ABSTRACT:Well-defined poly(vinylphenol-co-styrene) random copolymers (P(VPh-r-St)) were prepared by living radical polymerization mediated by 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl. The copolymers showed no micellization in 1,4-dioxane, the nonselective solvent. Dynamic light scattering demonstrated that the copolymers formed micelles in the presence of ,!-diamine. The copolymer with the molecular weight of M n Œ 8690 and the VPh/St unit ratio of 0.50/0.50 produced the micelles with ca. 90 nm as a hydrodynamic radius at 0.2 of the molar ratio of 1,4-butanediamine (BDA) to the VPh unit. It was found that the micellization occurred by intermolecular aggregation through hydrogen bond cross-linking between the VPh units by BDA, because the hydrodynamic radius and the aggregation number of the micelles increased with an increase in the copolymer concentration. The hydrodynamic radius of the micelles decreased with increasing the molecular weight of the copolymer, supporting the micellization by the intermolecular aggregation. And further, the micellar size also decreased with a decreasing the VPh ratio in the copolymer at the molecular weight constant.KEY Many useful micelles consist of macromolecules.
12-14Recently, the importance of the macromolecular micelles has been increasing because of the structural stability and the environmental safety. There are a number of publications on micelles prepared from amphiphilic block 15-22 and graft copolymers. 23,24 An increase in the number of publications on them has been accelerated since well-defined block and graft copolymers came to be prepared more easily by living radical polymerization techniques than by living ionic polymerization. [25][26][27] Micelles for amphiphilic random copolymers have also been well-studied on the basis of the advantage of convenient procedure for preparing the random copolymers over block and graft copolymers.
28-32While many amphiphilic copolymers are utilized for preparing micelles, ''nonamphiphilic'' copolymers attract considerable attention in recent years because of the advantages in the molecular design. We have already released publications on the micelle formation of a nonamphiphilic block copolymer consisting of poly(vinylphenol) and polystyrene (PVPh-b-PSt).
33,34The copolymer forms the micelles in the presence of ,!-diamine through hydrogen bond cross-linking in a nonselective solvent. We found that poly(vinylphenol-co-styrene) random copolymers (P(VPh-r-St)) showed a great difference from the PVPh-b-PSt diblock copolymer in the micellization by ,!-diamine. This paper describes the micelle formation of the nonamphiphilic P(VPh-r-St) random copolymers by ,!-diamine.
EXPERIMENTAL
MeasurementsGel permeation chromatography (GPC) was performed with a HLC-802A instrument by Tosoh Corp. equipped with RI and UV detectors. Two polystyrene gel columns, Tosoh TSK gel G4000H 8 and G2000H 8 , were used with THF as the eluent at 42 C. 1 H NMR spectra were obtained with a Bruker ARX-500 NMR spectrometer by Bruker Co. Light scattering exp...