Polyurethane microphase separation

There have only been a very limited number of studies on multiblock copolymers with controlled block length (we exclude here the vast literature on random block copolymers such as polyurethanes). Microphase separation in (PS-PI) linear multiblocks with 1 < n < 4 with nearly equal block lengths was studied by Spontak and co-workers (Smith et al. 1993,1994). All (symmetric) samples were... 

Thermoplastic elastomeric behavior requires that the block copolymer develop a microheterogeneous two-phase network morphology. Theory predicts that microphase separation will occur at shorter block lengths as the polarity difference between the A and B blocks increases. This prediction is borne out as the block lengths required for the polyether-polyurethane, polyester-polyurethane, and polyether-polyester multiblock copolymers to exhibit thermoplastic elastomeric behavior are considerably shorter than for the styrene-diene-styrene triblock copolymers. 

One alternative is to select precursors which form a gas as a reaction product in situ during the network formation of thermosets. However this approach is restricted to a very limited number of precursors reacting via a polycondensation mechanism to split off a gas. For example, flexible polyurethane foams are commercially produced using CO2 that is liberated as a reaction product of the isocyanate monomer with water [5]. Very recently, Macosko and coworkers studied the macroscopic cell opening mechanism in polyurethane foams and unraveled a microphase separation occurring in the cell walls. This leads to nanosized domains, which are considered as hard segments and responsible for a rise in modulus after the cell opening [6]. 

The variation of Tg of the soft matrix in segmented polyurethanes as a function of composition or segmental chemical structure has been monitored and used as an indicator of the degree of microphase separation. Factors influencing the phase-separation process in these MDI-based polyurethanes have been summarized by Aitken and Jeffs (69) as follows (a) crystallization of either component, (b) the steric hin-... 

In interpenetrating polymer networks, chemical crosslinking and phase separation and their timing affect properties. Fumed silica, alumina, and carbon fiber were used in a network developed Ifom polyurethane and polycslcracrylalc. The presence of fillers affected many properties. Conversion rates were higher in the presence of fillers. Also, microphase separation was affected. As a result of these two changes the filled material was unrecognizable from the unfilled material. 

The microphase separation of a semi-interpenetrating network based on polyurethane and poly(epoxy isocyanurate) containing Fe2O3 was studied by dynamic mechanical spectroscopy. The preferential absorption of polyurethane on... 

Interdomain Communicaton via Magnetic Spin Diffusion in a Microphase-Separated Polyurethane Elastomer... 

Microdomain size in phase-separated copolymers plays a fundamental role in determining various macroscopic physical properties in the solid state. The difference in segmental mobility between the hard and soft domains governs the physical properties of microphase-separated polyurethane elastomers [7]. In this respect, the development of structure-property relations at the molecular level which relate directly to macroscopic behavior is the focus of this sub-section. One can exploit the well-documented difference between domain mobility [7-10] and the i3C NMR chemical shift distinction between the 0 .H2 resonances in the hard and soft segments to probe the microdomain morphology of polyether-... 

Proton spin-temperature equilibration between the hard- and soft-segment-rich domains of the polyurethane elastomer on the order of 10-100 ms might be considered fast relative to a macroscopically phase-separated blend [26] or copolymer, but slow relative to a strongly interacting mixture [25]. This is reasonable for a microphase-separated material whose solid state morphology has been the subject of considerable theoretical and experimental research. Under fortuitous circumstances, intimate (near-neighbor) contact between dissimilar molecules in a mixture can be studied via direct measurement of proton spin diffusion in a two-dimensional application of the 1H-CRAM PS experiment (Combined Rotation And Multiple Pulse Spectroscopy). Belfiore et al. [17,25,31] have detected intermolecular dipolar communication in a hydrogen-bonded cocrystallized solid solution of poly(ethylene oxide) and resorcinol on the f00-/xs time scale, whereas Ernst and coworkers [26] report the absence of proton spin diffusion on the 100-ms time scale for an immiscible blend of polystyrene and poly(vinyl methyl ether), cast from chloroform. 

An influence of plasticizers on the strength of polyurethane block-copolymers depends on some factors such as an influence of plasticizers on the microphase separation... 

K. Kojio, S. Nakashima and M. Furukawa, Microphase-separated structure and mechanical properties of norbornane diisocyanate-based polyurethanes . Polymer, 2007, 48, 997-1004. 

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