5-substituted triazolinyls as novel counter radicals in controlled radical polymerization

The work is devoted to synthesis of new triazolinyl stable radical derivatives with different substituents at the 5-position of the triazolinyl ring. Obtained results showed great influence of these substituents on the stability of the radical. Electron-rich aromatic substituents at this position stabilize the radical while electron-poor aromatics decrease the stability of the triazolinyl. The triazolinyl radicals synthesized were used as additives for kinetic investigations of controlled radical polymerization of styrene and methylmethacrylate (MMA). The studies performed showed that the more stable radicals provide better control for the polymerization of styrene. In the same time certain instability of the radical is required for realization of controlled polymerization of methylmethacrylate. Based on the kinetic investigations controlled radical polymerization of a variety of monomers including 4-vinylpyridine (4-VP), ethylmethacrylate (EMA), 2,2,2-trifluoroethylmethacrylate (FEMA) and n-butylmethacrylate (BMA)was successfully carried out. Polystyrene and polymethylmethacrylate macroinitiators prepared by triazolinyl mediated controlled radical polymerization were efficiently reinitiated in the presence of a variety of monomers leading to the formation of block copolymers. Using this method PS-b-P-4-VP, PMMA-b-PS, PMMA-b-PBMA, PMMA-b-PFEMA, and PMMA-b-Poly-tert-butylacrylate were successfully synthesized. The results obtained during this work showed the efficiency and flexibility of the method allowing preparation of a range of advanced macromolecular structures.

Modeling the molecular weight distribution of block copolymer formation in a reversible addition-fragmentation chain transfer mediated living radical polymerization

Block copolymers have become an integral part of the preparation of complex architectures through self-assembly. The use of reversible addition-fragmentation chain transfer (RAFT) allows blocks ranging from functional to nonfunctional polymers to be made with predictable molecular weight distributions. This article models block formation by varying many of the kinetic parameters. The simulations provide insight into the overall polydispersities (PDIs) that will be obtained when the chain-transfer constants in the main equilibrium steps are varied from 100 to 0.5. When the first dormant block [polymer-S-C(Z)=S] has a PDI of 1 and the second propagating radical has a low reactivity to the RAFT moiety, the overall PDI will be greater than 1 and dependent on the weight fraction of each block. When the first block has a PDI of 2 and the second propagating radical has a low reactivity to the RAFT moiety, the PDI will decrease to around 1.5 because of random coupling of two broad distributions. It is also shown how we can in principle use only one RAFT agent to obtain block copolymers with any desired molecular weight distribution. We can accomplish this by maintaining the monomer concentration at a constant level in the reactor over the course of the reaction. (c) 2005 Wiley Periodicals, Inc.

Synthesis and Aggregation Behavior of Pluronic F87/Poly(acrylic acid) Block Copolymer with Doxorubicin

Poly(acrylic acid) (PAA) was grafted onto both termini of Pluronic F87 (PEO₆₇-PPO₃₉-PEO₆₇) via atom transfer radical polymerization to produce a novel muco-adhesive block copolymer PAA₈₀-b-F₈₇-b-PAA₈₀. It was observed that PAA₈₀-F₈₇-PAA₈₀ forms stable complexes with weakly basic anti-cancer drug, Doxorubicin. Thermodynamic changes due to the drug binding to the copolymer were assessed at different pH by isothermal titration calorimetry (ITC). The formation of the polymer/drug complexes was studied by turbidimetric titration and dynamic light scattering. Doxorubicin and PAA-b-F87-b-PAA block copolymer are found to interact strongly in aqueous solution via non-covalent interactions over a wide pH range. At pH>4.35, drug binding is due to electrostatic interactions. Hydrogen-bond also plays a role in the stabilization of the PAA₈₀-F₈₇-PAA₈₀/DOX complex. At pH 7.4 (α=0.8), the size and stability of polymer/drug complex depend strongly on the doxorubicin concentration. When CDOX <0.13mM, the PAA₈₀-F₈₇-PAA₈₀ copolymer forms stable inter-chain complexes with DOX (110 ~ 150 nm). When CDOX >0.13mM, as suggested by the light scattering result, the reorganization of the polymer/drug complex is believed to occur. With further addition of DOX (CDOX >0.34mM), sharp increase in the turbidity indicates the formation of large aggregates, followed by phase separation. The onset of a sharp enthalpy increase corresponds to the formation of a stoichiometric complex.

The Effects of Pi-Pi Stacking on the Controlled Radical Polymerization of Vinyl Aromatics

The atom transfer radical polymerization (ATRP) of styrene (St) was conducted in the presence of varying equivalence (eq) of hexafluorobenzene (HFB) and octafluorotoluene (OFT) to probe the effects of pi-pi stacking on the rate of the polymerization and on the tacticity of the resulting polystyrene (PSt). The extent of the pi-pi stacking interaction between HFB/OFT and the terminal polystyrenic phenyl group was also investigated as a function of solvent, both non-aromatic solvents (THF and hexanes) and aromatic solvents (benzene and toluene). In all cases the presence of HFB or OFT resulted in a decrease in monomer conversion indicating a reduction in the rate of the polymerization with greater retardation of the rate with increase eq of HFB or OFT (0.5 eq to 1 eq HFB/OFT compared to St). Additionally, when aromatic solvents were used instead of non-aromatic solvents the effect of the HFB/OFT on the rate was minimized, consistent with the aromatic solvent competitively interacting with the HFB/OFT. The effects of temperature and ligand strength on the ATRP of St in the presence of HFB were also probed. It was found that when using N,N,N’,N’,N’’-pentamethyldiethylenetriamine (PMDETA) as the ligand the effects of HFB at 38o were the same as at 86oC. When tris[2-(dimethylamino)ethyl]-amine (Me6TREN) was used as the ligand at 38o there was a decrease in monomer conversion similar to the analogous PMDETA reaction. When the polymerization was conducted at 86oC there was no effect on the monomer conversion with HFB present compared to when HFB was absent. To investigate the pi-pi stacking effect even further, the reverse pi-pi stacking system was observed by conducting the ATRP of pentafluorostyrene (PFSt) in the presence of varying eq of benzene and toluene, which in both cases resulted in an increase in monomer conversion compared to when benzene or toluene were absent; in summary the rate of the ATRP of PFSt increases when benzene or toluene waas present in the reaction. The pi-pi stacking interaction between the HFB/OFT and the dormant alkyl bromide of the polymer chain was verified by 1H-NMR with 1-bromoethylbenzene as the alkyl bromide. Also verified by 1H-NMR was the interaction between HFB/OFT and St and the interaction between PFSt and benzene. In all 1H-NMR spectra a perturbation in the aromatic and/or vinyl peaks was observed when the pi-pi stacking agent was present compared to when it was absent. The tacticity of the PSt formed in the presence of 1 eq of HFB was compared to the PSt formed in the absence of HFB by observing the C1 signal in their 13C-NMR spectra, but no change in shape or chemical shift of the signal was observed indicating that there was no change in tacticity.

Controlled Radical Polymerization of Styrene and Methyl Acrylate in the Presence of Reversible Addition-Fragmentation Chain Transfer Agents, Phenylethyl Phenyl Dithioacetate and Phenyldithioacetic Acid

The use of phenyldithioacetic acid (PDA) in homopolymerizations of styrene or methyl acrylate produced only a small fraction of chains with dithioester end groups. The polymerizations using 1-phenylentyl phenyldithioacetate (PEPDTA) and PDA in the same reaction showed that PDA had little or no influence on the rate or molecular weight distribution even when a 1:1 ratio is used. The mechanistic pathway for the polymerizations in the presence of PDA seemed to be different for each monomer. Styrene favors addition of styrene to PDA via a Markovnikov type addition to form a reactive RAFT agent. The polymer was shown by double detection SEC to contain dithioester end groups over the whole distribution. This polymer was then used in a chain extension experiment and the M-n was close to theory. A unique feature of this work was that PDA could be used to form a RAFT agent in situ by heating a mixture of styrene and PDA for 24 h at 70 degrees C and then polymerizing in the presence of AIBN to give a linear increase in Mn and low values of PDI (< 1.14). In the case of the polymerization of MA with PDA, the mechanism was proposed to be via degradative chain transfer. (c) 2005 Wiley Periodicals, Inc.

Supramolecular polymers azo-containing : photo-responsive block copolymer elastomers and homopolymers

Beaucoup d'efforts dans le domaine des matériaux polymères sont déployés pour développer de nouveaux matériaux fonctionnels pour des applications spécifiques, souvent très sophistiquées, en employant des méthodes simplifiées de synthèse et de préparation. Cette thèse porte sur les polymères photosensibles – i.e. des matériaux fonctionnels qui répondent de diverses manières à la lumière – qui sont préparés à l'aide de la chimie supramoléculaire – i.e. une méthode de préparation qui repose sur l'auto-assemblage spontané de motifs moléculaires plus simples via des interactions non covalentes pour former le matériau final désiré. Deux types de matériaux photosensibles ont été ciblés, à savoir les élastomères thermoplastiques à base de copolymères à blocs (TPE) et les complexes d'homopolymères photosensibles. Les TPEs sont des matériaux bien connus, et même commercialisés, qui sont généralement composés d’un copolymère tribloc, avec un bloc central très flexible et des blocs terminaux rigides qui présentent une séparation de phase menant à des domaines durs isolés, composés des blocs terminaux rigides, dans une matrice molle formée du bloc central flexible, et ils ont l'avantage d'être recyclable. Pour la première fois, au meilleur de notre connaissance, nous avons préparé ces matériaux avec des propriétés photosensibles, basé sur la complexation supramoléculaire entre un copolymère tribloc simple parent et une petite molécule possédant une fonctionnalité photosensible via un groupe azobenzène. Plus précisément, il s’agit de la complexation ionique entre la forme quaternisée d'un copolymère à blocs, le poly(méthacrylate de diméthylaminoéthyle)-poly(acrylate de n-butyle)-poly(méthacrylate de diméthylaminoéthyle) (PDM-PnBA-PDM), synthétisé par polymérisation radicalaire par transfert d’atomes (ATRP), et l'orange de méthyle (MO), un composé azo disponible commercialement comportant un groupement SO3 -. Le PnBA possède une température de transition vitreuse en dessous de la température ambiante (-46 °C) et les blocs terminaux de PDM complexés avec le MO ont une température de transition vitreuse élevée (140-180 °C, en fonction de la masse molaire). Des tests simples d'élasticité montrent que les copolymères à blocs complexés avec des fractions massiques allant de 20 à 30% présentent un caractère élastomère. Des mesures d’AFM et de TEM (microscopie à force atomique et électronique à ii transmission) de films préparés à l’aide de la méthode de la tournette, montrent une corrélation entre le caractère élastomère et les morphologies où les blocs rigides forment une phase minoritaire dispersée (domaines sphériques ou cylindriques courts). Une phase dure continue (morphologie inversée) est observée pour une fraction massique en blocs rigides d'environ 37%, ce qui est beaucoup plus faible que celle observée pour les copolymères à blocs neutres, dû aux interactions ioniques. La réversibilité de la photoisomérisation a été démontrée pour ces matériaux, à la fois en solution et sous forme de film. La synthèse du copolymère à blocs PDM-PnBA-PDM a ensuite été optimisée en utilisant la technique d'échange d'halogène en ATRP, ainsi qu’en apportant d'autres modifications à la recette de polymérisation. Des produits monodisperses ont été obtenus à la fois pour la macroamorceur et le copolymère à blocs. À partir d'un seul copolymère à blocs parent, une série de copolymères à blocs partiellement/complètement quaternisés et complexés ont été préparés. Des tests préliminaires de traction sur les copolymères à blocs complexés avec le MO ont montré que leur élasticité est corrélée avec la fraction massique du bloc dur, qui peut être ajustée par le degré de quaternisation et de complexation. Finalement, une série de complexes d'homopolymères auto-assemblés à partir du PDM et de trois dérivés azobenzènes portant des groupes (OH, COOH et SO3) capables d'interactions directionnelles avec le groupement amino du PDM ont été préparés, où les dérivés azo sont associés avec le PDM, respectivement, via des interactions hydrogène, des liaisons ioniques combinées à une liaison hydrogène à travers un transfert de proton (acidebase), et des interactions purement ioniques. L'influence de la teneur en azo et du type de liaison sur la facilité d’inscription des réseaux de diffraction (SRG) a été étudiée. L’efficacité de diffraction des SRGs et la profondeur des réseaux inscrits à partir de films préparés à la méthode de la tournette montrent que la liaison ionique et une teneur élevée en azo conduit à une formation plus efficace des SRGs.

Self-Assembly of Stimuli-Responsive Water-Soluble [60]Fullerene End-Capped Ampholytic Block Copolymer

Well-defined, water-soluble, pH and temperature stimuli-responsive [60]fullerene (C₆₀) containing ampholytic block copolymer of poly((methacrylic acid)-block-(2-(dimethylamino)ethyl methacrylate))-block–C₆₀ (P(MAA-b-DMAEMA)-b-C₆₀) was synthesized by the atom transfer radical polymerization (ATRP) technique. The self-assembly behaviour of the C₆₀ containing polyampholyte in aqueous solution was characterized by dynamic light scattering (DLS), and transmission electron microscopy. This amphiphilic mono-C₆₀ end-capped block copolymer shows enhanced solubility in aqueous medium at room and elevated temperatures and at low and high pH but phase-separates at intermediate pH of between 5.4 and 8.8. The self assembly of the copolymer is different from that of P(MAA-b-DMAEMA). Examination of the association behavior using DLS revealed the co-existence of unimers and aggregates at low pH at all temperatures studied, with the association being driven by the balance of hydrophobic and electrostatic interactions. Unimers and aggregates of different microstructures are also observed at high pH and at temperatures below the lower critical solution temperature (LCST) of PDMAEMA. At high pH and at temperatures above the LCST of PDMAEMA, the formation of micelles and aggregates co-existing in solution is driven by the combination of hydrophobic, electrostatic, and charge-transfer interactions.

Phase behavior and rheological analysis of reverse liquid crystals and W/I2, W/H2 gel emulsions using an amphiphilic block copolymer.

This article reports the phase behavior determi- nation of a system forming reverse liquid crystals and the formation of novel disperse systems in the two-phase region. The studied system is formed by water, cyclohexane, and Pluronic L-121, an amphiphilic block copolymer considered of special interest due to its aggregation and structural proper- ties. This system forms reverse cubic (I2) and reverse hexagonal (H2) phases at high polymer concentrations. These reverse phases are of particular interest since in the two-phase region, stable high internal phase reverse emulsions can be formed. The characterization of the I2 and H2 phases and of the derived gel emulsions was performed with small-angle X-ray scattering (SAXS) and rheometry, and the influence of temperature and water content was studied. TheH2 phase experimented a thermal transition to an I2 phase when temperature was increased, which presented an Fd3m structure. All samples showed a strong shear thinning behavior from low shear rates. The elasticmodulus (G0) in the I2 phase was around 1 order of magnitude higher than in theH2 phase. G0 was predominantly higher than the viscousmodulus (G00). In the gel emulsions,G0 was nearly frequency-independent, indicating their gel type nature. Contrarily to water-in-oil (W/O) normal emulsions, in W/I2 and W/H2 gel emulsions, G0, the complex viscosity (|η*|), and the yield stress (τ0) decreased with increasing water content, since the highly viscous microstructure of the con- tinuous phase was responsible for the high viscosity and elastic behavior of the emulsions, instead of the volumefraction of dispersed phase and droplet size. A rheological analysis, in which the cooperative flow theory, the soft glass rheology model, and the slip plane model were analyzed and compared, was performed to obtain one single model that could describe the non-Maxwellian behavior of both reverse phases and highly concentrated emulsions and to characterize their microstructure with the rheological properties.

Spontaneous condensation in DNA-polystyrene-b-poly(l-lysine) polyelectrolyte block copolymer mixtures

We investigated the condensation of calf thymus DNA by amphiphilic polystyrene(m)-b-poly(l-lysine)(n) block copolymers (PSm-b- PLys(n), m, n = degree of polymerization), using small-angle X-ray scattering, polarized optical microscopy and laser scanning confocal microscopy. Microscopy studies showed that the DNA condenses in the form of fibrillar precipitates, with an irregular structure, due to electrostatic interactions between PLys and DNA. This is not modified by the presence of hydrophobic PS block. Scattering experiments show that the structure of the polyplexes corresponds to a local order of DNA rods which becomes more compact upon increasing n. It can be concluded that for DNA/ PSm-b- PLys(n) polyplexes, the balance between the PLys block length and the excess charge in the system plays an essential role in the formation of a liquid crystalline phase.

Wormlike micelle formation and flow alignment of a pluronic block copolymer in aqueous solution

The self-assembly into wormlike micelles of a poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) triblock copolymer Pluronic P84 in aqueous salt solution (2 M NaCl) has been studied by rheology, small-angle X-ray and neutron scattering (SAXS/SANS), and light scattering. Measurements of the flow curves by controlled stress rheometry indicated phase separation under flow. SAXS on solutions subjected to capillary flow showed alignment of micelles at intermediate shear rates, although loss of alignment was observed for high shear rates. For dilute solutions, SAXS and static light scattering data on unaligned samples could be superposed over three decades in scattering vector, providing unique information on the wormlike micelle structure over several length scales. SANS data provided information on even shorter length scales, in particular, concerning "blob" scattering from the micelle corona. The data could be modeled based on a system of semiflexible self-avoiding cylinders with a circular cross-section, as described by the wormlike chain model with excluded volume interactions. The micelle structure was compared at two temperatures close to the cloud point (47 degrees C). The micellar radius was found not to vary with temperature in this region, although the contour length increased with increasing temperature, whereas the Kuhn length decreased. These variations result in an increase of the low-concentration radius of gyration with increasing temperature. This was consistent with dynamic light scattering results, and, applying theoretical results from the literature, this is in agreement with an increase in endcap energy due to changes in hydration of the poly(ethylene oxide) blocks as the temperature is increased.

Effect of architecture on the phase behavior of AB-type block copolymer melts

Equilibrium phase diagrams are calculated for a selection of two-component block copolymer architectures using self-consistent field theory (SCFT). The topology of the phase diagrams is relatively unaffected by differences in architecture, but the phase boundaries shift significantly in composition. The shifts are consistent with the decomposition of architectures into constituent units as proposed by Gido and coworkers, but there are significant quantitative deviations from this principle in the intermediate-segregation regime. Although the complex phase windows continue to be dominated by the gyroid (G) phase, the regions of the newly discovered Fddd (O^70) phase become appreciable for certain architectures and the perforated-lamellar (PL) phase becomes stable when the complex phase windows shift towards high compositional asymmetry.

Nanostructures, Semicrytalline Morphology, and Nanoscale Confinement Effect on the Crystallization Kinetics in Self-Organized Block Copolymer/Thermoset Blends

This work reports the first instance of self-organized thermoset blends containing diblock copolymers with a crystallizable thermoset-immiscible block. Nanostructured thermoset blends of bisphenol A-type epoxy resin (ER) and a low-molecular-weight (M-n = 1400) amphiphilic polyethylene-block-poly(ethylene oxide) (EEO) symmetric diblock copolymer were prepared using 4,4'-methylenedianiline (MDA) as curing agent and were characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), small-angle X-ray scattering (SAXS), and differential scanning calorimetry (DSC). All the MDA-cured ER/EEO blends do not show macroscopic phase separation but exhibit microstructures. The ER selectively mixes with the epoxy-miscible PEO block in the EEO diblock copolymer whereas the crystallizable PE blocks that are immiscible with ER form separate microdomains at nanoscales in the blends. The PE crystals with size on nanoscales are formed and restricted within the individual spherical micelles in the nanostructured ER/EEO blends with EEO content up to 30 wt %. The spherical micelles are highly aggregated in the blends containing 40 and 50 wt % EEO. The PE dentritic crystallites exist in the blend containing 50 wt % EEO whereas the blends with even higher EEO content are completely volume-filled with PE spherulites. The semicrystalline microphase-separated lamellae in the symmetric EEO diblock copolymer are swollen in the blend with decreasing EEO content, followed by a structural transition to aggregated spherical micellar phase morphology and, eventually, spherical micellar phase morphology at the lowest EEO contents. Three morphological regimes are identified, corresponding precisely to the three regimes of crystallization kinetics of the PE blocks. The nanoscale confinement effect on the crystallization kinetics in nanostructured thermoset blends is revealed for the first time. This new phenomenon is explained on the basis of homogeneous nucleation controlled crystallization within nanoscale confined environments in the block copolymer/thermoset blends.

Study of the kinetics and mechanism of rapid self-assembly in block copolymer thin films during solvo-microwave annealing

Microwave annealing is an emerging technique for achieving ordered patterns of block copolymer films on substrates. Little is understood about the mechanisms of microphase separation during the microwave annealing process and how it promotes the microphase separation of the blocks. Here, we use controlled power microwave irradiation in the presence of tetrahydrofuran (THF) solvent, to achieve lateral microphase separation in high- lamellar-forming poly(styrene-b-lactic acid) PS-b-PLA. A highly ordered line pattern was formed within seconds on silicon, germanium and silicon on insulator (SOI) substrates. In-situ temperature measurement of the silicon substrate coupled to condition changes during "solvo-microwave" annealing allowed understanding of the processes to be attained. Our results suggest that the substrate has little effect on the ordering process and is essentially microwave transparent but rather, it is direct heating of the polar THF molecules that causes microphase separation. It is postulated that the rapid interaction of THF with microwaves and the resultant temperature increase to 55 degrees C within seconds causes an increase of the vapor pressure of the solvent from 19.8 to 70 kPa. This enriched vapor environment increases the plasticity of both PS and PLA chains and leads to the fast self-assembly kinetics. Comparing the patterns formed on silicon, germanium and silicon on insulator (SOI) and also an in situ temperature measurement of silicon in the oven confirms the significance of the solvent over the role of substrate heating during "solvo-microwave" annealing. Besides the short annealing time which has technological importance, the coherence length is on a micron scale and dewetting is not observed after annealing. The etched pattern (PLA was removed by an Ar/O-2 reactive ion etch) was transferred to the underlying silicon substrate fabricating sub-20 nm silicon nanowires over large areas demonstrating that the morphology is consistent both across and through the film.