BACKGROUND OF THE INVENTION
1. Field of the Invention
[0001] The present invention relates to a fire extinguishing composition comprising polyethyleneimine
or a derivative thereof, and more particularly to a fire extinguishing composition
which is superior in terms of rapid extinguishing performance, flame resistance, fuel
resistance, and reignition prevention performance.
2. Description of the Background Art
[0002] Generally, in the case of fires involving polar solvents such as alcohols, ketones,
esters, ethers and amines, even if fire extinguishing is attempted with a typical
petroleum fire extinguishing composition, the foam disappears soon after contacting
the combustion surface, and the fire is unable to be extinguished. As a result, the
following types of compositions have been proposed as polar solvent fire extinguishing
compositions:
- (1) protein hydrolysates to which a metallic soap has been added,
- (2) synthetic surfactants to which a metallic soap has been added,
- (3) protein hydrolysates to which a fluorine based surfactant has been added (a fluorinated
protein), and
- (4) fluorine based surfactants to which a water soluble high molecular weight material
has been added to form a thixotropic liquid.
[0003] Of these compositions, fire extinguishing compositions of type (4) above are aqueous
film forming foam compositions based on a fluorine based surfactant, to which a water
soluble high molecular weight material (such as a polysaccharide) has been added to
give thixotropic properties. On contact with a polar solvent, foams which consist
of this type of composition lose water at the combustion interface, and the remaining
water soluble high molecular weight material, incorporating air bubbles, forms a gel-like
mat across the solvent surface, preventing direct contact between the upper part of
foam and the solvent, and covering the entire combustion surface. It is believed that
the fire is then extinguished by cooling and smothering effects. Compared with the
fire extinguishing compositions of types (1), (2) and (3) above, compositions of type
(4) offer better foam development on the combustion surface, and also offer an improved
fire extinguishing effect.
[0004] However, assuming the mechanism above, wherein the gel-like mat of the water soluble
high molecular weight material protects the foam from the solvent, fire extinguishing
compositions of the type (4) above will display poor fire extinguishing effect on
solvents such as alcohols (such as isopropyl alcohol and t-butanol) or propylene oxide
which have large heats of combustion or are highly volatile, and so depending on the
type of solvent, the dilution ratio of the composition concentrate may need to be
increased, which makes handling somewhat troublesome. Moreover, because fire extinguishing
compositions of the type (4) described above rely on smothering utilizing the covering
effect of the gel-like mat, good effects are displayed in so-called soft running methods
where the foam is poured gently onto the surface of the fuel along the side wall of
a tank such as in a foam chamber, but in methods where the foam is shot directly onto
the solvent surface from the foam discharge nozzle of a chemical fire engine or the
like, a method which represents the most common fire fighting strategy, the surface
of the fuel is disturbed, meaning the gel-like mat can sink and the fuel surface can
reappear above the mat and reignite, and consequently problems still remain over the
performance of these type (4) compositions in actual fire fighting situations.
[0005] Furthermore, these fire extinguishing compositions incorporate large amounts of water
soluble high molecular weight material, and so the composition concentrate is extremely
viscous (at least 1200 mm
2/s), and moreover the viscosity value varies considerably with temperature. Consequently,
considerable care needs to be taken with the fire extinguishing equipment (such as
mixers and piping), and there are handling concerns associated with the practical
application of these types of compositions to existing equipment. Furthermore, conventionally
these type of fire extinguishing compositions have been prone to forming a thin membrane
(skin) on the surface of the liquid and on the walls of the tank during storage, and
moreover producing sedimentation on the bottom of the tank, and problems have also
arisen over the life of the product with concerns that they do not cope with extended
storage. In addition, these types of fire extinguishing compositions also have a relatively
high freezing point of approximately 0°C, and because they are not reversible in terms
of freezing and remelting, use or storage of such compositions in cold regions requires
special considerations.
[0006] An example of a fire extinguishing composition which displays superior fuel resistance,
flame resistance (for example, reignition sealing) and heat resistance when compared
with conventional compositions was disclosed by the present applicants in
Japanese Unexamined Patent Application, First Publication No. Sho-59-230566, and comprises a surfactant with an anionic hydrophilic group and a cationic water
soluble high molecular weight compound, mixed with a third constituent comprising
a polybasic acid compound of 3 to 24 carbon atoms.
[0007] However, although this fire extinguishing composition is able to be used for extinguishing
both polar solvent fires and non-polar solvents, the time required to extinguish a
fire is relatively long, and the composition could not be claimed to offer rapid fire
extinguishing performance. In addition, the composition also has problems in terms
of flame resistance, and reignition prevention. Furthermore, in actual fire fighting
activity, when the fire extinguishing composition concentrate was diluted with either
fresh water or sea water, problems arose in terms of the extended stability of the
diluted solution, with cloudiness developing in the diluted solution.
[0008] Similarily, in
US 4,536,298, the present applicant disclosed a fire extinguishing composition which comprises
a surfactant and a cationic water-soluble polymeric substance, wherein the surfactant
is a fluorine-containing aminosulfonate-type surface-active agent. Optionally, the
composition also contains a polybasic acid compound.
[0009] WO 96/05889 relates to water-soluble fluorochemical foam stabilizers and film formers derived
from polyamines, perfluoroalkyl group containing esters or acid halides and hydrophilic
and hydrophobic group-containing compounds which react with primary, secondary and
tertiary amino groups.
BRIEF SUMMARY OF THE INVENTION
[0010] An object of the present invention is to provide a fire extinguishing composition
which when compared with conventional fire extinguishing compositions displays superior
rapid fire extinguishing performance, flame resistance, fuel resistance and reignition
prevention performance, for both non-polar solvent fires and polar solvent fires,
as well as displaying superior stability as a diluted solution.
[0011] In order to achieve the above object, the present invention is a fire extinguishing
composition which comprises a cationic polyamine based high molecular weight compound
(A) which has primary, secondary, and tertiary cationic groups within the molecular
structure, a surfactant with an anionic hydrophilic group (B) and a polybasic acid
compound (C)
characterized in that said primary cationic groups account for no more than 40% by weight of the total
cationic groups within the molecule.
[0012] Moreover, the present invention provides a method for extinguishing fire, comprising
the steps of providing a fire extinguishing composition according to the present invention;
and applying the composition to a fire.
[0013] The fire extinguishing composition of the present invention forms a foam which is
extremely stable with respect to polar solvents, and yet also forms an aqueous film
on the surface of non-polar solvents such as petroleum, and offers flame resistance
and fuel resistance properties which display markedly improved rapid fire extinguishing
performance and reignition prevention.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
[0014]
FIG. 1 is a nuclear magnetic resonance spectrum of a polyethyleneimine.
FIG. 2 is a diagram showing the chemical structures corresponding with the peak numbers
on the nuclear magnetic resonance spectrum shown in FIG. 1.
DETAILED DESCRIPTION OF THE INVENTION
[0015] The cationic polyamine based high molecular weight compound (A) used in the present
invention refers to a high molecular weight compound which incorporates cationic groups
such as amino groups, ammonium groups, pyridinium groups or quaternary ammonium groups,
and is a water soluble high molecular weight compound with a solubility in conventional
water of at least 0.1 % by weight.
[0016] The cationic groups described above comprise primary, secondary and tertiary groups,
and the cationic groups can exist on either the main chain or a side chain of the
polyamine based high molecular weight compound.
[0017] There are no particular restrictions on the relative proportions of primary, secondary
and tertiary cationic groups, although in the present invention, for the reasons outlined
below, primary cationic groups must account for no more than 40% by weight of the
total cationic groups.
[0018] The degree of polymerization of the water soluble high molecular weight compound
is regulated by the water solubility of the compound, and from the oligomer region,
degrees of polymerization of at least several tens of thousands, namely weight average
molecular weights of 1,000 to 1,000,000 are typical, with values of 4,000 to 300,000
being preferred, and degrees of polymerization of 50,000 to 100,000 being the most
desirable in terms of producing a composition with the most superior fire extinguishing
performance, flame resistance and fuel resistance with respect to polar solvents.
[0019] Specific examples of the cationic polyamine based high molecular weight compound
(A) include those detailed below, although it should be noted that the present invention
is in no way limited by these specific examples.
- A-I
- polyethyleneimine
- A-II
- N-substituted polyethyleneimine
Examples of the N-substituted group
include -CnH2n+1, -CONHCnH2n+1, -COCnH2n+1, and -(CH2CH2O)n-H (where n represents an integer of 1 to 6).
- A-III
- condensation products of melamine and formaldehyde
- A-IV
- condensation products of guanidine and formaldehyde
[0021] A fire extinguishing composition of the present invention must not only display the
type of performance required of a foam type fire extinguishing composition with rapid
fire extinguishing performance, flame resistance, and an ability to retain a layer
of foam on the liquid surface of both non-water soluble hazardous materials and water
soluble hazardous materials, namely fuel resistance, but must also satisfy certain
basic properties of specific gravity, pour point, viscosity, hydrogen ion concentration,
sedimentation, and corrosiveness and the like as stipulated in the national certification
regulations, which are based on a ministerial ordinance (Ministry of Home Affairs
Ordinance No. 26) brought into effect on December 9, 1975 and defining the technical
specifications relating to foam type fire extinguishing compositions. Consequently,
in order to reach compatibility between fire extinguishing performance and basic performance,
it is necessary to mix the main constituent of the fire extinguishing composition
with a variety of other additives such as additional foam stabilizers, freezing point
depressants, rust prevention agents, and pH regulators and the like.
[0022] A variety of cationic polyamine based high molecular weight compounds, such as those
described above, can be used as the main constituent of a fire extinguishing composition
which complies with the above requirements, but as mentioned above, it is a requirement
that primary cationic groups within the compound account for no more than 40% by weight
of the total cationic groups.
[0023] If a cationic polyamine based high molecular weight compound in which the proportion
of primary cationic groups exceeds 40% by weight is used, then not only does sedimentation
occur in an aqueous solution produced by mixing 3 to 6 parts by weight of the foam
fire extinguishing composition concentrate with 97 to 94 parts of fresh water or sea
water, which raises a dilution stability problem in that the composition does not
satisfy one of the technical specifications of the Ministry of Home Affairs Ordinance
No. 26, but furthermore, sedimentation can block the tips of the various types of
nozzles used in actual fire fighting activity, resulting in unexpected situations
which inhibit effective fire fighting.
[0024] Moreover, in terms of fire extinguishing performance, using a compound in which the
proportion of primary cationic groups accounts for no more than 40% by weight of the
total number of cationic groups results in even superior performance in terms of rapid
fire extinguishing performance, flame resistance, fuel resistance, and reignition
prevention performance.
[0025] Cationic polyamine based high molecular weight compounds in which the proportion
of primary cationic groups accounts for no more than 40% by weight of the total number
of cationic groups, and the secondary cationic groups account for at least 35% by
weight of the total cationic groups, display even more superior effects in terms of
fire extinguishing performance and dilution stability, and are consequently preferred.
[0026] Furthermore, in selecting a suitable cationic polyamine based high molecular weight
compound, consideration of compatibility with additives such as additional foam stabilizers,
freezing point depressants, rust prevention agents, and pH regulators, as well as
consideration of other factors such as cost merit, safety with regards to both personnel
and the environment, and the availability of the raw materials, results in polyethyleneimine
or partially modified polyethyleneimine being used in preference.
[0027] Identification of the relative proportions of primary, secondary and tertiary cationic
groups within the cationic polyamine based high molecular weight compound can be determined
by using nuclear magnetic resonance spectroscopy to record a
13C-NMR spectrum, and then using the spectral peaks, chemical shift values, and integration
curves to calculate the relative weight proportions of primary, secondary and tertiary
cationic groups (-NH
2, -NH-, -N= in the case of polyethyleneimine) within the molecule.
[0028] There are no particular restrictions on the method of manufacturing the cationic
polyamine based high molecular weight compound according to the present invention,
although a typical method of manufacturing polyethyleneimine comprises synthesizing
ethyleneimine by a direct cyclodehydration of gaseous mono ethanolamine in the presence
of a solid acid-base catalyst, and then subjecting the ethyleneimine produced by this
method to a ring-opening polymerization in the presence of an acid catalyst to form
polyethyleneimine. Reaction kinetics mean that polyethyleneimine manufactured in this
manner will not be a perfectly linear macromolecule, but will rather be a high molecular
weight compound with a branched structure comprising primary, secondary and tertiary
amine groups, as shown in the chemical equation below. Furthermore, the acid catalyst
used in the ring-opening polymerization of ethyleneimine may utilize any of the mineral
acid, inorganic or organometallic based Lewis acids, although the branched structure
will vary depending on the catalyst used, as will the ratio of primary, secondary
and tertiary amines within the produced molecule.
[0029] Furthermore, in order to improve fuel resistance,
a surfactant (B) with an anionic hydrophilic group is also included in the fire extinguishing
composition of the present invention. A surfactant with an anionic hydrophilic group
undergoes an electrostatic interaction with the cationic polyamine based high molecular
weight compound (A), and the surfactant in the present invention is a compound with
at least one anionic hydrophilic group within each molecule.
[0030] Preferred anionic hydrophilic groups include groups such as -COOH, -SO
3H, -OSO
3H, and -OP(OH)
2, with -SO
3H being particularly desirable. Furthermore, in terms of counter ions for the cationic
groups, compounds with organic or inorganic anionic groups may also be used.
[0031] The hydrophilic group of the surfactant may incorporate one or more of the same,
or different anionic groups, or alternatively, an amphoteric ion type surfactant which
incorporates a cationic hydrophilic group and/or a nonionic group in addition to the
anionic hydrophilic group, is also possible. Of these various options, amphoteric
ion type surfactants are preferred for compatibility reasons.
[0032] Examples of the hydrophobic group of the surfactant include aliphatic hydrocarbon
groups of 6 or more carbon atoms, dihydrocarbyl siloxane chains, or fluorinated aliphatic
groups of 3 to 20 carbon atoms and preferably 6 to 16 carbon atoms. Of these hydrophobic
groups, fluorinated aliphatic groups are particularly desirable as they offer improved
fuel resistance. Furthermore, the surfactant may also comprise a mixture of different
surfactants with different hydrophobic groups.
[0033] The surfactants with an anionic hydrophilic group (B) used in the fire extinguishing
composition of the present invention can be broadly classified into: (B-1) fluorine
containing amino acid type amphoteric surfactants, (B-2) fluorine containing aminosulfonate
type surfactants, (B-3) fluorine containing aminocarboxylate type surfactants, (B-4)
fluorine containing trianion type amphoteric surfactants, (B-5) fluorine containing
tricarboxylic acid type amphoteric surfactants, (B-6) fluorine containing sulfobetaine
type amphoteric surfactants, (B-7) fluorine containing aminosulfate type surfactants,
(B-8) fluorine containing sulfatobetaine type surfactants, (B-9) fluorine containing
sulfobetaine type surfactants, (B-10) fluorine containing amine oxide type surfactants,
and (B-11) other surfactants.
[0034] The fluorine containing amino acid type amphoteric surfactants B-1 are compounds
represented by the general formula (B-1):
(In the formula, Rf represents a fluorinated aliphatic group of 3 to 20 carbon atoms,
Y represents either -SO
2- or -CO-, and Q
1 and Q
2 represent organic bivalent linking groups such as aliphatic hydrocarbon groups, aliphatic
hydrocarbon groups substituted with hydroxyl groups, aromatic hydrocarbon groups,
substituted aromatic hydrocarbon groups, or combinations thereof, with preferred groups
including straight chain alkylene groups of 1 to 6 carbon atoms, the 2-hydroxypropan-1,3-diyl
group, the 2-methoxypropan-1,3-diyl group, the 2-ethoxypropan-1,3-diyl group, and
the 2-propoxypropan-1,3-diyl group. R
1 and R
2 represent hydrogen atoms, aliphatic hydrocarbon groups of 1 to 12 carbon atoms, or
aliphatic hydrocarbon groups which have been substituted with hydrophilic groups,
or R
1 and R
2 may be linked together forming a ring with the adjacent nitrogen atom. A represents
an anionic hydrophilic group such as -COO
-, -SO
3-, -OSO
3-, or -OP(OH)O
-. M represents a hydrogen atom, an alkali metal, an alkali earth metal, an ammonium
group, or an organic cationic group.)
[0036] The fluorine containing aminosulfonate type surfactants (B-2) are compounds represented
by the general formula (B-2):
Rf-Z-Q
1-N(R)-Q
2-SO
2M
(In the formula, Rf represents a fluorinated aliphatic group of 3 to 20 carbon atoms,
Z represents a bivalent linking group such as -SO
2N(R
1)-, -CON(R
1)-,
-(CH
2CH
2)
iSO
2N(R
1)-, or compounds covered by the general formula
or the general formula
(where R
1 is a hydrogen atom or an alkyl group of 1 to 12 carbon atoms, and i is an integer
from 1 to 10), and Q
1 represents a straight chain alkylene group of 1 to 6 carbon atoms, the 2-hydroxypropan-1,3-diyl
group, the 2-ethoxypropan-1,3-diyl group, or the 2-propoxypropan-1,3-diyl group.
[0037] R represents a hydrogen atom, an alkyl group of 1 to 3 carbon atoms, a hydroxyalkyl
group, -Q
2SO
3M, or -(CH
2)
kCOOM (where k is an integer of 1 to 4), Q
2 represents a straight chain alkylene group of 1 to 5 carbon atoms, the 2-hydroxypropan-1,3-diyl
group, the 2-ethoxypropan-1,3-diyl group, the 2-propoxypropan-1,3-diyl group, or a
bivalent linking group represented by the general formula below.
M represents a hydrogen atom, an alkali metal, an alkali earth metal, or a cationic
atom or group of atoms represented by the formula below.
-N(H)
m(R
4)
4-m
(In the formula, R
4 represents an alkyl group of 1 to 3 carbon atoms, or a hydroxyalkyl group, and m
is an integer of 0 to 4.))
[0038] Specific examples of this (B-2) compound are shown below, although the present invention
is not limited by the specific examples shown.
[0039]
B-2-a C
8F
17SO
2NH(CH
2)
3N(CH
3)(CH
2)
3SO
3Na
B-2-b C
8F
17SO
2NH(CH
2)
3N(CH
2CH
2OH)(CH
2)
3SO
3Na
B-2-c C
6F
13SO
2N(CH
3)(CH
2)
3N(C
2H
5)CH
2CH(OH)CH
2SO
3K
B-2-d C
7F
15CONH(CH
2)
2N(CH
3)(CH
2)
3SO
3Na
B-2-f C
8F
17CH
2CH
2SO
2NH(CH
2)
3N(CH
3)(CH
2)
3SO
3Na
B-2-j C
8F
17(OCH
2CH
2)
2N(CH
3)(CH
2)
3SO
3·N(C
2H
5)
4
B-2-k C
7F
15CH
2CH
2SCH
2COO(CH
2)
2N(CH
3)(CH
2)
2SO
3Na
B-2-l C
3F
7OCF(CF
3)CF
2OCF(CF
3)CF
2CONH(CH
2)
3N(CH
3)(CH
2)
3SO
3Na
B-2-m CF
3CF
2CF
2[OCF(CF
3)CF
2]
4OCF(CF
3)CF
2CONH(CH
2)
3N(CH
3)(CH
2)
2SO
3K
[0040] The fluorine containing aminocarboxylate type surfactants (B-3) are compounds represented
by the general formula (B-3):
(In the formula, Rf represents a polyfluoroalkyl group, a polyfluoroalkenyl group,
a polyfluorocyclohexyl group, a polyfluorocyclohexyl alkyl group or a polyfluorocyclohexyl
alkenyl group of 3 to 20 carbon atoms which may also incorporate oxygen atoms, and
Z represents a linking group of one of the formulae below.
or
(In the formulae, R
1 represents an alkyl group, an alkenyl group or an aromatic ring containing monovalent
group incorporating of 1 to 18 carbon atoms, and i represents an integer of 1 to 3.)
Q represents a bivalent linking group of one of the formula below.
or
(In the formulae, l represents an integer of 1 to 6, m and n each represent an integer
of 2 to 6, and p and q each represent the number 2 or 3 respectively.) Q
1 and Q
2 each represent a alkylene group of 1 to 3 carbon atoms. M
1 and M
2 each represent a hydrogen atom or an inorganic or an organic cation.)
[0042] The fluorine containing trianion type amphoteric surfactants (B-4) are compounds
represented by the general formula (B-4):
(In the formula, Rf represents a fluorinated aliphatic group of 3 to 20 carbon atoms,
Z represents a bivalent linking group, Q represents a straight chain alkylene group
of 1 to 6 carbon atoms, the 2-hydroxypropan-1,3-diyl
group, -(CH
2)
m-O-(CH
2)
n- (where m and n are each integers from 2 to 6) or -(CH
2)
p-O-(CH
2)
2-O-(CH
2)
q- (where p and q each represent the number 2 or 3 respectively). Q
1, Q
2 and Q
3 represent bivalent groups such as aliphatic hydrocarbon groups of 1 to 8 carbon atoms,
aliphatic hydrocarbon groups of 1 to 8 carbon atoms with substituted hydroxyl groups,
or bivalent groups represented by the general formula
(where in the formula, r represents either the number 1 or the number 2), A
1 represents an anionic atom grouping
of -SO
3- or -OSO
3-, A
2 and A
3 also represents an anionic atom grouping of -SO
3- or -OSO
3-, -COO
-, or -OP(=O)(OH)O
-, M
1, M
2 and M
3 each represent a hydrogen atom or an inorganic or an organic cation, and X
- represents an inorganic or an organic anion such as OH
-, Cl
-, Br
-, I
-, ClO
4-, 1/2SO
42-, CH
3SO
4-, NO
3-, CH
3COO
- or the phosphate ion.)
[0044] The fluorine containing tricarboxylic acid type amphoteric surfactants (B-5) are
compounds represented by the general formula (B-5) :
(In the formula, Rf represents a fluorinated aliphatic group of 3 to 20 carbon atoms,
and Z
represents -SO
2-, -CO-, -(CH
2)
l-SO
2-, -(CH
2)
l-CO- (where l represents an integer from 1 to 6), or a bivalent group
represented by either the formula
or the formula
R
1 represents the 2-hydroxyethyl group, a group represented by the general formula -(CH
2)
a-O-(CH
2)
b-CH
3 (where a represents an integer from 2 to 10, and b represents an integer from 1 to
9), or an alkyl group of 1 to 12 carbon atoms, Q
1 represents a straight chain alkylene group of 2 to 6 carbon atoms, the 2-hydroxypropan-1,3-diyl
group, or a bivalent group represented by the general formula -(CH
2)
d-O-(CH
2)
e- (where d and e each represent an integer from 2 to 6), X represents an inorganic
or an organic anion, m
1, m
2 and m
3 each represent an independent integer from 1 to 3, and M
1, M
2 and M
3 each represent independently a hydrogen atom, or an inorganic or an organic cation.)
[0046] The fluorine containing sulfobetaine type amphoteric surfactants (B-6) are compounds
represented by the general formula (B-6):
(In the formula, Rf represents a group comprising a fluorinated aliphatic group of
3 to 20 carbon atoms, Z represents a bivalent linking group incorporating a sulfonamide
group or a carbonamide group, Q
1, Q
2 and Q
3 each represent independently a bivalent aliphatic group of 1 to 12 carbon atoms,
an aliphatic hydrocarbon group substituted with a hydroxyl group, an aromatic hydrocarbon
group, or a bivalent group formed through a combination of the above groups. R represents
a hydrogen atom, a hydrocarbyl group of 1 to 12 carbon atoms, or a -(CH
2CH
2O)
iH or a -(CH
2CH(CH
3)O)
iH group (where i represents an integer of 1 to 20), A represents an anionic atom grouping
of -SO
2-, -COO
-, -OSO
2-, or -OP(=O) (OH)O
-, M
1 and M
2 each represent a hydrogen atom or an inorganic or an organic cation, and X represents
an inorganic or an organic anion.)
[0048] The fluorine containing aminosulfate type surfactants (B-7) are compounds represented
by the general formula (B-7):
(In the formula, Rf represents a fluorinated aliphatic group of 3 to 20 carbon atoms,
Z represents -SO
2-, -CO-, a bivalent group represented by one of the formulae
or -(CH
2)
a-CO- (where a represents an integer of 1 to 10), R
1 represents a hydrogen atom, an alkyl group of 1 to 12 carbon atoms, a -(CH
2)
b-OR
3 group or a -(CH
2CH
2O)
d-R
2 group (where b represents an integer from 1 to 10, d represents an integer of 1 to
20, and R
3 represents a lower alkyl group or alkoxyl group), and Y represents -(CH
2)
e-, -(CH
2)
p-O-(CH
2)
2-O-(CH
2)
q- or -(CH
2)
g-O-(CH
2)
h- (where e represents an integer of 2 to 12, p and q each represent independently
a value of 2 or 3, and g and h each represent independently an integer of 1 to 6).
R
2 represents a hydrogen atom, an alkyl group, alkenyl group, or hydroxyl substituted
alkyl group of 1 to 18 carbon atoms, a -(CH
2CH
2)
m-H group (where m represents an integer of 2 to 20), Q
1OSO
3M, Q
1SO
2M or (CH
2)
iCOOM (where i represents an integer from 1 to 4).
Q
1 represents a straight chain alkyl group of 2 to 12 carbon atoms, the 2-hydroxypropan-1,3-diyl
group
or -(CH
2CH
2O)
k-CH
2CH
2- (where k represents an integer from 1 to 50). M represents a hydrogen atom or an
inorganic or an organic cation.)
[0049] Specific examples of this (B-7) compound are shown below, although the present invention
is not limited by the specific examples shown.
B-7-c C
7F
15CON(CH
3)(CH
2)
3N(CH
3)CH
2CH
2OSO
3NH
4
B-7-d C
7F
15CONH(CH
2)
6N(CH
2CH
2OSO
3Na)
2
B-7-i C
8F
17CH
2CH
2SO
2NH(CH
2)
3N(CH
3)(CH
2)
4OSO
3Na
[0050] The fluorine containing sulfatobetaine type surfactants (B-8) are compounds represented
by the general formula (B-8):
(In the formula, Rf represents a fluorinated aliphatic group of 3 to 20 carbon atoms,
Z represents -SO
2-, -CO-,
or -(CH
2)
a-CO- (where a represents an integer of 1 to 10), R
1 represents a hydrogen atom, an alkyl group of 1 to 12 carbon atoms, a -(CH
2)
b-OR
3 group or a -(CH
2CH
2O)
d-R
2 group (where b represents an integer from 1 to 10, d represents an integer of 1 to
20, and R
2 represents a lower alkyl group or alkoxyl group), and Y represents -(CH
2)
e-, -(CH
2)
p-O-(CH
2)
2-O-(CH
2)
q- or -(CH
2)
g-O-(CH
2)
h- (where e represents an integer of 2 to 12, p and q each represent independently
a value of 2 or 3, and g and h each represent independently an integer of 1 to 6).
R
2 and R
3 each represent independently an alkyl group, alkenyl group, hydroxyl substituted
alkyl group, or aromatic substituted alkyl group of 1 to 18 carbon atoms, or a -(CH
2CH
2O)
i-H group (where i represents an integer of 2 to 20), or alternatively R
2 and R
3 may be linked together to form a heterocyclic ring with the adjacent nitrogen atom,
and Q
1 represents a straight chain alkylene chain of 2 to 12 carbon atoms, the 2-hydroxypropan-1,3-diyl
group
or-(CH
2CH
2O)
k-CH
2CH
2- (where k represents an integer from 1 to 50).)
[0052] The fluorine containing sulfobetaine type surfactants (B-9) are compounds represented
by the general formula (B-9):
(In the formula, Rf represents a fluorinated aliphatic group of 3 to 20 carbon atoms
which may incorporate an oxygen atom, or a fluorinated alicyclic group, Z represents
a bivalent linking group, Q
1 represents a straight chain alkylene chain of 1 to 6 carbon atoms, or -(CH
2)
m-O-(CH
2)
n- or -(CH
2)
p-O-(CH
2)
2-O-(CH
2)
q- (where m and n each represent an integer of 2 to 6, and p and q each represent independently
a value of 2 or 3), Q
2 represents a straight chain alkylene chain of 1 to 6 carbon atoms, the 2-hydroxypropan-1,3-diyl
group or -(CH
2CH
2O)
r-CH
2CH
2- (where r represents an integer from 1 to 3), and
R
1 and R
2 each represent independently an alkyl group of 1 to 8 carbon atoms, an alkyl group
or alkenyl group which incorporates 1 to 3 ether oxygen atoms, a benzyl group or a
-(CH
2CH
2O)
s-H group (where s represents an integer from 1 to 11).)
[0054] In the compounds from B-1 to B-9 described above, M
1, M
2 and M
3 each represent independently a hydrogen atom or an inorganic or an organic cation.
Examples of preferred inorganic or organic cations include Li
+, Na
+, K
+, Ca
+, Mg
+, [N(H)
s(R)
4-s]
+ (where R is an alkyl group of 1 to 4 carbon atoms or a hydroxyethyl group, and s
represents an integer from 0 to 4), or
In contrast, X represents an inorganic or an organic anion. Examples of preferred
inorganic or organic anions include OH
-, Cl
-, Br
-, I
-, ClO
4-, 1/2SO
4-, CH
3SO
4-, NO
3-, CH
3COO
- or the phosphate ion.
[0055] Furthermore, the fluorine containing amine oxide type surfactants (B-10) are compounds
represented by the general formula (B-10):
(In the formula, Rf represents a fluorinated aliphatic group of 8 to 18 carbon atoms,
or a fluorinated alicyclic group of 10 to 20 carbon atoms with either an ether oxygen
atom or thioether linkage, Q represents -SO
2- or -CO-, R
1 represents H, an alkyl group of 1 to 6 carbon atoms, a halogenated alkyl group of
1 to 6 carbon atoms, -OH, -SH, an alkoxyl group of 1 to 6 carbon atoms, a thioalkyl
group of 1 to 6 carbon atoms, -NO
2, -CN, or NRR'- (where R and R' each represent H or an alkyl group of 1 to 6 carbon
atoms), R
2 and R
3 each represent H, an alkyl group of 1 to 6 carbon atoms, a halogenated alkyl group
of 1 to 6 carbon atoms, -OH, -SH, an alkoxyl group of 1 to 6 carbon atoms, a thioalkyl
group of 1 to 6 carbon atoms, -NO
2, -CN, NRR'- (where R and R' each represent H or an alkyl group of 1 to 6 carbon atoms),
or an alicyclic group which incorporates a hetero atom, an alicyclic group which does
not incorporate a hetero atom, or an alicyclic group in which either the entire alicyclic
ring, or a portion thereof, is substituted with alkyl groups, and finally n is an
integer from 2 to 6).
[0057] Examples of surfactants (B-11) other than the surfactants (B-1) to (B-10) which are
able to be used in the fire extinguishing composition of the present invention include
compounds represented by the formulae (B-11-a) to (B-11-g) shown below, although the
present invention is not limited to the compounds shown.
B-11-b C
11H
23CONHCH
2CH
2N(CH
2COONa)
2
B-11-e C
8F
17SO
2N(C
3H
7)CH
2COOK
B-11-f C
8F
17SO
2N(C
3H
7)CH
2CH
2SO
3Na
B-11-g C
7F
15CON(C
3H
7)(CH
2)
3SO
3Na
[0058] The mixing proportions of the cationic polyamine based high molecular weight compound
(A) and the surfactant (B) should preferably be within a weight ratio range from 5:1
to 1:3, with ratios within a range from 3:1 to 1:1 being even more desirable.
[0059] By adding a polybasic acid compound (C) to a fire extinguishing composition of the
present invention, the polybasic acid compound undergoes an electrostatic interaction
with the polyethyleneimine or derivative thereof, thereby improving the flame resistance
and fuel resistance of the composition even further.
[0060] Provided the polybasic acid compound (C) is a compound which incorporates an acid
group within the molecule, there are no restrictions on the type or the number of
acid groups, nor on the length of the carbon chain or the molecular weight, and any
compound can be used. Furthermore, such a polybasic acid compound (C) is a compound
with no surfactant properties, and suitable examples include dibasic, tribasic, tetrabasic,
pentabasic or hexabasic acids of 3 to 24 carbon atoms with an aromatic group, an aliphatic
group or a heterocyclic ring or the like, or the alkali metal salts or ammonium salts
of such acids. The acid group in the polybasic acid compound (C) may be a carboxylic
acid group, a sulfonic acid group, or a phosphoric acid group or the like. Furthermore,
in those cases where polybasic acid compounds are used, either a single compound,
or two or more different compounds may be used in combination. Of these various polybasic
acid compounds (C), dibasic acid compounds of 4 to 18 carbon atoms are particularly
desirable from the viewpoint of compatibility.
[0062] The mixing proportions of the cationic polyamine based high molecular weight compound
(A) and the polybasic acid compound (C) should preferably be within a weight ratio
range from 5:1 to 1:3, with ratios within a range from 4:1 to 1:1 being even more
desirable.
[0063] In the fire extinguishing composition of the present invention where a surfactant
with an anionic hydrophilic group (B) and a polybasic acid compound (C) are included
in the fire extinguishing composition of the present invention, the mixing proportions
of the cationic polyamine based high molecular weight compound (A) with the surfactant
with an anionic hydrophilic group (B) and the polybasic acid compound (C) will vary
depending on the combination of the constituents, although typically weight ratios
(B):[(A)+(C)] within a range from 2:1 to 1:50 are preferable, with ratios within a
range from 1:1 to 1:10 being even more desirable. By maintaining the mixing ratio
of the other constituents relative to the surfactant with an anionic hydrophilic group
(B) within the above range, a water insoluble complex does not form with the surfactant
with an anionic hydrophilic group (B), and so the foaming properties can be maintained.
Even if the mixing ratio is greater than the above range, no marked deterioration
is observed in foaming ability, flame resistance, heat resistance or fuel resistance,
but by maintaining the mixing ratio within the above range, large increases in the
viscosity of the fire extinguishing composition concentrate can be avoided, and corresponding
reductions in the commercial value of the composition can be prevented.
[0064] The fire extinguishing composition of the present invention displays superior solubility
stability in both concentrated and diluted forms, and as such offers excellent extended
storage. Furthermore, because of the superior solubility and low viscosity of the
composition, a strong concentrate with a high dilution ratio can be easily manufactured.
The kinematic viscosity of a concentrate with a 3% dilution ratio can be suppressed
to a value of no more than 100 mm
2/s at 20°C, which results in excellent handling properties. Furthermore, because the
amount of the cationic polyamine based high molecular weight compound (A) added can
be kept to a reasonably small amount, little deleterious effect is observed on the
performance of the composition, and the freezing point of the fire extinguishing composition
concentrate can be kept below -5°C.
[0065] According to the present invention, in order to improve the fire extinguishing performance
against non-polar solvents such as petroleum, a suitable amount of a surfactant (D)
with a cationic hydrophilic group may also be included in the composition with the
aim of effectively lowering the surface tension and the interfacial tension with petroleum
of the aqueous solution of the fire extinguishing composition.
[0066] There are no restrictions on the surfactant with a cationic hydrophilic group (D)
provided the surfactant incorporates a cationic hydrophilic group. Examples of the
cationic hydrophilic group of the surfactant with a cationic hydrophilic group (D)
include pyridinium salts, quaternary ammonium salts, imidazaolinium salts, and benzalkonium
salts. Of these cationic hydrophilic groups, pyridinium salts and quaternary ammonium
salts are preferred from the viewpoint of compatibility, and quaternary ammonium salts
are particularly desirable. Furthermore, examples of suitable counter ions for the
cationic group include organic and inorganic anions.
[0067] Examples of the hydrophobic group of the surfactant (D) include aliphatic hydrocarbon
groups of 6 or more carbon atoms, dihydrocarbyl siloxane chains, or fluorinated aliphatic
groups of 3 to 20 carbon atoms and preferably 6 to 16 carbon atoms. Of these surfactants
(D), surfactants with fluorinated aliphatic groups are particularly desirable as they
offer improved fire extinguishing performance.
[0068] Examples of the surfactant with a cationic hydrophilic group (D) include compounds
represented by the general formula (D-1):
(In the formula, Rf represents a fluorinated aliphatic group of 3 to 20 carbon atoms
which may also incorporate oxygen atoms, and Y represents a bivalent group such as
-(CH
2CH
2)
i-, -CH
2CH
2SCH
2COO-, -(CH
2CH
2)
i-SO
2-, -(CH
2CH
2)
i-CO-,
or
(where i represents an integer from 1 to 6). R represents a hydrogen atom or an aliphatic
hydrocarbon group of 1 to 6 carbon atoms, and Q
1 represents an aliphatic hydrocarbon group, an aliphatic hydrocarbon group substituted
with a hydroxyl group, an aromatic hydrocarbon group or a substituted aromatic hydrocarbon
group, although a straight chain alkylene group of 1 to 6 carbon atoms is preferred.
R
1 to R
3 can represent the same group or different groups, and each represent a hydrogen atom
or an aliphatic hydrocarbon group of 1 to 6 carbon atoms, and X
- represents an organic or an inorganic anion.)
[0069] In addition, a variety of additives may also be added to a fire extinguishing composition
of the present invention. Such additives include additional foam stabilizers, freezing
point depressants, rust prevention agents, and pH regulators and the like.
[0070] Additional foam stabilizers are mainly additives used for adjusting the expansion
ratio or drainage, and suitable examples include non-ionic surfactants such as glycerin
aliphatic esters, propylene glycol fatty acid esters, sorbitan fatty acid esters,
polyoxyethylene sorbitol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene
polyoxypropylene ethers, polyethylene glycol fatty acid esters, alkyl alkanol amides
and alkyl polyglucosides; amphoteric surfactants such as betaine alkyl dimethylaminoacetate,
alkyl dimethylamine oxides, alkyl carboxymethylhydroxyethyl imidazolium betaine, alkylamide
propyl betaine, and alkylhydroxy sulfobetaine; as well as polyethylene glycol, polyvinyl
alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, gum arabic, sodium alginate,
polypropylene glycol and polyvinyl resin.
[0071] Examples of suitable freezing point depressants include ethylene glycol, propylene
glycol, the cellosolve compounds (ethyl cellosolve and butyl cellosolve), caribtol
compounds (ethyl carbitol, butyl carbitol, hexyl carbitol and octyl carbitol), lower
alcohols (isopropyl alcohol, butanol, octanol), and urea.
[0072] Rust prevention agents and pH regulators can utilize any of the various commonly
known compounds, and there are no particular restrictions.
[0073] As follows is a description of a method of using a fire extinguishing composition
of the present invention.
[0074] The fire extinguishing composition of the present invention can be used as a fire
extinguishing agent by using known methods for blowing in, or mixing, air, carbon
dioxide, nitrogen, a low boiling point fluorocarbon such as difluorodicholoromethane,
or another suitable non-flammable gas with the composition.
[0075] In other words, because the viscosity of the fire extinguishing composition concentrate
of the present invention is comparatively low, a strong concentrate can be stored
in a storage tank, and then at the time of use, normal methods can be used for introducing
the composition into a water flow and adjusting the dilution ratio at some point before
the mixture reaches a device such as a fire extinguishing apparatus or foam nozzle.
Foam is then generated by blowing in, or mixing a non-flammable gas such as air, and
the foam is discharged over the flame or sent under the surface of the flame. Alternatively,
the composition can be prediluted to a usable concentration, and then used to fill
devices such as fire extinguishers, parking lot fire extinguishing equipment, fixed
fire extinguishing equipment for hazardous materials, or packaged fire extinguishing
equipment.
[0076] Furthermore, examples of suitable methods for discharging the fire extinguishing
composition of the present invention include the use of any of those discharge nozzles
commonly used in the industry for delivering fire extinguishing compositions, and
desired performance levels are able to be achieved.
[0077] Examples of suitable nozzles include the foam chamber and ISO standard compliant
nozzle most widely used for petroleum tanks and the like, UL standard compliant nozzles,
MIL standard compliant nozzles, hand nozzles attached to chemical fire engines and
the like, air foam hand nozzles, SSI nozzles, the Japan Marine Standards Association
specified HK nozzle, as well as foam heads used in driving lot fire extinguishing
equipment, and spray heads and the like.
[0078] As described above, fire extinguishing compositions of the present invention can
be used in a wide variety of discharge methods. Furthermore, a fire extinguishing
composition of the present invention can also be applied to a wider range of fires
than conventional fire extinguishing compositions. Specific examples of the use of
the compositions of this invention include deployment on chemical fire engines and
concentrate carrier vehicles employed by public fire fighting organizations, as well
as deployment at petroleum sites or industrial sites with crude oil tanks or other
hazardous material facilities, airport facilities, harbor facilities or shipping vessels
involved in the loading of hazardous materials, gas stands, underground parking lots,
buildings, tunnels and bridges. Furthermore, in addition to hazardous liquid material
fires, the compositions can also be used on general fires such as timber fires in
housing, or rubber and plastic fires such as tire fires.
[0079] In addition, because fire extinguishing compositions of the present invention display
superior qualities of fuel resistance, flame resistance, heat resistance and foam
forming properties, the strong concentrate or diluted aqueous solution can also be
used for extinguishing cooking oil or salad oil fires by pouring directly onto the
combustion surface to smother or cool the fire. Furthermore, a fire extinguishing
composition of the present invention also displays superior stability of the diluted
solution, and so the diluted solution can be used for filling spray cans and then
used as simple household fire extinguishers.
[0080] Moreover, the foam generated from a fire extinguishing composition of the present
invention is able to exist in a stable manner on aqueous solutions based on water,
sol-gel type materials, sludge and pollutants, as well as various organic solvents
and organic materials. Consequently, the volatilization of volatile materials from
this wide range of materials can be suppressed, enabling the compositions of the present
invention to also be used for preventing the ignition of flammable materials, and
preventing the generation of odors.
[0081] Furthermore, the fire extinguishing compositions of the present invention may also
be used in combination with powdered fire extinguishing compositions, protein based
foam fire extinguishing compositions and synthetic interface foam fire extinguishing
compositions comprising materials such as sodium bicarbonate, potassium bicarbonate,
magnesium bicarbonate, ammonium sulfate, ammonium phosphate, and calcium carbonate.
EXAMPLES
[0082] As follows is a more detailed description of the present invention with reference
to examples. In the following examples and comparative examples, all % values refer
to weight percentage values.
Synthetic Example 1
[0083] In a stainless steel flask equipped with a thermometer, a nitrogen gas inlet tube,
a stirrer, and a reflux condenser fitted with a dehydration tube, was placed 60 g
of acetic acid, and 473 g of polyethyleneimine with a weight ratio between the primary
amine, secondary amine, and tertiary amine groups of 39:45:16, and a dehydration reaction
was then permitted to proceed under an atmosphere of nitrogen for 10 hours at a temperature
of 180 to 240°C. Following completion of the reaction, ion exchange water was added
to the reaction products to yield solid matter which was 50% by weight N-acylated
polyethyleneimine (A-II-1). Analysis of the N-acylated polyethyleneimine (A-II-1)
revealed that 10% of the total cationic groups had been acylated.
Synthetic Example 2
[0084] In a stainless steel flask equipped with a thermometer, a nitrogen gas inlet tube,
a stirrer, and a reflux condenser fitted with a dehydration tube, was placed 60 g
of acetic acid, and 473 g of polyethyleneimine with a weight ratio between the primary
amine, secondary amine, and tertiary amine groups of 55:33:12, and a dehydration reaction
was then permitted to proceed under an atmosphere of nitrogen for 10 hours at a temperature
of 180 to 240°C. Following completion of the reaction, ion exchange water was added
to the reaction products to yield solid matter which was 50% by weight N-acylated
polyethyleneimine (A-II-2). Analysis of the N-acylated polyethyleneimine (A-II-2)
revealed that 10% of the total cationic groups had been acylated.
Analysis Example
[0085] FIG. 1 is an NMR spectrum of a sample of a polyethyleneimine (A-I) representing the
cationic polyamine based high molecular weight compound (A), which was measured using
an EX-27 FT-NMR device manufactured by NEC Corporation, Ltd. The measurement conditions
are listed below.
Solvent: D2O
Measurement temperature: 28°C
Measurement mode: COM
Nucleus observed: 13C
Illuminating nucleus: 1H (67.70 MHz)
Pulse width: 4.1 µs
[0087] Table 1 shows the relative proportions of primary amine, secondary amine and tertiary
amine groups measured by the above method for polyethyleneimine (A-I) samples representing
the cationic polyamine based high molecular weight compound (A), including "EPOMIN
P-1050" manufactured by Nippon Shokubai Co. Ltd. (hereafter abbreviated as (A-I-1)),
"LUPASOL P" manufactured by BASF Corporation Ltd. of Germany (and hereafter abbreviated
as (A-I-2)), N-acylated polyethyleneimine (A-II-1) and (A-II-2) produced by the synthetic
example 1 and the synthetic example 2 respectively, as well as derivatives thereof.
Table 1
Cationic polyamine based high molecular weight compound (A) |
Primary amines |
Secondary amines |
Tertiary amines |
A-I-1 |
38 % by |
42 % by |
20 % by |
|
weight |
weight |
weight |
A-I-2 |
44 % by |
33 % by |
23 % by |
|
weight |
weight |
weight |
A-II-1 |
35 % by |
45 % by |
20 % by |
|
weight |
weight |
weight |
A-II-2 |
50 % by |
30 % by |
20 % by |
|
weight |
weight |
weight |
Examples 1 to 40
Composition
[0088]
Cationic polyamine based high molecular weight compound (A) 6%
Surfactant with an anionic hydrophilic group (B) 3%
Polybasic acid compound (C) 4%
Butyl carbitol 15%
Ethylene glycol 15%
Water 57%
[0089] A cationic polyamine based high molecular weight compound (A), a surfactant with
an anionic hydrophilic group (B), and a polybasic acid compound (C) as shown in table
2 and table 3 below, were mixed together in the proportions listed above, and a small
amount of 5(N) hydrochloric acid was added to adjust the pH to 7.5. The external appearance,
freezing point, kinematic viscosity as measured at -10°C, and the amount of sedimentation
in a 3% solution diluted with water from the water supply, for the produced fire extinguishing
compositions (3% concentrates), are shown in Table 2 and Table 3 in accordance with
the technical specifications listed in the Ministry of Home Affairs Ordinance No.
26.
Table 2
Example No. |
(A) |
(B) |
(C) |
External appearance |
Freezing point |
Kinematic viscosity |
Sedimentation amount |
Example 1 |
A-I-1 |
B-1-a |
C-1 (n=4) |
totally |
-19°C |
126 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 2 |
A-I-1 |
B-1-m |
C-1 (n=4) |
totally |
-18°C |
133 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 3 |
A-I-1 |
B-1-t |
C-1 (n=6) |
totally |
-17°C |
132 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 4 |
A-II-1 |
B-1-e |
C-2 |
totally |
-17°C |
100 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 5 |
A-II-1 |
B-1-h |
C-4 |
totally |
-17°C |
144 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 6 |
A-II-1 |
B-1-n |
C-3 |
totally |
-18°C |
122 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 7 |
A-II-1 |
B-1-m |
C-13 |
totally |
-16°C |
119 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 8 |
A-I-1 |
B-1-u |
C-16 |
totally |
-19°C |
136 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 9 |
A-I-1 |
B-2-a |
C-23 |
totally |
-18°C |
140 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 10 |
A-I-1 |
B-2-c |
C-1 (n=4) |
totally |
-18°C |
97 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 11 |
A-I-1 |
B-2-j |
C-24 |
totally |
-17°C |
111 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 12 |
A-I-1 |
B-2-o |
C-31 (q=2) |
totally |
-20°C |
125 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 13 |
A-II-1 |
B-2-g |
C-28 |
totally |
-16°C |
133 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 14 |
A-II-1 |
B-2-c |
C-1 (n=6) |
totally |
-18°C |
124 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 15 |
A-II-1 |
B-2-c |
C-16 |
totally |
-17°C |
129 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 16 |
A-II-1 |
B-2-k |
C-10 |
totally |
-17°C |
130 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 17 |
A-I-1 |
B-3-i |
C-17 |
totally |
-16°C |
117 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 18 |
A-II-1 |
B-3-d |
C-7 |
totally |
-16°C |
140 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 19 |
A-I-1 |
B-4-b |
C-1 (n=4) |
totally |
-19°C |
118 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 20 |
A-I-1 |
B-4-e |
C-14 |
totally |
-18°C |
123 cst |
trace |
|
|
|
|
transparent |
|
|
|
Table 3
Example No. |
(A) |
(B) |
(C) |
External appearance |
Freezing point |
Kinematic viscosity |
Sedimentation amount |
Example 21 |
A-I-1 |
B-4-g |
C-14 |
totally |
-16°C |
117 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 22 |
A-I-1 |
B-5-c |
C-1 (n=2) |
totally |
-17°C |
134 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 23 |
A-I-1 |
B-5-i |
C-10 |
totally |
-17°C |
128 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 24 |
A-I-1 |
B-6-d |
D-1 (n=4) |
totally |
-18°C |
139 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 25 |
A-I-1 |
B-6-c |
C-11 |
totally |
-18°C |
131 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 26 |
A-I-1 |
B-6-b |
C-28 |
totally |
-19°C |
113 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 27 |
A-II-1 |
B-6-a |
C-16 |
totally |
-16°C |
122 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 28 |
A-II-1 |
B-6-f |
C-22 |
totally |
-20°C |
137 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 29 |
A-II-1 |
B-6-e |
C-3 |
totally |
-18°C |
140 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 30 |
A-II-1 |
B-6-a |
C-26 |
totally |
-17°C |
117 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 31 |
A-II-1 |
B-7-g |
C-16 |
totally |
-18°C |
130 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 32 |
A-I-1 |
B-7-k |
C-18 |
totally |
-16°C |
109 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 33 |
A-I-1 |
B-8-d |
C-23 |
totally |
-17°C |
122 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 34 |
A-I-1 |
B-8-e |
C-24 |
totally |
-18°C |
150 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 35 |
A-I-1 |
B-9-a |
C-28 |
totally |
-18°C |
149 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 36 |
A-II-1 |
B-9-e |
C-31 |
totally |
-17°C |
128 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 37 |
A-I-1 |
B-9-I |
C-1 (n=8) |
totally |
-17°C |
134 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 38 |
A-I-1 |
B-9-a |
C-1 (n=4) |
totally |
-16°C |
133 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 39 |
A-I-1 |
B-10-a |
C-1 (n=4) |
totally |
-18°C |
162 cst |
trace |
|
|
|
|
transparent |
|
|
|
Example 40 |
A-I-1 |
B-10-b |
C-10 |
totally |
-19°C |
169 cst |
trace |
|
|
|
|
transparent |
|
|
|
[0090] In addition, fire extinguishing experiments were conducted on a non-polar solvent
(a solvent for which the solubility in 100 g of water at 20°C is less than 1 g) based
on the methods described in the Ministry of Home Affairs Ordinance No. 26, and the
results of these experiments are shown in table 4, table 5, table 6 and table 7. Specifically,
200 L of n-heptane was used as fuel in a fire model with a combustion surface area
of 4 m
2 (B-20 scale), and the precombustion period was set at 1 minute. The dilute solutions
for use in the fire extinguishing experiments were generated by diluting the concentrated
solutions shown in each of the examples with water by a factor of 33.3 times. Each
dilute solution was then used for filling a pressurized tank with 100 liters of solution,
and subsequent foam generation was carried out with a standard foam generation nozzle
used for testing aqueous film forming foam fire extinguishing compositions (as per
national certification), using a nitrogen pressure of 7 kg/cm
2, a discharge speed of 10 liters/minute, and a total discharge time of 5 minutes.
The temperature of the dilute solution was adjusted to a value of 20°C±2°C in each
case. Experiments were conducted on the time taken for a 90% coverage of the combustion
surface area (90% control time) as an indication of the relative superiority of the
foam expansion speed, and the time taken for complete fire extinguishing which represents
the most salient measure of fire extinguishing speed. In addition, a vapor seal experiment
which acts as an indication of reignition prevention, and a burn back experiment which
acts as an indication of flame resistance were also performed.
Table 4
|
Diluting water used |
Dilution ratio |
Combustion solvent |
90% control time |
Extinguishing time (seconds) |
Vapor seal experiment |
Burn back experiment |
Example 1 |
fresh water |
3% |
n-heptane |
30 seconds |
71 |
no ignition |
5 cm2 |
sea water |
3% |
n-heptane |
31 seconds |
86 |
no ignition |
20 cm2 |
Example 2 |
fresh water |
3% |
n-heptane |
30 seconds |
78 |
no ignition |
10 cm2 |
sea water |
3% |
n-heptane |
36 seconds |
84 |
no ignition |
10 cm2 |
Example 3 |
fresh water |
3% |
n-heptane |
33 seconds |
68 |
no ignition |
6 cm2 |
sea water |
3% |
n-heptane |
34 seconds |
80 |
no ignition |
15 cm2 |
Example 4 |
fresh water |
3% |
n-heptane |
31 seconds |
73 |
no ignition |
20 cm2 |
sea water |
3% |
n-heptane |
36 seconds |
79 |
no ignition |
30 cm2 |
Example 5 |
fresh water |
3% |
n-heptane |
36 seconds |
80 |
no ignition |
0 cm2 |
sea water |
3% |
n-heptane |
33 seconds |
85 |
no ignition |
0 cm2 |
Example 6 |
fresh water |
3% |
n-heptane |
33 seconds |
73 |
no ignition |
8 cm2 |
sea water |
3% |
n-heptane |
37 seconds |
78 |
no ignition |
11 cm2 |
Example 7 |
fresh water |
3% |
n-heptane |
30 seconds |
69 |
no ignition |
0 cm2 |
sea water |
3% |
n-heptane |
32 seconds |
76 |
no ignition |
20 cm2 |
Example 8 |
fresh water |
3% |
n-heptane |
31 seconds |
72 |
no ignition |
0 cm2 |
sea water |
3% |
n-heptane |
31 seconds |
78 |
no ignition |
0 cm2 |
Example 9 |
fresh water |
3% |
n-heptane |
29 seconds |
67 |
no ignition |
2 cm2 |
sea water |
3% |
n-heptane |
28 seconds |
72 |
no ignition |
3 cm2 |
Example 10 |
fresh water |
3% |
n-heptane |
36 seconds |
80 |
no ignition |
30 cm2 |
sea water |
3% |
n-heptane |
34 seconds |
82 |
no ignition |
35 cm2 |
Example 11 |
fresh water |
3% |
n-heptane |
35 seconds |
79 |
no ignition |
0 cm2 |
sea water |
3% |
n-heptane |
36 seconds |
87 |
no ignition |
0 cm2 |
Example 12 |
fresh water |
3% |
n-heptane |
30 seconds |
84 |
no ignition |
10 cm2 |
sea water |
3% |
n-heptane |
33 seconds |
88 |
no ignition |
20 cm2 |
Table 5
|
Diluting water used |
Dilution ratio |
Combustion solvent |
90% control time |
Extinguishing time (seconds) |
Vapor seal experiment |
Burn back experiment |
Example 13 |
fresh water |
3% |
n-heptane |
29 seconds |
73 |
no ignition |
0 cm2 |
sea water |
3% |
n-heptane |
28 seconds |
79 |
no ignition |
0 cm2 |
Example 14 |
fresh water |
3% |
n-heptane |
37 seconds |
86 |
no ignition |
10 cm2 |
sea water |
3% |
n-heptane |
35 seconds |
93 |
no ignition |
0 cm2 |
Example 15 |
fresh water |
3% |
n-heptane |
35 seconds |
77 |
no ignition |
20 cm2 |
sea water |
3% |
n-heptane |
34 seconds |
81 |
no ignition |
30 cm2 |
Example 16 |
fresh water |
3% |
n-heptane |
34 seconds |
82 |
no ignition |
0 cm2 |
sea water |
3% |
n-heptane |
35 seconds |
78 |
no ignition |
0 cm2 |
Example 17 |
fresh water |
3% |
n-heptane |
38 seconds |
90 |
no ignition |
50 cm2 |
sea water |
3% |
n-heptane |
39 seconds |
96 |
no ignition |
10 cm2 |
Example 18 |
fresh water |
3% |
n-heptane |
37 seconds |
87 |
no ignition |
0 cm2 |
sea water |
3% |
n-heptane |
38 seconds |
91 |
no ignition |
0 cm2 |
Example 19 |
fresh water |
3% |
n-heptane |
29 seconds |
71 |
no ignition |
18 cm2 |
sea water |
3% |
n-heptane |
29 seconds |
74 |
no ignition |
31 cm2 |
Example 20 |
fresh water |
3% |
n-heptane |
31 seconds |
75 |
no ignition |
22 cm2 |
sea water |
3% |
n-heptane |
33 seconds |
77 |
no ignition |
0 cm2 |
Example 21 |
fresh water |
3% |
n-heptane |
29 seconds |
70 |
no ignition |
0 cm2 |
sea water |
3% |
n-heptane |
28 seconds |
75 |
no ignition |
0 cm2 |
Example 22 |
fresh water |
3% |
n-heptane |
35 seconds |
88 |
no ignition |
45 cm2 |
sea water |
3% |
n-heptane |
36 seconds |
86 |
no ignition |
30 cm2 |
Example 23 |
fresh water |
3% |
n-heptane |
33 seconds |
90 |
no ignition |
0 cm2 |
sea water |
3% |
n-heptane |
34 seconds |
93 |
no ignition |
10 cm2 |
Example 24 |
fresh water |
3% |
n-heptane |
29 seconds |
75 |
no ignition |
0 cm2 |
sea water |
3% |
n-heptane |
28 seconds |
74 |
no ignition |
0 cm2 |
Table 6
|
Diluting water used |
Dilution ratio |
Combustion solvent |
90% control time |
Extinguishing time (seconds) |
Vapor seal experiment |
Burn back experiment |
Example 25 |
fresh water |
3% |
n-heptane |
32 seconds |
76 |
no ignition |
20 cm2 |
sea water |
3% |
n-heptane |
31 seconds |
76 |
no ignition |
30 cm2 |
Example 26 |
fresh water |
3% |
n-heptane |
35 seconds |
82 |
no ignition |
26 cm2 |
sea water |
3% |
n-heptane |
36 seconds |
90 |
no ignition |
12 cm2 |
Example 27 |
fresh water |
3% |
n-heptane |
31 seconds |
71 |
no ignition |
0 cm2 |
sea water |
3% |
n-heptane |
29 seconds |
76 |
no ignition |
0 cm2 |
Example 28 |
fresh water |
3% |
n-heptane |
29 seconds |
74 |
no ignition |
30 cm2 |
sea water |
3% |
n-heptane |
28 seconds |
76 |
no ignition |
35 cm2 |
Example 29 |
fresh water |
3% |
n-heptane |
31 seconds |
82 |
no ignition |
10 cm2 |
sea water |
3% |
n-heptane |
33 seconds |
85 |
no ignition |
0 cm2 |
Example 30 |
fresh water |
3% |
n-heptane |
31 seconds |
81 |
no ignition |
38 cm2 |
sea water |
3% |
n-heptane |
30 seconds |
87 |
no ignition |
25 cm2 |
Example 31 |
fresh water |
3% |
n-heptane |
36 seconds |
95 |
no ignition |
50 cm2 |
sea water |
3% |
n-heptane |
38 seconds |
98 |
no ignition |
60 cm2 |
Example 32 |
fresh water |
3% |
n-heptane |
37 seconds |
97 |
no ignition |
5 cm2 |
sea water |
3% |
n-heptane |
35 seconds |
93 |
no ignition |
0 cm2 |
Example 33 |
fresh water |
3% |
n-heptane |
36 seconds |
99 |
no ignition |
0 cm2 |
sea water |
3% |
n-heptane |
36 seconds |
91 |
no ignition |
0 cm2 |
Example 34 |
fresh water |
3% |
n-heptane |
31 seconds |
93 |
no ignition |
14 cm2 |
sea water |
3% |
n-heptane |
31 seconds |
92 |
no ignition |
15 cm2 |
Example 35 |
fresh water |
3% |
n-heptane |
30 seconds |
80 |
no ignition |
10 cm2 |
sea water |
3% |
n-heptane |
33 seconds |
83 |
no ignition |
30 cm2 |
Example 36 |
fresh water |
3% |
n-heptane |
31 seconds |
80 |
no ignition |
20 cm2 |
sea water |
3% |
n-heptane |
33 seconds |
79 |
no ignition |
26 cm2 |
Table 7
|
Diluting water used |
Dilution ratio |
Combustion solvent |
90% control time |
Extinguishing time (seconds) |
Vapor seal experiment |
Burn back experiment |
Example 37 |
fresh water |
3% |
n-heptane |
29 seconds |
83 |
no ignition |
50 cm2 |
sea water |
3% |
n-heptane |
28 seconds |
85 |
no ignition |
35 cm2 |
Example 38 |
fresh water |
3% |
n-heptane |
33 seconds |
78 |
no ignition |
48 cm2 |
sea water |
3% |
n-heptane |
35 seconds |
76 |
no ignition |
25 cm2 |
Example 39 |
fresh water |
3% |
n-heptane |
40 seconds |
102 |
no ignition |
50 cm2 |
sea water |
3% |
n-heptane |
39 seconds |
99 |
no ignition |
0 cm2 |
Example 40 |
fresh water |
3% |
n-heptane |
38 seconds |
100 |
no ignition |
60 cm2 |
sea water |
3% |
n-heptane |
38 seconds |
103 |
no ignition |
45 cm2 |
[0091] Furthermore, fire extinguishing experiments were also conducted on a polar solvent
(a solvent for which the solubility in 100 g of water at 20°C is at least 1 g) based
on the methods described in the Fire Fighting Hazards No. 71, and the results of these
experiments are shown in table 8, table 9, table 10 and table 11. Specifically, 400
L of each solvent was used as fuel in a fire model with a combustion surface area
of 4 m
2 (B-20 scale: coefficient 1), and the precombustion period was set at 1 minute. The
dilute solutions for use in the fire extinguishing experiments were generated by diluting
the concentrated solutions shown in each of the examples with water by a factor of
33.3 times. Each dilute solution was then used for filling a pressurized tank with
100 liters of solution, and subsequent foam generation was carried out with a standard
foam generation nozzle used for testing aqueous film forming foam fire extinguishing
compositions (as per national certification), using a nitrogen pressure of 7 kg/cm
2, a discharge speed of 10 liters/minute, and a total discharge time of 5 minutes.
The temperature of the dilute solution was adjusted to a value of 20°C±2°C in each
case. Experiments were conducted on the time taken for a 90% coverage of the combustion
surface area (90% control time) as an indication of the relative superiority of the
foam expansion speed (and also as a measure of the fuel resistance of the foam relative
to the polar solvent), and the time taken for complete fire extinguishing which represents
the most salient measure of fire extinguishing speed. In addition, a vapor seal experiment
which acts as an indication of reignition prevention, and a burn back experiment which
acts as an indication of flame resistance were also performed in the same manner as
for the non-polar solvents described above.
Table 8
Example No. |
Diluting water used |
Dilution ratio |
Combustion solvent |
Foam magnification (times) |
90% control time (seconds) |
Extinguishing time (seconds) |
Vapor seal experiment |
Burn back experiment (cm2) |
Example 1 |
fresh water |
3% |
2-propanol |
6.2 |
42 |
111 |
no ignition |
65 |
sea water |
3% |
2-propanol |
6.4 |
44 |
112 |
no ignition |
70 |
Example 2 |
fresh water |
3% |
2-propanol |
6.3 |
45 |
115 |
no ignition |
68 |
sea water |
3% |
2-propanol |
6.3 |
46 |
113 |
no ignition |
75 |
Example 3 |
fresh water |
3% |
methanol |
6.3 |
34 |
70 |
no ignition |
10 |
sea water |
3% |
methanol |
6.3 |
38 |
65 |
no ignition |
15 |
Example 4 |
fresh water |
3% |
acetone |
6.2 |
30 |
81 |
no ignition |
45 |
sea water |
3% |
acetone |
6.2 |
30 |
85 |
no ignition |
36 |
Example 5 |
fresh water |
3% |
acetone |
6.0 |
33 |
79 |
no ignition |
33 |
sea water |
3% |
acetone |
6.0 |
33 |
77 |
no ignition |
31 |
Example 6 |
fresh water |
3% |
propylene oxide |
6.1 |
29 |
55 |
no ignition |
20 |
sea water |
3% |
propylene oxide |
6.1 |
27 |
54 |
no ignition |
26 |
Example 7 |
fresh water |
3% |
2-propanol |
6.3 |
41 |
111 |
no ignition |
75 |
sea water |
3% |
2-propanol |
6.4 |
45 |
108 |
no ignition |
68 |
Example 8 |
fresh water |
3% |
acetone |
6.1 |
30 |
75 |
no ignition |
20 |
sea water |
3% |
acetone |
6.3 |
29 |
81 |
no ignition |
18 |
Example 9 |
fresh water |
3% |
methanol |
6.2 |
29 |
68 |
no ignition |
14 |
sea water |
3% |
methanol |
6.3 |
28 |
62 |
no ignition |
10 |
Example 10 |
fresh water |
3% |
methanol |
6.1 |
30 |
74 |
no ignition |
20 |
sea water |
3% |
methanol |
6.1 |
31 |
72 |
no ignition |
33 |
Table 9
Example No. |
Diluting water used |
Dilution ratio |
Combustion solvent |
Foam magnification (times) |
90% control time (seconds) |
Extinguishing time (seconds) |
Vapor seal experiment |
Burn back experiment (cm2) |
Example 11 |
fresh water |
3% |
acetone |
6.3 |
35 |
82 |
no ignition |
36 |
sea water |
3% |
acetone |
6.2 |
38 |
77 |
no ignition |
17 |
Example 12 |
fresh water |
3% |
methanol |
5.9 |
26 |
61 |
no ignition |
5 |
sea water |
3% |
methanol |
6.0 |
29 |
63 |
no ignition |
14 |
Example 13 |
fresh water |
3% |
propylene oxide |
6.4 |
26 |
57 |
no ignition |
20 |
sea water |
3% |
propylene oxide |
6.3 |
24 |
56 |
no ignition |
26 |
Example 14 |
fresh water |
3% |
2-propanol |
6.2 |
39 |
119 |
no ignition |
64 |
sea water |
3% |
2-propanol |
6.2 |
33 |
104 |
no ignition |
62 |
Example 15 |
fresh water |
3% |
acetone |
6.0 |
39 |
87 |
no ignition |
40 |
sea water |
3% |
acetone |
6.0 |
41 |
81 |
no ignition |
39 |
Example 16 |
fresh water |
3% |
acetone |
6.3 |
44 |
90 |
no ignition |
24 |
sea water |
3% |
acetone |
6.4 |
43 |
95 |
no ignition |
27 |
Example 17 |
fresh water |
3% |
acetone |
6.1 |
37 |
88 |
no ignition |
75 |
sea water |
3% |
acetone |
6.3 |
34 |
79 |
no ignition |
66 |
Example 18 |
fresh water |
3% |
2-propanol |
5.8 |
45 |
131 |
no ignition |
76 |
sea water |
3% |
2-propanol |
5.7 |
47 |
122 |
no ignition |
80 |
Example 19 |
fresh water |
3% |
acetone |
6.1 |
38 |
83 |
no ignition |
33 |
sea water |
3% |
acetone |
6.1 |
37 |
80 |
no ignition |
44 |
Example 20 |
fresh water |
3% |
propylene oxide |
6.1 |
24 |
61 |
no ignition |
10 |
sea water |
3% |
propylene oxide |
6.2 |
26 |
59 |
no ignition |
11 |
Table 10
Example No. |
Diluting water used |
Dilution ratio |
Combustion solvent |
Foam magnification (times) |
90% control time (seconds) |
Extinguishing time (seconds) |
Burn back Vapor seal experiment (cm2) |
Example 21 |
fresh water |
3% |
acetone |
5.9 |
31 |
94 |
no ignition |
32 |
sea water |
3% |
acetone |
6.0 |
35 |
98 |
no ignition |
36 |
Example 22 |
fresh water |
3% |
propylene oxide |
6.2 |
24 |
55 |
no ignition |
20 |
sea water |
3% |
propylene oxide |
6.2 |
23 |
54 |
no ignition |
22 |
Example 23 |
fresh water |
3% |
acetone |
6.1 |
29 |
82 |
no ignition |
18 |
sea water |
3% |
acetone |
6.1 |
28 |
80 |
no ignition |
19 |
Example 24 |
fresh water |
3% |
2-propanol |
6.1 |
47 |
122 |
no ignition |
55 |
sea water |
3% |
2-propanol |
6.0 |
44 |
126 |
no ignition |
74 |
Example 25 |
fresh water |
3% |
methanol |
6.3 |
25 |
59 |
no ignition |
10 |
sea water |
3% |
methanol |
6.2 |
24 |
57 |
no ignition |
13 |
Example 26 |
fresh water |
3% |
acetone |
6.0 |
30 |
86 |
no ignition |
33 |
sea water |
3% |
acetone |
6.0 |
29 |
83 |
no ignition |
31 |
Example 27 |
fresh water |
3% |
acetone |
6.1 |
32 |
85 |
no ignition |
29 |
sea water |
3% |
acetone |
6.1 |
33 |
86 |
no ignition |
22 |
Example 28 |
fresh water |
3% |
methanol |
6.2 |
22 |
58 |
no ignition |
22 |
sea water |
3% |
methanol |
6.2 |
23 |
56 |
no ignition |
18 |
Example 29 |
fresh water |
3% |
2-propanol |
6.5 |
43 |
119 |
no ignition |
80 |
sea water |
3% |
2-propanol |
6.3 |
46 |
112 |
no ignition |
68 |
Example 30 |
fresh water |
3% |
acetone |
6.0 |
26 |
91 |
no ignition |
40 |
sea water |
3% |
acetone |
6.0 |
24 |
98 |
no ignition |
35 |
Table 11
Example No. |
Diluting water used |
Dilution ratio |
Combustion solvent |
Foam magnification (times) |
90% control time (seconds) |
Extinguishing time (seconds) |
Vapor seal experiment |
Burn back experiment (cm2) |
Example 31 |
fresh water |
3% |
methanol |
5.7 |
24 |
89 |
no ignition |
36 |
sea water |
3% |
methanol |
6.1 |
28 |
91 |
no ignition |
17 |
Example 32 |
fresh water |
3% |
acetone |
6.2 |
27 |
89 |
no ignition |
34 |
sea water |
3% |
acetone |
6.2 |
29 |
84 |
no ignition |
44 |
Example 33 |
fresh water |
3% |
methanol |
6.0 |
27 |
91 |
no ignition |
33 |
sea water |
3% |
methanol |
6.0 |
31 |
90 |
no ignition |
32 |
Example 34 |
fresh water |
3% |
methanol |
5.9 |
23 |
64 |
no ignition |
13 |
sea water |
3% |
methanol |
6.2 |
24 |
67 |
no ignition |
15 |
Example 35 |
fresh water |
3% |
2-propanol |
6.1 |
45 |
139 |
no ignition |
77 |
sea water |
3% |
2-propanol |
6.1 |
47 |
136 |
no ignition |
69 |
Example 36 |
fresh water |
3% |
2-propanol |
6.2 |
44 |
113 |
no ignition |
77 |
sea water |
3% |
2-propanol |
6.2 |
45 |
117 |
no ignition |
61 |
Example 37 |
fresh water |
3% |
2-propanol |
6.2 |
49 |
131 |
no ignition |
76 |
sea water |
3% |
2-propanol |
6.1 |
48 |
134 |
no ignition |
71 |
Example 38 |
fresh water |
3% |
methanol |
6.5 |
21 |
61 |
no ignition |
22 |
sea water |
3% |
methanol |
6.4 |
24 |
69 |
no ignition |
23 |
Example 39 |
fresh water |
3% |
methanol |
6.3 |
26 |
76 |
no ignition |
9 |
sea water |
3% |
methanol |
6.1 |
27 |
79 |
no ignition |
6 |
Example 40 |
fresh water |
3% |
methanol |
6.0 |
33 |
85 |
no ignition |
20 |
sea water |
3% |
methanol |
6.0 |
31 |
84 |
no ignition |
35 |
Experimental methods and Evaluation standards
Foam magnification:
[0092] Foam generated from an experimental standard foam generation nozzle used for testing
aqueous film forming foam fire extinguishing compositions (as per national certification)
was used to fill a foam collection tank (volume V: 1400 ml, weight W1 g) as prescribed
in the Ministry of Home Affairs Ordinance No. 26, and the total weight (W2 g) of the
foam filled collection tank was measured. The foam magnification was then calculated
using the formula below.
90% Control time:
[0093] This value represents the time period from commencement of the foam discharge, until
90% of the combustion surface area of the fire model (combustion surface area 4 m
2: B-20 scale) was covered with foam.
Extinguishing time:
[0094] This value represents the time period from commencement of the foam discharge until
the flames on the fire model had been completely extinguished.
Vapor seal experiment:
[0095] On three occasions, namely 1 minute, 7 minutes and 11 minutes after the completion
of the foam discharge, a torch was ignited and the flame brought close enough to touch
the foam surface. The flame was then moved across the entire foam surface to observe
whether or not the fuel would reignite.
Burn back experiment:
[0096] 15 minutes after the completion of the foam discharge, a 225 cm
2 hole was opened up in the center of the fire model, and the fuel thereunder was forcibly
reignited. Five minutes after this ignition, the degree to which the combustion surface
had expanded was evaluated.
Comparative Examples 1 to 21
[0097] For comparative purposes, fire extinguishing compositions (3% concentrates) were
prepared using the same compositions and mixing methods as the examples described
above, but with the exception that a polyethyleneimine or an N-propyl polyethyleneimine
in which the amount of primary amine groups exceeds 40% and the amount of secondary
amine groups is less than 35%, was used as the cationic polyamine based high molecular
weight compound (A) of the present invention.
[0098] The compounds used for the cationic polyamine based high molecular weight compound
(A), the surfactant with an anionic hydrophilic group (B) and the polybasic acid compound
(C) are shown in table 12, together with the external appearance, freezing point,
kinematic viscosity, and the amount of sedimentation in a 3% solution diluted with
water from the water supply, for the produced fire extinguishing compositions (3%
concentrates) carried out in accordance with the technical specifications listed in
the Ministry of Home Affairs Ordinance No. 26.
[0099] In addition, fire extinguishing experiments were conducted for thixotropic water
soluble high molecular weight material containing fire extinguishing compositions
(incorporating a fluorine based surfactant, a commercially available product), and
the results of the experiments for non-polar solvents are shown in table 13, table
14 and table 15, whereas the results of the experiments for polar solvents are shown
in table 16, table 17 and table 18. In these tables the number in the right hand most
column refers to the example corresponding with that particular comparative example.
Table 12
Comparative Example No. |
(A) |
(B) |
(C) |
External appearance |
Freezing point |
Kinematic viscosity |
Sedimentation amount |
1 |
A-I-2 |
B-1-a |
C-1 (n=4) |
totally transparent |
-19°C |
126 cst |
0.5 v% |
2 |
A-I-2 |
B-1-t |
C-1 (n=6) |
totally transparent |
-17°C |
132 cst |
0.5 v% |
3 |
A-II-2 |
B-1-h |
C-4 |
totally transparent |
-17°C |
144 cst |
0.3 v% |
4 |
A-II-2 |
B-1-m |
C-13 |
totally transparent |
-16°C |
119 cst |
0.4 v% |
5 |
A-I-2 |
B-2-a |
C-23 |
totally transparent |
-18°C |
140 cst |
0.5 v% |
6 |
A-I-2 |
B-2-j |
C-24 |
totally transparent |
-17°C |
111 cst |
0.6 v% |
7 |
A-II-2 |
B-2-g |
C-28 |
totally transparent |
-16°C |
133 cst |
0.3 v% |
8 |
A-II-2 |
B-2-c |
C-16 |
totally transparent |
-17°C |
129 cst |
0.2 v% |
9 |
A-I-2 |
B-3-i |
C-17 |
totally transparent |
-16°C |
117 cst |
0.5 v% |
10 |
A-I-2 |
B-4-b |
C-1 (n=4) |
totally transparent |
-19°C |
118 cst |
0.5 v% |
11 |
A-I-2 |
B-4-g |
C-14 |
totally transparent |
-16°C |
117 cst |
0.5 v% |
12 |
A-I-2 |
B-5-i |
C-10 |
totally transparent |
-17°C |
128 cst |
0.4 v% |
13 |
A-I-2 |
B-6-c |
C-11 |
totally transparent |
-18°C |
131 cst |
0.5.% |
14 |
A-II-2 |
B-6-a |
C-16 |
totally transparent |
-16°C |
122 cst |
0.5 v% |
15 |
A-II-2 |
B-6-e |
C-3 |
totally transparent |
-18°C |
140 cst |
0.4 v% |
16 |
A-II-2 |
B-7-g |
C-16 |
totally transparent |
-18°C |
130 cst |
0.3 v% |
17 |
A-I-2 |
B-8-d |
C-23 |
totally transparent |
-17°C |
122 cst |
0.5 v% |
18 |
A-I-2 |
B-9-a |
C-28 |
totally transparent |
-18°C |
149 cst |
0.5 v% |
19 |
A-I-2 |
B-9-I |
C-1 (n=8) |
totally transparent |
-17°C |
134 cst |
0.4 v% |
20 |
A-I-2 |
B-10-b |
C-1 (n=4) |
totally transparent |
-18°C |
162 cst |
0.5 v% |
21 |
A-I-2 |
B-10-b |
C-10 |
totally transparent |
-19°C |
169 cst |
trace |
Table 13
Comparative Example |
Diluting water used |
Dilution ratio |
Combustion solvent |
90% control time (seconds) |
Extinguishing time (seconds) |
Vapor seal experiment |
Burn back experiment (cm2) |
Corresponding Example |
1 |
fresh water |
3% |
n-heptane |
46 |
111 |
no ignition |
100 |
1 |
sea water |
3% |
n-heptane |
50 |
127 |
no ignition |
97 |
2 |
fresh water |
3% |
n-heptane |
44 |
119 |
no ignition |
50 |
3 |
sea water |
3% |
n-heptane |
45 |
135 |
no ignition |
120 |
3 |
fresh water |
3% |
n-heptane |
50 |
131 |
no ignition |
100 |
5 |
sea water |
3% |
n-heptane |
48 |
133 |
no ignition |
122 |
4 |
fresh water |
3% |
n-heptane |
41 |
108 |
no ignition |
90 |
7 |
sea water |
3% |
n-heptane |
43 |
125 |
no ignition |
80 |
5 |
fresh water |
3% |
n-heptane |
39 |
150 |
no ignition |
90 |
9 |
sea water |
3% |
n-heptane |
44 |
177 |
no ignition |
154 |
6 |
fresh water |
3% |
n-heptane |
50 |
164 |
no ignition |
99 |
11 |
sea water |
3% |
n-heptane |
47 |
172 |
no ignition |
112 |
7 |
fresh water |
3% |
n-heptane |
45 |
156 |
no ignition |
130 |
13 |
sea water |
3% |
n-heptane |
43 |
168 |
no ignition |
140 |
Table 14
Comparative Example |
Diluting water used |
Dilution ratio |
Combustion solvent |
90% control time (seconds) |
Extinguishing time (seconds) |
Vapor seal experiment |
Burn back experiment (cm2) |
Corresponding Example |
8 |
fresh water |
3% |
n-heptane |
42 |
129 |
no ignition |
100 |
15 |
sea water |
3% |
n-heptane |
44 |
146 |
no ignition |
122 |
9 |
fresh water |
3% |
n-heptane |
53 |
153 |
no ignition |
166 |
17 |
sea water |
3% |
n-heptane |
55 |
176 |
no ignition |
177 |
10 |
fresh water |
3% |
n-heptane |
38 |
131 |
no ignition |
188 |
19 |
sea water |
3% |
n-heptane |
40 |
148 |
no ignition |
130 |
11 |
fresh water |
3% |
n-heptane |
42 |
120 |
no ignition |
98 |
21 |
sea water |
3% |
n-heptane |
41 |
125 |
no ignition |
70 |
12 |
fresh water |
3% |
n-heptane |
42 |
142 |
no ignition |
120 |
23 |
sea water |
3% |
n-heptane |
45 |
144 |
no ignition |
129 |
13 |
fresh water |
3% |
n-heptane |
37 |
114 |
no ignition |
189 |
25 |
sea water |
3% |
n-heptane |
38 |
115 |
no ignition |
150 |
14 |
fresh water |
3% |
n-heptane |
46 |
164 |
no ignition |
123 |
27 |
sea water |
3% |
n-heptane |
48 |
152 |
no ignition |
144 |
Table 15
Comparative Example |
Diluting water used |
Dilution ratio |
Combustion solvent |
90% control time (seconds) |
Extinguishing time (seconds) |
Vapor seal experiment |
Burn back experiment (cm2) |
Corresponding Example |
15 |
fresh water |
3% |
n-heptane |
43 |
153 |
no ignition |
118 |
29 |
sea water |
3% |
n-heptane |
42 |
160 |
no ignition |
150 |
16 |
fresh water |
3% |
n-heptane |
49 |
180 |
no ignition |
200 |
31 |
sea water |
3% |
n-heptane |
46 |
197 |
no ignition |
120 |
17 |
fresh water |
3% |
n-heptane |
43 |
142 |
no ignition |
120 |
33 |
sea water |
3% |
n-heptane |
48 |
157 |
no ignition |
102 |
18 |
fresh water |
3% |
n-heptane |
45 |
141 |
no ignition |
111 |
35 |
sea water |
3% |
n-heptane |
47 |
149 |
no ignition |
122 |
19 |
fresh water |
3% |
n-heptane |
39 |
163 |
no ignition |
167 |
37 |
sea water |
3% |
n-heptane |
40 |
174 |
no ignition |
155 |
20 |
fresh water |
3% |
n-heptane |
59 |
181 |
no ignition |
180 |
39 |
sea water |
3% |
n-heptane |
53 |
191 |
no ignition |
168 |
21 |
fresh water |
3% |
n-heptane |
71 |
253 |
no ignition |
235 |
|
sea water |
3% |
n-heptane |
77 |
283 |
no ignition |
250 |
Table 16
Comparative Example |
Diluting water used |
Dilution ratio % |
Combustion solvent |
Foam magnification (times) |
90% control time (seconds) |
Extinguishing time (seconds) |
Vapor seal experiment |
Burn back experiment (cm2) |
Corresponding Example |
1 |
fresh water |
3% |
2-propanol |
6.3 |
56 |
171 |
no ignition |
211 |
1 |
sea water |
3% |
2-propanol |
6.1 |
59 |
187 |
no ignition |
153 |
2 |
fresh water |
3% |
methanol |
6.2 |
45 |
114 |
no ignition |
95 |
3 |
sea water |
3% |
methanol |
6.3 |
44 |
118 |
no ignition |
75 |
3 |
fresh water |
3% |
acetone |
5.9 |
50 |
137 |
no ignition |
100 |
5 |
sea water |
3% |
acetone |
6.1 |
51 |
142 |
no ignition |
90 |
4 |
fresh water |
3% |
2-propanol |
6.2 |
66 |
205 |
no ignition |
185 |
7 |
sea water |
3% |
2-propanol |
6.2 |
70 |
194 |
no ignition |
154 |
5 |
fresh water |
3% |
methanol |
6.2 |
47 |
135 |
no ignition |
99 |
9 |
sea water |
3% |
methanol |
6.3 |
46 |
123 |
no ignition |
77 |
6 |
fresh water |
3% |
acetone |
6.3 |
52 |
143 |
no ignition |
112 |
11 |
sea water |
3% |
acetone |
6.3 |
51 |
133 |
no ignition |
123 |
7 |
fresh water |
3% |
propylene oxide |
6.3 |
41 |
126 |
no ignition |
95 |
13 |
sea water |
3% |
propylene oxide |
6.3 |
42 |
127 |
no ignition |
90 |
Table 17
Comparative Example |
Diluting water used |
Dilution ratio % |
Combustion solvent |
Foam magnification (times) |
90% control time (seconds) |
Extinguishing time (seconds) |
Vapor seal experiment |
Burn back experiment (cm2) |
Corresponding Example |
8 |
fresh water |
3% |
acetone |
6.1 |
50 |
142 |
no ignition |
123 |
15 |
sea water |
3% |
acetone |
6.2 |
49 |
163 |
no ignition |
115 |
9 |
fresh water |
3% |
acetone |
6.0 |
49 |
178 |
no ignition |
203 |
17 |
sea water |
3% |
acetone |
6.1 |
50 |
193 |
no ignition |
177 |
10 |
fresh water |
3% |
acetone |
6.0 |
51 |
135 |
no ignition |
180 |
19 |
sea water |
3% |
acetone |
6.1 |
52 |
131 |
no ignition |
175 |
11 |
fresh water |
3% |
acetone |
6.1 |
46 |
142 |
no ignition |
235 |
21 |
sea water |
3% |
acetone |
6.0 |
48 |
139 |
no ignition |
201 |
12 |
fresh water |
3% |
acetone |
6.0 |
44 |
141 |
no ignition |
154 |
23 |
sea water |
3% |
acetone |
6.0 |
43 |
164 |
no ignition |
132 |
13 |
fresh water |
3% |
methanol |
6.2 |
40 |
106 |
no ignition |
94 |
25 |
sea water |
3% |
methanol |
6.1 |
41 |
115 |
no ignition |
88 |
14 |
fresh water |
3% |
acetone |
6.0 |
45 |
139 |
no ignition |
120 |
27 |
sea water |
3% |
acetone |
6.0 |
43 |
135 |
no ignition |
116 |
Table 18
Comparative Example |
Diluting water used |
Dilution ratio % |
Combustion solvent |
Foam magnification (times) |
90% control time (seconds) |
Extinguishing time (seconds) |
Vapor seal experiment |
Burn back experiment (cm2) |
Corresponding Example |
15 |
fresh water |
3% |
2-propanol |
6.3 |
53 |
181 |
no ignition |
200 |
29 |
sea water |
3% |
2-propanol |
6.3 |
57 |
170 |
no ignition |
185 |
16 |
fresh water |
3% |
methanol |
5.9 |
40 |
200 |
no ignition |
160 |
31 |
sea water |
3% |
methanol |
6.0 |
39 |
216 |
no ignition |
144 |
17 |
fresh water |
3% |
methanol |
5.9 |
41 |
149 |
no ignition |
120 |
33 |
sea water |
3% |
methanol |
6.0 |
43 |
146 |
no ignition |
109 |
18 |
fresh water |
3% |
2-propanol |
6.1 |
61 |
202 |
no ignition |
277 |
35 |
sea water |
3% |
2-propanol |
6.0 |
58 |
200 |
no ignition |
255 |
19 |
fresh water |
3% |
2-propanol |
6.3 |
58 |
180 |
no ignition |
188 |
37 |
sea water |
3% |
2-propanol |
6.3 |
55 |
131 |
no ignition |
164 |
20 |
fresh water |
3% |
acetone |
6.2 |
37 |
174 |
no ignition |
70 |
39 |
sea water |
3% |
acetone |
6.2 |
37 |
169 |
no ignition |
65 |
21 |
fresh water |
3% |
2-propanol |
6.2 |
80 |
* |
not performed |
- |
|
sea water |
3% |
2-propanol |
6.0 |
78 |
* |
not performed |
- |
* means the fire was not extinguished. |