Accession Number : ADA616518


Title :   Mechanisms of Decreased Moisture Uptake in ortho- Methylated Di(Cyanate Esters)


Corporate Author : AIR FORCE RESEARCH LAB EDWARDS AFB CA AEROSPACE SYSTEMS DIRECTORATE


Personal Author(s) : Guenthner, Andrew J ; Wright, Michael E ; Chafin, Andrew P ; Reams, Josiah T ; Lamison, Kevin R ; Ford, Michael D ; Kirby, Shawn P ; Zavala, Jacob J ; Mabry, Joseph M


Full Text : https://apps.dtic.mil/dtic/tr/fulltext/u2/a616518.pdf


Report Date : Oct 2014


Pagination or Media Count : 107


Abstract : 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- cyanurate 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 parts per million of dibutyl tin dilaurate (DBTDL), compared to analogous uncatalyzed networks, showed that hydrolytic stability was dramatically affected by catalyst choice, while thermo-chemical stability was also impacted. These results provide important insights into the mechanisms that determine structure-property relationships in polycyanurate networks.


Descriptors :   *CYANATES , *ESTERS , *MOISTURE , ABSORPTION , ACIDS , ARYL RADICALS , BROMIDES , BUTYL RADICALS , CATALYSIS , CATALYSTS , CONVERSION , COPPER , CYANOGEN , HYDROLYSIS , INTERACTIONS , METHYL RADICALS , MIXTURES , NETWORKS , PROPANE , REDUCTION , STABILITY , THERMODYNAMICS , WATER


Subject Categories : Organic Chemistry


Distribution Statement : APPROVED FOR PUBLIC RELEASE