Document g20E7p2wEJpway8MmeXnzwBGa

Vcl. 5 (IIEOKOCARRONS AM) ciij.oroiiydrocarbons 2X9 21. 'V. J. D.ivry, J. Inft. 1`rlrol. 31, 73-SS (121.7). . 2.3. F. M. !;<<. ril., Ciilo'ir In-lct (Cl), lfll .Sucirly .if Dyers :unl Colourists, Bradford, York shire, 1221; Fopiilement, lil'JS. 2d. Brit. .'110,210 (June 20, 1!*2'.)), N. Bcmrctl ami W. C. 8prent (to Imperial Chemical Indus tries Ltd.). 27. l-.S. I' ll. 1,.' .77,133 (Oct. 13, 122.7), A. George (to M.-iUiiraon Alkali Works). U S. l'at. 1,.721,.11.3 (July G, 1020), F. li. Stockellurk (to Matliirson Alkali Works). 22. Cicr. Put. 231,220 (1200) (to Bariisrhc Anilin- iind Stnla-Kahrik A.G.). Of? yJtrsn UsJ C H. SlDI Heydcn Newport Chemical Corporation / CHLORINATED lHPHENYL AND RELATED COMPOUNDS / . / Piphony i (diphenyl), tcrphcnyls, higher polyphenyls, or mixtures of these coin- vmnds ran lie chlorinated to give products which have outstanding chemical and thermal stabilities. Individual isomers, which range from liquids to high-melting crystalline solids, are of little commercial importance whereas the mixed chlorinated tomponents have considerable commercial significance. ' Registered trademarks for some commercial brands of chlorinated biphenyls in the United States arc the following: Arodor (.Monsanto Company), Chiorextol (Ailis-Chalmors Manufacturing Company), Dvkanol (ComcII-Dubilier Division, Federal Pacific Electric Company), Jnertcen (Westinghousc Electric Corporation), Noilamoi (AVagnor Electric Corporation), Pyranoi (General Electric Company), and Thcrminol (Monsanto Company). Some other registered trademarks or trade names for commercial chlorinated biphenyls found throughout the world are the following: C'oplien (I. G. Farbenindustric A.G., Germany), Ecnclor (Caffaro, Italy),- Kaur.echlor (ix,'r.egafuchi Chemical Co., Japan), Pyralcr.c (Prodclcc, France), and Sovol (Russia). _ Commercial manufacture of the Aroclor brand of chlorinated biphenyls was started in 1929. -These products vary from mobile oily liquids to white crystalline solids and hard noncrystallinu resins. Because of the many forms and properties, they have found applications in many diverse fields---in electrical insulation, fire- n.si:lar.t heat-transfer ar.d hydraulic fluids, lubricants for use at high temperatures and pressures, sealant and expansion media, and as constituents in elastomers, ad* hesives, paints, lacquers, varnishes, pigments, and waxes. Physical and Chemical Properties The physical properties 'of individual chlorobiphenyl isomers vary widely as may be seen in Table .1. Mixed isomers as produced in a commercial product have physical properties which are quite different from those of the individual isomers. This is particularly true for the solidification point. Chlorinated biphenyls, in general, are considered to be inert materials. IIoxv- ever, they will react with certain reagents when treated under rather rigorous condi tions. For example, chlorobiphenyls will react with sodium hydroxide at elevated temperatures to yield phenolic materials (28). . Mixtures of chlorinated biphenyls, such as those found in commercial products, will not react with acids, alkalies, or water under normal to moderately-'rigorous conditions (29). They are insoluble in water, glycerol, and the glycols. The oils and DSW 379698 STLCOPCB4100470 230 CIII.OUOCAKBONS AND CIILOKOIIYDKOCAKBONS resins arc readily soluble in most of tlic common organic solvents, but most of the hard crystalline inoinlwrs are loss soluble than the liquids or softer resins. The chlorinated biphenyl mixtures arc Hondrying even when exposed to air in thin films. They arc permanently thermoplastic and except for the lower chlorinated members are nonflammable. The resins will adhere strongly to smooth surfaces such as glass, metal, varnished or lacquered surfaces. Most of the common metals and alloys ," /. . Tablet. Physical Properties of Chlorobiphcnvls . ' * Compound / t / Moll inn point, *C IlnilinK point, *C (mm IIK) Bibliography references *i-rliI*irobiphcnyl 3-rhlnrobiplienyl 4-rlilorobiplieiiyl / / / 34 89 75.5;76;74 2G7-21K; 151 (12) 284-285 125(14) 2f2'-<lirhl('riil>ijiiicnyl / 3,3#-<iir!ilr*bi|1ipnyl / 4,4'-<!i iilonibipheiiyl / 3/wlicMoruMp!icnyl / 2,5-<hchlr>bi|>}irnyl 2,3-<li<-bl<>rubipliciiyl 2,4'-<l:chl<>rol![;!;r-iiyl 69; Gl-02 2.3; 29 322-324; 320-326 148 315-319 3G 1GG(10) 171 (15); 182 (30) 4G;49-50 195-200(15) - 172 (30) - .. 44 2,4,5-ln<:li!<irol,iphctiyl 2,3,5-triclilombiphciiyl 2,4,4'-triehlor. .biphenyl 2,S,4'-triehlorohiphcnyl 3,5,4'-trirhlorubipiicnyl .3,4,2'-tricl.lnrnbiphenyl 3,5,2'-tnchlorobi|)hcnyl 78-79 41 55-50 07 SS 65-GO 5S ` 3,4,3',4'-tclrnchl<jrobipl\enyl .3,4,2',5'-tctra<Mori .biphenyl / 2,6,2'1U'-tctrnrhlorobiplicnyl ' 2,5,3',5'-tctracliiorol>iphenyl 2,4,2 ',4 '-tet rarh lornhipl icnyl 2,S,2',j'-totraciilorbiplicnyl - 172 103 - 198 . 1G2 83 84-85 230(50) 2,4,'i,3',4'-prntaclil<irobiphcnyl 179 195-220 (10) 3,4,5,3',iVi'-hexarhlon .biphenyl 2,4,ri,2',4',6'-hexarlilor(ibipliPnyl - ins . ' 1U.5-112 ; 2,3,4,5,2',4',5'-hcplnclilonibiphcnyl ` ,s` 240-280 (20) ` 2,31.r>,0,2'13',5',6'-oi-L-a;lihinibiphcnyl 161 213,4,5,G,2',3',4',5'16'-.lecaehl<,robiphenyl 310 (1-3) (4.5) (2,0,7) (.8,9) (9-12) (2,9,12) (13.14) (14,15) (10,17) 05) 05,18) - - (19) (13) (9,20) ' (21) (13) (22) -(13) (11.23) (21) (23) (23) (12,24) (25) (19,20) (23) (12,27) (19) (23) (23) ; have excellent resistance to the chlorinated biphenyls even at elevated temperatures. However, copper and some copper alloys arc affected to a limited extent and show pene tration rates between 0.0014 and 0.014 in./yr. Many plastic materials of construction are attacked by chlorinated biphenyls. In addition to high resistance to thermal degradation, they also have many interesting electrical properties. The general properties of the more important members of the Aroclor brand of chlorinated biphenyl products are shown in Table 2 and the electrical -properties are shown in Table 3. DSW 379699 STLCOPCB4100471 Vol. 5 C1ILOKOCAUBOXS ANI) CIILOkOIIYDROCAIUJONS T u M ; 2. General Properties of Sumo Aroelijra / / DSW 379700 STLCOPCB4100472 / 292 CIll.OKOCAKBONS AND CIJLOKOIIYDKOCARBONS Tulilc 3. Kli'i:Uic:il l'ro|>ortiin of Soma Aroclorx Ilirlarlrii: coii.-tunl at 1000 cyclin' AriMiof ' 25*C 1IK)*C rj:ij fi.7 4.0 1242 7>.S 4.!l 1248 5.0 4.A 1251 5.0 4.3 1200 4.3 3.7 120S 2.5 5442 3.0 4.9 5454 2.7 4.2 54CO 2.5 3.7 4405 2.7 3.3 " A.STM D-150-47T. ASTM D-257-4G. ASTM'D-149-44. TiWHtivily,* iH'in at KW'C, flUO V, tie Dielectric alrcngili,* kV ubove 500 X 10* . / ` abovo 500 X 10* / above 500 X 10* / above 500 X 10* / t / above 500 X 10* / >35 >35 >35 >35 Power factor,' tOUVl, 1000 eyries, % <0.1 <0.1 <0.1' <0.1 Manufacture A numlii-i* of the pure rompoumls formed by the chlorination of biphenyl, tcr- phenyl, or more complex polyphcnyls are crystalline solids, some of which have very high melting points (30). However, mixtures containing a numlicrof such compounds may l>c either liquids or noncrystalliuc resins. Chlorination of aromatic hydro carbons to various levels not only gives several isomers of the same chlorinc.contont but also gives appreciable, portions of the isomers of compounds of higher and lower chlorine contents (31,32). At any level of chlorine content, batch chlorination gives the highest proportion of compounds corresponding in composition to the average chlorine content, whereas single-stage continuous chlorination gives the lowest pro portion of such compounds. As the numitcr of stages is increased, multistage con tinuous chlorination gives compositions approaching thoso obtained by batch chlo rination. The proport ion o the various isomers and of compounds of higher and lower chlorine contents than the average i3 also influenced by factors such as temperature, quantity and kind of catalyst employed, degree.and type of agitation, and rate of admission of the chlorine. ' ' ' A procedure for carrying out a single-stage fluid-bed chlorination is described in the patent literature for polychlorination of biphenyl (33). Continuous liquid chlo rination in a multiple-stage unit can also lw used. Batch chlorination has been found to be particularly well suited for the manufacture of the various products (32,34). The chlorinators may be cylindrical steel towers, 3 ft in diameter and 18 ft high, which arc equipped with chlorine distributors at the bottom und with coils for heating and cooling the material undergoing reaction, l'uinps provide agitation by circulating the liquid charge. The lower half of the chlorinutore is filled with iron turnings, which have been burned free of oil and moisture. In German practice, the chlorino- tors arc agitated 10,000-liter lead-lined vessels, and ferric chloride is used ns the catalyst instead of iron turnings'. Fifteen kg of ferrio chloride is used for each charge DSW 379701 STLCOPCB4100473 Vol. 5 CHLOROCARBONS AND CIILOROHYDROCARBONS 293 Raw Materials. The raw material used depends on the type of chlorinated material to lc produced; anhydrous chlorine is us<>d as the chlorinating agent in all rases. In general, it. can Ik: said that hipltcnvl alone gives liquid or soft, sticky nou- crystallino products up to a chlorine content of M%, low-melting resinous products between GO and G3% chlorine content, and partly crystalline or crystalline products of much higher molting points at chlorine contents above <V>% (.'12). It\ the case of products that arc solid at ordinary temperatures, the higher the proportion of ter- phcnvls or mote complex polyplienyls in the mixture before chlorination, the higher the softening point and the less the crystallizing tendency of the chlorinated product after distillation. Tor those products that are solid or partly crystalline at room temperature, the higher the chlorine content, the higher the softening point, and the greater the tendency of the material to crystallize (34). Preparation of Crude Chlorinated Biphenyl. Tor the manufacture of any given grade of chlorinated biphenyl, the chlorinator is charged with the proper raw material cr mixture of raw materials to give the desired product in an amount sufficient to cover the catalyst 1h\1 and to permit circulation. Then the flow of vaporized chlorine is started and the charge is circulated with the pump. Throughout the chlorination, the temperature is kept well above the melting point of the mixture, hut below 150 C, to avoid excessive sublimation and plugging of the line discharging the hydrogen eldyridc produced by the chlorination. Samples are withdrawn for examination from time to time, until the desired chlorine content has Ijccn reached. At the lower.chlorine contents, specific gravity measurements arc taken using a hydrometer to determine the eoni()Osition. After the product has become too viscous or has readied too high a melting point for convenient determination of the specific gravity at temperatures lielow ltXTC, the degree of chlorination is determined by measuring the hold point as the material crystallizes, or by the ball-and-ring softening-point test. (30). T]io_ time required for chlorination is 12 to 30 hr, depending upon the chlorine content of the product. The anhydrous hydrogen chloride, which is evolved during the chlorina- tioiis, is absorbed in water in equipment of conventional design. / Distillation of Crude Products. Although the crude products find some applica tions, for most purposes further purification i3 necessary to remove the color, and the traces of hydrogen chloride and ferric chloride (32,34,35). The methods of purification arc somewhat different for the different types of end products. The high-melting solid products arc difficult to distill. Distillation under mluced pressure is particularly difficult as it is desirable to keep the boiling point, above the solidification point. Generally, these products arc distilled in gas-fired retorls at atmospheric pressure. The distillate is flaked on chilled rolls. From practical considerations of quality and better overall processing efficiency, the liquid and resinous products arc distilled at lower temperatures in more conventional equipment under reduced pressure. The crude liquid and resinous products arc held at an elevated temperature and blown with dry air for several hours, after which a-few tenths of 1% of lime or sodium hydrox ide is stirred with the material to react with any remaining hydrogen chloride or ferric chloride. This is followed by batch distillation under reduced pressure. Compicto distillation and mixing of the distillate is necessary in order to obtain uniform material of the desired composition. .' If increased electrical resistivity is desired, the material is. stirred at an elevated temperature with a few tenths of of well-dried fuller's earth and then filtered through paper (35,37). / 294 CHLOROCARBONS AND CIILOROHYDROCARBONS Containers and Shipping ' The liquid chlorinated biphenyls arc packed and shipped in galvanizcd-stoel drums or in lank cars constructed of nonrusting metals such ns aluminum or tincoated met-aL The resinous products arc packed and shipped in open-top galvanizcd, steel drums7and the high-melting solid products arc packed and shipped in bags. The railroad shipping classification is Resin Synthetic NOIBN. ' Health and Safety Factors Prolonged exposure to chlorinated biphenyl vapor evolved at high temperature can lead to systemic toxic effects. Inhalation tests on animals indicate that the maximum safe concentration of vapor is in the range of 0.5 to 1.0 mg of the lower chlorinated biphenyl mixtures per cubic meter of air. The threshold limits (maxi mum allowable concentration for an eight-hour working day) set by the Amcricar/ Conference of Governmental Industrial Hygienists arc 1.0 mg of the lower chlorin ated biphenyl compounds (42% chlorine) per cubic meter of air and 0.5 mg of the more highly chlorinated biphenyl compounds (5-1% chlorine) per cubic meter of, air. When chlorinated biphenyl compounds are used at elevated temperatures, engineering controls must be applied, cither by the use of closed systems or by effective local mechanical exhaust ventilation together with general workroom exhaust. Although the chlorinated biphenyls are not normally skin irritants, their solvent ^action can remove natural protective oils and fats, and lead to drying and cracking of the skin. Also, continuous or repeated skin contact with chlorinated biphenyls should be avoided because of the possible occurrence of a condition called "chloracnc" {38}. ./ Electrical Applications. All of the uses of the chlorinated biphenyls depend on their chemical stability and their physical properties, which may he varied to suit tho specific application. One very important use is os dielectric mediums in such applica tions as fluids for transformers and ns impregnants for capacitors and condensers (29, 30,39-44). Chlorinated biphenyls, used either alone or in'blends with other ma terials such as trichlorobcn/.cnc, meet the need for a fire-resistant dielectric fluid with a high resistivity, a high dielectric strength, a relatively high dielectric constant, and a very low power factor. By replacing hydrocarbon oil with chlorinated biphenyls or mixtures of chlorinated biphenyls with trichlorobenzcne, it lias been possible to redesign equipment with a great reduction in size for the same capacity and voltage. At the same time, the fire hazards have been eliminated. See also Dielectrics and piezoelectrics; Insulation, electrical. / . The maximum dielectric constant of commercial chlorinated biphenyl mixtures at 1000 cycles and 25C is approximately G.0. In recent years, considerable attention has been given to upgrading this property (45-48). Combinations of fractional. distillation, chlorination, and isomerization can be used to obtain dielectric constants of 7.0 or slightly above. Direct synthesis of specific trichlorobiphenyl isomers can be utilized to obtain dielectric constants in the order of 10 (49). Improved analytical techniques, primarily capillary go3 chromatography (50), have been of great aid in studying the complex chlorobiphenyl paixturcs. DSW 379703 STLCOPCB4100475 Vol. 5 CIILOKOCAKliONS AND CHLOKOIIYDKOCAKIJONS 295 Other important- electrical applications for the chlorinated biphenyls arc as imprcgnnnts for cotton or ;isl test os-liber insulation as const itueuts of asphalt- base wire-impregnating compounds, and as plasticizers in wire-coal ing compounds, particularly tlmsc coulaining neoprene, rubber, or combinations of |silyvinyl chloride, cthylcelfuloso, and polyvinyl butyral (.>2-55). Also, chlorinated biphenyls arc em ployed as scaling mediums for electrical insulators and as impregnauts for carlKm resistors to reduce the influence of moisture. Plastics, Lacquers, Paints, and Varnishes. Chlorinated biphenyls are compatible with most of the common plastic materials and resins, and are soluble in paint and varnish oils (20). In combination with asphalt, ethylcellulosc, chlorinated rublxir, Pliolite (styrene-butadiene copolymer), or other plastic materials, they are used ex tensively in protective coalings for wood, metal, and concrete (33,56,57). In com bination with dioctyl phthalutc, they are coplastici/.ers for polyvinyl chloride compo sitions (2!),3S). Sec also Coatings, industrial; Paint. In paints and varnishes the hard resinous chlorinated biphenyls are used to impart increased hardness to the films, and the softer resins arc used to give flexi bility. The role of these materials is similar to that of the oil, except that they do not oxidize and lose flexibility on ageing. In nitrocellulose lacquers, chlorinated bi phenyls arc employed either alone or in combination with other plasticizers and resins to impart increased weather resistance, luster, adhesion, and decreased burning rate (57--C0). The hard, white, crystalline chlorinated biphenyls of high melting point arc useful as pigments with various plasties (Gl). Adhesives (qv). The resinous products are used in synthetic adhesive com positions in combination with such base materials as polyvinyl acetate, ethylcellulosc, chlorinated rubber, polyvinyl butyral, isoprene-styrene copolymer, and polyiso- butylere. Chlorinated biphenyls arc used in the preparation of coatings of pressuro- rupturablc capsules for adhesive tape (02). / Lubricants (qv). Chlorinated biphenyls find application as lubricants under extreme conditions such as highly oxidizing conditions, high temperatures, extreme pressures, or submerged locations. Mixtures with other oils to form heavior-than- watcr lubricants arc used in submerged locations, such as bridge rollers. /Lubricants for extreme pressures arc made-by adding up to 15% of the chlorinated biphenyls to petroleum hvdrocarlxm oils. ' Heat-Transfer Media (qv). Chlorinated biphenyls have l>eeu used for some time in indirect heating applications (03). 'decently, products of this type sold by Mon santo Company under the registered trademark Therminol liave been introduced, which are specifically directed to use as heat-transfer media (64). These fluids are particularly well suited for efficient and safe operation in applications involving flammable materials where uniform temperatures arc required and for high-tempera ture (bulk temperatures of 600F) indirect heating. Specifically designed units for such applications are required to prevent local overheating." . Miscellaneous Applications. Carnauba wax may be extended by blending with chlorinated biphenyl in combination with ccrcsin and paraffin (29,G5). Satisfactory waxes and polishes arc prepared without the use of carnauba wax by blending ouricury (licuri) wax with chlorinated biphenyl, ccrcsin, and paraffin. Chlorinated biphenyls are ingredients of many fire-resistant compositions. Fire-retarding paints usually contain antimony oxide or barium sulfate in addition to the chlorinated biphenyL In making fireproof fiberboard, emulsified chlorinated biphenyl is added to the fiber DSW 379704 STLCOPCB4100476 2'JG ClILOKOCAKBONS AND CIILOUOIIYDKOCAKBONS slock (GO). Morlifyiug waxes arc tultltxl to chlorinated biphenyl in tli<; preparation of tdxtile-ronting materials. In addition to the uses listed above, chlorinated biphenyls are ingredients of some sealing compounds for use with wood or canvas lo give; protection against moisture, mildew, or attacks of organisms. They arc also used in formulating calking com pounds, powdered metal pastes, some soil-jjoison and wood-preserving compositions, paper transparentizers, and printing inks. Carbonless reproducing paper is made by an encapsulation procedure which uses chlorinated biphenyl as part of the formula tion (67) (see Encapsulation). ' Bibliography * ``Chloriiialrd Diphenyls" under ``Chlorine Compounds, Organic" in ECT 1st ed., Yol. 3, pp. S20-832, by C. F. Booth, Monsanto Cheniii'td Company. 1. F. Dell, J. Chem. Soe. 131,2773 (1928). / 2. Dcmaclhcn, Ann. Chem. I.ichujl IS9, 13S, 142 (IH77)./ 3. K. H. Zaheer and S. A. F.weh, J. Ind. Chem. Soe. 21,27 (1944). 4. M. Gomhrrg amt \V. E. Baehmann, J. Am. Chem. Hoc. 46, 2343 (1924). j '/ / o. Ibid., 49,250(1927). G. CJ. Schultz, .Inn. Chem. Lit bigs 174, 209 (1S74). 7. 1C. Bamberger, Her. Deal. Chem. Gel. 29, -IGu (1890). 8. J. J. Dobbie, J. J. Fox, and A. J. II. Gauge, J. Chem. Soe. 99, !G19 (1911). / / ./ / 9. I,. Majcarcili, D. Gatti, IC. Jor.a, and V. Lcouriui, Gait. Chim. ILai. 59,808-870 (1920). 10. H. II. Hodgson, J. Chem. Soe. 149, 745 (19115). J 11. J. C. Coin, J. Chem. Soe. 85, 7 (1904). / 12. F. I'llmann, .Inn. Chem. Liebig* 332, 64-5G (1904). / 13. L. E. llinkcl and D. H. Hey, J. Chem. Soe. 131,27.SG-27S8 (1928). / .' 14. H. A. Scarborough and \V. A. V/atcra, J. Chem. See. 130,93 94 (1927). / 15. T. Crauw, lice. Trav. Chim. 50, 753(1931). '/ 1G. W. Blakely and H. A. Scarborough, J. Chem. Soe. 130, 3007 (1027). / 17. IV. Zcraterk and C. Schulz, Chem. Abslr. 3G, 5G.W (1942). / IS. C. Find and V. BcUavita, Gate. Chim. tbil. G4,335 (1934). / 1!). Y. S. %d'kiud and M. V. Belikova, J. Gen. Chem. USSR (Smjl. 7'rn/isl.) 8, 1918 (1939). ' 20. II. Kainiuilz with H. Uohni, ISrr. DeuL Chen. Ges. 60, 743 (1927). / 21. V. Bell.ivita, Gael. ('him. Itnl. 65, G32 (1935). / 22. L. Mascareili, D. Gatti, and li. ly>ngo, Ga:z. Chim. Itill. 63. 05-1 (1933). 23. F. I.. W. Van Kooamalcn, Rce. Trav. Chim. 53. 359 (1934). / 24. Fr. Fichtcr and M. Adler, Ilclv. Chim. Acta 9. 2S7 (1026>. / 25. H. Meyer and A. Hofmann, Mor.atzh. Chem. 33, 145 (1917). / 2G. II. Schmidt and (J. Schultz, Ann. Chem. Liebig* 207. 340 (1881). 27. I,. W. Pickett, F. G. Walter, and It. Franco, J. Am. Chem. Soe. 58,2290(1930). 28. Brit. Pat. 779,221 (July 17, 1957) (lo Progil). - 29. The Aroelor Cnmpoundi, booklet, Monsanto Co., St. Louis, Mo. 30. F. M. Clark, Trans. Elcelrochem. Soe. 63.59-71 (1934)./ 31. R. B. MaeMuilin, Chem. Eng. Progr. 44 (3), 183-1SS (1948). 32. U.S. Pats. 1,31*2,397 and t,S92,39S (Doc. 27, 1932), R. L. Jenkins (to Swuuu Research; re assigned to Monsanto Chemical Co.J. / . 33. U.S. Pal. 3,029,295 (April 10, 1C-G2), Robert Thermet and Ludovio Parvi (to SocidUS d'Electro- chimic D'Elcclromrtallurgic ct dea Acidriea Electriques d'Ugine). - 34. U.S. Pat. 1,892,400 (Dee. 27, 1932), R. L. Jenkins and J. A. Sikaraki (to Swann Research; reassigned lo Monsanto Cheinicid Co.). / * _ 35. J. \Y. J. Fay ami J. II. Kicluird*, "Impregnants Used in German Psjtcr Capacitors," Office Tech. Sen. PR Kept. 75852(1047); RIOS (Urilish Intelligence Objective! Subcommittee) Einr.l UepL 80S. 30. ``Xonmctallie Materials" ASTM SUL E38-4ST, Part UI-A (1940). 37. US. Pat. 1,994,302 (March 12,1935), JF. M. Clark (to Gcneriil Electric Co.). Vol. 5 CHLOItOCAIUlONS AN!) CIILOKOim)KOCAKHONS /2<J7 18. . 1 rrnlor Pla.-lirizcrs, Tcrli. Hull. Xu. PI/-.')< )G, Mim-Vintii Ci., SI. Liuis, Mo., l)e< 19. la. H. Bundum mid S. T. M minder, Ccn. Eler. AVw. 42,210-:219 (1919). 10. F. M. CPirk, fmt. Eng. Chem. 23. G9.S-702 (1937). _ 41. W. Jacks..n, l'roe. Hoy. Soe. (Ixnulon) Err. .1 133. 158-100 (1933). ' 42. A. 11. While ami ? O. Mmpii, J. Franklin fnxl. 216, 033-044 (1911). 4.1. U.S. Pat. l,S1ii,ISrt(Dcr. 13. 1911),O. 11. MrCuUnugh and R. L. Jenkins(loSwuim Research; renysigned to Mensantii Chemical Co.). / 14. U.S. Fats. I,111 I..171 and I,! HI, 4.Vi (Oct. 17, 111.31). F. M. Clark (to General Electric Co.). 13. I'.S. Fat. 1,0.18,107 (June 3, 1HG2), H. I. Wcingurlcn (to Monsanto Chemical Co.). . 40. U.S. Fat. 1,003,297 (Dec. 11, 1%2), H. I. Wcingarlcn (U> Monsanto Chemical Co.). 47. H. I. Wcingarlcn, J. Org. Chem. 26, 4347--1330 (1001). / 4S. Ibid., 27, 2021-2020 (10G2). / 41). U.S. Fat. 2,1)77,310 (March 28, 1001), It. I. Weingartcu (lo Monsanto Chemical Co.). 3(1. II. I. Wcingarlcn, W. D. Rosa, J. M. Schiater, and G. Wheeler, Jr., AnaL Chim. Ada 26, 391- 1114(11102). / 31. IhS. Fat. 1,810,147 (June 14, 11)32), J. H. Young (to H. II. Ri.bcrls.rn Co.). 32. U.S. Fat. 2,121), 137 (Sept. 0, IMS), E. W. Troclandcr and W. C. Wilson (to Pyroxylin Products). 33. U.S. Fat. 2,1111,204 (Sept. 11, 191S), F. M. Clark ami J. H. Koenig (lot'cneral Electric Co.). 34. U.S. Fill. 2,111,1)10 (Dec. 27, 1918), W. C. 1 layman (U, Ocncral Klcetric Co.). 53. U.S. Pat. 2,158,281 (May lo, 1919), J. G. Ford and C. F. Hill (to Wcalingliouso Electric and Manufacturing Co.). . / 30. Arorlnr Herins and Plasticizers for Chlorinated JluUicr, Tet-U. Hull. PL-311, Monsanto Co., St. Ism is, Mn., April 1902. / 57. .trorlor Fire Uelardimj Plaslirizers and Mrxlijicrs for Epoxy llesins, Tech. Hull. CS-14, Monsanto Co., St. Ismis, Mo., Nov. 11Mil). -VS. II. W. Bnwron, 7'a ini Tcel.nnl. 2, 25-27 (1937).' __ 59. II. A. Gardner and G. (1, Sword, Sail. Faint, Varnish Ixia/ner .Issue. Ed. Ecc. Cire. So. 66, 100-101(1918). 00. IL L. Jenkins and It. X. Foster, tnd. Eng. Chetn. 23, 1302-1303 (1931). _ 01. U.S.'Fat. 2,077,700 (April 20, 1917), E. Klein (to E. I. du Font do Xeinours & Co., Inc.). G2. U.S. Pal. 2,9.88,401 (June II, 1901), H. J. Eichel (to Xaliunal Cash Register Co.). 01. W. J. Davis and P. G. Bcnigiius, Chem. Eng. Prog. 59, 39--42 (1903). . 04. TherminU Fit Fluid Heal Systems, booklet, Monsanto Co., St. Louis, Mo. 05. G. W: Wood. Hfg. Chemid 19 (3), 09-llVt (1948). - GO. U-S. l'at. 2.010,053 (Feb. II, 191U), R.' G. Quinn (to International Paper Co.). 07. U.S. Pat. 2,343,300 (April 1951) li.K. Green and It. W. Sandberg (to National Cash Register Co.). / . H. L. Hubuahu Monsanto Company CHLORINATED NAPHTHALENES Laurent, in 18.TI, observed that waxlike materials resulted from reaction of chlorine with nuphtlialcuc in the presence of certain catalysts. These chlorination products were further studied by Fischer in 1878. ft was more than twenty years later, however, that Aylsworth discerned their technological potentialities (l). Chemically and physically, the chlorine derivatives of naphthalene presented investigators with a much more complex problem than the chlorobenzenes. Following Erlcmneycr's establishment of the fused-ring structure of naphthalene in I8G(i, niuny years elapsed before many of the theoretically jxissible chlorination derivatives of tho compound were isolated and .identified; even today the positions of the subktituent chlorine atoms in all isolated tctrachloro- and pcntucliloronaphthalcucs have not been allocated with certainty (see Table 1). Physically, the dilliculty of isolating isomers from the mixtures produced by chloriuation of naphthalene is such that indiroct