JPS5838569A - Foam 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 fluorosurfactant, fluorine-containing aminosulfonate.

Some fluorosurfactants can significantly lower the surface tension of water and may form an aqueous film on the surface of water-inhibitable flammable solvents such as gasoline. A fire extinguishing agent that is effective in preventing oil fires from re-igniting by applying this property has already been proposed in the specification of Time 1840-20080. However, these known fluorine-containing surfactants which have the ability to form a water film 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 in large enough quantities to produce an effect, the viscosity increases significantly, making it impractical. do not have.

In addition, known fluorosurfactants with excellent foam stability are listed in the table below.
The ability to reduce interfacial tension is insufficient and the ability to form a water film is poor. In order to solve this problem, an attempt has been made to add a hydrocarbon bulk surfactant to a seven-layer surfactant to mainly lower the interfacial tension between oil and water and increase the ability to form a water film ( For example, see Japanese Patent Publication No. 48-23161). However, since the addition of a hydrocarbon surfactant increases the lipophilicity of the fire extinguishing foam, the intrusion of combustion oil vapor into the foam is facilitated, resulting in a decrease in the oil resistance or flame resistance of the foam.

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

The present inventors have made extensive efforts to find a fluorosurfactant that has sufficient water-forming properties even without the use of a hydrocarbon surfactant, and has excellent foam stability, heat resistance, and solubility resistance. As a result of our research, we have discovered that fluorinated aminosulfonate, a new fluorinated surfactant shown in the following General (4I), has a well-balanced variety of essential properties for extinguishing fires, and can be used as a foam extinguishing agent for oil fires. As a result of further investigation, we found that the fluorine-containing compound represented by the general formula (II) was blended with the fluorine-containing aminosulfonate to improve water film formation. formability,
The present invention was completed based on the discovery that the heat resistance, solubility resistance, etc. of foam can be synergistically improved.

That is, the present invention is based on the general formula % (%) [wherein Rf is a fluorinated aliphatic group having 3 to 16 carbon atoms, and preferred examples of such groups include Bar70roalkyl group or Bar70 It is a loalknyl group, and may be linear, branched, or a combination thereof.

2 is a divalent linking group containing a sulfamide or carboamide group, -8o, N-1-CON-1-(CH,)
,ysO□NR,-1-(cpeng)pONuma-1→-C>
80. Groups such as N- or -O-C>C0NRt (wherein R7 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group, and ! represents an integer of 2 to 6) are preferred.

Q 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 (-CC11t); (However, m is 2 represents an integer of ~12), -(CI(,)錡0
- (CH*) town <where nll and 1nfi represent integers from 1 to 6), -CH, CH(OH)CH, or -
Groups such as cu and (=X'Hr) are preferred.

RI is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or (
CHtCHzO)lH (where l represents an integer from 1 to 20).

Q 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.
represents an integer from 2 to 12), Pe■2H(OH)CH,
Groups such as -1 or -C4-/D- are preferred.

M is a hydrogen atom or an inorganic or organic cation, Lfi+, N company P, Cm", &", NH,", (N
(H) p(R) q)” (where R is an alkyl group having 1 to 4 carbon atoms or a hydroxyethyl group, p and q are integers of 0 to 4 and satisfy p + q = 4) or ○ N.H.
” is preferred. ] A fire extinguishing foam characterized by having excellent heat resistance and solubility resistance, which is characterized by containing a fluorine-containing aminosulfonate represented by the following, and the fluorine-containing aminosulfone T etc. , in the formula, Rf' is a fluorinated aliphatic group having 5 to 16 carbon atoms, and preferred examples of such groups include perfluoroalkyl groups or bar-70 alkenyl groups, which may be linear, branched or Any combination of these may be used.

W bar Z' (CH,C)40)I Hl-Z'Q,
'NR, 'R- (However, z' is a divalent linking group containing a hasulfamide group or a carboxamide group.
008%-,-(C barrel, 780-Atsushi-1be c3) J-y
σ group φ-o ()-so-4-, or peHC) (ON
Preferred are groups such as kidney (where 4' is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group, and I' is an integer of 2 to 6). j is an integer of 0 to 5, Q 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; −(CHt)H= (However, m
'represents an integer from 2 to 12), (CHri1ii70(
Groups such as CH Note, / (where m, ', m, ' represent an integer of 1 to 6), -CH, CH(OH)CH, -1 or C of 10 are preferable.

R, / and di may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 6 atoms, or -(CH, CH, O
) represents jH) Ma? , :Her (cnrikY (however, kl
! 1 to 6f) Integer, Y represents -OH or -8H)
It can be summarized as a foam fire extinguishing agent with excellent heat resistance and flame resistance, which is characterized by containing a fluorine-containing compound shown in the following.

Specific examples of the fluorine-containing aminosulfonate and fluorine-containing compound used in the present invention are as follows, (
Shown in section B).

(A) C,F,,80. N (CHt)J (CH
, ), 80. NaC,F,So,N (CH,),,N
(CH!%SO, ; Peng (B) et Fl? 80J'
Hm (4F1,801NHCH.

9F,,CoNHCH,CH,OH To F,, 80! NH (CH crystal NH.

CIIF, So, NH(CH,), NHCH.

C, F,, CONH(CH crystal N (CI Ml) IC
, F'1. So,N (CH,)CI(,CH(OH)
CH,N (CH,CM,OH).

C4FIs 801N (CHz CHt OH) (
CHri5N(CHs)a to Fl, CH, OH, 80,
N (CH, 入■(cas)Co Fry ()-Q
-80tN (CHRIIN (CtHs)tc,,r,
, -o-O-coNcu, Q CH, NH.

comaF,,C0NH(CH,),0(CH,),NH(
CH,CHtOH)c,F,,So,NH(CH,),
ff1NH.

The fluorine-containing aminosulfonate of the present invention can be produced by various methods, but preferred methods include the following, for example.

Production method 1: RfZQ,N [(a fluorine-containing amine represented by R)] is generally produced by reacting a nine-roalkanesulfonate, a halohydroxyalkanesulfonate, a 7-roarylenesulfonate, or a sultone in the presence or absence of an alkali. 5RI) A method for producing a fluorine-containing aminosulfonate in high yield Production method 2: Reacting R,N to produce a fluorine-containing hydroxyamine RfZC
H, ΣHCHINI (R1 is produced. A method for producing a fluorine-containing aminosulfonate according to Production Method 1 using this as a raw material.

Production method 3: A method for producing a fluorine-containing aminosulfonate by reacting a fluorine-containing epoxide represented by Rf Z CHffi (4-9) with 7-minosulfonic acids HR, NQ, So, and H.

According to the findings of the present inventors, the fluorine-containing aminosulfonate according to the present invention has a sulfonic acid type anionic group and a cationic group formed by a secondary or tertiary amino group in the molecule, so that it has a neutral pH range. It was discovered that it behaves as an amphoteric surfactant having both an anionic group and a cationic group in its molecule in an aqueous solution, and has the best performance in the neutral pH range in terms of interfacial tension lowering and foam stability. was found to be expressed.

The extinguishing agent is preferably used in a neutral pH range from the viewpoint of safety to the human body, living things, etc., corrosiveness of storage containers, etc., and from this point of view as well, the usefulness of the fluorine-containing aminosulfonate is recognized.

Furthermore, as mentioned above, fluorine-containing aminosulfonates behave in a zwitterionic manner in the neutral pH region, and therefore have good compatibility with anionic, cationic, nonionic, and amphoteric ionic 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 aminosulfonate,
Foam properties can be improved by adding preferably 10 to 100% by weight. In particular, when the stock solution of protein fire extinguishing agent contains 0.01 to 5% by weight of fluorinated aminosulfonate, the fluidity, oil resistance, heat resistance, and flame resistance of the foam are significantly improved, making it suitable for use in fluorinated protein fire extinguishing agent. It was also found to be optimal as a surfactant.

As mentioned above, the fluorine-containing aminosulfonate according to the present invention is highly compatible with other surfactants and exhibits a synergistic effect*.
However, the synergistic effect with the fluorine-containing compounds shown in the general order is particularly remarkable. In this case, the mixing ratio of the fluorine-containing aminosulfonate 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 compound of general formula (2) is water-insoluble or has low water solubility in the neutral pH region, and therefore, even if it is added in a mixing ratio higher than the above, it will not be compatible and will actually impair foam properties. If the amount added is less than this mixing ratio, the synergistic effect will be reduced.

When using the fluorine-containing aminosulfonate of the present invention or a mixture of the fluorine-containing aminosulfonate and a general fluorine-containing compound as a water film-forming fire extinguishing agent, the amount added should be adjusted according to the required performance. Can be varied widely. It generally ranges from 1 to 100% by weight, preferably from 10 to 100% by weight of the total amount of surfactant in the fire extinguishing agent. If the amount added is below this range, the effect on water film formation properties or foam properties will be small. ! Various additives can be added. 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 travel screw, and examples include polyethylene glycol, polyvinylalpour, polyhinylpyrrolidone, carboxymethyl cellulose, gum arabic, sodium alginate, polypropylene glycol, polyvinyl/ There are resins, etc. Freezing point depressants include ethylene glycol, phlopylene glycol, cellosolves (ethyl hepatolol, butyl cellosolve), carpitols (ethyl carpitol, butyl carpitol), lower alcohols (inpropyl alcohol, butanol), or urea. . As the rust preventive agent and buffering agent, various types 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,
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 degree of dilution is adjusted by the usual method, for example, by sucking the concentrated stock solution into a water stream on the way to a fire extinguisher or foam nozzle, and then air It can also be applied by blowing in or mixing a nonflammable gas such as K, and then emitting or sending the foam from above or below the top surface.

The extinguishing agent of the present invention is used in combination with powder extinguishing agents, protein foam extinguishing agents, foam extinguishing agents for wood fires, etc., which have components such as Nanda bicarbonate, potassium bicarbonate, magnesium bicarbonate, ammonium sulfate, ammonium phosphate, and calcium carbonate. can do.

Next, the present invention will be explained in more detail with reference to Examples. In the following examples, all percentages are by weight, and all other ratios are by weight.

Examples 1 to 4 and Comparative Examples 1 to 2 Fluorine surfactant Q, 2% butylcarpitol 10% water
A small fire extinguisher for water-forming foam fire extinguishing agent (Japan Fire Protection Certification Association U51 type fire extinguisher) was filled with 3It of the composition consisting of 98.0%, and the discharge amount was 1t/cIL and 61/Ml at a nitrogen pressure of 10.
The combustion area is 12m" (B-6
scale) fire extinguishing experiments were conducted. The results are shown in Table 1.

The fuel was ignited after being adjusted to 50°C and the extinguishing agent to 20°C, 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 commercially available water-forming fire extinguishing foam containing a fluorosurfactant (3% type) was diluted 3 to 3 times with water.

(*1) Heat resistance test: 20. m4 n-
A combustion dish with an inner diameter of 17.8 s and a depth of 5 sq. containing hebutane was placed in the center of the bubble surface, and ignited 1 minute after the end of radiation. It is confirmed whether the n-'X butane in the combustion dish ignites and spreads around it until it burns out.

(*2) Paper seal test: The heat resistance test is left on a light foam surface, and when 5 minutes have passed after the end of the radiation, ignite the ignition rod and bring the flame close enough to touch the foam surface and move it over the entire surface along the foam surface. Observe whether it ignites or not.

Examples 5 to 8 and Comparative Example 3 3=1 of fluorine-containing aminosulfonate and fluorine-containing compound
Mixture 0.2% and butylcarpitol 1:0
．． Table 2 shows the results of the water film formation experiment using a 7% tr-containing aqueous solution. Comparative Example 3 is an experiment in which a commercial product (3% type) of an aqueous film-forming fire extinguishing foam containing a fluorosurfactant was diluted 353 times.

(*3) Spreading time: Put 201 cyclohexane into a Petri dish with an inner diameter of 85 m, add fire extinguishing agent α051 to the center of the oil surface at 25°C, and measure the time until the water film completely spreads over the entire surface.

(*4) Flame blocking property: After the above test, α05- was further added, and after 1 minute, a 20U flame was placed 20WK above the center of the liquid level.
Measure the time until ignition.

Example 9 Cm F+s 5OzN (cHR)-50Ha
2% Butylcarpitol
25% water 68%
The surface tension of the aqueous solution obtained by diluting this fire extinguishing foam stock solution 356 times with synthetic seawater is 16.5 dyn@/cm.
The interfacial tension for cyclohexane is 4.1 dyne
/cm.

Example 10 NH, 2% H@e CIIF, 80. N((% N(CH,), OH, C
OO3% Butylcarpitol 25%
Polyethylene glycol-400010% water
The surface tension of the aqueous solution obtained by diluting this 57% fire extinguishing foam stock solution 343 times with synthetic seawater was 16.4 dyne/α, and the interfacial tension with respect to cyclohexane was 4.2 dyne/cIR.

Next, fire extinguishing experiments were conducted using the fire extinguishing foam of the present invention of Examples 9 and 10 and the conventional water-forming fire extinguishing foam (commercial product) K based on the method described in Ministry of Home Affairs Ordinance No. 26.

In addition, the fuel is n-hebutane, and the combustion area is 21 FL'' (B
Pre-combustion was performed for 1 minute using the fire model of -20). The extinguishing agent stock solution was diluted 5.6 times with fire extinguishing water, and the cumulative nitrogen pressure was 1oky/l, the discharge rate was 10/a, and the total discharge time was 5 minutes.The foam nozzle was made of water.

A standard foaming nozzle was used for defoaming fire extinguishing agent testing. The results are shown in Table 6.

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

(*6) Heat resistance test: 15 minutes after the end of radiation, the oil surface is exposed in the center of the bubble surface to form a square of 151 sides, and the patent characterizes the burning area 5 minutes after ignition. Applicant Dainippon Ink & Chemicals Co., Ltd. Kawamura Institute of Physical and Chemical Research

Claims (1)

[Claims] t General formula % Formula % () [However, in the formula, Rf is a fluorinated aliphatic group having 5 to 16 carbon atoms, and 2 is a divalent linkage containing a sulfamide group or a carboxamido group. group, Q and Q 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; R
1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or -(
cu, cl(tO)11 (where t represents an integer of 1 to 20, M is a water bulk atom or an inorganic or organic cation). A foam fire extinguishing agent characterized by excellent heat resistance and flame resistance. 2. The foam fire extinguishing agent according to claim 1, wherein Rf is a par70-roalkyl group having 3 to 16 carbon atoms. &2 is -8O ,NR,-1-CONR,-1-((4
4SOM-1-(CHa)lCONR,-1-oQso
,NR,,ttaha-oOcoNR,- (wherein, Y2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group, and 1 represents an integer of 2 to 6). The fire extinguishing foam described in item 2. 4, Q, -(CHt)H (however, m represents an integer from 2 to 12), -(CHa), r, 0-(CHa pigeon (however, I
"1sff't represents an integer from 1 to 6), -OH,C
H(on)CHa-,Mataha-CH,-(=)CH,-
A fire extinguishing foam according to claim 1.2 or 3 which is tearable. & Q, is -CCH, after (however, n represents an integer from 2 to 12), -CH, CH(OH)CHt-, Mataha-CH
,(>teji)le%jFFjll! Search range 1.2
．． The fire extinguishing foam according to item 3 or 4. & M is Ll”, Na”, K+, Cm” +, Mg”
+, NH4'', (N(H)p (R)q:l''(
(provided that R is an alkyl group having 1 to 4 carbon atoms or a hydroxyethyl group, plq is an integer of 0 to 4 and represents an integer satisfying p+q=4) or ONH+ Claim No. 1.2.3.4 or the fire extinguishing foam according to item 5. 7. The fluorine-containing aminosulfonate represented by general formula (1) is contained in the surfactant component in an amount of 1 to 100%, preferably 10 to 10%.
The fire extinguishing foam according to claim 1.2.3.4.5 or 6, containing 0%. & Fluorine-containing aminosulfonate represented by the general formula (1) and the general formula % formula % () [However, in the formula, Rf' is a fluorinated aliphatic group having 3 to 16 carbon atoms, wit, -Z' ( CH, CH, O)jHl
-Z'Q1'NR1'R1' (where 2' is a divalent linking group containing a sulfamide group or a carboxamide group, and j is 0
An integer of ~5, Ql' 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 group combining these, B, t, and g may be the same or different and may be a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or -(CH!cH!0)jH), or -(CHt)kY (provided that in 1., C1 to
6 (1) integer, Y represents OH or -8Ht). ] A fire extinguishing foam having excellent heat resistance and flame resistance, characterized by containing a fluorine-containing compound represented by the following. The mixing ratio of the fluorine-containing aminosulfonate represented by general formula (50I) and the fluorine-containing compound represented by general formula (II) is 100:1 to 1:2, preferably 20:1 to 1:2, by weight.
The fire extinguishing foam according to claim 8, wherein the ratio is 1:1. 1α The fluorine-containing aminosulfonate represented by the general formula (1) and the fluorine-containing compound represented by the general formula (II) are contained in the surfactant component in an amount of 1 to 100%, preferably 10 to 100%.
% of the fire extinguishing foam according to claim 8 or 9.