Double glass transition temperature

The blends of polysulfone with the a-methyl styrene polymers are immiscible, as evidenced by the double glass-transition temperatures in Table II. To improve the miscibility characteristics, polysulfone was modified in two ways. First, 25% of the bisphenol A was replaced by monomer I which contains a pendant ester group and, when no improvement resulted, the whole 50% of the bisphenol A was replaced. Again, the blends remain immiscible as evidenced from Figures 4 and 5 and from Table II. Further, the presence of the pendant ester group in polymer C does not improve the miscibility picture even though one would expect a favorable contribution from the carbonyl group on account of the miscibility of polycarbonate with the a-methyl styrene polymers. 

Inclusion of double bonds will stiffen the chain at the point of inclusion but at the same time may increase the flexibility of adjacent bonds. The net effect may therefore be to reduce the glass transition temperature and this appears to occur in 1,4-polybutadiene when compared with polyethylene. 

Polyisobutylene has a similar chemical backbone to butyl rubber, but does not contain double carbon-carbon bonds (only terminal unsaturation). Many of its characteristics are similar to butyl rubber (ageing and chemical resistance, low water absorption, low permeability). The polymers of the isobutylene family have very little tendency to crystallize. Their strength is reached by cross-linking instead of crystallization. The amorphous structure of these polymers is responsible for their flexibility, permanent tack and resistance to shock. Because the glass transition temperature is low (about —60°C), flexibility is maintained even at temperatures well below ambient temperature. 

The key to a controlled molecular weight build-up, which leads to the control of product properties such as glass transition temperature and melt viscosity, is the use of a molar excess of diisopropanolamine as a chain stopper. Thus, as a first step in the synthesis process, the cyclic anhydride is dosed slowly to an excess of amine to accommodate the exothermic reaction and prevent unwanted side reactions such as double acylation of diisopropanolamine. HPLC analysis has shown that the reaction mixture after the exothermic reaction is quite complex. Although the main component is the expected acid-diol, unreacted amine and amine salts are still present and small oligomers already formed. In the absence of any catalyst, a further increase of reaction temperature to 140-180°C leads to a rapid polycondensation. The expected amount of water is distilled (under vacuum, if required) from the hot polymer melt in approximately 2-6 h depending on the anhydride used. At the end of the synthesis the concentration of carboxylic acid groups value reaches the desired low level. 

Figure 30. Double-log plot of the spin-glass transition temperature, Tg, versus mole fraction of dopant for Co2+ CdSe nanocrystals. [Adapted from (70).]...

The relationship between Tg and molecular weight, M, is often described by the Fox and Flory equation 266 Tg = T/XJ - K/M, where T/XJ is the glass transition temperature of the polymer with infinite molecular weight and K is a constant characteristic of the polymer. For the malto-oligomer series, a double reciprocal plot of... 

Ethylene-norbornene copolymers, which have thermoplastic properties when heated above their glass transition temperatures of ca. 200-250°C, have been commercialized by Ticona GmbH under the trade name TOPAS (Tliermoplas-tic Olefin Polymer of Amorphous Structure). Their properties - exceptional transparency, low double refraction, high stiffnes and hardness, low permeability for moisture and excellent biocompatibility - make these ethylene-norbornene copolymers particularly valuable as engineering polymers, for optical applications and as materials for food and medical packaging. 

Acrylate rubbers which are employed in ASA contain no double bonds. For that reason, ASA is substantially more resistant to weathering than ABS. Owing to the polar acrylate component, ASA is also more resistant to stress cracking than ABS. ABS in turn has significant advantages in low-temperature impact resistance on account of the very low glass transition temperature of the polybutadiene rubber. 

A real example of the effect of temperature on the viscoelastic functions at T > Tg is shown in Figure 8.2. Here double logarithmic plots of the compliance function J t) versus time are shown at several temperatures for a solution of polystyrene My — 860,000) in tri-ra-tolyl phosphate (1) in which the weight fraction of polymer is 0.70. Because the glass transition temperature of the solution is 15°C, the isotherms were registered at... 

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