alternating incorporation of the amine and acid monomers may be attributed to the formation of ions pairs in solution, [21,22] rather than to a combination of electronrich and electron-poor monomers, as is the case for the classic example of the alternating copolymer of styrene and maleic anhydride.…”

“…It can only be speculated on the different reactions taking place, but the prominent new band at about 1 640 cm À1 suggests the formation of tertiary amide groups, as hypothesized before for copolymers of N-methyldiallylamine and maleic acid, perhaps as result of transalkylation and transacylation reactions. [10] DSC studies below the onset of thermal degradation, i.e., below 150 8C, did not indicate thermal transitions for copolymers 3a and 3b. However, heating and cooling traces of 3c (Figure 8), i.e., of the copolymer with the longest alkyl side chain, exhibit broad, but intense signals.…”

“…[5] Noteworthy, cyclocopolymerization of allylamine, diallylamine and Nmethyldiallylamine with maleic acid was occasionally reported to yield regular poly(ampholyte)s systems in the form of alternating copolymers. [6][7][8][9][10] This is an attractive approach to well-defined poly(ampholyte)s which generally must be prepared by the polymerization of specially designed monomers, [11][12][13][14] or by multistep synthesis via reactive precursor polymers. [15][16][17] Within other interesting potential uses, poly(ampholyte)s may serve as models or mimics of proteins, especially when bearing hydrophobic fragments that render them amphiphilic.…”

Solution Properties and Complexation of Polyampholytes based on N,N‐Dimethyldiallylammonium Chloride and Maleic Acid or Alkyl (Aryl) Derivatives of Maleamic Acids

“…[11][12][13][14] Modification of both N-substituents and maleic acid allows the design of various Summary: Solution properties of alternating polyampholytes based on N,N-dimethyldiallylammonium chloride and maleic acid as well as N,N-dimethyldiallylammonium and maleamic acid (butylmaleamic acid, phenylmaleamic acid, 4-butylphenylmaleamic acid) were studied in aqueous and aqueous-salt solutions. The isoelectric points (IEP) of the amphoteric macromolecules were determined.…”