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Resin Chemistry

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Phenolic Resins: A Century of Progress

Abstract

During the ensuing years since the last phenolic resins book was published, many new and remarkable developments have occurred in the realm of phenolic chemistry and are given in this chapter.

A critical examination of the first step or addition step (methylolation) in the preparation of resoles is described and how it can be controlled and compared with the typical resole resin preparations. It provides a vision into the preparation of mineral wool/glass insulation resins and ways to minimize the undesirable dimer/oligomer formation.

Different reactivities of the common methylolated phenols and phenol are ranked, and their resulting reactivities differ depending on whether formaldehyde is present or absent in the methylolated phenols.

Use of organic bases such as triethyl amine indicates that a much faster reaction of F with P occurs as compared to the use of NaOH under similar conditions, and primarily ortho directed intermediate 2-methylol phenol is obtained. Further more methylene ether linkages result in the final TEA resole.

Bisphenol F, the simplest oligomer of phenolic novolak, continues to elicit considerable activity related to improved and economical synthetic preparative methods.

A unique, novel novolak process involving heterogeneous/two phase method known as the PAPS process is discussed along with several features and favorable comparisons with existing novolaks. Features such as narrow MWD, high yield, low free phenol, and rapid reaction favor this new process. Current markets that are responding to PAPS novolaks are photoresists and novolak curing agents for epoxy resins.

Nanotechnology is being applied to resoles and novolaks as well as the closely related phenolic materials such as cyanate esters and benzoxazines. With very small amounts of nanoparticles (≤5%), these phenolic materials are significantly “upgraded” with resulting nanomodified phenolics exhibiting higher heat strength, higher modulus, T g, etc., with many of these resin characteristics carrying over into fiber reinforced composites.

A new phosphorous flame retardant additive known as DOPO is reported and is instrumental in providing UL 94 VO behavior to cured novolak epoxy electrical laminates.

Benzoxazines are emerging as a more desirable phenolic resin system available from resin manufacturers as well as formulators such as Gurit (prepreg) and Henkel (FRP matrix). Benzoxazines undergo ring opening without emitting any volatiles during cure and result in a cured product with excellent dimensional stability, low water absorption, and stable, low dielectric properties (many of which are unavailable from typical phenolic resins). These attractive features have been responsible for its large volume use in electronics and FRP.

An overview of all types of natural products used either as partial phenol replacement, solvent or co-reactant, or as a resin modifier are tabulated along with origin/source, role in resin preparation, and different application areas.

An unusual technical development that attracted the interest of the symposium attendees was delivered by Sumitomo Bakelite researchers at the Commemorate Centennial Baekeland 2007 Symposium held in Ghent, Belgium during September 25, 2007. It was proposed that the 3D polymer network of hexa cured phenolic novolak resin can undergo further improvement based on reported curelastomer, T g values, and DSC data. It is the view of the researchers based on phenolic resin conformations reached by using the Mark-Houwink-Sakarada equation as well as molecular simulations that higher T g, exceptional strength, and performance driven characteristics of the resulting cured phenolic systems can be attained if an extended, linear novolak with low amounts of branching is cured with hexa. Conventional novolaks possess a “coiled” structure with branching, and during hexa cure, some novolak sites are sheltered or unavailable for cure and result in a 3D polymer network that is not fully cured in spite of the availability of excess hexa.

A reaction that is being revisited consists of phenylene bisoxazoline (PBO) reacting with novolak, and this promises to lead to the commercialization of a polyaryl ether amide type polymer possessing high T g, high strength, and toughness exceeding multifunctional epoxy systems.

The capture and release of formaldehyde by aminoalcohols through the formation of an oxazolidine intermediate to facilitate the cure of phenolic resins has been commercialized as is shown in 2 different application areas. A pultrusion system based on novolak and oxazolidine is claimed to operate at line rates comparable to fast polyester pultrusion speeds. The other application involves the use of oxazolidine with PRF resin in the preparation of fiber reinforced FST duct systems.

The appendage of either an allyl or an ethynyl group to a novolak or resole followed by thermal cure leads to unusually high T g phenolic materials, close to 400°C and is of interest for ultra high performance organic matrix composites.

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    Louis Pilato

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Pilato, L. (2010). Resin Chemistry. In: Pilato, L. (eds) Phenolic Resins: A Century of Progress. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-04714-5_4

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