Polyurethane dynamic mechanical temperature

Thermal and thermomechanical analyses44 are very important for determining die upper and lower usage temperature of polymeric materials as well as showing how they behave between diose temperature extremes. An especially useful thermal technique for polyurethanes is dynamic mechanical analysis (DMA).45 Uiis is used to study dynamic viscoelastic properties and measures die ability to... 

Figure 9. Comparison of 11-Hz dynamic mechanical (open points) and DSC or TMA transition temperatures (filled points, Ref. 13) of 2,6-T-lP polyurethanes as a function of hard-segment content...

Dynamic mechanical property (DMP) measurements are used to evaluate the suitability of a polymer for a particular use in sound and vibration damping. Since the dynamic mechanical properties of a polyurethane are known to be affected by polymer morphology (4), it is important to establish the crystallization and melting behavior as well as the glass transition temperature of each polymer. Differential scanning calorimetry (DSC) was used to determine these properties and the data used to interpret the dynamic mechanical property results. 

A more selective approach consists in trying to influence the kinetics of formation of at least one network in this case, the two networks are formed more or less simultaneously, and the resulting morphology and properties can be expected to vary to some extent without changing the overall composition. The same system as previously studied, PUR/PAc, has been utilized in order to prepare a series of in situ simultaneous IPNs (SIM IPNs), by acting essentially on two synthesis parameters the temperature of the reaction medium and the amount of the polyurethane catalyst. Note that the term simultaneous refers to the onset of the reactions and not necessarily to the process. The kinetics of the two reactions are followed by Fourier transform infra-red (FTIR) spectroscopy as described earlier (7,8). In this contribution, the dynamic mechanical properties, especially the loss tangent behavior, have been examined with the aim to correlate the preceding synthesis parameters to the shape and temperature of the transitions of the IPNs. 

For this purpose, the dynamic mechanical properties of a series of 25/75 in situ SIM IPNs have been investigated (Figure 5). With 1% OcSn, the tan 8 vs temperature curve shows a classical shape, as for in situ SEQ IPNs and corroborates the kinetic results two separated transitions, broadened and damped, exist (10). The lower transition corresponding to the polyurethane phase, is shifted... 

A polyurethane (PU)/poly(n-butyl methacrylate) (PBMA) system has been selected for an investigation of the process of phase separation in immiscible polymer mixtures. Within this system, studies are made of the XX, lx, xl, and the 11 forms. In recognition of the incompatibility of PBMA with even the oligomeric soft segment precursor of the PU, no attempt was made to equalize the rates of formation of the component linear and network polymers. Rather, a slow PU formation process is conducted at room temperature in the presence of the PBMA precursors. At suitable times, a relatively rapid photopolymerization of the PBMA precursors is carried out in the medium of the slowly polymerizing PU. The expected result is a series of polymer mixtures essentially identical in component composition and differing experimentally only in the time between the onset of PU formation and the photoinitiation of the acrylic. This report focuses on the dynamic mechanical properties cf these materials and the morphologies seen by electron microscopy. 

The dynamic mechanical relaxations in the high temperature region are very weak and the glass transition was indistinguishable from the melting point (Fig. 4). However, the mechanical properties of polyurethanes with chemically crosslinked hard segments were quite different from uncrosslinked polyurethanes. In the linear adhesives (73-14 and 73-15), the rubbery plateau ends at the melting point of the... 

Figure L The low-temperature dynamic mechanical spectrum of Halthane 73-14 is typical of the 73-series polyurethane adhesives. Two secondary relaxations, Tp and Ty, are shown as peaks in the loss modulus at —100° and —150°C. The soft segment glass transition, Tg(SS), occurs at about —50°C. The frequency of oscillation was held constant during the measurement at 0.1 Hz.

Figure 12. Viscoelastic properties determined by Dynamic Mechanical Analysis at different temperatures for two-component epoxy (black lines B, C, D, F, H, L, M, O and P) and polyurethane (gray lines R and S) adhesives.

The way in which the chemical structure of the various chain extenders of Table 3.16 influences the thermal stability of polyurethane elastomers based on the molecule Capa 225/CHDI/chain extender in the molar ratio 1 2 1, respectively, is given in the following figures and tables. For example, Fig. 3.7 shows the dynamic mechanical thermal properties of a series of the polyurethane elastomers in which the variable is the chain extender. The temperature at which the value of the storage modulus (log E ) changes significantly is considered to indicate the limit of thermal stability of the polyurethane elastomers. 

It is well known that adhesives need to be low-modulus elastomers, so that the resin formulation has to be designed to give, after UV-curing, a soft material with a low glass transition temperature (Fg). Fig. 3 shows some typical elastic modulus E) and tan S profiles recorded by dynamic mechanical analysis for a UV-cured polyurethane-acrylate which is suitable for adhesives applications, based on its E and Tg values. It is quite soft, as shown by its Persoz hardness value of 50 s, on a scale that goes up to 400 s for glassy materials. 

J. L. Illinger, N. S. Schneider and F. E. Karasz, "Low Temperature Dynamic Mechanical Properties of Polyurethane-Polyether Block Copolymers", Poly. Eng. Sci. 1, 25 (1972). 

Abstract This chapter introduces the moisture-induced shape memory effect (SME) observed in supramolecular shape memory polymers, particularly shape memory polyurethane (SMPU), containing pyridine moieties. The moisture absorption of polyurethane networks containing pyridine moeties (PUPy) is discussed followed by an investigation into the effect of relative humidity (RH), temperature, BINA content and MDI-BDO content. The induence of moisture absorption on both the thermal properties and the dynamic mechanical properties of SMPUs is also described, along with the moisture-induced SME mechanism. 

---