Synthesis and Characterization of Poly[(1-trimethylsilyl-1-propyne)-co-(1-(4-azidobutyldimethylsilyl)-1-propyne)] Copolymers

Abstract

Poly(trimethylsilylpropyne) copolymers with bromobutyl side chains were synthesized from 1-trimethylsilyl-1-propyne and 1-(4-bromobutyldimethylsilyl)-1-propyne using a TaCl5/Ph3Bi catalyst system in toluene. After polymerization, azide groups were introduced into the polymers by phase transfer catalysis to yield polyResults from thermal analyses, elemental analyses, and IR spectroscopy confirm that the azide content in the copolymers matches the original comonomer feed ratios. Films of the copolymers were thermally cross-linked in vacuo, with the rate of azide decomposition monitored by the loss of the azide absorption band in the IR. For a copolymer with 15 mol % azide content, an activation energy of 130 kJ/mol was calculated from IR data collected over the azide decomposition temperature range. For the copolymer with the highest azide content (20 mol %), DSC measurements give -1.2 kJ/g for the enthalpy of azide decomposition. Swelling experiments performed on the cross-linked films indicate that a relatively low cross-link density (∼5%) is required to render membranes dimensionally stable in good solvents for the polymer.

Synthesis, Characterization, and Ion Sensing Application of Pyrene‐Containing Chemical Probes

“…Besides, the azide functional polymers ( P4–6 ) depicted a two‐step decomposition pattern. The first one was attributed to the evolution of N 2 gas as a result of thermal decomposition of azide‐functional groups and the second one was the overall thermal decomposition at relatively high temperatures.…”

Design, synthesis and thermal behaviour of a series of well-defined clickable and triggerable sulfonate polymers

“…The data clearly show that the weight loss of the branched polymers, occurring at approximately 150 C (9) and 200 C (11 and 13) in the temperature sweep experiment [ Fig. 4(b) differs from the theoretically calculated values in the case of isobutyl and neopentyl derivatives; 11% and 12% compared to 21% and 25% theoretical values for 11 and 13 (including release of nitrogen from the azide group), 69,70 respectively. The observed weight loss is attributed to removal of the protecting group from the sample.…”

A Facile Strategy for the Preparation of Azide Polymers via Room Temperature RAFT Polymerization by Redox Initiation

“…[2] Azide compounds and polymers are widely used as cross-linking materials, [3,4] high energetic materials, [5][6][7][8][9][10][11] and the materials for surface modification. [12][13][14] Since 2004, ''click'' chemistry has attracted much attention in polymer science, [15] and many functional polymer materials have been synthesized [16] by the click reaction between azido and alkyne groups.…”

“…According to the literatures, azide polymers are commonly prepared by chemical modification of polymers in biphase using sodium azide and chlorinated polymers, [3,9,[20][21][22] and some are obtained by living cationic ring-opening polymerization of cyclic ether azides. [5][6][7][8][9][10][11] However, it is well known that azido content in the polymer produced by chemical modification could not be controlled very well, and ionic polymerization requires stringent reaction conditions such as high purity of monomers and high vacuum techniques.…”