Anionic Polymerization - download pdf or read online

By L. J. Ferry

ISBN-10: 0387127925

ISBN-13: 9780387127927

This exhaustive reference textual content systematically introduces the fundamental theories and experimental tools of anionic polymerization in addition to the synthesis, research, and features of anionically polymerized items.

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141) were the first to study the poty(butadienyl)lithium anionic chain end using (b). They found no evidence of 1,2-chain ends and concluded that only t,4-structures having the lithium cy-bonded to the terminal carbon were present. A later study by Bywater et al. 6:1. Glaze et al. 36) obtained a highly resolved spectrum of neopentylallyllithium in toluene and found a cis :trans ratio of about 3:1. Bywater et al. 17 at --40 °C; calculation shows that this corresponds to an en-thalpy change of ca.

0 Ib@ exchange reaction; (RLi)z + R ' L i • T M E D A ~ ( R L i • R ' L i ) + R L i • T M E D A (40) o n the premise that t w o m o l e c u l e s o f T M E D A c o m p l e x and dissociate one dimer. It w o u l d b e e x p e c t e d t h a t the r a t e o f p o l y m e r i z a t i o n w o u l d reach an u p p e r (or lower) limit w h e n r = t unless a still m o r e (or less) reactive c o m p l e x c o n t a i n i n g a greater p r o p o r t i o n o f T M E D A c a n be f o r m e d at still h i g h e r values o f r.

T m) concentrations. These results of Glaze are in general accord with those of Makowski and Lynn 41~ who also found (via viscosity measurements) that the poly(butadienyl)lithium active center can exhibit a variable degree of aggregation. Furthermore, several of Worsfold's assessments seem to be open to question. The assertion that "the association (between the aUylic-lithium active centers) is between ionic species" can be contrasted with the evidence provided by NMR spectroscopy 36,134-143) which has shown that the carbon-lithium bond of allyliclithium species can possess considerable covalent character.

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Anionic Polymerization by L. J. Ferry

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