Poly colloid formation

Application of amphiphilic block copolymers for nanoparticle formation has been developed by several research groups. R. Schrock et al. prepared nanoparticles in segregated block copolymers in the sohd state [39] A. Eisenberg et al. used ionomer block copolymers and prepared semiconductor particles (PdS, CdS) [40] M. Moller et al. studied gold colloidals in thin films of block copolymers [41]. M. Antonietti et al. studied noble metal nanoparticle stabilized in block copolymer micelles for the purpose of catalysis [36]. Initial studies were focused on the use of poly(styrene)-folock-poly(4-vinylpyridine) (PS-b-P4VP) copolymers prepared by anionic polymerization and its application for noble metal colloid formation and stabilization in solvents such as toluene, THF or cyclohexane (Fig. 6.4) [42]. 

Another possible strategy towards colloids stabilized by micellar systems is the use of nonamphiphibc block copolymers containing metal binding ligands in only one of the blocks. For example, a poly(styrene)-fc ock-poly(m-vinyltriphenylphosphine) (PS-b-PPH) was examined with respect to its colloid formation properties (Fig. 6.5) [46]. 

After our success in preparation of the colloidal dispersions of Pt-core/Pd-shell bimetallic nanoparticles by simultaneous reduction of PdCl2 and H2PtCl6 in refluxing ethanol/water in the presence of poly(V-vinyl-2-pyrroli-done) [15,16] several reports have appeared on the formation of the core/shell-structured bimetallic nanoparticles by simultaneous reactions [5,52,68,183]. 

Unmodified poly(ethyleneimine) and poly(vinylpyrrolidinone) have also been used as polymeric ligands for complex formation with Rh(in), Pd(II), Ni(II), Pt(II) etc. aqueous solutions of these complexes catalyzed the hydrogenation of olefins, carbonyls, nitriles, aromatics etc. [94]. The products were separated by ultrafiltration while the water-soluble macromolecular catalysts were retained in the hydrogenation reactor. However, it is very likely, that during the preactivation with H2, nanosize metal particles were formed and the polymer-stabilized metal colloids [64,96] acted as catalysts in the hydrogenation of unsaturated substrates. 

Finally, two related studies can be mentioned here. It was noted that when a quartz plate was immersed overnight in a solution of Pb(C104)2 and poly(vinyl alcohol) through which H2S had been bubbled, a film formed on the plate parallel with formation of a colloidal PbS sol [47]. The film was extremely thin (maximum absorbance of <0.015 at 400 nm). The absorption spectrum of this film was similar to that of the PbS sol and consisted of several absorption peaks with an absorption onset of ca. 630 nm (1.97 eV). It is not clear that this is the true bandgap onset, for the same reasons as discussed previously (weak absorption close to the bandgap). The XRD crystal size of the precipitate was ca. 3 nm. 

The inter-relationship between colloid and polymer chemistries is completed by colloidal polymer particles. The formation of 50-nm-diameter, 100- to 200-nm-long polyaniline fibrils in a poly(acrylic acid)-template-guided polymerization, similar in many ways to those produced from polymerized SUVs (see above), provides a recent example of polymer colloids [449], The use of poly(styenesulfonic acid) as a template yielded globular polyaniline particles which were found to be quite different morphologically from those observed in the regular chemical synthesis of polyaniline [449]. 

Yang, S. C., H. X. Ge, et al. (2000). Formation of positively charged poly(butyl cyanoacrylate) nanoparticles stabilized with chitosan. Colloid Polym. Sci. 278 285-292. 

---