Chapter 15 Basic Polymer Chemistry: Thermosets PHENOL-FORMALDEHYDE POLYMERS (PHENOLIC RESINS) One-Stage Resins First we see the alkaline catalyst with phenol and formaldehyde reacting to form methylolphenols. OH o 9 2 if (+ para attack) ob gand ‘o-methylolphenel (+ p)‘The methylolphenols will react to form di- and trinuclear phenols at still free ortho and para positions. biased get 1.2 Two-Stage Resins ‘The second method, called a “two-stage” process, uses an acid catalyst and excess phenol to give a linear polymer that may be stored or sold. These are called novolacs and have no free methylol groups for cross-linking. OH How on fH .CH;—OH cH=0 + 81,-0n A ‘CH—OH =H", Wy 1H 8 " ny oat Ba upon orn. 22. (0 y - . a on om Cu.Thus in a separate second part of this “two-stage” process a cross-linking agent is added and further reaction occurs. Although formaldehyde may be added, quite often hexamethylenetetramine is used, which decomposes to formaldehyde and ammonia. Occasional nitrogen bridges occur in the final structure of some phenolics made by this method. on CH cH Cly—-NH—CH> é Cite ‘OH HO” H, CHa i HQ oH owe CH: (NH CH, OH ‘CHa ‘CHa a phenolic Other modifications in making phenolics are the incorporation of cresols or resorcinol as the phenol and acetaldehyde or furfural as the aldehyde. OH OH Q a Oe CH OH 0” ‘CH=O cresols resorcinol furfural2. UREA-FORMALDEHYDE POLYMERS (UREA RESINS) Urea will give cross-linked resins with formaldehyde. Methylolureas are formed first under alkaline conditions. © ° ° " 1 Hy= 1 NH)—C—NHp + OH°——» NH - CS SHES, Hy —C— cH —oP + Hho +o 4 1 NHy—C—NH—CH;—OH + OH® Continued reaction under acidic conditions gives a fairly linear, low molecular weight intermediate polymer. Q 8 Q 1 ga SL By MEDCo vii rcion Ee sila By MEE MOH 7 i Salt a NHy—C—NH—CH,—NH,—C—NH—CH—OH ——» ° O ° 4 H i NHy-—-C—NH—CH;—NH—C—NH—CH;—OH ——» H—(NH—C—NH—CH2);—OHHeating for an extended period of time under acidic conditions will give a complex thermoset polymer of poorly defined structure including ring formation, of which the following may be typical. ~~NH—C—N__N-C? CN N—C—N—CHyeere ere FN N-CHe we NK CH, CH aA MACS “-NH-C—N NC LON NAC Cl 0 FO) ' ‘ EO NH— CH f—NH- CH3. MELAMINE-FORMALDEHYDE POLYMERS (MELAMINE RESINS) Melamine, having three amino groups and six labile hydrogens, will form thermoset resins with formaldehyde. The chemistry is similar to that for the OO amen oo. Co G Or oO = Nib Nt Ni Ni ~Ch at (Cilawwe se ba, sO, Lok, 0 ha ae y 1 ad a CH, CH He w~CH—-N t i so Ni N JON etme OL, te NE ‘N’ ‘N’ CH CH th th : g : : eee Ore a melamine or Formica” resin