CA2269398A1 - Anti-icing composition for aircraft - Google Patents
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- CA2269398A1 CA2269398A1 CA 2269398 CA2269398A CA2269398A1 CA 2269398 A1 CA2269398 A1 CA 2269398A1 CA 2269398 CA2269398 CA 2269398 CA 2269398 A CA2269398 A CA 2269398A CA 2269398 A1 CA2269398 A1 CA 2269398A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
- C09K3/185—Thawing materials
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Abstract
The invention relates to the use of optical brighteners in aircraft deicing compositions for improving detection of the application of deicing compositions in poor visibility conditions and at night on the surface of aircraft. The invention also relates to an anti-icing composition for aircraft, comprising water, one or more glycols, one or more corrosion inhibitors, one or more surfactants, one or more pH regulators and one or more dyes, wherein the composition additionally comprises an optical brightener which absorbs ultraviolet light and displays a fluorescence in the visible spectral region. The invention further relates to a method for deicing aircraft by applying an anti-icing composition, wherein the anti-icing composition comprises an optical brightener, and wherein complete wetting of the aircraft is established by irradiating with ultraviolet light and observing the fluorescence.
Description
Clariant GmbH 1998DE415 Dr.KM/sch Description Anti-icing composition for aircraft The present invention relates to an anti-icing composition for aircraft and the use of fluorescent dyes or optical brighteners in anti-icing compositions for aircraft.
Deicing and anti-icing compositions for aircraft (called deicing compositions or deicing fluids below) are used for removing ice, snow and/or frost from aircraft surfaces and for avoiding such deposits on these surfaces. In wintry weather conditions, complete deicing of aircraft prior to take-off using deicing compositions and complete protection of the surface against re-icing are of crucial importance for 5 ensuring smooth and safe running of air traffic.
International standards ISO 11075/11078 and AMS 1424A/1428B distinguish between type I, type II and type IV fluids. Type I fluids essentially comprise glycol, water, corrosion inhibitors) surfactants, pH regulators and optionally a dye for improved recognition on the aircraft surface. Type II and type IV fluids additionally comprise a water-soluble polymer as thickener to achieve a highly viscous pseudoplastic consistency, which ensures long-term protection against re-icing (holdover time) on the aircraft surface.
An aircraft deicing composition is described, for example, in DE-A-24 23 893 and in EP-B-0 050 700, US-4 358 389, EP-B-0 231 869 and EP-B-0 360 183. It essentially comprises:
a) from 35 to 95% by weight of at least one glycol from the group consisting of alkylene glycols hawing from 2 to 3 carbon atoms and oxalkylene glycols having from 4 to 6 carbon atoms b) from 0.02 to 1.5% by weight of at least one surfactant from the group consisting of anionic and nonionic surfactants c) at least one corrosipn inhibitor in an effective amount d) at least one basic compound from the group consisting of alkali metal carbonates, alkali metal hydroxides and amines for setting a pH of from 7 to 11 e) optionally (in the case of type II and type IV deicing compositions) from 0.05 to 3% of at least one water-soluble polymer as thickener f) water as the remaining amount up to 100% by weight, based on the finished deicing composition.
0 Deicing compositions are usually applied down onto the aircraft surface by spraying the aircraft from a tanker vehicle from a lifting platform.
As is stated in ARP 4737 from the American Federal Aviation Administration (FAA), the complete removal of any ice and snow from the aircraft surface and the complete coverage with deicing fluid are of crucial importance for a safe take-off. In order to make it easier to detect whether the surrface is completely covered with deicing compositions, the deicing fluids have for some time been colored using standard commercial dyes. For example) AMS 14288 prescribes a green coloration for type IV fluids. In the normally poor light conditions which prevail during application of deicing compositions and of course at night, these dyes represent only a limited safety advantage.
The object on which this invention is based was thus to find dyes which are suitable for use in deicing fluids and which permit detection of the application of the deicing fluid even in poor light conditions.
Surprisingly, it has been found that optical brighteners achieve this object.
The invention thus provides for the use of optical brighteners in aircraft deicing compositions for improving detection of the application of deicing compositions in poor visibility conditions and at night on the surface of aircraft.
Deicing and anti-icing compositions for aircraft (called deicing compositions or deicing fluids below) are used for removing ice, snow and/or frost from aircraft surfaces and for avoiding such deposits on these surfaces. In wintry weather conditions, complete deicing of aircraft prior to take-off using deicing compositions and complete protection of the surface against re-icing are of crucial importance for 5 ensuring smooth and safe running of air traffic.
International standards ISO 11075/11078 and AMS 1424A/1428B distinguish between type I, type II and type IV fluids. Type I fluids essentially comprise glycol, water, corrosion inhibitors) surfactants, pH regulators and optionally a dye for improved recognition on the aircraft surface. Type II and type IV fluids additionally comprise a water-soluble polymer as thickener to achieve a highly viscous pseudoplastic consistency, which ensures long-term protection against re-icing (holdover time) on the aircraft surface.
An aircraft deicing composition is described, for example, in DE-A-24 23 893 and in EP-B-0 050 700, US-4 358 389, EP-B-0 231 869 and EP-B-0 360 183. It essentially comprises:
a) from 35 to 95% by weight of at least one glycol from the group consisting of alkylene glycols hawing from 2 to 3 carbon atoms and oxalkylene glycols having from 4 to 6 carbon atoms b) from 0.02 to 1.5% by weight of at least one surfactant from the group consisting of anionic and nonionic surfactants c) at least one corrosipn inhibitor in an effective amount d) at least one basic compound from the group consisting of alkali metal carbonates, alkali metal hydroxides and amines for setting a pH of from 7 to 11 e) optionally (in the case of type II and type IV deicing compositions) from 0.05 to 3% of at least one water-soluble polymer as thickener f) water as the remaining amount up to 100% by weight, based on the finished deicing composition.
0 Deicing compositions are usually applied down onto the aircraft surface by spraying the aircraft from a tanker vehicle from a lifting platform.
As is stated in ARP 4737 from the American Federal Aviation Administration (FAA), the complete removal of any ice and snow from the aircraft surface and the complete coverage with deicing fluid are of crucial importance for a safe take-off. In order to make it easier to detect whether the surrface is completely covered with deicing compositions, the deicing fluids have for some time been colored using standard commercial dyes. For example) AMS 14288 prescribes a green coloration for type IV fluids. In the normally poor light conditions which prevail during application of deicing compositions and of course at night, these dyes represent only a limited safety advantage.
The object on which this invention is based was thus to find dyes which are suitable for use in deicing fluids and which permit detection of the application of the deicing fluid even in poor light conditions.
Surprisingly, it has been found that optical brighteners achieve this object.
The invention thus provides for the use of optical brighteners in aircraft deicing compositions for improving detection of the application of deicing compositions in poor visibility conditions and at night on the surface of aircraft.
The invention also provides an anti-icing composition for aircraft, comprising water, one or more glycols, one or more corrosion inhibitors, one or more surfactants, one or more pH regulators and one or more dyes, wherein the composition additionally comprises an optical brightener which absorbs ultraviolet light and displays a fluorescence in the visible spectral region.
The invention further provides a method for the deicing of aircraft by applying an anti-icing composition, wherein the anti-icing composition comprises an optical brightener, and wherein the complete wetting of the aircraft is established by irradiating with ultraviolet light and observing the fluorescence.
In a preferred embodiment of the invention, the anti-icing composition comprises from 0.05 to 3% by weight, based on the anti-icing composition, of a water-soluble polymer as thickener.
Optical brighteners can generally be referred to as substances which absorb in the ultraviolet wavelength region and re-emit some of the absorbed electromagnetic radiation in the wavelength region of visible light. Preferred ultraviolet wavelengths are between 350 and 380 nm. Typical compounds for this application are of an anionic, cationic or nonionic nature.
Examples of suitable anionic optical brighteners are given below.
1 i(S03M)(0_3) 1 - (S03M)(0_3) ~N N
N/ ~~'-NH / ~ - / ~ NH~/ ~N
(1) ~N N
1 (S03M) (S03M) R1- (S03M)(0_3) (S03M)(0-3) in which R' is in each case independently OH, NH2 , O-(C,-C4)-alkyl, O-aryl, NH-(C,-C4)-alkyl, N-((C,-C,)-alkyl)2, N-((C,-C4)-alkyl)-((C,-C4)-hydroxyalkyl), N-((C,-C4)-hydroxyalkyl)Z, NH-aryl, morpholino, S-(C,-C4)-alkylaryl or CI, and M is Na+, K+, NH4+
or NH~4_a~Ra in which a = 1) 2 or 3 and R = C,-C4-hydroxyalkyl, in particular C2-hydroxyalkyl, the stoichiometric indices of the sulfonate groups being dependent on the type of radical R', namely on the number of such groups this radical can carry;
Ar2 0 \CH ~ N (2) /CH-N-Ark R2, in which Ar' and Arz independently of one another are substituted or unsubstituted 5 aryl radicals, and R2 and R2', which can be identical or different, are hydrogen, (C,-C4)-alkyl or phenyl;
Ar3 \CH ~ N (3) CH-N-Ar4 20 2, ~
R
in which Ar3 and Ar4 independently of one another are phenyl) Biphenyl or naphthyl radicals which can carry further substituents such as hydroxyl, (C,-Cs)-alkyl, (C,-C6)-alkoxy, halogen, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, 25 alkoxycarbonyl, sulfonic acid, sulfonic esters, alkylsulfonyl, arylsulfonyl) sulfonyl and sulfonamide groups;
/
(R3)m 30 R2HC ~N (4) R2~HC N
in which R3 is halogen or (C,-C6)-alkyl, R" is a substituted or unsubstituted (C,-Cs)-alkoxycarbonyl, (C,-Cs)-alkylsulfonyl, sulfonamide or sulfonic acid group, and m is zero, 1, 2 or 3;
CI
~\N
N~
(5) S02 CH2 C(CH3)2 S03M
CI
~\N
N
The invention further provides a method for the deicing of aircraft by applying an anti-icing composition, wherein the anti-icing composition comprises an optical brightener, and wherein the complete wetting of the aircraft is established by irradiating with ultraviolet light and observing the fluorescence.
In a preferred embodiment of the invention, the anti-icing composition comprises from 0.05 to 3% by weight, based on the anti-icing composition, of a water-soluble polymer as thickener.
Optical brighteners can generally be referred to as substances which absorb in the ultraviolet wavelength region and re-emit some of the absorbed electromagnetic radiation in the wavelength region of visible light. Preferred ultraviolet wavelengths are between 350 and 380 nm. Typical compounds for this application are of an anionic, cationic or nonionic nature.
Examples of suitable anionic optical brighteners are given below.
1 i(S03M)(0_3) 1 - (S03M)(0_3) ~N N
N/ ~~'-NH / ~ - / ~ NH~/ ~N
(1) ~N N
1 (S03M) (S03M) R1- (S03M)(0_3) (S03M)(0-3) in which R' is in each case independently OH, NH2 , O-(C,-C4)-alkyl, O-aryl, NH-(C,-C4)-alkyl, N-((C,-C,)-alkyl)2, N-((C,-C4)-alkyl)-((C,-C4)-hydroxyalkyl), N-((C,-C4)-hydroxyalkyl)Z, NH-aryl, morpholino, S-(C,-C4)-alkylaryl or CI, and M is Na+, K+, NH4+
or NH~4_a~Ra in which a = 1) 2 or 3 and R = C,-C4-hydroxyalkyl, in particular C2-hydroxyalkyl, the stoichiometric indices of the sulfonate groups being dependent on the type of radical R', namely on the number of such groups this radical can carry;
Ar2 0 \CH ~ N (2) /CH-N-Ark R2, in which Ar' and Arz independently of one another are substituted or unsubstituted 5 aryl radicals, and R2 and R2', which can be identical or different, are hydrogen, (C,-C4)-alkyl or phenyl;
Ar3 \CH ~ N (3) CH-N-Ar4 20 2, ~
R
in which Ar3 and Ar4 independently of one another are phenyl) Biphenyl or naphthyl radicals which can carry further substituents such as hydroxyl, (C,-Cs)-alkyl, (C,-C6)-alkoxy, halogen, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, 25 alkoxycarbonyl, sulfonic acid, sulfonic esters, alkylsulfonyl, arylsulfonyl) sulfonyl and sulfonamide groups;
/
(R3)m 30 R2HC ~N (4) R2~HC N
in which R3 is halogen or (C,-C6)-alkyl, R" is a substituted or unsubstituted (C,-Cs)-alkoxycarbonyl, (C,-Cs)-alkylsulfonyl, sulfonamide or sulfonic acid group, and m is zero, 1, 2 or 3;
CI
~\N
N~
(5) S02 CH2 C(CH3)2 S03M
CI
~\N
N
(6) CI
(7) Aryl / N\ ~ ~ N Aryl N
N, ~N ~ Ca) (9) 0 J n (S03M)1-2 (S03M)1_2 where RS = H, alkyl, oxalkyl, halogen, CN, COO-(C,-C4)-alkyl or CO-N[(C,-C4)-alkyl]z andn=Oor1;
(M03S)n (S03M)n S03M \
~N\ ( 20 ~ NON ~ ~ CH CH ~ ~ N 10) N N
(S03M)n i ~N\
CH CH ~ ~ N
~N ~ ~ (11) in which n is 0 or 1, / \ CH CH / ~ / ~ CH CH
(12) CI / ~ / ~ / ~ CH = CH / \ CI
CH = CH
( 13) CH = CH / ~ / ~ CH = CH / \ (14) U
~ / ~ ~ ~ , (1 -O- ~ ~ ~O~ a ~ / ~ ~ ~ , (1 O
(17) S03M O U ~ ~O v ~03M
/ \ / \ ~ ~ ~ (18) (S03M)3_4 The optical brighteners of a cationic nature are preferably compounds with a pyrazoline base structure which are in salt form, i.e. acid addition salts.
Suitable acids for this purpose are those which have colorless anions, such as, for example, C,-C3-alkanoates, C,-C4-alkanephosphates, C,-C4 alkanesulfonates, CZ C3-hydroxyalkanoates, phosphite, sulfamate, halides, methosulfate, p-toluenesulfonate, preferably those which have good solub~lities in water, for example Ars (19) HZC~ N
H2C--~-N Ar6 in which Ar5 and Are independently of one another are substituted or unsubstituted aryl radicals, and R6 is hydrogen, C,-C4 alkyl or phenyl.
Of particular interest are compounds of the formula Ar7 (20) H2C~ N
H2C--~--N Ar8 in which Ar, and Are independently of one another are phenyl, Biphenyl or naphthyl radicals which can carry further substituents such as hydroxyl, (C,-C6)-alkyl, (C,-Cs)-alkoxy, halogen, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, alkoxycarbonyl, sulfonic acid, sulfonic esters, alkylsulfonyl, arylsulfonyl, sulfonyl and sulfonamide groups, and R6 is as defined above.
Particular preference is given to compounds of the formula i (R7)m (21 ) HzCI ~ N
H2C -~-- N
Rg R$
in which R' is hydrogen, halogen or C,-Cs-alkyl, Re is a substituted or unsubstituted C,-C6-alkoxycarbonyl, C,-Cg-alkylsulfonyl, sulfonamide or sulfonic acid group, and m is zero, 1, 2 or 3) and RB is as defined above.
Particular preference is also given to compounds of the formula n+
r9 (22) HZCI ~ N
HzC~N / \ S~2 - R10 - N R9 R9 nA-in which Ars is a group of the formulae CI
R~ , ( \ , or ~ , i i 23a 23b 23c 23d R'° is substituted or unsubstituted C,-Cs alkylene, C,-C6-alkylene-O-C,-C6-alkylene, C,-Cg alkylene-CONH-C,-C6-alkylene, C,-C6-alkylene-COO-C,-C6 alkylene, -NH-Cz-C4 alkylene or -Cz-CQ hydroxyalkylene-NH-Cz-C4-alkylene, R9 is independently of one another hydrogen, C,-C6-alkyl, Cz-C6-5 hydroxyalkyl, or in each case two radicals R9 together with the N atom are a morpholino, pyrrolidino, piperidino, N-alkylpiperazino or N-hydroxyethylpiperazino group, R" and R'z independently of one another are hydrogen, methyl or chlorine, R6 and R' are as defined above, n is zero or 1, and A is a colorless anion.
10 Suitable and preferred pyrazoline brighteners are especially the compounds of the following formula Ark 0 (24) M2CI w N
HZC N ~ ~ S02 - R13 in which Ar'° is a 4-chlorophenyl group and R'3 is a group of the following formulae:
-NHz, -CzH4N(CH3)z, -CHzCHCH3N(CH3)z, -Czl"'~aOCzE.I4N(CH3)z, _ CHCH3CH2N(CH3)z or Ar'° is a 2-methyl-4,5-dichlorophenyl group and R'3 is a group of the formula -CZH4N(CH3)z) (CHz)X -OCOR'4 or (CHz)X OR'S, X is a number from to 4, R'4 is C,-Cg-alkyl, preferably C,-C3-alkyl or C,-C6-hydroxyalkyl, preferably C,-C3-hydroxyalkyl, and R'S is hydrogen or C,-Cg-alkyl, preferably C,-C3-alkyl.
Suitable C,-C6-alkyl radicals are unbranched and branched alkyl radicals, such as the methyl, ethyl, propyl, butyl, pentyl and hexyl radicals. The same applies to the C,-C8-alkoxy groups and the C,-Cg-alkylene groups.
Other compounds of a cationic nature are benzimidazole-benzofuran derivatives or benzimidazole-benzoxazole derivatives of the formula 1 ~ S02CH3 X N
\~/
R16 ~ ~ N ~ (25) R
in which X' is N or CH, R'6 is C,- to C4 alkoxy, and R" and R'8 independently of one another are C,- to C4-alkyl, and A is a colorless anion.
Other compounds of a cationic nature are based on coumarin:
.~ n (26) in which R'9 is H, CI or CHZCOOH, R2° is H, phenyl, COO-(C,- to C4 alkyl) or a group of the formula N~> (27) N
and R2' is O-C,-C4 alkyl, N-(C,-C4 alkyl)2, NH-CO-(C,-C4-alkyl) or a group of the formulae N ~ N CH3 N R25 -N~~ ~N -N ~ -N ~ or , , ~
28a 28b 28c 28d in which R22 and R23 independently of one another are phenyl, mono- or disulfonated phenyl, phenylamino, morpholino, -N(CHZCH20H)2, -N(CH3)(CHZCHZOH), -NH2, -N(C,-C4-Alkyl), -OCH3, -CI, NH-CH2CHZS03H or -NH-CHZCHZOH, and R24, Rzs and Rzs are H, C,-C4-alkyl or phenyl.
The optical brighteners of a nonionic nature preferably conform to the following formulae:
~ O j~- X 2-~ O U (291 in which R2' and RZ$ independently of one another are H or (C,-Cs)-alkyl, X3 is N or CH and X2 is a bond via 1,4-naphthyl, 2,5-thiophene, 2,5-furan, 1,4-phenyl, ethylene, stilbene, styryl or imidazo~yl units, N / ~ CH CH / \ B
X4 ~ ~ ~ n where X4 is O or S, R29 in the 5-position is a hydrogen or chlorine atom, a methyl or phenyl group and R3° is a hydrogen atom, or R29 and R3° are both a methyl group in 5,6- or 5,7-position, n is 0 or 1, and B is a cyano or carbo-(C,-C4)-alkoxy group or a group of the formulae ~~ -O ~O-N
O Rs2 N~Rs, N~Rs, N-N
(31 a) (31 b) (31 c) R~
N Rs3 N-(31 d) (31 e) in which R3' is (C,-C6)-alkyl, (C,-Cg)-chloroalkyl, (C,-C4)-alkoxy-(C,-C4)-alkyl, hydroxy-(C,-C4)-alkyl or a group of the formula -(CH2CH20)~-R35, n is 2 or 3 and R3s is hydrogen or (C,-C4)-alkyl, R32 is phenyl) halophenyl, (C,-C4)-alkylphenyl or (C,-C4)-5 alkoxyphenyl, R33 is (C,-C;,)-alkyl and R34 is cyano or carbo-(C,-C4)-alkoxy. In formula 31 e, the semicircle which has been drawn in indicates that a double bond is present) in each case between 2 of the nitrogen atoms, and consequently the radical R33 adopts a correspondingly suitable position for valence saturation.
Other preferred optical brighteners of a nonionic nature are:
CN CN
CH CH / \ CH CH ~ (32) where the CN groups are identical or different and can be in the ortho, meta or para position, -alkyl N ~N
_ ~O-alkyl ~.--~ N (33) (~) where R36 is hydrogen or alkoxy, R3' is alkoxy and R3° is alkyl, alkoxyalkyl or dialkylaminoalkyl, (35) R2g O O
~ (36) i O O
N(R~2)2 where R39 is phenyl or the group of the formula I
(37) -N~
N
and R4° is a group of the formulae N alkyl N
-N , ~ \
5 'N~ / ~ °~ N'N
(38a) (38b) and R'z is as defined above, N O
(39) ' N
(C~-C~-alkyl-OOC-- - O CH=CH2-COO-(C~-C~-alkyl (40) The use of such optical brighteners in small concentrations in aircraft deicing compositions makes it possible, by virtue of the fluorescence effect triggered by UV
light irradiation) to easily check, even in darkness, whether all of the surfaces of an aircraft are coated with anti-icing composition. This represents a safety advantage prior to the aircraft taking off. The invention is now illustrated in more detail by reference to examples.
Example 1:
Into 1000 g of a thickened aircraft anti-icing composition consisting of a) 500 g of 1,2-propylene glycol, b) 2 g of sodium alkylbenzenesulfonate as surfactant c) 1 g of benzotriazole as corrosion inhibitor d) 3.3 g of crosslinked polyacrylic acid as thickener e) 1.2 g of sodium hydroxide to adjust the pH to from 7.0 to 7.5 f) 0.05 g of green water-soluble dye and g) water as residual amount up to 1000 g were dissolved h) 0.05 g of an optical brightener of the formula N
NH~/ N (41 ).
N-S03Na NH
S03Na The deicing composition was poured onto an aluminum surface and illuminated in darkness with UV light of a wavelength of 350 nm. Complete coverage of the aluminum surface with deicing composition and thus complete protection against icing could be unambiguously observed from the blue green-white fluorescence.
On illumination with visible light, differentiation between aluminum surfaces coated with deicing compositions and unprotected aluminum surfaces was possible only to an inadequate degree.
Comparative Example 1:
The thickened deicing composition from Example 1, consisting of components a) to g) without the addition of the optical brightener h) was poured onto an aluminum surface. It was not possible to unambiguously assess complete coverage of the aluminum surface on illumination with visible light or UV light.
Example 2:
Into 1000 g of a thickened aircraft deicing composition comprising a) 600 g of monoethylene glycol, b) 2 g of fatty alcohol ethoxylate as surfactant c) 1 g of tolyltriazole end 1 g of sodium phosphate as corrosion inhibitors d) 2.5 g of xanthan as thickener and e) water as residual amount up to 1000 g were dissolved f) 0.05 g of a brightener as in Example 1.
The deicing composition was heated to 70°C and sprayed onto an aluminum surface covered with 1 mm of ice until the ice had melted and a protective film of deicing composition remained on the surface. By illuminating with UV light of a wavelength of 350 nm, it was clearly possible to observe from the white fluorescence complete coverage of the aluminum surface with deicing composition and thus complete protection against re-icing. On illumination with visible light, differentiation between aluminum surfaces coated with deicing composition and iced aluminum surfaces was possible only to an inadequate degree.
Comparative Example 2:
The thickened deicing composition from Example 2, consisting of components a) to e) without the addition of the optical brightener f) was heated to 70°C
and sprayed onto an aluminum surface coated with 1 mm of ice until the ice had melted and a protective film of deicing composition remained on the surface. Merely by omitting component f), in darkness it was not possible to differentiate between aluminum surfaces coated with deicing composition and iced aluminum surfaces by illumination with UV light. On illumination with visible light, a differentiation between aluminum surfaces coated with deicing composition and iced aluminum surfaces was possible only to an inadequate degree.
Example 3:
The procedure was as in Example 1. The optical brightener used was 0.05 g of a brightener of the formula CI
,N
N
(42) O
S02 - CH2 - CH2 - N~ - H COOH
Complete coverage of the AI surface with deicing composition was observed from the bluish fluorescence.
Example 4:
5 The procedure was as in Example 1, but 350 mg of the brightener of the formula X x ~N ~ ~ ~ O (43) O ~' O
were dissolved in 500 ml of propylene glycol with slight heating. Complete coverage of the AI surface with deicing composition was observed from the bluish fluorescence.
N, ~N ~ Ca) (9) 0 J n (S03M)1-2 (S03M)1_2 where RS = H, alkyl, oxalkyl, halogen, CN, COO-(C,-C4)-alkyl or CO-N[(C,-C4)-alkyl]z andn=Oor1;
(M03S)n (S03M)n S03M \
~N\ ( 20 ~ NON ~ ~ CH CH ~ ~ N 10) N N
(S03M)n i ~N\
CH CH ~ ~ N
~N ~ ~ (11) in which n is 0 or 1, / \ CH CH / ~ / ~ CH CH
(12) CI / ~ / ~ / ~ CH = CH / \ CI
CH = CH
( 13) CH = CH / ~ / ~ CH = CH / \ (14) U
~ / ~ ~ ~ , (1 -O- ~ ~ ~O~ a ~ / ~ ~ ~ , (1 O
(17) S03M O U ~ ~O v ~03M
/ \ / \ ~ ~ ~ (18) (S03M)3_4 The optical brighteners of a cationic nature are preferably compounds with a pyrazoline base structure which are in salt form, i.e. acid addition salts.
Suitable acids for this purpose are those which have colorless anions, such as, for example, C,-C3-alkanoates, C,-C4-alkanephosphates, C,-C4 alkanesulfonates, CZ C3-hydroxyalkanoates, phosphite, sulfamate, halides, methosulfate, p-toluenesulfonate, preferably those which have good solub~lities in water, for example Ars (19) HZC~ N
H2C--~-N Ar6 in which Ar5 and Are independently of one another are substituted or unsubstituted aryl radicals, and R6 is hydrogen, C,-C4 alkyl or phenyl.
Of particular interest are compounds of the formula Ar7 (20) H2C~ N
H2C--~--N Ar8 in which Ar, and Are independently of one another are phenyl, Biphenyl or naphthyl radicals which can carry further substituents such as hydroxyl, (C,-C6)-alkyl, (C,-Cs)-alkoxy, halogen, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, alkoxycarbonyl, sulfonic acid, sulfonic esters, alkylsulfonyl, arylsulfonyl, sulfonyl and sulfonamide groups, and R6 is as defined above.
Particular preference is given to compounds of the formula i (R7)m (21 ) HzCI ~ N
H2C -~-- N
Rg R$
in which R' is hydrogen, halogen or C,-Cs-alkyl, Re is a substituted or unsubstituted C,-C6-alkoxycarbonyl, C,-Cg-alkylsulfonyl, sulfonamide or sulfonic acid group, and m is zero, 1, 2 or 3) and RB is as defined above.
Particular preference is also given to compounds of the formula n+
r9 (22) HZCI ~ N
HzC~N / \ S~2 - R10 - N R9 R9 nA-in which Ars is a group of the formulae CI
R~ , ( \ , or ~ , i i 23a 23b 23c 23d R'° is substituted or unsubstituted C,-Cs alkylene, C,-C6-alkylene-O-C,-C6-alkylene, C,-Cg alkylene-CONH-C,-C6-alkylene, C,-C6-alkylene-COO-C,-C6 alkylene, -NH-Cz-C4 alkylene or -Cz-CQ hydroxyalkylene-NH-Cz-C4-alkylene, R9 is independently of one another hydrogen, C,-C6-alkyl, Cz-C6-5 hydroxyalkyl, or in each case two radicals R9 together with the N atom are a morpholino, pyrrolidino, piperidino, N-alkylpiperazino or N-hydroxyethylpiperazino group, R" and R'z independently of one another are hydrogen, methyl or chlorine, R6 and R' are as defined above, n is zero or 1, and A is a colorless anion.
10 Suitable and preferred pyrazoline brighteners are especially the compounds of the following formula Ark 0 (24) M2CI w N
HZC N ~ ~ S02 - R13 in which Ar'° is a 4-chlorophenyl group and R'3 is a group of the following formulae:
-NHz, -CzH4N(CH3)z, -CHzCHCH3N(CH3)z, -Czl"'~aOCzE.I4N(CH3)z, _ CHCH3CH2N(CH3)z or Ar'° is a 2-methyl-4,5-dichlorophenyl group and R'3 is a group of the formula -CZH4N(CH3)z) (CHz)X -OCOR'4 or (CHz)X OR'S, X is a number from to 4, R'4 is C,-Cg-alkyl, preferably C,-C3-alkyl or C,-C6-hydroxyalkyl, preferably C,-C3-hydroxyalkyl, and R'S is hydrogen or C,-Cg-alkyl, preferably C,-C3-alkyl.
Suitable C,-C6-alkyl radicals are unbranched and branched alkyl radicals, such as the methyl, ethyl, propyl, butyl, pentyl and hexyl radicals. The same applies to the C,-C8-alkoxy groups and the C,-Cg-alkylene groups.
Other compounds of a cationic nature are benzimidazole-benzofuran derivatives or benzimidazole-benzoxazole derivatives of the formula 1 ~ S02CH3 X N
\~/
R16 ~ ~ N ~ (25) R
in which X' is N or CH, R'6 is C,- to C4 alkoxy, and R" and R'8 independently of one another are C,- to C4-alkyl, and A is a colorless anion.
Other compounds of a cationic nature are based on coumarin:
.~ n (26) in which R'9 is H, CI or CHZCOOH, R2° is H, phenyl, COO-(C,- to C4 alkyl) or a group of the formula N~> (27) N
and R2' is O-C,-C4 alkyl, N-(C,-C4 alkyl)2, NH-CO-(C,-C4-alkyl) or a group of the formulae N ~ N CH3 N R25 -N~~ ~N -N ~ -N ~ or , , ~
28a 28b 28c 28d in which R22 and R23 independently of one another are phenyl, mono- or disulfonated phenyl, phenylamino, morpholino, -N(CHZCH20H)2, -N(CH3)(CHZCHZOH), -NH2, -N(C,-C4-Alkyl), -OCH3, -CI, NH-CH2CHZS03H or -NH-CHZCHZOH, and R24, Rzs and Rzs are H, C,-C4-alkyl or phenyl.
The optical brighteners of a nonionic nature preferably conform to the following formulae:
~ O j~- X 2-~ O U (291 in which R2' and RZ$ independently of one another are H or (C,-Cs)-alkyl, X3 is N or CH and X2 is a bond via 1,4-naphthyl, 2,5-thiophene, 2,5-furan, 1,4-phenyl, ethylene, stilbene, styryl or imidazo~yl units, N / ~ CH CH / \ B
X4 ~ ~ ~ n where X4 is O or S, R29 in the 5-position is a hydrogen or chlorine atom, a methyl or phenyl group and R3° is a hydrogen atom, or R29 and R3° are both a methyl group in 5,6- or 5,7-position, n is 0 or 1, and B is a cyano or carbo-(C,-C4)-alkoxy group or a group of the formulae ~~ -O ~O-N
O Rs2 N~Rs, N~Rs, N-N
(31 a) (31 b) (31 c) R~
N Rs3 N-(31 d) (31 e) in which R3' is (C,-C6)-alkyl, (C,-Cg)-chloroalkyl, (C,-C4)-alkoxy-(C,-C4)-alkyl, hydroxy-(C,-C4)-alkyl or a group of the formula -(CH2CH20)~-R35, n is 2 or 3 and R3s is hydrogen or (C,-C4)-alkyl, R32 is phenyl) halophenyl, (C,-C4)-alkylphenyl or (C,-C4)-5 alkoxyphenyl, R33 is (C,-C;,)-alkyl and R34 is cyano or carbo-(C,-C4)-alkoxy. In formula 31 e, the semicircle which has been drawn in indicates that a double bond is present) in each case between 2 of the nitrogen atoms, and consequently the radical R33 adopts a correspondingly suitable position for valence saturation.
Other preferred optical brighteners of a nonionic nature are:
CN CN
CH CH / \ CH CH ~ (32) where the CN groups are identical or different and can be in the ortho, meta or para position, -alkyl N ~N
_ ~O-alkyl ~.--~ N (33) (~) where R36 is hydrogen or alkoxy, R3' is alkoxy and R3° is alkyl, alkoxyalkyl or dialkylaminoalkyl, (35) R2g O O
~ (36) i O O
N(R~2)2 where R39 is phenyl or the group of the formula I
(37) -N~
N
and R4° is a group of the formulae N alkyl N
-N , ~ \
5 'N~ / ~ °~ N'N
(38a) (38b) and R'z is as defined above, N O
(39) ' N
(C~-C~-alkyl-OOC-- - O CH=CH2-COO-(C~-C~-alkyl (40) The use of such optical brighteners in small concentrations in aircraft deicing compositions makes it possible, by virtue of the fluorescence effect triggered by UV
light irradiation) to easily check, even in darkness, whether all of the surfaces of an aircraft are coated with anti-icing composition. This represents a safety advantage prior to the aircraft taking off. The invention is now illustrated in more detail by reference to examples.
Example 1:
Into 1000 g of a thickened aircraft anti-icing composition consisting of a) 500 g of 1,2-propylene glycol, b) 2 g of sodium alkylbenzenesulfonate as surfactant c) 1 g of benzotriazole as corrosion inhibitor d) 3.3 g of crosslinked polyacrylic acid as thickener e) 1.2 g of sodium hydroxide to adjust the pH to from 7.0 to 7.5 f) 0.05 g of green water-soluble dye and g) water as residual amount up to 1000 g were dissolved h) 0.05 g of an optical brightener of the formula N
NH~/ N (41 ).
N-S03Na NH
S03Na The deicing composition was poured onto an aluminum surface and illuminated in darkness with UV light of a wavelength of 350 nm. Complete coverage of the aluminum surface with deicing composition and thus complete protection against icing could be unambiguously observed from the blue green-white fluorescence.
On illumination with visible light, differentiation between aluminum surfaces coated with deicing compositions and unprotected aluminum surfaces was possible only to an inadequate degree.
Comparative Example 1:
The thickened deicing composition from Example 1, consisting of components a) to g) without the addition of the optical brightener h) was poured onto an aluminum surface. It was not possible to unambiguously assess complete coverage of the aluminum surface on illumination with visible light or UV light.
Example 2:
Into 1000 g of a thickened aircraft deicing composition comprising a) 600 g of monoethylene glycol, b) 2 g of fatty alcohol ethoxylate as surfactant c) 1 g of tolyltriazole end 1 g of sodium phosphate as corrosion inhibitors d) 2.5 g of xanthan as thickener and e) water as residual amount up to 1000 g were dissolved f) 0.05 g of a brightener as in Example 1.
The deicing composition was heated to 70°C and sprayed onto an aluminum surface covered with 1 mm of ice until the ice had melted and a protective film of deicing composition remained on the surface. By illuminating with UV light of a wavelength of 350 nm, it was clearly possible to observe from the white fluorescence complete coverage of the aluminum surface with deicing composition and thus complete protection against re-icing. On illumination with visible light, differentiation between aluminum surfaces coated with deicing composition and iced aluminum surfaces was possible only to an inadequate degree.
Comparative Example 2:
The thickened deicing composition from Example 2, consisting of components a) to e) without the addition of the optical brightener f) was heated to 70°C
and sprayed onto an aluminum surface coated with 1 mm of ice until the ice had melted and a protective film of deicing composition remained on the surface. Merely by omitting component f), in darkness it was not possible to differentiate between aluminum surfaces coated with deicing composition and iced aluminum surfaces by illumination with UV light. On illumination with visible light, a differentiation between aluminum surfaces coated with deicing composition and iced aluminum surfaces was possible only to an inadequate degree.
Example 3:
The procedure was as in Example 1. The optical brightener used was 0.05 g of a brightener of the formula CI
,N
N
(42) O
S02 - CH2 - CH2 - N~ - H COOH
Complete coverage of the AI surface with deicing composition was observed from the bluish fluorescence.
Example 4:
5 The procedure was as in Example 1, but 350 mg of the brightener of the formula X x ~N ~ ~ ~ O (43) O ~' O
were dissolved in 500 ml of propylene glycol with slight heating. Complete coverage of the AI surface with deicing composition was observed from the bluish fluorescence.
Claims (6)
1) An anti-icing composition for aircraft comprising water, one or more glycols, one or more corrosion inhibitors, one or more surfactants, one or more pH
regulators and one or more dyes, wherein the composition additionally comprises an optical brightener which absorbs ultraviolet light and displays a fluorescence in the visible spectral region.
regulators and one or more dyes, wherein the composition additionally comprises an optical brightener which absorbs ultraviolet light and displays a fluorescence in the visible spectral region.
2) An anti-icing composition as claimed in claim 1 wherein the content of thickener is from 0.05 to 3% by weight, based on the anti-icing composition.
3) An anti-icing composition as claimed in claim 1 and/or 2, wherein the optical brightener is an anionic, cationic or nonionic optical brightener or a mixture of such brighteners.
4) An anti-icing composition as claimed in one or more of claims 1 to 3, which comprises optical brighteners in amounts of from 0.001 to 0.5% by weight, based on the anti-icing composition.
5) The use of optical brighteners in anti-icing compositions for aircraft for improving detection of the application of the anti-icing compositions in poor visibility conditions and at night on the surface of aircraft.
6) A method for deicing aircraft by applying an anti-icing composition, wherein the anti-icing composition comprises an optical brightener, and wherein the complete wetting of the aircraft is established by irradiating with ultraviolet light and observing the fluorescence.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1998116796 DE19816796A1 (en) | 1998-04-16 | 1998-04-16 | Anti-icing agents for aircraft |
| DE19816796.2 | 1998-04-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2269398A1 true CA2269398A1 (en) | 1999-10-16 |
Family
ID=7864669
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2269398 Abandoned CA2269398A1 (en) | 1998-04-16 | 1999-04-15 | Anti-icing composition for aircraft |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0950700A1 (en) |
| CA (1) | CA2269398A1 (en) |
| DE (1) | DE19816796A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013190331A2 (en) * | 2012-06-22 | 2013-12-27 | Esseco Uk Limited | Composition, system and method for preventing formation of frozen water or for causing the same to melt |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2792324B1 (en) * | 1999-04-14 | 2006-10-06 | Sfim Ind | IMPROVEMENTS IN THE DETECTION OF THE PRESENCE OF FROZEN, ICE OR SNOW, AS WELL AS THE PRESENCE OF A DEFROSTING OR ANTI-FROZEN LIQUID, ON THE SURFACE OF AN AIRCRAFT, SUCH AS AN AIRCRAFT ON THE GROUND |
| DE20209157U1 (en) | 2002-06-13 | 2002-10-31 | Nutrinova Nutrition Specialties & Food Ingredients GmbH, 65929 Frankfurt | Detectable agent for wood treatment |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5039439A (en) * | 1989-03-17 | 1991-08-13 | Massachusetts Institute Of Technology | Optically indicating surface de-icing fluids |
| AT399597B (en) * | 1991-08-29 | 1995-06-26 | Scharsching Helmut Dr | METHOD FOR LARGE AREA MEASUREMENT OF DIFFERENT AMOUNTS OF DEFUMER TO PREVENT SMOOTHNESS ON TRAFFIC AREAS |
| DE4333646A1 (en) * | 1993-10-02 | 1995-04-06 | Hoechst Ag | De-icing and anti-icing agents for aircraft |
| DE4412790A1 (en) * | 1994-04-14 | 1995-10-19 | Hoechst Ag | Polymer-thickened deicing agent and anti-icing agent for aircraft |
| US5708068A (en) * | 1995-01-16 | 1998-01-13 | Union Carbide Chemicals & Plastics Technology Corporation | Aircraft deicing/anti-icing fluids thickened by associative polymers |
-
1998
- 1998-04-16 DE DE1998116796 patent/DE19816796A1/en not_active Withdrawn
-
1999
- 1999-04-09 EP EP99106979A patent/EP0950700A1/en not_active Withdrawn
- 1999-04-15 CA CA 2269398 patent/CA2269398A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013190331A2 (en) * | 2012-06-22 | 2013-12-27 | Esseco Uk Limited | Composition, system and method for preventing formation of frozen water or for causing the same to melt |
| WO2013190331A3 (en) * | 2012-06-22 | 2014-03-06 | Esseco Uk Limited | Composition, system and method for preventing formation of frozen water or for causing the same to melt |
| US10072191B2 (en) | 2012-06-22 | 2018-09-11 | Esseco Uk Limited | Composition, system and method for preventing formation of frozen water or for causing the same to melt |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0950700A1 (en) | 1999-10-20 |
| DE19816796A1 (en) | 1999-10-21 |
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