Biosynthesis and incorporation of side-chain-truncated lignin monomers to reduce lignin polymerization and enhance saccharification
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Aymerick, Eudes↗
SEARCH · Engineering Papers
Results for “POLYMERIZATION”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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Single-Crystal Linear Polymers Through Visible Light-Triggered Topochemical Quantitative Polymerization
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bio-inspired↗
Polymeric Schiff bases. XIII - The direct synthesis of cross-linked polymeric azomethines.
Cross-linked polymers obtained by direct reaction of aryl polycarbonyls with aryl polyamines, studying char yields effect
Dalelio, G. F.↗
Polymeric Schiff bases. XV - The synthesis of cross-linked polymeric azomethines from amino aryl ketones.
Cross-links effect on char yields of azomethine polymers produced by aryl diamines with aryl diketones
Dalelio, G. F.↗
Self-Propagating Frontal Polymerization in Water at Ambient Pressure
Advances in polymer chemistry have led to the development of monomers and initiation agents that enable propagating free-radical polymerization fronts to exist. These fronts are driven by the exothermicity of the polymerization reaction and the transport of heat from the polymerized product to the reactant monomer/solvent/initiator solution. The thermal energy transported to the reactant solution causes the initiator to decompose, yielding free radicals, which start the free radical polymerization process as discussed in recent reviews. The use of polymerization processes based on propagating fronts has numerous applications. Perhaps the most important of these is that it enables rapid curing of polymers without external heating since the polymerization process itself provides the high temperatures necessary to initiate and sustain polymerization. This process also enables more uniform curing of arbitrarily thick samples since it does not rely on heat transfer from an external source, which will necessarily cause the temperature history of the sample to vary with distance from the surface according to a diffusion-like process. Frontal polymerization also enables filling and sealing of structures having cavities of arbitrary shape without having to externally heat the structure. Water at atmospheric pressure is most convenient solvent to employ and the most important for practical applications (because of the cost and environmental issues associated with DMSO and other solvents). Nevertheless, to our knowledge, steady, self-propagating polymerization fronts have not been reported in water at atmospheric pressure. Currently, polymerization fronts require a high boiling point solvent (either water at high pressures or an alternative solvent such as dimethyl sulfoxide (DMSO) (boiling point 189 C at atmospheric pressure.) Early work on frontal polymerization, employed pressures up to 5000 atm in order to avoid boiling of the monomer/solvent/initiator solution. High boiling point solutions are needed because in order to produce a propagating front, a high front temperature is needed to produce sufficiently rapid decomposition of the free radical initiator and subsequent free radical polymerization and heat release at a rate faster than heat losses remove thermal energy from the system. (While the conduction heat loss rate increases linearly with temperature, the free radical initiator decomposition is a high activation energy process whose rate increases much more rapidly than linearly with temperature, thus as the temperature decreases, the ratio of heat loss to heat generation increases, eventually leading to extinction of the front if the temperature is too low.) In order to obtain atmospheric pressure frontal polymerization in water, it is necessary to identify a monomer/initiator combination that is water soluble and will not extinguish even when the peak temperature (T*) is less than 100 C. In this work acrylic acid (AA) was chosen as the monomer because is it one of the most reactive monomers and can polymerize readily at low temperatures even without initiators. Ammonium persulfate (AP) was chosen as the initiator because it decomposes readily at low temperatures, produces relatively few bubbles and is commercially available. The propagation rates and extinction conditions of the fronts are studied for a range of AA and AP concentrations. Small amounts of fumed silica powder (Cab-o-sil, Cabot Corporation) were added to the solutions to inhibit buoyancy induced convection in the solutions; future studies will investigate the effects of buoyant convection within the solutions.
Olten, Nesrin↗
Micro-fluidic partitioning between polymeric sheets for chemical amplification and processing
A system for fluid partitioning for chemical amplification or other chemical processing or separations of a sample, comprising a first dispenser of a first polymeric sheet, wherein the first polymeric sheet contains chambers; a second dispenser of a second polymeric sheet wherein the first dispenser and the second dispenser are positioned so that the first polymeric sheet and the second polymeric sheet become parallel; a dispenser of the fluid positioned to dispense the fluid between the first polymeric sheet and the second polymeric sheet; and a seal unit that seals the first polymeric sheet and the second polymeric sheet together thereby sealing the sample between the first polymeric sheet and the second polymeric sheet and partitioning the fluid for chemical amplification or other chemical processing or separations.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Micro-fluidic partitioning between polymeric sheets for chemical amplification and processing
A system for fluid partitioning for chemical amplification or other chemical processing or separations of a sample, comprising a first dispenser of a first polymeric sheet, wherein the first polymeric sheet contains chambers; a second dispenser of a second polymeric sheet wherein the first dispenser and the second dispenser are positioned so that the first polymeric sheet and the second polymeric sheet become parallel; a dispenser of the fluid positioned to dispense the fluid between the first polymeric sheet and the second polymeric sheet; and a seal unit that seals the first polymeric sheet and the second polymeric sheet together thereby sealing the sample between the first polymeric sheet and the second polymeric sheet and partitioning the fluid for chemical amplification or other chemical processing or separations.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Polythiophene thin films by surface-initiated polymerization: Mechanistic and structural studies
The ability to control nanoscale morphology and molecular organization in organic semiconducting polymer thin films is an important prerequisite for enhancing the efficiency of organic thin-film devices including organic light-emitting and photovoltaic devices. The current “top-down” paradigm for making such devices is based on utilizing solution-based processing (e.g., spin-casting) of soluble semiconducting polymers. This approach typically provides only modest control over nanoscale molecular organization and polymer chain alignment. A promising alternative to using solutions of presynthesized semiconducting polymers pursues instead a “bottom-up” approach to prepare surface-grafted semiconducting polymer thin films by surface-initiated polymerization of small-molecule monomers. Herein, we describe the development of an efficient method to prepare polythiophene thin films utilizing surface-initiated Kumada catalyst transfer polymerization. In this study, we provided evidence that the surface-initiated polymerization occurs by the highly robust controlled (quasi-“living”) chain-growth mechanism. Further optimization of this method enabled reliable preparation of polythiophene thin films with thickness up to 100 nm. Extensive structural studies of the resulting thin films using X-ray and neutron scattering methods as well as ultraviolet photoemission spectroscopy revealed detailed information on molecular organization and the bulk morphology of the films, and enabled further optimization of the polymerization protocol. One of the remarkable findings was that surface-initiated polymerization delivers polymer thin films showing complex molecular organization, where polythiophene chains assemble into lateral crystalline domains of about 3.2 nm size, with individual polymer chains folded to form in-plane aligned and densely packed oligomeric segments (7-8 thiophene units per each segment) within each domain. Achieving such a complex mesoscale organization is virtually impossible with traditional methods relying on solution processing of presynthesized polymers. Another significant advantage of surface-confined polymer thin films is their remarkable stability toward organic solvents and other processing conditions. In addition to controlled bulk morphology, uniform molecular organization, and stability, a unique feature of the surface-initiated polymerization is that it can be used for the preparation of large-area uniformly nanopatterned polymer thin films. Lastly, this was demonstrated using a combination of particle lithography and surface-initiated polymerization. In general, surface-initiated polymerization is not limited to polythiophene but can be also expanded toward other classes of semiconducting polymers and copolymers.
36 MATERIALS SCIENCE↗
Thermally Stable, Piezoelectric and Pyroelectric Polymeric Substrates
A thermally stable, piezoelectric and pyroelectric polymeric substrate was prepared. This thermally stable, piezoelectric and pyroelectric polymeric substrate may be used to prepare electromechanical transducers, thermomechanical transducers, accelerometers. acoustic sensors, infrared sensors, pressure sensors, vibration sensors, impact sensors, in-situ temperature sensors, in-situ stress/strain sensors, micro actuators, switches, adjustable fresnel lenses, speakers, tactile sensors. weather sensors, micro positioners, ultrasonic devices, power generators, tunable reflectors, microphones, and hydrophones. The process for preparing these polymeric substrates includes: providing a polymeric substrate having a softening temperature greater than 1000 C; depositing a metal electrode material onto the polymer film; attaching a plurality of electrical leads to the metal electrode coated polymeric substrate; heating the metal electrode coated polymeric substrate in a low dielectric medium; applying a voltage to the heated metal electrode coated polymeric substrate to induce polarization; and cooling the polarized metal electrode coated polymeric electrode while maintaining a constant voltage.
Simpson, Joycely O.↗
Method of Making Thermally Stable, Piezoelectric and Proelectric Polymeric Substrates
A thermally stable, piezoelectric and pyroelectric polymeric substrate was prepared. This thermally stable, piezoelectric and pyroelectric polymeric substrate may be used to prepare electromechanical transducers, thermomechanical transducers, accelerometers, acoustic sensors, infrared sensors, pressure sensors, vibration sensors, impact sensors. in-situ temperature sensors, in-situ stress/strain sensors, micro actuators, switches, adjustable fresnel lenses, speakers, tactile sensors, weather sensors, micro positioners, ultrasonic devices, power generators, tunable reflectors, microphones, and hydrophones. The process for preparing these polymeric substrates includes: providing a polymeric substrate having a softening temperature greater than 100 C; depositing a metal electrode material onto the polymer film; attaching a plurality of electrical leads to the metal electrode coated polymeric substrate; heating the metal electrode coated polymeric substrate in a low dielectric medium: applying a voltage to the heated metal electrode coated polymeric substrate to induce polarization; and cooling the polarized metal electrode coated polymeric electrode while maintaining a constant voltage.
Simpson, Joycelyn O.↗
Thermally Stable, Piezoelectric and Pyroelectric Polymeric Substrates and Method Relating Thereto
A thermally stable, piezoelectric and pyroelectric polymeric substrate was prepared, This thermally stable, piezoelectric and pyroelectric polymeric substrate may be used to prepare electromechanical transducers, thermomechanical transducers, accelerometers, acoustic sensors, infrared sensors, pressure sensors, vibration sensors, impact sensors. in-situ temperature sensors, in-situ stress/strain sensors, micro actuators, switches. adjustable fresnel lenses, speakers, tactile sensors, weather sensors, micro positioners, ultrasonic devices, power generators, tunable reflectors, microphones, and hydrophones. The process for preparing these polymeric substrates includes: providing a polymeric substrate having a softening temperature greater than 100 C; depositing a metal electrode material onto the polymer film; attaching a plurality of electrical leads to the metal electrode coated polymeric substrates; heating the metal electrode coated polymeric substrate in a low dielectric medium; applying a voltage to the heated metal electrode coated polymeric substrate to induce polarization; and cooling the polarized metal electrode coated polymeric electrode while maintaining a constant voltage.
Joycelyn O Simpson↗
Hydrogen-Doped Polymeric Carbon Monoxide at High Pressure
The ability to control materials stability, bonding, and transformation by thermo-mechanical and chemical means is significant for development of high-energy-density extended solids. We report that doping hydrogen (~10%) in carbon monoxide (CO) can greatly lower the polymerization pressure of CO and enhance the stability of recovered polymeric CO products at ambient conditions. Hydrogen-doped CO crystallizes into well-grown dendrites of β-CO-like phase at 3.2 GPa, which polymerizes to highly unsaturated black polymer (phase I) at ~4.7 (5.8) GPa. Upon further compression, this highly colored polymer transforms into a translucent 3D network structure (phase II) at 6–7 (10–17) GPa and then a transparent 2D layer structure (phase III) at 20–30 (30–60) GPa. A similar series of transformations are also found in pure CO but at considerably higher transition pressures, as noted in parentheses. All polymeric phases are recoverable at ambient conditions, exhibiting an array of phase stability and novel properties such as chemically unstable phase I, highly luminescent phase II, and highly transparent layered phase III. The density of recovered products ranges from ~2.3 g/cm 3 to 3.6 g/cm 3 , depending on the pressure recovered. The recovered products are highly disordered but slowly decompose to crystalline solids of anhydrous polymeric oxalic acid while exhibiting interesting crystal morphologies such as nm-cobs, nm-lamellar layers, and μm-bales. Here, the present first-principles MD simulations suggest that the polymerization occurs at 6 (or 10) GPa in H 2 -doped (or pure) CO. While not directly participating in the reaction, the role of H 2 molecules is to enhance the mobility of CO molecules leading to the polymerization.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Ethylene Polymerizations Catalyzed by Fluorinated “Sandwich” Diimine-Nickel and Palladium Complexes
Nickel and palladium complexes bearing “sandwich” diimine ligands with perfluorinated aryl caps have been synthesized, characterized, and explored in ethylene polymerization reactions. The X-ray crystallographic analysis of the precatalysts 16 and 6b show differences from their non-fluorinated analogues 17 and 19, with the perfluorinated aryl caps centered precisely over the nickel and palladium centers which results in higher buried volumes of the metal centers relative to the non-fluorinated analogs. The sandwich diimine palladium complexes 5a and 5b containing perfluorinated aryl caps polymerize ethylene in a controlled fashion with activities that are substantially increased compared with their non-fluorinated analogues. Migratory insertion rates in relevant methyl ethylene complexes agree with activities exhibited in bulk polymerization experiments. DFT studies suggest that facility of ethylene rotation from its preferred orientation perpendicular to the Pd-alkyl bond into a parallel in-plane conformation contributes to the higher polymerization activity for 5b relative to 18a. For these palladium systems polymer molecular weights can be controlled via hydrogen addition (hydrogenolysis) which is unusual for late transition metal-catalyzed olefin polymerizations with no catalyst deactivation occurring. Sandwich diimine nickel complexes 6a and 6b with perfluorinated aryl caps show ethylene polymerization activities that are about half that of classical tetraisopropyl-substituted catalyst 2 but again are more active than the analogous nonfluorinated sandwich complexes. Ethylene polymerizations exhibit living behavior and branched ultra-high molecular weight polyethylenes (UHMWPEs) with very low molecular weight distributions (less than 1.1) are obtained. The activated nickel catalysts are stable in the absence of monomer and show good long-term stability at 25 °C.
36 MATERIALS SCIENCE↗
Confocal Raman Microscopy for Investigating Synthesis and Characterization of Individual Optically Trapped Vinyl-Polymerized Surfactant Particles
Small polymeric particles are increasingly employed as adsorbent materials, as molecular carriers, as delivery vehicles, and in preconcentration applications. The rational development of these materials requires in situ methods of analysis to characterize their synthesis, structure, and applications. Optical-trapping confocal Raman microscopy is a spectroscopic method capable of acquiring information at several stages of the development of such dispersed particulate materials. In the present study, an example material is developed and tested using confocal Raman microscopy for characterization at each stage of the process. Specifically, the method is used to investigate the synthesis, structure, and applications of individual polymeric surfactant particles produced by the vinyl polymerization of sodium 11-acrylamidoundecanoate (SAAU). The kinetics of polymerization can be monitored over time by measuring the loss of the acrylamide C=C functional groups using confocal Raman microscopy of particles optically trapped by the excitation laser, where, within the limits of detecting the vinyl functional group, the complete polymerization of the SAAU monomer was achieved. The polymerized SAAU particles are spherical, and they exhibit uniform access to water throughout their structure, as tested by the penetration of heavy water (D2O) and collection of spatially resolved Raman spectra from the interior of the particle. These porous particles contain hydrophobic domains that can be used to accumulate molecules for adsorption or carrier applications. This property was tested by using confocal Raman microscopy to measure the accumulation equilibria and kinetics of a model compound, dioxybenzone. The partitioning of this compound into the polymer surfactant could be determined on a quantitative basis using relative scattering cross sections of the SAAU monomer and the adsorbate. Furthermore, the study points out the utility of optical-trapping confocal Raman microscopy for investigating the synthesis, structure, and potential carrier applications of polymeric particle materials.
36 MATERIALS SCIENCE↗
Development and Implementation of an Automatic Continuous Online Monitoring and Control Platform for Polymerization Reactions to Sharply Boost Energy and Resource Efficiency in Polymer Manufacturing
The project goal was to create an energy saving paradigm shift in how polymers are manufactured in the 21st century. It used Automatic Continuous Online Monitoring of Polymerization reactions (ACOMP) integrated for the first time with automatic active control to create the innovative ‘ACOMP/Control Interface’, or ‘ACOMP/CI’. ACOMP/CI will begin the transformation from old, inefficient processes into highly evolved, energy and resource efficient ones. The ACOMP platform is broadly applicable to many types of reactions and processes throughout the vast polymer industry. The industry provides materials for sectors such as automotive, aerospace, oil recovery, agriculture, paints, resins, adhesives, pharmaceuticals and therapeutic proteins, optics, electronics, lightweight building materials, and many more. The U.S. chemical industry is one of the last major sectors in which the U.S. has top global stature. It consumes 24% of all U.S. manufacturing energy, produces over $800B of product annually, supports 25% of the U.S. GDP and employs over 6 million people. It is also a major source of GHG emissions. Polymers make up approximately 30% of this sector. It is estimated that annually 60 TBtu of energy could be saved and 3 million tons less of GHG emissions produced by optimizing production in the polyolefin manufacturing sector alone. The project scope included first time design and prototyping of an ACOMP/CI, creation of active reaction controllers, and demonstration of control capabilities on ideal, low concentration polymerization reactions. All these elements of the scope were met, including advances and findings not originally anticipated. Extensions to more complex reactions, beyond the reactor capabilities of the current project ACOMP/CI, such as polyolefins and other high pressure/high temperature reactions, are being proposed in Fall 2017 to CESMII, a DoE based NNMI. The initial proposal was for a three year funded project, but this was reduced to a two year project and budget due to funding constraints. Hence, some of the original plans, such as adaptation of the ACOMP/CI to more relevant industrial processes, such as emulsion and dispersion technologies, could not be carried out. A third year of funding was requested at the end of the project, but DoE did not have resources to grant this. The sub-contractor Fluence Analytics (previously Advanced Polymer Monitoring Technologies, Inc) designed, prototyped, and commissioned a working ACOMP/CI by June 2015. The reaction characteristics to be automatically controlled were i) conversion kinetics, ii) molecular weight, iii) copolymer composition, and iv) simultaneous molecular weight and composition. A two pronged control strategy was used. The Tulane/Fluence group took a basic principles approach that did not rely on kinetic models. The LSU group took a more complex, non-linear model-oriented approach involving complete kinetic descriptions of the reaction system Each of these approaches proved successful in their own way. By April 2016 fully automatic control of conversion and weight average molecular weight, Mw, trajectories was achieved using the Tulane/Fluence (TF) basic principles controller. Similar results were obtained by the LSU non-linear model controller by August 2016. The demonstration system was aqueous free radical polymerization of acrylamide, Am. The control variables were temperature and semi-batch feed to the reactor of Am monomer and initiator. A demonstration of active manual conversion control in an industrial process using high solids in inverse emulsion polymerization of Am was achieved. During Summer 2016 the TF controller was used in conjunction with a chain transfer agent, another control variable, to automatically produce multi-modal molecular weight distributions, MWD, in a single reactor. Industrially, multi-modal MWD are produced by mixing products made in separate reactors, requiring significant extra time, energy, and reactor resources. Recognizing the industrial potential a patent on automatic production of multi-modal polymers was filed, and DoE acknowledged. In Fall 2016 the TF team developed a basic principles controller for copolymer composition and demonstrated it on aqueous free radical copolymerization of comonomers Am and styrene sulfonate, SS. TF then fused the Mw and composition controllers to achieve simultaneous control of both Mw and copolymer composition trajectories. Numerous simultaneous trajectories were demonstrated, including a trimodal composition distribution with constant Mw. Meanwhile, the LSU group developed a Kalman filter to improve the results of their automatic Mw and conversion controller and successful tests were made. During the project the TF team developed a means of computing full MWD during polymer synthesis without need for any chromatographic separation, based on model distributions. This means the polymer product is ‘born characterized’ and this can eliminate post-manufacture analytical laboratory quality control. TF filed a joint patent application on this new approach to chromatography-free determination of MWD with acknowledgment to DoE. The Tulane group obtained a 60MHz NMR during the project and recently completed the first work on separating three comonomers, Am, SS, and Na-acrylate, with a first demonstration of terpolymer composition control with the TF basic principles controller. Widespread dissemination of ACOMP/CI in the polymer manufacturing sector will bolster DoE goals of energy efficiency and reduced GHG emissions: The ability to monitor and actively control polymerization reactions will lead to more efficient use of energy and non-renewable resources, plant and labor time, increase the safety of manufacturing personnel, and will enhance product quality and lead to feasibility of manufacturing of polymers currently too complex for industrial scale production, while leading to less GHG emissions per kilo of product, and allowing for increased U.S. competitiveness in this enormous manufacturing sector. When ACOMP/CI is expanded to the polyolefin industry it is estimated that 60 TeraBTU/year of energy can be saved. Much of this saving is anticipated to come from optimized control of grade changeovers in steady state reactors and maintenance of steady states. Conclusions: ACOMP’s ability to provide continuous realtime data streams of measured polymer and reaction characteristics made it possible, for the first time, to directly and automatically control free radical polymerization reactions. An industrial client of Fluence Analytics has requisitioned the first ACOMP/CI which uses the TF basic principles controller. This sets the stage for FA to add control features to the ACOMP systems it has begun to install on the industrial scale beginning in 2014. Recommendations: This successful project was mainly limited to ideal polymerizations not of an industrial sort. The most energy intensive portion of polymer manufacturing is polyolefins. Adoption of ACOMP/CI to this enormous industrial sector faces the enormous challenges of high temperature, high pressure continuous sampling and high temperature sensor operation to obtain the continuous data needed for direct reaction control. The project team has a strategy for achieving this ambitious goal and will present it in Fall 2017 as a proposal to CESMII/DoE. It is recommended that this upcoming proposal be funded in order to make full use of the achievements of this just ended DoE project as the next step towards making polyolefin ACOMP/CI an energy saving reality. It is projected that ACOMP/CI can have its first polyolefin testbed demonstrations within two years of beginning the proposed project.
32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
Surface-Initiated Atom Transfer Radical Polymerization Using Hydrogel Reactors
Atom transfer radical polymerization (ATRP) is a controlled radical polymerization method that enables the synthesis of tailored polymeric materials with low dispersity, highlighting its immense potential for green fabrication of advanced materials. However, its broader implementation is limited by challenges in product isolation, maintaining catalyst activity, and mitigating atmospheric sensitivity arising from oxygen-sensitive metal catalysts. Here, gelatin hydrogels (GHs) are introduced as a soft “reactor” matrix for interfacial ATRP, operating with minimal metal-catalyst loading while exhibiting possibly an organoreductive behavior. This strategy leverages activator regeneration via electron transfer through a ligand–metal charge-transfer (LMCT) mechanism to reduce oxidized metal catalysts within the GH network. Polymerization is evaluated by growing polymer brushes at an active interface formed between GHs swollen in monomer solution and an initiating surface, and sequential growth experiments confirmed that GH-mediated ATRP preserves living character. Under UV illumination, LMCT is activated, producing polymers both at the desired interface and within the GH bulk. UV–Vis spectroscopy revealed active reduction of Cu(II) to Cu(I) along with concentration-dependent complex formation, indicating dynamic coordination chemistry within the hydrogel. The redox-active arginine- and glutamic acid-rich gelatin backbone coordinates and reduces the metal center, enabling ATRP at ppm-level catalyst concentrations. While polymerization proceeds in GH-Cu(II) reactors, adding external mobile ligands to the GH results in longer polymer brushes. Here, the results reported here are exploratory. More experiments are needed to characterize polymer brush growth in GHs and compare it to conventional surface-initiated polymerization in solution.
Absorption↗
A General Autofluorescence Method to Characterize Polymerization Progress
An autofluorescence technique to characterize polymerization progress in real time/in line was developed, which functioned in the absence of typical fluorogenic groups on the monomer or polymer. The monomer dicyclopentadiene and polymer polydicyclopentadiene are hydrocarbons that lack traditional functional groups for fluorescence spectroscopy. Here, the autofluorescence of formulations containing this monomer and polymer during ruthenium-catalyzed ring-opening metathesis polymerization (ROMP) was harnessed for reaction monitoring. The methods fluorescence recovery after photobleaching (FRAP) and here-developed fluorescence lifetime recovery after photobleaching (FLRAP) characterized polymerization progress in these native systems—without requiring exogenous fluorophore. (Auto)fluorescence lifetime recovery changes during polymerization correlated linearly to degree of cure, providing a quantitative link with reaction progress. These changing signals also provided relative rates of background polymerization, enabling comparison of 10 different catalyst–inhibitor-stabilized formulations. Multiple-well analysis demonstrated suitability for future high-throughput evaluation of formulations for thermosets. Furthermore, the central concept of the combined autofluorescence and FLRAP/FRAP method may be extendable to monitoring other polymerization reactions previously overlooked for lack of an obvious fluorescence handle.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Ionic Liquid Facilitated Solvent‐Phase Polymerization of Ultrasmooth Coatings of Polycatecholamines
Mussel-inspired polycatecholamine coatings and films have proven to be versatile materials for surface modification. However, the progress of chemically modified coatings with tailored properties has been slow due to the lack of definitive evidence of their polymeric structure. Polycatecholamines form aggregates during polymerization, and their formation mechanism has been a subject of debate owing to their insolubility in traditional molecular solvents. Exploiting the capability of ionic liquids (ILs) to exhibit strong electrostatic interactions, herein, the first solution-phase polymerization approach is reported to achieve polymerization of four catecholamines – dopamine (DA), norepinephrine (NE), L-3,4-dihydroxyphenylalanine (L-DOPA), and adrenaline (AD). Kinetic control over the polymerization process in the solution phase enabled it to follow the process with 1 H NMR spectroscopy, revealing the formation of structural features of resulting complex heterogeneous and soluble polymers. The polymers are both covalent and associative in nature. Solution phase polymerization prevented the formation of large aggregates in the solution, thus facilitating the formation of coatings that are ultra-smooth and have root mean square roughness of the order of sub-nm to nm scale.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗