Polymerization of itaconic acid

Abstract

Polymerization of itaconic acid Summary-Poly(itaconic acid) (PIA) has been prepared by various methods namely in radical polymerization in the presence of various initiators and using water or dioxane as reaction medium, or by poly(itaconic anhydride) hydrolysis. The main purpose was to investigate the effect of method of synthesis on the chemical structure of the product. Possibilities of the structures described by Formula (II) or (III) occurring have been considered. The following methods were used for PIA characterization: FT-IR, 1 H NMR, 13 C NMR, elemental analysis, size exclusion chromatography and conductometric titration as well as potentiometric titration. The reasons of known phenomenon of limited availability of PIA carboxylic groups in titration conditions were discussed. Significant effect of drying conditions on the results obtained suggests the importance of keeping the drying conditions constant. Two types of neighborhood of methylene or carboxylic groups in PIA have been found.

High‐Molecular‐Weight Polyampholytes Synthesized via Daylight‐Induced, Initiator‐Free Radical Polymerization of Renewable Itaconic Acid

“…IA is a key substrate for production of aliphatic, unsaturated and saturated polyesters, degradable polyamides as well as condensation polymers bearing pyrrolidine ring in the main chain . The acid is also a well‐known low reactive vinyl monomer, and its free radical polymerization typically requires long reaction times and high amounts of an initiator . Based on our previous experience with persulphate‐initiated polymerization of the acid in aqueous media and in choline‐based DESs, we have asked ourselves whether it would be possible to prepare itaconic polymers via initiator‐free radical polymerization.…”

“…[17][18][19] The acid is also a well-known low reactive vinyl monomer, and its free radical polymerization typically requires long reaction times and high amounts of an initiator. [20][21][22][23][24] Based on our previous experience with persulphate-initiated polymerization of the acid in aqueous media [21,24] and in choline-based DESs, [25][26][27] we have asked ourselves whether it would be possible to prepare itaconic polymers via initiator-free radical polymerization. It is well known that spontaneous thermal radical polymerization at temperature >100 °C is possible for several reactive vinyl monomers, including styrene and acrylic monomers.…”

“…Another interesting feature of these prepared polymers is their abnormally high molecular weight greater than ≈800 000 g mol −1 (Figure 1C; Table S2 and Figure S22, Supporting Information), in contrast to 1000-100 000 g mol −1 reported for PIA prepared in water and other common organic solvents. [21][22][23]26] According to classical free radical polymerization theory in a first approximation: [36] a) rate of polymerization is proportional to k p /k t 0.5 , where k p and k t , are propagation and termination rate coefficients, respectively and b) molecular weight is inversely proportional to the termination rate. In addition, k t is dependent on the medium viscosity [37] (η), k t ≈ 1/η, therefore, a highly viscous media is expected to accelerate FRP from the initial stage and to give a high-molecular-weight polymer (Trommsdorff-Norrish-like effect).…”

Study of poly(itaconic acid) in aqueous solutions

“…It has been shown that the polymers obtained by various methods were really PIA of the following structure: and in particular, when appropriate conditions were used, neither significant decarboxylation took place dur-ing polymerization as previously suspected [2,3] nor any formation of anhydride structures could be observed. On the other hand, based on 13 C NMR [4][5][6], one can find that PIA polymers show different tacticity depending on the synthesis process.…”

“…An additional, very convincing argument for this structure is the founding [8] that methyl diester can be obtained by treating the product of itaconic acid polymerization with diazomethane. On the other hand, it has been found [2,3,5,6] that both conductometric and potentiometric titrations of PIA provide a result suggesting that the product contains only 50-60 % of carboxylic groups resulting from the unit structure.…”