Glass transition temperature hard segment

Figure 5. Dynamic shear modulus-temperature behavior (torsion pendulum, 1 Hz) of 50% w/w HS copolyurethanes based on diisocyanates FDI-a (F) and MDI (M). Soft segment glass transition and hard-segment melting are in the temperature regions indicated, respectively, by and Tm.

The melt temperature of a polyurethane is important for processibiUty. Melting should occur well below the decomposition temperature. Below the glass-transition temperature the molecular motion is frozen, and the material is only able to undergo small-scale elastic deformations. For amorphous polyurethane elastomers, the T of the soft segment is ca —50 to —60 " C, whereas for the amorphous hard segment, T is in the 20—100°C range. The T and T of the mote common macrodiols used in the manufacture of TPU are Hsted in Table 2. 

Urethane structural adhesives have a morphology that is inverse to the toughened epoxy just described. The urethanes have a rubber continuous phase, with glass transition temperatures of approximately —50°C. This phase is referred to as the .soft segment . Often, a discontinuous plastic phase forms within the soft segment, and that plastic phase may even be partially crystalline. This is referred to as the hard segment . A representation of the morphology is shown in Fig. 3 [34]. 

When chain segments can move relatively freely in cured polymers, it is most likely due to low crosslink density or the mobility of the molecular chain structure. The glass transition temperature is a measure of the mobility of the molecular chains in the polymer network as a function of temperature. The glass transition is the reversible change in a polymer from (or to) a rubbery condition to (or from) a hard and relatively glassy state condition (Fig. 3.14). This transition occurs at a temperature called the glass transition temperature or Tg. It is... 

Table I. Soft-Segment, Glass-Transition-Temperature Dependence on Hard-Segment Content for PTMO/MDI/BD(ET) - and PTMA/MDI/BD (ES) -Segmented Copolymers...

Figure 4. The large broad "maximum" in the loss tangent isotherm of 73-19 polyurethane adhesive at 40 C is attributed to hard segment development. This peak is not observed above 50 C because the hard segment glass transition temperature has been exceeded.

One further phenomena observed In all 73 systems Is the decrease In opacity on curing at elevated temperatures. Above about 60 C the poly(tetramethylene glycol) and excess Isocyanate become miscible. This miscibility may be assisted by the fact that the MDI-BDO hard segments are above their glass transition temperature. To an extent which has not been quantified as yet, llquld-llquld phase separation of MDI and MDI terminated polyol In the prepolymer at low temperatures preslsts Into the final adhesive. The dynamic mechanical behavior of transparent or opaque adhesive, l.e., cured at 60-100 C compared to room temperature are virtually Identical. Similar Immlsclblllty has been observed In other prepolymers (20). This does not appear to adversely affect the adhesive properties of these Halthanes. 

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