Copolymers, crystallization kinetic

Taking all the fact presented in this section into account, together with the synthesis method and fractionation results, we conclude that the purified copolymer separated from reaction products is an iPS-fo-iPP diblock copolymer consisting of iPS and iPP blocks it is definitely not a simple blend of homopolymers. On the other hand, the distinctive characteristics of the copolymers crystallization kinetics also indicate that, compared with homopolymers and the iPS-iPP blend, the purified copolymer is a true iPS-fo-iPP diblock copolymer (23). 

Besides its effects on morphology, comonomer sequence distribution also affects copolymer crystallization kinetics. In statistical copolymers, due to the broad distribution of crystaUizable sequence lengths, bimodal melting endotherms are typically observed. In block copolymers, the dynamics of crystallization have features characteristic of both homopolymer crystallization and microphase separation in amorphous block copolymers. In addition, the presence of order in the melt, even if the segregation strength is weak, hinders the development of the equihbrium spacing in the block copolymer solid-state structure. 

Modified amino acids such as N-acyl-dehydroalanine polymers and copolymers with N-vinyl-N-methyl acetamide seem to be particularly effective [396]. The crystallization kinetics in the presence of polyvinylpyrrolidone and tyrosine have been tested by time-resolved experiments [981]. An influence is evident on the particle size distribution of the hydrate [1433]. 

The crystallization kinetics of commercial polyolefins is to a large extent determined by the chain microstructure [58-60]. The kinetics and the regime [60] of the crystallization process determine not only the crystalline content, but also the structure of the interfaces of the polymer crystals (see also Chapter 7). This has a direct bearing on the mechanical properties like the modulus, toughness, and other end use properties of the polymer in fabricated items such as impact resistance and tear resistance. Such structure-property relationships are particularly important for polymers with high commercial importance in terms of the shear tonnage of polymer produced globally, like polyethylene and polyethylene-based copolymers. It is seen that in the case of LLDPE, which is... 

In order to study the overall crystallization kinetics of the PCL block within PPDX-fo-PCL diblock copolymers, Muller et al. [ 103] first crystallized the PPDX block until saturation by performing a special thermal procedure (it consisted of first cooling from the melt as in Fig. 6 to allow both blocks to crystallize, then the sample was heated to 62 °C and annealed at that temperature for 70 min, a temperature at which the PCL is molten, before quenching to a Tc where the PCL block isothermal crystallization was followed by DSC). With the use of such a procedure the overall isothermal crystallization of only the PCL block was determined in the diblock copolymers where the PPDX block was already crystallized. 

Recently, the isothermal crystallization kinetics of the PE block within SEC triblock copolymers was investigated [94]. When the PE content in the... 

Crystallization from the melt often leads to a distinct (usually lamellar) structure, with a different periodicity from the melt. Crystallization from solution can lead to non-lamellar crystalline structures, although these may often be trapped non-equilibrium morphologies. In addition to the formation of extended or folded chains, crystallization may also lead to gross orientational changes of chains. For example, chain folding with stems parallel to the lamellar interface has been observed for block copolymers containing poly(ethylene), whilst tilted structures may be formed by other crystalline block copolymers. The kinetics of crystallization have been studied in some detail, and appear to be largely similar to the crystallization dynamics of homopolymers. 

As fully described below, sPS has been found to be miscible with aPS, PPE, PYME, TMPC and styrene-l,l-diphenylethylene copolymer. Generally the reported investigations deal with the effect of the second component on crystalline features of sPS, such as polymorphic behavior, crystallization kinetics, morphology and growth rate of crystallites. Just one study reports on toughening sPS by adding suitable components. 

Crystallization in block copolymers has a profound effect on their structure. This review article focusses on the morphology of semicrystalline block copolymers, and those containing two crystallizable blocks. The effect of crystallization on mechanical properties is briefly considered. The extent of chain folding upon crystallization is discussed, as is the orientation of crystal stems with respect to the microstructure. The effect of selective solvent on solution crystallization is also highlighted. Recent work on crystallization kinetics is summarized and finally the theories for crystallization in block copolymers are outlined. 

The question regarding the mechanism(s) of the action of maleated coupling agents was approached via studying the crystallization kinetics in wood-fiber-filled polypropylene in the presence and the absence of a maleated polypropylene copolymer... 

Crystallization Kinetics. Typical isothermal crystallization curves, which were measured using cast films of both types of copolymers, are presented in Figures 9 and 10. At the early stage of crystallization, the effect of the noncrystalline PS block on the rate curves was only shifts of the degree of crystallinity [1 — A(t)] vs. time curve along the time axis. However, the extent of shift does not correspond to PS content in the block copolymers. The change in crystallization temperature also causes the crystallization curves to shift. At the initial stage of crystallization, these rate curves could be superimposed on the rate curve of the homo-PTHF (Mn = 6 X 104), and an Avrami exponent... 

---