Recent studies indicated that water treatment polymers such as poly(epichlorohydrin dimethylamine) (polyamine) and poly(diallyldimethylammonium chloride) (polyDADMAC) may form N-nitrosodimethylamine (NDMA) when in contact with chloramine water disinfectants. To minimize such potential risk and improve the polymer products, the mechanisms of how the polymers behave as NDMA precursors need to be elucidated. Direct chloramination of polymers and intermediate monomers in reagent water was conducted to probe the predominant mechanisms. The impact of polymer properties including polymer purity, polymer molecular weight and structure, residual dimethylamine (DMA), and other intermediate compounds involved in polymer synthesis, and reaction conditions such as pH, oxidant dose, and contact time on the NDMA formation potential (NDMA-FP) was investigated. Polymer degradation after reaction with chloramines was monitored at the molecular level using FT-IR and Raman spectroscopy. Overall, polyamines have greater NDMA-FP than polyDADMAC, and the NDMA formation from both polymers is strongly related to polymer degradation and DMA release during chloramination. Polyamines' tertiary amine chain ends play a major role in their NDMA-FP, while polyDADMACs' NDMA-FP is related to degradation of the quaternary ammonium ring group.
The NDMA formation potential (NDMA FP) of four commonly used amine-based cationic water treatment polymers was assessed in reactions with chlorine-based oxidants (free chlorine, monochloramine and chlorine dioxide) and nitrosifying agents (nitrite and nitrate). Relatively high dosages of polymers were directly exposed to oxidants for long reaction times in the FP tests to assess the potential to form NDMA and obtain mechanistic insight. Results show that the NDMA FP of the polymers generally follows the trend of aminomethylated polyacrylamide (Mannich polymer)>>poly(epichlorohydrin-dimethylamine) (polyamine) > poly(diallyldimethylammonium chloride) (polyDADMAC) > cationic polyacrylamide copolymer (cationic PAM). The high NDMA FP of Mannich polymer was largely due to the high amount of dimethylamine (DMA) residue in the polymer solution. For the other three polymers, the DMA concentration was increased after oxidation, indicating polymer degradation, and the trend of DMA increase agreed with that of NDMA FP. Among the oxidants, NDMA formation followed the order of monochloramine > free chlorine > chlorine dioxide, despite that the DMA release from the polymers caused by the oxidant followed the opposite order. At equal dosages, nitrite and nitrate generated NDMA from the polymers at levels comparable to those by free chlorine and chlorine dioxide; even so, the nitrosifying agents are unlikely to contribute significantly to NDMA formation due to expected lower concentrations in drinking water treatment systems. Jar tests followed by monochloramination of real water samples using conditions in line with those at potable water treatment plants generally showed relatively small contributions from polyamines and polyDADMACs to the overall NDMA formation.
The serendipitous formation of 2,5‐dimethoxy‐ 1,4‐benzoquinone is reported from the reaction of 1,4‐benzoquinone with methanol, DABCO, and paraformaldehyde. This monomer, and its di‐n‐butoxy analog, are also available from 2,5‐dihydroxy‐1,4‐benzoquinone. These materials are capable of novel polycondensation reactions with diamines such as 1,6‐hex‐anediamine. Use of m‐crexsol as polymerization solvent gave a dark, insoluble product while various amide solvents lead to orange or pink polymers that had average degrees of polymerization from 5 up to >30. These polymers, Plus model compounds obtained from 1‐aminopropane and N,N'‐ dimethyl‐1,6‐hexanediamine, were characterized by FTIR, solution, and solid‐state NMR.
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