KR20000010579A - Environmentally benign non-toxic fire flooding agents - Google Patents

Abstract

PURPOSE: A fire flooding agent is provided to be environmentally safe and to be non-toxic in both natural form and in fire exposed°C.Craded form. CONSTITUTION: Fire flooding and extinguishing agents and detoxifiers which are environmentally safe and non-toxic in both natural form and in fire exposed°C.Craded forms are disclosed. The flooding and streaming-type fire extinguishing agents are rich in low boiling, unsaturated halocarbon compounds having low liquid viscosity, and low boiling alkenes as detoxifying agents. The detoxifiers are conjugated double bond hydrocarbons.

Description

Environmentally Friendly Non-toxic Flood Extinguishing Media

Certain halocarbons, blowing agents, and extinguishing agents, such as CFC 11, CFC 12, and Halon 1301, which are widely used as refrigerants in recent years, accumulate in the stratosphere, destroying the ozone layer, which protects life on Earth from harmful radiation from the sun and space. It has been found to be harmful to the environment. These hazardous substances are being reduced in production.

Halocarbons have been used as extinguishing agents. Thacker's British Patent No. 1,603,867 describes monoterpenes, ie CFC 11 and CFC 12 mixed with volatile vegetable or citrus oils as extinguishing agents. Monoterpenes are defined by the molecular formula C ₁₀ H ₁₆ . As already stated, CFC 11 and CFC 12 are widely known to be harmful to the ozone layer.

Halocarbon extinguishing agents can be broadly divided into two types: stream type and flood type. Stream-type preparations are applied directly to the epicenter of the fire and must have a high boiling point so that they do not decompose until the fire epicenter is reached. Flooded formulations fill the space around the fire and soften the flames. It can be easily vaporized when the boiling point is low.

US Patent No. 4,826,610 to Derik A. Thacker, issued May 2, 1989, discloses one to 14 percent by weight of a sesquiterpene extinguishing agent substrate and one or more halocarbons, namely halon 11 Fire fighting compositions comprising (CFC 11), 12 (CFC 12), 113 (CFC 113), and 114 (CFC 114) are described. Sesquiterpenes are compounds of the formula C ₁₅ H ₂₄ . Solvents and dispersants may also be included. The composition is suitable for stream fire fighting conditions. The formulation is not ozone friendly.

US Patent No. 4,954,271 to Raymond W. Green, issued September 4, 1990, describes and protects an environmentally friendly high boiling stream stream extinguishing agent. The stream preparation comprises 50 weights of fluorochlorocarbon (a) selected from the group consisting of 1,1-dichloro-2,2,2-trifluoroethane and 1,2-dichloro-2,2-difluoroethane. % More than; Fluorocarbons selected from the group consisting of chlorodifluoromethane, 1-chloro-1,2,2,2-tetrafluoroethane, pentafluoroethane and 1,2,2,2-tetrafluoroethane (b ) Less than 48% by weight; And terpenes (e.g. citral, citronellal, citronellol, limonene, dipentene, menthol, terpinene, terpinolene, sylvestrene, savinen, metadiene, gingiberene, oxymene, myrcene, α Pinene, β-pinene, terpentin, camphor, phytol, vitamin A, abitic acid, squalene, lanosterol, saponin, oleanoic acid, lycopene, β-carotene, lutein, α-terpineol and p-cime) and unsaturated oils (E.g., oleic acid, linoleic acid, linolenic acid, eleosearic acid, lincanoic acid, ricinolic acid, palmitoleic acid, petroselenic acid, valsenic acid and erucic acid) (c) a mixture of 2 to 10% by weight.

In the chlorofluorocarbon streamlike mixture taught by Green, it is emphasized that at least 50% by weight of high boiling chlorofluorocarbons should be contained in the mixture. In contrast, the low boiling compound should be less than 50% by weight (see column 2, lines 22-27). In the examples described in the green patent, the amount of low boiling chlorofluorocarbons, such as CFC12, boiling at −30 ° C. is 15% by weight of the total formulation. The other components are very large and boil above 0 ° C. For example, in the examples of Green, column 4, line 61, the boiling point of the NAF internal mixture is referred to as 10 ° C. Thus, high boiling mixtures by green are the opposite of low boiling mixtures that are useful as streamed extinguishing agents and are actually suitable as flooded formulations.

Interesting are Fernandez, U.S. Patent No. 5,141,654, issued August 25, 1992, and U.S. Patent No. 5,393,438, issued February 28, 1995, because these two patents describe extinguishing agents. Because there is. Fernandez's two patents describe chlorofluorocarbons that are not fully halogenated, each halocarbon having at least one fluorine atom (see column 2, line 57 of US Pat. No. 5,141,654). However, halocarbons are used in pure form. Neither Fernandez's patent states that more than one detoxifying substance was used. In addition, none of Fernandez's patents describes the inherent importance of low boiling point chlorofluorocarbons.

Summary of the Invention

The present invention relates to a hydrochlorofluorocarbon. 21-dichlorofluoromethane,

Hydrochlorofluorocarbon.22-Chlorodifluoromethane,

Hydrofluorocarbon 23-trifluoromethane,

Hydrochlorofluorocarbon. 123 -2,2-dichloro-1,1-trifluoroethane,

Hydrochlorofluorocarbon. 123a-1,2-dichloro-1,1,2-trifluoroethane,

Hydrochlorofluorocarbon. 124-2-chloro-1,1,1,2-tetrafluoroethane,

Hydrochlorofluorocarbon. 124a-1-chloro-1,1,1,2-tetrafluoroethane,

Hydrofluorocarbon 125-pentafluoroethane,

Hydrochlorofluorocarbons. 131-chlorotrifluoroethane,

Hydrochlorofluorocarbon. 132-1,2-dichloro-1,1-difluoroethane,

Hydrochlorofluorocarbon. 133-2-chloro-1,1,1-trifluoroethane,

Hydrofluorocarbon 134a-1,1,1,2-tetrafluoroethane,

Hydrofluorocarbon 227-heptafluoropropane,

Hydrochlorofluorocarbons. 236-hexafluoropropane and

About 90 to about 100.0 weight percent of a halocarbon (a) selected from the group consisting of hydrofluorocarbon 245-pentafluoropropane and

Detox selected from the group consisting of ethene, propene, butene, isopropene, pentene, isopentene, trimethylethene, tetramethylethene, butadiene, 2-methylbutadiene, pentadiene, isobutylene and 1,3-butadiene Boil point is about -85 to 25 ℃, compounding molecular weight is about 70 to 250, vapor pressure is about 0.1 to about 5 Mpa at 25 ℃, characterized in that it comprises from 0.25 to 10% by weight, natural form And non-toxic and environmentally friendly fire extinguishing mixtures, both in the form degraded by exposure to flame.

In another aspect, the present invention relates to an additive for a halogenated extinguishing agent and a flood type extinguishing mixture consisting of one or more hydrocarbons having 2 to 6 carbon atoms and having at least one double bond, wherein the additive comprises It reduces the amount of hydrogen halides and carbonyl halides that occur when exposed to flames. Additives to halogenated extinguishing agents and extinguishing mixtures may have at least 4 carbon atoms and have at least two double bonds, where at least two double bonds are conjugated.

The additive is from the group consisting of ethene, propene, butene, isopropene, pentene, isopentene, trimethylethene, tetramethylethene, butadiene, 2-methylbutadiene, pentadiene, isobutylene and 1,3-butadiene Can be selected.

The present invention also relates to halogenated extinguishing agents and specific additives consisting of 1,3-butadiene, used for flooded extinguishing mixtures, wherein the additives are hydrogen halides and carbonyls that occur when the halogenated extinguishing agent and extinguishing mixture are exposed to flame. Reduce the amount of halides. The fluid viscosity of the mixture may be less than 1.0 centipoise at an initial boiling point of the mixture to a temperature of 25 ° C.

The present invention also relates to a nontoxic environmentally friendly fire extinguishing mixture for use in a flood type fire extinguishing technique, wherein said fire extinguishing mixture is about 82 wt% HCFC-22, about 9.5 wt% HCFC-124 and about 4.75 wt% HCFC-123 % And about 2% by weight of 1,3-butadiene.

The present invention includes novel flood-type and stream-type extinguishing agents and novel antidote which are environmentally safe and nontoxic both in natural form and in degraded form upon exposure to flame. .

The inventors have observed that halogenated hydrocarbons are very stable, long in life and difficult to decompose. Thus, when fully halogenated hydrocarbons are introduced into the stratosphere, it takes longer to decompose and thus the ozone layer destruction time is longer.

In particular, the two chlorofluorocarbons described in Tacker US Pat. No. 4,826,610 are fully halogenated compounds. In other words, all available substitution positions of the carbon main chain are occupied by chlorine or fluorine. Tacker did not realize that fully halogenated chlorofluorocarbon compounds were so stable and difficult to decompose that they were responsible for the destruction of the ozone layer surrounding the earth.

In particular, Green describes high boiling point fully halogenated chlorofluorocarbons and partially halogenated chlorofluorocarbon mixtures suitable as stream type extinguishing agents. The mixture of greens comprises the following chlorofluorocarbons: CFC 11, CFC 12, CFC 22, CFC 114, HCFC 123, HCFC 124, HFC 125, HCFC 132 and HFC 134. Among these chlorofluorocarbons, CFC 11, CFC 12 and CFC114 are fully halogenated chlorofluorocarbons. Green did not recognize the difference between fully halogenated chlorofluorocarbons and partially halogenated chlorofluorocarbons, and did not know that chlorofluorocarbons that were fully saturated with halogen atoms were difficult to decompose and harmful to the earth's ozone layer.

We have invented a class of low-boiling partially halogenated chlorofluorocarbon formulations that are ideal as flood extinguishing agents. In addition, the formulations are environmentally friendly because the halocarbons are not fully halogenated, ie always at least one hydrogen is present in the formulation comprising chlorofluorocarbons and fluorocarbons. In other words, the low-boiling partially halogenated chlorofluorocarbon compounds described herein provide one or more hydrogen moieties to each molecule such that these sites aid in the breakdown or degradation of the molecule.

As will be appreciated by those skilled in the art, the inclusion of hydrogen in a compound will change the physical and chemical properties of the compound sufficiently, but the compound containing the hydrogen atom will act or perform in a manner similar to a fully halogenated compound. You can't immediately predict or obviously know what to do. It will be appreciated by those skilled in the art that the inclusion of highly flammable and reactive elements of hydrogen in fully halogenated hydrocarbons in unbonded form results in partial halogenation of fully halogenated hydrocarbons, which dramatically alters the chemical properties of fully halogenated hydrocarbons. Can be. Those skilled in the art assume that it is not expected that partially halogenated aliphatic hydrocarbons can replace fully halogenated aliphatic hydrocarbons in the flooded digestion mixture, since the results are not predictable.

In addition, knowledge obtained from streamed halocarbon fire extinguishing agents cannot be predictably applied separately to flood halocarbon fire extinguishing agents.

When Tucker and Green developed a stream-type fire extinguishing formulation using a wide range of high-boiling, fully halogenated chlorofluorocarbons, they did not describe the fact that these chlorofluorocarbons would destroy the ozone layer surrounding the earth. In addition, Tacker and Green did not recognize the global warming effect of fully halogenated chlorofluorocarbons.

The flood type fire extinguishing mixtures described herein by the present inventors are partially halogenated halocarbons and very preferably are flood type fire extinguishing agents in natural form as well as in a degraded form that occurs when the extinguishing agent is exposed to a flame, which is unlikely to deplete ozone. Act as.

The present inventors also note that one of the low boiling halocarbons having 2 to 6 carbon atoms and one or more double bonds in each molecule for use in antidotes (or acid scavengers) in connection with the low boiling halocarbons used as immersion extinguishing agents. Invented the class.

Overall, the present inventors, when used in combination with a series of hydrochlorofluorocarbons and hydrofluorocarbon extinguishing agents, constitute an ideal flood extinguishing agent and also make the degraded halocarbons non-toxic and provide minimal damage to the global ozone layer. A series of lower alkenes antidote that induces was invented. The series of flood extinguishing agents I invented by the inventors do not contain bromofluorocarbons which have been found to have severe ozone damaging effects.

In contrast to streaming fire extinguishing agents into the fire epicenter, flooded extinguishing mixtures that fill a volume of space and extinguish the fire should be much more volatile than in the case of stream products. In the case of products for streams, the mixture must remain bondable and not decompose by heat until the fire epicenter is reached. In the case of flooded products, not only the need for binding of the mixture is reduced, but also the bonding is disadvantageous for the rapid dispersal of the extinguishing agent throughout the volume. Therefore, in the case of a flood product, it is preferable that the halocarbon constituting the extinguishing agent has a low boiling point. In addition, the boiling point of the detoxifying substance used in the formulation for the flood type product is preferably lower than that of the detoxifying substance used in the stream type product. Dispersion is facilitated when both halocarbons and antidotes have low boiling points.

Apart from this, the inventors have found that when some of the materials described by the tucker and the green are used in fire-extinguishing products (although the formulations of the green and the tucker are primarily intended for streamed use), the present invention is preferred in certain cases. Not terpin or sesquiterpin residues.

The inventors do not intend to be bound by any theory, but when halocarbon is used as a digestive agent, halogen trapping action by the antidote occurs on a molecular basis, so that halo is obtained to obtain the same degree of detoxification as in the case of high molecular weight compounds. It is believed that low molecular weight antidote should be present for the low molecular weight fraction of carbon.

The inventors have found that low boiling point low molecular weight hydrocarbons having two or more conjugated double bonds are particularly effective as antidote (acid scavenger) for low boiling halocarbons used as flood type digestive agents. When low-boiling halocarbons are used as flood extinguishing agents, during the halogen capture process, the intermediate product formed is resonance stable. Alkenes of 6 or less carbon atoms having one or more double bonds have higher vapor pressures and lower boiling points than terpene additives described by Green.

In addition, with regard to halocarbon and ozone depletion, the inventors wish not to be bound by the opposite theory. However, the following theory is provided to help understand why the low boiling halocarbons invented by the inventors are successful as environmentally friendly flood type fire extinguishing agents. The inventors believe that halocarbons containing one or more hydrogens are generally more environmentally friendly than fully halogenated halocarbons because they provide a location to be attacked by hydroxyl radicals even if one hydrogen is present in the halocarbon molecule. . This breaks down the halocarbon molecules and significantly reduces the lifetime of the halocarbon molecules in the atmosphere. The inventors believe that because the compound takes a long time to move from near the earth's surface into the upper stratosphere, the ozone reduction potential of the compound depends on the lifetime in the atmosphere. If the molecules are not held in the atmosphere for a long time, the global warming potential also depends on the lifetime in the atmosphere, because even with strong absorbing molecules, the time-integrated climatic forces are minimal. Thus, the present invention allows the use of partially halogenated halocarbons containing one or more hydrogens to provide molecular decomposition sites, whereby the compounds are relatively environmentally friendly.

The present inventors have used the low boiling point partially halogenated non-toxic mixture as follows when using a flooded or inert fire extinguishing technique, that is, releasing a extinguishing agent into a fired enclosed space to produce an extremely toxic decomposition product. It has been shown that it can quickly and safely extinguish a type of fire:

(a) Dichlorofluoromethane (HCFC 21)

Chlorodifluoromethane (HCFC 22)

Trifluoromethane (HFC 23)

Dichlorotrifluoroethane (HCFC 123)

Chlorotetrafluoroethane (HCFC 124)

Pentafluoroethane (HCFC 125)

Dichlorodifluoroethane (HCFC 132)

Chlorotrifluoroethane (HCFC 133)

Tetrafluoroethane (HCFC 134)

Heptafluoropropane (HFC 227)

Pentafluoropropane (HFC 245) and

90 to 99.9% of one or more of hexafluoropropane (HCFC 236); And

(b) 0.1 to 10% by weight of one or more hydrocarbons of 2 to 6 carbon atoms having one or more double bonds.

The mixture should be relatively volatile, preferably have a boiling point of −85 to 25 ° C., a molecular weight of 70 to 250 and a vapor pressure of about 0.1 to 5 MPa at 25 ° C.

Any one or more detoxifying hydrocarbons of 2 to 6 carbon atoms having one or more double bonds, from 0.1 to 10% by weight, may be one or more of the following low molecular weight alkenes:

Ethene, propene, butene, isopropene, pentene, isopentene, trimethylethene, tetramethylethene, butadiene, 2-methylbutadiene, pentadiene, isobutylene and 1,3-butadiene.

The correct choice of formulation and composition is in each case the cost, factors controlling the flow of fluids and vapors, factors controlling the physical properties of fluids and vapors, and the type of flooded extinguishing system required to maintain the desired volume (s). It will be controlled by the balance between the arrays.

In addition, the present inventors found that the low initial boiling point of a fire extinguishing agent is important in extinguishing a closed space by a flood type or inactivation technique. This is true for both halocarbons and antidote. In addition, the inventors have found that in such flood type extinguishing agents, it is important that they are volatilized at the same time because the boiling point of the antidote is almost identical to that of halocarbon.

Mixtures of the invention suitable as flooded or inactivated extinguishing agents have the following advantageous properties:

1. The flood type fire extinguishing mixture of the kind according to the present invention may be low in boiling point compound, and the binding force is not large. Thus, the flooded class described by the present inventors rapidly vaporizes and floods a predetermined space with a extinguishing agent at a concentration necessary to suppress or inactivate the gas phase to suppress or extinguish the fire in the enclosed space.

2. This type of low boiling flooded mixture allows the use of low boiling point antidote. These include low boiling lower unsaturated alkenes, and because of their low boiling point they can be successfully used as high boiling stream type extinguishing agents.

3. Surprisingly, it has been found that when the antidote is completely removed from the digestive mixture, the digestive capacity is less efficient than when the antidote compound is included in the formulation. In addition, if the detoxification of lower alkenes is omitted, the halocarbon extinguishing mixture decomposes due to heat from the fire, producing dangerous levels of toxic halogens and hydrogen halides.

4. The inventors have observed that as a physical property of the flood mixture to maximize the above mentioned properties, its boiling point should be in the range of -80 to -10 ° C. In addition, the liquid viscosity in the temperature range of the initial boiling point of the mixture to about 25 ℃ should be less than 1.0 centipoise.

Example 1

In one particular test, a measurement test chamber (0.5 × 3 × 3) with five standard port flames is flooded into a pipe system of approximately 3 m in total length. The pot flame is digested through a pipe in 10 seconds using 1 kg of a mixture of 96% by weight of chlorodifluoromethane and 4% by weight of limonene. This mixture has 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 chamber as in Example 1, five pot flames were added with 85% by weight of chlorodifluoromethane, 11.5% by weight of 1-chloro-1,2,2,2-tetrafluoro Digest in 10 seconds using 1 kg of a mixture consisting of ethane and 3.5 wt% dipentene.

Example 3

In a third evaluation using the same test chamber as in Example 1, five pot flames were prepared with 65 wt% chlorodifluoromethane, 15.5 wt% 1,2-dichlorotetrafluoroethane, 15.5 wt% Digest in 10 seconds using 1 kg of a mixture consisting of trichloromethane and 4% limonene.

Example 4

In a fourth application using the same test chamber as in Example 1, five pot flames were prepared with 65% by weight of dichlorodifluoromethane, 15.5% by weight of 1,2-dichlorotetrafluoroethane, 15.5% by weight. Digest in 10 seconds using 1 kg of a mixture consisting of trichloromethane and 4% limonene.

Example 5

In a fifth test using the same test chamber as in Example 1, five pot flames were prepared with about 65 wt% dichlorodifluoromethane, about 15.5 wt% 1,2-dichlorotetrafluoroethane, about 15.5 Digestion was performed in 10 seconds using 1 kg of a mixture consisting of wt% trichloromethane and about 4 wt% dipentene.

Example 6

In a sixth evaluation using the same test chamber as in Example 1, five pot flames were placed at about 75% by weight of chlorodifluoromethane, about 11.5% by weight of 1,1-dichloro2,2,2-triple Digestion is carried out in 10 seconds using 1 kg of a mixture consisting of uroethane, about 9.5 wt% 1-chloro-1,2,2,2-tetrafluoroethane and about 3.75 wt% limonene.

Example 7

In a fire extinguishing test performed with a HCFC mixture having a ratio of HCFC-22: HCFC-124: HCFC-123 of 82: 9.5: 4.75, when 2 parts by weight of 1,3-butadiene was added, hydrocarbon was added to the HCFC mixture. The resulting HF concentration was reduced by 60% compared to the test without addition.

These examples clearly demonstrate that low fluid viscosity and low boiling point play an important role in the use of the mixture as a variable necessary to achieve the optimum volume of flood extinguishing performance. It is an object of the present invention to obtain a mixture having an initial boiling point of about -60 ° C and a fluid viscosity of about 0.15 centipoise at 25 ° C.

As will be apparent to those skilled in the art in view of the above, many variations and modifications are possible to practice the invention without departing from its spirit or scope. Accordingly, the scope of the invention is defined in accordance with the material defined by the following claims.

Claims (12)

Chlorodifluoromethane, dichlorofluoromethane, trifluoromethane, dichlorotrifluoroethane, dichlorodifluoroethane, chlorotetrafluoroethane, chlorotrifluoroethane, pentafluoroethane, tetrafluoroethane, 90 to 99.9 weight percent of one or more halocarbons (a) selected from the group consisting of heptafluoropropane, hexafluoropropane and pentafluoropropane; and Non- both in its natural form and in its degraded form exposed to flame, characterized in that it comprises 0.1 to 10% by weight of an antidote (b) consisting of one or more hydrocarbons of 2 to 6 carbon atoms having one or more double bonds. Toxic, environmentally friendly, fire extinguishing mixture. The mixture of claim 1 wherein the mixture has a boiling point of about −85 to 25 ° C., a formula molecular weight of about 70 to 250, and a vapor pressure of about 0.1 to 5 Mpa at 25 ° C. 3. The hydrocarbon of claim 1 wherein the hydrocarbon having 2 to 6 carbon atoms is ethene, propene, butene, isopropene, pentene, isopentene, trimethylethene, tetramethylethene, butadiene, 2-methylbutadiene, pentadiene, iso A mixture selected from the group consisting of butylene and 1,3-butadiene. Hydrochlorofluorocarbon. 21-dichlorofluoromethane, Hydrochlorofluorocarbon.22-Chlorodifluoromethane, Hydrofluorocarbon 23-trifluoromethane, Hydrochlorofluorocarbon. 123 -2,2-dichloro-1,1-trifluoroethane, Hydrochlorofluorocarbon. 123a-1,2-dichloro-1,1,2-trifluoroethane, Hydrochlorofluorocarbon. 124-2-chloro-1,1,1,2-tetrafluoroethane, Hydrochlorofluorocarbon. 124a-1-chloro-1,1,1,2-tetrafluoroethane, Hydrofluorocarbon 125-pentafluoroethane, Hydrochlorofluorocarbons. 131-chlorotrifluoroethane, Hydrochlorofluorocarbon. 132-1,2-dichloro-1,1-difluoroethane, Hydrochlorofluorocarbon. 133-2-chloro-1,1,1-trifluoroethane, Hydrofluorocarbon 134a-1,1,1,2-tetrafluoroethane, Hydrofluorocarbon 227-heptafluoropropane, Hydrochlorofluorocarbons. 236-hexafluoropropane and About 90 to about 100.0 weight percent of a halocarbon (a) selected from the group consisting of hydrofluorocarbon 245-pentafluoropropane and Antidote selected from the group consisting of ethene, propene, butene, isopropene, pentene, isopentene, trimethylethene, tetramethylethene, butadiene, 2-methylbutadiene, pentadiene, isobutylene and 1,3-butadiene (b) a boiling point of about -85 to 25 ° C., a compounding molecular weight of about 70 to 250, a vapor pressure of about 0.1 to 5 Mpa at 25 ° C., characterized in that it comprises about 0.25 to 10% by weight, Flood-type digestive mixtures, both nontoxic and environmentally friendly, in both exposed and degraded forms. Halogenated hydrocarbon extinguishing agent or halogenated hydrocarbon flood type extinguishing mixture (a) and at least one hydrocarbon (b) having at least one double bond and having 2 to 6 carbon atoms, which is where the extinguishing agent or mixture (a) is exposed to flame A halogenated fire extinguishing agent of a flood type fire extinguishing mixture, comprising: a function of reducing the amount of hydrogen halide and carbonyl halide generated in the same. The halogenated extinguishing agent according to claim 5, wherein the at least one hydrocarbon has 4 or more carbon atoms, has at least two double bonds, and at least two of the double bonds are conjugated. 6. The additive of claim 5 wherein the additive is ethene, propene, butene, isopropene, pentene, isopentene, trimethylethene, tetramethylethene, butadiene, 2-methylbutadiene, pentadiene, isobutylene and 1,3 Halogenated extinguishing agents selected from the group consisting of butadiene. The hydrocarbon of claim 5, wherein the hydrocarbon is 1,3-butadiene present in an amount sufficient to reduce the amount of hydrogen halide and carbonyl halide produced when the halogenated hydrocarbon extinguishing agent and the extinguishing mixture are exposed to a flame. Halogenated Extinguishing Media. The mixture of claim 1 wherein the initial boiling point of the mixture is from -80 ° C to -10 ° C. The mixture of claim 3, wherein the fluid viscosity of the mixture is 1.0 centipoise or less at an initial boiling point of the mixture to 25 ° C. 5. The mixture of claim 4, wherein the fluid viscosity of the mixture is 1.0 centipoise or less at an initial boiling point of the mixture to 25 ° C. 6. Non-toxic environmentally friendly fire extinguishing for use in flood type fire extinguishing techniques, comprising about 82% by weight HCFC-22, about 9.5% by weight HCFC-124, about 4.75% by weight HCFC-123 and about 2% by weight 1,3-butadiene mixture.