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DISTILLATION P*IQ2\&A$
Monsanto Technical Data Sheet ,
February 26, 1954
Monsanto Chemical Company, Orgcnic Chemicals Division, St. Louis 1, Mo.
AROCLORS*, f/tf.40*, //.20\ PHENYLCYG.O HEXANE, IHCYCLOHEXYE
All of tlie 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 AROCLORS (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 many chemical reactions
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 AROCJ.OR 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 reMdues to facilitate re moval. This 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.
(Valuta trt Approiimtft)
Phonyleyclohotan*
Bicydohsiyl
AROCLOR 1242
AROCLOR 1248
AflOClOfl 1254
AROCLOR 1260
Ha-40
Hfl-20
OiitilUtion Rang*
239-24fC. 238*242C. 325-360'C. 340-375'C. 365*390C. :*85*420'C 340-.WC. 31 2*370*C.
Pour Point
2.5-S.fC.
1-3'C
minus 19*C minus 7C.
10C.
3t"C.
minus 25C- minu* 54*C.
Viscosity (SUS tt 100'F.)
ji.:i
34.2
80*93
185*240
1800-2500
72*78 (at 210'F.)
144
55.7 c\t`
Spocific fivlty
0.938 at
0.988 at
25V15.6*C. 2JV15.6*C.
1.380 at 25*/25C.
1.445 at 25*/25C.
1.538 at 25/25C.
1.620 at 25*/25*C
1.004 at 25/l 5C.
0.971 25#/15*C.
KIIMS-MUOI
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For further Information, contact
MONSANTO CHEMICAL COMPANY Organic Chamicali Division
800 North Twelfth DouievirJ St. Louis 1, Missouri
Printed in USA.
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PHF.NYLCYCLOHEXANE (Cycfoltexylbcnzcne) and
BICYCLOHEXYL (Dicyelohexyl)
; N Monsanto 1 j.
Phenylcyclohcxane and bicyclohexyl are high boiling, col >rless, oily liquids, free from objectionable odor and relatively free from toxicity.
Structurally, phenyl cyclohexane is composed of one aromatic six membered carbon ring and one aliphatic (hydrogenated) six membered carbon ring.
Bicyclohexyl 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-r ' tion, nitration, halogcnation and condensation with reactive chemical agents.
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The Informeilen eentolnod In thli bulletin U, o ew bed knowledge, true ond ettvrele, but oil recommendation* or ivCQCilion* ere modi VrlSiUk^ cveranter, unco Iho tondi'ion* el u*o ore beyond ovr ctntrel. The l\er.*on Chomlcot Campony d-icMm* toy lloV.I?)' Interred
In cennedlpn with the vte of tSeic data or iv68,io,"* .
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Ftnlhemoro, no thing eentolnod herein ihall be on#trv*d i recommendrltcn to vie erxy prorfvd In conflict with exlitlnt potenll cover* Inp eny material or Hi vie.
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LEXOLDMON005420
PMENYLCYCLOHEXANE (Cyclohexylbenxerte)
Phcnylcydohexanc is a product of hydrogenation of biphenyl under proper conditions to saturate one of ue benzene rings. Therefore, phcnylcydohexanc possesses the properties 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 be made from it. The physical, electrical and chemical properties of phcnylcyclohexane are described as follows:
PHYSICAL PROPERTIES
Molecular Weight: Appearance: Color: Odor: Specific Gravity(li) Pounds per Gallon (11) Refractive Index (11) Viscosity (11) Freezing Point (11) Distillation Ranee (11)
5r to 95f,'c Flash Point, open cup (11) Flame Pcint, 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 Liqv id
Water White Plcasait
0.938 :t 0.002 at 25/15.6 3. 7.82 (Av.)
1.523 0.002 at 25C. 31.2 Saybolt Seconds at I00F.
2.5-5.S^C.
239-- 244C. 210F. 220F.
Pressure, rnm.Hg.
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 eydes Volume Resistivity at 100C., 500 volts DC
2.54 2.45 0.22 50,000 x 10" c.l'mi-cm.
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COMPATIBILITY OP* PHSNYICYCLOHEXANS (II)
Phcnylcyclohexane is not soluble in water, but is miscible at 25C. with many solvents and oils of which the following are typical:
Solvent Acetone Bcnaent Carbon Tetrachloride Castor Oil Dichloromethane Ethyl Acetate Ethyl Alcohol
Glycerine Hexane Mineral Oil Stoddard Solvent Ttichlorobensene Xylene
Solubility
Miscible Miscible Miscible Miscible Miscible Miscible 44 ml. of phcnylcydo" hexane will dissolve in 100 ml. of alcohol at 25C. Immiscible Miscible Miscible Miscible Miscible Miscible
SOlUSfLITY OF SOME ORGANIC COMPOUNDS IN PHCNYLCYCLOHEXANE AT 25C. (II)
Solgto
Biphenyl DDT Naphthalene Paraffin Wax Stearic Acid Pentachlorophenol Santowax 0 Santowax M Santowax P Santowax R
`
,
Grams/100 Gms. i cyclohsxane
55 55 38 18 13
4.7 69 14
3.4 3.3
CHEMICAL PROPERTIES
p Cyclohexylbenieno Sulfonic Acid Pwnylcyclohexane can be readily sulfonatcd with lOOTr H.SO. (9). The barium, sodium, potassium, lead and nickel salts of the sulfonic acid have been prepared (6).
HjSO, C,,H,,--------------- > CtH,,,C,H,50,11 + H.O
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Nitro Cyclohoxylbeniene
_
A mixture of ortho ind para nitrocydohcxylbcnzcne can.bc prepared by nitration with HNO, and acetic acid (7), HNO, and acetic anhydride. (10), and fuming HNO, and H,SO, (6). The para isomer predominates. The corresponding amine s can be readily obtained by reduction of the nitro compounds.
C,,H,,
HNO,
-----------> C,H,,.ClH,NO, + H,0
H,SO,
(m.p.: Ortho, 45C; Para, 57C.) (b.p. Ortho, 1 nC; Para, 142C.) at 0.5 mm.
p-Cycfohoxylacetophanone 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- CHjCOCI .-------------- > CcHh*C6H4COCHj
(m.p. 68'9C.)
'
CMoromethyl Cyclohexylbeniene
The chloromethyl derivative of phcnylcyclohexanc has been made by reaction with paraformaldehyde* zinc chlo ride and HOI (1) (2) (3).
C,,H,,
HCI
.
------------------------- > aH,,.CcHCHICl paraformaldehyde
ZnCI*
p-Cyclohexylboniene Sulfonyl Chloride With chlorosulfonic acid, [>henylcyclohcxanc forms paracyclohcxylbcnzcne sulfonyl chloride in yields of 85% (5).
HSOjCi C,,H,,, --------------------> 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.
Br, C^H,,-------------> C*Hn.Cr.H|Br
I, (m.p. 60.4C.) (b.p. 153C.) at 10 mm.
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BI3LICGRAPHY
(1)
(2) (3) (4) (5) (6) (7) (8) (9)
(10) (ID (12) (13)
Bodroux and Thomassin, Bull. Soc. Chim. 6, 1411-16 (1939); C.A. 33, 93H
(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. Chem. Soc. 63, 3446-8 (1941).
Kursanoff, Annalcn 3_18, 309 (1901).
""
Mayes and Turner, j. Ch'cm. Soc. 1929, 500-8; C.A. 23, 2917 (1929).
Mow-ry. Renoll 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. Pr.tkt. 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)
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BICYCLOHEXYL (Dicyclohexyl)
Bicyclohcxyl 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
Apperanee 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 ri: 0.002 at 20C. 34.2 Saybolt 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.
7 O.f
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 scries.
(5) Fenskc, Myers and Quiggle, Ind. Eng. Chem. 42, 649-53 (1950).
PO. >3 J/l/53 1-M
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