JPS5838571A - Fire fighting agent - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fire extinguishing foam containing a novel fluorine-containing surfactant, a fluorine-containing aminosulfonate, and a fluorine-containing quaternary ammonium salt.

Some fluorosurfactants significantly lower the surface tension of water and may form an aqueous film on the surface of water-insoluble flammable solvents such as gasoline. A fire extinguishing agent effective for preventing re-ignition of oil fires utilizing this property has already been proposed in Japanese Patent Publication No. 40-20080.

However, these known fluorine-containing surfactants having water film-forming properties are not foam-stable hb+ and have the defect that the foam is easily destroyed by flame or heat. Attempts have also been made to improve this defect by adding foam stabilizers.

The viscosity effect is not sufficient, and if added in a large enough amount to produce the effect, the viscosity will increase significantly, making it impractical.

Furthermore, known fluorine-based surfactants which have excellent foam stability do not have sufficient ability to lower interfacial tension and are inferior in water film forming properties.

To solve this problem, it has been proposed to add a hydrocarbon surfactant to a fluorosurfactant to mainly lower the interfacial tension between oil and water and improve water film formation (for example, (Refer to the specification of Publication No. 4B-25161).

However, when a hydrocarbon surfactant is mixed, the lipophilicity of the fire extinguishing foam increases compared to K, which promotes the intrusion of combustion oil vapor into the foam, resulting in a decrease in the oil resistance or solubility of the foam.

This is a particularly significant drawback when extinguishing fires involving highly volatile flammable solvents such as gasoline.

The present inventors believe that hydrocarbon surfactants should not be used together (
, has sufficient water film formation properties and excellent foam stability.
As a result of intensive research into fluorinated surfactants with heat resistance and solubility resistance, we have developed a new fluorinated surfactant, fluorinated aminosulfonate, which is represented by the following general formula: A mixture of a novel fluorinated surfactant, a fluorinated quaternary ammonium salt, and a fluorinated compound shown in general fields, which has well-balanced properties of each 1 [41] necessary for fire extinguishing, and is a foam extinguishing agent for oil fires. The present invention was completed based on the discovery that it is optimal as a surfactant for fire extinguishing agents.

That is, the present invention is based on the following general formula % () () [However, in the formula, Rf, R〆 and Rf' may be the same or different, and are fluorinated aliphatic groups having 3 to 16 carbon atoms. Preferred examples of such groups include per7o-loalkyl groups and per70-roalkenyl groups, which may be linear, monobranched, or a combination thereof.

2 and 2' may be the same or different, and are a divalent linking group containing a sulfamide group or a carboxamide group.
O,NR,-1-CONB,-,-(CH,)j-80
,NR,-1-(CH,)j-CONB,-,-o-c
)-80,NR,-, Matach-oOcoNRt-1 (wherein R1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group, and j represents an integer of 2 to 6) are preferred.

Q, and Q, / may be the same or different, and are a divalent aliphatic group having 2 to 12 carbon atoms, an aliphatic hydrocarbon group substituted with a hydroxy group, an aromatic hydrocarbon group, or a combination thereof. -(CH,), -(where m is 2~
represents an integer of 12) s (CHt)m, O(C
ut)m, (however, "1s"! represents an integer from 1 to 6), -CH, CH(OH)OR, -, or -C
Groups such as H, -(]-cH, - and the like are preferred.

Tortoise and H, / may be the same or different, and are hydrogen atoms.

An alkyl group having 1 to 6 carbon atoms, or -(OH, CH, 0
)iH (provided that the bracket represents an integer from 1 to 20).

Q, and Q, / may be the same or different, and are a divalent aliphatic group having 2 to 12 carbon atoms, an aliphatic hydrocarbon group substituted with a hydroxy group, an aromatic hydrocarbon group, or a combination thereof. -(OHri11 (however, n is 2
-CM, 0H(OH)CHt
Groups such as -1, -OH, and -Qp are preferred.

Ql is a divalent aliphatic group having 1 to 12 carbon atoms, an aliphatic hydrocarbon group substituted with a hydroxy group, an aromatic hydrocarbon group, or a combination thereof. (represents an integer from 1 to 12), -CH, CH(OH)
CM, -1 or -cz-/:5- and the like are preferred.

M, M' and W may be the same or different and are hydrogen atoms or inorganic or organic cations, ◆ Li, Na, Ca%Mg, ("N(u)q(
R) r) (However, R is an alkyl group or hydroxyethyl group having 1 to 4 carbon atoms, q and r are integers of 0 to 4, and q
+y xx 4), or 0=
◆It's sowful.

X is an inorganic or organic anion such as OH-, C1-%Br-, l-1CI04%1S04.
cH, 5o4-1No, '', CH, COO-1 or a phosphoric acid group are preferred.

Wit-Z'(CH,CH,0)jH,-Z'Q7NR
jR7 (however, z# is a divalent linking group containing a sulfamide group or a carboand group 80.NR, '+, -CON
R knee, -(CM,) j'-8o, NRI'-.

-(cut)/-CONR,'-1-oQ 80. N.R.
,'-,*riGtbeto<]←C0NR,'-(However, R□
' is preferably a water bulk atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group (11 represents an integer of 2 to 6), j is an integer of 0 to 5, and QfM is an integer of 2 to 1 carbon atoms.
2 divalent aliphatic group, hydroxy group-substituted aliphatic hydrocarbon group, aromatic hydrocarbon group, or a combination thereof=(CHt)mI-(''However, 1'' is 2 to 1
represents an integer of 2), -(cH,)mr-〇-(cut
) mj - (where mr and i represent integers from 1 to 6).

-CH,CH(OH)CH,+, also it -CH,→
Groups such as (]-〇H, -, etc. are preferred.

The material and Br may be the same or different, and may be a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or -(cHaCH,O
) j represents H), or -(C4)ky (however, k
is an integer from 1 to 6, and Y is represented by →■ or -8H). Heat resistance and flame resistance 1! characterized by containing a fluorine-containing aminosulfonate, a fluorine-containing quaternary ammonium salt, and a fluorine-containing compound shown in ]! KK is summarized as an excellent fire extinguishing foam.

Specific examples of the fluorine-containing a≧nosulfonate, fluorine-containing quaternary ammonium salt and fluorine-containing compound used in the present invention are shown in the following (A1 section, (81), (0 section), respectively.

(A) OH OH (B) (0 C, F, So, NH.

C,F,,80. NHCH.

e, Fl, C0N1! OR,CI(,OHC,Fl,8
0. NH(OH,), NHIC@Fts 80tNH(
0%) sNHc horse C,? ,,C0NH(CHI)mN(
CtHs)mC,F,,80. N(CH,)OH,CH
(OH)Cl, N(OH,CH,OH).

C@Flg 80mN (CH1CH20H) (Cu
t)sN (CHs)tC,Fl,CHI(!H!80
．． N(OR,), Nu(CHI)C,F,, -o(Σ
8(%N(CHt)IN(CtHs)tC,F,, -o
<Σ5ONCHt Q CH*NH*Cge,,C0NH
(C bird)s O(CHt)sNH(Cut CHt
0H)C,F,,80. Nu((H,),N) The fluorine-containing aminosulfonate according to the present invention can be produced by various methods, but preferred methods include the following, for example.

Production method 1: Noralkane sulfonate, halohydroxyalkane sulfonate, haloarylene sulfonate,
Alternatively, a method for producing the fluorine-containing aminosulfonate shown in Ichimonna (■) in high yield by reacting sultone in the presence or absence of an alkali.

RINH to υ! A method for producing a fluorine-containing aminosulfonate according to the fluorine-containing hydroxyamine production method 1.

annosulfonic acid HRINQ, 80. A method for producing a fluorine-containing adenosulfonite by reacting H.

The fluorine-containing quaternary ammonium salt according to the present invention can be produced by various methods, but a preferred production method is ntZQx
NHRl, RfZQINR8Q180sNm or Rf
By reacting the compound represented by ZQ, NR, Q; AM' with haq alkanesulfonate, halohydroxyalkanesulfonate, haloarylene sulfonate or sultone in the presence or absence of an alkali, the general formula (I
) is the method for producing a fluorine-containing quaternary ammonium salt.

In the surfactant mixture according to the present invention, the mixing ratio of fluorine-containing quaternary ammonium salts such as Ichimonana I) fluorine-containing aminosulfonate and the like::a) is usually 50:1 to 50:1 by weight.
1:50 preferably in the range of 10:1 to 1:10,
In this two-component mixture, the mixing ratio of the fluorine-containing compound of general formula (to) is usually in the range of 10:1 to 1:2, preferably 50:1 to 1:1, in terms of weight ratio.

The fluorine-containing compound of the general formula is water-insoluble or has low water solubility in the neutral pH region, and therefore, even if added at a mixing ratio exceeding the above-mentioned mixing ratio, it will not be compatible with the fluorine-containing compound and will instead impair the foam 4I properties. If the amount added is less than this mixing ratio, the synergistic effect will be reduced.

According to the findings of the present inventors, the surfactant mixture related to the present FIA behaves as an amphoteric surfactant, and has the highest interfacial tension lowering and foam stabilizing effects in the medium to slightly alkaline pH range. It was found that the performance of

The extinguishing agent is preferably used in a neutral pH range from the viewpoint of safety to the human body, living things, etc., corrosivity of storage containers, etc., and from this point of view as well, the usefulness of the surfactant mixture can be seen.

Furthermore, as mentioned above, since the surfactant mixture behaves in a zwitterionic manner in the neutral pH region, it has good compatibility with any ionic surfactant, including anionic, cationic, nonionic, and amphoteric surfactants. It has also been found that it has the effect of synergistically improving foam properties such as foam stability, heat resistance, and solubility resistance. This property makes it a fluorine-based surfactant.

1 to 100 weight of #surfactant mixture in the surfactant component contained in a fire extinguishing agent such as a fire extinguishing agent such as a fluorine-free hydrocarbon surfactant or a mixture of both, or a protein foam fire extinguishing agent. %, preferably 10 to 100% by weight, the foam properties can be improved.

(α01
It has been found that when it is contained in an amount of up to 5% by coul, the fluidity, oil resistance, heat resistance and solubility of the foam are significantly improved, making it suitable as a surfactant for fluoroprotein foam fire extinguishing agents.

When using the surfactant mixture according to the invention as a water film-forming fire extinguishing foam, the amount added can be varied within a wide range depending on the required performance. Generally 1 to 100% by weight of the total amount of surfactant in the extinguishing agent, preferably 10 to 100%
The weight is within the range.

If the amount added is less than this range, the effect on water film formation properties or foam 4I injection will be small.

In addition to the surfactant component and water, various additives may be added to the fire extinguisher of the present invention, if necessary.

Additives include additional foam stabilizers, freezing point depressants, rust inhibitors, buffers, and the like.

Additional foam stabilizers are mainly added to adjust the foaming ratio or tension, such as polyethylene glycol.

Polyvinyl alcohol, polyvinyl pyrrolid/, carboxymethylcellulose, gum arabic, sodium alginate.

Examples include polypyrene glycol, polyvinyl resin, etc.

Freezing point depressants include ethylene glycol, propylene glycol, cellosolves (ethyl cellosolve, butyl cellosolve), calpitols (ethyljarbitol,
butylcarpitol), lower alcohols (isopropyl alcohol, butanol), and urea.

As the rust preventive agent and the softening agent, various types known in the industry can be used.

The fire extinguishing foams of this invention are applied in a known manner, namely by adding or admixing air, carbon dioxide, nitrogen, low boiling fluorocarbons such as difluorodichloromethane, or other suitable non-flammable gases.

The fire extinguishing foam of the present invention can be diluted in advance with water (e.g., fire extinguishing water, underground water, tap water, or seawater) to a working concentration and then stored and applied. It is used by diluting it with water.

It is stored as a concentrated undiluted solution, and when used, the dilution is adjusted in the usual way, for example, by sucking the concentrated undiluted solution into a water stream on the way to a fire extinguisher or foam nozzle, and then blowing in or mixing with a nonflammable gas such as air. It can also be applied by a method of foaming K and emitting or sending the foam from above or below the large surface.

The extinguishing agent of the present invention can be used in combination with powder extinguishing agents, protein foam extinguishing agents, foam extinguishing agents for wood fires, etc. containing sodium bicarbonate, potassium bicarbonate, magnesium bicarbonate, ammonium sulfate, ammonium phosphate, calcium carbonate, etc. I can do it.

Next, the present invention will be explained in more detail with reference to examples. In the following examples, all numbers indicate the amount of electricity in %.

Example 1 C,F,,80. NH, 2% polyethylene glycol (average molecular weight 4.Goo)
10% Butyl Calpitol
20% water
63% Example 2 C,F,,80. N (0%), N% 80. Na
2% C, F, 80. NH(CH,), NH,2
% polyethylene glyco-AI (average molecular weight 4,000)
10% Butyl Calpitol
20% water
65% 900 d of each of the compositions of Examples 1 and 2 was diluted with water to make 3 ml, filled in a small fire extinguisher for water-forming foam fire extinguishing agent (type 3J fire extinguisher approved by the Japan Fire Protection Certification Association), and heated to a nitrogen pressure of 10 A fire extinguishing experiment was carried out using mono-hebutane as fuel and a combustion area of t2 m'' (B-6 scale) with a discharge rate of 6 j /ls'' and a discharge rate of 6 j /win. The results are shown in Table 1.

The fuel was adjusted to 30°C and the extinguishing agent to 20°C, then ignited, and the fire was extinguished using a pre-combustion 1 minute diameter small fire extinguisher.

Comparative Example 1 is an experiment conducted by diluting a commercially available water-forming fire extinguishing foam containing fluorosurfactant (3% shop) with water to a factor of 353 ($1) Heat resistance test: After irradiating the entire amount of extinguishing agent Grave of 20114-
A combustion dish containing hebutane with an inner diameter of 178 mm and a depth of 5 mm is placed in the center of the bubble surface, and ignited one minute after the end of the emission.

It is confirmed whether or not the flame-hebutane in the combustion dish ignites and spreads until it burns out.

(*2) Paper seal test: The foam surface that has passed the heat resistance test is left for a while, and when 5 minutes have passed after the end of the radiation, the ignition rod is ignited and the flame is brought close enough to touch the foam surface and moved over the entire surface along the foam surface. Observe whether it ignites or not.

Table 2 shows the measurement of quick solubility in order to examine the heat resistance of water film formation. The 343-fold diluted solutions of Example 1.2 and Comparative Example 1 were used as test solutions.

Table 2 (Main black) Spreading time: 2011 d of cyclohexane was placed in a Petri dish with an inner diameter of 85 M, and the test w1α05 was conducted at 25°C.
mg is added to the center surface of the oil surface, and the time until the water film has completely spread over the entire surface is measured.

($4) Rapid solubility: After the above test, αQ5+wj is further added and after 1 minute, a 20 m flame is placed 20 cm above the center of the liquid level and the time until ignition is measured.

Table 3 shows the results of extinguishing experiments based on the method described in Ministry of Home Affairs Ordinance No. 26.

That is, the fuel was n-hebutane, a fire model with a combustion area of 2♂ (B-20 scale) was used, and the pre-combustion was set to be 1 minute. Example 1.
2 and Comparative Example 1 with fire extinguishing water.
Fill a pressurized tank with 100 ml of the diluted solution, set the nitrogen pressure to 1011/IK', the discharge rate to 101/rmin, and the total discharge time to 5 minutes, and extinguish the fire by foaming with a standard foaming nozzle for testing water-forming foam fire extinguishing agents. We conducted an experiment.

(*5) Paper seal test: Use a torch for 15 minutes after irradiation (bring the flame close to the foam surface and observe whether it ignites or not.

(*6) Heat resistance test: 15 minutes after radiation ends, oil is exposed in the center of the foam surface to form a square of 151 sides, and a patent application is applied to characterize the burning area 5 minutes after ignition. Kawamura Physical and Chemical Research Institute Foundation

Claims (1)

[Claims] t General formula % Formula % () [However, in the formula, Rf is a fluorinated aliphatic group having 3 to 16 carbon atoms, and 2 is a divalent linking group containing a sulfamide group or a carboxamide group. Yes, Ql and Q! is a divalent aliphatic group having a vertical prime number of 2 to 12, an aliphatic hydrocarbon group substituted with a hydroxy group, an aromatic hydrocarbon group, or a combination thereof;
is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or -(CH
leH,0) iH (where l represents an integer of 1 to 20), and V is a hydrogen atom or an inorganic or organic cation. ] A fluorine-containing amino sulfonate represented by [wherein Rf' is a fluorinated aliphatic group having 3 to 16 carbon atoms, and 2' is a divalent linking group containing a sulfamide group or a carboand group. q: and q' are a divalent aliphatic group having 2 to 12 carbon atoms, an aliphatic hydrocarbon group substituted with a hydroxyl group, an aromatic hydrocarbon group, or a combination thereof. ,Q,
is a divalent aliphatic group having 1 to 12 carbon atoms, an aliphatic hydrocarbon group substituted with a hydroxy group, an aromatic hydrocarbon group, or a combination thereof. - hydrogen atom, alkyl group having 1 to 6 carbon atoms, or -(
CH, CHffiO)iH (where 1 represents an integer from 1 to 20), and A is -SO or -COO. M' and M' are hydrogen atoms or inorganic or organic cations, and X is an inorganic or organic anion. ] and a fluorine-containing quaternary ammonium salt represented by the general formula % formula % ( ) [wherein Rf' is a fluorinated aliphatic group having 3 to 16 carbon atoms, Wit-Z'(CHICHtO)jHl- 2tv 侃;R
*' (However, LZ' is a divalent linking group j containing a hasulfamide group or a carboxamido group, and 91' is a divalent aliphatic group having 2 to 12 carbon atoms, an aliphatic group substituted with a hydroxy group. A hydrocarbon group, an aromatic hydrocarbon group or a combination thereof, Rr and R- may be the same or different, and a hydrogen atom, an alkyl group having 1-6 carbon atoms or -(CH, CM, 0) jH). Also, it −(CH,)kY (however, niha1~6(1
) integer, Y represents -OH or -8H) A fire extinguishing foam with excellent heat resistance and solubility resistance, characterized by containing a fluorine-containing compound represented by the following. 2. Rf, R〆 and nf may be the same or different, and the number of carbon atoms! The fire extinguishing foam according to claim 1, which is a perfluoroalkyl group of S to 16. (5) z, z' and zl may be the same or different. -(IO, NR, +, -CONB, -11-(CH,
)jH0,NR,-1-(CHI)JCON%,-
o (koto80.NRself or 10→ko) -CONR, -
(However, the bird represents a hydrogen atom, an alkyl group or hydroxyalkyl group having 1 to 6 carbon atoms, and j represents an integer of 2 to 6.)
The fire extinguishing foam according to claim 1 or 2. 4 Qq: and Qτ may be the same or different. -(CH,),; (where m represents an integer from 2 to 12), (CHz)m, -〇 (CHt --(however, ml
%m@represents an integer from 1 to 6), -CH,CH(OH
) Ca-1 or -CH, ->5CH, - The fire extinguishing foam according to claim 1.2 or 3. 5Q! and Q, / may be the same or different, -
(CH,)n- (however, the crane represents an integer from 12 to 12)
, -CH,CH(OH)CH,-. or (■=-0-) Claims 1 and 2.3
Or the fire extinguishing foam described in Section 4. &Q, is -(ca,)r (where p represents an integer from 1 to 12). -OH, C) I(OH)OH, -, *take-OR, @←
Claim 1.2, which is! 1.4 or 5. The fire extinguishing foam. χ M, M' and V'' may be the same or different (
, Ll". Na", K", Ca", Mg", (N(H)q
(R)r) (wherein R is an alkyl group having 1 to 4 carbon atoms or a hydroxyethyl group, q and r are integers of 0 to 4 and satisfy q+r=4) or 0- The fire extinguishing foam described in Section 1.2.3.4, 5 and 6. t x is ol', cP, are, Ie, ciop, 1
80. ”, 0 e e cH, go, , No, , C COO, or a phosphoric acid group Claim No. 1.2.5.4.5.6 or 7
Fire extinguishing foam as described in section. Negative The mixing ratio of the fluorine-containing aminosulfonate represented by the general formula (I) and the fluorine-containing quaternary ammonium salt represented by the general formula m is 50:1 to 1:50, preferably 10
:1 to 1:10 Claim No. 1.2.5.4
．． The fire extinguishing foam described in 5.6.7 or 8. 1a - Fluorine-containing anosulfonate shown by pattern hole ■)
The mixture of the fluorine-containing quaternary ammonium salt represented by the general formula (II) and the fluorine-containing compound represented by the general formula (to) is in a weight ratio of 1 no = 1 to 1:2, preferably 2.
Claim No. 1.2.3.4 which is 0:1 to 1:1
．． The fire extinguishing foam according to item 5, 6.7.8 or 9. A mixture of a fluorine-containing annosulfonate represented by the general formula (1), a fluorine-containing quaternary ammonium salt represented by the general formula (m), and a fluorine-containing compound represented by the general formula (1) is added to the surfactant component. ~100% preferably 10~
Claims 1, 2.3.4, 5 containing 100%
．． 6.7.8.9 or the incendiary agent described in 10.