NON-TOXIC, ENVIRONMENTALLY BENIGN FIRE EXTINGUISHANTS

Abstract: A fire extinguishing mixture of the following compounds: (a) 90 to 99.9 % wt. of one or more halocarbons of the formula: CWHXClYFZ wherein W is 1, 2, 3 or 4, X is any one of 0 to 9, Y is any one of 0 to 9 and Z is any one of 1 to 10 and (b) 0.1 to 10 % wt. of one or more detoxifying substances selected from the group consisting of alkenes, terpenes and unsaturated oils.

Description: NON-TOXIC, ENVIRONMENTALLY BENIGN FIRE EXTINGUISHANTS This invention pertains to fire extinguishing agents which are non-toxic and environmentally safe in both natural form and in degraded forms which may occur as a result of exposure to fire. United States Patent No. 4,954,271, issued September 4, 1990, Raymond . Green, discloses and protects environmentally amicable fire extinguishing agents compris¬ ing in combination: (a) more than 50% by weight of a fluorochlorocarbon selected from the group consisting of: l,l-dichloro-2, 2, 2-trifluoroethane, and l,2-dichloro-2, 2-difluoroethane; (b) less than 48% by weight of a fluoro- carbon selected from the group consisting of: chlorodi- fluoromethane, 1-chloro-l, 2, 2, 2-tetrafluoroethane, pentafluoroethane, 1, 2, 2, 2-tetrafluoroethane; and (c) a substance selected from the group consisting of terpenes: citral, citronellal, citronellol, limonene, dipentene, menthol, terpinene, terpinolene, sylvestrene, sabinene, methadiene, zingiberene, ocimene, myrcene, α-pinene, β- pinene, turpentine, camphor, phytol, vitamin A, abietic acid, squalene, lanosterol, saponin, oleanolic acid, lycopene, 3-carotene, lutein, -terpineol, and p-cymeme; and unsaturated oils; oleic acid, linoleic acid, linolenic acid, eleosearic acid, lincanic acid, ricinoleic acid, palmitoleic acid, petroselenic acid, vaccenic acid, and erucic acid, in the range of from 2 to 10% by weight. U.S. Patent No. 4,826,610, issued May 2, 1989, Derek A. Thacker, discloses a firefighting composition comprising one or more of Halons 11, 12, 113 and 114 together with 1% to 14% by weight of an extinguishant base including a sesquiterpene and one or more essential oils. Solvents and dispersing agents may also be provided. This composition is suited for stream type firefighting situ¬ ations. The formulation is not particularly ozone friend¬ ly- G.B. Patent No. 1,603,867, Derek A. Thacker, December 2, 1981, discloses a fire extinguisher formulation comprising trichlorofluoromethane (Halocarbon Number 11) and an additive comprised of a mono-terpene. The additive can include an essential oil such as citrus oil or pinene. Dichlorofluoromethane (Halocarbon Number 12) can be in¬ cluded in the formulation. A fire extinguishing mixture of the following compounds: (a) 90 to 99.9% wt. of one or more halocarbons of the formula: C u H χ Cl γ F z wherein ff is 1, 2, 3 or 4, X is any one of 0 to 9, Y is any one of 0 to 9 and Z is any one of 1 to 10, provided when is 1, X is 0 to 2, Y is 0 to 2, and Z is 1 to 3, the total to add up to 4; when is 2, X is 0 to 4, Y is 1 to 5, and Z is 1 to 5, the total to add up to 6; when is 3, X is 0 to 6, Y is 0 to 7, and Z is 1 to 8, the total to add up to 8; and when is 4, X is 0 to 8, Y is 0 to 9, and Z is 1 to 10, the total to add up to 10; and (b) 0.1 to 10% wt. of one or more detoxifying substances selected from the group consisting of: citral citronellal citronellol limonene dipentene menthol terpinene terpinolene sylvestrene sabinene menthadiene zingiberene ocimene myrcene alpha-pinene beta-pinene turpentine camphor phytol vitamin A abietic acid squalene lanosterol saponin oleanolic acid lycopene beta-carotene lutein alpha-terpineol para-cymene oleic acid linoleic acid linolenic acid eleostearic acid lincanic acid ricinoleic acid palmitoleic acid petroselenic acid vaccenic acid erucic acid ethene propene butene isopropene pentene isopentene trimethy1ethene tetramethy1ethene butadiene 2- ethylbutadiene pentadiene isobutylene the mixture having a boiling point of about -85°C to about 200°C, a molecular weight in the range of 70 to 400, and a vapour pressure of about MPa 0.1 to about 5. A fire fighting mixture of the formula: (a) 90% to 99.9% wt. of a chlorofluorocarbon or fluorocarbon selected from the group consisting of: hydrochlorofluorocarbon.13 chlorotrifluoromethane hydrochlorofluorocarbon.21 dichlorofluoromethane hydrochlorofluorocarbon.22 chlorodifluoromethane hydrochlorofluorocarbon.31 chlorofluoromethane hydrochlorofluorocarbon.121 1,1,2,2-tetrachloro- 1-fluoroethane hydrochlorofluorocarbon.122 1,1,2-trichloro-2,2- difluoroethane hydrochlorofluorocarbon.123 2,2-dichloro-l,1,1- trifluoroethane 1,2-dichloro-l,1,2- trifluoroethane hydrochlorofluorocarbon.124 2-chloro-l,1,1,2- tetrafluoroethane 1-chloro-l,1,2,2- tetrafluoroethane hydrochlorofluorocarbon 125 pentafluoroethane hydrochlorofluorocarbon.131 hydrochlorofluorocarbon.132 1,2-dichloro-1,1- difluoroethane hydrochlorofluorocarbon.133 2-chloro-l,1,1- trifluorethane hydrochlorofluorocarbon.134a 1,1,1,2- tetrafluoroethane hydrochlorofluorocarbon.141 1,2-dichloro-l- fluoroethane 1,1-dichloro-l- fluoroethane hexafluoropropane hydrochlorofluorocarbon.142 l-chloro-1,1- difluoroethane hydrochlorofluorocarbon.221 2-fluoropropane hydrochlorofluorocarbon.222 1,1-difluoro-1,2,2,3, 3-pentachloropropane hydrochlorofluorocarbon.223 hydrochlorofluorocarbon.224 hydrochlorofluorocarbon.225 3,3-dichloro-1,1,1,2, 2-pentafluoropropane 1,3-dichloro-1,1,2,2, 3-penta luoropropane hydrochloro luorocarbon.226 hydrochlorofluorocarbon.231 hydrochlorofluorocarbon.232 hydrochlorofluorocarbon.233 hydrochlorofluorocarbon.234 hydrochlorofluorocarbon.235 hydrochlorofluorocarbon.241 hydrochlorofluorocarbon.242 1,1,l-trichloro-2,2 • difluoropropane hydrochlorofluorocarbon.243 hydrochlorofluorocarbon.244 hydrochlorofluorocarbon.251 hydrochlorofluorocarbon.252 hydrochlorofluorocarbon.253 2-chloro-l,1,1- trifluoropropane hydrochlorofluorocarbon.261 1,2-dichloro-2- fluoropropane hydrochlorofluorocarbon.262 hydrochlorofluorocarbon.271 (b) 0 to 10% of one or more detoxifying substance selected from the group consisting of: citral citronellal citronellol limonene dipentene menthol terpinene terpinolene sylvestrene sabinene menthadiene zingiberene ocimene myrcene alpha-pinene beta-pinene turpentine camphor phytol vitamin A abietic acid squalene lanosterol saponin oleanolic acid lycopene beta-carotene lutein alpha-terpineol para-cymene oleic acid linoleic acid linolenic acid eleostearic acid lincanic acid ricinoleic acid palmitoleic acid petroselenic acid vaccenic acid erucic acid ethene propene butene isopropene pentene iεopentene trimethylethene tetramethylethene butadiene 2-methylbutadiene pentadiene isobutylene A fire extinguishing mixture for use in a flood¬ ing technique in an enclosed volume comprising: (a) more than 50 percent by weight of a substance selected from the group consisting of: dichlorodifluoromethane, 1,2-dichlorotetrafluoroethane, chlorodifluoromethane, 1-chloro-l,2,2,2-tetrafluoroethane, 1,l-dichloro-2,2 ,2-trifluoroethane, 1,2,2,2-tetrafluoroethane, pentafluroethane; (b) less than 48 percent by weight of a substance selected from the group consisting of: trichlorofluoromethane, 1,1-dichlorotetrafluoroethane, 1,2-dichloro-2,2-difluoroethane; and (c) between 0.25 and 10 percent by weight of a detoxifying substance selected from the group consisting of: citral citronellal citronellol limonene dipentene menthol terpinene terpinolene sylvestrene sabinene menthadiene zingiberene ocimene myrcene alpha-pinene beta-pinene turpentine camphor phytol vitamin A abietic acid squalene lanosterol saponin oleanolic acid lycopene beta-carotene lutein alpha-terpineol para-cymene oleic acid linoleic acid linolenic acid eleostearic acid lincanic acid ricinoleic acid palmitoleic acid petroselenic acid vaccenic acid erucic acid ethene propene butene isopropene pentene isopentene trimethy1ethene tetramethylethene butadiene 2-methylbutadiene pentadiene isopropenyl-1-methylcyclohexene isobutylene The initial boiling point of the mixture can be between -80°C and -10°C. The fluid viscosity of the mixture can be below 1.0 centipoise in the range between the initial boiling point of the mixture and 25"C. A fire extinguishing mixture for use in a flood¬ ing technique in an enclosed volume comprising: (a) at least 50 percent by weight of a substance selected from the group consisting of: chlorodifluoromethane, dichlorodifluoromethane; (b) less than 48 percent by weight of a substance selected from the group consisting of: 1-chloro-l,2,2,2-tetrafluoroethane, 1,2-dichlorotetrafluoroethane, trichlorofluoromethane, 1,l-dichloro-2,2,2-trifluoroethane; and (c) between 2 and 4 percent by weight of substance selected from the group consisting of: dipentene, and limonene. A specific fire extinguishing mixture can consist essentially of about 96 percent by weight of chlorodi- fluoromethane, and about 4 percent by weight of limonene. Another specific fire extinguishing mixture can consist essentially of about 85 percent by weight of chlorodi- fluoromethane, about 11.5 percent by weight of 1-chloro- 1,2,2,2-tetrafluoroethane, and about 3.5 percent by weight of dipentene. A further embodiment of fire extinguishing mixture can consist essentially of about 65 percent by weight of dichlorodifluoromethane, about 15.5 percent by weight of 1,2-dichlorotetrafluoroethane, about 15.5 percent by weight of trichlorofluoromethane, and about 4 percent by weight of limonene. A further version of fire extinguish¬ ing mixture can consist essentially of about 65 percent by weight of dichlorodifluoromethane, about 15.5 percent of 1,2-dichlorotetrafluoroethane, about 15.5 percent by weight of trichloro luoromethane, and about 4 percent by weight of dipentene. A variation embodiment of the fire extinguishing mixture can consist essentially of about 75 percent by weight of chlorodifluoromethane, about 11.75 percent by weight of l,l-dichloro-2,2,2-trifluoroethane, about 9.5 percent by weight of 1-chloro-l,2,2,2-tetrafluoroethane, and about 3.75 percent by weight of limonene. An alternative embodiment comprises about 4.75% wt. of 2,2-dichloro-l,l,l-trifluoroethane, about 82% wt. of chlorodifluoromethane, about 9.5% wt. of 2-chloro-l,1,1,2- tetrafluoroethane and about 3.75% wt. isopropenyl-1-methyl cyclohexen . The initial boiling point of the mixture prefer¬ ably can be between -80°C and -10"C. The fluid viscosity of the mixture can be below 1.0 centipoise between the initial boiling point of the mixture and 25°C. A fire extinguishing mixture of the formula: (a) about 1% wt. of 2,2-dichloro-l,l,l-trifluoro- ethane or l,2-dichloro-l,l,2-trifluoroethane; (b) about 9.5% wt. of 2-chloro-l,1,1,2-tetra- fluoroethane or 1-chloro-l,1,2,2-tetrafluoroethane; (c) about 79.5 to 88.5% wt. of chlorodifluoro¬ methane; and (d) about 1 to 10% wt. of isobutylene. A fire extinguishing mixture of the formula: (a) about 4 to 45% wt. of 2-chloro-l,1,1,2- tetrafluoroethane or 1-chloro-l,1,2,2-tetrafluoroethane; (b) about 50 to 90% wt. of pentafluoroethane; and (c) about 0 to 10% wt. of isobutylene. In this disclosure, the word "fire" refers explicitly to standardized testing fires as defined by authoritative regulatory bodies having jurisdiction in the areas of fire control, fire prevention, and fire fight- ing. We have invented a family of new chlorofluoro- carbon and fluorocarbon fire extinguishing agents that cause minimum damage to the ozone layer of the earth. The agents contain no bromofluorocarbons which have been discovered to have serious ozone damaging effect. Also, since chlorine is being discovered to be potentially harmful to the ozone layer, chlorine content of the chloro- fluorocarbons has been minimized. A standard regulatory test for evaluating flood¬ ing type fire extinguishants uses a test chamber measuring 0.5 x 3 x 3 metres containing five pot fires distributed evenly in the space. The extinguishant to be tested is pumped through a pipe system measuring 3 metres. A kilo¬ gram of extinguishant is pumped through the pipe system and the time taken to extinguish the fires is measured. When a flooding or inerting fire extinguishing technique is to be used, that is, where the extinguishant is released into an enclosed volume containing a fire, we have discovered that fires of this type are best extin¬ guished using mixtures as follows: (a) more than 50 percent by weight of the follow¬ ing seven compounds, singly or in combination: dichlorodifluoromethane, 1,2-dichlorotetrafluoroethane, chlorodifluoromethane, 1-chloro-l,2,2,2-tetrafluoroethane, 1,2,2,2-tetrafluoroethane, 1,l-dichloro-2,2,2-trifluoroethane, pentafluroethane; (b) less than 48 percent by weight of the follow¬ ing three compounds, singly or in combination: trichlorofluoromethane, 1 ,1-dichlorotetrafluoroethane , 1,2-dichloro-2,2-difluoroethane; and (c) between 0.25 and 10 percent by weight of any one or more of the following fifty-one alkenes, terpenes and unsaturated oils: citral citronellal citronellol limonene dipentene menthol terpinene terpinolene sylvestrene sabinene menthadiene zingiberene ocimene myrcene alpha-pinene beta-pinene turpentine camphor phytol vitamin A abietic acid squalene lanosterol saponin oleanolic acid lycopene beta-carotene lutein alpha-terpineol para-cymene oleic acid linoleic acid linolenic acid eleostearic acid lincanic acid ricinoleic acid palmitoleic acid petroselenic acid vaccenic acid erucic acid ethene propene butene isopropene pentene isopentene trimethylethene tetrameth 1ethene butadiene 2-methylbutadiene pentadiene isobutylene The precise choice of agents and compositions will be governed by a balance of cost, factors governing fluid and vapor flow, factors governing fluid and vapor physical characteristics, and the configuration of the extinguishant flooding system needed to protect the in¬ tended volume(s) . - li ¬ lt has been discovered that for extinguishing fires in enclosed volumes by flooding or inerting tech¬ niques, it is critical that the fluid viscosity and initial boiling points of the fire extinguishant are low. A number of other criteria are also important. The mixtures we have invented that are suitable for flooding or inerting fire extinguishing agents have the following characteristics and attributes: 1. The class of fire flooding mixtures according to the invention must be richer in lower boiling compounds, and not exhibit much cohesion. The flooding class described will rapidly vaporize and flood the intended volume to the concen- tration of extinguishant required to smother or inert the gaseous phase and prevent or extin¬ guish an included fire. 2. The lower boiling points exhibited by this class of flooding mixtures, can permit the list of detoxifying agents to include low boiling alkenes which cannot be successfully used with streaming extinguishants. 3. The relative quantities of detoxifying alkene, terpene, and unsaturated oil in the flooding mixtures described can be reduced because the flooding technique uses a fixed but larger quantity of extinguishing mixture than is re- quired for streaming type agents. 4. The low boiling fluorochlorocarbons listed in list (a) produce lower quantities of toxic halogens and hydrogen halides upon decomposition than do the higher boiling fluorochlorocarbons in list (b) . This permits lesser quantities of detoxifying agents to be used. When the detoxifying agents are eliminated completely from the fire extinguishing mixtures, we have found that fire extinguishing is less efficient than when the detoxifying compounds are included. Also, dangerous levels of toxic halogen and hydrogen halides are produced when the extinguishant mixture is decomposed by the heat of the fire. 6. The physical characteristics of a flooding mixture should have a boiling range between -80"C and -10°C. It should also have a liquid viscos¬ ity less than 1.0 centipoise in the temperature range from the initial boiling point of the mixture to approximately 25°C. Example 1 In one particular test, a test chamber measuring 0.5 x 3 x 3 meters and containing five standard pot fires was flooded pumping a pipe system about 3 meters in total length. The pot fires were inerted in less than 10 seconds by using 1 kg of a mixture consisting of 96 percent by weight of chlorodifluoromethane and 4 percent by weight of limonene through the pipe. This mixture had an initial boiling point of -40.5°C and a liquid viscosity of 0.21 centipoise at 25°C. Example 2 In another evaluation using the same test cham¬ ber as in Example 1, the five pot fires were inerted in less than 10 seconds using 1 kg of a mixture consisting of 85 percent by weight of chlorodifluoromethane, 11.5 percent by weight of 1-chloro-l,2,2,2-tetrafluoroethane, and 3.5 percent by weight of dipentene. Example 3 In a third test using the same test chamber as in Example 1, the five pot fires were inerted in less than 10 seconds using 1 kg of a mixture consisting of 65 percent by weight of chlorodifluoromethane, 15.5 percent by weight of 1,2-dichlorotetrafluoroethane, 15.5 percent by weight of trichlorofluoromethane, and 4 percent by weight of limonene. This mixture had an initial boiling point of -27°C and a fluid viscosity of 0.28 centipoise at 25°C. Example 4 In a fourth application using the same test chamber as in Example 1, the five pot fires were inerted in less than 10 seconds using 1 kg of a mixture consisting of 65 percent by weight of dichlorodifluoromethane, 15.5 percent by weight of 1,2-dichlorotetrafluoroethane, 15.5 percent by weight of trichlorofluoromethane and 4 percent by weight of limonene. This mixture exhibited an initial boiling point of -13°C and a viscosity of 0.36 centipoise at 25°C. Example 5 In a fifth test using the same test chamber as in Example 1, the five pot fires were inerted in less than 10 seconds using 1 kg of a mixture consisting of about 65 percent by weight of dichlorodifluoromethane, about 15.5 percent of 1,2-dichlorotetrafluoroethane, about 15.5 percent by weight of trichlorofluoromethane, and about 4 percent by weight of dipentene. Example 6 In a sixth evaluation using the same test cham¬ ber as in Example 1, the five pot fires were inerted in less than 10 seconds using 1 kg of a mixture consisting of about 75 percent by weight of chlorodifluoromethane, about 11.75 percent by weight of 1,l-dichloro-2,2,2-trifluoro¬ ethane, about 9.5 percent by weight of l-chloro-1,2,2,2- tetrafluoroethane, and about 3.75 percent by weight of limonene. These examples vividly demonstrate the key role that low fluid viscosity and low boiling point plays in parameterizing the mixtures required to achieve optimum volume of fire extinguishing performance. The goal is to achieve mixtures having an initial boiling point approxi- mating -60°C and a fluid viscosity approximating 0.15 centipoise at 25"C. The following ozone benign formulation has been invented to replace Halon 1301, which is a well known and widely used chlorofluorocarbon flooding extinguishant: 2,2 dichloro-1,1,1-trifluoroethane - 4.75% wt. ; chlorodifluoromethane - 82% wt. ; 2 chloro 1,1,1,2-tetrafluoroethane - 9.5% wt. ; isopropenyl-1-methyl cyclohexene - 3.75% wt. The properties of this formulation (called NAF S- III) compared to Halon 1301 are shown in Table 1. Table 1 Physical Properties Halon 1301 NAF S-III Ozone depletion potential Global warming potential Lifetime Molecular weight Boiling point at 1 atm. "C Critical temperature °C Critical pressure (psia) Critical density (kg/m 3 ) Density of liquid at 25° (g/ml) 1.57 1.20 Specific heat of liquid at 25°C [J/(kg.°C)3 870 1250 Heat of vaporization at boiling point (kJ/kg) 118.8 227 * estimated values

Claims: WHAT IS CLAIMED IS: 1. A fire extinguishing mixture of the following compounds: (a) 90 to 99.9% wt. of one or more halocarbons of the formula: C y H χ Cl γ F-. wherein W is 1, 2, 3 or 4, X is any one of 0 to 9, Y is any one of 0 to 9 and Z is any one of 1 to 10, provided when W is 1, X is 0 to 2, Y is 0 to 2, and Z is 1 to 3, the total to add up to 4; when W is 2 , X is 0 to 4, Y is 1 to 5, and Z is 1 to 5, the total to add up to 6; when W is 3, X is 0 to 6, Y is 0 to 7, and Z is 1 to 8, the total to add up to 8; and when W is 4, X is 0 to 8, Y is 0 to 9, and Z is 1 to 10, the total to add up to 10; and (b) 0.1 to 10% wt. of one or more detoxifying substances selected from the group consisting of: citral citronellal citronellol limonene dipentene menthol terpinene terpinolene sylvestrene sabinene menthadiene zingiberene ocimene myrcene alpha-pinene beta-pinene turpentine camphor phytol vitamin A abietic acid squalene lanosterol saponin oleanolic acid lycopene beta-carotene lutein alpha-terpineol para-cymene oleic acid linoleic acid linolenic acid eleostearic acid lincanic acid ricinoleic acid palmitoleic acid petroselenic acid vaccenic acid erucic acid ethene propene butene isopropene pentene isopentene trimethylethene tetramethylethene butadiene 2-methylbutadiene pentadiene isopropenyl-1-methyl cyclohexane isobutylene; the mixture having a boiling point of about -85"C to about 200°C, a molecular weight in the range of 70 to 400, and a vapour pressure of about MPa 0.1 to about 5. 2. A fire fighting mixture of the formula: (a) 90% to 99.9% wt. of a chlorofluorocairbon selected from the group consisting of: hydrochlorofluorocarbon.13 chlorotrifluoromethane hydrochlorofluorocarbon.21 dichlorofluoromethane hydrochlorofluorocarbon.22 chlorodifluoromethane hydrochlorofluorocarbon.31 chlorofluoromethane hydrochlorofluorocarbon.121 1,1,2,2-tetrachloro- 1-fluoroethane hydrochlorofluorocarbon.122 1,1,2-trichloro-2,2- difluoroethane hydrochlorofluorocarbon.123 2,2-dichloro-l,1,1- trifluoroethane 1,2-dichloro-l,1,2- trifluoroethane hydrochlorofluorocarbon.124 2-chloro-l,1,1,2- tetrafluoroethane 1-chloro-l,1,2,2- tetrafluoroethane hydrochlorofluorocarbon 125 pentafluoroethane hydrochlorofluorocarbon.131 hydrochlorofluorocarbon.132 1,2-dichloro-l,1- difluoroethane hydrochlorofluorocarbon.133 2-chloro-l,1,1- trifluorethane hydrochlorofluorocarbon.134a 1,1,1,2- tetrafluoroethane hydrochlorofluorocarbon.141 1,2-dichloro-l- fluoroethane 1,1-dichloro-l- fluoroethane hexafluoropropane hydrochlorofluorocarbon.142 1-chloro-l,1- difluoroethane hydrochlorofluorocarbon.221 2-fluoropropane hydrochlorofluorocarbon.222 1,1-difluoro-1,2,2,3, 3-pentachloropropane hydrochlorofluorocarbon.223 hydrochlorofluorocarbon.224 hydrochlorofluorocarbon.225 3, --dichl * oro-l,1,1,2, 2-pentafluoropropane 1,3-dichloro-1,1,2,2, 3-pentafluoropropane hydrochlorofluorocarbon.226 hydrochlorofluorocarbon.231 hydrochlorofluorocarbon.232 hydrochlorofluorocarbon.233 hydrochlorofluorocarbon.234 hydrochlorofluorocarbon.235 hydrochlorofluorocarbon.241 hydrochlorofluorocarbon.242 1,1,l-trichloro-2,2- difluoropropane hydrochlorofluorocarbon.243 hydrochlorofluorocarbon.244 hydrochlorofluorocarbon.251 hydrochlorofluorocarbon.252 hydrochlorofluorocarbon.253 2-chloro-l,1,1- trifluoropropane hydrochlorofluorocarbon.261 l,2-dichloro-2- fluoropropane hydrochlorofluorocarbon.262 hydrochlorofluorocarbon.271 (b) 0 to 10% of a detoxifying substance selected from the group consisting of: citral citronellal citronellol limonene dipentene menthol terpinene terpinolene sylvestrene sabinene menthadiene zingiberene ocimene myrcene alpha-pinene beta-pinene turpentine camphor phytol vitamin A abietic acid squalene lanosterol saponin oleanolic acid lycopene beta-carotene lutein alpha-terpineol para-cymene oleic acid linoleic acid linolenic acid ??eostearic acid lincanic acid ricinoleic acid acid vaccenic acid propene- butene isopropene pentene isopentene trimethylethene tetramethy1ethene butadiene 2- ethylbutadiene pentadiene isobutylene; 3. _ A fire extinguishing mixture for use in a iiood- ing technique in an enclosed volume comprising: (a) more than 50 percent by weight of a sub¬ stance selected from the group consisting of: dichlorodifluoromethane, 1,2-dichlorotetrafluoroethane , chlorodifluoromethane, 1-chloro-l,2,2,2-tetrafluoroethane , 1,l-dichloro-2,2,2-trifluoroethane 1,2,2,2-tetrafluoroethane, and pentafluroethane; (b) less than 48 percent by weight of a sub¬ stance selected from the group consisting of: trichlorofluoromethane, 1,1-dichlorotetrafluoroethane, and 1,2-dichloro-2,2-difluoroethane; (c) between 0.25 and 10 percent by weight of detoxifying substances selected from the group consisting of: citral citronellal citronellol limonene dipentene menthol terpinene terpinolene sylvestrene sabinene menthadiene zingiberene ocimene myrcene alpha-pinene beta-pinene turpentine camphor phytol vitamin A abietic acid squalene lanosterol saponin oleanolic acid lycopene beta-carotene lutein alpha-terpineol para-cymene oleic acid linoleic acid linolenic acid eleostearic palmitolgϊc erucic acid ethene propene butene isopropene pentene isopentene trimethylethene tetramethylethene butadiene 2-methylbutadiene pentadiene isobutylene 4. A mixture as claimed in claim 3 wherein the initial boiling point of the mixture is between -80°C and -10°C. 5. A mixture as claimed in claim 3 wherein the fluid viscosity of the mixture is below 1.0 centipoise between the initial boiling point of the mixture and 25°C. 6. A mixture as claimed in claim 4 wherein the fluid viscosity of the mixture is below 1.0 centipoise between the initial boiling point of the mixture and 25"C. 7. A fire extinguishing mixture for use in a flood¬ ing technique in an enclosed volume comprising: (a) at least 50 percent by weight of a substance selected from the group consisting of: chlorodifluoromethane, dichlorodifluoromethane; (b) less than 48 percent by weight of a sub- stance selected from the group consisting of: 1-chloro-l,2,2,2-tetrafluoroethane, 1,2-dichlorotetrafluoroethane, trichlorofluoromethane, 1,l-dichloro-2,2,2-trifluoroethane; and (c) between 2 and 4 percent by weight of a substance selected from the group consisting of: dipentene, and limonene. 8. A fire extinguishing mixture essentially of about 96 percent by weight of chlorodifluoromethane, and about 4 percent by weight of limonene. 9. A fire extinguishing mixture consisting essen¬ tially of about 85 percent by weight of chlorodifluoro¬ methane, about 11.5 percent by weight of l-σhloro-1,2,2,2- tetrafluoroethane, and about 3.5 percent by weight of dipentene. 10. A fire extinguishing mixture consisting eessen- tially of about 65 percent by weight of dichlorodifluoro- methane, about 15.5 percent by weight of 1,2-dichlorotetra- fluoroethane , about 15.5 percent by weight of trichloro- fluoroethane , and about 4 percent by weight of limonene. 11 A fire extinguishing mixture consisting essen- tially of about 65 percent by weight of dichlorodifluoro- methane, about 15.5 percent of 1,2-dichlorotetrafluoro¬ ethane, about 15.5 percent by weight of trichlorofluoro¬ methane, and about 4 percent by weight of dipentene. 12. A fire extinguishing mixture consisting essen¬ tially of about 75 percent by weight of chlorodifluoro¬ methane, about 11.75 percent by weight of 1,1-dichloro- 2,2,2-trifluoroethane, about 9.5 percent by weight of 1- chloro-1,2,2,2-tetrafluoroethane, and about 3.75 percent by weight of limonene. 13. A mixture as claimed in claim 7 wherein the initial boiling point of the mixture is between -80°C and -10°C. 14. A mixture as claimed in claim 7 wherein the fluid viscosity of the mixture is below 1.0 centipoise between the initial boiling point of the mixture and 25°C. 15. A fire extinguishing mixture for use in a flood- ing technique in an enclosed volume comprising: (a) more than 50 percent by weight of a sub¬ stance selected from the group consisting of: dichlorodifluoromethane, 1,2-dichlorotetrafluoroethane, chlorodifluoromethane, 1-chloro-l,2,2,2-tetrafluoroethane, 1,l-dichloro-2,2,2-trifluoroethane 1,2,2,2-tetrafluoroethane, and pentafluroethane; (b) less than 48 percent by weight of a sub¬ stance selected from the group consisting of: trichlorofluoromethane, 1,1-dichlorotetrafluoroethane, and 1,2-dichloro-2,2-difluoroethane; (c) between 0.25 and 10 percent by weight of detoxifying substances selected from the group consisting of: limonene ethene propene butene isopropene pentene isopentene trimethylethene tetramethylethene butadiene 2-methylbutadiene pentadiene dipentene isobutylene 16. A mixture as claimed in claim 15 wherein the initial boiling point of the mixture is between -80°C and -10°C. 17. A mixture as claimed in claim 15 wherein the fluid viscosity of the mixture is below 1.0 centipoise between the initial boiling point of the mixture and 25°C. 18. A mixture as claimed in claim 12 comprising about 4.75% wt. of 2,2-dichloro-l,l,l-trifluoroethane, about 82% wt. of chlorodifluoromethane, about 9.5% wt. of 2-chloro- 1,1,1,2-tetrafluoroethane and about 3.75% wt. isopropenyl- 1-methyl cyclohexene. 19. A fire extinguishing mixture of the formula: (a) about 1% wt. of 2,2-dichloro-l,l,l-trifluoro¬ ethane or 1,2-dichloro-1,1,2-trifluoroethane; (b) about 9.5% wt. of 2-chloro-l,1,1,2-tetra- fluoroethane or l-chloro-1,1,2,2-tetrafluoroethane; (c) about 79.5 to 88.5% wt. of chlorodifluoro¬ methane; and (d) about 1 to 10% wt. of isobutylene. 20. A fire extinguishing mixture of the formula: (a) about 4 to 45% wt. of 2-chloro-l,l,l,2- tetrafluoroethane or 1-chloro-l,1,2,2-tetrafluoroethane; (b) about 50 to 90% wt. of pentafluoroethane; and (c) about 0 to 10% wt. of isobutylene. AMENDED CLAIMS [received by the International Bureau on 12 July 1993 (12.07.93 ) ; original claims 1,2, 3, 7, and 15 amended; new claims 21-26 added; other claims unchanged (12 pages) ] 1. A fire extinguishing mixture of the following compounds : (a) 90 to 99 . 9% wt . of one or more halocarbons of the formula: C w H χ Cl γ F z wherein W is 1 , 2 , 3 or 4 , X is any one of 0 to 9 , Y is any one of 0 to 9 and Z is any one of 1 to 10 , provided when Y is present, X must be present, and when Y is greater than or equal to 1 , then X is greater than or equal to 1 , and when W is 1 , X is 0 to 2 , Y is 0 to 2 , and Z is 1 to 3 , the total to add up to 4 ; when W is 2 , X is 0 to 4 , Y is 1 to 5 , and Z is 1 to 5 , the total to add up to 6 ; when W is 3 , X is 0 to 6 , Y is 0 to 7 , and Z is 1 to 8 , the total to add up to 8 ; and when W is 4 , X is 0 to 8 , Y is 0 to 9 , and Z is 1 to 10 , the total to add up to 10 ; and (b) 0. 1 to 10% wt . of one or more detoxifying substances selected from the group consisting of : citral citronellal citronellol limonene dipentene menthol terpinene terpinolene sylvestrene sabinene menthadiene zingiberene ocimene myrcene alpha-pinene beta-pinene turpentine camphor phy ol vitamin A abietic acid squalene lanosterol saponin oleanolic acid lycopene beta-carotene lute in alpha-terpineol para-cymene oleic acid linoleic acid linolenic acid eleostearic acid lincanic acid ricinoleic acid palmitoleic acid petroselenic acid vaccenic acid erucic acid ethene propene butene pentene isopentene tri ethylethene tetramethylethene butadiene 2-methylbutadiene pentadiene isopropenyl-1-methyl cyclohexene isobutylene; the mixture having a boiling point of about -85°C to about 200°C, a molecular weight in the range of 70 to 400, and a vapour pressure of about MPa 0.1 to about 5. 2. A fire fighting mixture of the formula: (a) 90% to 100.0% wt. of one or more of a chloro- fluorocarbon or fluorocarbon selected from the group consisting of: hydrochlorofluorocarbon.13 chlorotrifluoromethane hydrochlorofluorocarbon.21 dichlorofluoromethane hydrochlorofluorocarbon.22 chlorodifluoromethane hydrochlorofluorocarbon.31 chlorofluoromethane hydrochlorofluorocarbon.121 1,1,2, 2-tetrachloro- 1-fluoroethane hydrochlorofluorocarbon.122 1, l,2-trichloro-2, 2- difluoroethane hydrochlorofluorocarbon.123 2,2-dichloro-l,1,1- trifluoroethane l,2-dichloro-l,l,2- trifluoroethane hydrochlorofluorocarbon.124 2-chloro-l, 1, 1,2- tetrafluoroethane 1-chloro-l,1,2,2- tetrafluoroethane hydrochlorofluorocarbon 125 pentafluoroethane hydrochlorofluorocarbon.131 hydrochlorofluorocarbon.132 1,2-dichloro-l, 1- difluoroethane hydrochlorofluorocarbon.133 2-chloro-l, 1, 1- trifluorethane hydrochlorofluorocarbon.134a 1,1,1,2- tetrafluoroethane hydrochlorofluorocarbon.141 1, 2-dichloro-l- fluoroethane 1, 1-dichloro-l- fluoroethane hexafluoropropane hydrochlorofluorocarbon.142 1-chloro-l, 1- difluoroethane hydrochlorofluorocarbon.221 2-fluoropropane hydrochlorofluorocarbon.222 1, 1-difluoro-1,2,2,3, 3-pentachloropropane hydrochlorofluorocarbon.223 hydrochlorofluorocarbon.224 hydrochlorofluorocarbon.225 3,3-dichloro-1,1,1,2, 2-pentafluoropropane 1, 3-dichloro-l,l,2,2, 3-pentafluoropropane hydrochlorofluorocarbon.226 hydrochlorofluorocarbon.231 - hydrochlorofluorocarbon.232 hydrochlorofluorocarbon.233 - hydrochlorofluorocarbon.234 - hydrochlorofluorocarbon.235 hydrochlorofluorocarbon.241 - hydrochlorofluorocarbon.242 1,1, 1-trichloro-2,2- difluoropropane hydrochlorofluorocarbon.243 - hydrochlorofluorocarbon.244 - hydrochlorofluorocarbon.251 - hydrochlorofluorocarbon.252 hydrochlorofluorocarbon.253 - 2-chloro-l,l, 1- trifluoropropane hydrochlorofluorocarbon.261 1,2-dichloro-2- fluoropropane hydrochlorofluorocarbon.262 hydrochlorofluorocarbon.271 (b) 0 to 10% wt. of one of more of a detoxifying substance selected from the group consisting of: citral citronellal citronellol limonene dipentene menthol terpinene terpinolene sylvestrene sabinene menthadiene zingiberene oci ene myrcene alpha-pinene beta-pinene turpentine camphor phytol vitamin A abietic acid squalene lanosterol saponin oleanolic acid lycopene beta-carotene lutein alpha-terpineol para-cymene oleic acid linoleic acid linolenic acid oleostearic acid lincanic acid ricinoleic acid palmitoleic acid petroselenic acid vaccenic acid erucic acid ethene propene butene pentene isopentene trimethylethene tetramethylethene butadiene 2- ethylbutadiene pentadiene isobutylene. 3. A fire extinguishing mixture for use in a flood¬ ing technique in an enclosed volume comprising: (a) more than 50 percent by weight of one or more of a substance selected from the group consisting of: chlorodifluoromethane, 1-chloro-l,2,2,2-tetrafluoroethane, 1, l-dichloro-2 ,2,2-trifluoroethane 1, 2 , 2,2-tetrafluoroethane, and pentafluroethane; (b) less than 48 percent by weight of one or more of a substance selected from the group consisting of: trichlorofluoromethane, 1, 2-dichloro-2,2-difluoroethane; (c) between 0.25 and 10 percent by weight of one or more detoxifying substances selected from the group consisting of: citral citronellal citronellol limonene dipentene menthol terpinene terpinolene sylvestrene sabinene menthadiene zingiberene ocimene myrcene alpha-pinene beta-pinene turpentine camphor phytol vitamin A abietic acid squalene lanosterol saponin oleanolic acid lycopene beta-carotene lutein alpha-terpineol para-cymene oleic acid linoleic acid linolenic acid oleostearic acid lincanic acid ricinoleic acid palmitoleic acid petroselenic acid vaccenic acid erucic acid ethene propene butene pentene isopentene trimethylethene tetramethylethene butadiene 2-methylbutadiene pentadiene isobutylene 4. A mixture as claimed in claim 3 wherein the initial boiling point of the mixture is between -80°C and -10°C. 5. A mixture as claimed in claim 3 wherein the fluid viscosity of the mixture is below 1.0 centipoise between the initial boiling point of the mixture and 25°C. 6. A mixture as claimed in claim 4 wherein the fluid viscosity of the mixture is below 1.0 centipoise between the initial boiling point of the mixture and 25°C. 7. A fire extinguishing mixture for use in a flood¬ ing technique in an enclosed volume comprising: (a) at least 50 percent by weight of chloro¬ difluoromethane; (b) less than 48 percent by weight of one or more of a substance selected from the group consisting of: 1-chloro-l, 2,2,2-tetrafluoroethane, 1,2-dichlorotetrafluoroethane, 1, l-dichloro-2,2,2-trifluoroethane; and (c) between 2 and 4 percent by weight of one or more of a substance selected from the group consisting of: dipentene, and limonene. 8. A fire extinguishing mixture consisting essen¬ tially of about 96 percent by weight of chlorodifluoro¬ methane, and about 4 percent by weight of limonene. 9. A fire extinguishing mixture consisting essen¬ tially of about 85 percent by weight of chlorodifluoro¬ methane, about 11.5 percent by weight of 1-chloro-l,2,2,2- tetrafluoroethane, and about 3.5 percent by weight of dipentene. 10. A fire extinguishing mixture consisting essen¬ tially of about 65 percent by weight of dichlorodifluoro¬ methane, about 15.5 percent by weight of 1,2-dichlorotetra- fluoroethane, about 15.5 percent by weight ,of trichloro- fluoroethane, and about 4 percent by weight of limonene. 11. A fire extinguishing mixture consisting essen¬ tially of about 65 percent by weight of dichlorodifluoro- methane, about 15.5 percent of 1, 2-dichlorotetrafluoro¬ ethane, about 15.5 percent by weight of trichlorofluoro¬ ethane, and about 4 percent by weight of dipentene. 12. A fire extinguishing mixture consisting essen- tially of about 75 percent by weight of chlorodifluoro¬ methane, about 11.75 percent by weight of 1, 1-dichloro- 2,2,2-trifluoroethane, about 9.5 percent by weight of 1- chloro-1,2,2,2-tetrafluoroethane, and about 3.75 percent by weight of limonene. 13. A mixture as claimed in claim 7 wherein the initial boiling point of the mixture is between -80°C and -10°C. 14. A mixture as claimed in claim 7 wherein the fluid viscosity of the mixture is below 1.0 centipoise between the initial boiling point of the mixture and 25°C. 15. A fire extinguishing mixture for use in a flood¬ ing technique in an enclosed volume comprising: (a) more than 50 percent by weight of one or more of a substance selected from the group consisting of: chlorodifluoromethane, 1-chloro-l,2,2,2-tetrafluoroethane, 1, l-dichloro-2,2,2-trifluoroethane 1,2,2,2-tetrafluoroethane, and pentafluroethane; (b) less than 48 percent by weight of 1,2- dichloro-2,2-difluoroethane; (c) between 0.25 and 10 percent by weight of one or more detoxifying substances selected from the group consisting of: limonene ethene propene butene isopropene pentene isopentene trimethylethene tetramethylethene butadiene 2-methylbutadiene pentadiene dipentene isobutylene 16. A mixture as claimed in claim 15 wherein the initial boiling point of the mixture is between -80°C and -10°C. 17. A mixture as claimed in claim 15 wherein the fluid viscosity of the mixture is below 1.0 centipoise between the initial boiling point of the mixture and 25°C. 18. A mixture as claimed in claim 12 comprising about 4.75% wt. of 2,2-dichloro-l, 1, 1-trifluoroethane, about 82% wt. of chlorodifluoromethane, about 9.5% wt. of 2-chloro- 1,1,1,2-tetrafluoroethane and about 3.75% wt. isopropenyl- 1-methyl cyclohexene. 19. A fire extinguishing mixture of the formula: (a) about 1% wt. of 2, 2-dichloro-l, 1, 1-trifluoro¬ ethane or 1,2-dichloro-l, 1, 2-trifluoroethane; (b) about 9.5% wt. of 2-chloro-l, 1, 1,2-tetra- fluoroethane or 1-chloro-l, 1, 2,2-tetrafluoroethane; (c) about 79.5 to 88.5% wt. of chlorodifluoro¬ methane; and (d) about 1 to 10% wt. of isobutylene. 20. A fire extinguishing mixture of the formula: (a) about 4 to 45% wt. of 2-chloro-l, 1, 1,2- tetrafluoroethane or 1-chloro-l, 1, 2, 2-tetrafluoroethane; (b) about 50 to 90% wt. of pentafluoroethane; and (c) about 0 to 10% wt. of isobutylene. 21. The use of a terpene or an unsaturated oil as a detoxifying substance in a fire extinguishant composition, which composition comprises one more halocarbons of the formula: C u H χ Cl γ F z wherein W is 1, 2, 3 or 4, X is any one of 0 to 9, Y is any one of 0 to 9 and Z is any one of 1 to 10, provided when Y is present, X must be present, and when Y is greater than or equal to 1, then X must be greater than or equal to 1, and when W is 1, X is 0 to 2 , Y is 0 to 2 , and Z is 1 to 3 , the total to add up to 4; when W is 2 , X iε 0 to 4, Y is 1 to 5, and Z is 1 to 5, the total to add up to 6; when W is 3, X is 0 to 6, Y is 0 to 7, and Z is 1 to 8, the total to add up to 8; and when W is 4, X is 0 to 8, Y is 0 to 9, and Z is 1 to 10, the total to add up to 10. 22. The use as claimed in claim 21 wherein said terpene or unsaturated oil is one or more of the substances selected from the group consisting of: citral citronellal citronellol limonene dipentene menthol terpinene terpinolene sylvestrene sabinene enthadiene zingiberene ocimene myrcene alpha-pinene beta-pinene turpentine camphor phytol vitamin A abietic acid squalene lanosterol saponin oleanolic acid lycopene beta-carotene lutein alpha-terpineol para-cymene oleic acid linoleic acid linolenic acid oleostearic acid lincanic acid ricinoleic acid palmitoleic acid petroselenic acid vaccenic acid erucic acid ethene propene butene pentene isopentene trimethylethene tetramethylethene butadiene 2-methylbutadiene pentadiene isopropenyl-1-methyl cyclohexene isobutylene; the mixture having a boiling point of about -85°C to about 200°C, a molecular weight in the range of 70 to 400, and a vapour pressure of about MPa 0.1 to about 5. 23. The use as claimed in claim 21 or 22 wherein the halocarbon comprises 90 to 99.9% wt. of the composition and the detoxifying substance comprises 0.1 to 10% wt. of one or more of the detoxifying substances. 24. The use of a terpene or an unsaturated oil as a detoxifying agent in a fire-extinguishing composition, which composition comprises one or more fluorocarbons selected from the group consisting of: hydrochlorofluorocarbon.13 chlorotrifluoromethane hydrochlorofluorocarbon.21 dichlorofluoromethane hydrochlorofluorocarbon.22 chlorodifluoromethane hydrochlorofluorocarbon.31 chlorofluoromethane hydrochlorofluorocarbon.121 1,1,2,2-tetrachloro- 1-fluoroethane hydrochlorofluorocarbon.122 1, l,2-trichloro-2,2- difluoroethane hydrochlorofluorocarbon.123 2,2-dichloro-l,1,1- trifluoroethane 1, 2-dichloro-l, 1,2- trifluoroethane hydrochlorofluorocarbon.124 2-chloro-l, 1,1,2- tetrafluoroethane 1-chloro-l,1,2,2- tetrafluoroethane hydrochlorofluorocarbon 125 pentafluoroethane hydrochlorofluorocarbon.131 hydrochlorofluorocarbon.132 1,2-dichloro-l, 1- difluoroethane hydrochlorofluorocarbon.133 2-chloro-l, 1,1- trifluorethane hydrochlorofluorocarbon.134a 1,1,1,2- tetrafluoroethane hydrochlorofluorocarbon.141 1,2-dichloro-l- fluoroethane 1, 1-dichloro-l- fluoroethane hexafluoropropane hydrochlorofluorocarbon.142 1-chloro-l, 1- difluoroethane hydrochlorofluorocarbon.221 2-fluoropropane hydrochlorofluorocarbon.222 1, 1-difluoro-1,2,2,3, 3-pentachloropropane hydrochlorofluorocarbon.223 hydrochlorofluorocarbon.224 hydrochlorofluorocarbon.225 3 , 3-dichloro-l,1,1,2, 2-pentafluoropropane 1, 3-dichloro-l, 1,2,2, 3-pentafluoropropane hydrochlorofluorocarbon.226 hydrochlorofluorocarbon.231 hydrochlorofluorocarbon.232 hydrochlorofluorocarbon.233 hydrochlorofluorocarbon.234 hydrochlorofluorocarbon.235 hydrochlorofluorocarbon.241 hydrochlorofluorocarbon.242 1,1, 1-trichloro-2,2- difluoropropane hydrochloro luorocarbon.243 hydrochlorofluorocarbon.244 hydrochlorofluorocarbon.251 hydrochlorofluorocarbon.252 hydrochlorofluorocarbon.253 2-chloro-l, 1,1- trifluoropropane hydrochlorofluorocarbon.261 l,2-dichloro-2- fluoropropane hydrochlorofluorocarbon.262 hydrochlorofluorocarbon.271 25. The use as claimed in claim 24 wherein the terpene or unsaturated oil is one or more of a detoxifying substance selected from the group consisting of: citral citronellal citronellol limonene dipentene menthol terpinene terpinolene sylvestrene sabinene menthadiene zingiberene ocimene myrcene alpha-pinene beta-pinene turpentine camphor phytol vitamin A abietic acid squalene lanosterol saponin oleanolic acid lycopene beta-carotene lutein alpha-terpineol para-cymene oleic acid linoleic acid linolenic acid oleostearic acid lincanic acid ricinoleic acid palmitoleic acid petroselenic acid vaccenic acid erucic acid ethene propene butene pentene isopentene trimethylethene tetrameth lethene butadiene 2- ethylbutadiene pentadiene isopropenyl-1-methyl cyclohexene isobutylene; the mixture having a boiling point of about -85°C to about 200°C, a molecular weight in the range of 70 to 400, and a vapour pressure of about MPa 0.1 to about 5. 26. The use as claimed in claim 25 wherein the fluorocarbon comprises 90% to 100% wt. of the composition and the detoxifying substance comprises 0 to 10% wt. of the composition.

Inventors: GUGLIELMI ELIO, GUGLIELMI, ELIO
Applicants: TAG INVESTMENTS INC, TAG INVESTMENTS INC.
Application year: 1992
Main classification: A62D1
IPC codes: A62D1