Document VDqYQ3eZmLDyzvveNN7JweGg
Vcl. 5
XTILOllOUAKHONS AND GHLOROIIYDROCAKUONS
2X9
?. i. W. J. Iktviy, J. Infl. I`ftml. 3!, 73-SS (I'.M.'i).
>
V..Y f. M. j;.%<. !., i `iilo'ir ln'lci (1*1), Iflt **<!., Sucii'ty of l)ycis ami ColimrisU, llrailfnrd, Yurk-
nliiiv, li'-M, Si:|;.!fiufiil, W-'-'v 'JO. Hril. l'nl. .ilO.VIO (June 26, r.>2'J), N. Heiinctl and W. C. Sprcnt (to Imperial Chemical Indus
tries Ud.).
^
27. l-.S. Pul. 1,.V>7,1'>3 (Oct. 13, l'.l'-1')), A. GcorgcRii Matliii'sim Alkali Wurku).
.
U-S. l'at. 1 ,.VJI ,.*13 (July 0, 11126), 1'. K. Slocki lhjck (to Mathii'Bon Alkali Works).
I'.'i. Cor. Put. 23-1,21)0 (10011) (to Badisrho Anilin-unil Soda-Kabrik A.G.).
*
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/ Heydon Newport Chemical Corporation
CHLORINATED BIPHENYL AND RELATED COMPOUNDS /
Biphony! (diphenyl), lerphonyls, higher polyphenyls, or mixtures of these corn-
;-.:.-ih!s ran l>e chlorinated to give products which have outstanding chemical and
thermal stabilities. Individual isomers, which range from liquids to high-inciting
crystalline solids, are of lit tle commercial importance whereas the mixed chlorinated
romponents have considerable commercial significance.
Registered trademarks for some commercial brands of chlorinated biphenyls in
the United States are the following: Aroeior (Monsanto Company), Chioroxtol
(AiiivChnhiiers Manufacturing Company), Dykanol (Corncll-Dub'ilicr Division,
Federal Pacific Electric Company), Incrtcen (Wcstinghouse Electric Corporation),
Noilansoi (Wagner Electric Corporation), Pyranol (General Electric Company),
ami Tlicrminol (Monsanto Company). Some other registered trademarks or trade
names for commercial chlorinated biphenyls found throughout the world are the
following: C'mphcn (I. G. Farbenindustric A.G., Germany), I'enclor (CalTaro, Italy),-
Kanr.echlor (K'vnogafuchi Chemical Co., Japan), Pyraicne (Prodclec, France), and
Sovol (Russia).
_
.
Commercial manufacture of the Aroclor brand of chlorinated biphenyh was
si rated in 1929. These products vary from mobile oily liquids to white crystalline
lolids and hard noncrystallion resins. Because of the many forms and properties,
Fi.ey have found applications in many diverse fields--in electrical insulation, fire-
) -i tar.t heat-transtcr and hydraulic fluids, lubricants for use at high temperatures'
.r.d pressures, sealant and expansion media, and as constituents in elastomers, ad*
hrsives, paints, lacqucra, varnishes, pigments, and waxes.
Physical and Chemical Properties
The physical properties of individual chlorobiphenyl isomers vary widely as
may bo seen in Table 1. Mixed isomers as produced in a commercial product have
physical properties which are quite different from those of the individual isomers.
This is particularly true for tlic solidification point.
.
Chlorinated biphenyls, in general, are considered to be inert materials. ITow-
over, they will react with certain reagents when treated under rather rigorous condi
. tions. For example, chlorobiphcnyls will react with sodium hydroxide at elevated
temperatures to yield phenolic materials (28).
.
Mixtures of chlorinated biphenyls, such as those found in commercial products,
will not react with acids, alkalies, or water under normal to moderately rigorous
- conditions (29). They are insoluble in water, glycerol, and the glycols. The oils and
/
DSW 330406
STLCOPCB4077050
. -/
290 CIILOitOCAUUONS AND CHLOROHYUROCAliliONS
.
rosins arc readily Ui in most of the common organic solvents, hut most of the hard crystalline members are less soluble than tl>e liquids or softer resins. The chlorinated biphenyl mixtures arc 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 as glass, metal, varnished or lacquered surfaces. Most of the common metals and alloys
/
.
Table 1. Physical Properties of Chlorobiphenyls
. Compound
. //s /
Mo! lint; point, C
Hoiling point, C(mm Hr)
OibliiiRmphy references
2-<-li!-irnbiplicnyt 3-clilnrobipbcnyl
4-rliUirnbiplionyl
/ /
/
34
2G7-26S; 154 (12)
. .89
2X4-2S5
75.5;70;74
125(14)
0-3)
(4,ft) (2,0,7)
2,2'-li<4il<>r<ibi;ihenyl / 3I3,-ilirhlor*il.iphpiiyl / 4,4'-ilirhlorobiplii.,iiyl / 3,.r;-<li(lil(iri>l>i;i!iciiyl 2,5-dicliii inibipiii'nyl 3,-1-iIirhlijriibiiilifiiyl 2,3-(lu,hlnriibiplic,nyI 2,4'-<li<4ilirobiplif-nyl
214l5-lrii'h1<irobiphcyl 2,3,5-trirlilnrobipliciiyl 2,4.4 'irichloi'.ibipbenyl 2,5,4 '-trirhiorobiphcnyl 3,5,4'-triohlorubiplienyl 3,4,2'-tri*:Iilornbiplienyl 3,5,2/-trich!>robi])hcnyl
. . 60; G1-G2
23; 29
322-324; 320-326
148 315-310
36 ICG (10)
171 (15); 1S2 (30)
4ft; 49-50
105-200(15)
.
172 (30)
- .. 44
78-79 41
-
55-5G G7
8S 05-6G
5S
(.> (9-12) (2,9,12) (13,14) (14,15) (16,17)
(15) (15,18)
(HO
(13) (9,20) (21) (13) (22) (13)
3,4,3',4'-tctr:i<'liIori>bipiienj'I 3,4,2',.V-lctr:i<4',lonibiphcnyl 2,0,2'pl>'-tctrnil)lf)robipbnnyl 2,5,3',5'-lctrarliinrobiplienyl 2,4,2',4 '-t-ei r:irh|imiHipl>enyl 2,5,2 VV-tstrachlornbiphenyl
'
172 103
' 19S 1C2 83
84-85
230 (50)
(H.23) (21) (23) (23)
(12,24) (25)
.
2,4,5,3 ',4 '-pont acl iloroi liphcnyl
179
195-220(10)
(19,2ft)
3,4,.r),3',4',.r>'-bcx:iohlonil)iphonyl 2l4,('iI2'14',f/-Jiox:ielilir<ibiplionyl '
ms 111.5-112
(23) (12,27)
/ 2f3Il,5l2',4',5'-lic|)tnrlil(ir<il)iplicnyI
240-281) (20)'
(19)
2,3,.'i,G,2',3',r>',6'-fiiL;i:lil<ir)bipbonyl
161 . .
(23)
2,3,4,.r>,G,2',3',4',.ri',r>'Hlocarhlnrobiphenyl
310
(23)
i
l l
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
arc 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 ore shown in Table 2 and the electrical properties are
shown in Table 3.
. '.
f
i
t
/ / /
DSW 330407
/
STLCOPCB4077051
Vol. 5
CIII.OKOCAKBONS AND CIILOKOIIYDllOCAKiiOXS
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/
SVV330408
STLCOPCB4077052
202 CIU-OKOOAKBONS AND ('III.OKOIIYl)KOCAKttONS
TnMc .1. Kleclriral ProjierlicH of Soum ArorlorH
Annlnf
1 )n`Iolrio coii.'tanl at 1000 cyclin'
` 25G
WlPC
rrHwtivily,* lH'iu at wot:,
500 V, tit;
Dielectric eirengili,* kV
Power factor,' iooe, WOO
cycles, %
rj.tj 1242 12 IS 12.VI 1200 120S 5442 Mil At GO 1405
' r>. 7 5.S 5.0 5.0
1.3 2.5 3.0 2.7 2.5 2.7
1.0 4.!l uljove 500 X 10* . / >35
4.6 ` above 500 X 10* / >35
4.3
above 500 X 10* /
>35
3.7 above 500 X 10* / >35
./ 4.9 above.500 X 10*
4.2 .
/
3.7 .
3.3
<0.1 <0.1 <0.1 <0.1
- A.STM D-150-47T. * ASTM D-2.77-40. * A STM D-MO-14.
Manufacture
/
A numlii'i* of the pure compounds formed by the. chlorination .of hiphcnyl, tcr-
pln-.nyl, or more complex polyphcnyls are crystalline solids, some of which have very
iii"h melting jioint-s (30). However,.mixtures containing a number of such compounds
may be either liquids or noncrystalline resins. Chlorination of aromatic hydro
carbons to various levels not only gives several isomers of the same chlorine content
hut 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 mimlx'r 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 hind 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 chlor-inaton; 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 chlorinators is filled with iron turnings,
which hnve been burned free of oil and moisture. In German practice, the chloritia-
tors arc agitated 10,000-litcr lead-lined vessels, and ferric chloride is used as the
catalyst instead of iron turnings'. Fifteen kg of ferric chloride is used for each charge
of G000 kg (35) of biphenyl.
/
4/
/ DSW 330409
STLCOPCB4077053
Vol. 5
CHLOROCARBONS AND CHLOROHYDItOCARBONS
203
Raw Materials. The raw material used depends on the type of chlorinated
material to he.produced; anhydrous chlorine is used as the'chlorinating agent in all
r:e-os. In general, it ean Ik; said lliat biphenyl alone gives liquid or soft., sticky non-
rrystalliue products up to a rhloriiie content of (><1%, low-melting resinous products
between 00 and 05% chlorine content, and partly crystalline or crystalline products
of much higher melting points at chlorine contents above 05% (32). In the case of '
products that arc solid at ordinary temperatures, the higher the proportion of ter-
phonyls or more complex polyphenyls 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 (3-1). '
Preparation of Crude Chlorinated Biphenyl. For the manufacture of any given / grade of chlorinated biphenyl, the chlorinator is charged with t.lio proper raw material /
cr 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 l.r>0C,
to avoid excessive sublimation and plugging of the line discharging the hydrogen
chloride produced by the chlorination. Samples are withdrawn for examination from
time to tin;e. until the desired chlorine content Inis 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 j/oiut for convenient determination of the specific gravity at temperatures
below llXTC, the degree, of chlorination is determined by measuring the hold point
as the material crystallizes, or by the hall-and-ring softening-point test (30). The
time required for chlorination is 12 to 30 hr, depending upon the chlorine content of
the product. The anhydrous hydrogen chloride, which is evolved during the chlorina
tion.-, 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 (32,34,3a). The methods of purification -
are somewhat different for the ilifTerent 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 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 resinous products arc distilled at
lower temperatures in more conventional equipment under reduced pressure. The
crude liquid and resinous products arc held at an elevated temperature and blown with dry air for several hours, after which a-few tenths of 1% of lime or sodium hydrox-
ide is stirred with the material to react with any remaining hydrogen chloride or ferric
chloride. This is followed by batch distillation under reduced pressure. Complete
distillation and mixing of the distillate is necessary in order to obtain uniforjn material
of the desired composition.
'
_'
If increased electrical resistivity is desired, the material is Btirred ut an elevated
temperature with a fow tenths of 1% of well-dried fuller's earth and then filtered through paper (35,37).
/
/ 330^
OS'N
STLCOPCB4077054
204 ' CIILOBOCAIIDONS AND CHLOROIIYDR/ OCARBONS
Containers and Shipping `
The liquid chlorinated biphenyls arc packed and shipped in galvnnizcd-stecl drums or in tank cars const meted of nonrusting metals such as aluminum or t ineoated metal. The resinous products arc packed and shipped in open-top galvanizcdstccl drums, and the high-melting solid products arc packed and shipped in bags. The railroad shipping classification is Itesin Synthetic NOIBN; '
Health and Safety Factors
t .
Prolonged exposure to chlorinated biphenyl vapor evolved at high temperature can lead to systemic toxic e(Teels. 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 hiphcnyl mixtures per cubic meter of air. The threshold limits (maxi mum allowable concentration for an eight-hour working day) set by the America)/ Conference of Governmental Industrial Hygienists are 1.0 mg of the lower chlorin ated hiphcnyl compounds (42% chlorine) per cubic meter of air and 0.5 mg of the more highly chlorinated hiphcnyl compounds (54% chlorine) per cubic meter of, air. When chlorinated biphenyl compounds are used at elevated temperatures, engineering controls must be applied, cither by the use of closed systems or by effective local mechanical exhaust ventilation together with general workroom exhaust. Although the chlorinated biphenyls are not normally skin irritants, their solvent action can remove natural protective oils and fats, and lead to drying and cracking of the skin. Also, continuous or repeated skin contact with chlorinated biphenyls should be avoided because of the possible occurrence of a condition called "chloracnc" (38).
./
Uses
/
Electrical Applications. 'All of the uses of the chlorinated biphenyls depend on
their chemical stability and their physical properties, which may he varied to suit the
specific application. One very important use is as dielectric mediums in such applica
tions as fluids for transformers and as impregnanls for capacitors and condensers (2!),
30,39--4 4). Chlorinated'biphenyls, used cither alone or in'blends with other ma
terials such as trichlorobcn/.cnc, meet the need for a fire-resistant dielectric fluid with
a high resistivity, a high dielectric strength, a relatively high dielectric constant, and
a very low power factor. By replacing hydrocarbon oil with chlorinated biphenyls
or mixtures of chlorinated biphenyls with trichlorobenzcne, it 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 G.0. In recent yearn, considerable attention
has been given to upgrading this property (45-48). Combinations of fractional.
distillation, chlorination, and isomerization can be uscd'to obtain dielectric constants
of 7.0 or Blightly above. Direct synthesis of specific trichlorobiphonyl isomers can
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
osnN
igyy-i pjMnTVT r~r'^V
STLCOPCB4077055
Vol.
C1IL0K0CAUB0NS AND CHLOUOIIYDKOCAIMIONS
295
Other important electrical applications for Mir chlorinated biphenyls arc as
impregnnuts'for rotton or ashcslus-liher insulation (51), as constituents of asphalt-
base wire-impregnating compounds, and as-plasticizers in wirc-cyaliug compounds,
particularly those containing neoprene, rubber, or combinations of polyvinyl chloride,
ethylcclluiose, and polyvinyl butyral (.*>2-55). Also, chlorinated biphenyls tire em
ployed as scaling mediums for electrical insulators and as imprcgnants for carlwin
resistors to reduce the influence of moisture.
Plastics, Lacquers, Paint:;, 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, ethylcclluiose, chlorinated rubber,
Pliolite (.styrene-butadiene, copolymer), or other plastic materials, they arc used ex
tensively in protective coatings for wood, metal, and concrete (38,'>(5,57). In com
bination with dioctyl phthalate, they are coplastici/.ers for polyvinyl chloride compo
sitions (29,3S). See also Coatings, industrial; Paint.
In paints and .varnishes the hard resinous chlorinated biphenyls an: used to
impart, increased hardness to tlie films, and the softer rosins arc used to give flexi
bility. The role of these materials is similar to that of the oil, except that they do not
oxidize and lose flexibility on ageing. In nitrocellulose lacquers, chlorinated bi
phenyls arc employed cither 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
arc useful a; pigments with various plastics (Gl).
Adhesives (qv). The resinous products are used in synthetic adhesive coin/
positions in combination with such base materials as polyvinyl acetate, cthylcelluiose,
chlorinated rubber, polyvinyl butyral, isoprene-styrene copolymer, and polyiso-
butyiere. Chlorinated biphenyls arc used in the preparation of coatings of pressurc-
rupturable capsules for adhesive tape (02).
/.
Lubricants (qv). Chlorinated biphenyls find application as lubricants under
extreme con. lit ions such as highly oxidizing conditions, high temperatures, extreme
pressures, or submerged locations. Mixtures with other oils to form heavior-lhan-
water lubricants arc used in submerged locations, such as hridge rollers. / Lubricants
for extreme pressures arc madeliy adding up to 15% of the chlorinate^ biphenyls to
petroleum hydrocarbon oils.
Heat-Transfer Media (qv). Chlorinated biphenyls have been used for some time
in indirect heating applications (63). Decently, products of this type sold by Mon
santo Company under the registered trademark Therminol have been introduced,
which are specifically directed to use as heat-transfer media (6-1). These fluids are
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 G00F) indirect heating. Specifically designed units for
such applications are required to prevent local overheating' Miscellaneous Applications. Carnauba wax may be extended by blending with
chlorinated biphenyl in combination with ccrcsin and paraffin (29,(55). Satisfactory
waxes and polishes are prepared without the use of carnauba wax l>y blending ouricury
(licuri) ffux with chlorinated biphenyl, ccrcsin, and paraffin. Chlorinated biphenyls
arc ingredients of many fire-resistant compositions. Fire-retarding paints usually contain antimony oxide or barium eulfate in addition to the chlorinated biphenyl.
In making fireproof fiberboard, emulsified chlorinated biphenyl is added to the fiber
/
DSW 330412
STLCOPCB4077056
2`Jfi ClILOKOCAimONS AND CHLOKOIIYDKOCAKBONS
*
slock (tUi). Modifying w:im*s arc added to rhlnrimtted biphenyl in the preparation of It'Ntile-rnutiiig materials.
In addition to the uses lisp'd above, chlorinated biphenyls are ingredients of sonic sealing compounds for use with wood or canvas to give protect ion against moisture, mildew, or attacks of organisms. They are also used iu 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
"
"Chiorinaleil Diphenyls" under "Chlorinu Compounds, Organic;" in ECT 1st ed.f Vot. 3, pp. 820-832,
by C. l`\ Booth, Monsanto Chemical Company.
.
1. I'. Hell. J- <'hi hi. Soc. 131,2773 (1928).
'
2. Dcmsrlhcn, Ann. 'Chan. Liebigs 169, 138, 142 (1877).,
3. S. H. 7/ahi-er ami S. A. lomrch, J. Ind. ('Item. Sor.. 21,27 (1044).
4. M. Gomberg and \V. E. Uachmanii, J. Am. Chem. Hoc. 46, 2343 (1024).
. Ibid., 49, 2.V) (1027). . G. Schultz, .Inn. Clum. Liebigs 174,200 (1874).
7. E. Humhci'ger, Jlrr. Deni. Chem. Gel. 29, 403 (1890). 8. J. .1. Dubbic, .1. J. Fx, and A. J. II. Gauge, J. Chan. Soc. 99, 1010 (1911).
9. I,. Miwnrcili, I). Gatti, E. Jona, and V. Leonrini, Cuzz. C/.im. Ilui 39, 808-870 (19^6).
10. H. II. Hodgson, J. Chan. Hoc. 149. 745 (1010).
11. J. C. Coin, J. ( hem. Hoc. 85, 7 (1004).
12. F. Ullmaim, .Inn. Chem. Liebigs 332, 54-50 (1904).
13. L. E. 1 liukcl and 1). II. Hey, J. Chan. Soc. 131,2780-2788 (1928). 14. H. A. Scarborough and W. A. Waters, J. Chem. Soc. 130, 93-94 (1927).
15. T. Cranw, lice. Trav. Chini. 50, 753 (1931).
10. W. Blakely and II. A. Scarborough, J. Chan. Soc. 130, 3007 (1927). 17. W.Zcrucck ami C. Sdiiitz, Chem. z\bstr. 36, 50.58' (1942).' 18. C. Finzi ami V. Bcllavita, Gazz. Chim. lUil. 04,335 (1034).
19. Y. S. Xul'kiml and M. V. Belikova, J. Gen. Chem. USSli (Engl. Truant;) 8, 1918 ( >030).
'20. II. Kaiuinh z with H. ltnhm, Her. Deal. Chem. Gea. 60, 743 (1927). /
21. V. Bcllavita, Cuzz. Chim. lint. 65, 032 (1935).
/
.
22. L. Mascurcili, II. Gatti, ami B. 1/ongo, Gazz. Chim. Ital. G3, 054 (1^33).
23. I': W. Van lionsmalen, AVc. Troo. Chim. 53, 359 (1934). /
24. Fr. Fichter and M. Adler, liclv. Chim. Acla 9, 287 (1920). / 25. II. Meyer ami A. Hofmann, ilonalsh. Chem. 38, 145(1017). / 20. H. Sdiinidl and G. Schultz, Ann. Chem. Liebigs 207, 340 (1SM1).
- .
27. I/. W. Pickd t, F. G. Walter, and H. Franco, J. Am. Chem. Soc. 58, *2290 (1030).
28. Brit. Pat. 779,221 (July 17, 1957) (lo Progil).
20. The Arnclor CnmpouiuD, booklet, Monsanto Co., St. Louis, Mo.
30. F. M. (ilark. Trims. Elcclrochan. Soc. 65, 59-71 (1034). /
.
31. It. U. MacMullia, Chan. Eng. I'rogr. 44 (3), 183 -188 ^1048).
32. U.S. Pain. 1,892,397 and 1,S92,398 (l)ce. 27, 1932), It. L. Jenkins (to Swunu Research; re- t
assigned to Monsanto Chcinieol Co.J.
.1
33. U.S. Pal. 3,029,295 (April 10, 1902), Robert Thermet and Ludovic Purvi (to Socictd d'Electro-
chiruic D'J-.'leclromrtallnrgie ct den Acilrics Elcctrirjucfl d'Ugine).
34. U.S. Pat. 1,892,400 (Dee. 27, 1932), R. I,. Jenkins and J. A. Sikurski (to Swunn Research;
reassigned to Monsanto Chemical Co.). /
3.5. J. W. J. Fay ami J. II. Hidmrd*, "Impregnunls Used in German Paper Capacitors," Ojjir.e Tech.
Serv. Vli Ite/il.
(1947); HKtS (lirilish JnltJligcnrc Objectives Subcommittee) Eirw.l Kept. 80S.
30. "N'onmelalhe Materials" A STSI Sid. E28-48T, Curt UI-A (1940).
37. U.S. Pat. 1,994,302 (March 12, 1935), F. M. Clark (to General Electric Co.).
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0S\N 3304A3
PTmT
STLCOPCB4077057
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Vo!. 5
CHLOKOCAUUONS AND CHLOKOJlVimOCAURONS jm
38. Arm lor pbi-tii izirs, Tccli. Hull. No. !Mr-3()G,. Miins:ml<i (Jo., St. I/iiuia, Mo., Dec. PJOll.
1,. H. Bum linn imd S. T. Mmimlcr, (.Vn. Eke. i,Vu. 42. 230-239 (1939).
10. F. M. CDrk, Iml. Eng. < 'hem. 20, 09X-702 (1937).
_
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41. W. Joi 'kS'.u, Free. Ii'm/. Sue. (l.omlmi) Srr. .1 153, I.5S-10G (1935).
/
42. A. H. While ion! S. o' Mmj::ui, J. Franklin fnsl. 216, 035-044 (1933).
/
43. I'.S. Put. 1 ,N:ii'i, 1 SO (Utr. 15, 1931), O. It. McCullough anil R. L. Jenkins (to Swum Research;
rcaasigncO to Monsanto Chemical Co.).
t
44. r.S. Pals. 1,031,373 ami 1,931,455 (Oct. 17, 1033), F. M. Clark (to (Icncral Electric Co.).
15. U.S. Pal. 3,ii3S,ll)7 (June 5, 1002), H. I. Wcingarlen (to Monsanto Clicmiciil Co.).
IG. U.S. Pat. 3,iKiX,297 (Dee. 11, 1002), H. I. Weingarten (to Monsanto Chemical Co.).
47. H. I. WcingarU'ii, J. Org. Chan. 26, 4347-4350(1001).
/
4X. Ibid., 27, 2021-2020 (1002).
..
<
40. I'.S. Pat. 2.077,510 (March 2S, 1001), H. I. Weingarten (hi .Muns.mln Chemical Co.).
50. II. 1. Wrinpirlen, W. D. Ross, J. M. Schlater, anil G. Wheeler, Jr., .truii. Chim. Acta 20, 391
304 (1002).
./
.">1. V.S. Pat. 1,850,147 (June 14, 1032), J. H. Young(to II. 11. UnberUinn Co.).
~
.52. I'.S. Pal.2,120,157 (Sept. 0, 103R), 15. W.TriH-lnmlcr ami W. C. Wilwm (to Pyroxylin Proilucts).
5.3. U.S. Pat. 2,130,201 (Sept. 13, 195S), !'. M. Clark ami J. 11. Kinane (In General liloclric Co.).
54. I'.S. Pal. 2,141,910 (Dee. 27, 193S), W. C. Havinim (to General Kleetric Co.).
55. U.S. Pat. 2,I5S,2S1 (May 10, 1030), J. G. Ford ami C. F. Hill (to Wc-stinRlnnisc Electric ami
Manufacturing Co.).
50. Arorlor /trains and Flnstieizrrs for Chlorinated lCubber, Tech. Boll. 1M/-311, Monsanto Co.,
St. Dims, Mo., April 10112.
/
57. Arorlor Fire /Irlanling Fln-tirizcrs anil Modifier* for Epoxy Hexing, Tech. Bull. CS-14, Muneanto
On., St. 1 .a,ii:h. Mo., Nov. 1900.
.
.58. II. W. Bo'.vron, Faint Tnl.nul. 2, 25 27 (1037).
50. K. A. Ganh.er ami G. <1. Sword, Null. Faint, Varnish /^ici/ncr Asnoc. Sei. Fee. Eire. No. 55,
KK1-103 (103S).
.
00. It. I,. Jenkins and R. N. Poster, Iml. Enij. ('hem. 23, 1302-1305 (P.I31).
01. U.S. Pal. 2,077,700 (April 20, 1037), 15. Klein (to K. I. do Poiu de Nemours & Co., Inc.).
02. U.S. Pal. 2,OSS,401 (June 13, lt'til), H. J. Eiehel (to National Cash Register Co.).
03. W. J. Davis and P. G. Benigmis, Chem. Eng. Prog. 50, 30-42 (1003).
0-1.. Thcrminol F.ll Final Ueol Systems, booklet, Monsanto Co., St. Louis, Mo.
05. G. W. Wood. ,U/!7. Chemist 10 (3), 00-104 (1948).
00. U.S. Pat. 2,050,0.53 (Peh. 11, 1030), It.' G. Quinn (to International Paper Co.).
07. U.S. Pat. 2,548,300 (April 1051) B. Jv. Green and It. W. Sandberg (to National Cush Register
Co.).
/
/ II. L. HUBiiAllt)
. Monsanto Company
CHLORINATED NAPHTHALENES
Laurent, in IK.33, 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. ft was more than twenty years
later, however, that Avlsworth 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
Erlcnmeyor'.s establishment of the fused-ring structure of naphthalene in 18(i0, muny
years elapsed before many >f the. theoretically possible chlorination derivatives of the
compound were isolated and .identified; even today the positions of the substituent
chlorine atoms in all isolated tetrachloro- and pontachloroiinphthaloncs have not been
allocated with certainty (see Table 1). Physically, the difliculty of isolating-isomers
from the mixtures produced by chlorination of naphthalene is such that indirect
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330414 DS\N