Enhancing the colloidal stability of nanoparticles dispersions, in order to extend the utilization time without any loss of performance, is desired. Prior works have confirmed the electrosteric stabilization of colloidal particles by so-called “amino-quat-primer” polymers, hyperbranched poly(ethylenimine) polymers containing amino groups and quaternized groups. In this work, a systematic investigation on the factors influencing the polymer-particle-interactions was carried out. Hence, aqueous silica-nanoparticle-dispersions were polymer-functionalized; their dispersions stability was studied using turbidity analysis; and the particle surface charge was examined employing electrophoretic measurements. Five key factors influencing the polymer-particle-interaction were defined, including: the polymer-particle-ratio, the degree of polymerization and the degree of functionalization of the polymer, the dispersion pH and the salt concentration. Alternatingly occurring areas of stable, unstable and again stable dispersions with an increasing polymer-particle-ratio occurred due to a charge reversal of bare, negatively charged to polymer-covered, positively charged particles. An additional area of unstable dispersions at very high polymer concentrations was assumed to arise from depletion forces of non-adsorbed free polymer. Stable, positively charged, polymer-covered silica nanoparticles were obtained for optimized conditions regarding the five key factors. After the dispersion stability enhancement, the new amino-functionalized surface could be used for further modifications, e.g. to result in a compatibility with a polymer matrix to fabricate highly functional polymer / inorganic hybrid materials.

Nanoparticles promise many interesting applications because of their exceptional chemical and physical properties. Therefore nanoparticles offer a pathway for the fabrication of new functional, smart materials. Since the primary particle strongly tends to strong agglomeration, and since the surface of nanoparticles is often not compatible with polymers, it is not possible to disperse single particles homogeneously in a polymer melt. Formations of agglomerates are responsible for strong differences in concentration of the nanoparticles in the material matrix and therefore impede a homogeneous property profile. Furthermore properties of compounds are not only determined by single components, but considerably by the interface between these single components. Hence, a strong chemical and physical adhesion between the constituents is required. Thus, surface modification of nanoparticles is a crucial issue. This work focuses on the control of the particle/polymer interface in composite materials which has a thickness of some nanometers. This interface regulates the compatibility of the surface of the nanoparticles and their environment. This interface is also the place where the transmission of energy between nanoparticle and polymer occurs. The interlayer of this boundary surface should be occupied with functional “primer”-macromolecules that provide at least two types of functional groups: one species of functional group should assure the bonding of the primer to the surface of the nanoparticle, and the second type enables the compatibilizing to the matrix, and when indicated also the covalent adhesion to the ambient polymer system. The macromolecular scaffold of the primer permits the selective adjustment of important interface properties as elasticity, durability and the surface energy of the particle – matrix interface. Within this thesis hyperbranched polyethylene (PEI) imine was used as starting platform for “Quat-Primer Polymers” bearing a multitude of functional moieties in form of primary, secondary and tertiary amino groups. Chapter 2 gives a literature – review on hyperbranched polymers – with focus on PEI, stabilization of colloids by polymers, as well as polymer – “nanocomposites”. In Chapter 3 the reaction of PEI with glycidyltrimethylammonium chloride will be described to obtain hyperbranched polymers that consist of (i) the hyperbranched PEI scaffold, (ii) primary, secondary and tertiary amino groups that can be used for further modification reactions with amino-reactive compounds, and (iii) ammonium moieties that can adsorb to negatively charged surfaces. It will be shown that these Quat-Primer polymers have the ability to stabilize several nanoparticles in water to form aqueous dispersions and that they are capable to partially deagglomerate nanoparticles leading to smaller diameters of the particles in the dispersion. Additionally the reaction of hyperbranched polyethylene imine with glycidol will be described displaying a possibility to change the reactivity of the functional groups and exhibiting that also the generated hydroxyl groups generated by the ring-opening reaction of epoxides with PEI react with epoxide rings to form ether linkages. In Chapter 4 the synthesis of several amino-reactive ATRP initiators will be described and two methods to graft PMMA arms to “Quat-Primer polymers” presented in the previous chapter including the “grafting from” and the “grafting to” technique. These synthesized Quat-Primer polymers bearing ammonium moieties, as well as PMMA arms can be used to fabricate PMMA nanocomposites with homogeneously distributed nanoparticles. The developed method allow for grafting monomers that can be used in ATRP polymerization, including acrylates, acrylonitriles and styrenes, to hyperbranched polyethylene imine. Chapter 5 will display pathways to graft caprolactam derivatives to hyperbranched polyethylene imine to generate Quat-Primer polymers bearing ammonium moieties, as well as caprolactam rings. These quat-primer polymers can be used for the fabrication of PA-6 nanocomposites by dispersing nanoparticles in presence of these Quat-Primer polymers and subsequent polymerization.

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An A2 + B3 polymerization for the synthesis of hyperbranched polymers was altered using oligomeric precursors in place of either one or both of the monomer pairs to synthesize highly branched macromolecules. Unique topologies that are intermediates between long-chain branched and hyperbranched structures were obtained and the term "highly branched" was used to define these novel architectures. Various types of highly branched polymers, such as polyurethanes, poly(urethane urea)s, poly(ether ester)s, and poly(arylene ether)s were synthesized using the oligomeric A2 + B3 strategy. The molar mass of the oligomeric precursor permitted the control of the molar mass between branch points, which led to interesting macromolecular properties, such as superior mechanical performance to conventional hyperbranched polymers, disrupted crystallinity, improved processibility, and a multitude of functional end groups. Highly branched poly(urethane urea)s and polyurethanes exhibited microphase-separated morphologies as denoted by dynamic mechanical analysis. The similarity in soft segment glass transition behavior and mechanical properties of the branched systems with that of the linear analogues suggested these materials have considerable promise for a variety of applications. When a polycaprolactone triol was utilized as the B3 oligomer for the synthesis of highly branched polyurethane elastomers, the high degree of branching resulted in a completely amorphous soft segment, whereas the linear analogue with equivalent soft segment molar mass retained the crystallinity of polycaprolactone segment. Oligomeric A2 + B3 methodology was further utilized to tailor the degree of branching of poly(ether ester)s that were developed based on slow addition of dilute solution of poly(ethylene glycol) (PEG) (A2) to a dilute solution of 1,3,5-benzenetricarbonyl trichloride (B3) at room temperature in the presence of triethylamine. A revised definition of the degree of branching was proposed to accurately describe the branched poly(ether ester)s and the degree of branching decreased as the molar mass of the PEG diols was increased. Moreover, branched poly(arylene ether)s were prepared via a similar oligomeric A2 + B3 polymerization of phenol endcapped telechelic poly(arylene ether sulfone) oligomers (A2) and tris(4-fluorophenyl) phosphine oxide (B3) in solution. Highly branched poly(ether ester)s were also synthesized in the melt phase using the oligomeric A2 + B3 polymerization strategy. Melt polymerization effectively limited the cyclization reactions, which are common in A2 + B3 polymerizations in solution, and overcame the need for large amounts of polymerization solvent typical of A2 + B3 systems. Finally, a new family of telechelic polyester ionomers was synthesized based on phosphonium bromide salt end groups and branching allowed the incorporation of higher levels of ionic end groups compared to linear analogues. / Ph. D.