Resole synthesis

While novolac links may form at elevated temperature during resole synthesis (Scheme 1.12), the preferred synthesis of novolac resins takes place under acid conditions (pH from 1 to 4) and with an excess of phenol. In this case the methylol intermediates cannot be isolated since they react rapidly to give methyene-bridged structures with relative molar mass <2000, as shown in Scheme 1.15. 

As we have already mentioned, the cure of resoles takes place primarily through further extension of the condensation process, though the conditions are usually considerably different from those of synthesis. The changes in conditions normally include exposure to much higher temperatures and higher concentrations of polymer than are seen in resin synthesis. The pH of the medium may also... 

In addition to the normal methylene linkage formation involved in polymerization with both resoles and novolaes, other, usually less desirable, eondensation by-products are also seen in novolac synthesis. Among these are benzodioxanes and dibenzyl ethers. The reaction pH has significant effect on the relative amounts produced. Fig. 15 shows typical structures for these by-products. When such byproducts are present, the meaning of the molar ratio changes and variability with respect to molecular weight development, glass transition point, and solubility may be seen. They also lead to poor raw material utilization. 

This chapter emphasizes the recent mechanistic and kinetic findings on phenolic oligomer syntheses and network formation. The synthesis and characterization of both novolac- and resole-type phenolic resins and dieir resulting networks are described. Three types of networks, novolac-hexamethylenetetramine (HMTA),... 

MATERIALS FOR THE SYNTHESIS OF NOVOLAC AND RESOLE PHENOLIC OLIGOMERS... 

A Statistical study of phenol-formaldehyde resol resin synthesis reaction... 

The final structure of resins produced depends on the reaction condition. Formaldehyde to phenol (F/P) and hydroxyl to phenol (OH/P) molar ratios as well as ruction temperahne were the most important parameters in synthesis of resols. In this study, the effect of F/P and OH/P wt%, and reaction temperature on the chemical structure (mono-, di- and trisubstitution of methyrol group, methylene bridge, phenolic hemiformals, etc.) was studied utilizing a two-level full factorial experimental design. The result obtained may be applied to control the physical and chemical properties of pre-polymer. 

A two level full factorial experimental design with three variables, F/P molar ratio, OH/P wt %, and reaction temperature was implemented to analyses the effect of variables on the synthesis reaction of PF resol resin. Based on the composition of 16 components of 10 samples, the effect of three independent variables on the chemical structure was anal3 ed by using 3 way ANOVA of SPSS. The present study provides that experimental design is a very valuable and capable tool for evaluating multiple variables in resin production. 

Phenol-formaldehyde resins using prepolymers such as novolaks and resols are widely used in industrial fields. These resins show excellent toughness and thermal-resistant properties, but the general concern over the toxicity of formaldehyde has resulted in limitations on their preparation and use. Therefore, an alternative process for the synthesis of phenolic polymers avoiding the use of formaldehyde is strongly desired. 

J. Monni, R Niemela, L. Alvila and T.T. Rakkanen, Online monitoring of synthesis and curing of phenol-formaldehyde resol resins by Raman spectroscopy. Polymer, 49, 3865-3874 (2008). 

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). 

Only a few studies have tackled the problem of deriving a detailed kinetic model of the phenol-formaldehyde reactive system, mainly because of its complexity. In recent years, a generalized procedure has been reported in [11,14] that allows one to build a detailed model for the synthesis of resol-type phenolic resins. This procedure is based on a group contribution method and virtually allows one to estimate the kinetic parameters of every possible reaction taking place in the system. 

Phenolic resins for plywood are typically caustic-catalyzed phenol-formaldehyde resoles. Typical resins are water solutions containing 40-44 percent resin solids composed of 23 - 25 percent phenol, 5-7 percent sodium hydroxide and 10 - 12 percent formaldehyde. The ratio of formaldehyde to phenol in a resin has a decided effect on performance characteristics as does the synthesis procedure used in manufacturing the resin. 

Reimer-Tiemann reaction 685, 1071 Resole resins 1457, 1458, 1460 model compounds of 1476-1487 synthesis of 1475, 1476 Resol prepolymers 969 Resonance Assisted Hydrogen Bonding (RAHB) 552... 

The cross-linked polymers obtained from the addition-cure approach are often a complex arrangement of atoms bonded in heterocyclic and carbocyclic rings. However, the objective in the preparation of these systems is not simplicity. It is to obtain systems with the desirable properties of phenolic resins retained and the undesirable properties improved or removed. Voids are an undesirable result in the synthesis of both resols and novolacs. Hence, addition-cure phenolic resins are designed to avoid this result. Ease and flexibility of processing are also sought in the addition-cure systems. 

Byun, H.Y. Choi, M.H. Chung, I.J. Synthesis and characterization of resol type phenolic resin/layered silicate nanocomposites. Chem. Mater. 2001, 13, 4221-4226. 

Wang, H. Zhao, T. Yan, Y. Yu, Y. Synthesis of resol-layered silicate nanocomposites by reaction exfoliation with acid-modified montmorillonite. J. Appl. Polym. Sci. 2004, 92, 791-797. 

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