Polydisperse reaction

Comonomer is exhausted at relatively low conversion (20), but a random copolymer is nevertheless obtained. This is because a very facile transacetalisation reaction allows for essentially random redistribution of the comonomer units (18) and also results in a polydispersity index near 2.0 (21). 

The minimum polydispersity index from a free-radical polymerization is 1.5 if termination is by combination, or 2.0 if chains ate terminated by disproportionation and/or transfer. Changes in concentrations and temperature during the reaction can lead to much greater polydispersities, however. These concepts of polymerization reaction engineering have been introduced in more detail elsewhere (6). 

Most of the LFRP research ia the 1990s is focused on the use of nitroxides as the stable free radical. The main problems associated with nitroxide-mediated styrene polymerizations are slow polymerization rate and the iaability to make high molecular weight narrow-polydispersity PS. This iaability is likely to be the result of side reactions of the living end lea ding to termination rather than propagation (183). The polymerization rate can be accelerated by the addition of acids to the process (184). The mechanism of the accelerative effect of the acid is not certain. 

Issues to be considered in selecting the best stabilizing system are polymeric chain branching which increases with high temperature and the presence of some stabilizers, polydispersity of the particles produced, and grafting copolymerization, which may occur because of the reaction of vinyl acetate with emulsifiers such as poly(vinyl alcohol) (43,44). 

Assuming that no intramolecular or side reactions take place and that all groups are equireactive, the polydispersity index, 7P, of hyperbranched polymers obtained by step-growth polymerization of ABX monomers is given by Eq. (2.2), where pA is die conversion in A groups.196 Note that the classical Flory relationship DPn = 1/(1 — pa) holds for ABX monomer polymerizations ... 

Furthermore, the reaction scheme implies that the molecular weight distribution is Poisson-like — i.e. very narrow — as it had been shown earlier on theoretical basis by Flory 8), Gold 9), and Szwarc l0>. Even though two (or more) types of active species add monomer at very different rates, the polydispersity remains narrow, provided solvation/desolvation and ionic dissociation/association processes are fast U). 

The inlet monomer concentration was varied sinusoidally to determine the effect of these changes on Dp, the time-averaged polydispersity, when compared with the steady-state case. For the unsteady state CSTR, the pseudo steady-state assumption for active centres was used to simplify computations. In both of the mechanisms considered, D increases with respect to the steady-state value (for constant conversion and number average chain length y ) as the frequency of the oscillation in the monomer feed concentration is decreased. The maximum deviation in D thus occurs as lo 0. However, it was predicted that the value of D could only be increased by 10-325S with respect to the steady state depending on reaction mechanism and the amplitude of the oscillating feed. Laurence and Vasudevan (12) considered a reaction with combination termination and no chain transfer. 

To run the residence time distribution experiments under conditions which would simulate the conditions occurring during chemical reaction, solutions of 15 weight percent and 30 percent polystyrene in benzene as well as pure benzene were used as the fluid medium. The polystyrene used in the RTD experiment was prepared in a batch reactor and had a number average degree of polymerization of 320 and a polydispersity index, DI, of 1.17. 

Silane radical atom transfer (SRAA) was demonstrated as an efficient, metal-free method to generate polystyrene of controllable molecular weight and low polydispersity index values. (TMSlsSi radicals were generated in situ by reaction of (TMSlsSiH with thermally generated f-BuO radicals as depicted in Scheme 14. (TMSlsSi radicals in the presence of polystyrene bromide (PS -Br), effectively abstract the bromine from the chain terminus and generate macroradicals that undergo coupling reactions (Reaction 70). 

Example 13.3 The conversion of a self-condensing reaction can be limited to give polymers with finite lengths. How does the polydispersity of these polymers compare with those in Example 13.2 where the reaction went to completion with imperfect stoichiometry Make the comparison at the same average chain length. 

The interest in hyperbranched polymers arises from the fact that they combine some features of dendrimers, for example, an increasing number of end groups and a compact structure in solution, with the ease of preparation of hn-ear polymers by means of a one-pot reaction. However, the polydispersities are usually high and their structures are less regular than those of dendrimers. Another important advantage is the extension of the concept of hyperbranched polymers towards vinyl monomers and chain growth processes, which opens unexpected possibilities. 

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