He Xian-hui. / "November 1998." / Thesis (Ph.D.)--Chinese University of Hong Kong, 1998. / Includes bibliographical references (p. 218-230). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Mode of access: World Wide Web. / Abstracts in English and Chinese.

Please read the abstract (Synopsis) in the section 00frontof this document / Thesis (PhD (Chemical Engineering))--University of Pretoria, 2007. / Chemical Engineering / unrestricted

"Chain walking” catalytic polymerization CWCP is a powerful tool for the one-pot synthesis of a unique class of hyperbranched polyethylene HBPE-based macromolecules with a controllable molecular weight, topology, and composition. This dissertation focuses on new synthetic routes to prepare HBPE-based macromolecular architectures by combining the CWCP technique with ring opening polymerization ROP, atom–transfer radical polymerization ATRP, and “click” chemistry. Taking advantage of end-functionalized HBPE, and a new ethynyl-soketal star-shape agent, we were able to synthesize different types of the HBPE-based architectures including hyperbranched-on-hyperbranched core-shell nanostructure, and miktoarm-star-HBPE-based block copolymers. The first part of the dissertation provides a general introduction to the synthesis of polyethylene types with controllable structures. Well-defined polyethylene with different macromolecule architectures were synthesized either for academic or industrial purposes. In the second part, the HBPE with different topologies was synthesized by CWCP, using a α-diimine Pd (II) catalyst. The effect of the temperature and pressure on the catalyst activity and polymer properties, including branch content, molecular weight, distribution, and thermal properties were studied. Two series of samples were synthesized: a) serial samples (A) under pressures of 1, 5, and 27 atm at 5˚C, and b) serial samples (B) at temperatures of 5, 15, and 35 ˚C under 5 atm. Proton nuclear magnetic resonance spectroscopy, 1H NMR, and gel permeation chromatography, GPC, analysis were used to calculate the branching content, molecular weight, and distribution, whereas differential scanning calorimetry, DSC, was used to record the melting and glass transition temperatures as well as the degree of the crystallinity. Well-defined HBPE-based core diblock copolymers with predictable amphiphilic properties are studied in the third part of the project. Hyperbranched polyethylene-b-poly(N-isopropylacrylamide), HBPE-b-PNIPAM, and hyperbranched polyethylene-b-poly(solketal acrylate), HBPE-b-PSA, were successfully synthesized by combining CWCP and ATRP. The synthetic methodology includes the following steps; a) synthesis of multifunction hyperbranched polyethylene initiators HBPE-MI by direct copolymerization of ethylene with 2-(2-bromoisobutyryloxy)ethyl acrylate BIEA in the presence of a α-diimine Pd(II) catalyst, and b) HBPE-MI with α-bromoester groups used as initiation sites for ATRP. Proton nuclear magnetic resonance spectroscopy, 1H NMR, gel permeation chromatography,GPC, and Fourier transform infrared, FT-IR, spectroscopy, were used for determining the molecular and composition structures. Also, differential scanning calorimetry, DSC, and thermogravimetric analysis, TGA, were used to record the melting temperature and to study the thermal stability, respectively. In the fourth part, a well-defined 3-miktoarm star copolymer 3μ-HBPE(PCL)2 (HBPE: hyperbranched polyethylene, PCL: poly(ε-caprolactone) was synthesized by combining CWCP, ring opening polymerization, ROP, and “click” chemistry. The synthetic methodology includes the following steps: a) synthesis of azido-functionalized hyperbranched polyethylene HBPE-N3 by CWCP of ethylene with the α-diimine Pd(II) catalyst, followed by quenching with an excess of 4-vinylbenzyl chloride and transformation of –Cl to the azido group with sodium azide, b) synthesis of in-chain ethynyl-functionalized poly(ε-caprolactone), (PCL)2-C≡CH by ROP of ε-CL with ethynylfunctionalized solketal [3-(prop-2-yn-1-yloxy) propane-1,2-diol] as a bifunctional initiator, in the presence of P2-t-Bu phosphazene super base, and c) “clicking” HBPE-N3 and (PCL)2-C≡CH using the copper(I)-catalyzed alkyne–azide cycloaddition CuAAC. Proton nuclear magnetic resonance spectroscopy, 1H NMR, gel permeation chromatography, GPC, and Fourier transform infrared, FT-IR, spectroscopy, were used to determine the molecular and composition structures. Also, the differential scanning calorimetry, DSC, was used to record the melting point temperature. The fifth part illustrates the self-assembly behavior of the HBPE-based block copolymers of poly(N-isopropylacrylamide), NIPAM, and poly(ε-caprolactone), PCL, at room temperature in water and a petroleum ether-selective solvent for NIPAM and PCL respectively. The synthesized copolymers HBPE-b-NIPAM and 3μ-HBPE(PCL)2 revealed either core-shell nanostructure in vesicles or worms and worm-likes branches, as confirmed by combining the analysis of dynamic light scattering, DLS, transmission electron microscopy, TEM, and atomic force spectroscopy, AFM. All the findings presented in this dissertation emphasize the utility of "living" CWCP to synthesize end-functionalized HBPE, and new star-linkage HBPE-based complex architectures. The summary and future works concerning predictable properties and applications are discussed in the sixth part.

Silica nanoparticles (SiO2 NPs) were prepared and functionalized with polyethylene (PE@SiO2 NPs) using the surface-initiated polyhomologation (SI polyhomologation) technique. Polyolefin nanocomposites were fabricated later by melt mixing of different ratios of the as-prepared SiO2 NPs and PE@SiO2 NPs with linear low-density polyethylene (LLDPE) and low-density polyethylene (LDPE) matrices. Firstly, SiO2 NPs were modified with different alkoxysilane ligands, dichloro(divinyl)silane (DCDVS), allyl trimethoxysilane (ATMS), and vinyl triethoxylsilane (VTES). Subsequently, thexylborane, an initiator for SI polyhomologation, was immobilized to the modified surface of SiO2 NPs through hydroboration reactions. Polyhomologation was then allowed to proceed by adding monomer solution to form polyethylene brushes covalently bonded to the surface of the NPs. Physicochemical characterization had confirmed the morphology, chemical structure, and thermal stability for each step of modification reactions. LLDPE and LDPE nanocomposites were prepared by extrusion with SiO2 NPs and PE@SiO2 NPs as nanofillers. Finally, tensile tests and morphological SEM-based analyses are presented to discuss the influence of the grafted PE on both the dispersion of the fillers and the mechanical properties of the filler/matrix interphase.

In industry the effective mixing and de-agglomeration of two solid particles is vital in applications that require the intimate contact of homogeneously mixed reagents. One such application is in the preparation of pyrotechnic delay elements with reproducible burn speeds. The concept of surfactant assisted particle micro-mixing is proposed. This theory is based in the use of two amphiphilic polymeric surfactants to form two separate stable dispersions of the two solid particles to be mixed, but with the subsequent requirement that the dispersants are able to interact with each other. The formation of the individual dispersions allows for the deagglomeration of the particles and thus their preparation for homogeneous mixing, which is facilitated by the interacting surfactants. Low molecular mass block copolymers of styrene and acrylic acid and poly( ethylene oxide)-poly(propylene oxide) (PEO-PPO) surfactants are the proposed dispersants which will allow for the surfactant interaction by means of hydrogen bonding between the poly(acrylic acid) block and the PEO. The poly(styrene-co-acrylic acid) block copolymer will be synthesised via Atom Transfer Radical Polymerisation (ATRP) and subsequently used in the dispersion experiments. The synthesis of the polystyrene macroinitiators to initiate the block copolymerisation of the t-butyl acrylate was carried out satisfactorily, with good molecular masses and molecular mass distributions. In addition, lH-NMR analysis carried out on the polystyrene macroinitiators confirmed their synthesis. The use of the polystyrene macroinitiators was successful in synthesising poly(styrene-co-t-butyl acrylate) block copolymers with slightly higher polydispersities in comparison to the macroinitiatiators themselves, but acceptable. Hydrolysis of the poly(styrene-co-t-butyl acrylate) block copolymer to poly(styrene-co-acrylic acid) was successful in the presence of trifluoroacetic acid as catalyst. Attempts to hydrolyse in basic conditions (NaOH) and alternatively in acidic conditions (HCI) were not successful. Use of the poly(styrene-co-acrylic acid) amphiphilic block copolymer to emulsion polymerise styrene requires the ionised form of the polymer and was therefore not favourable to observe surfactant-surfactant hydrogen bonding. In addition, attempts to synthesise a wax emulsion stabilised by a PEO containing surfactant proved to be unsuccessful. Subsequently, the micro-mixing experiments were carried out by using a poly(acrylic acid) stabilised melamine dispersion and a commercially available PEO containing surfactant stabilised wax emulsion. The interaction between the melamine and the poly(acrylic acid) allows for the formation of a stable melamine dispersion at above 7% poly(acrylic acid) : melamine ratio (mass basis). Analysis by SEM shows that without the poly( acrylic acid) dispersant no wax particles are found to occur on the melamine particle surface. However, in an attempt to determine whether the amount of wax interaction increases with poly(acrylic acid) content, it was found that in the absence of poly(acrylic acid) dispersant, the most amount of wax precipitated out with the melamine. This is possibly attributable to the preferential occlusion of the wax particles between the melamine particles rather than surface attachment. Introduction of the poly(acrylic acid), however, shows via SEM analysis that the hydrogen bond interaction between the acrylic acid group and the ethylene oxide group does occur, since the attachment of the wax particles on the melamine particle surface is observed. Although results show that the surfactant-surfactant interaction allows for the micro¬mixing of particles, some refinement is required with respect to the systems that this phenomenon can be applied to. In addition, factors such as particle type, particle size and surfactant type will influence the micro-mixing interaction. It is therefore recommended that these factors be investigated in order to completely identify the micro-mixing phenomenon. / Dissertation (M Eng (Chemical Engineering))--University of Pretoria, 2006. / Chemical Engineering / unrestricted