Novel Novolac-Phthalonitrile and Siloxane-Phthalonitrile Resins cured with low melting Novolac Oligomers for Flame Retardant Structural Thermosets

The chemical modification of low molecular weight novolac oligomers and siloxane/silane-containing monomers has led to novel phthalonitrile derivatives with low glass transition temperatures, ranging from -25 to 75 ºC. Multi-functional, low molecular weight phenol-formaldehyde novolac resins were blended with these novel phthalonitrile derivatives to achieve low viscosity resin blends. Moderate temperatures and rapid curing cycles were employed (200 ºC, 1 h and 225 ºC, 4h) to produce networks with high glass transition temperatures (> 250 ºC). A decrease in the sharp band at 2230 cm⁻¹, attributed to the nitrile functionality of the phthalonitrile resin, was monitored in FTIR studies and indicated the progress of the reactions. Ninety percent conversion was achieved within ~ 30 min. Thermal analysis of siloxane-phthalonitrile/novolac networks cured for 1h at 200 ºC and 4h at 225 ºC did not exhibit glass transition temperatures below 250 ºC. In dynamic TGA studies, 5% weight loss temperatures up to 418 ºC were observed, and the materials exhibited 50 to 56 % char at 800 ºC in nitrogen. Networks prepared from a resin blend containing 50 weight% of a phthalonitrile derivative of a 260 g mol⁻¹ novolac oligomer, 50 weight% of the 260 g mol⁻¹ novolac oligomer, and 1.5 mol % triphenylphosphine (based on novolac) (NOV/NOV/TPP) cured at 200 ºC for 1h, did not exhibit a Tg below 250 ºC via DSC. These networks exhibited a 5% weight loss temperature of 350 ºC, and 70 % char at 800 ºC in TGA studies under nitrogen. This degree of char formation makes these materials appealing for use in carbon-carbon composites. Post-curing these networks at 200 ºC for 1h, and then at 225 ºC for 4h, resulted in high thermo-oxidative stability, with a 5% weight loss observed at 447 ºC and 50 % char at 800 ºC. Blending tetramethyldisiloxane phthalonitrile monomers with 260 g mol⁻¹ novolac oligomers afforded prepolymer resins with low melt viscosities, 560 mPa s at 80 ºC. Such viscosities may allow these resins to be processed via vacuum assisted resin transfer molding (VARTM) at low temperatures and heated at elevated temperatures to produce flame resistant three-dimensional networks.

Name thesis:degree_name

Master of Science

Level thesis:degree_level

masters

Discipline thesis:degree_discipline

Chemistry

Department dc:contributor.department

Chemistry

Grantor dc:publisher

Virginia Tech

Year dc:date.issued

2003

Author dc:creator

• Hardrict, Shauntrece Nicole

Chair dc:contributor.committeechair

• Riffle, Judy S.

Committee members dc:contributor.committeemember

• Esker, Alan R.
• McGrath, James E.

• novolac
• phenolic networks
• phthalonitrile
• flame retardance
• composite matrix

Statement dc:rights

• In Copyright

Licence dc:rights.uri

• http://rightsstatements.org/vocab/InC/1.0/

Dc Identifier Other

etd-01012004-153124

OAI identifier oai:identifier

oai:vtechworks.lib.vt.edu:10919/9669