While<b> </b>polycations based on 2-(dimethylamino)ethyl (meth)acrylate are used in applications ranging from biomaterials to wastewater treatment, their remarkable difference in hydrolytic stability of the ester group remains little explored. This presentation will discuss how the nature of the α-substituent affects the ester hydrolysis of such polymers, with emphasis on the resulting shift of net polymer charge from cationic towards anionic. 2-(Dimethylamino)ethyl 2-hydroxymethyl acrylate (DHMA) will be introduced as a new, very hydrolytically labile, cationic acrylate monomer that can be used in a homopolymer and to tune copolymer hydrolyses. DHMA synthesis and free radical polymerization are described, including reactivity ratios for protected derivatives of DHMA with 2-(dimethylamino)ethyl acrylate (DMAEA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA). Hydrolyses of PDHMA, PDMAEA, PDMAEMA, and PDHMA containing copolymers in pH 5 and 7 buffer will be presented. Results from hydrolysis studies showed that the presence of the hydroxymethyl α-substituent in PDHMA led to rates of hydrolysis two to three orders of magnitude faster than the already rapid hydrolysis of PDMAEA. As well, copolymers of DHMA showed an increase in rates of hydrolyses with increased mol fractions of DHMA, which provides a new route to adjusting acrylate ester reactivity of such copolymers in aqueous media.

Charge-shifting polycations with tunable rates of hydrolysis

256th National Meeting (2018)

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