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Odian Book 2-12. Common Engineering Thermosets (Not elastomers). Bismaleimides Epoxies Phenol / Formaldehyde Sheet Molding Compound Polyurethanes** **Also thermoplastics. Step & Chain Growth. Step & Chain Growth. Step Growth. Chain Growth. Step Growth. Epoxy Systems.
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Odian Book 2-12
Common Engineering Thermosets(Not elastomers) • Bismaleimides • Epoxies • Phenol / Formaldehyde • Sheet Molding Compound • Polyurethanes** **Also thermoplastics Step & Chain Growth Step & Chain Growth Step Growth Chain Growth Step Growth
Epoxy Systems f = 2 “Tube A” f = 4 “Tube B” Mechanism Network
Advantageous Properties of epoxies High chemical and solvent resistance Outstanding adhesion to many substrates Good impact resistance Good electrical properties Epoxy Systems
Epoxy Systems f = 2 “Tube A” f = 4 “Tube B” Network
Epoxy Systems Diglycidal Ether of Bisphenol-A (DGEBA)
Epichlorohydrin: Background Chlorine intensive - 4 atoms of chlorine/epi Yields: - chlorination: 82% - HOCl and closure: 92% Byproducts: - chlorinated organics Hydraulic load: - 47 lbs water/lb of epi
Epoxy Systems <Mn> ≈ 15,000 – 20,000 g/mol Viscous liquid to solid
Polyurethanes and Polyureas • Thermoplastics • Thermosets
Important Starting Materials for Polyurethanes Relative rates 30,000x • Diisocyantes • Polymeric Glycols (aka polyols) • MW < 3,000 g/mol • Chain extenders • Catalysts • Trialkyl tin acetate • Dialkyl tin diacetate
Diisocyanates • Diphenylmethane diisocyanate (MDI) • Toluene diisocyanate (TDI) • Dicyclohexylmethane diisocyanate (H-MDI) • Hexamethylene diisocyanate (HDI) • Cycloaliphatics
Diisocyanates • Phosgenation
Chain Extenders • For urethanes • For ureas
Polyurethane Fibers Excess Pre-polymer Chain extenders
Phenol Formaldehyde Resins • 1872 – Invented by Bayer • 1907 – First patent and commercial process by Baekeland • Success: First wholly synthetic polymer used commercially
Phenol Formaldehyde Resins • Excellent thermal stability • High char yield • Low smoke generation • Low smoke toxicity
Base-Catalyzed Phenol-Formaldehyde Resins (Resols) • Base catalyzed • Excess formaldehyde • Resols cure with heat alone
Base-Catalyzed Phenol-Formaldehyde Resins (Resols) • Excess formaldehyde • Resols cure with heat alone
Base-Catalyzed Phenol-Formaldehyde Resins (Resols) • Cure of resole prepolymer proceeds under neutral or acidic conditions and at elevated temperature. • Crosslinking occurs via the continued formation of methylene links and the formation of dibenzyl ether linkages. • Higher temperatures favor the formation of methylene bridges • Both are condensation reactions and produce water
Acid-Catalyzed Phenol-Formaldehyde Resins (Novolacs) • Acid Catalyzed • Excess phenol • No hydroxy methyl groups • Tg = 40 C • MW = 1 – 3000 g/mol • Require second additive for cure • Hexamethylene tetraamine