8 search hits
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Polarmodifikation von Butadienkautschuk mit Polyethylenglykol
(2002)
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Mabel Graf
- Die Darstellung von polarmodifizierten Polybutadienen durch Reaktion von lebenden Polybutadienylanionen mit endfunktionalisierten Polyethylenglykolen (PEG) wurde untersucht. Hierzu wurden zwei unterschiedlichen Typen endfunktionalisierter Polyethylenglykole synthetisiert. Bei der Copolymersynthese waren Reaktionssystem und Reaktionsstrategie durch die gewünschte Anwendung bestimmt. Um in Kautschukmischungen für Reifen zur Verbesserung der Kautschuk-Füllstoff-Wechselwirkung eingesetzt werden zu können, sollten die Polybutadiene einen hohen Anteil an 1,4-Vernüpfungen haben. Die Modifikation mit den funktionalisierten PEG sollte mittels einfacher und kostengünstiger Reaktionen erfolgen. Zunächst wurde die Reaktion von PEG mit substituierbarer Endgruppe mit Polybutadienyl-lithium betrachtet. Dazu wurden PEG mit Chlor-, Iod- und Sulfonsäureester-Endgruppen eingesetzt. Letztere Endgruppen waren unter den gegebenen Bedingungen nicht für eine Polarmodifikation des PB geeignet. Mit den halogenfunktionalisierten Polyethylenglykolen wurden Kopplungsgrade von bis zu 50 % d. Th. erreicht. Auftretende Nebenprodukte konnten mittels Flüssigchromatographie unter kritischen Bedingungen (LACCC) und deren Kopplung mit der Größenausschlusschromatographie (GPC) analysiert und so der Reaktions-ablauf aufgeklärt werden. Die Einfachheit der Reaktion begründet ein industrielles Interesse, aufgrund des Reaktionsmechanismus ist jedoch eine vollständige Reaktion mit lebenden Polybutadienylanionen nicht möglich. Als Alternative wurde eine Kopplungsreaktion von Polybutadienyllithium mit PEG mit nicht homopolymerisierbarer Doppelbindung betrachtet. Hierfür wurden PEG mit 1,1-Diphenyl-ethylen- (DPE) und Benzophenon-Endgruppe hergestellt. Bei der Reaktion mit dem DPE-funktionalisierten Polyether wurden zahlreiche Nebenprodukte gefunden. Die Modifikation mit benzophenonfunktionalisierten PEG führte zu Produkten mit einem Polyetheranteil von bis zu 67 % d. Theorie. Auch bei dieser Reaktion wurden Nebenprodukte beobachtet, deren Bildung mittels LACCC/GPC aufgeklärt werden konnte. Durch Veränderung einiger Parameter kann dieser Reaktionstyp kontrollierbarer gemacht werden und kann so eine interessante Methode zur Darstellung von Blockcopolymeren oder verzweigten Polymeren aus Dienen und Polyethylenglykolen darstellen. Im Rahmen einer Industriekooperation wurden unter Verwendung chlorfunktionalisierter PEG mehrere modifizierte Polybutadiene in Mengen von je 500 g hergestellt. Diese wurden vom Kooperationspartner in reifentypischen Kautschukmischungen umgesetzt. Die mechanischen Eigenschaften dieser Mischungen und der daraus erhaltenen Vulkanisate wurden mit typischen Methoden bestimmt. Ein ausgeprägter Einfluss des eingebrachten PEG-Anteils auf die Eigenschaften der Vulkanisate konnte aufgrund der geringen Menge Polyethylenglykol bezogen auf die Gesamtmischung nicht festgestellt werden.
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New block copolymers of Isobutylene by combination of cationic and anionic polymerizations
(2004)
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Nemesio Martínez-Castro
- The studies presented in this thesis deal with the new block copolymers of isobutylene by combination of cationic and anionic polymerizations, which are new materials with numerous promising potential applications. A new method for the synthesis of tailored polyisobutylene(PIB)-based block copolymer by combination of controlled / living cationic and anionic polymerizations has been developed. In addition and parallel to these subjects, new synthetic routes for preparation of telechelic PIBs and conductive polymers have been investigated. The PIB precursors used for subsequent anionic polymerization and other processes were prepared by controlled / living cationic polymerization of isobutylene followed by quenching with thiophene under selected conditions. Quantitative functionalization of living PIB with thiophene (T) has been achieved. The process is complicated by coupling between living PIB and PIB-T formed by in situ deprotonation. By lithiation of PIB-T a new, convenient method has been demonstrated for the synthesis of PIB-based block copolymers, involving anionic initiation of tert-butyl methacrylate. A major improvement is that for an industrial process, lithiation by n-BuLi is much more convenient than metalation by Na/K alloy, which had to be used in former processes. Block copolymers with narrow and unimodal molecular weight distribution (MWD) were synthesized under well-controlled conditions. The lithiated thiophene-capped PIB was also used to prepare four-armed star PIB via chlorosilane coupling. Using the same method, new amphiphilic block copolymers, namely PIB-b-poly(N,N-dimethylacrylamide) and PIB-b-poly(ethylene oxide) were synthesized. The anionic polymerization of N,N-dimethylacrylamide (DMAAm) was carried out with a binary initiator system prepared from thienyllithium and the Lewis acids triethylaluminium (Et3Al), diethylzinc (Et2Zn) or triethylborane (Et3B) in THF. Polymerizations proceeded in a homogeneous manner and gave polymers having controlled molecular weights. However, in presence of alkoxides the polymerization results in polymers insoluble in THF, even using Et3Al. Finally, lithiated PIB-T, in conjunction with Lewis acids, was used to initiate the living anionic polymerization of DMAAm, resulting in the new amphiphilic block copolymer PIB-b-PDMAAm. The anionic polymerization of ethylene oxide (EO) was carried out with a binary initiator system prepared from thienyllithium and the polyiminophosphazene base tBu-P4 in THF. Lithilated PIB-T- in conjunction with tBu-P4 was used to initiate the living anionic polymerization of ethylene oxide. In a second method, PIB-b-PEO was synthesized using hydroxyl end-capped PIB as macroinitiator in conjunction with tBu-P4. The aggregation behavior in dilute aqueous solutions of a PIB-b-PEO copolymer, produced from the combination of cationic and anionic polymerizations, was investigated by dynamic light scattering in aqueous solution. The monoaddition of ethylene oxide to lithiated PIB-T is demonstrated as a new pathway for the synthesis of hydroxy-functional PIB (PIB-OH). This is a useful alternative to the tedious procedures used in the literature so far. PIB-OH was successfully used as a macroinitiator for the ring-opening polymerizations of L-lactide and epsilon-caprolactone catalyzed by stannous octoate. Combination of chromatographic methods and MALDI-TOF ass spectrometry gave information about the side reactions during polymerization. Quantitative functionalization of living PIB with 2-bromothiophene has been achieved. Using various coupling methods, this polymer was convertet to a macromonomer with a pendant thiophene group, which is accessible in the 1- and 5-position. Oxidative copolymerization with thiophene led to graft copolymers consisting of polythiophene-graft-PIB.
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New Double-Responsive Micelles of Block Copolymers Based on N,N-Diethylacrylamide: Synthesis, Kinetics, Micellization, and Application as Emulsion Stabilizers
(2005)
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Xavier André
- Thermo- and pH-responsive block copolymers based on (meth)acrylic acid and N,N-diethylacrylamide were synthesized and their aqueous solution behavior was studied. Such bishydrophilic block copolymers represent an interesting class of stimuli-responsive water-soluble materials whose macroscopic properties can be triggered at the molecular level by tuning the temperature, the pH and the ionic strength of the solution. A new method was introduced for the synthesis of well-defined poly(N,N-diethylacrylamide) (PDEAAm) via living anionic polymerization using ethyl alpha-lithioisobutyrate (EiBLi) in the presence of triethylaluminium (Et3Al) as Lewis acid in tetrahydrofuran (THF) at -78 °C. Kinetic investigations were performed using in-situ Fourier-transform Near-Infrared (FT-NIR) fiber-optic spectroscopy. This is the first mechanistic study of the anionic polymerization of a dialkylacrylamide. The polymerization follows first order kinetics with respect to the effective concentration of active chains, [P*]0, but shows complex kinetics with respect to the actual monomer and initial aluminum concentrations. Upon addition of Et3Al, the polymerization rate constant, kp decreases, which is explained by the formation of an amidoenolate chain end/Et3Al complex of lower reactivity. It involves two equilibria: between noncoordinated and Et3Al-coordinated chain ends (deactivation of chain ends) as well as between free and Et3Al-activated monomer (activated monomer mechanism). These two effects are in a delicate balance that depends on the ratio of the concentrations of Et3Al, monomer, and chain ends. Thus, the polymerization rate of this system is governed simultaneously by the complex interplay between the activation of monomer (dependent on monomer and Et3Al concentrations) and the deactivation of chain ends (dependent on the ratio of concentrations of Et3Al to initiator). Polymers with narrow molecular weight distribution are obtained, indicating that the rate of interconversion between the different chain end species is greater than the polymerization rate. In contrast, such well-defined polymers are not found in the absence of Et3Al. PDEAAm polymers, synthesized using organolithium initiator in the presence of Et3Al, are rich in heterotactic (mr) triads and exhibit Lower Critical Solution Temperatures (LCST) in water with a cloud point at Tc = ca. 31 °C. By extending this synthetic concept and using poly(tert-butyl acrylate)-Li, and poly(tert-butyl methacrylate)-Li as macroinitiators, well-defined poly(tert-butyl acrylate)-block-PDEAAm, and poly(tert-butyl methacrylate)-block-PDEAAm block copolymers were obtained. Although the blocking efficiencies remained below 70 % a separation of block and homopolymers was easily possible. The narrowly distributed (AA)45-b-(DEAAm)360 block copolymer obtained after hydrolysis of the protecting tert-butyl groups exhibits interesting ‘schizophrenic’ micellization behavior in response to temperature, to pH, and to ionic strength of the aqueous media. Due to its asymmetric composition, two opposite micellar structures are expected. Indeed, the existence of different micellar aggregates, i.e., ‘crew-cut’ micelles with a PDEAAm core and inverse star-like micelles with PAA core, was proven by several analytical techniques, like Small-Angle Neutron Scattering (SANS), Dynamic and Static Light Scattering (DLS, SLS) and Cryo Transmission Electron Microscopy (cryo-TEM). Furthermore, all the transitions were found to be reversible. Finally, the synthesized bishydrophilic block copolymers were used for batch emulsion polymerizations of styrene, methyl methacrylate and n-butyl acrylate. In all cases, latexes with remarkable long-term stabilities were obtained, which is a very interesting feature from the colloidal point of view. The stabilization efficiency was found to be essentially adjustable by the pH due to the loss of the PDEAAm segment inside the latex particle. A detailed analysis of the particle size and particle size distribution was carried out using a variety of methods, including DLS, TEM and Asymmetric Flow Field-Flow Fractionation (AF-FFF).
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Micelles and Interpolyelectrolyte Complexes formed by Polyisobutylene-block-Poly([meth]acrylic acid) - Synthesis of Polymers and Characterization in Aqueous Solutions
(2007)
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Markus Burkhardt
- In this work PIB-b-PMAA copolymers with low PDI were studied, which self-assemble in aqueous solutions. A wide range of hydrophobic and hydrophilic block lengths were synthesized via combination of cationic an anionic polymerization. The data we have obtained by means of SANS and DLS point to an interesting dynamic behaviour of such micelles reacting on external stimulus of changes in pH from 10 to 7 and 5 respectively. The response is not only related to a change of the degree of neutralization of the PMAA block in the corona. Quantitative evaluation of SANS curves also shows a change of the size of the hydrophobic core formed by the PIB blocks, due to a change of the aggregation numbers. From cryo-TEM, a spherical shape of the micelles is clearly seen. This allows us to evaluate the SANS data using a model of a spherical particle with protruding arms. Evaluation of the SANS curves evidences about changes in Nagg with pH and with ionic strength. The higher the pH is, the more the arms of the micelle repel their neighbours and the higher the area at the core-corona interface of the micelle is. This leads to decreasing values of Nagg with rising pH. An increase in ionic strength has an opposite effect, resulting in higher Nagg upon improving screening of the charges of the PMAA. DLS measurements also show the response of the corona of the micelle on external stimuli. In principle, the PMAA block is more stretched the higher the number of charges on the arms of the micelles are. This also leads to an increasing Rh. Here the hydrophilic block dominates the response of the aggregate. For DLS, the influence of the PIB core and therefore the changes in Nagg can be neglected due to the longer PMAA block compared to the PIB block of the copolymers used in this work. Potentiometric titrations also show an effect of the ionic strength on the apparent pKa value, shifting it to lower values with increasing cNaCl, while the length of the hydrophilic block seems to play a minor role. For the evaluation of the cmc for different diblock copolymers the PIB block determines the properties of the micellar assemblies as well. The cmc clearly depends on the length of the hydrophobic PIB block. The longer the block is, the lower the cmc is found to be. Additionally a detailed investigation of IPECs formed by PIB-b-PMAA with P4VPQ is presented. The PIB-b-PMAA described above, are used to form water-soluble complexes with core-shell-corona structure. From cryo-TEM images, a spherical shape of the IPECs can be concluded. Slight differences in the overall shape of the complexed micelle give a hint on the proposed structure. The process of formation of complexes can be subdivided in a kinetically driven and a thermodynamically driven process. Upon addition of the polycation to the micellar PIB-b-PMAA solution, first an increase in turbidity of the solution can be observed. In this kinetically driven regime, large assemblies of micelles are formed. With time, these aggregates are equilibrating toward the thermodynamically more stable species of a single micelle with a complex species formed around the hydrophobic PIB core. The formation process can also be seen by means of SANS, leading to higher scattering intensity with increasing Z. SANS was used to follow the salt-induced dissociation of the complex as well. Increasing ionic strength of the IPEC solution leads to a release of the polycation, starting from about 0.2 M NaCl. Beyond 0.6 M NaCl, almost no difference in scattering behaviour of the IPEC solution compared to pure micelles can be stated. This suggests a total dissociation of the IPEC. By means of titration with a sodium selective electrode, the decrease of the activity of the Na ions can be explained by substitution of the polycation due to Manning condensation. Additionally the influence of point of time of addition of salt to an aqueous solution of a new diblock copolymer, PIB-b-PAA, is presented. By means of cryo-TEM, DLS and SANS an effect on the shape of the particles formed in solution could be obtained, whether the salt was added before dissolution (BD) or after dissolution of the polymer (PD). For the BD samples, a high PD of the particles can be seen from in cryo-TEM. Additionally sedimentation of a certain part of the polymer is another hint on larger aggregates. For the PD samples, spherical micelles with a core-corona structure are visible. According to cryo-TEM, their PDI is quite low. This suggests that interparticle exchange of unimers between the micelles is possible, at least before addition of the NaCl. Furthermore, it was shown, that changing the counterion to the "softer" Cs still allows the formation of equilibrium structures for BD samples, as seen from the spherical structure in cryo-TEM images. The influence of solvent for the SANS samples leads to a similar scattering behaviour for all measured samples.
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Functional Nanostructures from well-defined Block Copolymers: Stimuli-responsive Membranes, Multicompartment Micelles, and Interpolyelectrolyte Complexes
(2009)
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Felix Schacher
- In dieser Arbeit werden die Synthese, die Charakterisierung und die Selbstaggregation von Blockco- und Terpolymeren sowohl des AB- als auch des ABC-Typs beschrieben. Lebende anionische Polymerisation wurde herangezogen, um wohldefinierte Materialien zu erhalten. Diese wurden anschließend verwendet um Nanostrukturen mit definierten Funktionalitäten herzustellen. In einem ersten Ansatz wurden fünf Serien von Polybutadien-block-poly(2-vinylpyridin)-block-poly(tert-butylmethacrylat) (BVT) Blockterpolymeren synthetisiert. Daraufhin wurden deren Eigenschaften in Dünnfilmen untersucht. Die Zielsetzung bestand darin, mikrophasenseparierte Strukturen herzustellen und diese als mögliche Vorstufen zur Herstellung schaltbarer Komposit-Membranen zu verwenden. Dazu wurden Dünnfilme (Dicke unter 100 nm) durch Aufschleudern auf eine Oberfläche (z.B. Silizium) aufgebracht und der Prozess der Selbstanordnung durch nachfolgendes Quellen und Tempern im kontrollierten Lösungsmitteldampf beschleunigt. Auf diese Weise gelangen intensive Untersuchungen an Modellsystemen. Außerdem wurde das morphologische Verhalten derartiger BVT-Terpolymere sorgfältig analysiert und mit den jeweiligen Volumenstrukturen verglichen. Mittels einer anderen Strategie, nämlich über den Nichtlösungsmittel induzierten Phasenseparationsprozess (NIPS), konnten intelligente Ultrafiltrationsmembranen hergestellt werden. Dazu wurden amphiphile Polystyrol-block-poly(N,N-dimethylaminoethylmethacrylat) (PS-b-PDMAEMA) Diblockcopolymere synthetisiert. Konzentrierte Lösungen dieser Materialien wurden mittels einer Rakel in definierten Filmdicken auf Glasplatten aufgetragen. Nach dem Ausfällen der Polymerfilme in einem Wasserbad wurden schaltbare asymmetrische Membranen erhalten. PS bildet die Matrix während PDMAEMA hauptsächlich die Porenwände bedeckt. Das Ansprechen dieser Systeme auf Änderungen des pH-Wertes oder der Umgebungstemperatur wurde auf die Eigenschaften des hydrophilen PDMAEMA Blocks zurückgeführt. Nach ersten Ergebnissen hinsichtlich der Poren dieser Membranen und ihrer Verwendung zur selektiven Filtration von Nanopartikeln unterschiedlicher Größe wurde der Einfluss verschiedener Parameter während der Filmherstellung auf Morphologie und Durchlässigkeit der Membranen untersucht. Neben PS-b-PDMAEMA wurden verschiedene andere Blockcopolymere mit PDMAEMA als zweitem Block hergestellt: PB-b-PDMAEMA, Poly(tert-Butoxystyrol)-block-PDMAEMA sowie Polyethylenoxid-block-PDMAEMA. Im letztgenannten Fall wurde eine neuartige Ein-Topf-Strategie angewandt. Dadurch wurde während der Reaktion direkt von einem Oxoanion-Kettenende auf ein Carbanion-Kettenende gewechselt. Die Kinetik aller DMAEMA-Polymerisationen zeigte, dass der Zusatz von Phosphazen-Base im Falle der Polymerisation von PEO-b-PDMAEMA zu einer deutlich langsameren Reaktionsgeschwindigkeit verglichen mit Polymerisationen in Gegenwart von Alkoxiden führt. Ein dritter Teil dieser Doktorarbeit befasste sich mit der Selbstanordnung von BVT Blockterpolymeren in Lösung. In Aceton, einem selektiven Lösungsmittel für PB, wurden sehr eng verteilte Mizellen mit einem uneinheitlichen Kern gebildet. Sie besaßen einen PB-Kern, eine uneinheitliche Schale aus P2VP sowie eine PtBMA-Corona. Der Mizellkern wurde mit verschiedenen Methoden vernetzt wodurch die Aggregate ohne Strukturveränderung in nicht-selektive Lösungsmittel wie z.B. Dioxan überführt werden konnten. Schließlich wurden an den zuvor gebildeten und charakterisierten Mizellen polymeranaloge Modifikationen durchgeführt. Der PtBMA-Block wurde zu Polymethacrylsäure (MAA) hydrolysiert. Gegebenenfalls wurde zuvor der P2VP-Block durch Quaternisierung mit Methyliodid in einen starken Polyelektrolyten verwandelt. Auf diese Weise wurden amphiphile Blockterpolymere mit entweder einem oder zwei pH-sensitiven Blöcken erhalten. Das Aggregationsverhalten dieser Systeme in Abhängigkeit von pH-Wert und Salzgehalt wurde anschließend untersucht. Mizellen mit einem weichen PB-Kern, einer P2VP-Schale und einer MAA-Corona wurden gebildet. Unter bestimmten Voraussetzungen werden intramizellare Interpolyelektrolytkomplexe (IPECs) gebildet. Daraus resultierten Multikompartiment-Mizellen mit einer uneinheitlichen Schale. Außerdem wurde die IPEC-Bildung dieser Syteme mit entgegengesetzt geladenen Poly(N-methyl-2-vinylpyridinium)-block-polyethylenoxid Diblockcopolymeren untersucht. Es konnte eine weitere Schale durch die elektrostatisch induzierte IPEC-Bildung zwischen PMAA und P2VPq geformt werden. PEO diente als stabilisierende Corona der neu gebildeten Strukturen. Die zeitliche Entwicklung solcher Aggregate wurde weiter untersucht und sternförmige Zwischenzustände konnten identifiziert werden. Abschließend wurde die Bildung von Gold-Nanopartikeln selektiv innerhalb der IPEC-Schale dieser Mizellen demonstriert.
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Polymeric Nanoparticles for the Modification of Polyurethane Coatings
(2011)
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Sandrine Tea
- Rubber-based nanomodifiers were successfully synthesized following two different strategies and were used as impact modifiers in polyurethane (PU) automotive clearcoats to improve chip resistance. Various narrowly distributed polybutadiene-b-poly(methyl methacrylate) (B-M) block copolymers differing in composition and molecular weights were synthesized and studied with respect to their self-assembly in organic selective solvents. Dynamic light scattering and transmission electron microscopy measurements revealed that spherical micelles were obtained in acetonitrile for all block copolymers, independently of the polymer concentration. Their radii varied from 11 to 69 nm depending on the molecular weight of the initial linear block copolymer and their aggregation behavior in acetonitrile followed the model established by Förster and Antonietti for strongly segregated block copolymers. In DMF and acetone, block copolymers with 85 %wt PMMA were dissolved as unimers. For lower methacrylate contents, the sizes of the obtained spherical micelles were decreasing from DMF to acetone independently of the polymer concentration. The calculated interaction parameters confirmed acetonitrile as the best solvent for PMMA followed by DMF and acetone as the poorest one. The size of the spherical aggregates could be tuned by the molecular weight and/or by the nature of the selective solvent. Polybutadiene-b-poly(n-butly acrylate) (B-nBA), polybutadiene-b-poly(n-butyl methacrylate) (B-nBMA) and polybutadiene-b-poly(t-butyl methacrylate) (B-tBMA) did not show such a large choice in selective solvents and spherical micelles were obtained in DMF, DMAc and acetone respectively. Cross-linking of the polybutadiene core of the obtained micelles was performed in solution using two different methods: cold vulcanization and radical reaction upon the decomposition of a photo-initiator under UV radiation. Both methods allow retaining the spherical shape of the micelles leading to narrowly distributed non fusible nanospheres. In the case of B-M nanoparticles, the degree of cross-linking seemed independent of the amount of cross-linker used. Unlikely, B-nBMA and B-nBA nanoparticles exhibited increasing degrees of cross-linking with the amount of photo-initiator introduced. Their degrees of cross-linking were particularly lower than those of B-M nanoparticles. The hydrolysis of the t-BMA corona of the nanoparticles obtained from B-tBMA linear block copolymers self-assembly in selective solvent resulted in water soluble nanoparticles carrying acid functions and thus potentially exhibiting pH-responsive behavior. Various hyperstars consisting of a hyperbranched PB core and (meth)acrylate arms were synthesized by anionic self-condensing vinyl copolymerization (SCVCP) of divinylbenzene and butadiene followed by the anionic polymerization of the linear (meth)acrylate arms. The amount of hyperbranched products resulting from SCVCP could be enhanced by introducing additional DVB to the reaction while polymerizing. The topology of the hyperbranched PB cores was confirmed by viscosity measurements. All Mark-Houwink-Sakurada exponents were significantly below the value for linear PB. The initiation of (meth)acrylate arms was confirmed by NMR spectroscopy. Upon the arm-growth reaction, the branched topology was retained as witnessed by further viscosity measurements. The introduction of cross-linked nanoparticles based on linear block copolymers did not disturb the transparency of PU coatings. Even after curing reaction, the nanoparticles were well-dispersed into the coating. TEM observations confirmed this last result where neither aggregation nor flocculation of the cross-linked nanoparticles was observed. Hyperstar polymers were found to undergo self-assembly upon the curing reaction leading to “onion-like” structured aggregates, in the case of PMMA hyperstars, with sizes as large as 200 nm. Aggregates of the same size order were observed for the other hyperstars but no defined structures were found. For all hyperstar modified coatings, the transparency of the films was altered. In both cases, cross-linked nanoparticles and hyperstar modified coatings, improvements of chip resistance were observed. The improvements were even better with increasing amount of cross-linked nanoparticles but no effect was noticed on the hardness of the coatings. Similar trends were observed for the hyperstar modified coatings.
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Synthesis, Characterization, and Properties of Tailored Functional Block Copolymers
(2011)
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Robin Pettau
- This thesis covers the design, synthesis, characterization, and application of functional block copolymers (BCP) based on a polymer analogous approach and includes three main subjects. The first subject is the implementation of a specially constructed reactor setup for sequential anionic polymerization that allows parallel block copolymer synthesis based on one identical A-block on a lab scale. For this reason, this setup facilitates the preparation of block copolymer series in a combinatorial fashion. It consists of one main reactor and three secondary reactors with individual temperature control. The addition of monomers or additives to each reactor can be handled separately. AB diblock copolymer and ABC triblock copolymer series were prepared with different lengths of the final block as well as different chemical structures of the last block. The second subject covers the synthesis, characterization, processing and application of new liquid crystalline azobenzene-containing block copolymers designed as materials for holographic data storage. Therefore, these polymers contained an amorphous, optical inert poly(methyl methacrylate) (PMMA) or polystyrene (PS) matrix and a functional segment based on polyhydroxystyrene (PHS). Different lengths of flexible spacers and/or mixtures of two spacer lengths were employed to connect the mesogenic chromophores to the polymer backbone. The structure-property relation of functionalized BCPs and the resulting mesophase was investigated. Holographic experiments were conducted on selected examples of the photo-addressable polymers. Smectic annealed samples or amorphous quenched samples were obtained by different sample preparation methods to investigate the influence of the liquid crystalline order. While the initial sensitivity to light induced orientation of the polymer systems remained unaffected, the writing times and level of postdevelopment were improved for quenched samples. Variation in spacer lengths resulted in decreasing smectic order with decreasing spacer length as well as for mixtures of two different spacer lengths promoting lower writing times in the holographic experiments. Additionally, the temperature dependence of the temporal evolution of the refractive index modulation in the smectic polymers was studied. A significant decrease of writing times and an enhancement of the postdevelopment were revealed at elevated temperatures. Stable holographic gratings could be obtained even at 100 °C. 1.1 mm thick samples, that are a prerequisite for volume holographic data storage with a high data storage density, were prepared by injection molding of blends of photoaddressable BCPs with PMMA or PS. Preliminary results confirmed the long-term stability of inscribed holographic gratings and demonstrated angular multiplexing of holographic volume gratings. The third subject covers the synthesis and characterization of new cyanobiphenyl-containing ABA triblock copolymers and their application as BCP gelators for the low molecular weight liquid crystal (LC) 4-cyano-4’-(pentyl)biphenyl (5CB). Based on the selective solubility of the A and B blocks in the nematic solvent, ABA triblock copolymers can be used for the thermoreversible gelation of 5CB. To this end, ABA and ABA’ triblock copolymers comprised of PS A-blocks and a cyanobiphenyl-functionalized PHS B-block with a high degree of polymerization were prepared by the combination of anionic polymerization, using two different synthetic routes, and polymer analogous attachment of the mesogens. Series of linear gelators were prepared with variations in B-block length, A-block lengths and star shaped BCPs by coupling linear ABA’ triblock copolymers. Structure-property relations of the cyanobiphenyl-functionalized polymers regarding the mesophase characterization revealed a dependence of solubility in the nematic 5CB on spacer length. A comprehensive study was conducted to investigate the influence of the BCP backbone and architecture on the gelation of 5CB. Oscillating rheology measurements and thermal characterization were employed to investigate the thermoreversible LC gels. Most of the BCP gelators achieved gelation of 5CB at a mass concentration of 5 wt%. The properties of the different gels where compared at this fixed concentration. The influence of the gelator backbone on the gel properties was investigated by comparing different sets of triblock copolymers. While a short functionalized B-block resulted in high network density and, thus, a high elasticity of the gel the length of the A-blocks influenced the node stability. The LC gel using a star-shaped gealtor exhibited a significantly higher elasticity than with the respective linear block copolymer gelator.
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Template-Directed Synthesis of One-Dimensional Hybrid Nanostructures from Cylindrical Polymer Brushes
(2012)
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Markus Müllner
- The thesis deals with the study of cylindrical polymer brushes (CPBs) and their use in template chemistry. Herein, we developed template-directed syntheses of one-dimensional (1D) hybrid nanostructures in which CPBs served as 1D soft templates. So called ‘molecular’ core-shell or core-shell-corona CPBs, as well as CPBs obtained through microphase separation of diblock copolymers, were applied as templates for the preparation of various types of 1D organic-inorganic hybrid nanomaterials. Well-defined molecular core-shell and core-shell-corona CPBs with a narrow molecular weight distribution in both the backbone and the side chains have been synthesized via the combination of several polymerization techniques. Anionic polymerization has enabled the precise synthesis of polymer backbones, whereas atom transfer radical polymerization and ring-opening polymerization have allowed the sequential growth of side chains via the ‘grafting-from’ approach. Depending upon the desired functional 1D hybrid nanostructures, different combinations of core, shell and corona have been chosen. Core-shell-corona CPBs with a poly(tert-butyl acrylate) (PtBA) core, a poly(3-acryloylpropyl trimethoxysilane) (PAPTS) shell and a poly[oligo (ethylene glycol) methyl ether methacrylate] (POEGMA) corona were hydrolyzed by aqueous ammonia to produce water-soluble organo-silica hybrid nanotubes. As the trimethoxysilyl group was directly incorporated into the structure of the CPBs, we avoided the addition of an external inorganic precursor. Amphiphilic core-shell-corona CPBs with a hydrophobic poly(ε-caprolactone) (PCL) core, a hydrophilic poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) shell and a hydrophilic POEGMA corona were used as 1D templates and nanoreactors for the fabrication of titania dioxide (TiO2) semiconductor nanotubes. The cationic PDMAEMA shell was loaded with a negatively charged titania precursor, namely titanium(IV) bis(ammonium lactate) dihydroxide (TALH). TALH underwent hydrolysis within the CPB shell upon heating above 70 °C. Accordingly, crystalline (that is, anatase) TiO2 hybrid nanotubes with a very well defined thickness were obtained. Subsequently, the diameter of the hybrid nanotubes was adjusted by modifying the side chain length of the PDMAEMA shell. Amphiphilic core-shell CPBs with a hydrophobic PCL core and a hydrophilic PDMAEMA shell were employed for the fabrication of silica nanotubes with different aspect ratios. Tetramethyl orthosilicate (TMOS) was used for the deposition of silica into the PDMAEMA shell. Several polymers with different dimensions, with respect to length as well as core and shell diameter, were synthesized and used as templates for the fabrication 1D silica nanostructures. Furthermore, silica nanotubes were obtained after acid treatment or calcination, and catalytically active porous nanomaterials were produced via the embedment of metal nanoparticles within the silica shell. All the hybrid nanotubes templated by molecular core-shell and core-shell-corona CPBs were uniform in length as well as diameter, due to the narrow molecular weight distribution of the CPB backbone and side chains. Moreover, the POEGMA corona in the core-shell-corona CPBs served as a shielding layer and protected the nanotubes from agglomeration and intermolecular crosslinking during the hybrid formation. Additionally, POEGMA rendered the hybrid nanomaterials soluble in various solvents, including water. Water-soluble core-shell CPBs were obtained from microphase separated cast films of polystyrene-b-poly(allyl methacrylate) (PS-PAMA) diblock copolymers. After UV-crosslinking of the cylindrical PAMA domains, CPBs with a PS shell and a crosslinked PAMA core were obtained. Subsequent sulfonation rendered the PS shell into poly(styrenesulfonic acid) and thereby made it water-soluble. The negatively charged brush templates were infiltrated with oppositely charged TiO2 nanocrystals to produce crystalline TiO2 hybrid nanowires. Further, it was possible to adjust the crystal structure of the nanostructures to either a rutile or anatase structure. The presented novel 1D hybrid nanomaterials based on CPBs have many potential applications due to their electronic, catalytic and semiconducting properties.
