JPH0542230A - Fire extinguishing agent - Google Patents

Abstract

PURPOSE:To enhance fire extinguishing effect as well as to prevent environment from being damaged by letting agent include saturated halogenated hydro-carbon, cyclic saturated halogenated hydro-carbon and unsaturated halogenated hydro-carbon which are substituted by fluorine with the respective quantities of carbon set as specified, and concurrently letting agent include halogenated hydro-carbon the hydrogen atoms and the chloride atoms of which are less in quantity than carbon atoms. CONSTITUTION:(1) Chain shaped or branching shaped saturated fluorine hydrocarbon, for example, CHF3 in which carbon is 1 to 4 in quantity while being substituted by fluorine, and hydrogen atoms are less in quantity than carbon atoms. (2) Cyclic saturated fluorine hydro-carbon, for example, C3H2F4 in which carbon is 3 to 4 in quantity while being saturated by fluorine, and hydrogen atoms are less in quantity than carbon atoms. (3) Chain shaped or branching shaped unsaturated fluorine hydro-carbon having one double bond, for example, CH2=(CF3)2 in which carbon is 3 to 4 while being substituted by fluorine, and hydrogen atom are less in quantity than carbon atoms. Agent is made up of more than one kind of hydro-carbon selected out of items (1) through (3) as mentioned herein above.

Description

Detailed Description of the Invention

[0001]

This invention relates to fire extinguishing agents.

[0002]

2. Description of the Related Art Conventionally, halogenated hydrocarbons have been mainly used as fire extinguishing agents, and among them, fire extinguishing agents containing a bromine atom, which have a large fire extinguishing effect and are stable even at high temperatures, are widely used.

However, a fire extinguishing agent containing a bromine atom has a particularly large ozone depletion coefficient (hereinafter abbreviated as ODP), and when it is released into the atmosphere, it destroys the ozone layer very efficiently, and as a result, the earth including human beings is destroyed. It has been pointed out that it has a serious adverse effect on the above ecosystem.

Therefore, there is an urgent need to develop a new fire extinguishing agent that does not destroy the ozone layer and can replace the conventional fire extinguishing agent containing a bromine atom.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a fire extinguisher having a large fire extinguishing effect and having no influence on the ozone layer even when it is released into the atmosphere.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, a composition containing a specific halogenated hydrocarbon alone or mixed has excellent properties as a fire extinguishing agent. It was found that the present invention has been completed.

That is, the present invention provides (1) a chain or branched saturated halogenated hydrocarbon having 1 to 4 carbon atoms and substituted with fluorine and / or chlorine, and (2) 3 carbon atoms. A cyclic saturated halogenated hydrocarbon having 4 to 4 and (3) 3 to 4 carbon atoms and a chain or branched having 1 double bond substituted with fluorine Containing at least one selected from the group consisting of unsaturated halogenated hydrocarbons, and in (1), (2) and (3), the number of hydrogen atoms and the number of chlorine atoms are always equal to or less than the number of carbon atoms. An extinguishing agent containing at least one halogenated hydrocarbon is provided.

The present invention also provides (1a) a chain or branched saturated fluorinated hydrocarbon having 1 to 4 carbon atoms, which is substituted with fluorine and has a hydrogen atom number which is always less than or equal to carbon atom,
(2a) a cyclic saturated fluorinated hydrocarbon having 3 to 4 carbon atoms, which is substituted with fluorine and the number of hydrogen atoms is always smaller than the number of carbon atoms, and (3a) having 3 to 4 carbon atoms, with fluorine. A fire extinguishing agent containing at least one selected from the group consisting of chain or branched unsaturated fluorinated hydrocarbons having one substituted double bond and the number of hydrogen atoms always being smaller than the number of carbon atoms. Is provided.

Further, the present invention provides (1b) a chain or branched saturated fluorinated carbon having 1 to 4 carbon atoms, (2b)
Cyclic saturated fluorinated carbon having 3 to 4 carbon atoms and (3
b) A fire extinguisher containing at least one member selected from the group consisting of chain or branched unsaturated fluorinated carbons having 3 to 4 carbon atoms and one double bond. is there.

Furthermore, the present invention is (1c) having 1 to 1 carbon atoms.
The present invention provides a fire extinguisher containing saturated fluorinated chlorinated hydrocarbons having three, substituted with fluorine and chlorine, and the numbers of hydrogen atoms and chlorine atoms are always equal to or less than the number of carbon atoms.

Furthermore, the present invention provides fluorinated hydrocarbons represented by (1a), (2a) and (3a), (1b) (2)
b) and fluorinated carbon represented by (3b), and (1
A fire extinguishing agent containing at least two members of the group consisting of fluorinated chlorinated hydrocarbons represented by c).

Examples of the fluorinated hydrocarbon represented by (1a), (2a) and (3a) include (1) CHF ₃ ; trifluoromethane (HFC23, coded in parentheses below) (2) CHF ₂ CHF ₂ ; 1,1,2,2-tetrafluoroethane (HFC134) (3) CH ₂ FCF ₃ ; 1,1,1,2-tetrafluoroethane (HFC134a) (4) CHF ₂ CF ₃ ; pentafluoroethane (HFC
125) (5) CHF ₂ CHFCF ₃ ; 1,1,1,2,3,3
- hexafluoropropane _{(HFC236ea) (6) CF 3} CHFCF 3; 1,1,1,2,3,3,
3-heptafluoropropane (HFC227ea) (7) CHF ₂ CF ₂ CF ₃ ; 1,1,1,2,2
3,3-heptafluoropropane (HFC227c
_{a) (8) CH 2 =} C (CF 3) 2; hexafluoroisobutene _{(HFC1336) (9) C 3} H 2 F 4; tetrafluoro cyclopropane (C-234) (10) C 3 HF 5; pentafluoro cyclopropane (C-225) (11) C 4 H 3 F 5; pentafluorobutane cyclobutane (C-345) (12) C 4 H 2 F 6; hexafluoro cyclobutane (C-336) (13) C 4 HF 7 Heptafluorocyclobutane (C
-327) and the like.

Examples of the fluorinated carbon represented by (1b), (2b) and (3b) include (14) CF ₄ ; tetrafluoromethane (FC14) (15) C ₂ F ₆ ; hexafluoroethane (FC11).
6) (16) C ₃ F ₈ ; octafluoropropane (FC21
8) (17) C ₄ F ₈ ; octafluorocyclobutane (FC
_{-C318) (18) C 3 F} 6; hexafluoropropene (FC 21
6) etc. are mentioned.

Examples of the fluorinated chlorinated hydrocarbon represented by (1c) include (19) CHClF ₂ ; chlorodifluoromethane (HCF)
C22) (20) CHCl ₂ CF ₃ ; 1,1-dichloro-2,2
2-trifluoroethane _{(HCFC123) (21) CHClFCClF 2} ; 1,2- dichloro-1,
1,2-Trifluoroethane (HCFC123a) (22) CHF ₂ CCl ₂ F; 1,1-dichloro-1,
2,2-trifluoroethane _{(HCFC123b) (23) CHClFCF 3} ; 1- chloro -1,2,2,2
- tetrafluoroethane _{(HCFC124) (24) CHF 2} CClF 2; 1- chloro -1, 1,
2-tetrafluoroethane (HCFC124a) and the like can be mentioned.

Fluorinated hydrocarbons represented by (1a), (2a) and (3a), fluorinated carbons represented by (1b), (2b) and (3b), and fluorinated represented by (1c). Extinguishing agents containing at least two members of the group consisting of chlorinated hydrocarbons include (1a), (2a) and (3a), (1b)
It may contain two or more kinds selected from each single group represented by (2b) and (3b) or (1c).

When the compounds represented by (1a), (2a) and (3a), the compounds represented by (1b), (2b) and (3b) or the compound represented by (1c) are mixed respectively, The mixing ratio is arbitrary, but a preferable mixing composition is determined in consideration of vapor pressure, injection characteristics, boiling point and the like.

When the fire extinguishing agent of the present invention is composed of two kinds of halogenated hydrocarbons, preferable combinations are as follows.

That is, a preferable combination when two kinds of compounds represented by (1a), (2a) and (3a) are contained is (a) CHF ₃ ; CHF ₂ C with respect to trifluoromethane.
F ₃ ; pentafluoroethane, (b) CHF ₃ ; CF ₃ CH for trifluoromethane
FCF ₃ ; 1,1,1,2,3,3,3-heptafluoropropane, (c) CHF ₂ CF ₃ ; pentafluoroethane and CHF
₂ CF ₂ CF ₃ ; 1,1,1,2,2,3,3-heptafluoropropane, (d) CF ₃ CHFCF ₃ ; 1,1,1,2,3,3,3
3-heptafluoropropane and CHF ₂ CF ₂ CF ₃ ;
1,1,1,2,2,3,3-heptafluoropropane, (e) CHF ₂ CF ₃ ; pentafluoroethane and CF ₃
CHFCF ₃ ; 1,1,1,2,3,3,3-heptafluoropropane, (f) CHF ₃ ; trifluoromethane and CHF ₂ CF ₂
CF ₃ ; a combination of 1,1,1,2,2,3,3-heptafluoropropane.

A preferred combination of the two compounds represented by (1b), (2b) and (3b) is (g) CF ₄ ; tetrafluoromethane and C ₄ F ₈ ; octafluorocyclobutane. is there.

A preferred combination of the two compounds represented by (1c) is (h) CHClF ₂ ; chlorodifluoromethane and CHClF
CF ₃ ; 1-chloro-1,2,2,2-tetrafluoroethane and (i) CHClF ₂ ; chlorodifluoromethane and CHCl ₂
CF _3; a combination of 1,1-dichloro-2,2,2-trifluoroethane.

A preferable combination of the compounds represented by (1a), (2a) and (3a) and the compounds represented by (1b), (2b) and (3b) respectively is (j) CF ₃ CHFCF ₃ ; 1,1,1,2,3,3
3-heptafluoropropane and CF _4; a combination of octafluorocyclobutane; tetrafluoromethane and (k) CHF _3; trifluoromethane and C ₄ F _8.

A preferable combination of the compounds represented by (1a), (2a) and (3a) and the compound represented by (1c) is (1) CF ₃ CHFCF ₃ ; , 1, 2, 3, 3,
3-heptafluoropropane and CHClF ₂ ; chlorodifluoromethane and (m) CHF ₂ CF ₃ ; pentafluoroethane and CHCl
₂ CF ₃ ; a combination of 1,1-dichloro-2,2,2-trifluoroethane.

A preferable combination of the compounds represented by (1b), (2b) and (3b) and the compound represented by (1c) is (n) CF ₄ ; tetrafluoromethane and CHCl 2. ₂ C
F ₃ ; 1,1-dichloro-2,2,2-trifluoroethane and (o) C ₄ F ₈ ; octafluoropropane and CHClFC
F ₃ ; A combination of 1-chloro-1,2,2,2-tetrafluoroethane.

The compounding ratio of these 15 types of suitable combinations of fire extinguishing agents is preferably 95 to 5 mol% of one compound and 5 to 95 mol% of the other compound.

The fire extinguishing agent of the present invention may include, for example, one or more gaseous propellants that promote the release of the extinguishing agent from the fire extinguisher. Examples of such propellants include nitrogen and carbon dioxide.

[0026]

The fire extinguisher of the present invention can provide a safe fire extinguisher having a fire extinguishing performance equivalent to that of conventional fire extinguishing agents, a small ozone depletion potential, and no adverse effect on the global environment.

[0027]

EXAMPLES Examples and comparative examples will be shown below to further clarify the features of the present invention.

[0028]

Example 1 For the purpose of evaluating the extinguishing performance of the extinguishing agent of the present invention, the extinguishing agent concentration of the present invention and the comparative product were measured by the cup burner method for the extinguishing agent concentration (Fire Defense Research Institute Report No. 57). (March 1984) page 4).

In the measurement, n-heptane was used as a fuel, air was supplied at a flow rate of 15 l / min, and the extinguishant was gradually added to measure the extinguishant concentration when the flame disappeared.

The measurement results of the extinction concentration are shown in Table 1 below.

[0031]

[Table 1]

CF, which is a regulated CFC in the category in Table 1,
R502 containing C115 and carbon dioxide were measured as comparative examples.

Further, the mixture (HCFC12
4: FC-C318 = 66: 34) shows the composition at the time of azeotropic distillation.

From the results shown in Table 1, it became clear that the fire extinguishing agent of the present invention has excellent fire extinguishing properties.

[0035]

[Example 2] A fire extinguishing test using one second model of A fire was carried out in accordance with the Ministerial Ordinance that establishes the technical standard of the fire extinguisher, which was established based on the provisions of Article 21-2, Paragraph 2 of the Fire Service Act. did.

For the above-mentioned fire, the time until the extinguishing agent extinguished by extinguishing the extinguishing agent pressurized alone with 8 kg / cm ² G of nitrogen and extinguishing the extinguishing agent and the amount of the extinguishing agent required for that were measured as the release amount. ..

The test results are shown in Table 2.

[0038]Table 2 Extinguishing agent release amount Fire extinguishing time (G) (seconds) HFC23 1770 14.2 HFC134 1660 13.3 HFC134a 1620 12.9 HFC125 1490 11.9 HFC236ea 1370 11.0 HFiB 1280 10.2 HFC227ea 1290 10.3 FC14 2000 16.0 FC218 1300 810C18. .5 HFC23 / 125 (25/75 mol%) 1530 12.2 (50/50 mol%) 1570 12.6 (75/25 mol%) 1690 13.5 HFC23 / 227ea (25/75 mol%) 1360 10.9 (50 / 50mol%) 1430 11.4 (75 / 25mol%) 1640 13.1 HFC125 / 227ea (25 / 75mol%) 1300 10.4 (50 / 50mol%) 1340 10.7 (75 / 25mol%) 1400 11.2 HFC227ca 1260 10.2 HFC23 / 227ca (50 / 50mol%) 1450 11.3 HFC125 / 227ca (50 / 50mol%) 1340 10.6 HFC227ea / 227ca(50/50 mol%) 1270 10.2 From the results shown in Table 2, the fire extinguishing agent of the present invention is effective against the above A fire.
It was confirmed that it has excellent fire extinguishing properties.

[0039]

[Example 3] A second fire extinguishing test for a B fire was carried out in accordance with a ministerial ordinance defining the technical standards of the fire extinguisher, which was established based on the provisions of Article 21-2, Paragraph 2 of the Fire Service Act.

8 for a B fire with a burning surface area of 0.2 m ^2.
The time taken to extinguish a single or mixed extinguishant pressurized with nitrogen of kg / cm ² G and extinguishing the fire, and the amount of the extinguishant required for the extinguishing agent were measured as the amount released.

The test results are shown in Table 3.

[0042]Table 3 Extinguishing agent release amount Fire extinguishing time (G) (seconds) HFC23 440 3.5 HFC134 420 3.4 HFC134a 400 3.3 HFC125 370 3.0 HFC236ea 340 2.7 HFiB 320 2.6 HFC227ea 320 2.6 FC14 500 4.0 FC218 320 320 FC-C318 330 2 .7 HFC23 / 125 (25/75 mol%) 380 3.0 (50/50 mol%) 390 3.1 (75/25 mol%) 410 3.3 HFC23 / 227ea (25/75 mol%) 340 2.7 (50 / 50 mol%) 360 3.0 (75/25 mol%) 400 3.3 HFC125 / 227ea (25/75 mol%) 320 2.6 (50/50 mol%) 330 2.7 (75/25 mol%) 350 2. 8 HFC227ca 320 2.6 HFC23 / 227ca (50/50 mol%) 380 3.0 HFC125 / 227ca (50/50 mol%) 340 2.8 HFC227ea / 227ca (50/50 mol%) 320 2.6 FC14 / FC-C318 (50 / 50 mol%) 400 3.2 HCFC22 / HCFC124 (50/50 mol%) 380 3.0 HCFC22 / HCFC123 (50/50 mol%) 370 3.0 HFC227ea / FC14 (50/50 mol%) 380 3.0 HFC23 / FC -C318 (50/50 mol%) 360 3.0 HFC227ea / HCFC22 (50/50 mol%) 370 3.0 HFC125 / HCFC123 (50/50 mol%) 360 3.0 FC14 / HCFC12 (50 / 50mol%) 400 3.2 FC218 / HCFC124(50/50 mol%) 330 2.8 From the results in Table 3, the fire extinguishing agent of the present invention is effective against the B fire.
It was confirmed that it has excellent fire extinguishing properties.

[0043]

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Satoshi Ide 1-1 Nishiichitsuya, Settsu City, Osaka Prefecture Daikin Industries, Ltd. Yodogawa Manufacturing Co., Ltd. (72) Inventor Hiroshi Momoda Nishiichitsuya 1-1, Settsu City, Osaka Prefecture Daikin Industries, Ltd. Yodogawa Manufacturing Co., Ltd.

Claims (8)

[Claims] 1. A chain or branched saturated halogenated hydrocarbon having (1) 1 to 4 carbon atoms and substituted with fluorine and / or chlorine, and (2) having 3 to 4 carbon atoms. A cyclic saturated halogenated hydrocarbon substituted with fluorine and (3) a chain or branched unsaturated halogen having 3 to 4 carbon atoms and having one fluorine-substituted double bond A halogenated carbon containing at least one selected from the group consisting of hydrocarbons, and in (1), (2) and (3), the number of hydrogen atoms and the number of chlorine atoms are always equal to or less than the number of carbon atoms. Extinguishing media containing at least one hydrogen. 2. (1a) a chain or branched saturated fluorinated hydrocarbon having 1 to 4 carbon atoms, which is substituted with fluorine and the number of hydrogen atoms is always less than or equal to carbon atoms, (2a) Cyclic saturated fluorinated hydrocarbons having 3 to 4 carbon atoms and substituted with fluorine and having a hydrogen atom number always smaller than that of carbon atoms, and (3a) having 3 to 4 carbon atoms and substituted with fluorine. The compound according to claim 1, which has at least one selected from the group consisting of chain or branched unsaturated fluorinated hydrocarbons having one double bond and having a hydrogen atom number always smaller than the carbon atom number. Extinguishing media. 3. (1b) a chain or branched saturated fluorinated carbon having 1 to 4 carbon atoms, (2b) a cyclic saturated fluorinated carbon having 3 to 4 carbon atoms, and (3b) carbon number. 3-4
At least one selected from the group consisting of chain- or branched-chain unsaturated fluorinated carbons having one and one double bond
The fire extinguisher according to claim 1, comprising a seed. 4. (1c) a saturated chain or branched chain having 1 to 3 carbon atoms, substituted by fluorine and chlorine, and the number of hydrogen atoms and the number of chlorine atoms are always less than or equal to carbon atoms, respectively. The fire extinguisher according to claim 1, which comprises a fluorinated chlorinated hydrocarbon. 5. A fluorinated hydrocarbon represented by (1a), (2a) and (3a), a fluorinated carbon represented by (1b), (2b) and (3b), and (1c). The fire extinguisher according to claim 1, comprising at least two members selected from the group consisting of fluorinated chlorinated hydrocarbons. 6. Fluorinated hydrocarbons represented by (1a), (2a) and (3a) are CHF ₃ ; trifluoromethane, CHF ₂ CHF ₂ ; 1,1,2,2-tetrafluoroethane, CH ₂ FCF ₃ ; 1,1,1,2-tetrafluoroethane, CHF ₂ CF ₃ ; pentafluoroethane, CHF ₂ CHFCF ₃ ; 1,1,1,2,3,3-hexafluoropropane, CF ₃ CHFCF ₃ ; 1,1,1,2,3,3,3-heptafluoropropane, CHF ₂ CF ₂ CF ₃ ; 1,1,1,2,2,3,3-
_{Heptafluoropropane, CH 2 = C (CF 3} ) 2; hexafluoroisobutene, C ₃ H ₂ F _4; tetrafluoro cyclopropane, C ₃ HF _5; pentafluoropropane cyclopropane, C ₄ H ₃ F _5; pentafluoro-cyclobutane , C ₄ H ₂ F ₆ ; hexafluorocyclobutane and C ₄ HF ₇ ; heptafluorocyclobutane, wherein the fluorinated carbon represented by (1b), (2b) and (3b) is CF ₄ Tetrafluoromethane, C ₂ F ₆ ; hexafluoroethane, C ₃ F ₈ ; octafluoropropane, C ₄ F ₈ ; octafluorocyclobutane and C ₃ F ₆ , at least one of hexafluoropropene, and The fluorinated chlorinated hydrocarbon represented by (1c) is CHClF ₂ ; chlorodifluoromethane, CHC l ₂ CF ₃ ; 1,1-dichloro-2,2,2-trifluoroethane, CHClFCClF ₂ ; 1,2-dichloro-1,1,2-trifluoroethane, CHF ₂ CCl ₂ F; 1,1- dichloro-1,2,2-trifluoroethane, CHClFCF _3; 1- chloro-1,2,2,2-tetrafluoroethane and CHF ₂ CClF _2; 1- chloro-1,1,2,2-tetrafluoroethane The fire extinguisher according to claim 5, which is at least one kind of ethane. 7. Fluorinated hydrocarbons represented by (1a), (2a) and (3a) are CHF ₃ ; trifluoromethane, CHF ₂ CF ₃ ; pentafluoroethane, CF ₃ CHFCF ₃ ; 1,1,1 , 2,3,3,3-heptafluoropropane, CHF ₂ CF ₂ CF ₃ ; 1,1,1,2,2,3,3-
At least one kind of heptafluoropropane, wherein the fluorinated carbon represented by (1b), (2b) and (3b) is CF ₄ ; tetrafluoromethane, C ₃ F ₈ ; octafluoropropane and C ₄ F ₈ ; at least one of octafluorocyclobutane
And a fluorinated chlorinated hydrocarbon represented by (1c) is CHClF ₂ ; chlorodifluoromethane, CHCl ₂ CF ₃ ; 1,1-dichloro-2,2,2-trifluoroethane, CHClFCF ₃ ; 1-chloro-1,2,2,2-tetrafluoroethane and CHF ₂ CClF ₂ ; at least one of 1-chloro-1,1,2,2-tetrafluoroethane. Extinguishing media listed. 8. (a) CHF ₃ ; trifluoromethane and C
HF ₂ CF ₃ ; pentafluoroethane, (b) CHF ₃ ; trifluoromethane and CF ₃ CHFC
F _{3; 1,1,1,2,3,3,3-heptafluoropropane, (c) CHF 2 CF 3} ; pentafluoroethane and CHF
₂ CF ₂ CF ₃ ; 1,1,1,2,2,3,3-heptafluoropropane, (d) CF ₃ CHFCF ₃ ; 1,1,1,2,3,3,3
3-heptafluoropropane and CHF ₂ CF ₂ CF ₃ ;
1,1,1,2,2,3,3-heptafluoropropane, (e) CHF ₂ CF ₃ ; pentafluoroethane and CF ₃
CHFCF ₃ ; 1,1,1,2,3,3,3-heptafluoropropane, (f) CHF ₃ ; trifluoromethane and CHF ₂ CF ₂
CF _3; 1,1,1,2,2,3,3-heptafluoropropane, (g) CF _4; tetrafluoromethane and C ₄ F _8; octafluorocyclobutane, (h) CHClF _2; and chlorodifluoromethane CHClF
CF ₃ ; 1-chloro-1,2,2,2-tetrafluoroethane (i) CHClF ₂ ; chlorodifluoromethane and CHCl ₂
CF ₃ ; 1,1-dichloro-2,2,2-trifluoroethane, (j) CF ₃ CHFCF ₃ ; 1,1,1,2,3,3
3-heptafluoropropane and CF ₄ ; tetrafluoromethane, (k) CHF ₃ ; trifluoromethane and C ₄ F ₈ ; octafluorocyclobutane (l) CF ₃ CHFCF ₃ ; 1, 1, 1, 2, _{3, 3} ,
3-heptafluoropropane and CHClF ₂ ; chlorodifluoromethane, (m) CHF ₂ CF ₃ ; pentafluoroethane and CHCl
₂ CF ₃ ; 1,1-dichloro-2,2,2-trifluoroethane, (n) CF ₄ ; tetrafluoromethane and CHCl ₂ C
F ₃ ; 1,1-dichloro-2,2,2-trifluoroethane and (o) C ₄ F ₈ ; octafluoropropane and CHClFC
The fire extinguisher according to claim 6, which is one of the group consisting of F ₃ ; 1-chloro-1,2,2,2-tetrafluoroethane.