Modulus changes copolymerization

T and are the glass-transition temperatures in K of the homopolymers and are the weight fractions of the comonomers (49). Because the glass-transition temperature is directly related to many other material properties, changes in T by copolymerization cause changes in other properties too. Polymer properties that depend on the glass-transition temperature include physical state, rate of thermal expansion, thermal properties, torsional modulus, refractive index, dissipation factor, brittle impact resistance, flow and heat distortion properties, and minimum film-forming temperature of polymer latex... 

Plasticizer and Copolymerization change the glass transition temperature as discussed in Chapter 1. Plasticixers have little effect on Copolymerization can change although less strongly than 7 x. As a result, the basic modulus-temperature and modulus-time curves are shifted as shown in Figure 8 for different compositions. The shift in the modulus-temperature curve is essentially the same as the shift in TK. The shift in the modulus-time curve includes this plus the effect of any change in ()jr... 

The photoelastic behavior of nonionized PAAm network and ionized P(AAm/MNa) network prepared by the copolymerization of AAm with MNa ( MNa = 0.05) was investigated in water-acetone mixtures [31]. For a pure PAAm network, the dependences of all photoelastic functions (see Eqs. (15) and (16)), i.e. modulus G, strain-optical function A and stress-optical coefficient C, on the acetone concentration in the mixtures are continuous (Fig. 17). At ac = 54 vol %, the ionized network undergoes a transition which gives rise to jumpwise change in G, A and C also the refractive index of the gel n8 changes discontinuously. While in the collapsed state the optical functions A and C are negative, in the expanded state they are positive. 

These cyclics can change the properties of the network in which they are trapped. Because they restrict to some extent the motions of the network chains, they should increase the modulus of an elastomer. Some small but possibly significant increases in low-deformation moduli have, in fact, been observed [192], Also, when PDMS cyclics are trapped in a thermoplastic material, they can act as a plasticizer that is in a sense intermediate to the usual external (dissolved) and internal (copolymerized) varieties. Interesting changes in mechanical properties have been observed in materials of this type [197]. 

If La " acts merely to increase the glass transition temperature, as a result of copolymerization then the "rubbery modulus of the material should not necessarily change if, on the other hand, it does crosslink the material, then the rubbery modidus should change in a manner predicted by the kinetic theory. 

Novel sulfonated and carboxylated ionomers having "blocky" structures were synthesized via two completely different methods. Sulfonated ionomers were prepared by a fairly complex emulsion copolymerization of n-butyl acrylate and sulfonated styrene (Na or K salt) using a water soluble initiator system. Carboxylated ionomers were obtained by the hydrolysis of styrene-isobutyl-methacrylate block copolymers which have been produced by carefully controlled living anionic polymerization. Characterization of these materials showed the formation of novel ionomeric structures with dramatic improvements in the modulus-temperature behavior and also, in some cases, the stress-strain properties. However no change was observed in the glass transition temperature (DSC) of the ionomers when compared with their non-ionic counterparts, which is a strong indication of the formation of blocky structures. 

Because sporting goods are used by humans, they must be stable at the temperatures at which they will be used. If glass transition temperature (which is due to the molecular motion of polymer chains) is to he used as the energy absorption mechanism, the sudden change in modulus at the glass transition often causes unstable properties. If other viscoelastic properties are to be used for energy absorption, it is necessary either to copolymerize monomers or to mix polymers of different mohilities [6] (see Fig. 5) [7]. 

---