Polyurethane networks, shear modulus

Gel Point and Shear Modulus. Trifunctional and tetrafunc-tional polyurethane(25,26,28) and trifunctional polyester net-works (32) have been studied. The gelation data for the reaction systems forming the polyurethane networks were those discussed with reference to Figure 6 and Table II. 

Table IV. Shear modulus and Tg of polyurethane networks prepared from bulk reactios (29). G(298K) - shear modulus at 298K, (a) from uniaxial...

The equilibrium shear modulus of two similar polyurethane elastomers is shown to depend on both the concentration of elastically active chains, vc, and topological interactions between such chains (trapped entanglements). The elastomers were carefully prepared in different ways from the same amounts of toluene-2,4-diisocyanate, a polypropylene oxide) (PPO) triol, a dihydroxy-terminated PPO, and a monohydroxy PPO in small amount. Provided the network junctions do not fluctuate significantly, the modulus of both elastomers can be expressed as c( 1 + ve/vc)RT, the average value of vth>c being 0.61. The quantity vc equals TeG ax/RT, where TeG ax is the contribution of the topological interactions to the modulus. Both vc and Te were calculated from the sol fraction and the initial formulation. Discussed briefly is the dependence of the ultimate tensile properties on extension rate. 

Experimental results on reactions forming tri- and tetrafunctional polyurethane and trifunctional polyester networks are discussed with particular consideration of intramolecular reaction and its effect on shear modulus of the networks formed at complete reaction. The amount of pre-gel intramolecular reaction is shown to be significant for non-linear polymerisations, even for reactions in bulk. Gel-points are delayed by an amount which depends on the dilution of a reaction system and the functionalities and chain structures of the reactants. Shear moduli are generally markedly lower than those expected for the perfect networks corresponding to the various reaction systems, and are shown empirically to be closely related to amounts of pre-gel intramolecular reaction. Deviations from Gaussian stress-strain behaviour are reported which relate to the low molar-mass of chains between junction points. 

Neither the uniform strain model nor the uniform stress model is appropriate for this microstructure. Consequently, the elastic moduli of polyurethanes lie between the limits set by Eqs (4.11) and (4.12). For a network chain of Me = 6000, the rubber elasticity theory of Eq. (3.20) predicts a shear modulus of about 0.4 MPa. The hard blocks will have the typical 3GPa Young s modulus of glassy polymers. Increases in the hard block content cause the Young s modulus to increase from 30 to 500 MPa (Fig. 7.13). For automobile panel applications it is usual to have a high per cent of hard blocks so that the room temperature flexural modulus is 500 MPa. 

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