Document JBzebDjappr6vN26x9X4G4QB

Vol.5 CHLOROCARIIONS AND CIILOROIIYDROCAKBONH 289 24. W. J. U.ivry, J. ln*t. J'Hrol. 31. 73-KS ( 25. F. M. llimc, !., Colour Imler (('.!), IL rtl., Society of Dyer* ami Oolourixtil, ItnuUorU, York- Mliirc, 1(1'24, Supplement, 1928. 20. Bril. Fat. 310,910 (June 26, 1929), N. Uetinelt and W. C. Sprent (to Imperial Chemical Indus trie* Ltd.). 27. U.8. Pat. 1,657,153 (Oct. 13, 1925), A. George (to Malliieaou Alkali Works). 28. U.8. Pat. 1,501,545 (July 0, 192G), K. E. Stockelliark (to Mathioson Alkali Works). 29. Ger. Pat. 234,200 (1000) (to Badisrlie Anilin- und Soda-Fabrik A.G.). /9b H. Sidi / Heyden Newport Chemical Corporation CHLORINATED BIPHENYL AND RELATED COMPOUNDS f , / Biphenyl (diphenyl), lerphcnyls, higher polyphenyls, or mixtures of these com pounds can 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 components have considerable commercial significance. Registered trademarks for some commercial brands of chlorinated biphenyls in the United States arc the following: Aroclor (Monsanto Company), Chlorcxtol (Allis-Chalmcrs Manufacturing Company), Dykanol (Corncll-Dubilier Division, Federal Pacific Electric Company), Iuerteen (Wcstinghousc Electric Corporation), Noflamol (Wagner Electric Corporation), Pyranol (General Electric Company), and Therminoi (Monsanto Company). Some other registered trademarks or trade names for commercial chlorinated biphenyls found throughout the world are the following: Clophen (I. G. Farbenindustrie A.G., Germany), Fcnclor (Caffaro, Italy),- Kannechlor (Ivanegafuchi Chemical Co., Japan), PyralenC (Prodelec, 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 noncrystalline resins. Because of the many forms and properties, they have found applications in many diverse fields--in electrical insulation, fire- resistant beat-transfer and hydraulic fluids, lubricants for use at high temperatures and pressures, sealant and expansion media, and an constituents in elastomers, ad" hesives, paints, lacquers, varnishes, pigments, and waxes. Physical and Chemical Properties The physical properties of individual chlorobiphcnyl isomers vary widoly as may be seen in Table 1. Mixed isomers as produced in a commercial product have physical properties which arc 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. How ever, they will react with certain reagents when treated under rather rigorous condi tions. For example, chlorobiphcnyls will re^ct 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 / / / , ; OSNN j STLCOPCB4078792 ?J0 CIII.OUOCAKIJONS AND ClILOROlIYDlCOCAItBONS rosin* arc readily soluble in most of the common organic, solvents, hut most of tlie hard crystalline inomtx'rs arc less soluble than the liquids or softer rosins. The rhlorinutcd biphenyl mixtures are nondrying 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 os gloss, metal, varnished or lacquered surfaces. Most of the common metals and alloys Table 1. Physical Properties of Chlorobiphcnyls Compound / 2-rblornbiphenvl 3-rhlnrobiplienyl 4-nlilorobiphenyl N 2,2'-dirhlorobiphcnyl 3,3'-<Jirhlnn>hip)iciiyl 4,4'-dirlilorobiphnyl , 3,5-dichlori (biphenyl 2,.rwliclili>roijiphrnyl 3,4-diclUorobiphenyl 2,3-dirhlurobiplicnyl 2,4'-(Jirhli)robiplienyl / / / / 2,4,5-trichlorobiphcnyl 2,3,5-triclilnrobiphcnyl 2,4,4 '-irichlorobiphcny 1 2,5,4'-trichlorobiphcnyl 3,5,4 '-trichlorobiphcnyl 3,4,2'-trichiorobiplienyI 3,5,2 '-trichlorobiphcnyl 3,4,3',4'-tctruchlorobiphcnyl 3,4,2',5'-tetnirhlorobiphp.nyl 2, b,2 ',0 '-tctrachlorol hplicn y1 2,5,3 ',5'-tetrachlorol>iphenyl 2,4,2',4'-tetrachli>robiphenyl 2,.5,2',.V-letrachlon ibiphenyl 2,4,5,3'14'-peiitachl<irol>iphenyl 3,4,5,3'.4',5'-hexuohlombiphcnyl 2,4,6,2',4',6'-hexarlili>r<>bi,>lipnyl 2,3,4l5,2'l4',5'-hcpiaclilri>biphcnyl 2,3,.r>,Gl2',3',5',6'-o<itn<-lil<>rnbiphenyl 2,3,4,.'),0,2',3',4',.r)',f/-<lprarhlori)biphenyl Molting point, "C 34 80 75.5;76;74 60; 01-02 23; 20 148 3G 40; 40-50 44 78-70 41 55-50 67 88 05-06 58 172 103 JOS 102 83 84-85 179 108 111.5-112 101 3)0 lioiling point, *C (mm Hr) 267-208; 154 (12) 284-285 125(14) 322-324 ; 320- 326 315-310 100(10) 171 (15); 182 (30) 105-200(15) 172 (30) 230 (50) 105-220 (10) 240-280 (20) Bibliography references (1-3) (4,5) (2,0,7) (8,0) (0-12) (2,0,12) (13,14) (14,16) 06,17) (15) (15,18) (10) (13) (0,20) (2D (13) (22) (13) (11,23) (21) (23) (23) (12,24) (25) (19,20) (23) (12.27) (10) (23) (23) have excellent resistance to the chlorinated biphenyls even at elevated temperatures. However, copper and some copper alloys are 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 chlorinutcd biphenyls. In addition to high resistance to thormol 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. ., \ I t i DSW 332217 / w STLCOPCB4078793 Vol. 5 CHLOUOCAUBONS ANI) CHLOltOIIYDItOCAKBONS CO I 3 o . s*o N O -CT4 4I s a ----o-- o |A i IK 9 I & <c o r- CO o 2 * ** s /- /3 / i * ||? aOS * s, I C' C Ci 7 *3 e.eo '&* | xa ir .9 w & Sc CH o a s A O Z/ co $ 4> C 4cP V / 4> c/ a> V o c. c 4> C 4* c o o/ 5 c o oo C C/ c -C cA S3 c / o c o c v c // 4C) o, S3 \' oa a> o a o o S3 V d o a 247 4) e o aa N V J &8 s i so Q Col S' CO CO 46 s*r s " .A 9 Sai o-- 8O'-o'**' Cl o-`O oqO o ??o oT*CO!o"* t** O ^^ it -I, 2 < 12 2. 2 2 .4. 2 -i 2 ci* 2 4 JS 4. g a 'r 8 * ^ S "^ a^a -sw ^s^^ s> -'8w *** w8*a*^. W'8 va*- *a-- ^a *a--* 3 oO ii 15 o S/ M > I "3M t ?g n > 8 ---o c5 S J tfl s 1 8 *3 "5 ! 1- _ E-& tc 5 .2k =5 t =^2 Jr'S*. A2 -a2 4S 3 " * ?_ Zv a, * *-' 'si =a rfi i sif.^Si S .9 o i: r, S! 9 9 3 S SJ 3 2 6* Cl Cl C* Cl cj 2 C Cl jjjj j oScSisSSJj I i I 1 i I ] i e < % 8 fc / DSW 332218 __________t STLCOPCB4078794 292 CIlLOUOCAItKONK AND CIILOKOIIYDKOCARBONS Manufacture A numlx'i- of (lie pure compounds formed by the chlorinat ion of biphenyl, torphcnyl, or more complex polyphcnyls are cryRtullinc solids, some of which have very high melting points (:<0). However, mixtures containing a numlx-r of such compounds may be cither liquids or noncrystalline resins. Chlorination of aromatic hydro carbons to various levels not only gives several isomers of the same chlorine content 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 nuinlxjr of stages is increased, multistage con tinuous chlorination gives compositions approaching those obtained by batch chlo rination. The proportion of the various isomers and of compounds of higher and lower chlorine contents than the average is 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 singlo-stage fluid-l>cd chlorination is described in the patent literature for polychlorination of biphenyl (33). Continuous liquid chlo rination in a multiple-stage unit can also l>e used. Batch chlorination has been found to be particularly well suited for the manufacture of the various products (32,34). The chlorinatora may lc cylindrical steel towers, 3 ft in diameter and 18 ft high, which arc equipped with chlorine distributors at the ijottom und with coils for heating and cooling the material undergoing reaction. Pumps provide agitation by circulating the liquid charge. The lower half of the chlorinutors is filhxi with iron turnings, which have been burned free of oil and moisture. In German practice, the chlorinotore are agitated 10,000-litcr lead-lined vessels, and ferric chloride is used as the catalyst instead of iron turning?'. Fifteen kg of ferric ohloride is used for each charge of 0000 kg (35) of biphenyl. / . . ' , x / DSW 332219 '* .................. . ........... . f 1(1 llll""' STLCOPCB4078795 Vol. 5 CHLOROCARBONS AND CHLOKOHY1)KOCARBONS 293 Raw Materials. Tlio raw material used depends on tlic type of chlorinated material to he produced; anhydrous chlorine is used as tlie chlorinating agent in all eases. In geueml, it can Ik1 said that biphenyl alone gives liquid or soft, sticky nou- crystallinc products up to a chlorine content of (i()%, low-melting resinous products ix'tweeu (10 and 60% chlorine content, and partly crystalline or crystalline products of much higher melting points at chlorine contents above (W% (32). In the caw- of ' products that arc solid at ordinary temperatures, the higher the proportion of tor- plienyls or more complex polyphcuyls in the mixture before chlorination, the higher the softening point and the less the crystallizing tendency of the chlorinated product after distillation. For those products that arc 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. For the manufacture of any given grade of chlorinated biphenyl, the chlorinator is charged with the proper raw material / or mixture of raw materials to give the desired product in an amount .sufficient to/ cover the catalyst lied and to permit circulation. Then the flow of vaporizwl chlorine is started and the charge is circulated with the pump. Throughout the chlorination, the temperature is kept well above the inciting point of the mixture, but below 160 C, to avoid excessive sublimation and plugging of the line discharging tho hydrogen chloride produced by the chlorination. Samples arc withdrawn for examination from time to time until the desired chlorine content lias been reached. At the lower chlorine contents, specific gravity measurements are taken using a hydrometer to determine < the composition. After the product has become too viscous or has reached too high a melting point for convenient determination of the specific gravity at temperatures lielow 100C, the degree of chlorination is determined by measuring the hold point os tho material crystallizes, or by the hall-and-ring softening-point tost (3(5). The time required for chlorination is 12 to 36 hr, dopending upon the chlorine content of the product. The anhydrous hydrogen chloride, which is evolved during tho chlorina- tions, is alisorbed in water in equipment of conventional design. Distillation of Crude Products. Although the crude products find some applica tions, for most purposes further purification is necessary to remove the color, and the traces of hydrogen chloride and ferric chloride (32,34,3T>). The methods of purification - are somewhat different for tho different types of end products. The high-melting solid product s arc difficult to distill. Distillation under reduced pressure is particularly difficult as it is desirable to keep the boiling point above the solidification point. Generally, these products are distilled in gas-fired retorts at atmospheric pressure. The distillate is flaked on chilled rolls. From practical considerations of quality and better overall processing efficiency, the liquid and ruinous products are distilled ut lower temperatures in more conventional equipment under reduced pressure. Tho cnide liquid and resinous products are 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 forric chloride. This is followed by batch distillation under reduced pressure. Complete distillation and mixing of the distillate is necessary in order to obtain uniform material of the desired composition. If increased eloctrical resistivity is desired, the material is stirred at &n elevated temperature with a few tenths of of well-dried fuller's earth and then filtered through paper (3/5,37). ' DSW 332220 -I STLCOPCB4078796 204 CHLOKOCAUBONS AND CHLOROHYDROCARBONS Containers and Shipping Tin- liquid diloihinted 1 >ipljonyls arc packed and shipped in galvauixod-stcol drums or in tank cars const.meted of lionrusting metals such as aluminum or tincoatcd metal. The resinous products arc packed and shipped in open-top galvanixcd steel drums, and the high-melting solid products arc packed and shipped in bags. The railroad shipping classification is Resin Synthetic NOIBN. ' Health and Safety Factors 1'rolongod exposure' to chlorinated biphenyl vapor evolved at high temperat can load to systemic toxic effects. Inhalation tests on animals indicate that maximum safe concentration of vapor is in the range of 0.5 to 1.0 mg of the lo chlorinated biphenyl mixtures per cubic meter of air. The threshold limits (nil mum allowable concentration for an eight-hour working day) set by the Amcri 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 nig of the more highly chlorinated biphenyl compounds (54% chlorine) per cubic metor of,air. When chlorinated biphenyl compounds are used at elevated temperatures, engineering controls must be applied, either 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 qf the Bkin. Also, continuous or repeated skin contact with chlorinated biphenyls7 should be avoided because of the possible occurrence of a condition called "chl< nc" (38). Uses Electrical Applications. All of the uses of the chlorinated biphenyls depend on their chemical stability and their physical properties, which may Ire varied to suit the specific application. One very important use is as dielectric mediums in such applico- tions as fluids for transformers and us imprognunts for capacitors and condensers (20, 30,d`J -11). Chlorinated biphenyls, used either alone or in blends with other ma terials such as trichlorobcnzcnc, meet the need for a fire-resistant dielectric fluid with a high r sistivity, 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 26C is approximately 6.0. 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 alxive. Direct synthesis of specific trichlorobiphonyl isomers con be utilized to obtain dielectric constants in the order of 10 (49). Improved analytical techniques, primarily capillary gas chromatography (50), have been of great aid in studying the complex chlorobi urea. ( , ,, * j ' 1 'i . / osnnmm* ) STLCOPCB4078797 Vol. 5 CHLOROCARUONS AND CHLOROIIYDROCARBONS 295 Other important electrical applications for the chlorinated biphenyls nit; os imprcgiiants for cotton or :islioslo.s-lil>cr insulation (.51), tut constituents of asphalt- b:iso wire-impregnating compounds, nnd its pl;istici/,cix in wire-mating coinpounils, particularly those containing neoprene, rubber, or combinations of |>olyviiiyl chloride, ethylcclluloso, and polyvinyl butyral (52-55). Also, chlorinated biphenyls are em ployed as sealing mediums for electrical insulators and as impregnants for carl>on resistors to reduce the influence of moisture. Plastics, Lacquers, Paints, and Varnishes. . Chlorinated biphenyls arc compatible with most of the common plastic materials and resins, and are soluble in paint and varnish oils (2d)- In combination with asphalt, cthylccllulosc, chlorinated rubber, 1'liolitc (styrene-butadiene copolymer), or other plastic materials, they arc usod ex tensively in protective coatings for wood, metal, and concrete 18,50,57). In com bination with dioclyl phthalatc, they arc coplustici/.ers for polyvinyl chloride compo sitions (29,118). See also Coatings, industrial; I'aint. In paints and varnishes the hard resinous chlorinate! biphenyls art! used to impart increased hardness to the films, and the softer resins arc usod 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 are employed either alone or in combination with other plasticizers and resins to impart increased weather resistance, luster, adhesion, and decreased burning rate (57-GO). The hard, white, crystalline chlorinated biphenyls of high melting point arc useful as pigments with various plastics (61). Adhesives (qv). The resinous products are used in synthetic adhesive corn/ positions in combination with such base materials as polyvinyl acetate, ethylccllulose, chlorinated rubber, polyvinyl butyral, isoprene-styrenc copolymer, and polyiso butylene. Chlorinated biphenyls are used in the preparation of coatings of preepure- rupturable capsules for adhesive tape (G2). / 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 heavier-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 hydrocarlxm oils. ' Heat-Transfer Media (qv). Chlorinated biphenyls have l>ccn used for some time in indirect heating applications (G3). Recently, products of this type sold by Mon santo Company under the registered trademark Thcrminol have 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 fianunable 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 oombiitation with ccrcsin and paraffin (29,65). 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 / OSVSf 332222 STLCOPCB4078798 296 ClILOItOCAItltONS AND ClILOUOUYDItOCAltllONS slock (<)0). Modifying w.i\c* arc added In chlorinaUxl 1 >iplx*nyl in Die preparation of U'xtilc-roaling materials. In addition to Die uses listed altuvc, chlorinabxl biphenyls uro ingredients of hoiiiu sealing compounds fur use with wood or canvas to give protection against moisture, mildew, or attacks of organisms. They arc also used in formulating calking com pounds, powdered metal pastes, some soil-poison und wood-preserving compositions, paper transparentizers, and printing inks. Carbonless reproducing papor is mado by an encapsulation procedure which uses chlorinated biphenyl as port of the formula tion (67) (see Encapsulation). Bibliography ' "Chlnrimilod 1 liplieuyla" under "Chlorine Compounds, Organic" in KCT 1st ed., VuL 3, pp. 836-833, by C. F. Booth, Monsanto Clvcmical Company. 1. F. Hell, J. Chem. Soc. 131,2773 (1028). , 2. DeniBctlicn, Ann. Chem. Liebig* 189, 138, 142 (1877)v 3. S. H. Zaheer and S. A. Fnaoeh, J. Ind. Chem. Soc. 21, 27 (1944). 4. M. Gotnlicrg and W. E. Daclimann, J. Am. Chem. See. 48, 2343 (1024). 5. Ibid., 49. 250(1027). G. Cl. Schultz, Ann. Chem. Liebig* 174, 200 (1874). 7. E. Bamberger, Her. Deul. Chem. Get. 29, 405 (1800). 8. J. J. Dobbie, J. J. Fox, and A. J. II. Gauge, J. Chem. Soc. 99, 1G10 (1011). 0. L. Mnscarolli, D. Catti, E. Jona, and V. Leonciui, Got*. Chim. Ital. 59, 868-870(It 10. H. II. Hodgson, J. Chem. Soc. 149, 745 (1946). 11. J. C. Coin, J. Chem. Soc. 85, 7 (1004). 12. F. Ullmann, Ann. ('hem. Liebig* 832, 54-5G (1004). 13. L. E. Hinkcl and L). H. Hey, J. Chem. Soc. 131,2780-2788 (1028). 14. H. A. Scarborough and W. A. Waters, J. Chem. Soc. 130, 03-04 (1027). 15. T. Crnuw, Itee. Tran. Chim. 50, 7.53 (1031). 1C. W. Blakely and II. A. Scarborough, J. Chem. Soc. 130, 3007 (1027). 17. W. Zerwock and C. ScIniU, Chem. Ab*tr. 38, 5058* (1042). IS. C. Finxi and V. Bcltavita, Gmz. Chim. Ital. 64, 335 (1034). 19. Y. S. Znl'kind ;uid M. V. Belikova, J. Gen. Chem. USSIl (Engl. Trunel/,>8. 1018(1030). 20. H. Uaudniti with II. Hdhm, Her. Deul. Chem. Get. 60, 743 (1927). / 21. V. Bcllnvilu, Gate. ('him. Ital. 65, 632 (1035). / 22. L. Mascnrclli, 1). Galti, and B. Longo, Gait. Chim. Ital. 63, 054 (1033). 23. F. L. W. Van Rooemalcn, lice. Trav. Chim. 53, 350 (1934). J 24. Fr. Fichtcr and M. Adler, Debt. Chim. Acta 9, `287 (1020). / 25. H. Meyer and A. Hofmann, Mortalth. Chem. 38, 145 (1017). / 26. II. Schmidt and G. Schultz, Ann. Chem. Liebig 207, 340 (1881). 27. L. W. Pickett, F. G. Wnlter, and H. France, J. Am. Chem. Ijoc. 58,2200 (1030). 28. Brit. Pat. 779,221 (.July 17, 1057) (to Progil). 29. The Aroclor Compounds, booklet, Monsanto Co., St. Louis, Mo. 30. F. M. Clark, Tran*. Elerlrochem. Soc. 65, 50-71 (1034). ' 31. R. B. MacMullin, CUm. Eng. Progr. 44 (3), 183-188 (1948). 32. U.S. l'ats. 1,892,397 and 1,802,398 (Dec. 27, 1032), It. L. Jenkins (to Swsuu tasonrch; re- # assigned to Monsanto Chemical Co.). / 33. U.S. Pat. 3,029,295 (April 10, 1002), Rohort Thormet and Ludovio Psrri (to SocidtA d'Electro- chimie D'EIcctromelallurgic at dee Aci6ries Eleclriquee d'Ugine). 34. U.S. Pat. 1,802,400 (Dec. 27, 1032), ,R. L. Jenkins and J. A. Sikorski (to Swann Research; reassigned to Monsanto Chemical Co.). 3.5. J. W. J. Fay luid J. II. Kicliurds, "Impregnants Used in German Pojicr Cupacilors." OJUe Tack. Serv. PH Ilepi. 7MJiO (1947); HIOS (Hrilith Intelligence Objective* Subcommittee) Pinal HepL SU3. 36. "Nonmotollic Materials" ASTM Std. E9d-ltT, Part H/-A (1040). 37. U.S. Pat. 1,004,302 (March 12, 1035),>. M. Clark (to Genera] Electrio Go.). 0S\N 332223 fW- I M ^l|M STLCOPCB4078799 / / VoJ. 5 CIILOKIX1AKUONS ANI) ClILOItOllYDItOCAltUONS /2*J7 /38. Amhtr I'lnalirizcT*, Tcrli. Hull. No. P1/-300,.MoMmuOt Oo., St. I>>uis, Mo., 1)m;. I'J IK). U H. Runihnn and S. T. Miiiimlrr, Gen. Kief- Iter. 42, 21(0-2.1!) (11)11!)). 40. H. M. Clark, lmi. Eng. Chrm. 29, (HIM--T<12 (10117). 41. !V. Jackson, /*w. titty. Sac. (ixtntlmt) See. ,-t 152, 158-100 (1 935). 42. A. II. White and S. 0. Morgan, J Franklin Innl. 215, 635-044 (1933). / 43. P.8. Pat. 1,836,180 (Der. \!i, 1931), C. R. McCullough amt It. L. Jenkins (to Hwiuiii Research; reassigned In Munsantn Clieinieul Co.). / 44. (lit. Pals. 1,031,373 and 1,931,455 (Oct. 17, 1033), V. M. Clark (U General Electric Co.). 45. I'.S. Pal. 3,938,107 (June 3, 1002), H. I. Woingarten (to Monsanto Chemical Co.). 40. U.S. Pnt. 3,068,207 (Dor. 11, 1002), H. I. Weingarlcn (to Monsanto Chcirucal Co.). 47. H. I. Weingartcn. J. Org. Chan. 20, 4347-4300 (1061). / 4S. Ibid., 27, 2024-2020 (1062). / 40. t'.S. Pnt. 2,077,510 (March 28, 1901), II. I. Weinuartcn (to Monsunlo.Cliomical Co.). 5(1. II. I. Weingarten, W. D. lloas, J. M. Bchlater, and G. Wlioeler, Jr., Altai. Chim. Acta 25, 301 304 (1002). / 51. U.S. Pnt. 1,830,147 (June 14, 1032), J. H. Young (to }[. II. RoborUMMt Co.). 52. 11.8. PnL 2,120,157(Sept. 0,1038), E. \V. Tmclnmlcr and W. C. tyllaon (U> Pyroxylin PrwlueU). 53. U.S. Pat. 2,130,264 (Kept. 13, 1038), F. M. Clark and J. H. Koenig (to (ionorol Electric Co.). 54. UA Pat. 2,141,010 (Dee. 27, 1938), W. C. Dayman (to General Electric Co.). 55. IUJ. Pat. 2,158,281 (May 10, 1930), J. G. Kurd and C. F. Uill (to Woslinghouao Electric and Manufacturing Co.). 50. Aroetor lieeint and Pltielicuer* for Chlarinalod Rubber, Tech. Dull. PL-311, Monsanto Co., Kt. Louis, Mo., A]>ril 1002. .' 57. A roelor Fir Retarding PUmlirizem anti Sfodifiertfor E/tajcy lUtine, Tech. Dull. C8-14, Monsanto Co., Kt. Diuis, Mo., Nov. 1!M>4). 58. H. W. Dowrnn, Painl Technol. 2. 25-27 (1937). 59. H. A. Gardner and G. G. Sword, Natl. Painl, Varnish l/acqiter /Issue. Set. Sec. Ctre. No. 66, 109-103(1938). 00. It. L. Jenkins and It. N. Foster, Ind. Eng. Chan. 23, 1302-1305 (1931). 01. U.S. Pat. 2,077,700 (April 20, 1937), E. Klein (to E. I. du Pont do Nemours A Co., Inc.). 62. IT.S. Pat. 2,988,401 (June 13, 1001), H. J. Eichel (to Xulionai Cush Register Co.). 03. W. J. Davis and P. G. Benigr.us, Chem. Eng. Prog. 59, 30-42 (1003). 04. Thcrminol PR Fluid Heal Systems, booklet, Monsanto Co., St. Louis, Mo. 65. G. W. Wood, Mfg. Chemist 19 (3), 90-104 (1948). GO. U.S. Pat. 2,030,053 (Feb. 11, 1936), It/G. Quinn (to International Pupcr Co.). 07. U.S. Pat. 2,548,366 (April lOol) B. K. Green and It. W. Sandberg (to National Cash Register Co.). / H. L. Hubhakd Monsanto Compuny CHLORINATED NAPHTHALENES Luurcut, in 1833, olwcrvcd that waxlike materials resulted from rotetiou of chlorine with naphthalene in the presence of certain catalysts. These chlorination products were further studied by l'ischcr in 1878. It was more tliun twenty yeans later, however, that Aylsworth discerned their technological potentialities (1). Chemically and physically, the chlorine derivatives of naphthalono presented investigators with a much more complex problem tliun the chlorobenzenes. Following Erlcniucycr's establishment of the fusod-ring structure of nuphthalono in 18(iti, many years clapstxl before muny of the theoretically jsiHsihle chlorination derivatives of tho compound were isolated and identified; uven today the positions of tho substituent chlorine atoms in all isolated tetrocliloro- and pentuchloronnphthalenos^iavo not boon allocated with certainty (see Table 1). Physically, the dilliculty of isolating iso mors from tjic mixtures produced by chlorination of naphthalene is such that indiroot i V J"i" STLCOPCB4078800 2*J8 CHLOBOCAKBONS AN1) ClILOBOIIYDUOCAltBONS routes in licit usually bo employed for their preparation. Only 1-vhloronaphlhnleuo j (cr-chloronaphthnlone) juul (x:tachloronnphlhnleuo can lx- readily isolated from the / products of chlorinating naphthalene directly to the appropriate chlorine content./ Apart from 1-chloronaplithalcuc, the industrial chlorinated naphthalenes uro liquid or solid mixtures of polychloronaphthalenes, defined by their chlorine contents, approximate melting points, and, frequently, also by their color. / Table 1. Known Miglx'r CliluriiiaOil Naphthalenes / Inotucr 1 ,2-iliilil* iiinmplll lialeue l,'l-<li<'liliirimnplitliali'iie I,l-4lirliliiii>ii:iphl lialeue 1 ..'WUicliIoroiiaplillialene 1.0-ilirlil<>r<inuphl.linleiie 1.7-<lu:lilitrtHiupiilhuIenc 1 ,K-ciicl>l(>rofin(>hlliuJ<oic 2,li-(lichl<inmuplit)mlone 2.0-<lielil<>r<mnpliMmlenc 2.7-<lirlilonmiiplitlialnir Mp. *C 115 01 5 07 5 100.5 IS. 5 0.1.5 ss.6 i:t5 120 lit / up, *t; ,,M.n (775 nun Mg) 2S7 285.5 285 .1', I.:ui7 1.2007*-* *1. i OlKiN**-* .' / j 1 022S- / 1.201l-` / 1.2024"'/ ( 1 OOP2*` 1 0230"-1 Isomer Mp, *C Isomer Mp, <: l,'2,*MrichlnruiKiphi Imlnic ll2,4-lru,l>l<>nm;iplilhnl<Mie 1 ,`2,fMrirliloionapl)t lialcnc 1 ,2,C-triehlumnnplil.liuleiie l ,`2,7-1 rirhlornimphUuilcno 1,2,S-l.ri<'lil<imimphllinlcnc 1 ,'i,.VlnrhlorunnphUt;klrnc 1 nrliloronaphllialenc 1 /i,7*lntlilnnn;ipM.ltalchc l,`t,N-lriclil<>riiua|>hLh:ilcnc 1 .J.-V-LriclilonKuiiihllmlcnc 1 .^.(i-LriililoroDitplilhuk'iM! I.O.T-IrlchlomnnpliUialene 2,2,0-lrirlilornnupliUmlene si \n 7N *12.5 ss. Ml 111 SO. 5 1 111 SO. 5 i;u 05 100.5 00.5 ' ! ,'2/1,`1-lr tract ilornhaplitlmlcnu JVl4;lr;w)i)onniaplil Imicno 2/,5,S-u*lrncltJ.unma|lil lutlcnc 1 ,-l,;c,.r-tclr:u'liloronnplil lialeue l,5,s,x-lelraeliloronaphUialrne 1 , racliinronnpiit ludcnc ^(..(-..r-tctniclilonmaplithulcnc JV.x, r-LetraelilomuapliUmlene x,.r-U'lrHeliIomiiapliUi.'ilene t,2,:t,'1,5-|ienlneliloronnplil.liiilcnil,5,i,i,^-|'iiUielil(innmphilmlene l,2,.'l,4l5,0,H-licplueliloronnplilhnleue 1,2,11,4,5,0,7,X-oeLaelilornnapliUialene lo.s i:;i . imp i:i HI iso I0O 10-1 170 10S.5 177 104 i,r2 | *i I ! j 1 i 1 i !1 1 i ii )! * .. 1< s, : When naphthalene is chlorinated in the absence of chlorination catalysts, the chlorine combines udditivcly at the double Ixmds to form hydrochlnronuphthalcncs. 'i'hcse have no industrial applications. Although Aylsworth, shortly after 11)00, ]>utented the nse of chlorinated naph thalenes for impregnating wood, paper, textiles, and other materials (2), it was during World War I that the chlorinated naphthalene "waxes'' l>ccamc of inqtorUuicc as protective coating materials, particularly in (lermany, where they were then manu factured by Chcmischc h'abrik Gricsheim-Klekt.mu uixl known ns "I'erua" waxes. Well-known series of chlorinated naphthalenes are manufactured by Mayer in Germany (Xihrcn waxes), Hoppers Company, Inc., in the United States (I lalowaxi*), and Iiuperial Chemical Industries Ltd., in tin; UuiUsl Kingdom (S*s:kuy waxes). It has long \>eeu known that the chlorinated naphthalenes ciui have a dernuititic action and that inhalation of tho fumes they evolve in the molten slab; can euusu serious, and sometimes fatal, damage to the liver. Although properly organised pro- 4 { f / DSW 332225 STLCOPCB4078801