Understanding the Grafting of Telechelic Polymers on a Solid Substrate to Form Loops

Recent experimental and theoretical studies have demonstrated that relative to singly tethered chains, the presence of polymer loops at interfaces significantly improves interfacial properties such as adhesion, friction, and wettability. In the present study, a simple system was studied to examine the formation of polymeric loops on a solid surface, where the grafting of carboxylic acid terminated telechelic polystyrene from the melt to an epoxy functionalized silicon is chosen. The impact of telechelic molecular weight, grafting temperature, and surface functionality on the telechelic attachment process is studied. It was found that grafting of the telechelic to the surface at both ends to form loops is the primary product of this grafting process. Moreover, examination of the kinetics of the grafting process indicates that it is reaction controlled. Fluorescence tagging of the dangling ends of singly bound chains provides a mechanism to monitor their time evolution during grafting, and these results indicate that the grafting process is accurately described by recent Monte Carlo simulation work. The results also provide a method to control the extent of loop formation at interfaces and therefore provide an opportunity to further understand the role of the loops in the interfacial properties in multicomponent polymer systems.

The effects of additives and chemical modification on the solution properties of thermo-sensitive polymers

Cette thèse concerne l’étude de phase de séparation de deux polymères thermosensibles connus-poly(N-isopropylacylamide) (PNIPAM) et poly(2-isopropyl-2-oxazoline) (PIPOZ). Parmi des études variées sur ces deux polymères, il y a encore deux parties de leurs propriétés thermiques inexplicites à être étudiées. Une partie concerne l’effet de consolvant de PNIPAM dans l’eau et un autre solvant hydromiscible. L’autre est l’effet de propriétés de groupes terminaux de chaînes sur la séparation de phase de PIPOZ. Pour ce faire, nous avons d’abord étudié l’effet de l’architecture de chaînes sur l’effet de cosolvant de PNIPAMs dans le mélange de méthanol/eau en utilisant un PNIPAM en étoile avec 4 branches et un PNIPAM cyclique comme modèles. Avec PNIPAM en étoile, l’adhérence de branches PNIPAM de à un cœur hydrophobique provoque une réduction de Tc (la température du point de turbidité) et une enthalpie plus faible de la transition de phase. En revanche, la Tc de PNIPAM en étoile dépend de la masse molaire de polymère. La coopérativité de déhydratation diminue pour PNIPAM en étoile et PNIPAM cyclique à cause de la limite topologique. Une étude sur l’influence de concentration en polymère sur l’effet de cosolvant de PNIPAM dans le mélange méthanol/eau a montré qu’une séparation de phase liquide-liquide macroscopique (MLLPS) a lieu pour une solution de PNIPAM dans le mélange méthanol/eau avec la fraction molaire de méthanol entre 0.127 et 0.421 et la concentration en PNIPAM est constante à 10 g.L-1. Après deux jours d’équilibration à température ambiante, la suspension turbide de PNIPAM dans le mélange méthanol/eau se sépare en deux phases dont une phase possède beaucoup plus de PNIPAM que l’autre. Un diagramme de phase qui montre la MLLPS pour le mélange PNIPAM/eau/méthanol a été établi à base de données expérimentales. La taille et la morphologie de gouttelettes dans la phase riche en polymère condensée dépendent de la fraction molaire de méthanol. Parce que la présence de méthanol influence la tension de surface des gouttelettes liquides, un équilibre lent de la séparation de phase pour PNIPAM/eau/méthanol système a été accéléré et une séparation de phase liquide-liquide macroscopique apparait. Afin d’étudier l’effet de groupes terminaux sur les propriétés de solution de PIPOZ, deux PIPOZs téléchéliques avec groupe perfluorodécanyle (FPIPOZ) ou groupe octadécyle (C18PIPOZ) comme extrémités de chaîne ont été synthétisés. Les valeurs de Tc des polymères téléchéliques ont beaucoup diminué par rapport à celle de PIPOZ. Des micelles stables se forment dans des solutions aqueuses de polymères téléchéliques. La micellization et la séparation de phase de ces polymères dans l’eau ont été étudiées. La séparation de phase de PIPOZs téléchéliques suit le mécanisme de MLLPS. Des différences en tailles de gouttelettes formées à l’intérieur de solutions de deux polymères ont été observées. Pour étudier profondément les différences dans le comportement d’association entre deux polymères téléchéliques, les intensités des signaux de polymères correspondants et les temps de relaxation T1, T2 ont été mesurés. Des valeurs de T2 de protons correspondants aux IPOZs sont plus hautes.

New methods for the functionalization of metathesis polymers

Two general strategies for the functionalization of metathesis polymers are presented in this dissertation. Introducing Sacrificial Synthesis, many of the limitations of ruthenium-catalyzed ROMP have been overcome. Here, the living ROMP polymer to be functionalized was turned into a diblock copolymer by polymerizing dioxepine monomers onto the desired first polymer block. The second block was then later removed to leave “half-a-dioxepin”, i.e. exactly one hydroxyl group, at the chain-end. The efficiency of Sacrificial Synthesis is also studied. Thiol groups were also placed by a sacrificial strategy based on cyclic thioacetals. 2-Phenyl-1,3-dithiepin could be polymerized and subsequently cleaved by hydrogenation with Raney-Nickel. The presence of thiol groups on the chain end has been proven by chemical means (derivatization) and by coating gold-nanoparticles. The second strategy, vinyl lactone quenchingv is a termination reaction based on vinyl esters. After a metathesis step, an inactive Fischer-type carbene is formed. Such acyl carbenes are unstable and self-decompose to set an inactive ruthenium complex and the functional group free without changing the reaction conditions. The two compounds vinylene carbonate and 3H-furanone gave rise to the placement of aldehydes and carboxylic acids at the polymer chain ends without the necessity to perform any deprotection steps after the functionalization. The development of those two functionalization methods led to several applications. By reacting hydroxyl-functionalized ROMP-polymers with norbornene acid, macromonomers were formed which were subsequently polymerized to the respective graft-copolymers. Also, the derivatization of the same functionalized polymers with propargylic acid gave rise to alkyne-functionalized polymers which were conjugated with azides. Furthermore, “ugly stars”, i.e. long-chain branched structures were synthesized by polycondensation of ABn-type macromonomers and telechelic polymers were accessed combining the described functionalization techniques.

Étude des poly(2-alkyl-2-oxazoline)s munis d'extrémités hydrophobes en solution aqueuse et à linterface eau/air

Thèse numérisée par la Division de la gestion de documents et des archives de l'Université de Montréal

Studies of the cationic polymerisation of vinylic and energetic cyclic ether monomers

The cationic polymerisation of various monomers, including cyclic ethers bearing energetic nitrate ester (-ON02) groups, substituted styrenes and isobutylene has been investigated. The main reaction studied has been the ring-opening polymerisation of 3- (nitratomethyl)-3-methyl oxetane (NIMMO) using the alcohol/BF3.0Et2 binary initiator system. A series of di-, tri- and tetrafunctional telechelic polymers has been synthesised. In order to optimise the system, achieve controlled molecular weight polymers and understand the mechanism of polymerisation the effects of certain parameters on the molecular weight distribution, as determined by Size Exclusion Chromatography, have been examined. This shows the molecular weight achieved depends on a combination of factors including -OH concentration, addition rate of monomer and, most importantly, temperature. A lower temperature and OH concentration tends to produce higher molecular weight, whereas, slower addition rates of monomer, either have no significant effect or produce a lower molecular weight polymer. These factors were used to increase the formation of a cyclic oligomer, by a side reaction, and suggest, that the polymerisation of NIMMO is complicated with endbiting and back biting reactions, along with other transfer/termination processes. These observations appear to fit the model of an active-chain end mechanism. Another cyclic monomer, glycidyl nitrate (GLYN), has been polymerised by the activated monomer mechanism. Various other monomers have been used to end-cap the polymer chains to produce hydroxy ends which are expected to form more stable urethane links, than the glycidyl nitrate ends, when cured with isocyanates. A novel monomer, butadiene oxide dinitrate (BODN), has been prepared and its homopolymerisation and copolymerisation with GL YN studied. In concurrent work the carbocationic polymerisations of isobutylene or substituted styrenes have been studied. Materials with narrow molecular weight distributions have been prepared using the diphenyl phosphate/BCl3 initiator. These systems and monomers are expected to be used in the synthesis of thermoplastic elastomers.

Self-assembly of telechelic tyrosine end-capped PEO and poly(alanine) polymers in aqueous solution

The self-assembly in aqueous solution of three novel telechelic conjugates comprising a central hydrophilic polymer and short (trimeric or pentameric) tyrosine end-caps has been investigated. Two of the conjugates have a central poly(oxyethylene) (polyethylene oxide, PEO) central block with different molar masses. The other conjugate has a central poly(l-alanine) (PAla) sequence in a purely amino-acid based conjugate. All three conjugates self-assemble into β-sheet based fibrillar structures, although the fibrillar morphology revealed by cryogenic-TEM is distinct for the three polymers—in particular the Tyr5-PEO6k-Tyr5 forms a population of short straight fibrils in contrast to the more diffuse fibril aggregates observed for Tyr5-PEO2k-Tyr5 and Tyr3-PAla-Tyr3. Hydrogel formation was not observed for these samples (in contrast to prior work on related systems) up to quite high concentrations, showing that it is possible to prepare solutions of peptide–polymer-peptide conjugates with hydrophobic end-caps without conformational constraints associated with hydrogelation. The Tyr5-PEO6k-Tyr5 shows significant PEO crystallization upon drying in contrast to the Tyr5-PEO2k-Tyr5 conjugate. Our findings point to the remarkable ability of short hydrophobic peptide end groups to modulate the self-assembly properties of polymers in solution in model peptide-capped “associative polymers”. Retention of fluidity at high conjugate concentration may be valuable in potential future applications of these conjugates as bioresponsive or biocompatible materials, for example exploiting the enzyme-responsiveness of the tyrosine end-groups

Thermodynamic Study Of The Micellization Of Zwitterionic Surfactants And Their Interaction With Polymers In Water By Isothermal Titration Calorimetry.

The micellization of a homologous series of zwitterionic surfactants, a group of sulfobetaines, was studied using isothermal titration calorimetry (ITC) in the temperature range from 15 to 65 °C. The increase in both temperature and the alkyl chain length leads to more negative values of ΔGmic(0) , favoring the micellization. The entropic term (ΔSmic(0)) is predominant at lower temperatures, and above ca. 55-65 °C, the enthalpic term (ΔHmic(0)) becomes prevalent, figuring a jointly driven process as the temperature increases. The interaction of these sulfobetaines with different polymers was also studied by ITC. Among the polymers studied, only two induced the formation of micellar aggregates at lower surfactant concentration: poly(acrylic acid), PAA, probably due to the formation of hydrogen bonds between the carboxylic group of the polymer and the sulfonate group of the surfactant, and poly(sodium 4-styrenesulfonate), PSS, probably due to the incorporation of the hydrophobic styrene group into the micelles. The prevalence of the hydrophobic and not the electrostatic contributions to the interaction between sulfobetaine and PSS was confirmed by an increased interaction enthalpy in the presence of electrolytes (NaCl) and by the observation of a significant temperature dependence, the latter consistent with the proposed removal of hydrophobic groups from water.

Triboelectricity In Insulating Polymers: Evidence For A Mechanochemical Mechanism.

Transfer of reaction products formed on the surfaces of two mutually rubbed dielectric solids makes an important if not dominating contribution to triboelectricity. New evidence in support of this statement is presented in this report, based on analytical electron microscopy coupled to electrostatic potential mapping techniques. Mechanical action on contacting surface asperities transforms them into hot-spots for free-radical formation, followed by electron transfer producing cationic and anionic polymer fragments, according to their electronegativity. Polymer ions accumulate creating domains with excess charge because they are formed at fracture surfaces of pulled-out asperities. Another factor for charge segregation is the low polymer mixing entropy, following Flory and Huggins. The formation of fractal charge patterns that was previously described is thus the result of polymer fragment fractal scatter on both contacting surfaces. The present results contribute to the explanation of the centuries-old difficulties for understanding the triboelectric series and triboelectricity in general, as well as the dissipative nature of friction, and they may lead to better control of friction and its consequences.

Polímeros biomiméticos em química analítica. Parte 1: preparo e aplicações de MIP (Molecularly Imprinted Polymers) em técnicas de extração e separação

MIPs are synthetic polymers that are used as biomimetic materials simulating the mechanism verified in natural entities such as antibodies and enzymes. Although MIPs have been successfully used as an outstanding tool for enhancing the selectivity or different analytical approaches, such as separation science and electrochemical and optical sensors, several parameters must be optimized during their synthesis. Therefore, the state-of-the-art of MIP production as well as the different polymerization methods are discussed. The potential selectivity of MIPs in the extraction and separation techniques focusing mainly on environmental, clinical and pharmaceutical samples as applications for analytical purposes is presented.

Polímeros biomiméticos em química analítica. Parte 2: aplicações de MIP (Molecularly Imprinted Polymers) no desenvolvimento de sensores químicos

The aim of this paper is the description of the strategies and advances in the use of MIP in the development of chemical sensors. MIP has been considered an emerging technology, which allows the synthesis of materials that can mimic some highly specific natural receptors such as antibodies and enzymes. In recent years a great number of publications have demonstrated a growth in their use as sensing phases in the construction of sensors . Thus, the MIP technology became very attractive as a promising analytical tool for the development of sensors.

An apparatus for in situ spectroscopy of radiation damage of polymers by bombardment with high-energy heavy ions

A new target station providing Fourier transform infrared (FT-IR) spectroscopy and residual gas analysis (RGA) for in situ observation of ion-induced changes in polymers has been installed at the GSI Helmholtz Centre for Heavy Ion Research. The installations as well as first in situ measurements at room temperature are presented here. A foil of polyimide Kapton HN (R) was irradiated with 1.1 GeV Au ions. During irradiation several in situ FT-IR spectra were recorded. Simultaneously outgassing degradation products were detected with the RGA. In the IR spectra nearly all bands decrease due to the degradation of the molecular structure. In the region from 3000 to 2700 cm(-1) vibration bands of saturated hydrocarbons not reported in literature so far became visible. The outgassing experiments show a mixture of C(2)H(4), CO, and N(2) as the main outgassing components of polyimide. The ability to combine both analytical methods and the opportunity to measure a whole fluence series within a single experiment show the efficiency of the new setup. (C) 2011 American Institute of Physics. [doi:10.1063/1.3571301]

Substrate/semiconductor interface effects on the emission efficiency of luminescent polymers

The importance of interface effects for organic devices has long been recognized, but getting detailed knowledge of the extent of such effects remains a major challenge because of the difficulty in distinguishing from bulk effects. This paper addresses the interface effects on the emission efficiency of poly(p-phenylene vinylene) (PPV), by producing layer-by-layer (LBL) films of PPV alternated with dodecylbenzenesulfonate. Films with thickness varying from similar to 15 to 225 nm had the structural defects controlled empirically by converting the films at two temperatures, 110 and 230 degrees C, while the optical properties were characterized by using optical absorption, photoluminescence (PL), and photoluminescence excitation spectra. Blueshifts in the absorption and PL spectra for LBL films with less than 25 bilayers (<40-50 nm) pointed to a larger number of PPV segments with low conjugation degree, regardless of the conversion temperature. For these thin films, the mean free-path for diffusion of photoexcited carriers decreased, and energy transfer may have been hampered owing to the low mobility of the excited carriers. The emission efficiency was then found to depend on the concentration of structural defects, i.e., on the conversion temperature. For thick films with more than 25 bilayers, on the other hand, the PL signal did not depend on the PPV conversion temperature. We also checked that the interface effects were not caused by waveguiding properties of the excited light. Overall, the electronic states at the interface were more localized, and this applied to film thickness of up to 40-50 nm. Because this is a typical film thickness in devices, the implication from the findings here is that interface phenomena should be a primary concern for the design of any organic device. (C) 2011 American Institute of Physics. [doi:10.1063/1.3622143]

Thermodynamic modeling of pyroelectric and piezoelectric properties of cellular polymers

A thermodynamic approach is presented to model devices manufactured with cellular polymers. They are heterogeneous nonpolar space-charge electrets that exhibit much higher piezoelectricity than the well-known ferroelectric polymers. Their pyroelectric and piezoelectric properties are characterized by adequate coefficients which quantify the performance of devices manufactured with those materials. The method presented in this contribution to calculate those coefficients is exact and consistent avoiding ad hoc simplifications introduced in other approaches. The results obtained by this method allow drawing conclusions regarding device optimization.

Thermal diffusivity of polymers by modified angstrom method

The nature of the molecular structure of plastics makes the properties of such materials markedly temperature dependent. In addition, the continuous increase in the utilization of polymeric materials in many specific applications has demanded knowledge of their physical properties, both during their processing as raw material, as well as over the working temperature range of the final polymer product. Thermal conductivity, thermal diffusivity and specific heat, namely the thermal properties, are the three most important physical properties of a material that are needed for heat transfer calculations. Recently, among several different methods for the determination of the thermal diffusivity and thermal conductivity, transient techniques have become the preferable way for measuring thermal properties of materials. In this work, a very simple and low cost variation of the well known Angstrom method is employed in the experimental determination of the thermal diffusivity of some selected polymers. Cylindrical shaped samples 3 cm diameter and 7 cm high were prepared by cutting from long cylindrical commercial bars. The reproducibility is very good, and the results obtained were checked against results obtained by the hot wire technique, laser flash technique, and when possible, they were also compared with data found in the literature. Thermal conductivity may be then derived from the thermal diffusivity with the knowledge of the bulk density and the specific heat, easily obtained by differential scanning calorimetry. (C) 2009 Elsevier Ltd. All rights reserved.