The synthesis and characterization of copolymers containing 2‐ethylhexyl methacrylate and a quadruple‐hydrogen‐bonding site, 2‐ureido‐4[1H]‐pyrimidone methacrylate (UPyMA), are described. An analogous dimeric hydrogen‐bond‐containing copolymer based on 2‐ethylhexyl methacrylate and methacrylic acid (PEHMA‐co‐MAA) was also synthesized for comparative purposes. The glass‐transition temperatures of the poly(2‐ethylhexyl methacrylate‐co‐2‐ureido‐4[1H]‐pyrimidone methacrylate) (PEHMA‐co‐UPyMA) series increased linearly with increasing UPyMA content. Creep compliance measurements as a function of temperature indicated a decrease in the creep compliance with increasing UPyMA content over the range of 1–10 mol % UPyMA. Melt rheological analysis also showed an increase and lengthening of the plateau modulus as a function of frequency with increasing UPyMA content, as well as increasing complex viscosity as a function of temperature. The analogous PEHMA‐co‐MAA copolymer, which contained 11 mol % methacrylic acid, showed, in the melt rheological analysis, behavior similar to that of the PEHMA‐co‐UPyMA copolymer containing only 1 mol % UPyMA units. The multiple‐hydrogen‐bond‐containing copolymers were successfully analyzed with time–temperature superposition for the construction of master curves. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4618–4631, 2005
A series of linear and randomly branched poly(alkyl methacrylate)s with pendant 2-ureido-4[1H]-pyrimidone (UPy) groups, which form quadruple hydrogen bonds, were synthesized, and the role of molecular topology on intermolecular hydrogen bonding was investigated. In solution rheological studies of poly(methyl methacrylate-co-UPy methacrylate) (PMMA-co-UPyMA) copolymers, a branched copolymer in the nonassociated state displayed a larger entanglement concentration (C e) than a linear copolymer of equal molar mass. However, Ce of the branched copolymer approached the Ce of the linear analogue as the degree of hydrogen bond associations increased in solution, which suggested the reduced chain dimensions of the branched structure were overcome upon intermolecular association of the UPy groups. A series of linear and branched poly(2-ethylhexyl methacrylate-co-UPy methacrylate) (PEHMA-co-UPyMA) copolymers with 0-10 mol % UPy were utilized for melt rheological studies. A decrease in zero shear viscosity (η 0) and relaxation time suggested that branching reduced entanglement couplings for the unfunctionalized PEHMA homopolymer, and the η0 and relaxation time of the branched and linear polymers approached each another as the UPy content was increased from 0 to 10 mol %. Furthermore, as the UPy content was increased in the copolymer, the plateau modulus (G N 0 ) systematically increased, and the plateau region systematically broadened independent of the chain architecture. Thus, reversible hydrogen-bonding associations between UPy groups dominated the rheological behavior of linear and branched chains in both solution and the melt phase.
Self-healing macromolecular structures, submicron capsules and fibers with molecular recognition, stimuliresponsive molecules, solvent-free rheological reversibility, multivalency in rational drug design, and the emergence of new fields of adaptive and evolutive chemistry will require a predictive synergy of tailored non-covalent and covalent bonding in molecular design. Supramolecular chemistry has emerged as a stimulating focal point that will enable these scientific and technological discoveries, and biorecognition and biomolecular organization often serve as the inspiration for the future design of supramolecular assemblies. Linear and branched macromolecules are conventionally prepared using unique combinations of step-growth and chain polymerization strategies wherein the repeating units are irreversibly connected using stable covalent bonds. Moreover, optimum physical properties and commercial success of macromolecules are derived from our ability to prepare exceptionally high molecular weights in a controlled fashion. Although high molecular weight linear macromolecules are desirable for the optimization of physical performance and commercial impact, high molecular weights often compromise future solvent-free manufacturing, melt processability, thermal stability, and recyclability of the final products. Our recent efforts have demonstrated the utility of living anionic polymerization techniques to place functionality at desired positions on the polymer backbone. This control allowed investigation of the relationship between topology and tailored functionality, a fundamental investigation that may lead to interesting adaptive and smart applications. Specifically, the synthesis of polyisoprene homopolymers in a variety of topologies was performed, as well as the introduction of complementary hydrogen bonding to diverse families of hydroxyl containing polymeric and monomeric precursors.
Microcapsules are micron-sized hollow particles that can be synthesized with fluid encapsulated in the interior. The microcapsules can be used as a potential actuation technique by incorporating stimulus-responsive materials, such as permeselective, light-sensitive and electrically sensitive materials. The microcapsules range from 10 to 80 microns in diameter and wall thickness normalized to radius might range from 0.05 to 0.5. The actuation concept is to control the size of the microcapsules by varying the interior fluid pressure using an external stimulus. This paper presents efforts to model the performance and capabilities of microcapsules as micro actuators. We assume the pressure of the fluid inside of the microcapsules can be controlled by certain technique, such as thermal, electro or optical stimulus to the fluid. This paper will focus at modeling the performance of microcapsules under known pressure variation of fluid inside. First the paper compares a thin-wall model to a thick-wall model and identifies that thin-wall theory is not accurate enough for microcapsules. Simulation results show that energy density inthe order of 3J/cm3 is theoreticaly achievable for thick microspheres. Two type of materials are studied as the materials encapsulated in microcapsules. Their constitutive equations are then incorporated into the thick-wall model. Simulations show hydrocarbon solvents are much more efficient than ideal gas in terms of actuation performance.
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