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C H E M I C A L A ID S !?s r M onw n?c Technical'
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Monsanto Technical Data Sheet ,
February 26, 1954
Monsanto Chemical Company, Orgcnic Chemicals Division, St. Louis 1, Mo.
D iS t !i.L A T IO N FS C B Lh/vfty j
AROCLORS*, f/tf.40*, //.20\ PHENYLCYCXOHEXANE, IHCYCLOHEXYE
All of the above materials are Monsanto chemicals which can be of value in certain distillation problems. These materials are high boiling solvents pos^ssing good heat stability. The A ROC 1.0RS (a series of chlorinated polyphcnyls) are especially noted for their chemical inertness. The other chemicals may also <erve as inert solvents. Consequently, these materials all find use as distillation aids where the lower boiling material is subject to decomposition from localized overheating, and in ca<cs where distillation residues arc resinous or solid materials which are difficult to clean out of the still pot, The Monsanto chemicals listed also find considerable application as inert media for map.'' ch^mma! sriwv><
An example.of the value of such distillation aids is a case where a product distilling at about 78C. at 40 mm. Hg. was separated without fractionation from AROCLOR 1242 which, at the same pressure, boils at 210'C. Another product boiling at ICO-C. at 2 mm, Hg. required only moderate ftaclionatior, to separate it from A ROCLOR 1 242 boiling at 13SC. (at 2 mm. Hg.).
Which material to use in a given situation can be determined from the table of properties which appears on the next page. When reduced pressures are involved, further data may be obtained upon request.
AROCLOR products 1242, 1248, 1254 and 1260 are liquids with progressively in creasing boiling points. These liquids act t$> a stable heel in the still and allow ali of the desired end product to be recovered. In cases where the distillation residue normally tends to polymerize into gummy materials or to decompose into solids, th liquid AROCLOR compounds can be used to keep the residue as a free-flowing fluid for easier removal. Also, by allowing better heat transfer in the fluid, excessive decomposition and product loss can be minimized.
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In addition to the liquid A ROCLOR products. Monsanto offers A ROC LOR 5460, a resinous solid which has been used to pla-iicize solid still reMclues to facilitate re moval. 7'his resin cannot be recovered and is discarded with the residue. From 25% to 30% of A ROCLOR 5460, based on total residue weight, will satisfactorily plas ticize most such residues.
When used as distillation aids, the liquid A ROCLOR compounds can be reused several times and either discarded or distilled to restore their original refined state.
Used as stable solvents for reactions conducted in an inert liquid phase, the liquid A ROCLOR compounds perform very well. Mere again, the liquids can usually be used several times before discarding or re-purifying.
The other chemicals listed are included to offer a wider choice of boiling points both at normal and at reduced pressures. The table below will help to choose the correct compound for your reaction or distillation situation. Your Monsanto representative will be glad to discuss specific problems and to provide or obtain other data needed.
{Voluos r ApprotimaU)
Phonyleyclohatano
Bicydohaiyl
AROCLOR 1242
AROCLOR AROCIOR AROCLOR
1248
1254
1260
Ha-4 0
Hfl-20
Distillation Rang*
239-244'C. 238-242`C. 325'360'C. 340-375'C. 365*390C. :85*4:o'C 340*396C. 3i:*370*C.
Pour Point
2.5*5.5*C.
1*3C.
minus 19C minus 7C.
10C.
31 "C.
minus 25C- minu* 54C.
Viscosity (SUS at lOO'F.)
34.2
80*93
185*240
1800-2500
72*78
(at 210F.)
144
55.7
Spocific ravlty
0.938 at
0.988 at
1.380 at
25V15.6*C. 2JV15.6*C. 25*/25C.
1.445 at 25/25,C.
1.538 at 25/25C.
1.620 at 25*/25*C
1.004 at 25/l 5C.
0.971 25#/15*C.
i *
For further information, confect - -
MONSANTO CHEMICAL COMPANY Organic Chamicali Division
800 North Twelfth SoulevirJ Sf. Louis 1, Missouri
Pnnud u. U.S.A.
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PHF.NYLCYCLOHEXANE
(Cyclcltcxylbenxcne) and
BICYCLOHEXYL (Dicyelohexyl)
; N Monsanto
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Phcnylcyclohcxane and bicyclohcxyl are high boiling, col >rless, oily liquids, free from objectionable odor and relatively free from toxicity.
Structurally, phcnylcyclohcxanc is composed of one aromatic six membered carbon ring and one aliphatic (hydrogenated) six membered carbon ring.
Bicyclohcxyl is composed of two aliphatic six membered carbon rings (both
saturated with hydrogen).
.
Both products are suggested for use as high boiling solvents and compatibiliting agents and penetrating agents.
Interesting derivatives can be made from phenylcyclohexanc by sulfona:>' tion, nitration, halogcnation and condensation with reactive chemical agents.
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PMENYLCYCLOHEXANE (Cyclohcxylbenxenc)
Phcnylcydohcxanc is a product of hydrogenation of biphenyl under proper conditions to saturate one of t.ie benzene rings. Therefore, pbenylcydohexanc possesses the probities of both aromatic and aliphatic nature. It is a high boiling, colorless, oily liquid, free from objectionable odor and relatively free from toxicity. Phcnylcydohcxanc is of interest as a high boiling solvent and compatibilizing agent and penetrating agent. It possesses good electrical resistance, and interesting derivatives can he made from it. The physical, electrical and chemical properties of phcnylcydohcxanc are described as follows:
PHYSICAL PROPERTIES
Molecular Weight: Appearance: Color: Odor: Specific Gravity (11) Pounds per Gallon (11) ' Refractive Index (U) Viscosity (11) Freezing Point (11) Distillation Ranee (11)
5# to 95# Flash Point, open cup (11) Flame Point, open cup (11) Vapor Pressure (11) (12)
Temperature, cC.
20 30 40 50 70 . 100 136.65 163.6 186.25 221.7 240.1
160 25 Colorless Oily Liqi id
Water White Plcasa it
0.938 . 0.002 at 25/15.6::. 7.82 (A\.)
1.523 0.002 at 25C. 31.2 Saybolt Seconds at 100F.
2.5'5.5CC.
239-- 244C. 210F. 220F.
Pressure, tnnvH
0.1 0.15 0.30 0.60 2.0 9.0 40.0 100.0 200.0 500.0 760.0.
Electrical Properties --Typical Values (II)
Dielectric Constant at 25C. -- 60 cycles to 100 kc Dielectric Constant at 100C.--60 cycles to 100 kc Power Factor at 100C. -- 60 cycles Volume Resistivity at lOO^C., 500 volts DC
2.54 2.45
0.22#
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COMPATIBILITY Of* PWENYLCYCLOH EXAN S (II)
lohexane is not soluble in water, but is miscible at 25C. with many solvents and < are typical:
Solvent
Acetone Bcnsent Carbon Tetrachloride Castor Oil Dichloromethane Ethyl Acetate Ethyl Alcohol
, '
Glycerine Hexane Mineral Oil Stoddard Solvent Trichlorobenzene Xylene
Solubility
Miscible Miscible Miscible Miscible Miscible Miscible 44 ml. of phcnylcyclo" hexane will dissolve in 100 ml. of alcohol at 25C. * Immiscible Miscible Miscible Miscible Miscible Miscible
SOLUBILITY OF SOME ORGANIC COMPOUNDS IN PHENYLCYCLOHEXANE AT 25C. (II)
SoMo
Biphenyl DDT Naphthalene Paraffin Wax Stearic Acid Pentachlorophenol Santowax 0 Santowax M Santowax P Santowax R
`
*
Grams/100 Gms. Phenyl-
cyclohexane
55 55 38 18 13
4.7 69 14
3.4 3.3
CHEMICAL PROPERTIES
p Cyclohexylbenieno Sulfonic Acid Ptcnylcydohexanc can be readily sulfonatcd with 100$- HaS04 (9). The barium, sodium, potassium, lead a-'.d nickel salts of the sulfonic acid have been prepared (6).
HjSO CitHi,-------------- > C,H,,.C.HlSOJH + H.O
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Nitro Cyclohoxylbeniene
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A mixture of ortho and para nitrocydohcxylbcnztnc can.bc prepared by nitration with HNO, and acetic acid (7), UNO, and acetic anhydride (10), and fuming HNO, and H,S04 (6). The para isomer predominates. The corresponding amine $ can be readily obtained by reduction o( the rtitro compounds.
HNO,
C,,H,,------------- > C.H,,.C6H4NO, + H20
h,so
(m.p,: Ortho, 45C; Para, 57C.) (b.p. Ortho, 113C; Para, 142&C.) at 0.5 mm.
p-Cycfohoxylacetophnone The ketone derivative is obtained by condensing acetyl chloride (7) (8) or acetic anhydride (4) with phenyl* cyclohexane in the pre& ncc of aluminum chloride.
AICU
C,*H,6 4- CHjCOCl .-------------> CtHu-CEHCOCH,
(m.p. 68'9C.)
CMoromethy/ Cyc/ohexylbeniene
*
The chloromethyl derivative of phcnylcyclohexanc has been made by reaction with paraformaldehyde, zinc chlo ride and HOI (1) (2) (3).
C,,H,,
HC1 ----------------------------- > C..Hn.CcH4CH:Cl paraformaldehyde
ZnCl
p-Cyclohexylbonzene Sulfonyl Chloride With chlorosulfonic acid, [ihenylcyclohcxanc forms paracyclohcxylbcnzcne sulfonyl chloride in yields of 85$r (5).
HSO.C1 -------------------- > C.H,,.C,H.SO,Cl
(m.p. 160C.)
p-BromocycIohexylbenzene Jn an excess of phcnylcyclohexanc with an iodine catalyst bromination proceeds to the p-bromo derivative (1) (13). The bromide forms the Grignard reagent.
C,,H,
Br, -------- > CflHn.Cr.H1Br I, (m.p, 60.4C.)
(b.p. 153C.) at 10 mm.
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BI3L10GRAPHY
(1)
(2) (3) (4) (5) (6) (7) (8) (9)
(10) (11) (12) (U)
Bodroux and Thomassin, Bull. Soc. Cbim 6, 1411-16 (193S>); C.A. 33, 9314
(1939).
Braun, Irmish, Nclles, Ber. 66, 1471 (1933); C.A. 28, 139 (1934). Chadwick, Monsanto Chemical Co., Anniston, Ala., Unpublished Report.
Chang, J. Chinese Chem. Soc., 2, 216-220 (1934); C.A. 29, 459 (1935).
Huntress and Antenrieth, J. Am. Cb.cm. Soc. 63_, 3446-8 (1941).
Kurs.moff, Annalcn 3_18, 309 (1901).
""
Mayes and Turner, j. Chfcm. Soc. 1929, 500-8; C.A. 2 J, 2947 (1929).
Mowry. Rcnoll and Huber, J, Am. Chem. Soc. 68, 1105 (1946).
Nametkin and Pokrovskaya, Doklady Akad Nauk. S.S.S.R. 61_, 1043 (1948);
C.A. 43, 2957 (1949).
Ncunhocffcr, J. Prakt. Chem. 133, 9-5-109 (1932); C.A. 26, 2435 (1932).
Monsanto Specifications and Unpublished Data.
Fenske, Myers and Quiggle, Ind. Eng,.Chem, 42, 649-52 (1950).
Marvel and Himel, J. Am. Chem. Soc. 6^, 1550 (1940).
(See next page for BICYCLOHEXYL)
*4-
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BICYCLOHEXYL (Uicyclohcxyl)
Bicydohcxyl is a product of the hydrogenation of biphenyl under proper conditions to saturate both aromatic rings. The material is a colorless oil possessing a pleasant odor. It is relatively non-toxic to higher animals.
U. S. Patent 2,448,093 L. D. Gittings) includes dicyclohcxyl as an ingredient in penetrating oil. Military Specifications MIL-F-7197 lists dicyclohcxyl as a rubber swelling reference fluid (1).
Molecular Weight Appe ranee Color Odor Specific Gravity (2) Pounds per Gallon (3) Refractive Index (1) (2) Viscosity (2)
Freezing Point (2)
Distillation Range (2) 5% to 95%
Flash Point, open cup (1)
#
Flame Point, open cup (2)
Aniline Point, C. (2) <3)
Vapor Pressure (2) (5)
Temperature, C.
20*
30 40 50 70 . 100 134.35 161.2 184.45 220.15 238.5
PHYSICAL PROPERTIES
166.30 Clear, mobile liquid
Water white Pleasant
0.883 0.002 at 25/15.6C. 7.37 (Average)
1.4800 0.002 at 20C. 34.2 Saylxjlt Seconds at lOO^F
3.07 Centistokes at 100F. 1.23 Cen istokes at 210F.
1*3C. ` 238-242C.
215F. 220F. 48.2C.
Pressure, mm Hg.
~ Chi 0.2 0.4 0.8 2.5
10.5 40 100 200 500 760
BIBLIOGRAPHY
(1) Military Specification MIL-F-7197 (May 15, 1951) --Air Development Force, Wright-Patterson Air Force Base, Ohio.
(2) Monsanto Specification and Unpublished Data.
(3) Jo, Wood and Gamer, J. Inst. Petroleum 28, 159-71 (1942); C.A. 37, 4886 (1943).
(4) Goodman and Wise, National Advisory Committee for Aeronautics, Technical
Note 2419, January 25, 1951; 2-Alkylbiphenyl and the two isomerio 2-aIkylbicyclohexyl series.
(5) Fenskc, Myers and Quiggle, Ind. Eng. Chem. 42, 649-53 (1950).
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