Resole, crosslinking

There are some reports proposing that structures not present in the aqueous resole are formed during cure, to include 2,2-diphenyl ethanol and 1,1,3,3-tetraphenyl propane crosslink structures [132,158,159]. However, these have not... 

Used for crosslinking novolacs or catalyzing resole syntheses, HMTA is prepared by reacting formaldehyde with ammonia (Fig. 7.5). The reaction is reversible at high temperatures, especially above 250°C. HMTA can also be hydrolyzed in the presence of water. 

Quinone methides are the key intermediates in both resole resin syntheses and crosslinking reactions. They form by the dehydration of hydroxymethylphenols or dimethylether linkages (Fig. 7.24). Resonance forms for quinone methides include both quinoid and benzoid structures (Fig. 7.25). The oligomerization or crosslinking reaction proceeds by nucleophilic attack on the quinone methide carbon. 

Resole resins are generally crosslinked under neutral conditions between 130 and 200° C or in the presence of an acid catalyst such as hydrochloric acid, phosphoric acid, p-toluenesulfonic acid, and phenolsulfonic acid under ambient conditions.3 The mechanisms for crosslinking under acidic conditions are similar to acid-catalyzed novolac formation. Quinone methides are the key reaction intermediates. Further condensation reactions in resole resin syntheses under basic conditions at elevated temperatures also lead to crosslinking. 

Crosslinking resoles in the presence of sodium carbonate or potassium carbonate lead to preferential formation of ortho-ortho methylene linkages.63 Resole networks crosslinked under basic conditions showed that crosslink density depends on the degree of hydroxymethyl substitution, which is affected by the formaldehyde-to-phenol ratio, the reaction time, and the type and concentration of catalyst (uncatalyzed, with 2% NaOH, with 5% NaOH).64 As expected, NaOH accelerated the rates of both hydroxymethyl substitution and methylene ether formation. Significant rate increases were observed for ortho substitutions as die amount of NaOH increased. The para substitution, which does not occur in the absence of the catalyst, formed only in small amounts in the presence of NaOH. 

A number of analytical techniques such as FTIR spectroscopy,65-66 13C NMR,67,68 solid-state 13 C NMR,69 GPC or size exclusion chromatography (SEC),67-72 HPLC,73 mass spectrometric analysis,74 differential scanning calorimetry (DSC),67 75 76 and dynamic mechanical analysis (DMA)77 78 have been utilized to characterize resole syntheses and crosslinking reactions. Packed-column supercritical fluid chromatography with a negative-ion atmospheric pressure chemical ionization mass spectrometric detector has also been used to separate and characterize resoles resins.79 This section provides some examples of how these techniques are used in practical applications. 

Novolac network degradation mechanisms vary from tiiose of resole networks due to differences in crosslinking metiiods. Nitrogen-containing linkages must also be considered when HMTA (or other crosslinking agent) was used to cure novolac networks. For example, tribenzylamines, formed in HMTA-cured novolac networks, decompose to cresols and azomethines (Fig. 7.50). 

Crosslinking in phenol-formaldehyde resins is carried out on essentially linear prepolymers which have been formed by having one of the components in sufficient excess to minimise crosslinking during the initial step. These prepolymers may be one of two kinds the so-called resoles or the so-called novolaks. 

The route to crosslinked phenol-formaldehyde resins via resoles corresponds to that used by Baekeland in his original commercial technique. They now tend to be used for adhesives, binders, and laminates. The resole... 

The crosslinking of resoles is slightly more straightforward than that of novolaks, if only because there are fewer possible chemical structures involved in the setting reaction or finished structure. Since resoles are prepared under alkaline conditions, crosslinking is generally preceded by neutralisation. This enhances the ease with which network structures can form when the resin is simply heated. 

The reaction mixture is dehydrated at temperatures as high as 160°C (higher temperatures can be tolerated than with resoles). The prepolymer is cooled, crushed, blended with 5-15% hexamethylenetetramine, (CH2)6N4, and sold to the fabricator. Hexamethylenetetramine, referred to as hexa, is the product of the reaction of 6 mol of formaldehyde and 4 mol of ammonia. Curring occurs rapidly on heating with the formation of both methylene and ben-zylamine crosslinking bridges between benzene rings. The crosslinked network is pictured as... 

Dase-catalyzed phenol-formaldehyde resins polymerized with a mole ratio of formaldehyde to phenol greater than one pose an interesting molecular weight characterization problem. This system is a dynamic one with active methylol end groups. Branched and crosslinked structures are formed, and in general, the separation of the resin from the reaction mixture is difficult. Figure 1 illustrates the chemical nature of a resole resin. 

Due to the presence of reactive CH2OH groups, resol oligomers may be converted into highly crosslinked products without the addition of hardeners. Heat curing is conducted at T 130 200°C. The polycondensation mechanisms are complex and different bridges are possible CH2-0-CH2-and CH2. The latter is thermodynamically the most stable. Therefore the methylene bridges are the prevalent crosslinks in cured resols. 

For phenolic resins of the resols type, numerous voids (a few micrometers in size) are formed during the synthesis. The average diameter and distribution of voids depend strongly on the cure cycle their presence, together with the high values of crosslink density, explain the low fracture resistance of these networks (Wolfram et al., 1999). 

Resols (phenol-formaldehyde resins) are commercially used for effective crosslinking of EPDM in the production of thermoplastic vulcanisates [8]. General studies on rubber crosslinking for different diene rubbers are presented here. 

These adhesives are generally based on blends of solid epoxy resins with resole-type phenolic resin. The epoxy resin component is often not the predominant component in the blend, depending on the end properties required. Phenolics are compatible with epoxy resins and will react through the phenolic hydroxyl group. The amount of phenolic resin used is generally much greater than that required to crosslink with the epoxy, so one can debate whether (1) the epoxy toughens the phenolic adhesive or (2) the phenolic increases the heat resistance of the epoxy. 

Finally, various Mannich bases used as catalysts in the crosslinking of oligomers (see also Chap. V, A.2.), are worth mentioning. Their basic properties are applied in the curing of epoxy oligomers- as well as in the production of polyurethanes and, less frequently, in the crosslinking of resols. - Compounds of types 426 and 427 are employed mostly for the above purposes. 

The functionalization reaction, which is particularly applied to collagen, is based on the aminomethylation of various substrates (see also Table 34, Chap. Ill) by employing the NH2 groups of the protein as Mannich amine reagents. Formaldehyde is preferred for crosslinking however, other agents, such as resols (see 432 in Chap. Ill,... 

The functionality may vary with reaction conditions. For example, in base-catalyzed copolymerization of phenol and formaldehyde, both monomers are bifunctional at ambient temperature, but phenol becomes trifunctional if the temperature is raised sufficiently. Copolymerization at ambient temperature can produce essentially linear, liquid, resole-type "prepolymers" of low molecular weight. Upon acidification and heat-curing, methylene and ether crosslinks formed by the now trifunctional phenol units transform the polymer into an insoluble resin [7] (see next page). The original Bakelite was such a "thermosetting" product. 

Classification. Phenolic foam is divided broadly into two categories. One is the novolac type and the other is the resol type (see Figure 55). In the novolac type, phenol and formaldehyde react in the presence of an acid catalyst and link the linear condensation product by a methylene bond. The basic curable crosslinking agent, such as hexamethylene tetramine and blowing agent are added to the linear condensation product and the resultant product is molded at elevated temperatures and high pressure. 

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