Document jy84BdZmX0R3Q2k9gjzK8ORd2
Vo!. 5
` tmOltOdUtUONS AND CIILOttOnVimoCAKBONS
289
24 W. J. Duvey, J. In$t. Petrol. Jl, 73-68 (1INf>).
2.4. F. M. H*we, fil., Colour Index (Cl), 1st *6., Society of Dycnj and Colourists, Bradford, York*
aliirc, 1924; Supplement, 1928.
20. lirit. Bat. 3)0,910 (June 20, 1029), N. Bennett and \V. C. Sprenl (to Imperial Cheinicel Indue-
tries Lid.).
.
27. U.S. Pal. 1,.V7,I.VI (Oct. 13, 102.r), A. Ccorpe (lo M;lll.ic-a..n Alk.ili \V,>rU/.
28. |l.R! I'l.t. I,Ml,.VI,r. (July 0, 1020), F. 15. 6tockHI>rk (to Mt.hie*n Alkali 'Yorks).
20- Cor. J 'at.. 234,701) (1909) (to Dadisclie Amlin- utid Sods-Kubi ik A.C.).
H. Sidi . Ileyden Newport Chemical Corporation
CHLORINATED BIPHENYL AND RELATED COMPOUNDS
Biphenyl (diphenyl), lerphenyls, higher polyphcnyis, or mixtures of these com
pounds can he chlorinated to give products whicli 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 are the following: Aroclor (Monsanto Company), Chlorcxtol
(AUm-Chnlmcrs Manufacturing Company), Dykanol (Corncll-Dubilier Division,
Federal Pacific Electric Company), Inertccn (Westinghousc Electric Corporation),
Noflamo! (Wagner Electric Corporation), Pyranol (General Electric Company),
and Thcminol (Monsanto Company). Some other registered trademarks or trade
names for commercial chlorinated biphenyls found throughout the world arc the
following: Olophon (I. G. Farbenindustrie A.G., Germany), Fcnclor (CafTaro, Italy),
Kanncchlor (Kanegafuchi Chemical Co., Japan), Pyralcne (rrodelec, France), and
Sovo) (Russia).
-
Commercial manufacture of the Aroclor brand of chlorinated biphenyls was
started in 1029. These products vary from mobile oily liquids to white crystalline
solids and hard noncrystalline reams. Because of .the many forms and properties,
they have found applications in many' diverse Helds--in electrical insulation, fire-
resistant heat-transfer and hydraulic fluids, lubricants for urc 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
Tho physical properties of individual chforobiphenyl isomers vary widely as may be seen in Table 1. Mixed isomers os produced in a commercial product have physioal 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 os those found iu commercial products, will not react with acids, alkalies, or water under normal to moderately rigorous conditions (29). They are insoluble in wator, glycerol, and the glycols. The oils and
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290 CHLOROCAIIBONS AND CHDOltOHYDUOCAUBONS
resins me 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 nomlrying even when exposed to air in thin films. They are permanently thermoplastic and except for the lower chlorinutcd mcmlmrs aro nonflammable. The resins will adhere st rongly to smooth surfaces Riich as glass, metal, varnished or lacquered surfaces. Most of the common metals and alloys
Table I. Physical Properties of Cliltir<i1>iphcnyli
Compound
2-chloiobipbenyl 3-ch)orobiphonyl
4-chlorobiphenyl
2,2'-diclilorobiphenyl 3,3'-<iicMorot>iplienyl 4,4 '-dichlorobipbenyl 3,5-dichlorobiphcyl'
2,5-dichlorobipbcnyl
3,4-dichlnrobipheiiyl 2,3>dichlorr)biphenyi 2,4 '-dichlorobipbenyl
2,4,5*lrichUrobip)nsiyl 2,3,5-lrichlurobiphcnyl 2,4,4'VneblorobiphYyi 2,5,4 '-trichlorobiphcnyl
3,5,4'-IrieUlorohipUenyl 3,4,2'-trichlorobiphonyI 3,5j2'-trichlorokiplienyl
3,4,3',4'-lftrftcblorobiphcn.vl 3,4,2',5''UstrrMorobipbcnyl
2,0,2',G'-(olracJ>lorobipheuyt 2,fl,3',5'-loU-uchlorobiphenyl 2,4l2',4'-telrachlorob>phe>iyl 2l5,2',.V-telrachlorobiphenyi
2,4,5,3 ',4 '-pentnchlorobiphenyl
3,4,5,3`,4',5'-hexachlorobiphenyl 2,4,0,2',4 ',6'-l>cxftcliIorobiphcnyl
2,3,4,5,2'l4',5'-heplachlc*robiphenyl
2t3,5,0,2',3'l5,,0'-ocUhlorobiphcnyl
2,3,4,5,6,2',3',4',5',8'-def*chlorobiphenyl
Melting point, "C
34 89 75.5;7G;74
50; 01-02 23; 29 148 30
46;49-60
44
78-70 41
55-50 G7 88
65-GG 68
172 103 198 162 83 84-85
179
108 111.5-112
101
310
Moiling point, *C (mm Hg) 207-208; 154 (12)
284-285 125 (14) 322-324; 320-320 315-310 JOG (10) 171 (15); 182 (30) 195-200(15) 172 (30)
'
230 (50)
105 220(10)
240-2S0 (20)
lliliiingrnpliy reference's
(1-3) (4,5) (2,0,7)
(8,0) (9-12) (2,0,12) (13,14) (14,15) (10,17) (IS) (15,18)
(19) (13) (9,20) (21) (13) (22) 03)
(11,23) (21) (23) (23)
(12,24) (25)
(10,20)
(23) (12,27)
(10)
(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.
.
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Table 2. Cenerai Properties of Some Aroclon
Material
Form and color
Specific gravity
Araclur 1221' Aroclor 1232 Aroclor 1242 Aroclor 1248 Arodor 1254 Aroclor 1200 Aroclor 1252 Aroclor 1268 Aroclor 1270 Aroclor 4465 Aroclor 5442 Aroclor 5460 Arodor 2565
|
I
IR
colorless, mobile oil 1.182-1.192
(25/15.5'C)
almost edoriese,
1.273-1.280
mobile oil
(25/15.5*0
almost colorlesa,
1.381-1.392
mobile oil
(25/15.5'C)
yellow-green tinted, 1.405-1.415
mobile oil
(65/15 5*0
light yellow, viscous i.495-1.505
oil (65/15.5*0
light yellow, soft, 1.555-1.566
sticky, resin
(90/15.5*0
1.572-1.533
clear resin
(90/15.5*0
white to off-white 1.804-1.811
powder white crystalline
(25/25*0 1.944-1.960
powder
(25/25*C)
transparent, yellow,
1.670
brittle resin
(25/25*C)
yellow, transparent,
1.470
sticky resin
(25/25*C)
clear, yellow-to-am-
1.870
ber, brittle resin (25/25*C)
black, opaque,
1.734
brittle resin
(25/25*0
Distillation range,* *C (corr) .
275-320
Flash
point,*
c
Fir*
point,*
c
141^50 176
290-325 152-154 233
325-36G 176-180 none
340-375 193-196 nohe
365-390
none none
385-420
none none
^95-425
none none
435-450
none none
450-460
none none
230-320 (4 mm Hg) 215-300 (4 mm Hg)
2SO-335 (3 mm Hg)
none 247 none none
none >350 none none
Pour
point/ *C
Softening
point,*
c
crystals st 1*C -35.5
0 1.617-1.61S
1.620-1.622
Viscosity/ sec
37 3*C 9S.9*C
3S~tl
30-31
44-51
31-32
-19
1.627-1.629
82-92
34-35
--7
1.630-1.631 185-240
36-37
10 1.639-1.641 1500-2500 44-43
31 35-38
1.647-1.649 1.6501-1.6517
72-73 8G-IQQ
150-170*
249-300*
60-66
1.664-1.667
46 46-52
90-150 (130*C) 300-400
03-105.5 1.600-1.605
66-72
* ASTM D-20 (modified). * Cleveland open cup. * Cleveland open cup; none indicates no fire point up to boiling temperature. 4 ASTM E>-97, * ASTM E-28- 1 Saj-bolt Universal, ASTM D~83. * Lost two digits indicate approximate chlorine content, ie, Aroclor 1221 contains about 21% chlorine. * Hold point on solidification.
CllLOHOCAUDONS AND CHLOROIIYURUCARBONS
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292 CIILOKOCARDONS AND CIILOKOHYDItOCAItBONS
Table 3. Ulcclricftl Properties of Some Arodore
Dielectric constant at 1000 cycles"
Aroolor
25*C
100*0
1232 1212 1248 1254 12(10 1208 5442 5454 MOO 4405
5.7 5.8 6.6 6.0 4.3 2.5 3.0 2.7 2.5 2.7 _
4.0 4.0 4.0 4.3 3.7
4.0 4.2 3.7 3.3
* ASTM D-1G0-47T. * ASTA1 D-257-40. * ASTM D-149-44.
VoJimie resistivity,1 U-cm ut 100"C, 500 V, dc
above 500 X 10* above 500 X 10* above 500 X 10* above 500 X 10*
above 500 X 10*
Dielectric strength," kV
>35 >35 >35 >35
Power factor,* 100*C. 1000
eyries, %
<0.1 <0.1 <0.1 <0.1
Manufacture
'
A niimlwr of the pure compounds formed by tho chlorination of biphenyl, ter-
phcnyl, or morc complcx polyphcnyls are crystalline solids, some of which have very
high melting points (30). However, mixtures containing a number of such compounds
may bo cither liquids or noncrystalliuc resins. Chlorination of aromatic hydro
carbons to various levels not only gives several isomers of the same ehlormo 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 tho number of stages is increased, multistage con
tinuous chlorination gives compositions approaching' those obtained by batch chlo
rination. The proportion of tho 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 hits boon found
to be particularly well suited for the manufacture of the various products (32,34).
The chlorinatore may be cylindrical steel towers, 3 ft in diameter and 18 ft high,
which are equipped with chlorine distributors at the bottom and with coils for heating
and cooling the material undergoing reaction. Pumps provide agitation by circulating
the liquid charge. The lower half of the chlorinatore is flHod with iron turnings,
which ltave been burned free of oil and moisture. In German practice, the chlorinn-
tore 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 need for each charge
of 6000 kg (35) of biphenyl
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ClILOltOCAKBONS AND ClILOKOlIYimOCARBONS
2U3
Haw Materials. Tho raw material used depends on the type of clilouiiatvd material to be produced; anhydrous chlorine is used as the chlorinating ngent in all caHen. In genera), 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 )>ctwccn GO and 65% chlorine content, and partly crystalline or crystalline products of much* higher melting points at chlorine contents above 05% (32). In tho ease of products that are solid at ordinary temperatures, the higher the proportion of tcrphcnyls or more complex polyphcnyls in tho mixture, before chlorination, the higher the softening point and the less tho crystallizing tendency of the chlorinated product after distillation. For those products that aro solid or partly crystalline at room temperature, the higher tho chlorine content, the higher the softening {joint, and the greater the tendency of the material to crystallise (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 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 inciting point of the mixture, but below I50C, to avoid excessive sublimation and plugging of the line discharging the hydrogen chloride produced by the chlorination. Samptes arc withdrawn for examination from
lime to time until tho desired chlorine content has 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"C,i the degree of chlorination is determined by measuring tho hold point as the material crystallizes, or by the ball-and-ring softening-point test (3G). The time required for chlorination is 12 to 3G hr, depending upon the chlorine content of the product. The anhydrous hydrogen chloride, which is evolved during the cliloi illa tions, is altsorbcd 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 clHoride (32,34,35). The methods of purification are somewhat different for the different types of end products. The high-melting solid products arc difficult to distill. Distillation under reduced pressure is particularly difficult os 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 bolter overall processing efficiency, the liquid and rasinous 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 Btirred at an elevated
temperature with a few tenths of 1% of well-dried fuller's earth and thon filtered through paper (35,37).
HUNS 097670
204 ClILOItOCAUBONS AND CIILOKOUYDUOCAUBONS
Containers and Shipping
The liquid chlorinated biphenyls arc packed and shipped in galvanimi-sleel drums or in tank cars constructed of nonnesting metals such as aluminum or tincoated metal. The resinous products arc packed and shipped in open-top galvanisedstccl drums, and the high-melting solid products arc packed and shipped in bogs. The railroad shipping classification is Kosin Synthetic NOIBN.
Health and Safety Factors
Prolonged exposure to chlorinated biphenyl vapor evolved nt high temperature can lead to systemic toxic effects. Inhalation tests on animals indicate that lire 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 American Conference of Governmental Industrial Hygienists are 1.0 mg of the lower chlorin ated biphenyl compounds (42% chlorine) pur 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 doing 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).
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 other ma terials such as trichlorobcnscne, meet the need for s fire-resistant dielectric fluid with a high resistivity, A high dielectric strength, a relatively high dielectric constant, and a very low power factor Jty replacing hydrocarbon oil with chlorinated biphenyls or mixtures of chlorinated biphenyls with trichlorobcnzcnc, it has been possible to redesign equipment with a great reduction in size for the same capacity and voltage. At the same time, the fire liasards have been eliminated. See also Dielectrics and piesoclcctries; Insulation, electrical.
The maximum dielectric constant of commercial chlorinated biphenyl mixtures at 1000 cycles and 25 C is approximately 5.0. In recent years, considerable attention has been given to upgrading this property (45-48). Combinations of fractional distillation, chlorination, and isomerisation can be used to obtain dielectric constants of 7.0 or slightly above. Direct synthesis of specific trichlorobiphenyl isomers can be utilised 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 chlorobiphenyl mixtures.
MONS 097671
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ClILOltOCAKBONS ANl) uilohohyduocaiuions
295
Other important electrical applications for the chlorinated biphenyls are as
impregnants for cotton or asbestos-fiber insulation (51), as constituents of asphalt-
base wire-impregnating compounds, and as plasticizers in wire-coating compounds,
particularly those containing neoprene, rubber, or combinations of polyvinyl chloride,
othylcciluiosc, and polyvinyl butyral (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
witli most of the common plastic materials and resins, and arc soluble in paint and
varnish oils (29). In combination with asphalt, cthylcellulosc, chlorinated rubber,
Pliolitc (styrene-butadiene copolymer), or other plastic materials, they arc used ex
tensively in protective coatings for wood, metal, and concrete (38,50,57). In com
bination with dioctyl phtlmlato, they are coplasticizers 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 arc used to give flexi
bility. The role of these materials is similar to that of the oil, except that they da not
oxidise 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
(57-00). The hard, white, crystalline chlorinated biphenyls of high melting point
are useful ns pigments with various plastics (01).
Adhesives (qv). The resinous products are used in synthetic adhesive com
positions in combination with such base materials as polyvinyl acetate, cthylcellulosc,
chlorinated rubber, polyvinyl butyral, uoproue-styrcnc copolymer, and polyiso-
butylcne. Chlorinated biphenyls arc used in the preparation of coatings of preasure-
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 hcavicr-lhan-
waler lubricants are 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
in indirect heating applications (03). Recently, products of this type sold by Mon
santo Company under the registered trademark Thcnninol 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 arc required and for high-tempera
ture (bulk temperatures of 000*10 indirect heating. Specifically designed units for
such applications arc required to prevent local overheating.
tr
Miscellaneous Applications. Camauba wax may be extonded by blending with chlorinated biphenyl in combination with corcsin and paraffin (29,05). Satisfactory
t
V
waxes and polishes arc prepared without the use of camauba wax by blending ouricury (licuri) wax with chlorinated biphenyl, ceresin, 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
MGNS 09 76 72
296 CIILOKOCAUBONS ANDCHLOitOlIYDitOCAKUONS
stock (GG). Modifying waxes arc added to chlorinated biphenyl in Dio preparation of textile-coating materials.
lii addition to tiic uses listed above, chlorinated biphenyls arc ingredients of some sealing compounds for U60 with wood or caiivas 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 tvansparentizers, and printing inks. Carbonless reproducing paper is made by an encapsulation procedure which uses chlorinated biphenyl os part of the formula tion (07) (sec Encapsulation).
Bibliography
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'
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-
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. I !
Vul. 5
CHLOUOCAKBONS AND CilLOltOilYDKUCAJtBONS
21)7
38, Aiwlor Plaxtieiser*, Tccli. Hull. No. l'L-300, MonflauUi Co., Si. J>om*, Mo., Occ. 1%U. 3D. L. II. Uumlinn and 8. 7'. Mnumktr, Gen. birr. Rev. 42, 230-2311 (103!)). 40. F. M. Clark, ind. Eng. Chan. 29, 01)8-702 (1037). 41. \V. Jackson, Pron. Roy. Soc. {Inruion) Srr. A 153, 158 -100 (1030). 42. A. H. While and S. 0. Morgan, J. Franklin Inst. 216, 635 -044 (1033). 43. U.J>. Put. 1,8210,180 (Dec. 15,1931), C. R. McCullough nnd K. L. Jenkins (to Swann lloaearch;
reamii'iied to Monsanto Chemical Co.). 44. 1J.S. Pa(a. 1.031,373 and 1,031,455 (Oct. 17, 1033), F. M. Clark (to Gcnorsl Kloclric Co.). 45. U.S. Pat. 3,038,107 (June 6,10G2), U. I. Woingarton (to Moimnnlo Chemical Co.). 40. U.S. Pat. 3,008,297 (Doc. ) I, 1062), 71.1. Woingarton (to Monsanto Chemical Co.). 47. H. I. WemKsrUm, J. Org. Chan. 28,4347-4350 (1061). 48. Ibid., 27, 2024-2026 (1062). 40. U.S. Pat. 2,077,516 (March 28, 1961), H. I. Wningnrtcn (to Monsanto Clicininil ('.). 50. 11. 7. Weingarton, W. D. Host, J. M. Schiater, and G. Wheeler, Jr., Anal. Chun. Ariu 2C, 3!U-
304 (1062). 61. U S Pnt. 1,830,147 (June 14, 1932), J. H. Young (to II. II. Robertson Co ). 62. U.S. Pat. 2,120,157(Sept. 6, 1038), E. W. Troclnndernnd W. C. Wilson (to Pyroxylin Prmli-cls). 53. U.S. Pat. 2,130,264 (Sept. 13,1038), F. M. Clark and J. H. Koenig (to General Electric Co.). 54. U.S. Pnt. 2,141,010 (Dec. 27, 1938), W. C. Haymnn (to General Electric Co.). 55. U.S. Pat. 2,168,281 (May 16, 1039), J. G. Ford and C. F. llill (to Wwliughouso Electric and
Mnnufacturing Co.). GO. Arocier Retina and Plaalicuert /or Chlorinated Rubber, Tech. Bull. PJ/-3I1, Monsanto Co.,
St. ].otiis, Mo., April 1002. 67. Arodor Fite Retarding Plaelicitcrs and Modifiers for Epoxy ftesini, Tech. Bull. CS>14, Monsanto
Co., St. l^niis, Mo., Nov. 1060. 68. H. W. Bowron, Paint Technol. 2, 26-27 (1037). 60. II. A. Gardner and G. G. Sword, Neil, Point, Varnish Lacquer Aetot. Sli. Sec. Circ. No. SC,
100-103 (1038). 00. H. L. Jonkins and R. N. Foster, Jnd. Eng. Chan. 23, 1302-1365(1031). 61. U.S. Pat. 2,077,700 (April 20,1037), E. Klein (to E. 1. du Pout dc Nemours k Co., Inc.). 62. U.S. Pnt. 2,088,461 (June 13, 1061), 11. J. Eichel (to Xstioiml Cash HegisierCu.). 03. W. J. Davis nnd P. O. Benignus, Chem. Eng. Prog. 59,30-42 (1063). 64. Thcnninol Fit Fluid Heal Syeleme, booklet, Monsanto Co., St. Louis, Met. 06. G. W. Wood, MJg. Chemist 19 (3), 00-104 (1048). 00. U.S. Pnt. 2,030,653 (Feb. 1), 1036), H. G. Quinn (tnlntenmlihual Paper Go ). 07. U.R, Tnt. 2,548,300 (April 1951) B. K. Greon and H. \Y. Sandberg (In National C;u>h Register
Co.).
' ]I. L. lluniurui
Monsanto Company
CHLORINATED NAPHTHALENES
taurcut, in 1833, observed that waxlike materials resulted from reaction of chlorine with nophtlialene 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 AyUwoith discerned their technological potentialities (1).
Cliemically and physically, the chlorine derivatives of nftphthalcno presented investigators wit!) a much more complex problem than the chlorobenzenes. Following Erlenmeyer's establishment of the (used-ring structure of naphthalene in 18GC, many years clopsod bofore many of the theoretically possible chlorination derivatives of the oompound were isolated and identified; even today the positions of the substituent chlorine atoms in all isolated tctrachloro- and pcntachloronuphthalonoe have not been allocated with certainty (see Tahlo 1). Physically, the dilliculty of isolating isomci* from the mixtures produced by chlorination of naphthalene is such that indiroct
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