Thermosets phenol-formaldehyde

The addition of small percentages of Na+-montmorillomte (NaMMT) nanoclay does not appear to improve much the performance of thermosetting phenol-formaldehyde (PF) and phenol-uiea-formeildehyde (PUF) resins used as adhesives for plywood and for wood particleboard. X-ray diffraction (XRD) studies indicated that NaMMT does not become completely exfoliated when mixed in small proportions to PF resins, contrary to that observed for acid-setting urea-formaldehyde (UF) resins. Differential scaiming calorimetry (DSC) indicated that NaMMT has no accelerating effect on the curing of alkaline PF resins, contrary to that observed for UF resins. 

Thermosetting phenol-formaldehyde 1 synthetic chipboard and plywood... 

Details Invention of thermosetting phenol formaldehyde resin called Bakellte ... 

The use of fillers in pol3uners has been going on for years. In the early history of filled pol5oners, fillers were added to the polymers rather empirically. Woodflour was one of the first fillers used in thermosetting phenol-formaldehyde resins because the combination was found to be valuable in enhancing certain properties whereas the addition of some other finely divided material to such resins conferred no benefit at all and hence was never done. The presence of the woodflour increased... 

Thermoset Phenol-formaldehyde resin Elastomer Styrene butadiene rubber Thermoplastic Polypropylene Wood flour/cotton flock Carbon black Calcium carbonate/talc... 

Thermosets Phenol-formaldehyde (PF) resins 49 50 49 D-F (Novolak resins)... 

The greatest volume of wood adhesives for structural applications are thermosetting phenol-formaldehyde (PF) or urea-formaldehyde (UF) polymers or their derivatives. PFs are the commodity for exterior applications, while UFs are the commodity for interior applications. Because each composite product and the associated process may require a somewhat different resin, many variations of PF and UF resins are available. Isocyanate crosslinking resins are used to a lesser extent than PFs or UFs in manufactured board. Although these resins impart a durable, water resistant bond suitable for exterior application, the cost per pound of adhesive is greater than for PFs or UFs. 

In practice, synthetic polymers are sometimes divided into two classes, thermosetting and thermo-plMtic. Those polymers which in their original condition will fiow and can be moulded by heat and pressime, but which in their finished or cured state cannot be re softened or moulded are known as thermo setting (examples phenol formaldehyde or urea formaldehyde polymer). Thermoplastic polymers can be resoftened and remoulded by heat (examples ethylene polymers and polymers of acrylic esters). 

Reactions with Aldehydes and Ketones. An important use for alkylphenols is ia phenol—formaldehyde resias. These resias are classified as resoles or aovolaks (see Phenolic resins). Resoles are produced whea oae or more moles of formaldehyde react with oae mole of pheaol uader basic catalysis. These resias are thermosets. Novolaks are thermoplastic resias formed whea an excess of phenol reacts with formaldehyde under acidic conditions. The acid protonates formaldehyde to generate the alkylating electrophile (17). 

Amino resins are thermosetting polymers made by combining an aldehyde with a compound containing an amino (—NH2) group. Urea—formaldehyde (U/F) accounts for over 80% of amino resins melamine—formaldehyde accounts for most of the rest. Other aldehydes and other amino compounds are used to a very minor extent. The first commercially important amino resin appeared about 1930, or some 20 years after the introduction of phenol—formaldehyde resins and plastics (see Phenolic resins). 

Glassy, or vitreous, carbon is a black, shiny, dense, brittle material with a vitreous or glasslike appearance (10,11). It is produced by the controUed pyrolysis of thermosetting resins phenol—formaldehyde and polyurethanes are among the most common precursors. Unlike conventional artificial graphites, glassy carbon has no filler material. The Hquid resin itself becomes the binder. 

Most processors of fiber-reinforced composites choose a phenol formaldehyde (phenoHc) resin because these resins are inherently fire retardant, are highly heat resistant, and are very low in cost. When exposed to flames they give off very Htde smoke and that smoke is of low immediate toxicity. PhenoHc resins (qv) are often not chosen, however, because the resole types have limited shelf stabiHty, both resole and novolac types release volatiles during their condensation cure, formaldehyde [50-00-0] emissions are possible during both handling and cure, and the polymers formed are brittle compared with other thermosetting resins. 

Today the phenol-formaldehyde moulding compositions do not have the eminent position they held until about 1950. In some, important applications they have been replaced by other materials, thermosetting and thermoplastic, whilst they have in the past two decades found use in few new outlets. However, the general increase in standards of living for much of this period has increased the sales of many products which use phenolics and consequently the overall use of phenol-formaldehyde moulding powders has been well maintained. 

By far the preponderance of the 3400 kt of current worldwide phenolic resin production is in the form of phenol-formaldehyde (PF) reaction products. Phenol and formaldehyde are currently two of the most available monomers on earth. About 6000 kt of phenol and 10,000 kt of formaldehyde (100% basis) were produced in 1998 [55,56]. The organic raw materials for synthesis of phenol and formaldehyde are cumene (derived from benzene and propylene) and methanol, respectively. These materials are, in turn, obtained from petroleum and natural gas at relatively low cost ([57], pp. 10-26 [58], pp. 1-30). Cost is one of the most important advantages of phenolics in most applications. It is critical to the acceptance of phenolics for wood panel manufacture. With the exception of urea-formaldehyde resins, PF resins are the lowest cost thermosetting resins available. In addition to its synthesis from low cost monomers, phenolic resin costs are often further reduced by extension with fillers such as clays, chalk, rags, wood flours, nutshell flours, grain flours, starches, lignins, tannins, and various other low eost materials. Often these fillers and extenders improve the performance of the phenolic for a particular use while reducing cost. 

Phenol-formaldehyde resins are the oldest thermosetting polymers. They are produced by a condensation reaction between phenol and formaldehyde. Although many attempts were made to use the product and control the conditions for the acid-catalyzed reaction described by Bayer in 1872, there was no commercial production of the resin until the exhaustive work by Baekeland was published in 1909. In this paper, he describes the product as far superior to amber for pipe stem and similar articles, less flexible but more durable than celluloid, odorless, and fire-resistant. ° The reaction between phenol and formaldehyde is either base or acid catalyzed, and the polymers are termed resols (for the base catalyzed) and novalacs (for the acid catalyzed). 

Phenolic phenol formaldehydes (PFs) are the low-cost workhorse of the electrical industry (particularly in the past) low creep, excellent dimensional stability, good chemical resistance, good weatherability. Molded black or brown opaque handles for cookware are familiar applications. Also used as a caramel colored impregnating plastics for wood or cloth laminates, and (with reinforcement) for brake linings and many under-the-hood automotive electricals. There are different grades of phenolics that range from very low cost (with low performances) to high cost (with superior performances). The first of the thermosets to be injection-molded (1909). 

Phenol, along with formaldehyde, is used to produce a very important and versatile group of polymers known as phenolics or phenol-formaldehyde resins. These resins can be either thermoplastic or thermosetting, depending on the amount of formaldehyde used. A larger ratio of formaldehyde to phenol promotes crosslinking to produce more rigid materials. 

The major disadvantage associated with urea-formaldehyde adhesives as compared with the other thermosetting wood adhesives, such as phenol-formaldehyde and polymeric diisocyanates, is their lack of resistance to moist conditions, especially in combination with heat. These conditions lead to a reversal of the bond-forming reactions and the release of formaldehyde, so these resins are usually used for the manufacture of products intended for interior use only. However, even when used for interior purposes, the slow release of formaldehyde (a suspected carcinogen) from products bonded with urea-formaldehyde adhesives is observed. 

Thermosets differ molecularly from thermoplastics in that their individual chains are anchored to one another through crosslinks. The resulting network creates cohesive materials that demonstrate better thermal stability, rigidity, and dimensional stability than thermoplastics. Some examples of traditional thermosets are melamine-formaldehyde resins, which are used to treat fabrics to make them wrinkle-free, and Bakelite (a phenol-formaldehyde resin), a historically important polymer used in many applications, such as costume jewelry, electrical switches, and radio casings. 

Other spherical fillers include carbon black. This has several roles particularly in combination with elastomers, e.g., black pigment, anti-oxidant and UV stabiliser, reinforcing filler, and an electrical conductor when used at 60% concentration. Wood flour is particularly effective in phenol/formaldehyde and melamine or urea/formaldehyde thermoset resins because the phenolic lignin component in the wood reacts with the methylol groups (-CH2OH) in the growing polymer. 

The two major uses of phenol in 1995 were the production of bisphenol-A (35%) and the production of phenolic resins (34%) (CMR 1996). The largest use for bisphenol-A is as an intermediate in the production of epoxy resins (Thurman 1982). Phenol-formaldehyde resins comprise over 95% of this market (Thurman 1982). The plywood adhesive industry required 26% of the total production of phenolic resins in 1977. These low-cost, versatile, thermoset resins have other major uses in the construction, automotive, and appliance industries (Thurman 1982). 

In principle, molecular sieve carbons (MSC) can be achieved by the pyrolysis of thermosetting polymers such as polyvinylidene chloride, polyfurfuryl alcohol, cellulose, cellulose triacetate, polyacrylonitrile and phenol formaldehyde (Koresh 1980). An example is given by Trimm and Cooper (1970,1973) for the preparation of MSC (mixed with metallic compounds) for catalyst systems. A mixture of furfuryl alcohol, platinum oxide and formaldehyde was heated to 40°C and additional formaldehyde was added to ensure the... 

Table 12.3 summarizes the uses of formaldehyde. Two important thermosetting plastics, urea- and phenol-copolymers, take nearly one half the formaldehyde manufactured. Urea-formaldehyde resins are used in particleboard, phenol-formaldehyde resins in plywood. 1,4-Butanediol is made for some polyesters and is an example of acetylene chemistry that has not yet been replaced. Tetrahydrofiiran (THF) is a common solvent that is made by dehydration of 1,4-butanediol. 

What was the first synthetic plastic Although some nineteenth-century experiments should be mentioned, such as the 1869 molding process for cellulose nitrate discovered by John and Isaiah Hyatt, probably the first major breakthrough came in 1910 with Leo Baekeland s discovery of phenol formaldehyde resins (Bakelite ). These are still the leading thermoset plastics made today. The pioneering work of Wallace Carothers at Du Pont in 1929 produced the nylons now used primarily as fibers but known as the beginning of thermoplastic resin technology. 

The chemical structures of thermosets are generally much more diverse than the commodity thermoplastics. The most common types of thermosets are the phenol-formaldehydes (PF), urea-formaldehydes (UF), melamine-formaldehydes (MF), epoxies (EP), polyurethanes (PU), and polyimides (PI). Appendix 2 shows the chemical structure of these important thermosetting polymers. 

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