WO1996004961B1

WO1996004961B1 - Synergistic surfactant compositions and fire fighting concentrates thereof

Info

Publication number: WO1996004961B1
Application number: PCT/US1995/010682
Authority: WO
Filing date: 1995-07-27
Publication date: 1996-03-07
Anticipated expiration: 1997-02-11

Abstract

This invention relates to synergistic surfactant compositions based on water insoluble amphoteric fluorochemical surfactants and water soluble anionic hydrocarbon or fluorochemical surfactants of the sulfate or sulfonate type and aqueous film forming foam agents derived from such synergistic surfactant compositions and a method to treat the aqueous waste stream generated by such aqueous film forming foam agents.

Claims

AMENDED CLAIMS

[received by the International Bureau on 13 February 1996 (13.02.96);

original claims 2-5 and 7-10 amended; remaining claims unchanged (8 pages)]

1. A synergistic surfactant composition providing a surface tension in water of 20 dynes/cm or below said composition comprising from 5 to 95% by weight of a fluoroaliphatic amphoteric surfactant having a solubility of less than

0.01% in water at 25° C and from 5 to 95% by weight of a water soluble

hydrocarbon or fluoroaliphatic anionic sulfate or sulfonate surfactant.

2. The synergistic surfactant composition of claim 1 comprising a

fluoroaliphatic amphotenc surfactant of the formula

R_f-L₁-N⁺(R₁)(R₂)-(CH₂)_mQ- wherein

R_f is a straight or branched chain perfluoroalkyl group with 5 to 18 carbon atoms;

L₁ is a bivalent linking group with 1 to 4 carbon atoms;

R₁ and R₂ each are alkyl or hydroxyalkyl with 1 to 4 carbon atoms or

hydrogen, where only one of the R₁ and R₂ substitutes can be

hydrogen;

Q- is -COO- or -SO₃- and

m is 1 to 4

and comprising an anionic sulfate or sulfonate surfactant of the formula

R-L₂-Q₂

wherein

R is either R_f or R_h where R_f is a straight or branched chain perfluoroalkyl group with 3 to 18 carbon atoms and R_h is a straight or branched alkyl, alkenyl, cyclυalkanyl or cyeloparaffin group with 6 to 18 carbon atoms;

L₂ is either a bond between R and Q₂ or a bivalent linking group;

Q₂ is either -SO₃M or -OSO₃M and

M is a counterion.

3. The synergistic surfactant composition of claim 2, comprising a fluoroaliphatic amphoteric surfactant of formula

R_f-L₁-N-(R₁)(R₂)-(CH₂)_mQ- wherein

R_f is a straight or branched pcrfluoroaikyl group with 5 to 13 carbon atoms, L₁ is a bivalent linking group -CHF-(CH₂)₂- or -(CH₂)₃-;

R₁ and R₂ are methyl;

Q is -COO- or-SO₃- and

m is 1 if Q is -COO- and 3 if Q is -SO₃- and comprising a sulfate surfactant of formula wherein

R is an alkyl group with 8 to 14 carbons;

L₂ is a bond between R and Q₂ or -(OCH₂CH₂)_n, where n is 1 to 3;

Q₂ is -OSO₃M and

M is sodium or potassium.

4. The synergistic surfactant composition of claim 2, comprising a fluoroaliphatic surfactant of formula

R_f L₁-N⁺(R₁)(R₂HCH₂)_m-Q- .

wherein L₁ is a mixture of bivalent linking groups -CHF-(CH₂)₂- and -(CH₂)₃

R₁ and R₂ are methyl,

Q- is -COO- or -SO₃- and

m is 1 if Q is -COO- and 3 if Q- is -SO₃- and comprising a sulfate surfactant of formula

R-L₂-Q₂

wherein

R is an alkyl group with 8 to 14 carbons;

L₂ is a bond between R and Q₂ or -(OCH₂CH₂)_n, where n is 1 to 3;

Q₂ is -OSO₃M and

M is sodium or potassium.

5. The synergistic surfactant composition of claim 2, comprising a fluoroaliphatic amphotenc surfactant of formula

R_f-L₁-N⁺(R₁)(R₂)-(CH₂)_m-Q- wherein

R_f is a straight or branched perfluoroalkyl group with 5 to 13 carbon

atoms,

L, is a mixture of bivalent linking groups -CHF-(CH₂)₂- and -(CH₂)₃-;

R₁ and R₂ are methyl;

Q- is a mixture of -COO- and -SO₃- and

R-L₃-Q₂

wherein

R is an alkyl group with 8 to 14 carbons

L₂ is a bond between R and Q₂ or -(OCH₂CH₂)_n, where n is 1 to 3;

Q is -OSO₃M and

M is sodium or potassium.

6. An aqueous film forming concentrate composition capable upon

dilution with water and upon aeration to form a fire fighting foam for

extinguishing or preventing fires by suppressing the vaporization of flammable liquids, said concentrate comprising:

A. 0.5 to 10% by weight of a fluoroaliphatic amphotenc surfactant

according to claim 1;

B. 1.0 to 40% by weight of a sulfate or sulfonate surfactant

according to claim 1,

C. 0 to 40% by weight of an amphotenc and nonionic hydrocarbon

surfactant,

D. 0 to 70% by weight of a water miscible solvent,

E. 0 to 3% of a fluorochemical synergist,

F. 0 to 3% of a water soluble polymeric film former,

G. 0 to 10% of a polymeric foam stabilizer,

H. 0 to 5% of a polyelectrolytc,

I. Water in tha amount to make up the balance of 100%.

7. The aqueous film forming concentrate according to claim 6,

comprising

A. 0 5 to 4% by weight of a fluoroaliphatic amphotenc surfactant

of the formula

R_f-L₁-N⁺(R₁ )(R₂HCH₂)_mQ- wherein

R_f is a straight or branched chain pcrfluoroaikyl group with 5 to 18 carbon atoms;

L₁ is a bivalent linking group with 1 to 4 carbon atoms;

R₁ and R₂ each are alkyl or hydroxyalkyl with 1 to 4 carbon atoms or hydrogen, where only one of the R₁ and R₂ substitutes can be hydrogen;

Q- is -COO- or -SO₃- and

m is 1 to 4;

B. 1.0 to 20% by weight of a sulfate or sulfonate surfactant of the formula

R-L₂-Q₂

wherein

R is either R_f or R_h where R_f is a straight or branched chain perfluoroalkyl group with 3 to 18 carbon atoms and R_h is a straight or branched alkyl, alkenyl. cycloalkanyl or cycloparaflh group with 6 to 18 carbon atoms;

L₂ is either a bond between R and Q₂ or a bivalent linking group;

Q₂ is either -SO₃M or -OSO₃M and

M is a counterion;

C. 0 to 20% by weight of an amphotcric and nonionic hydrocarbon

surfactant;

D. 5 to 30% by weight of a water miscible solvent;

E. 0 to 1.5% by weight of a fluorochemical synergist;

F. 0 to 1.5% of a polysaccharide as a film former;

G. 0 to 5% of a polymeric foam stabilizer comprising hydrolyzed

protein, starches, polyvinyl alcohol and polyacrylamides.

H. 0 to 3% of a polyelectrolyte;

I. Water in the amount to make up the balance of 100%.

8. An aqueous film forming concentrate according to claim 6,

comprising

A. 0.5 to 4% by weight of a fluoroaliphatic amphoteric surfactant of formula

R_f-L₁-N⁺(R₁ )(R₂HCH₂)_mQ

wherein

R_f is a straight or branched perfluoroalkyl group with 5 to 13 carbon atoms,

L₁ is a bivalent linking group -CHF-(CH₂)₂- or -(CH₂)₃-;

R₁ and R₂ are methyl;

Q is -COO- or -SO₃- and

m is 1 if Q is -COO- and 3 if Q is -SO₃-;

B. 1.0 to 20% by weight of a sulfate surfactant of formula

R-L₂-Q₂

wherein

R is an alkyl group with 8 to 14 carbons;

L₂ is a bond between R and Q₂ or -(OCH₂CH₂)_n, where n is 1 to 3;

Q₂ is -OSO₃M and

M is sodium or potassium;

C. 1.0 to 20% by weight of a hydrocarbon surfactant, selected from an

amphoteric hydrocarbon surfactant from a) organic compounds containing amino and carboxy groups, or b) organic compounds containing amino and sulfo groups; and a nonionic hydrocarbon surfactant selected from polyoxyethylene derivatives of alkyl phenols, linear or branched alcohols, fatty acids; alkyl glucosides and polyglucosidcs and block copolymers containing polyoxyethylene and polyoxypropylene units.

D. 5 to 25% by weight of a water miscible solvent, selected from diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, ethylene glycol and propylene glycol.

E. 0 to 1.0% by weight of a fluorochemical synergist comprising ion pair

complexes derived from anionic and cationic fluorochemical surfactants or anionic hydrocarbon surfactants and cationic fluorochemical surfactants;

F. 0 to 1.5% of a thixotropic polysacchαride;

G. 0 to 5% of a polymeric foam stabilizer, comprising polyvinyl

alcohol and polyacrylamldes;

H. 0.5 to 2% of a polyelectrolyte comprising magnesium sulfate

heptahydrate;

1. Water in the amount to make up the balance of 100%.

9. An aqueous film forming concentrate according to claim 6, comprising

A. 0 5 to 4% by weight of a fluoroaliphatic surfactant of formula

R_f-L₁-N⁺(R₁ )(R₂HCH₂)_m-Q-.

wherein

R_f is a straight or branched perfluoroalkyl group with 5 to 13 carbon atoms,

L₁ is a mixture of bivalent linking groups -CHF-(CH₂)₂- and -(CH₂)₃

R₁ and R₂ are methyl,

Q- is -COO- or -SO₃- and

m is 1 if Q is -COO- and 3 if Q- is -SO₃- ;

B . 1.0 to 20% by weight of a sulfate surfactant of formula

R-L₂-Q₂

wherein

R is an alkyl group with 8 to 14 carbons;

L ₂ is a bond between R and Q₂ or -(OCH₂CH₂)_n, wherein n is 1 to 3;

Q₂ is -OSO₃M and

M is sodium or potassium;

C. 1.0 to 20% by weight of hydrocarbon surractant, selected from an amphoteric hydrocarbon surfactant from a) organic compounds containing amino and carboxy groups, or b) organic compounds containing amino and sulfo groups; and a nonionic hydrocarbon surfactant selected from polyoxyethylene derivatives of alkyl phenols, linear or branched alcohols, fatty acids; alkyl glucosides and polyglucosides and block copolymers containing polyoxyethylene and polyoxypropylcne units.

E. 0 to 1.0% by weight of a fluorochemical synergist comprising ion pair

F. 0 to 1.5% of a thixotropic polysaccharide;

U. 0 to 5% of a polymeric foam stabilizer, comprising polyvinyl

alcohol and polyacrylamides;

H. 0.5 to 2% of a poly electrolyte comprising magnesium sulfate

heptahydrate;

I. Water in the amount to make up the balance of 100%.

10. An aqueous film forming concentrate according to claim 6, comprising

A. 0.5 to 4% by weight of a fluoroaliphatic surfactant of formula

R_f-L₁-N⁺(R₁ )(R₂HCH₂)_m-Q- wherein

R_f is a straight or branched perfluoroalkyl group with 5 to 13 carbon atoms,

L₁ is a mixture of bivalent linking groups -CHF-(CH₂)₂- and -(CH₂)₃-;

R₁ and R₂ are methyl;

Q- is a mixture of -COO- and -SO₃- and

ra is 1 if Q is -COO- and 3 if Q- is -SO₃- ;

B. 1 to 20% by weight of a sulfate surfactant of formula

R-L₂-Q₂

wherein

R is an alkyl group with 8 to 14 carbons

L₂ is a bond between R and Q₂ or -(OCH₂CH₂)_n, where n is 1 to 3;

Q is -OSO₃M and

M is sodium or potassium.

C. 1.0 to 20% by weight of hydrocarbon surfactant, selected from an amphoteric hydrocarbon surfactant from a) organic compounds containing amino and carboxy groups, or b) organic compounds containing amino and sulfo groups; and a nonionic hydrocarbon surfactant selected from polyoxyethylene derivatives of alkyl phenols, linear or branched alcohols, fatty acids; alkyl glucosides and polygluco sides and block copolymers containing polyoxyethylene and polyoxypropylene units.

D. 5 to 25% by weight of a water miscible solvent, selected from diethylcne glycol monobutyl ether, dipropylene glycol monobutyl ether, ethylene glycol and propylene glycol.

E. 0 to 1.0% by weight of a fluorochemical synergist comprising ion pair

F. 0 to 1.5% of a thixotropic polysaccharide;

G. 0 to 5% of a polymeric foam stabilizer, comprising poly vinyl

alcohol and polyacrylamides;

H. 0.5 to 2% of a polyelectrolyte comprising magnesium sulfate

heptahydrate;

I . Water in the amount to make up the balance of 100%.

11. Method to treat aqueous waste streams obtained from aqueous film

forming concentrates of claim 6 upon proportioning with water by treating such waste streams with cationic polyelectrolytes and by removing the precipitate

formed by conventional methods such as filtration, centrifuging or application to drying beds.

12. Method according to claim 11, comprising cationic polyelectrolytes selected from poly(ethyleneamine); poly(2-hydroxypropyl-1-N-methylammonium chloride); poIy(2-hydroxypropyl-1,1-N-dimethylammonium chloride); poly[N

dimethylaminomethyl)-acrylamide]; poly-2-vinylimidazolinum bisulfate);

poly(diallyldimethylammonium chloride); poly(N,N-dimethylamino ethylmethacrylate) neutralized or quatemizcd; and poly[N-dimethylamino- propyl)-methacrylamide].

STATEMENT UNDER ARTICLE 19

In claim 2, grammatical changes have been made in the definitions of R₁, R₃, and R. The definition of L₂ has been clarified by replacing the term "zero" with a definition of the absence of L₂. The definition of M has been clarified to eliminate the presentation of examples.

In claim 3, the term "A synergistic" has been replaced with "The synergistic" in referring to a previous claim. The definition of L₂ has been clarified by replacing the term "zero" with a definition of the absence of L₂ and the definition of n being 1 to 3 replacing the subscripted "1 to 3".

In claim 4, the term "A synergistic" has been replaced with "The synergistic'' in referring to a previous claim. The definition of L₂ has been clarified by replacing the term "zero" with a definition of the absence of L₂ and the definition of n being 1 to 3 replacing the subscripted "1 to 3".

In claim 5, the term "A synergistic" has been replaced with "The synergistic" in referring to a previous claim. The definition of L₂ has been clarified by replacing the term "zero" with a definition of the absence of L, and the definition of n being 1 to 3 replacing the subscripted "1 to 3".

In claim 7, the reference to "a fluoroaliphatic amphoteric surfactant according to claim 2" has been replaced with the formula and definition of the fluoroaliphatic amphoteric surfactant of claim 2. The reference to "a sulfate or sulfonate surfactant according to claim 2" has been replaced with the formula and definition of the sulfate or sulfonate surfactant of claim 2.

In claim 8, the reference to "a fluoroaliphatic amphoteric surfactant according to claim 3" has been replaced with the formula and definition of die fluoroaliphatic amphoteric surfactant of claim 3. The reference to "a sulfate surfactant according to claim 3" has been replaced with the formula and definition of the sulfate surfactant of claim 3.

In claim 9, the reference to "a fluoroaliphatic surfactant according to claim 4" has been replaced with the formula and definition of the fluoroaliphatic surfactant of claim 4. The reference to "a sulfate surfactant according to claim 4" has been replaced with the formula and definition of the sulfate surfactant of claim 4.

In claim 10, the reference to "a fluoroaliphatic surfactant according to claim 5" has been replaced with the formula and definition of the fluoroaliphatic surfactant of claim 5. The reference to "a sulfate surfactant according to claim 5" has been replaced with the formula and definition of the sulfate surfactant of claim 5.