CA1090550A - Use of odoriferous compounds to detect gas losses in freon systems - Google Patents
Use of odoriferous compounds to detect gas losses in freon systemsInfo
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- CA1090550A CA1090550A CA292,634A CA292634A CA1090550A CA 1090550 A CA1090550 A CA 1090550A CA 292634 A CA292634 A CA 292634A CA 1090550 A CA1090550 A CA 1090550A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/066—Cooling mixtures; De-icing compositions
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01M—TESTING STATIC OR DYNAMIC BALANCE OF MACHINES OR STRUCTURES; TESTING OF STRUCTURES OR APPARATUS, NOT OTHERWISE PROVIDED FOR
- G01M3/00—Investigating fluid-tightness of structures
- G01M3/02—Investigating fluid-tightness of structures by using fluid or vacuum
- G01M3/04—Investigating fluid-tightness of structures by using fluid or vacuum by detecting the presence of fluid at the leakage point
- G01M3/20—Investigating fluid-tightness of structures by using fluid or vacuum by detecting the presence of fluid at the leakage point using special tracer materials, e.g. dye, fluorescent material, radioactive material
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- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
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- Thermal Sciences (AREA)
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- Organic Chemistry (AREA)
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Abstract
Use of Odoriferous Compounds to Detect Gas Losses in Freon Systems Abstract of the Disclosure A series of compounds are disclosed which are useful as odorants to warn of loss of refrigerant gas from refrigeration systems. These compounds are chemically inert in the presence of the refrigerant and can resist the high temperatures encountered in the compression cycle.
Description
De Simone Case 5 10~0550 The present invention relates to the addition of stable odoriferous components ~odorants) to chlorofluorocarbons, used as heat transfer media in refrigerant systems, to serve as a de tection system to warn of loss of refrigerant to the environment.
Such a warning system has become highly desirable in limiting chlorofluorocarbon 1088 to the atmosphere, in light of the detri-mental effect these materials are alleged to have on the earth's ozone layer. Additionally, in absence of a warning system, such leaks frequently go undetected for quite ~ome time, resulting in economic 1088 through substantial losses of coolant and reduced efficiency of the refrigeration system.
There are a number of criteria which an odorant detec-tion system must fulfill in order to be of use in the typical chlorofluorocarbon refrigerant systems. It has been found that traditionally compounded fragrance compositions cau~e problems in at least one, and more often in several trouble areas. For example, the compressors used in chlorofluorocarbon refrigerant systems, eapecially those employed in large capacity industrial cooling systems, can develop internal temperatures in the chloro-fluorocarbon medium during the compression cycle of as high as350 to 400F. This temperature is usually highest at the expan-sion device or di~charge orifice and at this point, most heat sensitive odorant materials are likely to cause problems by resini-fying or carbonizing, thus causinq fouling or blocking of the orifice.
In addition to stability requirements for avoidance of fouling as just mentioned, there are other criteria which an odorant must fulfill. It must not roact with the chlorofluoro-carbon in the presence of other #ystem components, such as the various metals of construction, drying agent~, lubricating oils and electrical insulation, which are normally found in refrigera-tion systems. Al~o, th- odorant mu~t not degrade in the presence
Such a warning system has become highly desirable in limiting chlorofluorocarbon 1088 to the atmosphere, in light of the detri-mental effect these materials are alleged to have on the earth's ozone layer. Additionally, in absence of a warning system, such leaks frequently go undetected for quite ~ome time, resulting in economic 1088 through substantial losses of coolant and reduced efficiency of the refrigeration system.
There are a number of criteria which an odorant detec-tion system must fulfill in order to be of use in the typical chlorofluorocarbon refrigerant systems. It has been found that traditionally compounded fragrance compositions cau~e problems in at least one, and more often in several trouble areas. For example, the compressors used in chlorofluorocarbon refrigerant systems, eapecially those employed in large capacity industrial cooling systems, can develop internal temperatures in the chloro-fluorocarbon medium during the compression cycle of as high as350 to 400F. This temperature is usually highest at the expan-sion device or di~charge orifice and at this point, most heat sensitive odorant materials are likely to cause problems by resini-fying or carbonizing, thus causinq fouling or blocking of the orifice.
In addition to stability requirements for avoidance of fouling as just mentioned, there are other criteria which an odorant must fulfill. It must not roact with the chlorofluoro-carbon in the presence of other #ystem components, such as the various metals of construction, drying agent~, lubricating oils and electrical insulation, which are normally found in refrigera-tion systems. Al~o, th- odorant mu~t not degrade in the presence
-2-of trace contaminants in the system, such as air, moisture, or acidulants. It has been found that certain frequently used fragrance co~ponents can cause greater than normal corrosion of the metal components used in chlorofluorocarbon refrigeration systems, such as steel, aluminum, and copper. One common phenomenon encountered in refrigerant systems is "copper plating" of the steel components caused by deposition from ~he copper metal parts of the system and it is imperative that the odoriferous additives do not accelerate this process beyond its normal rate. Refrigera-tion systems have integral dryer material cartridges containing awater trapping agent such as alumina, silica or molecular sieves to remove traces of moisture which would otherwise cause corrosion of the metal materials of construction. The odorant material must not irreversibly absorb onto the drying agents so as to clog them or otherwise interact and alter their efficiency.
The lubricating oil to refrigerant chlorofluorocarbon ratios can vary from one to four for household refrigerant systems to one to one hundred, and preferably one to thirty-five, for large industrial cooling syste~s. Insolubility can result in oiling out or precipitation of the odorant and can cause clogging at the orifice, dryer cartridge, or the moving parts of the com-pressor, or it can cause a change in the viscosity or lubricity of the lubricant oil. Also, if the odorant is not fully miscible with either the oil or the chlorofluorocarbon, it can pool out and not distribute evenly throughout the system, in which case, it will not be available at the leak site. It mu~t not, however, diJso~Ye or cause blistering or ~oftening of in~ulation on the internal electrical components of the refrigeration systems.
Additionally, the odorant's toxicity to humans must be low at the intended effective use level and it should dissipate readily after the leak i8 stopped 80 as not to give a false alarm after the leak is repaired.
~090ss0 It is the object of this invention to provide certain classes of compounds which, when added to a fluorocarbon re-frigerant system, will serve as leak detectors without contrib-uting to any of the problems set forth hereinabove.
Thus, in accordance with the concept of this invention, there is set forth hereinafter a series of groups of compounds which have been found to have utility as leak detection warning materials which are stable in fluorocarbon refrigerants under conditions of use of such systems:
I. Aliphatic and cycloaliphatic ethers II. Aromatic ethers III. Aliphatic and cycloaliphatic alcohols IV. Aromatic alcohols V. Alkyl sulfides VI. Aliphatic and aromatic nitriles YII. Terpene hydrocarbons VIII. Benzenoid hydrocarbons IX. Aliphatic, cycloaliphatic and aromatic ketones X. Esters XI. Phenols XII. Lactones XIII. Alpha-diketones The amount of the odorant compound used is subject to wLde variation. Generally speaking, the amount will be between about 0.01 and 5%, preferably about 0.01 and 1%, ba~ed on the total weight of lubricant and refrigerant. The precise amount to be employed will depend to a considerable degree upon the odor int nsity of the particular odorant employed. The amount will al80 be limited, in some instance~, by the solubility of the odorant in the lubricant refrigerant mixture.
Within the classes listed above, specific exemplary compounds are li~ted in the following tabulation:
10~0550 I. Aliphatic and cycloaliphatic ethers (a) the cineoles (b) isoamyl heptyl ether (cl. citronellal dimethyl acetal tdl geranyl methyl ether (e) alpha-cedrene epoxide lfl cedrol methyl ether II. Aromatic ethers (a~ diphenyl oxide (b~ dihydroanethole lc~ l-phenyl-21(1'-ethoxy)ethoxylethane ~d~ isobutyl benzyl ether Ce) propyl phenyl ethyl ether Cf~ methyl chaYicol (g) para-cresyl benzyl ether ohl 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexa~ethyl-cyclopenta-gamma-2-benzopyran III. ~ hatic and cYcloaliphatic alcohol (al diisobutyl carbinol :~ 20 (b) dihydro-alpha-terpineol (c) linalool ; (d) tetrahydrolinalool (e) n-hexanol lf) cis-3-hexenol-1 (g) fenchol (h) 3,7-dimethyl-octanol-1 (il alpha-terpineol borneol IV. Aromatic alcohols _ (al phenyl dimethyl carbinol (b) benzyl alcohol (c~ phenyl ethyl alcohol 5_ (d) cinnamyl alcohol (e) para-hydroxymethyl cumene V. Alkyl sulfides (a) dimethyl sulfide (bl dipropyl sulfide VI. Aliphatic and aromatic nitriles ~a) dimethyl cyclohexene nitriles (b) 2,3-dLmethyl-2-nonene nitrile (cl decane nitrile (d~ geranylonitrile ~el 2,4,5-trimethyl benzonitrile (f) 4-phenyl butyronitrile (gl 3-phenyl propionitrile ohl p-methoxy benzonitrile YII. Ter~ene hydrocarbon~
(a) alpha-pinene (bl dipentene (cl beta-caryophyllene ~dl longifolene (e) cedrene ~fl camphene ~g) ~\3-carene YIII. Benzenoid hxdrocarbons ~al p-cymene (b) l-methyl naphthalene (cl 2-methyl naphthalene ld) cumene IX. Xetones .
(a) 2-octanone ~1 amyl phenyl ketone (c) dlphenyl ketone (d) benzyl acetone (e) menthone ~f2 carvone ; (g) para-tertiary butyl cyclohexanone (h~ methyl heptenone X. Esters ~a) diethyl phthalate (b) hexyl hexanoate (c) methyl-2-octynoate (d2 benzyl propionate (e~ isobornyl acetate ~f) para-tertiary butyl cyclohexyl acetate XI. Phenol~
~a2 thymol (b) quaiacol ~c2 eugenol ~dl para-ethyl phenol ~e) methyl salicylate ~f) chavicol (g) creosol XII. Lactones :
(a) 3-n-butylidene phthalide (b) 3-n-butyl phthalide I (c) 15-hydroxypentadecanoic acid lactone j ~d) delta-decalactone ¦ (e) gamma-hexalactone ¦ XIII. Diketones I (a) S-ethyl-3-bydroxy-4-methyl-2 (SH-furanone) (b) 3-methyl-1,2-cyclohexane dione -(c) 3-ethyl cyclopentanedione - . 10905SO
In order to Yerify that odorous materials survive the heating cycle within refrigeration units, the following test is employed. The odorant is combined with chlorofluorocarbon s d lubricating oil and sealed in a glass ampoule with planchets of copper, steel and aluminum. After a suitable heating period, the tubes are observed visually for darkening of oil and plating of copper on the steel planchet. Darkening of the oil indicates a decomposition of the odorant or of the refrigerant lubricant mix-ture by the action of the odorant. Plating of copper on the planchet indicates corrosion of the copper elements within the system. The planchets are evaluated by comparison with a control planchet heated in a mixture of lubricant and refrigerant con-taining no odorant.
B Example 1 Sealed Pyrex glass tubes were prepared containing 2 ml.
of dichlorodifluoromethane (Freon 12, E. I. du Pont de Nemours Register), 2 cc. of mixed alkyl benzenes lubricant (Suniso 3 GS
oil, Sun Oil Company Register), and 0.01% odorant. Strips of steel, copper and aluminum were placed in the above-described fluid mixture and tubes sealed prior to heating at 350F. for 192 hours. Duplicate tubes were prepared for each odorant and visual results after 24, 96, and 192 hours ~ere recorded (see Table I). In this series, the aluminum strips remained unchanged, the copper was bright initially, but had a dull appearance when first observed after 24 hours at 350F., and did not change sub-- stantially after. Copper plate formed on the steel strip to an increasing extent with exposure. In some cases, corrosion appeared as well. Observations on copper plating are recorded in the column headed ~stoel~. The colors of the liquids passed through their initial stage of clear water-white to pale yellow, yellow amber, broffn and black, but at different rates for the variow samples.
10gO550 The materials shown in Table I were the odorant products which were observed to be compatible ~nder the test conditions and which did not give decomposition of the oil or plating beyond that observed for the control. All products were run in duplicate te~ts, which gave identical results in all cases shown.
' 1~90550 ~ + m m + m m m + +
~a .,~
+++ ++++++
~1 m m m m m m m m m .~ ~
~ P. z ~ ~
m c~ ~ ~ ~o .o E~
¦ m m m m m m m m m ~ o ~n E~
!~ u P. ~ ~ m m
The lubricating oil to refrigerant chlorofluorocarbon ratios can vary from one to four for household refrigerant systems to one to one hundred, and preferably one to thirty-five, for large industrial cooling syste~s. Insolubility can result in oiling out or precipitation of the odorant and can cause clogging at the orifice, dryer cartridge, or the moving parts of the com-pressor, or it can cause a change in the viscosity or lubricity of the lubricant oil. Also, if the odorant is not fully miscible with either the oil or the chlorofluorocarbon, it can pool out and not distribute evenly throughout the system, in which case, it will not be available at the leak site. It mu~t not, however, diJso~Ye or cause blistering or ~oftening of in~ulation on the internal electrical components of the refrigeration systems.
Additionally, the odorant's toxicity to humans must be low at the intended effective use level and it should dissipate readily after the leak i8 stopped 80 as not to give a false alarm after the leak is repaired.
~090ss0 It is the object of this invention to provide certain classes of compounds which, when added to a fluorocarbon re-frigerant system, will serve as leak detectors without contrib-uting to any of the problems set forth hereinabove.
Thus, in accordance with the concept of this invention, there is set forth hereinafter a series of groups of compounds which have been found to have utility as leak detection warning materials which are stable in fluorocarbon refrigerants under conditions of use of such systems:
I. Aliphatic and cycloaliphatic ethers II. Aromatic ethers III. Aliphatic and cycloaliphatic alcohols IV. Aromatic alcohols V. Alkyl sulfides VI. Aliphatic and aromatic nitriles YII. Terpene hydrocarbons VIII. Benzenoid hydrocarbons IX. Aliphatic, cycloaliphatic and aromatic ketones X. Esters XI. Phenols XII. Lactones XIII. Alpha-diketones The amount of the odorant compound used is subject to wLde variation. Generally speaking, the amount will be between about 0.01 and 5%, preferably about 0.01 and 1%, ba~ed on the total weight of lubricant and refrigerant. The precise amount to be employed will depend to a considerable degree upon the odor int nsity of the particular odorant employed. The amount will al80 be limited, in some instance~, by the solubility of the odorant in the lubricant refrigerant mixture.
Within the classes listed above, specific exemplary compounds are li~ted in the following tabulation:
10~0550 I. Aliphatic and cycloaliphatic ethers (a) the cineoles (b) isoamyl heptyl ether (cl. citronellal dimethyl acetal tdl geranyl methyl ether (e) alpha-cedrene epoxide lfl cedrol methyl ether II. Aromatic ethers (a~ diphenyl oxide (b~ dihydroanethole lc~ l-phenyl-21(1'-ethoxy)ethoxylethane ~d~ isobutyl benzyl ether Ce) propyl phenyl ethyl ether Cf~ methyl chaYicol (g) para-cresyl benzyl ether ohl 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexa~ethyl-cyclopenta-gamma-2-benzopyran III. ~ hatic and cYcloaliphatic alcohol (al diisobutyl carbinol :~ 20 (b) dihydro-alpha-terpineol (c) linalool ; (d) tetrahydrolinalool (e) n-hexanol lf) cis-3-hexenol-1 (g) fenchol (h) 3,7-dimethyl-octanol-1 (il alpha-terpineol borneol IV. Aromatic alcohols _ (al phenyl dimethyl carbinol (b) benzyl alcohol (c~ phenyl ethyl alcohol 5_ (d) cinnamyl alcohol (e) para-hydroxymethyl cumene V. Alkyl sulfides (a) dimethyl sulfide (bl dipropyl sulfide VI. Aliphatic and aromatic nitriles ~a) dimethyl cyclohexene nitriles (b) 2,3-dLmethyl-2-nonene nitrile (cl decane nitrile (d~ geranylonitrile ~el 2,4,5-trimethyl benzonitrile (f) 4-phenyl butyronitrile (gl 3-phenyl propionitrile ohl p-methoxy benzonitrile YII. Ter~ene hydrocarbon~
(a) alpha-pinene (bl dipentene (cl beta-caryophyllene ~dl longifolene (e) cedrene ~fl camphene ~g) ~\3-carene YIII. Benzenoid hxdrocarbons ~al p-cymene (b) l-methyl naphthalene (cl 2-methyl naphthalene ld) cumene IX. Xetones .
(a) 2-octanone ~1 amyl phenyl ketone (c) dlphenyl ketone (d) benzyl acetone (e) menthone ~f2 carvone ; (g) para-tertiary butyl cyclohexanone (h~ methyl heptenone X. Esters ~a) diethyl phthalate (b) hexyl hexanoate (c) methyl-2-octynoate (d2 benzyl propionate (e~ isobornyl acetate ~f) para-tertiary butyl cyclohexyl acetate XI. Phenol~
~a2 thymol (b) quaiacol ~c2 eugenol ~dl para-ethyl phenol ~e) methyl salicylate ~f) chavicol (g) creosol XII. Lactones :
(a) 3-n-butylidene phthalide (b) 3-n-butyl phthalide I (c) 15-hydroxypentadecanoic acid lactone j ~d) delta-decalactone ¦ (e) gamma-hexalactone ¦ XIII. Diketones I (a) S-ethyl-3-bydroxy-4-methyl-2 (SH-furanone) (b) 3-methyl-1,2-cyclohexane dione -(c) 3-ethyl cyclopentanedione - . 10905SO
In order to Yerify that odorous materials survive the heating cycle within refrigeration units, the following test is employed. The odorant is combined with chlorofluorocarbon s d lubricating oil and sealed in a glass ampoule with planchets of copper, steel and aluminum. After a suitable heating period, the tubes are observed visually for darkening of oil and plating of copper on the steel planchet. Darkening of the oil indicates a decomposition of the odorant or of the refrigerant lubricant mix-ture by the action of the odorant. Plating of copper on the planchet indicates corrosion of the copper elements within the system. The planchets are evaluated by comparison with a control planchet heated in a mixture of lubricant and refrigerant con-taining no odorant.
B Example 1 Sealed Pyrex glass tubes were prepared containing 2 ml.
of dichlorodifluoromethane (Freon 12, E. I. du Pont de Nemours Register), 2 cc. of mixed alkyl benzenes lubricant (Suniso 3 GS
oil, Sun Oil Company Register), and 0.01% odorant. Strips of steel, copper and aluminum were placed in the above-described fluid mixture and tubes sealed prior to heating at 350F. for 192 hours. Duplicate tubes were prepared for each odorant and visual results after 24, 96, and 192 hours ~ere recorded (see Table I). In this series, the aluminum strips remained unchanged, the copper was bright initially, but had a dull appearance when first observed after 24 hours at 350F., and did not change sub-- stantially after. Copper plate formed on the steel strip to an increasing extent with exposure. In some cases, corrosion appeared as well. Observations on copper plating are recorded in the column headed ~stoel~. The colors of the liquids passed through their initial stage of clear water-white to pale yellow, yellow amber, broffn and black, but at different rates for the variow samples.
10gO550 The materials shown in Table I were the odorant products which were observed to be compatible ~nder the test conditions and which did not give decomposition of the oil or plating beyond that observed for the control. All products were run in duplicate te~ts, which gave identical results in all cases shown.
' 1~90550 ~ + m m + m m m + +
~a .,~
+++ ++++++
~1 m m m m m m m m m .~ ~
~ P. z ~ ~
m c~ ~ ~ ~o .o E~
¦ m m m m m m m m m ~ o ~n E~
!~ u P. ~ ~ m m
3 llllll - o ~l ~ ~ ~
O
o I, 8 ,, , 8 ~ `~
l~gOSSO
~ ¦ m m m m m m m + m m sl ~ ~5 a~ ~1 _, ~ ++++++++++
a~ m m m m m m m ~ m m . U~
.
O
3 3~ ~
~ 01 m m m m m m m m m m i~
~ ~ .
~ .
3 z o ~1 ~ .C ~ ~
~ 3 ~ e ~ a ~ i ~
lW0550 Example 2 SEALED TUBE STABILITY OF ODORANTS
Tests were conducted under the same conditions as in Example I, except that the weight of odorant was 1% by weight B in the Suniso 3 GS oil and the duration only 24 hours at 350F. Using the same code as in Example I, the results are displayed in Table II:
Observation Compound Liquid Steel Control #1 2+ C+
Control ~2 1 C
Mixed 1,4- and 1,8-Cineoles 1 C
2,4- and 3,5-Dimethyl-3- 2 C+
Cyclohexene Nitriles Dimethyl Sulfide 2 C+
1,8-Cineole 1 C
Diisobutyl Carbinol 1 C
Menthone 1 C
Dihydro-alpha-Terpineol 1 C
Tetrahydrolinalool 1 C
Diphenyl Oxide . 1 C
Dihydro Anethole 1 C
`2,3-Dimethyl-2-Nonene Nitrile 2+ C+
n-Hexyl Alcohol 1 C
Phenyl Dimethyl Carbinol 1 C
Alpha-Pinene 1 C
: Decane Nitrile 1 C
2-Octanone 1 C
Para-Cymene 1 C
Fenchol 1 C
Example 3 An odorant composition to be used as a chlorofluoro-carbon leak indicator was made up as follows:
Compound Weight in Grams 3,7-Dimethyl-l-Octanol 200 Diphenyl Oxide 9 Dimethyl Sulfide Mixed 1,4- and 1,8-Cineoles 380 2,4- and 3,5-Dimethyl-3- Cyclohexene 50 Nitrile 1,8-Cineole 100 Menthone . 50 Tetrahydrolinalool 200 ¦ Hexanol 10 Total 1000 The above odorant composition wa~ incorporated at 2~ into a 9~ ~xt~e ~ uorotr~ch~oromethane and di~lorodlf~uoro-methane, respecti~ely, enclo~ed in an aerosol can witb spray nozzle. Release of 1.0 g. of the aerosol mixt~re into a well-ventilated room, SO feet by 25 feet, with 12-foo~ ceil-ing, was readily detectable within 20 feet of the spray's origin for over 2 minutes.
Example 4 An odorant composition was formulated as described below:
Compound Weiqht in Grams Diphenyl Oxide 10 Mixed 1,4- and 1,8-Cineoles 100 Diisobutyl Carbinol 30 ~90sso Compound Wei~ht in Grams Dihydro-alpha-Terpineol 250 Dihydro Anethole 50 n-Hexanol 10 Phenyl Dimethyl Carbinol 50 Alpha-Pinene 300 2-Octanone 200 Total 1000 The above composition was incorporated into a chlorofluoro-carbon aerosol spray at 0.2% concentration, as in Example 3,and tested in a similar manner. Release of 1.7 g. of the odorant and chlorofluorocarbon mixture into a 50-foot by 25-foot room, as described in Example 3, was readily detected over a span of several minutes within 20 feet of where the odorant was sprayed.
Example 5 A solution of 10 g. of 2% dimethyl sulfide in fluorotrichloromethane was charged into an aerosol can and 90 g. of dichlorodifluoromethane charged with pressure. When 0.2 g. of the can contents were released to the atmosphere in a room as described in Example 3, the odorant was detectable within 10 to 20 feet of the release site for 1 or 2 minutes and d~ssipated rapidly theresfter.
.
1~190550 Example 6 Additional testing of odorants was conducted as in Example 2 with results shown in the table below. Phenols, acetals, lactones, ester~ of aliphatic and aromatic carboxylic acids and alkynes were found stable under accelerated tests con-ducted in the simulated refrigeration system.
TABLE III
0 - better than control 1 - slightly better than control 2 - same as control 3 - worse than control - unacceptable Result Compound 96 hrs. 288 hrs. Remarks N-methyl-2-pyrrolidinone 3 3 Dipropyl disulfide 3 3 Difuryl disulfide 3 3 Thiophenol 3 3 2-Octanone 2 2 Odorant Composition A* 2 2 1-Phenyl-2-1~1'-ethoxy~ 2 2 ethoxy]ethane CVerotyl, PFW register) Anethole 2 2 Alpha-terpineol 2 2 Thioacetone 2 3 Attacks aluminum 2,6-Dinitro-3-methoxy-1- 2 3 Coking methyl-4-tertiary butyl benzone S-Ethyl-3-hydroxy-~- 2 2 methyl-2(5H-)furanone Diethyl phthalate 2 2 Propionic acid 2 2 Re~ult Compound 96 hrs.- 288 hrs. Remarks Cis-3-hexenOl-1 2 Heptaldehyde 2 3 Odorant Composition B** 1 2 Thymol Dipentene Cyclohexyl mercaptan 1 3Turns copper blue-gray 10 Hexyl hexanoate 1 0 Methyl-2-octynoate ~eta-caryophyllene 1 2 Butyric acid 0 3Attacks aluminum *Odorant Compo~ition A
Component Partq by Weight 3,7-Dimethyl octanol 100.0 Dimethyl sulfide 0.5 Diphenyl oxide 9 5 ~ixed 1,4- and 1,8-cineoles 240.0 2,~- and 3,5-Cyclohox-3-en nitriles25.0 Eucalyptol 50.0 Diisobutyl carbinol 15.0 Menthone 25.0 Dihydro-alpha-terpineol 125.0 Tetrahydrolinalool 100.0 Dihydroanotholo 25.0 ~exanol 10.0 Phenyldimethyl carbinol 25.0 Alpha-pinone 150.0 2-Octanone 100.0 Total 1000.0 ~*Odorant Composition B
; Com~onent Parts by Woight Dimethyl sulfide 60.0 Menthone 50.0 Diphenyl oxide 150.0 Tetrahydrolinalool 100.0 Tetrahydrogeraniol 500.0 Methyl ~al~cylate 100.0 Roso oxide 10.0 Dihydroanothole 30.0 ~otal 1000.0
O
o I, 8 ,, , 8 ~ `~
l~gOSSO
~ ¦ m m m m m m m + m m sl ~ ~5 a~ ~1 _, ~ ++++++++++
a~ m m m m m m m ~ m m . U~
.
O
3 3~ ~
~ 01 m m m m m m m m m m i~
~ ~ .
~ .
3 z o ~1 ~ .C ~ ~
~ 3 ~ e ~ a ~ i ~
lW0550 Example 2 SEALED TUBE STABILITY OF ODORANTS
Tests were conducted under the same conditions as in Example I, except that the weight of odorant was 1% by weight B in the Suniso 3 GS oil and the duration only 24 hours at 350F. Using the same code as in Example I, the results are displayed in Table II:
Observation Compound Liquid Steel Control #1 2+ C+
Control ~2 1 C
Mixed 1,4- and 1,8-Cineoles 1 C
2,4- and 3,5-Dimethyl-3- 2 C+
Cyclohexene Nitriles Dimethyl Sulfide 2 C+
1,8-Cineole 1 C
Diisobutyl Carbinol 1 C
Menthone 1 C
Dihydro-alpha-Terpineol 1 C
Tetrahydrolinalool 1 C
Diphenyl Oxide . 1 C
Dihydro Anethole 1 C
`2,3-Dimethyl-2-Nonene Nitrile 2+ C+
n-Hexyl Alcohol 1 C
Phenyl Dimethyl Carbinol 1 C
Alpha-Pinene 1 C
: Decane Nitrile 1 C
2-Octanone 1 C
Para-Cymene 1 C
Fenchol 1 C
Example 3 An odorant composition to be used as a chlorofluoro-carbon leak indicator was made up as follows:
Compound Weight in Grams 3,7-Dimethyl-l-Octanol 200 Diphenyl Oxide 9 Dimethyl Sulfide Mixed 1,4- and 1,8-Cineoles 380 2,4- and 3,5-Dimethyl-3- Cyclohexene 50 Nitrile 1,8-Cineole 100 Menthone . 50 Tetrahydrolinalool 200 ¦ Hexanol 10 Total 1000 The above odorant composition wa~ incorporated at 2~ into a 9~ ~xt~e ~ uorotr~ch~oromethane and di~lorodlf~uoro-methane, respecti~ely, enclo~ed in an aerosol can witb spray nozzle. Release of 1.0 g. of the aerosol mixt~re into a well-ventilated room, SO feet by 25 feet, with 12-foo~ ceil-ing, was readily detectable within 20 feet of the spray's origin for over 2 minutes.
Example 4 An odorant composition was formulated as described below:
Compound Weiqht in Grams Diphenyl Oxide 10 Mixed 1,4- and 1,8-Cineoles 100 Diisobutyl Carbinol 30 ~90sso Compound Wei~ht in Grams Dihydro-alpha-Terpineol 250 Dihydro Anethole 50 n-Hexanol 10 Phenyl Dimethyl Carbinol 50 Alpha-Pinene 300 2-Octanone 200 Total 1000 The above composition was incorporated into a chlorofluoro-carbon aerosol spray at 0.2% concentration, as in Example 3,and tested in a similar manner. Release of 1.7 g. of the odorant and chlorofluorocarbon mixture into a 50-foot by 25-foot room, as described in Example 3, was readily detected over a span of several minutes within 20 feet of where the odorant was sprayed.
Example 5 A solution of 10 g. of 2% dimethyl sulfide in fluorotrichloromethane was charged into an aerosol can and 90 g. of dichlorodifluoromethane charged with pressure. When 0.2 g. of the can contents were released to the atmosphere in a room as described in Example 3, the odorant was detectable within 10 to 20 feet of the release site for 1 or 2 minutes and d~ssipated rapidly theresfter.
.
1~190550 Example 6 Additional testing of odorants was conducted as in Example 2 with results shown in the table below. Phenols, acetals, lactones, ester~ of aliphatic and aromatic carboxylic acids and alkynes were found stable under accelerated tests con-ducted in the simulated refrigeration system.
TABLE III
0 - better than control 1 - slightly better than control 2 - same as control 3 - worse than control - unacceptable Result Compound 96 hrs. 288 hrs. Remarks N-methyl-2-pyrrolidinone 3 3 Dipropyl disulfide 3 3 Difuryl disulfide 3 3 Thiophenol 3 3 2-Octanone 2 2 Odorant Composition A* 2 2 1-Phenyl-2-1~1'-ethoxy~ 2 2 ethoxy]ethane CVerotyl, PFW register) Anethole 2 2 Alpha-terpineol 2 2 Thioacetone 2 3 Attacks aluminum 2,6-Dinitro-3-methoxy-1- 2 3 Coking methyl-4-tertiary butyl benzone S-Ethyl-3-hydroxy-~- 2 2 methyl-2(5H-)furanone Diethyl phthalate 2 2 Propionic acid 2 2 Re~ult Compound 96 hrs.- 288 hrs. Remarks Cis-3-hexenOl-1 2 Heptaldehyde 2 3 Odorant Composition B** 1 2 Thymol Dipentene Cyclohexyl mercaptan 1 3Turns copper blue-gray 10 Hexyl hexanoate 1 0 Methyl-2-octynoate ~eta-caryophyllene 1 2 Butyric acid 0 3Attacks aluminum *Odorant Compo~ition A
Component Partq by Weight 3,7-Dimethyl octanol 100.0 Dimethyl sulfide 0.5 Diphenyl oxide 9 5 ~ixed 1,4- and 1,8-cineoles 240.0 2,~- and 3,5-Cyclohox-3-en nitriles25.0 Eucalyptol 50.0 Diisobutyl carbinol 15.0 Menthone 25.0 Dihydro-alpha-terpineol 125.0 Tetrahydrolinalool 100.0 Dihydroanotholo 25.0 ~exanol 10.0 Phenyldimethyl carbinol 25.0 Alpha-pinone 150.0 2-Octanone 100.0 Total 1000.0 ~*Odorant Composition B
; Com~onent Parts by Woight Dimethyl sulfide 60.0 Menthone 50.0 Diphenyl oxide 150.0 Tetrahydrolinalool 100.0 Tetrahydrogeraniol 500.0 Methyl ~al~cylate 100.0 Roso oxide 10.0 Dihydroanothole 30.0 ~otal 1000.0
Claims (15)
1. In a refrigerant liquid system containing fluoro-carbon refrigerant and a lubricating oil in a ratio of about 1 part of fluorocarbon to about 4 to 100 parts of lubricating oil, the improvement which comprises said system containing about 0.01 to 5% by weight, based on the combined weight of fluorocarbon and lubricating oil, of an odorant selected from the class consisting of I. Aliphatic and cycloaliphatic ethers II. Aromatic ethers III. Aliphatic alcohols of at least 4 carbon atoms and cycloaliphatic alcohols IV. Aromatic alcohols V. Alkyl sulfides VI. Aliphatic and aromatic nitriles VII. Terpene hydrocarbons VIII. Benzenoid hydrocarbons IX. Aliphatic, cycloaliphatic and aromatic ketones X. Hydrocarbon esters XI. Phenols XII. Lactones XIII. Alpha-diketones.
2. A system according to claim 1, wherein said odorant is present in an amount of about 0.01 to 1% by weight.
3. A system according to claim 1 or 2, wherein said odorant is an aliphatic or cycloaliphatic ether selected from the group consisting of -(a) the cineoles (b) isoamyl heptyl ether (c) citronellal dimethyl acetal (d) geranyl methyl ether (e) alpha-cedrene epoxide, and (f) cedrol methyl ether.
4. A system according to claim 1 or 2, wherein said odorant is an aromatic ether selected from the group con-sisting of -(a) diphenyl oxide (b) dihydroanethole (c) 1-phenyl-2[(1'-ethoxy)ethoxy]ethane (d) isobutyl benzyl ether (e) propyl phenyl ethyl ether (f) methyl chavicol (g) para-cresyl benzyl ether, and (h) 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2-benzopyran.
5. A system according to claim 1 or 2, wherein said odorant is an aliphatic or cycloaliphatic alcohol selected from the group consisting of -(a) diisobutyl carbinol (b) dihydro-alpha-terpineol (c) linalool (d) tetrahydrolinalool (e) n-hexanol (f) cis-3-hexenol-1 (g) fenchol (h) 3,7-dimethyl-octanol-1 (i) alpha-terpineol, and (j) borneol.
6. A system according to claim 1 or 2, wherein said odorant is an aromatic alcohol selected from the group consisting of -(a) phenyl dimethyl carbinol (b) benzyl alcohol (c) phenyl ethyl alcohol (d) cinnamyl alcohol, and (e) para-hydroxymethyl cumene.
7. A system according to claim 1 or 2, wherein said odorant is alkyl sulfide selected from the group consisting of dimethyl sulfide and dipropyl sulfide.
8. A system according to claim 1 or 2, wherein said odorant is a nitrile selected from the group consisting of -(a) dimethyl cyclohexene nitriles (b) 2,3-dimethyl-2-nonene nitrile (c) decane nitrile (d) geranylonitrile (e) 2,4,5-trimethyl benzonitrile (f) 4-phenyl butyronitrile (g) 3-phenyl propionitrile, and (h) p-methoxy benzonitrile.
9. A system according to claim 1 or 2, wherein said odorant is a terpene hydrocarbon selected from the group consisting of -(a) alpha-pinene (b) dipentene (c) beta-caryophyllene (d) longifolene (e) cedrene (f) camphene, and (g) .DELTA.3-carene.
10. A system according to claim 1 or 2, wherein said odorant is a benzenoid hydrocarbon selected from the group consisting of -(a) p-cymene (b) 1-methyl naphthalene (c) 2-methyl naphthalene, and (d) cumene.
11. A system according to claim 1 or 2, wherein said odorant is a ketone selected from the group consisting of -(a) 2-octanone (b) amyl phenyl ketone (c) diphenyl ketone (d) benzyl acetone (e) menthone (f) carvone (g) para-tertiary butyl cyclohexanone, and (h) methyl heptenone.
12. A system according to claim 1 or 2, wherein said odorant is an ester selected from the group consisting of -(a) diethyl phthalate (b) hexyl hexanoate (c) methyl-2-octynoate (d) benzyl propionate (e) isobornyl acetate, and (f) para-tertiary butyl cyclohexyl acetate.
13. A system according to claim 1 or 2, wherein said odorant is a phenol selected from the group consisting of -(a) thymol (b) quaiacol (c) eugenol (d) para-ethyl phenol (e) methyl salicylate (f) chavicol, and (g) creosol.
14. A system according to claim 1 or 2, wherein said odorant is a lactone selected from the group consisting of -(a) 3-n-butylidene phthalide (b) 3-n-butyl phthalide (c) 15-hydroxypentadecanoic acid lactone (d) delta-decalactone, and (e) gamma-hexalactone.
15. A system according to claim 1 or 2, wherein said odorant is a diketone selected from the group consisting of -(a) 5-ethyl-3-hydroxy-4-methyl-2 (5H-furanone) (b) 3-methyl-1,2-cyclohexane dione, and (c) 3-ethyl cyclopentanedione.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB5370876A GB1587907A (en) | 1976-12-23 | 1976-12-23 | Perfumed fluorocarbon compositions |
| GB53,708/76 | 1976-12-23 | ||
| GB719977 | 1977-02-21 | ||
| GB7,199/77 | 1977-02-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1090550A true CA1090550A (en) | 1980-12-02 |
Family
ID=26241264
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA292,634A Expired CA1090550A (en) | 1976-12-23 | 1977-12-07 | Use of odoriferous compounds to detect gas losses in freon systems |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5383148A (en) |
| CA (1) | CA1090550A (en) |
| DE (1) | DE2756655A1 (en) |
| FR (1) | FR2437430A1 (en) |
| NL (1) | NL7714260A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8562853B2 (en) | 2004-02-26 | 2013-10-22 | E I Du Pont De Nemours And Company | Tracer-containing compositions |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4294716A (en) | 1980-05-14 | 1981-10-13 | Saccavino Joseph F | Halocarbon and azeotrope refrigerant compositions containing offensive warning component |
| JPS59199796A (en) * | 1983-04-28 | 1984-11-12 | Honda Motor Co Ltd | Lubricating oil for two-cycle engine |
| US5167867A (en) * | 1989-09-26 | 1992-12-01 | Exxon Production Research Company | Test-fluid composition and method for detecting leaks in pipelines and associated facilities |
| CA1330516C (en) * | 1989-09-26 | 1994-07-05 | Leslie Ronald Quaife | Test-fluid composition and method for detecting leaks in pipelines and associated facilities |
| US9175201B2 (en) | 2004-12-21 | 2015-11-03 | Honeywell International Inc. | Stabilized iodocarbon compositions |
| CA2591130A1 (en) * | 2004-12-21 | 2006-06-29 | Honeywell International Inc. | Stabilized iodocarbon compositions |
| JP5129491B2 (en) * | 2007-02-27 | 2013-01-30 | Ｊｘ日鉱日石エネルギー株式会社 | Refrigerator oil composition and working fluid composition for refrigerator |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4937081A (en) * | 1972-08-16 | 1974-04-06 |
-
1977
- 1977-11-25 FR FR7735506A patent/FR2437430A1/en not_active Withdrawn
- 1977-12-07 CA CA292,634A patent/CA1090550A/en not_active Expired
- 1977-12-14 JP JP15041177A patent/JPS5383148A/en active Pending
- 1977-12-19 DE DE19772756655 patent/DE2756655A1/en active Pending
- 1977-12-22 NL NL7714260A patent/NL7714260A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8562853B2 (en) | 2004-02-26 | 2013-10-22 | E I Du Pont De Nemours And Company | Tracer-containing compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| NL7714260A (en) | 1978-06-27 |
| FR2437430A1 (en) | 1980-04-25 |
| JPS5383148A (en) | 1978-07-22 |
| DE2756655A1 (en) | 1978-06-29 |
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