Document wmkLrX9rdjJ84DBMgxY8r793
Vol. 5
CW.OKOCAKUONS AND CIlLOUOIIYDltOCAUBO.NS
j.v.)
2J, W. J. D;iv<\y, J. fust. Petrol 31, 73-88 (I'M/)).
2f>. K- M. Howe, c<l( alour Index (Cl), 1st cd., Sixuiay of Oyer* iukI Colourists, limilft.iil, Yorkuliiro, 1924; Supplement, 10118.
2ii. lint. l*ia. 310,010 (June 2G, 1929), N. Bennett and W. C. Sprent (to Imperial Chomieul Indus tries Ltd.).
27, U.B. Pat. 1..W7,1M (Oct. 13, 10*25), A. George (to MaU.iem.u Alkali Works). 28. U.S. Pat. 1,501,540 (July 0, 1020), t<\ 15. Stocke.lbiwk (to Mivtbmwm Alkali Works). 20. Ger. Put. 234,200 (1900) (to Ilodische Anilin- mid Sola-l'abnk A.G.).
M. SlDI Ileydcn Newport. Chemical Corporation
CHLORINATED BIPHENYL AND RELATED COMPOUNDS
Diphenyl (diphenyl), tcrplicnyls, higher polyphenyls, or mixtures of these com pounds ran \>e chlorinated to give products which have outstanding chemical and thermal stabilities. Individual isomers, which range from liquids to high-inching 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 are the following: Aroclor (Monsanto Company), Chlorextol (Allis-Chalincrs Manufacturing Company), Dykauol (Cornell-Dubilicr Division, Federal Pacific Electric Conipany), Incrtccn (Westinghouse Electric Corporation), Notfamol (Wagner Electric Corporation), Pyranol (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: Clophen (I. G. Farbenindustvio A.G.,Germany), Fcnclor (Caffaro, Italy), Kannechlor (Kanega/uchi Chemical Co., Japan), Pyralene (Prodeloc, 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 noncrystallme resins. Because of the many forms and properties, they have found applications in many diverse fields--in electrical insulation, fireresistant heat-transfer arid 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 soon 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. How ever, they will react with certain reagents when treated under rather rigorous condi tions. For example, chlorobiphcnyls will react with sodium hydroxido at elevated temperatures to yield phenolic materials (28).
Mixtures of chlorinated biphenyls, such as thoso found in commercial products, will not react with acids, alkalies, or water under normal to moderately rigorous conditions (29). Thoy are insoluble in water, glycerol, and the glycols. The oils and
MANS 0966-21
200 CIILOROCARBON'S AND CHLOUOHYDKOCARBONS
rosins arc readily soluble in most of the common organic solvents, but must oi tm.hard crystalline members are |e<s soluble than Uio liquids or soilcr resins. The chlorinated biphenyl mixtures m.- nondrying even when exposed to uir in tlnn fill,,.-. They are permanently thermoplastic and except lor the lower chlorinated mrmb. is arc nonflammable. Tin: resins will adhere strongly to smooth surfaces such as glass, metal, varnished or lacquered surfaces. Most of the common metals and alloys
Table I. 1'li.vninil PrunorticM .if Oilomhiplioiiv
Com).omul
Tdilorolhpiii'ti.v) 3-diliirobipliotiyI 4-clilunbij>licyl J.'J'-du'liIiiroliipliciiyl 3,3 '-U:hl>rol>ijls:iivl l.-l'-dii-liloi'iibiplu'iiyl
J.a-diehlorobiplu'uyl 3t-1-<Ji(:!il<>rolii|jlioivl 2,3-dirlilorobipbonyl 2,1' dielilorobipht'nyl
2,l,5-lnehli>r>bi|>lic>yl 2,3,5-lridi)ini*bi|lurnyl 2, J,4'*lnel)lnri>bi|>lii'tiyl 2,5,4'-tri<hlorubi|>hciiyl 3,vri,4'*U'iehlroliijiUeuyl 3,1,2'-Cl'i('.)i]ui'<)l)>|)lu'iiy] 3,5,2'-tridiloi'>b>i>heuyl
3,4,3', l'-lclracblorebipficnyl 3,4,2',5-Udmddorobiplieny) 2,(,2',6'-tfttrodilorobiphenyl 2,3,3 '..V-lotrachlorobiphony! 2,4,2',4'-U!t.radilorol>iphi,iiyl 2,5,2',5'-teUacldori>bipUcvyl
2,4,5,3',4'-pcntftchlnix)bi{)lieiiyl
3,4,.'5,3',4',5'-lcxHcljlorobiplirnyl 2,4,fi,2',4',6'-)oxucliloroUphenyl
2,3.4,5,2',4',5'*lu,i)Uf:hlorobi|jhonyl
2,3,.r),0,2',3',5',6'-orUM!hlort)biphciiyl
2,3,4,S,6,2',3',4',.r)',6'-dcciichlarobiphenyl
Melting point, *C
M S'.l 75.5;7G;74 5b; GI-G2 23, 2b 148 3G
40; -111 50
44 78 70
41 55-50
07 88 05-00 58
172 103 1118 102 83 84-85
179 198 111.5-112
101
310
Hulling ptiuil, *C (mm Mu'; 207-2GK, 154 (12)
2S4-2S5 125 (14) 322-321, 320-320 315-31!)
100(10) 171 (15); 182(30)
195 200(15) 172(30)
230 ( 50)
195-220 (10)
240-280(20)
illbm>ni
f) eb-'" <2,0.7)
( \'l) C> 12, (2.9.12, ( J 1, J , (14,15; (ir,.i7; (15) (15,ISl
(19) (13) (0,20) (21) (13) (22) (13)
(11,23) (21) (23) Cl'.\)
(I2.2i; (25)
(I0,20.i
(23) (12,27)
(19)
(23)
(23)
havo oxcoUont resistance to the chlorinated biphenyls even at elevated temperatures. However, copper and some clipper alloys arculTectod U> a limited extent and show jm netratioii rates between O.OIH-I and 0.01-1 in./yr. Many plastic materials of nnisinirlim. arc attacked by chlorinated biphenyls. In addition to hiuh resistance to thermal degradation, they also have many interesting electrical properties.
The general properties of the more important members of the Aroolor brand of chlorinated biphenyl products are shown in Tabic 2 and the electrical properties are shown in Tablo 3.
MQNS 096622
Tabic 2. General Properties of Some Aroclors
Material
Korin and color
?Ih?ci(ic gravity
Aroclor 1221* Arnclur 1 232 Aroclor 1213 Arorlor 1318 Aroclor 1264 Aroclor 12(30 Arwlur i 202 Aroclor 1208 Aroclor 1270 Aroclor 4100 Aroclor 0442 Aroclor 0400 Aroclor 2600
cnlorlc**, mobile oil 1. l'.J-l .192
(25 16 yo
flimeut rolorh'M, mobile oil
1.270-1.2S0 (25 13.5*C)
almost colorless,
I.3?I-1.302
mobile oil
(2* la.3*C)
yellow-green tinted, 1.41.15-1 415
mobile oil
(05.13.5*0)
light vdhnv, viscous 1 .495-1,605
oil (05/15.5*0)
light yellow, soft, 1.555-1.500
lickv, resin
(00/15.5*C)
light yellow, sticky, 1.572-1.583
elenr resin
(90/15.3*0)
white to ofT-while 1 504-I.SH
powder white ( I'stallino
(25/23*0) 1.944-1.900
powder
(2S/M'C)
transparent, vcllow,
1.070
brittle resin
(M/WC)
yellow, transparent,
1.470
sticky resin
(25/25*0
clear, vclhm-to-mn*
1.070
bor, brittle resin (25/23*0)
black, opaque,
1.734
brittle rosin
(23. 26*0)
Distillation range,*
*C (corr)
275-320
Flush point/
0
141- 150
Fire point,*
*C
17G
290-325
152-154 238
325-3GG
170 ISO none
340 375
103-100 nono
3G5-3U0 385-120
none nono
none
none
305-423
nono
none
433-450
tlflDO
nono
450-400
none
none
230-320 (4 mm Hg) 215-300 (4 mm Hg) 280-335 (5 mm Hg)
none 247 IIUllO MII'IU
none >350 IIUIIU none
Tour point/
C
crystals at 1"C -35.5
Softening point,* *C
no i cir i G1S
1.020 1 .022
,' -. i,, .
37 KT
in* o'C
38 It
,J0 -51
44 51
31 32
-19
1.627-1 029
82-92
.31
-7
1.030 l .05! IS5-21U
;;r,
10 1 G39 1 041 1.80U 2500 II IS
31
1.047 1 019
72 7s
35-38
1.6501-1 .0317
Mi HlO
150-170*
249-300*
00-GO
1.004-1 007
40 40"52 a
98-105.5 1.6tUi-l 005
90 15(1 M3irC) 500 UNI
00-72
* ASTM I>-20 (modified). * Cleveland open cup. * Cleveland open cup; none indicates no fire point tip to boiling temperature. 1 As I'M I `-'.*7 * ASTM K>2& ' Savl'oll I'tiiver* d, \STM D-S'v * Last two digits indicate approximate chlorine cmilcul, if, \rui.l >r I `-'I con la.m* ah* nit 21' , i hlorim*. 1 llokl point on Hulidilioation.
MONS 096623
202 CIILOROCAKBONS AND CHLOROHYDUOCARBONS
Table 3. Ktecirinil Properties of Some Arodora
Du-luuU'ic coijhUuI ut 1000 cycles*
Arudor
25 C
ionC
J'JUJ 1242 12IK rjM 1201) I20S 5442 5ir.i MOO 4405
5.7 -1 <> 5. X 4.') 5,i; I.ii
5.0 1.3 4.3 3.7 2.5 3.0 4.0 2.7 4.2 2.5 3.7 2.7 3.3
* ASTM D.J50.47T.
* ASTM D-257-4U. * ASTM J%140-44.
Volume resistivity,1, W-cm at 1(>U#C, 5U() V, dr:
al.nvu 501) X 10* above 500 X 10" ubuvu 500 X 10* above 500 X 10*
above 500 X 10*
Dielectric strength,* kV
>35 >35 >35 >35
Power 100*C, Him cycles.
-'<) l 51) l <0 1 <0. 1
Manufacture
A number of the pure compounds formed by the chlorination of biphenyl, tcrphonyl, or more complex polyphenyis are crystalline solids, some of which have very high moiling points (30). However, mixtures containing a number of such compound* may bo either liquids or mmcrystullino 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 tho isomers of compounds of higher and lower chlorine contents (31,32). At any level of chlorine content, batch chlorination gives tho 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 hatch chlo rination. Tho proportion of the various isomers and of compounds of higher and lower chlorine contents than the average is also influenced by factors such u t.oinprrutun-, quantity and kind of catalyst employed, degree and typo of agitation, and rale oi admission of tho chlorine.
A procedure for carrying out a singlc-stago fluid-bed chlorination is deserilsai m tho patent literature for polychlorination of biphenyl (33). Continuous liquid ehlnrination in a multiple-stage unit can also bo used. Batch chlorination has been found to bo particularly well suited for tho manufacture of the various products (32,3-0.
Tho chlorinators may bo cylindrical steel towers, 3 ft in diameter and lb ft logo, which aro equipped with chlorine distributors at tho bottom and with eoils for healing and cooling the material undergoing reaction. Pumps provide agitation by ciieulaimg the liquid charge. The lower half of the chlorinators is filled with iron turning.', which have been burned free of oil and moisture. In German practice, the chloriuators aro agitated 10,000-liter lead-lined vessels, and forrio chloride is used as the catalyst instead of iron turnings. Fifteen kg of ferric chloride is used for each charge of 0000 kg (35) of biphenyl.
HONS 096624
i.vl, U`ivo very i|>uumlM liydrocoutont d lower tit gives average .it progo conih clilo.d lower (TUUilC, rale of
rilx-d in id ehlou found -Mil), fl high, heating dilating uniingM, blorinun Uio i clmrge
Vo!. 5
CHLOKOCAKBONS AND U-ILOKOHYDROCARBONS
21)3
Raw Materials. The raw material used depends on the type of chlorinated material to bo produced; anhydrous chlorine is used as the chlorinating agent in all eases. In gom'ml, il. cun he said that biphenyl alone gives liquid or soft, sticky non* crystalline products up to a chlorine content of 1>0%, low-melting resinous producis between 00 and (m% chlorine content, and partly crystalline or crystalline product-, of much higher melting points at chlorine contents above (>.'>% (32). In the can- of products that aro solid at ordinary temperatures, the higher the proportion of icrphenvls or moro complex polypheuyls in the mixture before chlorination, the higher (lie soi'le.ning point and the less the crystallizing tendency of the chlorinated product idler distillation. For those, products that aro solid or partly crystalline at room temperature, the higher the chlorine content, the higher the softening point, and the great or the tendency of Iho material to crystallize (34).
Preparation of Crude Chlorinated Biphenyl. For the manufacture of any given grade of chlorinated biphenyl, the chlorinator is charged with t.hcr proper raw material or mixture of raw materials to give the desired product in an amount sufficient to cover I he catalyst bed and to permit circulation. Then the How of vaporized chlorine is started and the charge is circulated with the pump. Throughout the chlorination, t he temperature is kept well abovo the molting point of the mixture, but below 150 C, to avoid excessive sublimation and plugging of the line discharging the hydrogen chloride produced by the chlorination. Samples aro withdrawn for examination from time to time until the desired chlorine content has been reached. At the lower chlorine contents, specific gravity measurements arc 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 100C, the degree of chlorination is determined by measuring the hold point as tho material crystallises, or by thu bull-and-ring softening-point test (30). The lime required for chlorination is 12 to 36 hr, depending upon the chlorine content of thu product. The anhydrous hydrogen chloride, which is evolved during the chlorinul ions, is al>sorbcd in water in equipment of conventional design.
Distillation of Crude Products. Although the crude products find some applica tions, for moBt 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 different for the different types of end products. The high-melting solid products are difficult to distill. Distillation under reduced pressure is particularly difficult us it is desirable to keep the boiling point above the solidification point. Generally, theso products are distilled in gas-fired retorts at atmospheric pressure. Tho distillate is flaked on chilled rolls. From practical considerations of quality and butter overall processing efficiency, the liquid and resinous products arc distilled at lower temperatures in more conventional equipment under reduced pressure. The crude liquid aud 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 materia! 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 stirred at an elevated temperature with a few tenths of 1% of well-dried fuller's earth and then filtered
through paper (35,37).
MUNS 096625
204 CHLOROCARBONS AND CHLOROHYDltOCARBONS
Containers and Shipping
The liquid chlorinated biphenyls are packed and shipped in galvunized-stcd drums or in tank cans constructed of nonrusting metals such as aluminum or tincout<!(l metal. The resinous products are packed and shipped in open-top galvanizcds.eel drums, and the high-molting solid products are packed and shipped in hugs. 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) sot by the American Conference of Governmental Industrial Hygienists are 1.0 mg of tho lower chlorin ated biphenyl compounds (42% chlorine) per cubic meter of air and 0.5 mg of tho more highly chlorinated biphenyl compounds (54% chlorine) per cubic meter of air. When chlorinated biphenyl compounds arc used at elevated temperatures, engineering controls must bo 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 ho avoided because of the possible occurrence of a condition called '`chloracno" (38).
Uses
Electrical Applications. All ol the uses of the chlorinated biphenyls dcpe.no on their chemical stability and their physical properties, which may be varied to suit the specific application. One very important uso is as dioloctric mediums in such applica tions as fluids for transformers and as impregnants for capacitors and condensers (2D, 30,39-44). Chlorinated biphenyls, used either alone or in blends with oilier ma terials such as trichlorobcnzene, meet the need for a fire-resistant dielectric fluid with a high resistivity, a high dielectric strength, a relatively high dioloctric constant, ami a very low power factor. Hy replacing hydrocarbon oil with chlorinated biphenyls or mixtures of chlorinated biphenyls with try:hlorobcnzono, it lias been possible in 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 chiorinatod biphenyl mixtures at 1000 cycles and 25C is approximately 6.0. In roccnt years, considerable attention has been given to upgrading this property (45-48). Combinations of fractional distillation, chlorination, and isomerization cun ho used to obtain dielectric constants of 7.0 or slightly above. Direct synthesis of specific trichlorobiphcnyl isomers can bo utilized to obtain dielectric constants in tho ordor of 10 (49). Improved analytical techniques, primarily capillary gas chromatography (50), have been of great aid in studying the complex chlorobiphenyl mixtures.
MUNS 096626
l-ish'i'l >r tin.nizrd-
hag*.
lhi* lower vmaui rieun iloiiuof iho oi air. wring * local hough n ran > skill. i)J lie *).
ml on tit ihe iplic.a* i s (2b, r inu1 with t, and hcnyU bill to dtugo. s and
xUin-s ouiion :liniwU .slants i-m can lyticnl aid in
Vol. 5
CIILOttOCARBONS AND CllLOUOHYDUOCAUBONS
225
Other imjjortant electrical appHcation.s for the chlorinated biphenyls arc as
imprognanls for cotton or asbestos-liber insulation
us constituents of asphalt-
base wire-impregnating compounds, and as plasticizers in wire-coating compounds,
particularly those containing neoprene, rubber, or combinations of polyvinyl chloride,
elliyleelluloso, and polyvinyl hutyral (.72-on). Also, chlorinated biphenyls are em
ployed as scaling mediums for electrical insulators and as iinprcgnants for carbon
resistors to reduce the. influence of moisture.
Flashes, Lacquers, Paints, and Varnishes. Chlorinated biphenyls ure compatible
with most of the common plastic mutcriuls and resins, and arc soluble in paint and
varnish oils (*2'J). In combination with asphalt, cthylccllulosc, chlorinated rubber,
Idiolito (styrene-butadiene copolymer), or other plastic materials, they are used ex
tensively in protective! coalings lor wood, metal, and concrete (38,.r>6,.77). In com
bination with dioctyl phthaluto, they arc eoplastici/.ers for polyvinyl chloride compo
sitions (20,68). See also Coatings, industrial; Paint.
r.
In paints and varnishes the bat'd resinous chlorinated biphenyls are used to
impart increased hardness to the iilms, and the softer resins arc used to give lloxi-
hility. The rolo of these materials is similar to that of the oil, except that they do not
oxidize and lose flexibility on agoing. 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
(f>7-00). The hard, white, crystalline chlorinated biphenyls of high melting point
arc useful as pigments with various plastics (01).
Adhesives (qv). The resinous products arc used in synthetic adhesive com
positions in combination with such base materials as polyvinyl acetate, cthylcellulono,
chlorinated rubber, polyvinyl hutyral, isopreno-styreno copolymer, and polyiso*
butylene. Chlorinated biphenyls arc used in the preparation of coatings of pressuro-
rupturablc capsules for adhesive tape (62).
Lubricants (qv). Chlorinated biphenyls find application as lubricants miner
extreme conditions such as highly oxidizing conditions, high temperatures, extreme
pressures, or submerged locations. Mixtures with other oils to form henvier-thnn-
water lubricants are used in submerged locations, such as bridge rollers. Lubricants
for extreme pressures aro inode by adding up to 15% of the chlorinated biphenyls to
petroleum hydrocarbon oils.
Heat-Transfer Media (qv). Chlorinated biphenyls have been used for somo time
in indirect heating applications (63). 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 tc.m])eraturcs arc required and for high-tempera
ture (bulk temperatures of 600 F) 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 coresin and paraffin (20,65). 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
aro ingredients of many fire-resistant compositions. Fire-retarding paints usually
contain antimony oxido or barium sulfate in addition to the chlorinated biphenyl.
In making fireproof fiberboard, emulsified chlorinated biphenyl is added to the fiber
MGNS 096627
2% tmOKOCAUiiONS AND CHLOKOHYDKOCAJIBONS
stock (06). Modifying waxes are added to chlorinated biphenyl in the preparation of textilo-coating materials.
In addition to the uses listed above, chlorinated biphenyls arc ingredients of some sealing compounds for use with wood or canvas to give protection against mni.-imv, mildew, or attacks of organisms. They are also used in formulating calking com pounds, powdered metal pastes, some soil-poison and wood-preserving conijjoshiuiis. paper transparontiaers, and printing inks. Carbonless reproducing paper i.s made by an encapsulation procedure winch uses chlorinated biphenyl as part of the formula tion (07) (see Encapsulation).
Bibliography
"ChhiriimUd Diphenyls" wider ' Chlwino CompmimlH, Organic" in ECT 1st ml., Vol. J, pp. 826-832, by C. F. Boull), Mouh;iU> Chnmiud Cuiiipanj'.
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*"
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32. U.S. Pals. 1,802,307 and 1,892,398 (Doc. 27, 1932), R. L. Joukiiw (to Swann Reward.; roAssigned to Monsanto Chemical Co.).
33. U.S. Pat. 3,029,295 (April 19, 1002), Robert Thormot and Ludovio Parvi (to Souiiild d'Eloctmchimio D'ElcoLrometuIlurgio i>t don Acidries Eloclriquus d'Ugine).
34. U.S. PaL 1,892,400 (Don. 27, 1032), R. L. Jenkins and J. A. Siknrski (to Swann Research;
reassigned to Monsanto Chemical Co.). 35. J. W. J. Fay mu) J. II. Richanln, "IinproKiiunU lleutl in German Paper Capacitors," Ojjue. Tech.
Serv. 1*11 Kept. 76860 (1947); IIIOS (llritieh Intelligence Objective* Subcommittee) Final Uc/H j'.'/.l
30. "Noiimulullio Materials" ASTM Sid. ES8-4MT, hurl III-A (1940).
37. U.S. l'at, 1,994,302 (March 12,1935), F. M. Clark (to Goasm) Elootriu Co.).
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CiiLOttOCAKBONS AND CllLOltOHYDiiOCAJUJONS
297
;1S. Amrlor I'luAtfcizcn, Tech. Bull. No. PL*30(i, Monsanto Co., St. Louie, Mo., Dec. 1900. 39. L. II. Burnhan aiui S. T. Maunder, Cm. like. /lev. 42,230-230 (103!)). 10. V. M. Clark, lad. Eng. Chem. 29, G9S-702 (1037). II. W. Jackson, Proe. Hoy. Soc. ( Isnidim ) Srr. . I 153, 158-l00 (1935). 42. A. II. While and S. O. Morgan,./. Fr.mUin Inst. 210, 085-ii 14 (1933). 13. U.S. Pat. 1,S3G,IS0 (Dec:. I *i, 1031), C. R. MrCulluugh uml R. L. Jenkins (to S\va:ui RvHe.iirh;
reawagned to Monsanto Chemical Co.).
I.r. U.S. I'at. 3,1>MS,H)7 (Juno 5, 1902), II. 1. Woutgrulcn (to Moimanlo (.'Inimical Co.), 111. t'.S. Pal. 3,()1>S,297 (Dot;. 11, 1062), H. I. Weii>KvUm (W M.tii&mU. Chemical Co.). 17. It. 1. WoingarUm, ,/. Org. Chan. 2G, `1347-4330 (PJftl). IS, Hud., 27, 2021-2020 (10(12). 19. I .S. Pat. 2,977,310 (Mareli 2S, 1901), It. I. Weingarlcii (to MoiikiimIo ('licmical G<>J. .')(). 11. I. Wiiiugarten, W. D. Rom, J. M. Schlatcc, and O. Wheelin', Jr., .bud. (,7ui. ,bi< 2G, 391
394 (1902). 'll. I..S. Jt. 1,330,117 (Juno 14, 1932), J. H. Young (to II. II. RoUtrUon Co.). .',2. I .S. Pat. 2,129,157(Sept. 0, 10S.S), li. W. 'IWInuderaud W. (1. Wilwm(Ui P>i-u.\yliu PchIucU). 33. U.S. Pat. 2,130,204 (Sept. 13, 103ft), !'. M. Clark and J. II. Koenig (to General Electric Co.;. .VI. 1 I.S. Pat. 2,141,910 (Dee. 27, 1038), W. C. llayman (to General Electric Co.). 53. U.S. Pat. 2,158,281 (May 1C, 1030), J. G. Ford and C. K, Hill (to Wcstinghoueu Electric and
Manufacturing Co.). 50. Aroelor llenint and PUislitiecrs for Chlorinatod 1lubber, Tech. Bull. PL-311, Monsanto Ct.,
St. Ixniia, Mo., April 1002. 57. Aroelor Fire Retarding PUistiiners <m<J Modificrt for Epoxy Ilesint, Tech. Bull. CS-14, Munsiuitn
Co.. St. laiuia, Mo., Nov. 1900. :>S. H. W. Bowron, Paint Tcchnol. 2, 25 -27 (1937). 59. II. A. Gardner and G. G. Sword, Nutt. Paint, Vnmuth Ijuj/ucr .Uw. Sci. Sec. Circ. .Vo. JJ,
100-103 (1938). (10. R. I-. Jotikioa anil It. N. Fouler, hut. liny. Chutt. 23. 13021305 (1931). ill. U.S. Pat. 2,077,7(XI (April 20,1937), I'). Klein (to K. I. <lu Pont do Nemours it Go., Inc.). 02. U.S. Pal. 2,OSS,401 (Juno 18, 1901), II. J. Eiitluil (to National Cash Register Co.). 08. W. J. Davis and P. G. BcuigmiR, ChfM. Eng. Prog. 59, 89-42 (1008). (14. Therininol Fit Fluid llmt Systems, booklet, Monsanto Co., St. Louis, Mo. <15. G. W. Wood, Mfg. Chemist 19(3), 90-104(1948). CO. U.S. Pat. 2,080,058 (Pub. 11, 1980), II. G. Quinn (to Intorimtionui Paper Co.). 07. U.S. Put. 2,348,300 (April 1951) I). IC. Green and R. W. Sandburg (to National Cash Register
Co.).
If. L. llunuAiu) Monsanto Company
CHLORINATED NAPHTHALENES
Laurent, in 1888, observed that waxlike materials resulted from reaction of chlorine with naphthalene 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 Aylsworth 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 Erlenmeyer'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 mid identified; even today the positions of tho substituent chiorino atoms in all isolated tetrachloro- and pculachloronuphihalcnes have not been allocated with certainty (soo Tuhlo 1). Physically, tho dillioulty of isolating isomers from the mixtures produced by chlorination of nuphthaleno is such that indiroct
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