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Cationic Host–Guest Polymerization of N ‐Vinylcarbazole and Vinyl Ethers in MCM‐41, MCM‐48, and Nanoporous Glasses
Author(s) -
Spange Stefan,
Gräser Annett,
Huwe Andreas,
Kremer Friedrich,
Tintemann Carsten,
Behrens Peter
Publication year - 2001
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20010903)7:17<3722::aid-chem3722>3.0.co;2-j
Subject(s) - cationic polymerization , nanoporous , polymerization , polymer chemistry , living cationic polymerization , host (biology) , materials science , chemistry , chemical engineering , organic chemistry , radical polymerization , polymer , engineering , ecology , biology
Abstract The synthesis of poly(vinyl ether)s or polyvinylcarbazole under the conditions of constricted geometry can be achieved by means of cationic host–guest polymerisation of the corresponding monomers in the pores of MCM‐41 (pore diameter 3.6 nm), MCM‐48 (pore diameter 2.4 nm) and in nanoporous glasses (Gelsil ® with a pore diameter of 5 nm) with bis(4‐methoxyphenyl)methyl chloride (BMCC) or triphenylmethyl chloride as the internal surface initiator. The reaction products are new polymer/MCM‐41, polymer/MCM‐48 etc., host–guest hybrid materials. The molecular mass of the enclosed polymer and the degree of loading of the host compounds can be adjusted within certain limits. The molecular dynamics were investigated by using broad‐band dielectric spectroscopy. Under the conditions of constricted geometry, molecular fluctuation is observed as well as a secondary β ‐relaxation, which is hardly affected (in comparison with the free melt) and which corresponds to the relaxation between structural substates (dynamic glass transition). This process is several orders of magnitude faster in its relaxation rate than in the free melt and thus follows a confinement effect. This is already well known in lower molecular weight systems with constricted geometry.