JPS5838570A - Aqueous 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 novel fluorinated surfactant, an aqueous fire extinguishing foam containing a fluorinated adenosulfone.Some fluorinated surfactants significantly reduce the surface tension of water. let me,
In some cases, an aqueous film can be formed on the surface of water-insoluble flammable solvents such as gasoline. A fire extinguishing agent that is effective in preventing oil fires from re-igniting has already been developed in the 1970s.
This is proposed in the specification of No.-20080.

However, these known fluorine-containing surfactants having water-forming properties do not have sufficient foam stability and have the defect that the foam is easily destroyed by flame or heat. Attempts have been made to improve this defect by adding a foam stabilizer, but the effect is still insufficient, and when added too often, the viscosity increases significantly, making it impractical. It cannot be offered to

In addition, known fluorosurfactants with excellent foam stability are:
On the other hand, the interfacial tension lowering ability is insufficient and the water film forming property is poor.

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, 48-23161).

However, mixing a hydrocarbon surfactant increases the lipophilicity of the fire extinguishing foam, which facilitates 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 serious deficiency when extinguishing fires involving highly volatile flammable solvents such as gasoline.

The present inventors have achieved sufficient water film-forming properties without using a hydrocarbon surfactant in combination, and excellent foam stability.
As a result of intensive research into heat-resistant and solubility-resistant 7-wire surfactant injection agents, we have discovered a fluorine-containing quaternary ammonium salt, which is a novel fluorine-based surfactant represented by the following general formula (I). It was discovered that the above-mentioned fluorine-containing fluorine-containing material has a good balance of properties necessary for extinguishing fires and is ideal as a surfactant for fire extinguishing agents such as fire extinguishing foam for oil fires. The present invention has been completed based on the discovery that water film forming properties, foam heat resistance, solubility resistance, etc. can be synergistically improved by blending a fluorine-containing compound represented by the general formula ω with a class ammonium salt.

[However, in the formula, Rf is a fluorinated aliphatic group having 3 to 16 carbon atoms, and examples of preferable examples of such groups include a bar-70-roalkyl group and a par-70-roalkenyl group; , or a combination of these.

2 is a divalent linking group containing a sulfamide or carboxamide group, -80,NR,-, -CONR,-, -(CH
,) j-80RNR, -1-OQCONR, - (where 8. represents a hydrogen atom, an alkyl group or hydroxyalkyl group having 1 to 6 carbon atoms, and I represents an integer of 2 to 6)
Groups such as the like are preferred.

QI is 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, and -(':Ht)sr
(However, m represents an integer from 2 to 12), (OH,
)ml O(Cut)my- (where m, , m represents an integer from 1 to 6), -〇H, CH(OH)CH,
-1 and groups such as Gt -CH, +CH, - are preferred.

R1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or -
(CH, CH, 0) IH (where lGl to 20F represents an integer).

(bit is 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 -(cut)■ (where n is 2 -CH,0H(OH
) CH, -1, tahar, cu, Q and other groups are preferred.

Q7 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 -<CZ>-; C
However, n kt represents an integer from 1 to 12), -〇 Bird CH
Groups such as (OH)OH, -1 or -cH,0 are preferred.

M and M' may be the same or different and represent a hydrogen atom or an inorganic or organic cation;
”, K”, Ca, Mg, NH4, [N(H)P
(However, B is an alkyl group or hydroxyethyl group having 1 to 4 carbon atoms, p and q are integers of 0 to 4, and p+q
or α+ is preferable.] e e e X is an inorganic or organic anion, and OH, Cj% B
y.

eoee I, CjO,)80. , CH, SO2, NO,
, 0H8Cooe or a phosphate group are preferred. ] An aqueous fire extinguishing foam with excellent heat resistance and solubility, characterized by containing a fluorine-containing quaternary ammonium salt represented by the formula % and the general formula % () [However, In the formula, R/ is a fluorinated aliphatic group having 3 to 16 carbon atoms, and among such groups, preferable examples are a)-70roalkyl group or perfluoroalkenyl group, and are linear or branched. (or a combination of these).

Wet-Z'(CHROH,O)J I(,-z'c4
:MR:R7i where 2' is a divalent linking group containing a sulfamide group or a carboand group, -80,NR,'-1
-coNnnie, -(CH,)II -80,NR,'
-1-(C horse)lI-coNnl-1-o-<ko)-8
0, NR7-1 again! 10→5coNa;-<where m' represents a hydrogen atom, an alkyl group or hydroxyalkyl group having 1 to 6 carbon atoms, or an integer from I'JI family 2 to 6)
etc., j is an integer of O to 5, 91' is a divalent aliphatic group having 2 to 12 carbon atoms, an aliphatic hydrocarbon group substituted with a hydroxy group, an aromatic hydrocarbon group, or The combination of these is -CCut)zt (where m' represents an integer from 2 to 12), -(CH, kite'-0-(C
I, ) m, '- (however, Ell, ', ml represents an integer from 1 to 6), -CH, CH(OH)CH, -1 or -
Groups such as cH, OCR, - are preferred, R1' and R7
may be the same or different, hydrogen atom, carbon number 1-6
1 representing an alkyl group or -(CM, CHRO)jH, or -(CH,)kY (where k is an integer of 1 to 6,
Y represents 10H or 18H). ] It can be summarized as an aqueous fire extinguishing foam with excellent heat resistance and solubility resistance, which is characterized by containing the fluorine-containing compound shown below.

Specific examples of the fluorine-containing quaternary ammonium salt and fluorine-containing compound used in the present invention are as follows.
1m1).

(BI C,F,,So,NH.

C, F□S false NHCH.

C, Fl, C0NHCH, CH, OH C,F,,80. Nu(CH,), NH.

C,F',,So,NH(CH,)INHcH.

C,F,,C0NH(CHtN(C*H*)*C,F
,,So,N(CH,)CI(,CH(OH)CH,N
(CM, CH, OH).

C,F,,5OIN(CH,CHtOH) (CH,)
sN(CHs)*C8F,,CH@CH@80gNCC
He)mNH(CHa)e,F,,C0NH(CH,
), O(OH,), NH(CH,cH,0H)C,F,
, 80. The fluorine-containing quaternary ammonium salt of NH(CHa,,NH*He) can be produced by various methods, but the preferred production method is RfZQ, NHR,, RfZQ, N
R, Q, 80. Na or RfZQINR,Q7AM
fluorine-containing quaternary ammonium represented by the general formula Examples include methods for producing salt.

According to the findings of the present inventors, the surface, interfacial tension lowering and foam stabilizing effects of the fluorine-containing quaternary ammonium salt of the present invention can exhibit high forging performance in a neutral to slightly alkaline pH range. discovered.

It is preferable to use fire extinguishers in a neutral or weakly alkaline pH range from the viewpoint of safety to the human body, living things, etc. and corrosiveness of storage containers.From this point of view, the usefulness of the fluorine-containing quaternary ammonium salt is is recognized.

In addition, as mentioned above, fluorine-containing quaternary ammonium salts behave in a zwitterionic manner in the neutral pH region, and therefore have 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 flame resistance. Due to this property, the surfactant component contained in fire extinguishing agents such as fluorine surfactants, fluorine-free hydrocarbon surfactants, or mixtures of both, or protein foam fire extinguishers, 1 to 100% by weight of fluorine-containing quaternary ammonium salt,
Foam properties can be improved by adding preferably 10 to 1001% by weight. In particular, when the fluorinated quaternary ammonium salt is added to the stock solution of the protein fire extinguishing foam, the fluidity, oil resistance, heat resistance, and flame resistance of the foam are significantly improved, resulting in a fluorinated protein fire extinguishing agent. It has been found that it is also suitable as a surfactant for commercial use.

As mentioned above, the fluorine-containing quaternary ammonium salt according to the present invention has the property of being well compatible with other surfactants and exhibiting a synergistic effect, but especially with the fluorine-containing compound shown by = m (m). The effect is remarkable.

In this case, the mixing ratio of the fluorine-containing quaternary ammonium salt and the fluorine-containing compound is usually in the range of 100:1 to 1:2, preferably 50:1 to 1:1, by weight.

- The fluorine-containing compounds published by Monnakan are water-insoluble or have low water solubility in the neutral pH range, so even if they are added at a mixing ratio higher than the above, they will not be compatible with each other, and will actually impair foam percentage. Moreover, if the amount added is less than this mixing ratio, the synergistic effect will be reduced.

When using the fluorine-containing quaternary ammonium salt or the mixture of the fluorine-containing quaternary ammonium salt and the fluorine-containing compound of the present invention as a water film-forming fire extinguishing agent, the required performance can be met. The amount added can be varied within a wide range depending on the requirements. Generally, the amount is in the range of 1 to 10 at%, preferably 10 to 100% by weight, based on the total amount of surfactants in the fire extinguishing agent. If the amount added is less than this range, the water film forming property or foam 4I properties will not be achieved and the effect will be small.

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

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

Additional foam stabilizers are mainly added to adjust the expansion ratio or tray screw, and examples include polyethylene glycol, polyvinyl alcohol, polyvinylpyridone, carboxymethyl cellulose, gum arabic, sodium alginate, polypropylene glycol, and polyvinyl resin. ,
and so on.

Freezing point depressants include ethylene glycol, propylene glycol, cellosolves (ethyl cellosolve, butyl cellosolve), carpitols (ethyl carpitol,
butylcarpitol), lower alcohols (isopropyl alcohol, butanol 0, or urea, etc.).

Various rust preventives and buffers known in the industry can be used.

The fire extinguishing foam of the present invention can be prepared by blowing air, carbon dioxide, nitrogen, low boiling fluorocarbons such as difluorodichloromethane or other suitable non-flammable gases, or
Applied by mixing.

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 stored as a concentrated stock solution that can be diluted with water, and when used, the dilution level is adjusted by the usual method, such as sucking the concentrated stock solution into a water stream on the way to a fire extinguisher or foam nozzle, and the dilution is adjusted by air. It can also be applied by blowing in or mixing a nonflammable gas such as, to form foam, and by radiating or sending the foam from above or below the surface.

The fire extinguishing agent of the present invention is a dry powder fire extinguishing agent, a protein foam fire extinguishing agent, which has five components such as soda carbonate, potassium bicarbonate, magnon bicarbonate, ammonium sulfate, ammonium phosphate, and calci carbonate.
Can be used in combination with foam extinguishing agents for wood fires, etc.

Next, the present invention will be explained in more detail with reference to Examples.

In the following examples, all % represents weight %, and other ratios also represent weight ratios. Examples 1 to 4 and Comparative Examples 1 to 2 Fluorine surfactant 12% polyethylene glycol (average molecular weight 4,000) 0.8%
Butyl calpitol 10% water
Composition 31 consisting of 98.0% was filled with a small fire extinguisher for water-forming foam fire extinguishing agent (Japan Fire Protection Certification Association type I!51 type fire extinguisher), and the nitrogen pressure was 1.
A fire extinguishing experiment was conducted using n-hebutane as fuel with a combustion area of 12" (B-6 scale) at a discharge rate of 0 kf/ffi" and a discharge amount of 617 ml.

The results are shown in Table 1.

The fuel was adjusted to 50°C and the extinguishing agent to 20°C, then ignited, and after 1 minute of pre-combustion, the fire was extinguished using a small fire extinguisher.

Comparative Example 2 is an experiment in which a commercial product (3% type) of a water-forming fire extinguishing foam containing a fluorosurfactant was diluted 353 times with water.

Ca1) Heat resistance test: n- of 2011/ after irradiating the entire amount of extinguishing agent
A combustion dish with an inner diameter of 178 mm and a depth of 5 mm containing hebutane is placed in the center of the bubble surface, and ignited one minute after the end of the radiation. It is confirmed whether or not the n-hebutane in the combustion dish ignites and spreads until it burns out.

(*2) Paper sill test: The foam surface that has passed the heat resistance test is further left to stand, and after 5 minutes have elapsed since the end of the emission, the flame is brought close to the ignition rod and moved to the extent that it covers the foam surface Km, and the flame is moved over the entire surface along the foam surface. Observe whether it ignites or not.

Example 5 CaFtm801N(CHs)aN(eHg)t
2% Butyl Calpitol
25% water
The surface tension of the aqueous solution obtained by diluting this 68% fire extinguishing foam stock solution 353 times with synthetic seawater is 16.
It was 7dyn/-.

Example 6 C・F, M2O, NHt2% CBFws 802NH (CHt ) mN (CHs)
100005% Butylcarpitol
25% polyethylene glycol-400010
%water
The surface length force of an aqueous solution obtained by diluting this 57% fire extinguishing foam stock solution 355 times with synthetic seawater was 16.2 dyn·/-.

Next, in Examples 5 and 60, fire extinguishing experiments were conducted using the fire extinguishing foam of the present invention and a conventional water-forming fire extinguishing foam (commercially available product) based on the method described in Ministry of Home Affairs Ordinance No. 26.

The fuel is n-hegetane, and the combustion area is 2 m" CB-2.
Pre-combustion was carried out for 1 minute using the fire model of 0). Dilute the extinguishing agent undiluted solution with fire extinguishing water to a factor of 35 to 3, and apply nitrogen pressure to 10 k.
The discharge rate was 5F/d, the discharge rate was 10 rpm, and the total discharge time was 5 minutes. The foam nozzle used was a standard foam nozzle for testing water-forming foam fire extinguishing agents.

Claims (1)

[Scope of Claims] 1 General formula [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 carboxamide group* Q+ s QH and Q is a divalent fatty acid base having 1 to 12 carbon atoms, an aliphatic hydrocarbon group substituted with a hydroxy group, an aromatic hydrocarbon group, or a combination thereof, and R1 is a hydrogen atom and the number of carbon atoms. 1 to 6 alkyl groups or -(
ca, cll, o) quantity H (however, 1 represents an integer of 1 to 2.0), A is -so or -COO, M and W are hydrogen atoms or inorganic or organic cations. and X is an inorganic or organic anion. ] An aqueous fire extinguishing foam with excellent heat resistance and solubility resistance, which is characterized by containing a fluorine-containing quaternary ammonium salt. 2. The fire extinguishing foam according to claim 1, wherein Rf is a perf c1μ alkyl group having 3'-=16 carbon atoms. 5 z is -so, N4-. -CONR,-,-(cut
) Iso, Ng, -1-(C bird)jCONg! -1-0
Q80. N station, or -<Kokari C0NR, - (however, -
The fire extinguishing foam according to claim 1 or 2, wherein 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. 4. The fire extinguishing foam according to claim 1.2 or 6, wherein Q is -(ca,)- (where m represents an integer of 2 to 12). s Q, is -(CH,)n- (represents an integer from 2 to 12), -CH, CH(OH)CH, -1 or -
The fire extinguishing foam according to claim 2.3 or 4, which is CH-0→. 6Q≦ is -(CHt)p- (where p represents an integer from 1 to 12), -CH, CH(OH)OH1-1f ii
-ca! Q “Q Certain% Scope of Claims No. 1.2.3.
The fire extinguishing foam according to item 4 or 5. 7 M is Li”, Na, ?, Clt+, Nito\sL
", [N(I()P(R)(1)") (where R is an alkyl group having 1 to 4 carbon atoms or a droxyethyl group, p, q
is an integer from 0 to 4 that satisfies p+q-4) or QH◆Claim No. 1.2.3.4.5
Or the fire extinguishing foam described in Section 6. @xkao? , cio, Br electric Ie, C, Op, B
SO, e. CM! 10. ”,sap,CH,C00e,tit
Claim No. 1.2.3.4.5.6
Or the fire extinguishing foam described in Section 7. 9 General 50I) 1 to 100%, preferably 10 to 1% of the fluorine-containing quaternary ammonium salt represented by I) in the surfactant component.
Claims 1.2.3, 4.5.
6; The fire extinguishing foam according to item 7 or 8. Fluorine-containing quaternary ammonium salt represented by the formula %() [However, in the formula, the axis is a fluorinated aliphatic group having S to 16 carbon atoms, and Wkt -Z'( OH, 0% 0)jH, -Z'Q;N
1gR7 (however, LZ') t A divalent linking group j containing a sulfamide group or a carboxamide group is an integer of 0 to 5, Q and ' are a divalent aliphatic group having 2 to 12 carbon atoms, substituted with a hydroxy 7 group. an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group combining these; , 0) representing jH), or -
(C'H,)kY (where k is an integer from 1 to 6, Y is -O
An aqueous fire extinguishing foam having excellent heat resistance and solubility resistance, characterized by containing a fluorine-containing compound represented by the following: The mixing ratio of the fluorine-containing quaternary ammonium salt represented by the general formula (11) and the fluorine-containing compound represented by the general formula (m) is 10:t to 1:2, preferably 20:1 to 1:
1. The fire extinguishing foam according to claim 10, which is No. 1. 12 Claim 10: The surfactant component contains 1 to 100%, preferably 10 to 100%, of the fluorine-containing quaternary ammonium salt represented by General Formula 1 and the fluorine-containing compound represented by General Formula 1. Or fire extinguishing foam as described in Section 11.