Block copolymers glass transition temperature

The reactions of polyols, diisocyanates, and glycols, as described, do tend to produce block copolymers in which hard blocks with glass transition temperatures well above normal ambient temperature are separated by soft rubbery blocks. These polymers thus resemble the SBS triblock elastomers and, more closely, the polyether-ester thermoplastic elastomers of the Hytrel-type described earlier. 

Whereas random copolymers exhibit one T described by equation 38, block copolymers, because of this microphase separation, exhibit two glass-transition temperatures. The T of each block is close to, if not the same as, the homopolymer from which it was formed. Polymer properties are also affected by the arrangement of the blocks. This is shown for high styrene-containing or high molecular-weight styrene resias of various block arrangements ia Table 3. 

The most desirable annealing temperatures for amorphous plastics, certain blends, and block copolymers is just above their glass transition temperature (Tg) where the relaxation of stress and orientation is the most rapid. However, the required temperatures may cause excessive distortion and warping. 

Preparation and thermal crosslinking reactions of oc, -vinylbenzyl terminated polysulfone-b-polydimethylsiloxane, ABA type block copolymers have been discussed 282,313) However, relatively little characterization was reported. Molecular weights of polysulfone and PDMS segments in the copolymers were varied between 800-8,000 and 500-11,000 g/mole, respectively. After thermal curing, the networks obtained showed two phase morphologies as indicated by the detection of two glass transition temperatures (—123 °C and +200 °C) corresponding to PDMS and polysulfone phases, respectively. No mechanical characterization data were provided. 

Reactive compatibilization can also be accomplished by co-vulcanization at the interface of the component particles resulting in obliteration of phase boundary. For example, when cA-polybutadiene is blended with SBR (23.5% styrene), the two glass transition temperatures merge into one after vulcanization. Co-vulcanization may take place in two steps, namely generation of a block or graft copolymer during vulcanization at the phase interface and compatibilization of the components by thickening of the interface. However, this can only happen if the temperature of co-vulcanization is above the order-disorder transition and is between the upper and lower critical solution temperature (LCST) of the blend [20]. 

Various substituted styrene-alkyl methacrylate block copolymers and all-acrylic block copolymers have been synthesized in a controlled fashion demonstrating predictable molecular weight and narrow molecular weight distributions. Table I depicts various poly (t-butylstyrene)-b-poly(t-butyl methacrylate) (PTBS-PTBMA) and poly(methyl methacrylate)-b-poly(t-butyl methacrylate) (PMMA-PTBMA) samples. In addition, all-acrylic block copolymers based on poly(2-ethylhexyl methacrylate)-b-poly(t-butyl methacrylate) have been recently synthesized and offer many unique possibilities due to the low glass transition temperature of PEHMA. In most cases, a range of 5-25 wt.% of alkyl methacrylate was incorporated into the block copolymer. This composition not only facilitated solubility during subsequent hydrolysis but also limited the maximum level of derived ionic functionality. 

The nature of the hard domains differs for the various block copolymers. The amorphous polystyrene blocks in the ABA block copolymers are hard because the glass transition temperature (100°C) is considerably above ambient temperature, i.e., the polystyrene blocks are in the glassy state. However, there is some controversy about the nature of the hard domains in the various multiblock copolymers. The polyurethane blocks in the polyester-polyurethane and polyether-polyurethane copolymers have a glass transition temperature above ambient temperature but also derive their hard behavior from hydrogen-bonding and low levels of crystallinity. The aromatic polyester (usually terephthalate) blocks in the polyether-polyester multiblock copolymer appear to derive their hardness entirely from crystallinity. 

PVA Particles. Dispersions were prepared in order to examine stabilization for a core polymer having a glass transition temperature below the dispersion polymerization temperature. PVA particles prepared with a block copolymer having M PS) x 10000 showed a tendency to flocculate at ambient temperature during redispersion cycles to remove excess block copolymer, particularly if the dispersion polymerization had not proceeded to 100 conversion of monomer. It is well documented that on mixing solutions of polystyrene and poly(vinyl acetate) homopolymers phase separation tends to occur (10,11), and solubility studies (12) of PS in n-heptane suggest that PS blocks with Mn(PS) 10000 will be close to dissolution when dispersion polymerizations are performed at 3 +3 K. Consequently, we may postulate that for soft polymer particles the block copolymer is rejected from the particle because of an incompatibility effect and is adsorbed at the particle surface. If the block copolymer desorbs from the particle surface, then particle agglomeration will occur unless rapid adsorption of other copolymer molecules occurs from a reservoir of excess block copolymer. 

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