Phenol formaldehyde resins natural phenolics

Woodflour, a fine sawdust preferably obtained from softwoods such as pine, spruce and poplar, is the most commonly used filler. Somewhat fibrous in nature, it is not only an effective diluent for the resin to reduce exotheim and shrinkage, but it is also cheap and improves the impact strength of the mouldings. There is a good adhesion between phenol-formaldehyde resin and the woodflour and it is possible that some chemical bonding may occur. 

Carbon, hydrogen and possibly oxygen Resin and derivatives Natural drying oils Cellulose derivatives Alkyd resins Epoxy resins (uncured) Phenol-formaldehyde resins Polystyrene Acrylic resins Natural and synthetic rubbers Carbon monoxide Aldehydes (particularly formaldehyde, acrolein and unsaturated aldehydes) Carboxylic acids Phenols Unsaturated hydrocarbons Monomers, e.g. from polystyrene and acrylic resins... 

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. 

Seventy years ago, nearly all resources for the production of commodities and many technical products were materials derived from natural textiles. Textiles, ropes, canvas, and paper were made of local natural fibers, such as flax and hemp. Some of them are still used today. In 1908, the first composite materials were applied for the fabrication of big quantities of sheets, tubes, and pipes in electrotechnical usage (paper or cotton as reinforcement in sheets made of phenol- or melamine-formaldehyde resins). In 1896, for example, airplane seats and fuel tanks were made of natural fibers with a small content of polymeric binders [1]. 

These intermediates are too small to be used alone, but need to be enlarged and modified to obtain compatibility with other resins. In the case of the phenol formaldehyde resins this is achieved by either using para-substituted phenols where the substituent contains at least four carbon atoms or by reacting the intermediate with the natural resin, rosin, and then esterifying with glycerol or pentaerythritol. These resins have a limited use in stoved epoxy finishes where colour is not an important factor. 

Chlorinated rubber is also an effective bonding agent. It can be used for bonding neoprene, nitrile and natural rubbers to metals. Phenol formaldehyde resins have been used alone or in conjunction with chlorinated rubbers, but curing time is lengthy. 

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. 

The mechanical degradation and production of macroradicals can also be performed by mastication of polymers brought into a rubbery state by admixture with monomer several monomer-polymer systems were examined (10, 11). This technique was for instance studied for the cold mastication of natural rubber or butadiene copolymers in the presence of a vinyl monomer (13, 31, 52). The polymerization of methyl methacrylate or styrene during the mastication of natural rubber has yielded copolymers which remain soluble up to complete polymerization vinyl acetate, which could not produce graft copolymers by the chain transfer technique, failed also in this mastication procedure. Block and graft copolymers were also prepared by cross-addition of the macroradicals generated by the cold milling and mastication of mixtures of various elastomers and polymers, such as natural rubber/polymethyl methacrylate (74), natural rubber/butadiene-styrene rubbers (76) and even phenol-formaldehyde resin/nitrile rubber (125). 

In a first classification, we can distinguish (i) boards made with an external synthetic binder, such as urea-formaldehyde or phenol-formaldehyde resins for thermosets, and (ii) boards with internal natural binders. The products cited below do not constitute an exhaustive list. 

Urea-formaldehyde resins are used for applications in which the panel is not in contact with water. For applications with high level of humidity, the phenol-formaldehyde resins are required. In all cases, free formaldehyde constitutes a dangerous pollutant that is slowly released and can be particularly toxic in confined rooms. Recent research has been done to substitute this type of resin by natural binders, such as cross-linkable proteins (Silvestre et al., 2000 Yang et al., 2006). 

The natural product comprises veneers of real wood which have been sorted and joined edge-to-edge (for example, by stitching), and bonded under heat and pressure to layers of kraft paper impregnated with phenol-formaldehyde resin. A barrier layer immediately below the veneer is impregnated with melamine-formaldehyde resin and prevents upward migration of the darker phenolic resin. 

Carbonaceous materials (CMs) are sometimes also named polymeric carbons. They are mostly prepared by thermal decomposition of organic precursors. One strategy is pyrolysis of gaseous or vaporized hydrocarbons at the surface of heated substrates, a second is heating (pyrolysis) of natural or synthetic polymers, both in an inert atmosphere. The latter is of special interest, and according to Miyabayashi et al. [374], precursors such as condensed polycyclic hydrocarbons, polymeric heterocyclic compounds, phenol-formaldehyde resins, polyacrylonitrile or polyphenylene are heated to 300-3000 °C for 0.15-20 h. Sometimes, a temperature/time profile is run. The temperature range must be divided into two domains, namely... 

We learned much from nature with these early attempts to produce useful polymer products based on modified, or reconstituted ( semisynthetic ) natural polymers, and many of these processes are still in use today. The first of the purely synthetic commercial polymers came with the small-scale introduction of Bakelite in 1907. This phenol-formaldehyde resin product was developed by Leon Baekeland. It rapidly became a commercial reality with the formation of The General Bakelite Company by Baekeland, and construction of a larger plant at Perth Amboy, New Jersey, in 1910. At about this time styrene was being combined with dienes in the early commercialization of processes to produce synthetic rubber. Polystyrene itself was not a commercial product in Germany until 1930 and in the U.S.A. in 1937. The only other purely synthetic polymers that made a commercial appearance during this early development period were polyvinyl chloride and polyvinyl acetate, both in the early 1920s. 

Interesting results on emulsifier-natural stabiliser interactions were described in [243]. Ethoxylated phenol-formaldehyde resins were used as emulsifiers, e.g. polyalkylphenols-polyalkylene-poiyamines-formaldehyde ethoxylates (PAPAFE). PAPAFE containing more amino groups are able to solubilise asphaltenes. This leads to desorption of these natural surfactants from the interface, thus increasing the demulsifying effect. 

Elastomeric 1, Natural rubber. 2, Neoprene. 3, Nitrile. 4, Urethane. 5, Styrene-butadiene. Thermoplastic 6, Poly(vinyl acetate). 7, Polyamide. Thermosetting 8, Phenol-formaldehyde. 9, Resorcinol, Phenol-resorcinol/formaldehyde. 10, Epoxy. 11, urea-formaldehyde. Resin 12, Phenolic-poly(vinyl butyral). 13, Polyeser. Other 14, Cyanoacrylate. 15, Solvent. 

This class of adhesives contains some of the most traditional materials, for example animal glues and gums derived from natural sources, which are long-chain molecules, are soluble in water, and are either proteins or polysaccharides. Modern technology has brought other water-soluble materials into use for example, poly( vinyl alcohol) adhesives, and a host of resins based on phenol, mea, and formaldehyde (see Formaldehyde Resins in Chapter 4). 

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