A Polysiloxane Delivery Vehicle of Cyclic N-Halamine for Biocidal Coating of Cellulose in Supercritical CO2

Abstract

Cyclic N-halamines are highly antimicrobial, very stable, and not susceptible to bacterial resistance. A polysiloxane delivery vehicle was synthesized to deliver cyclic imide N-halamine onto cellulose via a benign and universal procedure that does not require a harmful solvent or chemical bonding. In brief, Knoevenagel condensation between barbituric acid and 4-hydroxybenzaldehyde furnished 5-(4-hydroxybenzylidene)pyrimidine-2,4,6-trione, whose phenolic O−H was subsequently reacted with the Si−H of poly(methylhydrosiloxane) (PMHS) via silane alcoholysis. The product of silane alcoholysis was interpenetrated into cellulose in supercritical CO2 (scCO2) at 50 °C, to form a continuous modification layer. The thickness of the modification layer positively correlated with interpenetration pressure in the experimental range of 10 to 28 MPa and reached a maximum value of 76.5 nm, which demonstrates the ability for tunable delivery, to control the loading of the imide N−H bond originating from barbituric acid unit. The imide N−H bonds on cellulose with the thickest modifier were then chlorinated into N−Cl counterparts using tert-butyl hypochlorite, to exert a powerful biocidability, providing ~7 log reductions of both S. aureus and E. coli in 20 min. The stability and rechargeability of the biocidability were both very promising, suggesting that the polysiloxane modifier has a satisfactory chemical structure and interlocks firmly with cellulose via scCO2 interpenetration.