US2912447A - Cyclic diol diester lubricants - Google Patents

Cyclic diol diester lubricants Download PDF

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Publication number
US2912447A
US2912447A US699530A US69953057A US2912447A US 2912447 A US2912447 A US 2912447A US 699530 A US699530 A US 699530A US 69953057 A US69953057 A US 69953057A US 2912447 A US2912447 A US 2912447A
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lubricants
cyclopentanedimethanol
diester
synthetic
norcamphanedimethanol
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US699530A
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Kent C Brannock
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Eastman Kodak Co
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Eastman Kodak Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
    • C07C69/28—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with dihydroxylic compounds

Definitions

  • R is an alkyl group containing 6 to 11 carbon atoms.
  • the present synthetic diesters of cyclic diols have considerable utility as lubricants.
  • lubricants having a wide range of viscosities and pour points can be obtained.
  • the present diesters can be used directly as lubricants or they can be blended with other lubricants. If desired, minor proportionate amounts of such conventional lubricant additives as antioxidants, extreme pressure additives, viscosity index improvers, thickeners, anticorrosion agents and related materials can be incorporated into the present diester lubricants.
  • diester lubricants namely, bis-(2-ethylhexyl)- sebacate and 2,2,4-trimethyl-1,3-pentanediol dipelargonate, as well as an 8 carbon branched chain oxo alcohol, diester of cyclohexane-l,1-diacetic acid, are compared. with typical diesters of the present invention by the data.
  • Typical cyclic diesters of the invention include:
  • Table 2 and Table 3 point-up the fact that k the synthetic lubricants of the present invention can be utilized at high temperatures as they possess excellent resistance to thermal degradation
  • the pour point data set out in Table 1 was determined by ASTM Method D-97-47 and the viscosity data set out in Table 1 and Table 2 was determined by ASTM Method D-88-44.
  • the data set out in Table 3 concerning the percent decomposition/hour of the various esters was based on the determination of the acid produced on heating samples of the various esters under nitrogen for eight hour periods.
  • Example I A mixture of 147 g. of cyclopentanecarboxaldehyde, 331 g. of 36% formalin and sufficient methanol to make a homogeneous solution, was added dropwise to a stirred solution-oi 105 g. of potassium hydroxide in 375 ml. of methanol over a 40 minute period. The resulting mixture was then heated under reflux for 5% hours, cooled, and 400 m1. of water added. The mixture was thereafter distilled until removal of the methanol was complete, and on cooling the residue, 1,1-cyclopentanedimethanol crystallized out.
  • 1,1-cyclopentanedimethanol crystals were removed from the reaction mixture by filtration, washed in cold water, and recrystallized from a hexane-chloroform mixture to give 123 g. of 1,1- cyclopentanedimethanol having a melting point of 98.5- 99.5 C. Thereafter, 1,1-cyclopentanedimethanol so prepared was esterified to prepare the present diester lubricents.
  • gyclopentanedimethanol were reacted to prepare 1,1-cyclopentanedimethanol dipelargonate boiling at 107-110" C. at 6 microns of mercury and having a 1.4575.
  • Example 2 A mixture of 1.2 moles of 1,1-cyclohexanethanol and 2.4 moles of n-octanoic acid was reacted and workedup as described in Example 1 (a) above.
  • the 1,1-cyclohexanedimethanol di-n-octanoate prepared boiled at C. at 5.4 microns of mercury and had n 1.4601.
  • Example 3 A 137 g. sample of -bicyclo(2,2,1)-5-heptene-2,2-dimethanol was hydrogenated over 15 g. of Raney nickel at 100 C. under a pressureot 1,000 p.s.i. to give 2,2- norcamphanedimethanol. A mixture of 1.2 moles of 2,2- norcamphanedimethanol and 2.4 moles of n-octanoic acid was reacted and worked-up as described in Example l (a) above. The 2,2-norcamphanedimethanol dicctanoate prepared boiled at -136 C. at 1 micron off mercury and had 92 1.4670.
  • a novel and hiy useful group of synthetic diester lubricants is provided.
  • a synthetic lubricant composition of high th stability consisting essentially of a diester selected from the group consisting of compounds of the formulas:
  • a synthetic lubricant composition of high thermal stability consisting essentially of a diester of the formula:
  • a synthetic lubricant composition of high thermal stability consisting essentially of 1,1-cyclopentanedimeth- O anol di-n-octanoate.
  • R is an alkyl group containing 6 to 11 carbon 10 atoms.
  • a synthetic lubricant composition of high thermal stability consisting essentially of a diester of the formula:
  • a synthetic lubricant composition of high thermal 5 stability consisting essentially of 1,1-cyclopentanedimethanol dipelargonate.
  • a synthetic lubricant composition of high thermal stability consisting essentially of 2,2-norcamphanedimethanol di-n-octanoate.

Description

United States Patent C) CY CLIC DIOL DIESTER LUBRICANTS Kent C. Brannock, Klngsport, Tenn assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application November 29, 1957 Serial No. 699,530
6 Claims. 01. 260-410 siderable amount of volatile material which is lost at high temperatures. Hydrocarbon lubricating oils particularly sufier where extreme conditions of temperature are encountered, such as in turbo-jet aircraft engines. High engine temperatures in turbo-jet aircraft engines are desirably employed to increase engine efliciency. In such a high temperature use, conventional hydrocarbon lubricating oils suffer thermal and oxidative breakdown to an undesirable degree.
In recent years a number of synthetic ester lubricants have been proposed to overcome some of the objections to hydrocarbon lubricating oils.
. It is an object of this invention to provide a new group of synthetic ester materials that have particular utility as lubricants and which are not subject to many of the disadvantages inherent to hydrocarbon lubricating oils. It is another object of the invention to provide novel synthetic ester lubricants which have lower pour points than hydrocarbon lubricants of comparable viscosity.
It is another object of this invention to provide a new class of synthetic ester lubricants having improved resistance to thermal degradation.
It is likewise an object of this invention to provide new synthetic ester lubricants especially adapted to meet the high temperature requirements desired for lubricating turbo-jet engines and for related uses.
Other objects will be apparent from the description and claims which follow.
CH CH O B C C O 0 CH, CHIOER O l l emails {I Hr and O CHrOEB 0 Hr J; CHrO ii R Wherein R is an alkyl group containing 6 to 11 carbon atoms. 1,1-cyclopentanedimethanol di-n-heptanoate; l,l-cyclopentanedimethanol di-n-octanoate; l,l-cyclopentanedimethanol dipelargonate; 1,1-cyclopentanedimethanol din-decanoate; 1,1-cyclopentanedimethanol di-n-undecanoate; 1,1-cyclopentanedimethanol di-n-dodecanoate; 1,1- cyclohexanehexanedimethanol di-n-heptanoate; 1,1-cyclohexanedimethanol di-n-octanoate; l,l-cyclohexanedimethanol dipelargonate; 1,1-cyclohexanedimethanol di-n-decanoate; 1,1-cyclohexanedimethanol di-n-undecanoate; 1,1- cyclohexanedimethanol di-n-dodecanoate; 2,2-norcamphenedimethanol di-n-heptanoate; 2,2-norcamphanedimethanol -di-n-octanoate; 2,2-norcamphenedimethanol dipelargonate; 2,2-norcamphanedimethanol di-n-decanoate; 2,2-norcamphanedimethanol di-n-undecanoate' and 2,2- norcamphanedime'thanol di-n-dodecanoate.
The present synthetic diesters of cyclic diols have considerable utility as lubricants. By varying the choice of the acyl moiety with which the 1,1-cyclopentanedimethanol; 1,1-cyclohexanedimethanol and 2,2-norcamphanedimethanol are esterified, lubricants having a wide range of viscosities and pour points can be obtained. The present diesters can be used directly as lubricants or they can be blended with other lubricants. If desired, minor proportionate amounts of such conventional lubricant additives as antioxidants, extreme pressure additives, viscosity index improvers, thickeners, anticorrosion agents and related materials can be incorporated into the present diester lubricants.
The viscosity and pour point characteristics of typical synthetic diesters of cyclic diols embodying this invention are illustrated in Table 1 below. In addition, a comparison is made with a typical hydrocarbon oil of comparable viscosity.
As can be seen from the'data set out in Table l,' the present synthetic lubricants have excellent viscosity and pour point characteristics.
The improved thermal stability of the present synthetic diester lubricants is illustrated by the data in Table 2 and Table 3 below. For purposes of comparison,
two known diester lubricants, namely, bis-(2-ethylhexyl)- sebacate and 2,2,4-trimethyl-1,3-pentanediol dipelargonate, as well as an 8 carbon branched chain oxo alcohol, diester of cyclohexane-l,1-diacetic acid, are compared. with typical diesters of the present invention by the data.
in Table 2 and Table 3.
Patented Nov. 10, 1959 Typical cyclic diesters of the invention include:
3 TABLE 2 Percent change in 100 F. viscosity Ester after 8 hour heating at indicated temperatune Bis-(Z-ethylhexyl) sebaeate 18% at 600 F. 3,2.4-Trlmethyl-L3-pentanedlol dipelargonate 16% at 550 F. Carbon oxo alcohol diester of 1,1-cyclohexanediacetic acid -19% at 600 F. 1,1-Cyclogentanedimethanol dlpelargonate l.4 0 at 600 F. 1,1-Cyclo exanedimethanol dl-n-octanoate +06% at 600 F. 2,2'Norcamphanedlmethan0l di-n-octanoate +29% at 600 F.
TABLE 3 Percent Decomposition/hour at- Ester 500 F. 525 F. 550 F. 575 F. 600 F.
lBis-(Z-ethylhexyl) sebacata. 0. 03 0. 11 0. 13 0. 59 1. 3 2,2,4-Trtu1ethyl-L3-pentanediol dlpelargonate 0.1 1. 09 8 Carbon 0x0 alcohol diester oi 1,1-cyolohezanediacetlc m-ld 0. 04 0- 17 1. 6 1,1-Cyclopentanedlmethano] dlpelargonate 0.02 0. 03 0. 04 1,1-Cyclohexanedlmethanol dl-n-octanoate 0. 003 0. 01 2,2-Norcamphanedlmethanol di-n'm'tannatp 0. 01 0.
The data in Table 2 and Table 3 point-up the fact that k the synthetic lubricants of the present invention can be utilized at high temperatures as they possess excellent resistance to thermal degradation The pour point data set out in Table 1 was determined by ASTM Method D-97-47 and the viscosity data set out in Table 1 and Table 2 was determined by ASTM Method D-88-44. The data set out in Table 3 concerning the percent decomposition/hour of the various esters was based on the determination of the acid produced on heating samples of the various esters under nitrogen for eight hour periods.
The following examples illustrate the preparation of typical diesters of the present invention from starting materials known in the art.
Example I A mixture of 147 g. of cyclopentanecarboxaldehyde, 331 g. of 36% formalin and sufficient methanol to make a homogeneous solution, was added dropwise to a stirred solution-oi 105 g. of potassium hydroxide in 375 ml. of methanol over a 40 minute period. The resulting mixture was then heated under reflux for 5% hours, cooled, and 400 m1. of water added. The mixture was thereafter distilled until removal of the methanol was complete, and on cooling the residue, 1,1-cyclopentanedimethanol crystallized out. The 1,1-cyclopentanedimethanol crystals were removed from the reaction mixture by filtration, washed in cold water, and recrystallized from a hexane-chloroform mixture to give 123 g. of 1,1- cyclopentanedimethanol having a melting point of 98.5- 99.5 C. Thereafter, 1,1-cyclopentanedimethanol so prepared was esterified to prepare the present diester lubricents.
(a) A mixture of 156 g. (1.2 moles) of 1,1-cyclopentanedimethanol, 346 g. (2.4 moles) of n-octanoic acid and ml. of xylene was refluxed in a reactor fitted with a Dean-Stark separator until water ceased to be evolved from the reaction mixture. The theoretical amount of water, 43 ml., was collected after 3 hours and the temperature of the reaction mixture had risen to 272 C. The resulting mixture was cooled, and thereafter washed with ml. of a 5% sodium hydroxide aqueous solution and then with 100 ml. of water. The xylene was stripped ofr by distillation and the resulting distillation residue further distilled in a molecular still to give 1,1- cyclopentanethanol dincctanoate boiling at 97- atoms.
gyclopentanedimethanol were reacted to prepare 1,1-cyclopentanedimethanol dipelargonate boiling at 107-110" C. at 6 microns of mercury and having a 1.4575.
Example 2 A mixture of 1.2 moles of 1,1-cyclohexanethanol and 2.4 moles of n-octanoic acid was reacted and workedup as described in Example 1 (a) above. The 1,1-cyclohexanedimethanol di-n-octanoate prepared boiled at C. at 5.4 microns of mercury and had n 1.4601.
Example 3 A 137 g. sample of -bicyclo(2,2,1)-5-heptene-2,2-dimethanol was hydrogenated over 15 g. of Raney nickel at 100 C. under a pressureot 1,000 p.s.i. to give 2,2- norcamphanedimethanol. A mixture of 1.2 moles of 2,2- norcamphanedimethanol and 2.4 moles of n-octanoic acid was reacted and worked-up as described in Example l (a) above. The 2,2-norcamphanedimethanol dicctanoate prepared boiled at -136 C. at 1 micron off mercury and had 92 1.4670.
While the above examples describe the esterification of 1,1 cyclopentanedimethanol; 1,1 cyclohexanedimethanol and 2,2-norcamphanedimethanol with particular organic acids, it is to be understood that in a like mer these cyclic diols can be esteiified with any organic acid having the formula RJJOOH wherein R is an alkyl group containing 6 to ll carmn Likewise, mixtures of such acids can be u to prepare the present diester lubricants.
Thus, by means of this invention, a novel and hiy useful group of synthetic diester lubricants is provided. The improved physical characteristics make the present diesters eminently suitable for use as lubricants in appli= cations where hydrocarbon lubricating oils are now used, as well as in high temperature applications where hydrocarbon lubricating oils are completely unsuitable. Be cause of their improved thermal stability at high temperatures, the present diester lubricants have particular utility for use in turbo-jet aircraft engines and for related high temperature applications.
The invention has been described in considerable d with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be efiected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.
I claim:
1. A synthetic lubricant composition of high th stability consisting essentially of a diester selected from the group consisting of compounds of the formulas:
O OHs C sO R C O L l omoiia and wherein R is an alkyl group zit-t": 6 to ill corhon atoms.
2. A synthetic lubricant composition of high thermal stability consisting essentially of a diester of the formula:
4. A synthetic lubricant composition of high thermal stability consisting essentially of 1,1-cyclopentanedimeth- O anol di-n-octanoate. II
wherein R is an alkyl group containing 6 to 11 carbon 10 atoms.
3. A synthetic lubricant composition of high thermal stability consisting essentially of a diester of the formula:
wherein R is an alkyl group containing 6 to 11 carbon atom!- 5. A synthetic lubricant composition of high thermal 5 stability consisting essentially of 1,1-cyclopentanedimethanol dipelargonate.
6. A synthetic lubricant composition of high thermal stability consisting essentially of 2,2-norcamphanedimethanol di-n-octanoate.
Refercnces Cited in the file of this patent UNITED STATES PATENTS Staib et al Mar. 13, 1956 Roelen et al Dec. 24, 1957 FOREIGN PATENTS Great Britain May 23, 1945 France Feb. 22, 1955

Claims (1)

1. A SYNTHETIC LUBRICANT COMPOSITION OF HIGH THERMAL STABILITY CONSISTING ESSENTIALLY OF A DIESTER SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS OF THE FORMULAS:
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3057815A (en) * 1958-10-13 1962-10-09 Exxon Research Engineering Co Esters of polymethylol cyclohexane and vinyl resin composition containing same
US3172897A (en) * 1961-08-23 1965-03-09 Pure Oil Co Esters of decahydronaphthalene dimethanol
US3239539A (en) * 1960-12-02 1966-03-08 Exxon Research Engineering Co Gem dimethylol alicyclic esters
US4528396A (en) * 1982-09-24 1985-07-09 Texaco Inc. Dicyclopentadiene derived ester compounds
US4895908A (en) * 1987-09-28 1990-01-23 Eastman Kodak Company Cyclopentadienylethanol and bis(2-hydroxyethyl)dicyclopentadiene esters and grafts thereof on carboxyl modified polyolefins
US6667284B2 (en) * 1999-03-26 2003-12-23 Pennzoil-Quaker State Company Lubricant for magnetic recording medium and use thereof
JP2006307064A (en) * 2005-04-28 2006-11-09 Idemitsu Kosan Co Ltd Power transmission lubricant
JP2006306773A (en) * 2005-04-28 2006-11-09 New Japan Chem Co Ltd Alicyclic dihydric alcohol ester
JP2006306987A (en) * 2005-04-28 2006-11-09 New Japan Chem Co Ltd Lubricating oil

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB569404A (en) * 1940-12-30 1945-05-23 Du Pont Manufacture of new esters and of compositions containing them
FR1087168A (en) * 1952-12-18 1955-02-22 Ruhrchemie Ag Process for preparing ester oils with low freezing point
US2738370A (en) * 1951-07-11 1956-03-13 Exxon Research Engineering Co Preparation of alicyclic glycols
US2817673A (en) * 1952-08-01 1957-12-24 Ruhrchemie Ag Tricyclodecane esters

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB569404A (en) * 1940-12-30 1945-05-23 Du Pont Manufacture of new esters and of compositions containing them
US2738370A (en) * 1951-07-11 1956-03-13 Exxon Research Engineering Co Preparation of alicyclic glycols
US2817673A (en) * 1952-08-01 1957-12-24 Ruhrchemie Ag Tricyclodecane esters
FR1087168A (en) * 1952-12-18 1955-02-22 Ruhrchemie Ag Process for preparing ester oils with low freezing point

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3057815A (en) * 1958-10-13 1962-10-09 Exxon Research Engineering Co Esters of polymethylol cyclohexane and vinyl resin composition containing same
US3239539A (en) * 1960-12-02 1966-03-08 Exxon Research Engineering Co Gem dimethylol alicyclic esters
US3172897A (en) * 1961-08-23 1965-03-09 Pure Oil Co Esters of decahydronaphthalene dimethanol
US4528396A (en) * 1982-09-24 1985-07-09 Texaco Inc. Dicyclopentadiene derived ester compounds
US4895908A (en) * 1987-09-28 1990-01-23 Eastman Kodak Company Cyclopentadienylethanol and bis(2-hydroxyethyl)dicyclopentadiene esters and grafts thereof on carboxyl modified polyolefins
US6667284B2 (en) * 1999-03-26 2003-12-23 Pennzoil-Quaker State Company Lubricant for magnetic recording medium and use thereof
JP2006307064A (en) * 2005-04-28 2006-11-09 Idemitsu Kosan Co Ltd Power transmission lubricant
JP2006306773A (en) * 2005-04-28 2006-11-09 New Japan Chem Co Ltd Alicyclic dihydric alcohol ester
JP2006306987A (en) * 2005-04-28 2006-11-09 New Japan Chem Co Ltd Lubricating oil
US20070037716A1 (en) * 2005-04-28 2007-02-15 Idemitsu Kosan Co., Ltd. Lubricants for power transmission

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