Resin acids industrial production

The industrial value of furfuryl alcohol is a consequence of its low viscosity, high reactivity, and the outstanding chemical, mechanical, and thermal properties of its polymers, corrosion resistance, nonburning, low smoke emission, and exceUent char formation. The reactivity profile of furfuryl alcohol and resins is such that final curing can take place at ambient temperature with strong acids or at elevated temperature with latent acids. Major markets for furfuryl alcohol resins include the production of cores and molds for casting metals, corrosion-resistant fiber-reinforced plastics (FRPs), binders for refractories and corrosion-resistant cements and mortars. 

Although catalytic hydration of ethylene oxide to maximize ethylene glycol production has been studied by a number of companies with numerous materials patented as catalysts, there has been no reported industrial manufacture of ethylene glycol via catalytic ethylene oxide hydrolysis. Studied catalysts include sulfonic acids, carboxyUc acids and salts, cation-exchange resins, acidic zeoHtes, haUdes, anion-exchange resins, metals, metal oxides, and metal salts (21—26). Carbon dioxide as a cocatalyst with many of the same materials has also received extensive study. 

The main characteristic properties of asbestos fibers that can be exploited in industrial appHcations (8) are their thermal, electrical, and sound insulation nonflammabiUty matrix reinforcement (cement, plastic, and resins) adsorption capacity (filtration, Hquid sterilization) wear and friction properties (friction materials) and chemical inertia (except in acids). These properties have led to several main classes of industrial products or appHcations... 

Esterification. The esterification of rosin provides important commercial products for the adhesive industry. Rosin esters are formed by the reaction of rosins with alcohols at elevated temperatures. Because the carboxyl group of the resin acids is hindered by attachment to a tertiary carbon, esterification with an alcohol can only be accomplished at elevated temperatures. This hindrance is in turn responsible for the high resistance of the resin acid ester linkage to cleavage by water, acid and alkali. 

MTBE is used on a large scale as an octane number boosting additive in unleaded gasoline. Sulfonic acid resins are applied as efficient catalysts for the industrial production of MTBE from methanol and isobutylene (222). Since 1987, investigations of the synthesis of MTBE with reactants in the gas phase have been performed with zeolites HY (223-225), H-Beta (226), HZSM-5 (224,225), and H-BZSM-5 (227) as catalysts. 

It is used in the manufacture of polyvinylpyrrolidone (PVP), in the manufacture of copolymers with, for example, aciv lic acid, acrylates, vinyl acetate and acrylonitrile and in the synthesis of phenolic resins. About 10-15% of the monomer is used in the pharmaceutical industry for the production of PVP-iodine complex used as a disinfectant. It is also used as a reactive solvent of ultraviolet-curable resins for the production of printing inks and paints as paper and textile auxiliaries, and as an additive in the cosmetics industry (Harreus, 1993). 

The oleoresinous exudate or "pitch of many conifers, but mainly pines, is the raw material for the major products of the naval stores industry. The oleoresin is produced in the epithelial cells which surround the resin canals. When the tree is wounded the resin canals are cut. The pressure of the epithelial cells forces die oleoresin to the surface of die wound where it is collected. The oleoresin is separated into two fractions by steam distillation. The volatile fraction is called gum turpentine and contains chiefly a mixture of monoterpenes but a smaller amount of sesquiterpenes is present also. The nonvolatile gum rosin 5 consists mainly of llie dilerpenuid resin acids and smaller amounts of esters, alcohols and steroids. Wood turpentine, wood rosin and a fraction of intermediate volatility, pine oil are obtained together by gasoline extrachon of the chipped wood of old pine stumps. Pine oil is largely a mixture of the monoterpenoids terpineol. borneol and fenchyl alcohol. Sulfate turpentine and its nonvolatile counterpart, tall oil, 5 are isolated as by-products of the kraft pulping process. Tall oil consists of nearly equal amounts of saponified fatty acid esters and resin acids. 

Turpentine is used in syntheses by llie chemical and pharmaceutical industries. It also is used as a paint thinner and as a component of polishes and cleaning compounds. Pine oil finds application as a penetrant, wetting agent and preservative, especially by the textile and paper industries, and as an inexpensive deodorant and disinfectant in specialty products. The resin acids are used in the production of ester gum, Glyptal resins and are indispensable in paper sizing,... 

Dehydroabietic acid 1, the main resin acid of disproportionated rosin, is a readily available hydrophenanthrene derivative and a useful starting material for the synthesis of industrial and/or physiologically important products (1), by introduction of suitable substituents in the aromatic ring, such as the nitro or amino groups. 

The synthesis of methyl /-butyl ether (MTBE) from isobutylene and methanol on TS-1 has been investigated. This reaction is catalyzed by acids and the industrial production is carried out with sulfonic acid resin catalysts. It has been reported that at 363-383 K the reaction proceeds in the presence of the acidic HZSM-5, but also on TS-1, which is much more weakly acidic. However, the characterization of the catalysts used is not completely satisfactory for instance, the IR spectra reported do not show the 960-cm 1 band that is always present in titanium-containing silicas. It is therefore possible that the materials with which the reaction has been studied are not pufe-phase TS-1. The catalytic activity for MTBE synthesis is, in any case, an interesting result, and further investigations with fully characterized catalysts are expected to provide a satisfactory interpretation of these results (Chang et al., 1992). 

The resultant fabrics are unique in that they have many functional property improvements thermal adaptability due to the phase change nature of the bound polyol, durable press or resiliency, soil release, reduction of static charge, antimicrobial activity, enhanced hydrophilicity and improved flex life, and resistance to pilling. Because of the different molecular weights of polyols, resins, acid catalysts, and fabric constructions, there are numerous modified fabrics that can be produced with sets of improved attributes. Each fabric must be carefully evaluated for optimum curing conditions and formulations to produce the desired product. Several licenses have been granted for this process. Various types of apparel, healthcare items, and industrial fabrics are currently evaluated for commercial production [381,382]. 

Wood is the raw material of the naval stores industry (77). Naval stores, so named because of their importance to the wooden ships of past centuries, consist of rosin (diterpene resin acids), turpentine (monoterpene hydrocarbons), and associated chemicals derived from pine (see Terpenoids). These were obtained by wounding the tree to yield pine gum, but the high labor costs have substantially reduced this production in the United States. Another source of rosin and turpentine is through extraction of old pine stumps, but this is a nonrenewable resource and this industry is in decline. The most important source of naval stores is spent sulfate pulping liquors from kraft pulping of pine. In 1995, U.S. production of rosin from all sources was estimated at under 300,000 metric tons and of turpentine at 70,000 metric tons. Distillation of tall oil provides, in addition to rosin, neady 128,000 metric tons of tail oil fatty acids annually (78). 

Methyl terf-butyl ether (MTBE) is an important industrial product used as oxygenate additive in reformulated gasoline. Environmental concern makes its future uncertain, however. Although mainly manufactured by reaction of isobutylene with methanol, it is also produced commercially from methanol and fcrr-butyl alcohol, a by-product of propylene oxide manufacture. Numerous observations from the use of heteropoly acids have been reported. These compounds were used either as neat acids [74], or supported on oxides [75], silica or K-10 montmorillonite [76]. They were also used in silica-included form [77] and as acidic cesium salts [74,77]. Other catalysts studied were sulfated ZrOj [76], Amberlyst 15 ion-exchange resin [76], HZSM-5 [76], HF-treated montmorillonite, and commercial mineral acid-activated clays [75]. Hydrogen fluoride-treatment of montmorillonite has been shown to furnish particularly active and stable acid sites thereby ensuring high MTBE selectivity (up to 94% at 413 K) [75]. 

Diols and triols are key intermediates in the industrial production of lubricants, surface coatings and synthetic resins. The classical pathway in the diol synthesis is based on the use of alkali-catalyzed aldolization followed by the Caimizzaro reaction [1]. Equilibrium amounts of sodium formate ions i.e. formic acid) are formed in the traditional reaction route. This is a serious drawback since formate has to be separated from the product mixture. The producer of diols and triols is forced to deal with a conqjonent which has a low market value. 

Soybean oil was not widely used for food until the 1930s, when oil-processing technologies advanced sufficiently to produce hydrogenated soybean oils with acceptable stability and flavor. Major industrial product uses for soybean oil today include paint and varnish, resins and plastics, and a source of fatty acids. The latter is often derived from refinery by-products (sometimes known as foots). 

Natural soybean oil is too viscous and reactive to atmospheric oxygen to be used in many biobased product applications. These limitations must be overcome for soybean oil to be used in fuels, cosmetics, and lubricants, but on the other hand, soybean oil is not sufficiently reactive to be used in most paints and coatings. Important end-use categories for which economic data exist include fatty acids, paints and varnishes, resins and plastics, drying-oil products, and other industrial products. Coating vehicles (paints and varnishes) and epoxidized oils (resins and plastics) comprise 50% of... 

The biochemical reaction catalyzed by epoxygenase in plants combines the common oilseed fatty acids, linoleic or linolenic acids, with O2, forming only H2O and epoxy fatty acids as products (CO2 and H2O are utilized to make linoleic or linolenic acids). A considerable market currently exists for epoxy fatty acids, particularly for resins, epoxy coatings, and plasticizers. The U.S. plasticizer market is estimated to be about 2 billion pounds per year (Hammond 1992). Presently, most of this is derived from petroleum. In addition, there is industrial interest in use of epoxy fatty acids in durable paints, resins, adhesives, insecticides and insect repellants, crop oil concentrates, and the formulation of carriers for slow-release pesticides and herbicides (Perdue 1989, Ayorinde et al. 1993). Also, epoxy fatty acids can readily and economically be converted to hydroxy and dihydroxy fatty acids and their derivatives, which are useful starting materials for the production of plastics as well as for detergents, lubricants, and lubricant additives. Such renewable derived lubricant and lubricant additives should facilitate use of plant/biomass-derived fuels. Examples of plastics that can be produced from hydroxy fatty acids are polyurethanes and polyesters (Weber et al. 1994). As commercial oilseeds are developed that accumulate epoxy fatty acids in the seed oil, it is likely that other valuable products would be developed to use this as an industrial chemical feedstock in the future. 

Polyamides are well-known industrial products having applications in many areas (7). For instance, the Nylon polymers (water-insoluble polyamides) are widely used in fibers. A water-soluble poly(aminoamide), derived from adipic acid and diethylene triamine, is the precursor to a well-known industrial resin (2). This poly(aminoamide) is currently produced by a chemical reaction at elevated temperatures which is accompanied by the formation of some branched structures. Subsequent derivatization of this polyamide produces a water-soluble resin, known for its ability to impart wet strength to paper and paper products (2a, 2b) and shrink proofing to wools and other textiles (2c). 

The first diflferentiation is used in various sectors of the wood-processing industry like the pulp and paper industry, as its chemical behaviour is defined by the polarity. Depending on the chemical pulping, certain extractives can show negative effects on the production, e.g. pinosylvin and its monomethyl ether during acid sulphite pulping. In contrast, other pine extractives (resin acids, terpenes, eic.) are useful by-products in Kraft pulping (see Section 9.4.3). 

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