Three types of amine-containing polyurethanes and poly(urethane−ureas), N-methyldiethanolamine (MDEA) and/or tetraethylenepentamine (TEPA) as the chain extender and poly(ethylene glycol) of MW 400 as the soft-segment component, have been studied by FTIR. The hydrogen bonding in hard and soft segments was examined for the extent of phase separation, and the microstructure was evidenced by differential scanning calorimetry (DSC). The temperature effects on the hydrogen bonding were also investigated. They show a significant amount of hydrogen bonding between the hard and soft segments. It indicates that there exists a large amount of partial phase mixing of hard and soft segments compared to the conventional polyurethanes. The bulky CH3 groups of MDEA in hard segments restrict the hydrogen bonding within the hard segments, while the TEPA-containing urethane−urea polymers have more distinct phase separation. However, all of the polymers studied are amorphous materials such that the dissolved soft segments in the hard-segment domains may interfere with molecular packing in the domains. It shows that the hydrogen bonding in these polymers persists up to 200 °C. The hydrogen bonding of NH to the ether oxygen decreases significantly at T > 50 °C.

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SYNOPSISAs an absorbent of C 0 2 , tetraethylenepentamine (TEPA) and/or N-methyldiethanolamine (MDEA) was introduced into the hard segment as chain extenders of the series urethane polymer (PU), urea-urethane polymer (PUU), and segmented urethane/urea-urethane copolymer (SPU) based on 4,4'-diphenylmethane &isocyanate (MDI) and either poly(ethy1ene glycol (PEG)-400 or -600. The obtained polymers thus contained a nearly equal weight composition of both soft and hard segments and were prepared as polymer membranes for permeation and sorption of COP. The properties of the polymer membranes were characterized using a Fourier transform IR spectrophotometer, thermal gravimetric analysis, and rheometric measurement. The permeation and sorption isotherms as a function of temperature and pressure as well as the activation energy of permeability and diffusivity and the enthalpy change of the solution were measured. The test temperatures were carried out above and below the Tgs of soft-segment domains or the Tgh of hard-segment domains. The steady-state permeability ( P ) and diffusion coefficients ( D ) obtained ranged from 1.01 to 12.9 barrer and 1.04 to 4.04 cm2/s, respectively, and the solubility coefficients ( S ) , from 0.529 to 3.43 cm3(STP)/cm3 polymer-atm at 10 atm and 35OC. The TEPA-containing polymer membranes showed a smaller P and D but a larger S than did MDEA-containing ones. The membranes comprising PEG-600 exhibit the values of P, D, and S at about 11.5-, 2.5-, and 4.5-fold the PEG-400 ones, respectively. For SPU membranes, above Tgs or T g h , the pressure dependencies of P followed the modified free-volume model. On the other hand, below Tg8, they exhibited a minimum permeability at a certain pressure caused by the plasticization action of sorbed COP. The sorption isotherms of CO, indicated that the membranes comprising PEG-400 can be described by a dual-mode sorption model below Tgs. Also, the SPU polymer membranes obied the Henry's law above Tgs as well as Tgh. The characteristic constants of the sorption model were also determined and are discussed.