Document ExXGvOBRgqxrpg3Ld1dJ4DjKV

Vol.5 ' CHLOROCARBONS AND CIILOItOmmOCAUBONS 289 24 \V. J. Uttvey, J. Inti. Petrol. SI, 73-68 (104.r,). 25. F. M. Howe, e<!., Colour Index (Cl), IbI ed., Society of Dyers ami Colourists, Bradford, York- Hliirp, 1924;Supplement., 1928. 20. Brit. Fat. 310,910 (Juno 20, 1929), N. Bennett and \V. C. Sprcnl (to Impcrinl Clieinical Indus tries Ltd.). .. 27. U.R. Fnt. 1,557,1.VI (Oct. 13, 1925), A. Ccorpo ff Alkali Works/. 28. t' S: Fat. 1,591,545 (July C, 1920), V. R Stockcll-ark (to Mulhicnon Alkali Works). 29. Cor. J 'ut.. 234,290 (1909) (to Diuliaclie Anilin- utid Soda-Fabtik A.G.). H. Sidi , Ileydcn Newport Chemical Corporation CHLORINATED BIPHENYL AND RELATED COMPOUNDS Biphenyl (diphenyl), terphenyls, higher polyphenyls, or mixtures of these com pounds can he 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 6omc commercial brands of chlorinated biphenyls in the United States are the following: Aroclor (Monsanto Company), Chlorcxtol (Allis-Chalmcrs Manufacturing Company), Dykanol (Cornell-Dubilier Division, Federal Pacific Electric Company), Inerleen (Westinghousc Electric Corporation), Noflamol (Wagner Electric Corporation), Pyranol (General Electric Company), and Thenninol (Monsanto Company). Some other registered trademarks or trade names for commercial chlorinated biphenyls found throughout the world arc the following: Olophen (I. G. Farbcnindustrie A.G., Germany), Fcnclor (Caffaro, Italy), Kannechlor (Kancgafuchi Chemical Co., Japan), Pyralcne (rrodelec, Fiance), and Sovol (Russia). Commercial manufacture of the Aroclor brand of chlorinated biphenyls was started in 1920. These products vary from mobile oily liquids to while 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 heat-transfer and 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 part icularly 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, 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 acid6, alkalies, or water under normal to moderately rigorous conditions (29). They arc insoluble in water, glycerol, and tire glycols. The oils and DSW 032958 i ! i it i .t i I i; !; 5 - * STLCOPCB4016920 290 CHL0R0CA11B0NS AND CHLOROHYDROCARBONS resins nrc readily soluble in most of the common organic solvents, but most of the hard crystalline members arc less soluble than the liquids or softer resins. The chlorinated biphenyl mixtures are nondrying even when exposed to air in thin films. They are permanently thermoplastic and except for the lower chloriuutcd 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 Table 1. Pliyaical Properties of Cliinrnbiphonyls Compound 2-clilorobi|>benyl 3-chlorobipbenyl 4-chIorobiphc.nyl ' 2,2'-dicli!orobiphcnyl 3,3'-dichtoroliipbenyl 4,4'-diclilorobip!ienyl 3,5-dicltlorobiphcnjT 2,5-dichlorobipbcnyl 3,4-diehlorobiphcnyI 2,3-dichlorobipheny) 2,4'-dicblorobiphenyl . 2,4,5-trielilorobiplicnyl 2,3,5-trichlorobiphcnyl 2,4,4 '-1 richlorobipbenyl 2,5,4'-trichlorobiphcnyl 3,5,4 -trichlorobiphcnyl 3,4,2'-trichlorobiphcnyJ 3,5^2'-(iichlorobiplienyl ' 3,4,3',4 '-Ictrachlorobiphenyl 3,4,2',5'-U:lrachloiobiphenyl 2,C,2',C'-tctracliiorobip)icnyl 215,3'I5'-tctrHchloi'obiphenyl 2,4,2',4'-tclrachiorob>phenyl 2,5,2',ft'-tetrach!orobiphenyl 2,4,5,3 ',4 '-pentachlorobipheny1 3,4,5,3',4',5'-licxaclilorobiphciiyl 2,4,0,2',4`,6'-bcxochlorobiphcnyl 2,314,5,2'14',5'-hcptachlorobiphenyl 2,3,5,0,2',3',5',0'-<iclachlorobiplienyl 2,3,4,5,6,2',3',4',5',6'-decBcliIorobiplienyl Melting point, C 34 89 75.5;7C;74 69; G1-G2 23 ; 29 148 3G 46;49-50 44 78-70 41 55-56 67 88 65-60 58 172 J03 198 162 83 84-85 170 198 111.5-112 ' 101 310 Boiling point, C (mm Hg) 2C7-2GS; 154 (12) 284-285 125(14) 322-324; 320-320 315-319 106(10) 171 (15); 182 (30) 195-200(15) 172 (30) 230 (50) 195-220(10) 240-2S0 (2C) Hililiogrnjjliy references (1-3) (4,5) (2,0,7) (8,9) (9-12) (2,9,12) 03,14) (14,15) (16,17) (15) 05,18) (19) (13) (9,2(1) (21) (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 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 arc shown in Table 3. . '. ' . . ' 1 . , ; , ; i 1 DSW 032959 * ^ .. . ' 1 . ... ,f ^ ' .. ^ . . .. ' \ . * '' * ' . , * STLCOPCB4016921 "y. i i 3 3 ,-A % o V) X o U> N> vC O' o </> Oo oo CO o i\V\------ O) to IISs)) Table 2. General Properties of Some Aroclora Material Aroclor 1221* Aroclor 1232 Aroclor 1242 Aroclor 1248 Arodor 1254 Aroclor 1260 Aroclor 1262 Aroclor 1268 Aroclor 1270 Aroclor 4455 Aroclor 5442 Aroclor 5460 Aroclor 2565 Form and color Specific gravity colorless, mobile oil 1.IS2-1.192 (25/15.5*C) almost colorless, 1.273-1.2f?0 mobile oil (25/15.5`C) almost colorless, 1.381-1.392 mobile oil (25/15.5"C) yellow-green tinted. 1.405-1.415 mobile oil (65/15.5"C) light yellow, viscous 1.495-1.505 oil (65/15.5C) light yellow, soft, 1,555-1.566 sticky, resin (90/15.5`C) light yellow, sticky, 1.572-1.5S3 clear resin (90/15.5*0) white to off-white 1.80-1-1.811 powder (25/25*0 white crystalline 1.944-1.960 powder (25/25C) transparent, yellow, 1.670 brittle resin (25/25"C) yellow, transparent, 1.470 sticky resin (25/25*0 clear, yeilow-to-am- 1.570 ber, brittle resin (25/25*0 black, opaque, 1.734 ` brittle resin (25/25*0 Distillation range,* *C (corr) 27.5-320 Flash point,* C 141-sl50 290-325 152-154 325-360 176-180 340-375 193-196 365-390 none 385-420 none ^595-425 none 43-5-450 none 450-460 none 230-320 (4 mm Hg) 21.5-300 (4 mm Hg) 2SO-335 '(5 mm Hg) none 247 none none Fire point,* C 170 233 Pour point,4 c crystals at 1*C -35.5 none -19 nohe -7 none 10 none 31 one 35-38 none none none >350 46' none none Softening point,* "C 150-170* 249-300* 66-66 46-52 93-105.5 66-72 n,, I.617-1.61S 1.620-1.622 1.627-1.629 1.630-1.631 1.639-1.641 1.647-1.649 1.6501-1.6517 1.664-1.667 1.660-1.605 Viscosity/sec 37 S*C 9S. 9*C 33-41 30-31 44-51 31-32 82-92 34-35 185-240 36-37 1S0O-25O0 44-48 72-78 S6-100 90-150 (130"C) 300-400 * ASTM D-20 (modified). * Cleveland open cup. * Cleveland open cup; none indicates no fire point up to boiling temperature. 4 ASTM D-97. * ASTM E-2S. r Saybolt Universal, ASTM D-83. ` Last two digits indicate approximate chlorine content, ie, Aroclor 1221 contains about 21% chlorine. 1 Hold point on solidification. CllLOKOCAlJBONS AND CHLOKOIIYDKOCAKBONS Vol. 5 |: f 1; 292 CIILOROCARfiONS AND C1ILOROIIYDROCARQONS Table 3. Rlcclricol Properties of Some Aroclorn Dielectric constant at 1000 cycles" Arcelor 25'C lOO'O 1232 1242 1248 1254 1200 1208 5442 5454 5400 4405 5.7 4.6 5.8 4.0 5.6 4.6 5.0 4.3 4.3 3.7 2.5 3.0 4.9 2.7 4.2 2.5 3.7 2.7 3.3 * ASTM D-150-47T. ASTM D-257-46. * ASTM D-149-44. Volume resistivity,* il-cm at 100'C, 600 V, dc above 500 X 10* above 500 X 10' above 500 X 10' above 500 X 10* al>ove 500 X 10' Dielectric strength,* kV >35 >35 >35 >35 Power factor,* 100C, 1000 cycles, % <0.1 <0.1 <0.1 <0.1 Manufacture ` A number of the pure compounds formed by the chlorination of biphenyl, ter- phcnyl, or morc'complcx polj'phenyls arc crystalline solids, some of which have very high melting points (30). However, mixtures containing a number of such compounds may be cither liquids or noncrystallinc 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 number 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 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 be 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 and with coils for heating and cooling the material undergoing reaction. Pump3 provide agitation by circulating the liquid charge. The lower hulf of the chlorinators is filled with iron turnings, which have been burned free of oil and moisture. In German practice, the chlorina tors are agitated 10,000-liter lead-lined vessels, and ferric chloride is used as the catalyst instead of iron turnings. Fifteen kg of ferric chloride is URcd for each charge of 6000 kg (35) of biphenyl. DSW 032961 i <: STLCOPCB4016923 r Vol.5 ' ClI LORO CARBONS AN1) CIILOKOIIYDUOCAUUONS 2<J3 Raw Materials. Tlic raw material used depends on the type of chlorinated material to be produced; anhydrous chlorine is used as the chlorinating agent in all cases. In general, it can lie said that biphenyl alone gives liquid or soft, sticky non crystalline products up to a chlorine content of 00%, low-melting resinous products lietwcen 00 and 65% chlorine content, and partly crystalline or crystalline products of much'higher melting points at chlorine contents ahovo 63% (32). In the ease of products that are solid at ordinary temperatures, the higher the proportion of tcrphenyls or more complex polyphcnyls 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 cldorinator 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 bed 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, but below 150C, to ovoid excessive sublimation and plugging of the line discharging the hydrogen chloride produced by the chlorination. Samples arc withdrawn for examination from lime 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 below 100"Collie degree of chlorination is determined by measuring the hold point as the material crystallizes, or by the bnll-and-rmg softening-point test (30). The time required for chlorination is 12 to 36 hr, depending upon the chlorine content of the product. The anhydrous hydrogen chloride, which is evolved during the clilorinalions, 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 is necessary to remove the color, and the traces of hydrogen chloride and ferric chloride (32,34,35). The methods of purification are somewhat diffcront for the different types of end products. The high-melting solid products 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 arc 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 resinous products arc distilled at lower temperatures in more conventional equipment under reduced pressure. The crude 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 ferric 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 electrical resistivity is desired, the material is Blirrcd at an elevated temperature with a few tenths of 1% of well-dried fuller's earth and Ihon filtered through paper (35,37). DSW 032962 i 5 * V i V .i ! ! iI [ I! !f Ii STLCOPCB4016924 v-^. `Yt r^s < ,sx.'. - w *Wn*. r*.-- ;< 2H ClILOltOCAUBONS AND CIILOROIIYDItOCARBONS Containers and Shipping The liquid chlorinated biphenyls arc packed and shipped in galvanized-sfeci drums or in tank care constructed of nonrusting metals such as aluminum or tincoated metal. The resinous products arc packed and shipped in open-top galvanizedstecl 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 Prolonged exposure to chlorinated biphenyl vapor evolved at high temperature can lead to systemic toxic effects. Inhalation tests on animals indicate that the maximum 6afc 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 American Conference of Governmental Industrial Hygienists are 1.0 mg of the lower chlorin ated biphenyl compounds (42% chlorine) pel cubic meter of air and 0.5 mg of the more highly chlorinated biphenyl compounds (54% chlorine) per cubic meter 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 arc 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 ``chloracuc'' (38). Uses Electrical Applications. All of the uses of the chlorinated biphenyls depend on their chemical stability and their physical properties, which may be varied to suit the specific application. One very important use is os dielectric mediums in such applica tions as fluids for transformers and as impregnants for capacitors and condensers (29, 30,39-44). Chlorinated biphenyls, used either alone or in blends with oilier ma terials such as trichlorobcnzcne, meet the need for a fire-resistant dielectric fluid with a high resist ivity, 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 trichlorobcnzcne, if, has 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 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 above. Direct synthesis of specific trichlorobiphenyl isomers can be utilized to obtain dielectric constants in the ordor of 10 (49). Improved analytical techniques, primarily capillary gas chromatography (50), have been of great aid in studying the complex chlorobiphenyl mixtures. . DSW 032963 l f-v- 1 r1 r~*-:T* STLCOPCB4016925 t Vol. C1ILOKOCAURONS AN1) CHLOHOHYDKOCAKUONS 205 Oilier imj>ortunt electrical applications for the chlorinated biphenyls are as imprcgnnnle for cotton or asbestos-fiber insolation (51), as constituents of asphaltbase wire-impregnating compounds, and as plasticizers in wire-coating compounds, particularly those containing neoprene, rubber, or combinations of polyvinyl chloride, cthylccllulosc, and polyvinyl bulyral (52-55). Also, chlorinated biphenyls arc em ployed as .scaling mediums for electrical insulators and as impregnants for carbon 1 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 (29). In combination with asphalt, cthylccllulosc, chlorinated rubber, Pliolite (styrene-butadiene copolymer), or other plastic materials, they are used ex tensively in protective coatings for wood, metal, and concrete (38,50,57). In com bination with dioctyl phthalatc, they are coplasticizcrs for polyvinyl chloride compo sitions (29,38). See also Coatings, industrial; Paint. In paints and varnishes the hard resinous chlorinated biphenyls arc used to impart increased hardness to the films, and the softer resins are 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 rosins to impart increased weather resistance, luster, adhesion, and decreased burning rate (57-60). The hard, white, crystalline chlorinated biphenyls of high melting point are useful as pigments with various plastics (61). Adhesives (qv). The resinous products are used in synthetic adhesive com positions in combination with such base materials as polyvinyl acetate, cthylccllulosc, chlorinated rubber, polyvinyl butyral, isoprene-styrene copolymer, and poly iso butylene. Chlorinated biphenyls are used in the preparation of coatings of pressurcrupturable capsules for adhesive tape (62). Lubricants (qv). Chlorinated biphenyls find application ns lubricants under extreme conditions such as highly oxidizing conditions, high temperatures, extreme pressures, or submerged locations. Mixtures with other oils to form hcnvier-lbanwalcr lubricants arc used in submerged locations, such as bridge rollers. Lubricants for extreme pressures are made by adding up to 15% of the chlorinated biphenyls to petroleum hydrocarbon oils. Heat-Transfer Media (qv). Chlorinated biphenyls have been used for some time `1 in indirect heating applications (G3). Recently, products of this type sold by Mon santo Company under the registered trademark Thcrminol have been introduced, which arc specifically directed to use as heat-transfer media (64). These fluids arc particularly well suited for efficient and safe operation in applications involving flammable materials where uniform temperatures are required and for high-tempera ture (bulk temperatures of 600F) indirect heating. Specifically designed units for such applications arc required to prevent local overheating. l Miscellaneous Applications. Camauba wax may be extended by blending with r chlorinated biphenyl in combination with ccrcsin and paraffin (29,65). Satisfactory t .. waxes and polishes arc prepared without the use or camauba wrax by blending ouricury T (ticuri) wax with chlorinated biphenyl, ceresin, and paraffin. Chlorinated biphenyls arc 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 il DSW 032964 STLCOPCB4016926 2U6 CIILOUOCAUBONS AND CHLOKOlIYDItOCARBONS slock (CC). Modifying waxes are added to chlorinated biphenyl in the preparation of textile-coating materials. In addition to the uses listed above, chlorinated biphenyls arc ingredients of some scaling compounds for 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 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 (G7) (see Encapsulation). Bibliography "Chlorine led Diphenyls" umlor "Clilnrino Compounds, Organic" in EC7' lsl ed., Vul. 3, pp. 826-832, by C. F. Booth, Monsanto Chemical Company. 1. F. Bell, J. Chem. Soc. 131,2773 (1928). . 2. Demsclhcn, Ann. Chem. Liebigt 189, 138, J42 (1877). 3. S. II. Znheer nnd S. A. Faseeh, J. Ind. Chem. Soc. 21, 27 (1944). ` 4. M. Gomborg and W. E. Bachmann, J. Am. Chem. Soc. 46, 2343 (1924). 5. /hid., 49, 250 (1927). C. G. Schultz, Ann. Chem. Liebigt 174 , 209 (1874). 7. E. Bamberger, Her. Deul. Chem. Get. 29, 405 (1890). 8. J. J. Dobbic, J. J. Fox, and A. J. H. Gauge, J. Chem. Soc. 99, 1019 (1911). 9. L. Masrarclli, D. Galti, E. Jona, and V. Lconcini, Gaze. Chim. Ital. 59, 808-870 (1929). 10. II. IT. Hodgson, J. Chan. Soc. 149, 746 (1046). 11. J. C. Coin, J. Chem. Soc. 85, 7 (J904). 12. F. Ulhimnn, Ann. Chem. Liehigt 332, 54- 56 (1904). 13. L. 15. Hinkel and D. II. Iley, J. Chem. Soc. 131, 2780-2788 (1928). 14. H, A. Scarborough and W. A. Waters, J. Chem. Soc. 130, 93-94 (1927). 15. T. Crnuw, Ren. Trav. Chim. 50, 753 (1931). 10. W. Blakely and II. A. Scarborough, J. Chrm. Soc. 130, 3007 (1027). 17. \Y. Zerweck and C. Schiltz, Chem. Abttr. 36, 50581 (1942). IS. C. Finzi nnd V. Bollavita, Gaze. Chim. Hal. G4, 335 (1934). 19. Y. 8. Zal'kind and M. V. Belikova, J. Gen. Chem. USSR {Engl. 7 Vans/.) 8, 1918 (1939). 20. II. llmtdnilE with II. B6hm, Her. Deul. Chem. Gee. 60, 743 (1927). 21. Y. Bollavita, Gait. Chim. llal. 65_, 032 (1935). 22. L. Masrarclli, D. Gatti, and B. Longo, Gaze. Chim. JUil. 63, 054 (1933). 23. F. L. W. Van Roosinalcn, Rec. Trav. Chim. 53, 359 (1934). ' 24. Fr. Fichler and M. Adler, llelv. Chim. Acla 9, 287 (1920). 25. H. Meyer and A. Hofmann, Monalth. Chem. 38, 145 (1917). 20. H. Schmidt and G. Schultz, Ann. Chem. Liebigs 201, 340 (1881). 27. L. W. Pickett, F. G. Waller, nnd II. France, J. Am. Chem. Soc. 58,2290 (1930). 28. Brit. Pat. 770,221 (July 17, 1007) (to Progil). 20. The Aroclor Compoundt, booklet, Monsanto Co., St. Louis, Mo. 30. F. M. Clark, Trant. Eledrochem. Soc. 65,59-71 (1934). 31. R. B. MacMullin, Chem. Eng. Progr. 44 (3), 183-188(1948). .32. U.S. Pats. 1,802,397 and 1,892,398 (Doc. 27, 1932), H. L. Jenkins (to Swann Research; rc- . assignod to Monsanto Chemical Co.). 33. U.S. Put. 3,029,296 (April 10, 1002), Robert Thermot and laidovic Parvi (to Sociele d'Kloclro- .elliptic D'Eieclroinetallurgic ct dea Acidries Elcctriqucs d'Uginc). 34. U.S. Pul. 1,802,400 (Doc. 27, 1032), H. L. Jenkins and J. A. Sikarski (to Bwnnn Research; reassigned to Monsanto Chemical Co.). 35. J. W. J. Fay and 3. H. Richards, "Imprcgnanls Used in Oorm.nt Paper Cnpnrilnrs," OJTuc Tech. /Jem. PR lie/il. 76S/>9 (1947); RIOS (Rritish Intelligence Objectives Subcommittee) Final liepi. A'US. ii. "Noimiolidlic Materials" A STM SUl. EtS-J,tT, Part IJ/-A (1940). 37. U.S. Pat. 1,994,302 (Murch 12,1935), F. M. Clark (to General Electric Co.). I ili i 1 1 I iIi I1 1 I 4 1 < f ! i j. i I l 5 rf f i f A I t osw 032965 I STLCOPCB4016927 . ) ' f . f .. * ( . t ., 1 ,i " j " ^ :>; !' . j I Voi. 5 ( CHLOIiOCARCONS AND CHLOltOUVDROCAUIiONS 297 38, Aroclor Plasticizers, Tecli. Hull. No. PL-300, Monsanto Co., St. Jenin, Mo., Dec. 1900. 39. L. H. Burnban and S. T. Mnundnr, Cert. Hire. Hcv. 42, 230-23!) (1039). <0. F. M. Clark, Ind. Eng. Chem. 29, 01)8-702 (1937). 4). W. Jackson, Fron. Hoy. Soc. {I/ontlon) Srr. A 153, 15S-1G0 (1935). 42. A. II. While and S. O. Morgan, J. Franklin Inst. 21G, G35 -044 (1933). 43. U.S. l'al. 1,836,180 (Dec. 15, 1931), C. R. McCullough and H. L. Jenkins (to Swann Uoacurclr, reassigned lo Monsanto Chemical Co.). 44. U.S. Pals. 1,931,373 and 1,931,455 (Oct. 17, 1933), F. M. Clark (to General Eloolric Co.). 45. U.S. Pul. 3,038,107 (June 5, 10G2), H. I. Weingarlon (to Monsanto Chemical Co.). 40. U.S. Pat. 3,008,297 (Dee. 11, 19G2), H. 1. Wcingarlen (to Monsanto Chemical Co.). 47. H. I. AVeingarlen, J. Org. Chem. 26, 4347-4350 (10G1). 48. Ibid., 27, 2024-202C (1062). 49. U.S. Pal. 2,077,516 (March 28, 1961), H. I. W'eingnrlcn (to Monsanto Chemical Cn.). 50. If. I. Weingarton, W. D. Iloss, J. M. Sehlater, and G. Wheeler, Jr., Anal. Chim. Acta 26, 391 394 (1962). 51. U.S. Pal. 1,836,147 (June 14, 1932), J. H. Young (to II. H. Robertson Cn.). 52. U.S. Pat. 2,129,157 (Sept. 6,1938), E. W, Troclandcrand W. C. Wilson (to Pyroxylin Products). 53. U.S. Pat. 2,130,264 (Sept."13, 1938), F. M. Clark and J. II. Koenig (to General Electric Co.). 64. U.S. Pat. 2,141,910 (Dec. 27, 1938), W. C. Dayman (to General Electric Co.). 55. U.S. Pat. 2,158,281 (May 10, 1939), J. G. Ford and C. F. llill (to WeslinghouseElectric and Manufacturing Co.). 56. Aroclor llcsina and Plasticizers for Chlorinated Rubber, Tech. Bull. P1/-3I1, Monsanto Co., St. l/ouis, Mo., April 1002. 57. A roclor Fire Hclarding Plasticizers and Modifiers for Epoxy Resins, Tech. Bull. CS-I4,Monsanto Co., St. lvouis, Mo., Nov. 1900. 58. H. W. Bowron, Faint Tcchnol. 2, 25-27 (1937). 59. II. A. Gardner and G. G. Sword, Natl. Paint, Varnish Lacquer Assoc.. Set. S'ce. Circ. No. 65, 100-103 (1938). 00. K. L. Jenkins and R. N. Foster, Ind. Eng. Chem. 23, 1302-1305 (1031). 61. U.S. Pat. 2,077,700 (April 20, 1937), E. Klein (lo E. I. du Pont dc Nemouvs & Co., Inc.). 62. U.S. Pat. 2,988,461 (June 13, 1061), 11. J. Eiche! (to National Cash Register Co.). . 03. W. J. Davis and P. G. Benignus, Chem. Eng. Frog. 59, 39-42 (1903). 04. Thcrminol Fit Fluid Ifeal Systems, booklet, Monsanto Co., St. Louis, Mo. 05. G. W. Wood, Mfg. Chemist 19 (3), 99-104 (1943). CG. U.S. Pal. 2,030,053 (Feb. 11, 1930), R. G. Quinn (In lulcnmlinuul Paper Co.). 07. U.S. Pal. 2,548,300 (April 1951) B. 1C. Green and K. W. Sandberg (lo National C;isli Register Co.). ` II. L. llimiiAni) Monsanto Company CHLORINATED NAPHTHALENES Laurent, in 1833, observed that waxlike materials resulted from reaction of chlorine with naphtlialcne in the presence of certain catalysts. These chlorination products were further studied by Fischer in 1878. It was more than twenty years later, however, that Aylsworlh discerned their technological potentialities (1). Chemically and physically, the chlorine derivatives of naphthalene presented investigators with a much more complex problem than the chlorobenzenes. Following Erlemncycr's establishment of the fused-ring structure of naphthalene in I860, many years elapsed before many of the theoretically possible chlorination derivatives of the compound were isolated and identified; even today the positions of the substituent chlorine atoms in all isolated fctrachloro-and ponlacliloronaphthalcnca hove not been allocated with certainty (see Table 1). Physically, the difficulty of isolating isomers from the mixtures produced by chlorination of naphthalene is such that indirect 1 ' : i j j i ! ( \ i ] i , . j ,! } , ' [ j if j 1 ., ! .. 1 ! .' DSW 032966 \ ,'l STLCOPCB4016928