Logo JG-Universität MainzProf. Dr. Axel Müller


PhD Thesis

Functional Cylindrical Polymer Brushes and Their Hybrids with Inorganic Nanoparticles

Youyong Xu (04/2004-09/2008)

Support: Axel H. E. Müller


Various cylindrical polymer brushes were synthesized via a grafting-from strategy. Very long poly(2-hydroxylethyl methacrylate) backbones of the brushes were prepared by anionic polymerization (DPn=1500), esterified with an ATRP initiator, and subsequently the side-chains were grafted by atom transfer radical polymerizations (ATRP). Cylindrical brushes with different architectures, such as brushes of single component, double-grafted brushes and core-shell brushes, were built according to the need of applications. A number of functional monomers were involved in the preparations of the brushes, providing possibilities for further functionalizations and uses. Nano-hybrids comprising organic cylindrical brushes and inorganic nanoparticles such as magnetite and polyhedral oligomeric silsesquioxane (POSS) were fabricated through non-covalent inclusion and covalent attachment respectively.

Double-grafted poly(lauryl methacrylate) brushes carry side-chains containing dodecyl short grafts. The long alkyl chains provided good solubility in hydro-carbon solvents like n-hexane and paraffin oil. DSC measurements revealed that they undergo side-chain crystallizations.

Grafting of N,N-dimethylaminoethyl methacrylate (DMAEMA) to the macro-initiator by ATRP yielded weak polyelectrolyte cylindrical brushes. They showed responsiveness to pH and salinity in solution. Strong cationic polyelectrolyte brushes were obtained by further quaternization of the PDMAEMA brushes. Their responses to counterions of different valencies were investigated. The addition of a sufficient amount of mono-valent salt induced the collapse of these brushes. When di- and tri-valent counterions were added, helical transition morphologies were recorded before the brushes collapsed into sphere-like structures. Special trivalent counterions, which can change valency through photo-aquation reactions, allowed switching the morphologies of the cationic brushes from worms to globules and back to worms.

The morphologies of the cationic brushes could also be tuned by forming ionic complexes with the anionic surfactant sodium dedecyl sulfonate (SDS) and supramolecular inclusion complexes between cyclodextrins (CDs) and SDS. The brushes underwent transitions from worms, over pearl-necklace structures to totally collapsed spheres when SDS was added. Introducing α- or β-cyclodextrins could bring the collapsed spheres back to worms. Adamantyl ammonium chloride, a more competitive inclusion agent, deprived SDS of CDs, and re-induced the spherical collapse of the brushes.

The morphologies of the cationic brushes could be regulated in a similar way by forming inter-polyelectrolyte complexes (IPECs) with anionic linear poly(sodium styrene sulfonate) (PSS) in highly diluted solutions. Worm-to-sphere switching with helix-like transition states was also observed.

A new strategy for the direct preparation of strong anionic polyelectrolyte cylindrical brushes without protection was introduced by forming supramolecular complexes between the monomer potassium sulfopropyl methacrylate (SPMA) and crown ether 18-crown-6 in DMSO using ATRP for the grafting-from processes. Well-defined worm-like morphologies were proven by atomic force microscopy (AFM) and cryogenic transmission microscopy (cryo-TEM).

Water soluble double-hydrophilic core-shell cylindrical brushes were prepared and showed pH responsiveness. Magnetic hybrid cylinders were formed by introducing magnetite nanoparticles into the core. They could be aligned on a large scale on the substrates by applying magnetic fields.

Finally, single-molecular hybrid cylinders were created by covalently attaching thiol-functionalized polyhedral oligomeric silsequioxane (POSS) to poly(glycidyl methacrylate) brushes. Their pyrolysis in air resulted in porous silica materials.

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