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Network structure and reaction mechanisms in high pressure and peroxide vulcanization of polybutadiene: Microstructural changes studied by 13 C solid‐state NMR
Author(s) -
Bellander Martin,
Stenberg Bengt,
Persson Sture
Publication year - 1999
Publication title -
journal of applied polymer science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.575
H-Index - 166
eISSN - 1097-4628
pISSN - 0021-8995
DOI - 10.1002/(sici)1097-4628(19990929)73:14<2799::aid-app2>3.0.co;2-5
Subject(s) - vulcanization , polybutadiene , peroxide , reaction mechanism , materials science , polymer chemistry , hydroxyl terminated polybutadiene , carbon black , elastomer , solid state , natural rubber , chemical engineering , chemistry , composite material , polymer , organic chemistry , copolymer , catalysis , engineering
This article is concerned with the microstructural changes during peroxide and high pressure vulcanization of polybutadiene that is unfilled and filled with carbon black. The main tool is 13 C solid‐state NMR; it shows that vinyl unsaturations are consumed in both filled and unfilled samples under peroxide and high pressure vulcanization. Chemical shift calculations of unvulcanized polybutadiene show good agreement with the observed peaks. Calculations of proposed structures, based on a possible reaction mechanism, suggest that a large number of peaks will appear, each at very low intensity. Nevertheless, some changes can be seen as a result of the crosslinking reaction, and the results provide support for the suggested reaction mechanism. Thus, the proposed addition crosslinking mechanism over vinyl unsaturations seems to be a reasonable explanation of the crosslink formation in high pressure vulcanization. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2799–2806, 1999