Diisocyanate modulus

In this contribution, we report equilibrium modulus and sol fraction measurements on diepoxidet-monoepoxide-diamine networks and polyoxypropylene triol-diisocyanate networks and a comparison with calculated values. A practically zero (epoxides) or low (polyurethanes) Mooney-Rivlin constant C and a low and accounted for wastage of bonds in elastically inactive cycles are the advantages of the systems. Plots of reduced modulus against the gel fraction have been used, because they have been found to minimize the effect of EIC, incompleteness of the reaction, or possible errors in analytical characteristics (16-20). A full account of the work on epoxy and polyurethane networks including the statistical derivation of various structural parameters will be published separately elsewhere. 

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. 

Studies have been made of the elastic (time-independent) properties of single-phase polyurethane elastomers, including those prepared from a diisocyanate, a triol, and a diol, such as dihydroxy-terminated poly (propylene oxide) (1,2), and also from dihydroxy-terminated polymers and a triisocyanate (3,4,5). In this paper, equilibrium stress-strain data for three polyurethane elastomers, carefully prepared and studied some years ago (6), are presented along with their shear moduli. For two of these elastomers, primarily, consideration is given to the contributions to the modulus of elastically active chains and topological interactions between such chains. Toward this end, the concentration of active chains, vc, is calculated from the sol fraction and the initial formulation which consisted of a diisocyanate, a triol, a dihydroxy-terminated polyether, and a small amount of monohydroxy polyether. As all active junctions are trifunctional, their concentration always... 

Diluent added during crosslinking has two main effects it Increases the population of elastically Inactive cycles and it weakens the interchain constraints. Studies of poly(oxypropylene) triol-diisocyanate networks in the presence of diluent have shown that the effect of diluent on the equilibrium modulus is much stronger than would correspond to the effect of cycles (Figure 10) (32) which again corroborates the concept of permanent interchain constraints. 

Thus, at zero equilibrium modulus we can write for a three-component binder consisting of a known crosslinker (assume f = 3.0), a known diisocyanate (assume f = 2.0) and a prepolymer of unknown functionality f ... 

Early work published in Saunders and Frisch, Volume II (Saunders 1962) shows how various properties change different diisocyanate-to-polyol ratios. As the NCO/OH ratio increases from 2 to 2.75, the main physical properties of tensile strength, modulus, tear strength, and hardness increase. Other positive improvements are compression set and resilience. The pot life and... 

Tan delta(S) TDI Tear strength material from its surface. Usually expressed in milligrams loss per number of cycles per a given load. The viscous modulus/elastic modulus. An abbreviation for toluene diisocyanate. The maximum force required to tear a specified specimen, the force acting mainly parallel to the major axis of the test specimen. 

Above the -relaxation process, the 2,4-TDI/PTMO polymer displayed a short rubbery plateau at a storage modulus of about 5 MPa while 2,6-TDI/PTMO was capable of crystallization, as evidenced by the ac-loss process. This difference in dynamic mechanical properties demonstrates the effect of a symmetric diisocyanate structure upon soft-segment properties. As previously discussed, single urethane links can sometimes be incorporated into the soft-segment phase. The introduction of only one of these diisocyanate molecules between two long PTMO chains inhibits crystallization if the diisocyanate is asymmetric. In the case of a symmetric diisocyanate, soft-segment crystallization above Tg can readily occur. The crystals formed were found to melt about 30°C below the reported melting point for PTMO homopolymer, 37°-43°C (19), possibly because of disruption of the crystal structure by the bulky diisocyanate units. 

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.

However, PLA can be pol5merized with diisocyanates to form poly(ester-urethane)s or with caprolactones to form poly(L-lactic acid-co-e-caprolactone-urethane)s. Such copolymers can be tailored as hard plastics or flexible elastomers and can have unique glass transition temperatures from -70°C to +60°C, tensile modulus from 2 MPa to 2000 MPa, and % strain from 1% to about 1000% (2). 

The treatment of wood fibres with isocyanate-bearing molecules and their incorporation into polyethylene were also recently studied [44]. In particular, the use of poly-(diphenylmethane diisocyanate) (XV) increased both the modulus of rupture (MOR) and the modulus of elasticity (MOE) of the ensuing composites. The use of stearic anhydride (XVI) as a novel compatibilizer further improved both MOR and MOE and enhanced the water resistance of the composites. 

---