New Uses of Naval Stores Products 0. 4.PicKWrl’ AND J. XI. SCHANTZ, Hercules Powder Company, Wilmington, Del. -OR
nlniiy years the chief v a r n i s h manufacture. Treat1)rrriri.o Ihr nost .irwrrtv odd Y .-.., P ~ P Rm~! ; r m to the .. ~ ~ .~.. . I ,..... ...... il -consumers of naval stores development the luood llaval stores industry, ment with hydrated lime greatly products-rosin and turincreases the softening point and pine oil, steam- and destructively dislilled wood lientine-have been t h e s o a p , r e d u c e s tho of rosin, ivaper size, and paint and varnish turpentines, and rosins have been added to the Limed rosin is usua~lymade by gum turpentine arid rosin products covered by the adding liydrated lime to nioiten i n d u s t r i c s . The term “naval stores”aisoinclridesseveralprodlerm “naual stores.” This naaer brieffv rosin alt,llough m e tliods have , “ reviews the sc~)peof ,leM n , s ~ofs muat stores resultirlllfrom been devised for reacting hyiicts in addition t.o gum tinpentineand gumrosiri. Thedevelopdrated lirnewithrosininsolution. proper reseurch. nient of the mood naval stores inSome of the newer u s e s oi limed rosin are: as a stiffeniiig dustry during the past tventyodd years has added pine oil, and stearnilist,illedand destruc- a i d naterpruofing material in box toes for shoes, ior the t,ivelydistilled wood turpeIitincsandwoodrosins;more recently manufacture of dry-battery sealing wax, canners’ sealing wax, tlie paper pulp industry has made available sulfate wood match head compositions, waterproofing wood board, gasket turpentine and liquid rosin. Fortunabely, there have been cementa, phonograph records, and similar molded materials; enough newly developed uses of naval stores products to dry core binders and core oils, molded floor covering, and make up for the losses sustained through obsolescence of numerous uratr:rproof adhesives. Rosin hardened with zinc processes or products or replacement by other maberinls. It and lead find similar but not as extensive applications. is the purpose of this paper to review briefly some of these A recently developed special limed wood rosin is being used newly doveloped uses to illustrate what properly directed re- to waterprooi Portland cements and bids fair to develop into search can aceoniplish in this field. an important outlet. Wood rosin producers have taken tho lead in supplying special grades of limed rosin to meet parRofiIN ticular industrial requirements. While the major portion of rosin used in the iorni of waterMixtures of rosin and various naxes or drying and nondrysoluble soaps is employed in laundry soap and paper size, ing oils form the bitse for a large number of adhesive products. tliere is an increasing use of rosin soaps ior other purposes. The adhesive used for fastening paper labels to metal conRosin soaps are excellent emulsifying agents and are widely tainers is generally rosin softened with paraffin oil. Tho adused for this purpose. Their use in aspiialt emulsions is now hesive used on sticky fly paper is largely rosin softened with uiidergoing rapid development. The demand for quick castor oil. Mixtures of rosin wit.li paraffin or other waxes are breaking emulsion3 for road-building purposes has provided widely used in cutlers’ cement, brush liandle cement, filler for a new market for rosin soap. Similar applications of asphalt cellokiid toilet articles, etc. Rosin and rubber form the base emulsified with rosin soap are found in tlie manufacture of for many adhesive materials. The rosin and rubher are infelt-base linoleum and roofing materials. corporated bg rriilling on a rubber mill, by dissolving in Considerahlc quantities of rosin soaps are used as ciniilsifiers neutral solvents, or by dissolving the rubber in molten rosin. in sheep dips, soluble disinfectants, cutting oils, scouring and Mixtures of rosin and rubber softened with oils, fats, or waxes scrubbing soaps, textile soaps, and metal polislies and clean- are widely used in surgical tape, spray tape, and various aders. Such applications are cornparatively new and have in- hesives for fastening papa, metal, arid iahrics to wood, metal, creased greatly during the past decade. Rosin soap is cheap, fabrics, or paper. Xost waterproof adhesives contain rosin an efficient emulsifying agent, available in large quanti- in some form. Some of the more recent demands for adhesives that have tie?, and is oasily prepared. In most cases caustic soda or soda ash is used as the saponifying agent; however, sometimes been met with compositions containing rosin are: for waterpotassium hydroxide, ammonia, or triethanolamine is em- proof Cellophane; for fastening sound-proofing and insulation to building walls; ior fastening sound-proofing materials to ployed. Rosin that has been partially saponified with hydrated automobile bodies; for fastening rubher to automobile runlime, zinc oxide, or litharge finds many uses aside from ning boards and rubber shock iiisulatioii to various automo.___I
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transparent paper, waterproofing materials, and cornpaunds for treating wood t,o prevent iu t. irifestat.ion. This resin has reniarkalrle resistance to t,he ion of caiistic alkalies and is admirably suited for the preparatiiin of casting materials reqiiircd to withstand exposure to alkalies. Hydrogenatiou of methyl abiet.at,e yields a water-white liquid wliich is inert to the action of alkalies and whicti undergoes little change on exposure t.o air and light. This product has been avaiiable in commercial quantities for the past two years and is filLding app1ic:ition in special finishing materials, particularly in the iiewlg developed dilorinated rubber paints. T l i e use of rosin and synthetic resins containing r-carsthe amonnt of tiirpeiitine eonsoiiied hy rnaiiirfacturcrs of paints; varnislitss, ;rnd plishes has greatly decreased. I'ct~rolourrisolvents are no%\-used in tliese products in amounts tlint h r ext!eed the quailtities of turpendine fonticrly used 112iiaii~t: tiicy arc cheaper and available in almost unlimited quantities. Tlie recent prodiiction of Irigli-a,lvenc~- petroleiiiii tiiinrierP is offering u inore serious threat of replacement of turpentine. I'ortunat,ely, recelit,trends in tlic pailit and v:irnisli i n d u s t r y have Irrouglit alxiut L: retnrn to turpeiitine and allied solvents, and rccent low pric lind n st,irnulating 14l'ci:t. It is iinperativc, liowevcr, that prdiirers ui' t.iirpentilie sliould develop ot,lier uses of tiirpciitine t,m providc rrrarkots for emrent, jirodiict,im. The cliimical iitiliaation of torpenline 115s not made rnucli imxress, alt,lioogli . . there :we two cstahlislied uses worthy OS mention. The most important is the we of iiiirrne derived froin turpentinc f o r tlre m a n u f a c t u r e of s y n t h c t i c csiriphor. Large quantities of synthetic c a m p h o r have heen p r o d u c e d in Q ~ r m a n va n d Enwlaiid a n d . more recentl?, in this country. Tlie prodncers of stem-distillcd wood turpentine have taken tlre lead in supplying very pure alpha-pinene for this purpose. Turpentine is also used for the mannfacture of synthetic terpineol and borneol. Lately, crude alylia-terpineol derived froin pilie oil mid crude borneol derived from the same sonrce, Iinve largely supplanted turpentine in these processes. Scveral rccent patents disclose tlie use oi tnrpentine or piiiene derived from turpentine for tlre manufacture of synt l i e t i c resins. This is an impurtant new outlet and may ~~
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:ind otlier cinulsifieri lulrricaiit,s. Siiliuri furized tcrperrc hydrocarlmns have latidy ci~nieinto u s e in highpressure luhricrnts. Hydrogenated rosin oils aiipear t.o have pmsii)ilitics as special luhicants, linrtioilarly wlicrc stainless ilahlc in addit,im to the @mi. M e t h y l abirtate id resin that has found
appIicnt,ion in iiitrricelluline iacquera, printing i n k y , adhesives,
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July, 1934
I N D U S T R I A L A N D E N G I N E E R I N G C TI E hI I S T R Y
provide the long sought market for large quantities of these products. A development of considerable importance is the preparation of an organic acid anhydride by condensing unsaturated polybasic anhydrides with terpene hydrocarbons and alcohols. These products, when esterified with alcohols, yield interesting resins that appear to have possibilities in protective coatings, insulation, molding compositions, etc. Polyhydric alcohols yield heat-convertible resins which are characterized by their good light fastness, pale color, and hardnes.. This new development appears to hare excellent possibilities for providing a large outlet for these products. Solvents rich in dipentene are derived from crude steamdistilled and destructively distilled wood turpentines or may be obtained by the dehydration of the terpineols found in pine oil. These solvents are used for the production of high-grade reclaimed rubber where they act as softeners and devulcanizers. Dipentene and allied hydrocarbons are also potential ran- materials for the manufacture of synthetic rubber. Polymerization of turpentine yields polymers that range from high-boiling liquids to resinous solids. Such products are available in large quantities as a mixture of these polymers. They have possibilities in insulating compounds, protective coatings, printing inks, and adhesives. They are neutral and relatively nonvolatile, harden slowly, and are miscible with most solvents and oils. The chief uses developed so far are as a rubber softener and for electrical insulation.
PINE OIL Pine oil is distinctly a product of the wood naval stores industry; it i, not found in the gum that exudes from living trees. Pine oil is the name giren to a series of terpene alcohols, ethers, and ketones that are found in the heart wood and stumps of pine trees. An approximate analysis of steamdistilled pine oil is.
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of the peak. This falling off in the demand for pine oil for flotation made development of new outlets imperative, and work in this direction was immediately started. I t was known from the early use of pine oil in disinfectants, cleaning compounds, scrubbing soaps, and as a frother for flotation that pine oil and certain of its constituents were good wetting agents. Work was therefore started to find an application for pine oil in other industrial processes where good wetting agents were required.
EXTRXTOR HOUSE The conieyor takes t h e chips t o t h e extractor house where a o o d rosin, turpentine, a n d pine oil are extracted with a solvent
RIost textile processes present the problem of obtaining quick, thorough, and uniform wetting of the goods being processed. The textile industry was selected as one which offered a large and stable outlet for pine oil. Work was started with some of the leading textile schools and textile mills, and considerable evidence mas gathered that beneficial results were t o be obtained through the use of pine oil in kier % % ,,boiling of cotton, dyeing of cotton, wool, and silk, degumming Terpene hydrocarbons 5-10 a-Terpineol 50-60 and scouring of silk, and, later on, deoiling and dyeing of Borneol 5-10 Other terpineols 15-25 Fenchyl alcohol 5-10 Terpene ethers 5-10 rayon. Today pine oil is a widely used material in all branches Ketones and phenols 1-2 of the textile industry. X large number of proprietary texIn the early development of the steam distillation process tile soaps, penetrants, and kier compounds contain pine oil. for obtaining naval store. from pine stump wood, the dis- A recent and important use of pine oil in the textile field is the posal of steam-distilled pine oil was a vital problem. Pine oils use of a special pine oil for the delustering of rayon either in had been previously obtained from the destructive distillation the manufacturing or finishing process. This includes both of pine vood and had found application in disinfectants and viscose and acetate rayon. in cleaning and scouring soaps. Steam-distilled pine oil iinother field investigated was the use of pine oil soap comsoon found similar applications and its unique wetting and binations as a laundry detergent. Cooperative work with the cleansing properties \?-ere recognized as of importance in Laundry Institute a t Joliet, Ill., and several large commercial these products. Steam-distilled pine oil and destructively laundries demonstrated that pine oil has value in laundry distilled pine oil in these early days were not uniform in detergents. Special pine oils were developed for this purpose. composition and were often contaminated with terpene hydro- While this development is still in its early stages, it is a large carbow and, in the case of steam-distilled pine oil, varying potential outlet for pine oil. Several laundry detergents that amounts of petroleum solvent used for extraction. Todav contain pine oil are on the market. great strides have been made in the refining of pine oil t o meet There are many proprietary cleamers that coiitain pine the demands of the manufacturers of disinfectants and of oil, such as scrubbing soaps, hand soaps, scouring soaps, dry cleaning and qcrubbing soaps so that pine oils of high alcohol cleaning soaps, dog soaps, mechanics’ soaps, medicinal soaps, content, of lo~vhydrocarbon content, and of dependable shaving soaps, etc. X fine toilet soap that contains pine oil uniformity are available. The use of pine oil in these prod- recently appeared. uct< has grown tremendously during the past ten years. Pine oil is now being used in the leather industry for deThe first large market for pine oil was as a frothing agent for greasing skins such as are used for the production of patent separation of minerals by flotation. This outlet for pine leather. Water-miscible pine oil compounds are used in oil soon became large enough t o consume most of the pine oil soaking heavy leather to promote penetration of natural available. The requirements of this single outlet for pine oil greases and to inhibit mold gron-th. Pine oil iq also used to were so great that little thought was given to the development promote penetration of fat-liquoring oils and in dyeing of of other outlets. When the slump came in the mining and leather. Pine oil is being used in rarious types of polishes flotation trades prior to the industrial depression, producers of such as metal, furniture, automobile, etc. It is also used pine oil started to build up stock9 of pine oil at an alarming in paint cleaners and in paint and varnish removers. rate. Today the amount of pine oil consumed as a frothing Another important use of pine oil is for the manufacture of agent in flotation is still quite large but only about 40 per cent essential oils. I t is employed in making terpin hydrate,
