Macromolecular Engineering by Carbocationic Techniques: New Polymers That Contain Elastomeric Sequences

The aim of this review was to outline some key concepts the macromolecular engineer can utilize in the task of assembling useful polymers. In addition to useful ultimate properties, convenient processing characteristics are also an important consideration. The way toward these objectives is by skillful combination of elementary events—by exploiting the mechanistic understanding of initiation, propagation, and termination processes. Tables V and VI summarize the processes surveyed and outlines the structures of macromolecules that can be synthesized by utilizing carbocationic macromolecular engineering. Table V summarizes the “Undisturbed” Systems i.e., systems in which only the monomer, initiator and coinitiator appear. Table VI shows the “Disturbed” Systems, i.e., systems in which, in addition to the three main species, others, such as proton traps or inifers, also appear. The Undisturbed Systems are further subdivided into Static and Dynamic (or Continuous) Techniques. Static methods use batch operations while dynamic techniques use continuous feeding of monomer(s). The flow of the examples from the top of Table V to the bottom of Table VI is by increasing complexities of the manipulations involved. Thus, the tables start with examples of materials whose synthesis requires only controlled initiation. In other words, controlled initiation alone will give rise to head-functionalized polymers (H = head group) or macromers or gTaft copolymers or bigrafts. for the materials in the second group of Table V, end-functionalized polymers (E = end group) or certain graft copolymers, only termination control is needed. Next, to prepare polymers whose head and end groups are tailor made, the macromolecular engineer has to combine controlled initiation plus termination. The same is true for grafts whose branches carry designed end groups. Combination of controlled termination plus initiation yields diblock copolymers.