Polycarboxylic acids are well-known to affect calcium carbonate crystallization. Agarwal et al. (Ind. Eng. Chem. Res. 2003, in press) reported previously the synthesis of polymaleimide by a variety of techniques and initiators. In the present work, the effect of these polymers on calcium carbonate crystallization was studied by a variety of techniques. Crystallization experiments were carried out in a 1-L LABMAX automated batch reactor, and the concentration of calcium in solution was determined in real time. Raman spectroscopy was used to determine the relative amount of various calcium carbonate polymorphs as the crystallization occurred. However, Raman spectroscopy is a scattering technique, which may make it surface selective, and therefore results from solids may not be representative of bulk of sample. X-ray diffraction (XRD) was used to compare the results obtained by Raman spectroscopy. Peak intensity ratios were used for both Raman spectroscopy and XRD for calibration and measurement purposes. The results obtained by these two techniques for final percent vaterite for calcium carbonate crystallization in the presence of polymeric additives were in agreement within 2%. Therefore, use of Raman spectroscopy for in situ measurement of polymorph composition during calcium carbonate crystallization appears accurate. Scanning electron microscopy (SEM) data were useful in understanding the crystal morphology and to determine crystal size.

Simplified syntheses of polymaleimide employing anionic polymerization (from the melt and from solution) and metal compound-alcohol initiators such as PbO, SnO, tin bis(2-ethyl hexanoate) in the presence of tert-butyl benzyl alcohol are presented. The resulting polymers contain a combination of C-N-and C-C-connected monomers. Preliminary structures of the polymers were determined using NMR spectroscopy. The ratio of C-N-and C-C-connected monomers was determined, and the percentage of C-N-connected monomer units was found to vary from 40 to 80%, with the higher percentage resulting from anionic polymerization. The molecular weights of the polymers, as determined by gel permeation chromatography (GPC) with aqueous mobile phase and sodium polyacrylates standards, ranged between 1100 and 4200 for anionic polymerization and were about 11 500 for metal oxide-alcohol initiated polymerization. Solution-phase properties of the polymaleimides were evaluated by calcium chelation and precipitation inhibition studies. On the basis of the measured properties of these polymers, they are proposed as biodegradable, low-impact detergent additives to substitute currently used compounds.

The effect of polymaleimide polymers on calcium carbonate crystallization was studied using nephelometry. Induction time and percent growth inhibition were determined for polymeric additives from the nephelometric data. The polymaleimide synthesized by KOH-initiated polymerization exhibited the greatest growth inhibition and longest nucleation time among the polymers investigated. Raman spectroscopy was used to determine the calcium carbonate polymorph formed in the presence of these polymeric additives.