화학공학소재연구정보센터
Langmuir, Vol.17, No.16, 4711-4716, 2001
Unusual thermoprecipitation behavior of Poly(N,N-diethylacrylamide) from aqueous solution in the presence of anionic surfactants
Surfactants (charged amphiphiles) are usually found to promote the solubility of reversibly water-soluble neutral polymers at concentrations above the critical aggregation concentration. Below that concentration or when no aggregates/micelles are formed, solubility is reduced presumably due to a simple salting out effect. In this paper, the effect of linear n-alkyl sulfates with chain length between 1 and 12 on the solubility of three oligomeric poly-N-alkylacrylamides, namely a poly(N-isopropylacrylamide), N1, and a poly(N,N-diethylacrylamide), D1, prepared by chain transfer polymerization, and a poly(N,N-diethylacrylamide), Al, prepared by anionic polymerization, are used to investigate these assumptions. The cloud point temperatures (CPT) of the oligomers are determined spectrophotometrically, while a fluorescence probe (1 mum pyrene) is used to follow the alkyl sulfate aggregation (micelle formation) in solution. N1 and D1 are found to be very similar in their behavior. Alkyl sulfates with n less than or equal to 4 (no micelle formation) show a simple salting out effect. In the presence of alkyl sulfates with chain lengths of 5, 6, and 8, the CPT of the solution passes through a minimum and then reaches a plateau/maximum at a level above the CPT observed in pure water. If the alkyl sulfate concentration is increased beyond the plateau region, the CPT decreases again. For alkyl chain length of n > 9, the CPT rises steadily with increasing alkyl sulfate concentration. Despite their much smaller size (factor 70) both NI and D1 hence show a solubility that corresponds to that observed by Schild and Tirrell (Langmuir 1991, 7, 665) for poly(N-isopropylacrylamide) polymers. The solubility of the predominantly isotactic oligomer Al, on the other hand, deviated considerably from this behavior (no CPT minimum, no salting out effect for butyl sulfate) and thus seems to challenge some of the general assumptions concerning the effect of surfactants at low concentration.