Mechanisms of Decreased Moisture Uptake in Ortho-Methylated Di(cyanate ester) Networks

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• 作者：Andrew J. Guenthner ; Michael E. Wright ; Andrew P. Chafin ; Josiah T. Reams ; Kevin R. Lamison ; Michael D. Ford ; Shawn P. J. Kirby ; Jacob J. Zavala ; Joseph M. Mabry
• 刊名：Macromolecules
• 出版年：2014
• 出版时间：November 25, 2014
• 年：2014
• 卷：47
• 期：22
• 页码：7691-7700
• 全文大小：436K
• ISSN：1520-5835

文摘

Decreases of up to 50% in the moisture uptake of polycyanurate networks based on 2,2-bis(4-cyanatophenyl)propane (BADCy) and 1,1-bis(4-cyanatophenyl)ethane (LECy) were observed when analogous networks containing a single methyl group ortho- to each aryl鈥揷yanurate linkage were prepared by reduction and acid-catalyzed coupling of salicylic acid followed by treatment with cyanogen bromide and subsequent cyclotrimerization. The differences in water uptake were observed despite similar decreases in packing fraction as conversion proceeded in all networks studied. Conversely, the presence or absence of methyl groups at arylene bridges, remote from the cyanurate oxygen, had no influence on water uptake. Vitrification during cure had little effect on either free volume development or moisture uptake. These results confirm that steric hindrance from ortho-methyl groups inhibits absorption of water presumably by decreasing the thermodynamic favorability of sterically permitted interaction with the cyanurate oxygen. A further examination of the effect of two different catalysts, 2 parts per hundred of a 30:1 by weight mixture of nonylphenol and copper(II) acetylacetonate and 500 ppm of dibutyltin dilaurate (DBTDL), compared to analogous uncatalyzed networks, showed that hydrolytic stability was dramatically affected by catalyst choice, while thermochemical stability was also impacted. These results provide important insights into the mechanisms that determine structure鈥損roperty relationships in polycyanurate networks.