NL1039557C2

NL1039557C2 - Novel liquid curing agents, corrosion inhibitors and surfactants ii.

Info

Publication number: NL1039557C2
Application number: NL1039557A
Authority: NL
Inventors: Alexander Maslow; Alexander Schoolen; Erik Alexander Bijpost
Original assignee: Holland Novochem Technical Coatings B V
Priority date: 2012-04-20
Filing date: 2012-04-20
Publication date: 2013-10-23

Description

P2012NL017

Title: Novel liquid curing agents, corrosion inhibitors and surfactants II Introduction

Fatty amine carboxylate salts, such as fatty amine acetate salts, produced from fatty amine and acetic acid, are common surface active compounds used in many applications.

5 However, one problem of this class of compounds is that they are solid, non-pourable products at room temperature and often up to about 45 °C or higher, leading to handling problems.

Further, due to health aspects, handling of solid fatty amine carboxylate salts requires the use of protection masks and protective clothes to protect one self against particles, dust and vapors. Patent WO2010/146030 describes an elegant liquid composition in which fatty 10 (poly)amines, are combined with carboxylic acid, preferably acetic or propionic acid, and water. The resulting mixtures are claimed to be stable over a long period of time. As the compositions contain water, the products are not always desired for both economic and technical reasons.

Hence there is still a need for higher concentrated, water (solvent) free, stable, liquid fatty (poly)amine composition. An objective of this invention is to formulate products, meeting the 15 mentioned criteria. Applicant has found recently that substituted phenols, such as salicylic acid, are excellent amine liquefiers. Moreover, upon applying the amine-phenols, excellent curing of epoxy-based systems is obtained.

As phenols are often solids, handling at large scale can sometimes be considered as troublesome. Another objective of this invention is to prepare both solvent- and water-free a 20 curing agents and/or surfactants and/or corrosion inhibitors, based on fatty (poly)amines and acidic liquids.

Invention 25 Applicant has surprisingly found that fatty (poly)amines can be liquefied upon mixing stoichiometric amounts of substituted aromatic sulphonic acids, organic phosphate esters, or long chain (C7 or higher), preferably branched or unsaturated, carboxylic acids. The resulting mixtures appeared even to be stable and liquid at temperatures around 0 °C. The liquid compositions are solvent-free compositions, having curing and/or surface active and/or corrosion 30 inhibitor properties, preferably comprising stoichiometric amounts of: 1039557 2 • An alkylated polyamine having formula (A) rhrh

R. /N N NL

5 ^ L Jn *

A

And a substituted aromatic sulphonic acid having formula (B), selected from: i) a benzene sulphonic acid having formula B1 10 ’’''Ck80-" ,=,, 15 ii) a naphtalene sulphonic acid having formula B2

Rbcr°'n(=, and iii) a polycondensated naphthalene sulphonic acid having formula B3 25 RV / R’\ )

30 Xyvso3H

/ (B3) 3 2) an organic phosphate ester having formula (C)

O

5 R"0 | OR" lr.

OR" 3) a fatty carboxylic acid having formula (D) 10

O

R.„/\X^OH (D) 15 wherein R represents an alkyl- or aryl group; R1 represents an alkyl, alkylene, aryl, carboxyl, alkenyl, ether, ketone, aldehyde, OH, NH2, N02, S03H, Cl, Br, F, I group; 20 R11 represents H, or an alkyl, aryl or alkylene group; R111 represents H, or an alkyl, aryl or alkylene group.

Preferably the R group in said alkylated polyamine (A) represents a linear or branched C1 - C24 alkyl or alkylaryl chain with integer n = 0 to 10. The amino groups in polyamine (A) are 25 connected via linear alkyl ((CH2)m), branched alkyl ((CH2)m), unsaturated alkyl ((CH2)(CH=CH)i. 3(CH2)), alkylaryl ((CH2)m(aryl), polyfaryl), alkylene or poly(alkylene) groups.

In a preferred embodiment the amino groups are connected via a propylene group ((CH2)3), whereas the alkyl group R is a dodecyl chain.

Bisalkylated amines (E), with the formula R1NHR2, wherein R1 and R2 represent 30 bis(fatty alkyl) amine with saturated, unsaturated, linear and/or branched C6-C24 alkyl chains or mixtures thereof can be liquefied upon admixing with acidic compounds B, C or D as well.

Additionally the polyamine can contain typical organic chemical substituents, such as polyethoxy or polypropoxy chains.

The aromatic sulphonic acids can be selected from typical single aromatics, such as 35 benzene, naphthalene, anthracene and all other known polycyclic hydrocarbons. In addition, 4 polycondensated (e.g. formaldehyde-condensated) naphthalene sulphonic acids were also found to act as liquifier for polyamines.

Both the aromatic and polycondensated aromatic sulphonic acids can further consists of one or more substituents R’, selected from the groups linear alkyl ((CH2)m)> branched alkyl 5 ((CH2)m), alkylaryl ((CH2)m(aryl), poly(aryl), alkylene or poly(alkylene) groups, COOH, carboxylate, OH, NH2i N02, S03H, COOR, Cl, Br, F, I, alkyl, alkenyl, ether, ketone (COR) or aldehyde (CHO), or a mixture thereof.

In a preferred embodiment, the aromatic sulphonic acid is dodecylbenzene sulphonic acid.

10 Organic phosphate esters (C) consist of one or more substituents R”, selected from the groups H, linear alkyl ((CH2)m), branched alkyl ((CH2)m), alkylaryl ((CH2)m(aryl), poly(aryl), alkylene or poly(alkylene) groups, or a mixture thereof. Additionally, the phosphate ester can contain typical organic chemical substituents, such as polyethoxy or polypropoxy chains.

In a preferred embodiment, the organic phosphate ester is a mixture of mono- and di 2-15 ethylhexylphosphate ester.

Long chain carboxylic acids (D) contain at least 7 carbon atoms. Substituent R’” can be selected from H, linear alkyl ((CH2)m), branched alkyl ((CH2)m), unsaturated alkyl ((CH2)(CH=CH)i.3(CH2)), alkylaryl ((CH2)m(aryl), poly(aryl), alkylene or poly(alkylene) groups, or mixtures thereof.

20 In a preferred embodiment, the carboxylic acid is neodecanoic acid.

Moreover, upon applying a stoichiometric ratios of either fatty (poly)amine or bisalkylated amines and acidic organic chemical compounds according the invention, good curing of i.e. epoxy-based systems and the like can be obtained. When combined with i.e. known epoxies 25 resins, the neutralized fatty (poly) amines form typical hydrophobic coatings.

In addition, it has been observed that products according the invention provide typical surface active properties. In aqueous media e.g. it can form stable organic films on metal surfaces, leading to corrosion protection. This technology can be applied in e.g. process water treatment. Even in highly corrosive liquids, such as urea-ammonium nitrate (32 N), good 30 corrosion inhibition has been observed at very low dosages (20 ppm).

5

Description

Fatty (poly)amines, such as alkylpropylenediamines, commercially available under the brand names Duomeen, Dinoramax etc, are solid at room temperature. Proper handling usually 5 can only occur upon warming up the product. At high temperature decomposition can take place, usually with release of ammonia. In addition, the amines are prone to oxidation, leading to lower performance. Applicant encountered these problems in practice and undertook a study to avoid these problems.

Neutralization of fatty amines is widely applied to optimize handling and decrease 10 (temporarily) the nucleophilic properties of the amine functionality. Commonly small carboxylic acids, such as acetic acid, are used for this purpose.

Aromatic sulphonic acids are extensively used in industry due to affordable costs and excellent surface active properties. Neutralized sulphonic acids are known as superior cleaning agents. The counter ions are usually selected from the groups sodium, potassium, ammonium 15 and small amines, such as triethanolamine and isopropylamine. Neutralization of aromatic sulphonic acids by fatty (poly)amines is to our knowledge not reported as such.

Organic phosphate esters are sometimes combined with fatty (mono)amines to be applied as fertilizer additive {e.g. EP 0 113 687). Recently, (mono) linear or cyclic amine phosphate ester formulations have been claimed being excellent corrosion inhibitors for bronze 20 (WO 2008/157603). Similar treatments applying polyamines, though straightforward, have not been published to date.

Patent WO2010/146030 describes an elegant liquid composition in which fatty (poly)amines, are combined with carboxylic acid comprising maximum six carbon atoms, preferably acetic or propionic acid, and water. Longer chain carboxylic acids have neither been 25 tested nor claimed.

Applicant has now observed that fatty (poly)amines can be liquefied upon mixing with substituted aromatic sulphonic acids, organic phosphate esters, or long chain (C7 or higher), preferably branched or unsaturated, carboxylic acids. Typical examples are, respectively, 30 dodecylbenzene sulphonic acid, 2-ethylhexylphosphate ester and neodecanoic acid. The components are prefarebly present in stoichiometric amounts.

The resulting mixtures appeared even to be stable and liquid at temperatures around 0 °C. The products dissolve very easily in water. The liquids having curing and/or surface active and/or corrosion inhibitor properties are thus based on a fatty amine and an acidic compound, 35 and comprise: 6 • An alkylated polyamine having formula (A) FL M N Nv 5 L Jn *

A

• and at least one compound selected from a substituted aromatic sulphonic acid having formula (B), selected from 10 i) a benzene sulphonic acid having formula B1 U" <B,) 15 ii) a naphtalene sulphonic acid having formula B2 20 R'x

ÏXXS0,H

(B2) 25 and iii) a polycondensated naphthalene sulphonic acid having formula B3 R'x )

Xyyso3H

30 R'x )

xyVs°3H

35 / (b3) 7 2) an organic phosphate ester having formula (C)

O

5 11 R"0 | OR" Ir.

OR" 10 3) a fatty carboxylic acid having formula (D)

O

(D) 15 wherein R represents an alkyl- or aryl group; R1 represents an alkyl, alkylene, aryl, carboxyl, alkenyl, ether, ketone, aldehyde, OH, NH2, N02, 20 S03H, Cl, Br, F, I group; R11 represents H, or an alkyl, aryl or alkylene group; R111 represents H, or an alkyl, aryl or alkylene group.

Preferably the R group in said alkylated polyamine (A) represents a linear or branched 25 C1 - C24 alkyl or alkylaryl chain with integer n = 0 to 10. The amino groups in polyamine (A) are connected via linear alkyl ((CH2)m), branched alkyl ((CH2)m), unsaturated alkyl ((CH2)(CH=CH)1. 3(CH2)), alkylaryl ((CH2)m(aryl), poly(aryl), alkylene or poly(alkylene) groups.

30 Bisalkylated amines (E), with the formula R1NHR2, wherein R1 and R2 represent bis(fatty alkyl) amine with saturated, unsaturated, linear and/or branched C6-C24 alkyl chains or mixtures thereof can be liquefied upon admixing with acidic compounds B, C or D as well.

8

The aromatic sulphonic acids can be selected from typical single aromatics, such as benzene, naphthalene, anthracene and all other known polycyclic hydrocarbons. In addition, polycondensated (e.g. formaldehyde-condensated) naphthalene sulphonic acids were also found to act as liquifier for polyamines.

5 Both the aromatic and polycondensated aromatic sulphonic acids can further consists of one or more substituents R’, selected from the groups linear alkyl ((CH2)m), branched alkyl ((CH2)m), alkylaryl ((CH2)m(aryl), poly(aryl), alkylene or poly(alkylene) groups, COOH, carboxylate, OH, NH2, N02, S03H, COOR, Cl, Br, F, I, alkyl, alkenyl, ether, ketone (COR) or aldehyde (CHO), or a mixture thereof.

10 In a preferred embodiment, the aromatic sulphonic acid is dodecylbenzene sulphonic acid.

Organic phosphate esters (C) consist of one or more substituents R”, selected from the groups H, linear alkyl ((CH2)m), branched alkyl ((CH2)m), alkylaryl ((CH2)m(aryl), poly(aryl), alkylene or poly(alkylene) groups, or a mixture thereof. Additionally, the phosphate ester can 15 contain typical organic chemical substituents, such as polyethoxy or polypropoxy chains.

In a preferred embodiment, the organic phosphate ester is a mixture of mono- and di 2-ethylhexylphosphate ester.

Long chain carboxylic acids (D) contain at least 7 carbon atoms. Substituent R’” can be selected from H, linear alkyl ((CH2)m), branched alkyl ((CH2)m), unsaturated alkyl 20 ((CH2)(CH=CH)1.3(CH2)), alkylaryl ((CH2)m(aryl), poly(aryl), alkylene or poly(alkylene) groups, or mixtures thereof.

In a preferred embodiment, the carboxylic acid is neodecanoic acid.

Moreover, upon applying a stoichiometric ratio of either fatty (poly)amine or bisalkylated 25 amines and acidic organic chemical compounds according the invention, excellent curing of i.e. epoxy-based systems and the like can be obtained.

The invention further relates to a process for the liquefaction of a fatty polyamine to obtain a solvent-free, stable, fatty polyamine composition, by mixing an alkylated polyamine having formula (A) with stoichiometric amounts of at least one compound having formula (B), (C) 30 or (D), as described above.

In addition, it has been observed that products according the invention provide typical surface active properties. In aqueous media e.g. it can form stable organic films on metal surfaces, leading to corrosion protection. This technology can be applied in e.g. cooling water treatment. Even in highly corrosive liquids, such as urea-ammonium nitrate (32 N), good 35 corrosion inhibition has been observed at very low dosages (20 ppm).

g

The present invention further relates to a method to protect surfaces, such as steel, carbon steel, stainless steel, polyethylenes, polypropylenes, polyacrylates, polyesters, wood, aluminum, ceramics and glass, very efficiently and long lasting, by applying a mixture comprising • 5-95% by weight of Glycidyl ether, and/or Glycidyl ester-containing resins and/or 5 epoxidized alkene compounds, and/or oxetane-group(s) containing compound and • 5-95% by weight of curing agent according to the invention comprising • 40-99% by weight of alkylated polyamine (A) • and 1-60% by weight of aromatic sulphonic acid (B) or organic phosphate ester (C) or long chain carboxylic acid (D), as disclosed above 10

Preferably a mixture is applied which comprises • 5-95% by weight of Glycidyl ether, and/or Glycidyl ester-containing resins and/or epoxidized alkene compounds, and/or oxetane-group(s) containing compounds • 5-95% by weight of a curing agent according to the invention comprising 15 • 40-99% by weight of alkylated polyamine (A) • and 1-60% by weight of aromatic sulphonic acid (B), and/or organic phosphate ester (C) and/or long chain carboxylic acid (D), as disclosed above

According to a preferred embodiment is the epoxy resin a reaction product from an 20 hydroxyl containing compound with epichlorohydrin, cycloaliphatic epoxy, phenolic epoxy, Novolac epoxy, end-capped epoxy, epoxidized cardanol resin/epoxidized cashew nut shell liquid, or mixture thereof, more specifically is the epoxy resin an epoxidized organosilane or siloxane, silicon epoxy resins, or mixture thereof.

25 According to another embodiment is the epoxidized alkene an epoxidized unsaturated natural oil or its corresponding fatty acids, or mixtures thereof, preferably is the epoxidized alkene epoxidized polydiene oligomer and/or epoxidized polydiene polymer.

The composition according to the invention can further be used to inhibit corrosion by using said composition in a corrosive aqueous liquid.

30 The corrosion inhibition is expediently obtained by using from 1 to 500 ppm of the composition as defined above based on the weight of the aqueous liquid.

Moreover, Applicant found that i.e. pour point depressants, solvents and compatiblizers, can contribute to easier processing the starting materials, but are definitely not necessary to maintain the properties of the reacted fatty (poly)amine composition.

10

It is obvious for those-skilled-in-the arts that liquidification by organic chemical acidification can be extended to a wide range of primary, secondary, tertiary amine containing compounds, either in monomeric form or in polymeric form. The latter compounds are commonly formed as byproduct in the production of amines.

5 For the specialist it is clear that the organic chemical acids range can also be extended to other acidic compounds, such as phosphonic acids and thioacids. By the proper choice of substituent acidity and stability towards liquid polyamines can be optimized.

The exceptional stability of the polyamine products is believed to originate from the formation of stable six-ring type of hydrogen bond compounds via the propylene diamine 10 functionality.

R\ >k N' NH

u 15

Examples:

The invention will be illustrated by a number of examples, but is not intended to limit the scope of the invention. Many modifications and variations can be made without departing from 20 its spirit and scope, as will be apparent to those skilled-in-the-arts.

Preparation of neutralized polvamines

Cocopropylene diamine (Duomeen CD - Akzo Nobel Surface Chemistry) is molten at 40 25 °C. 40 grams Duomeen CD is transferred into a glass beaker, equipped with a magnetic stirring bar and cooling, followed by dropwise addition of 24 grams dodecylbenzene sulphonic acid (approx. 1 :1 molar ratio). Almost immediately a drastic drop in viscosity is observed. Stirring is continued till a clear light yellow solution is obtained. The resulting mixture is divided over a number of glass flasks. The flasks are stored at 4 °C, 20 °C and 40 °C for at least one week.

30 Under all conditions, the liquid product remains stable.

In another experiment, 40 grams Duomeen CD is molten and transferred into a glass beaker, equipped with a magnetic stirring bar and cooling. Then slowly 24 grams 2-ethylhexylphoshate ester (average Mw = 245 g/mol) is added whilst continuously stirring the mixture. Finally a clear yellow solution is obtained, which has been subjected to several storage 11 tests. In each case a stable product remained, except at 4 °C due to solidification (solidification point of approximately 8 °C).

Analogously, 40 grams Duomeen CD is thoroughly mixed with 24 grams neodecanoic acid. An almost colorless liquid is obtained and remains stable at room temperature over a long 5 period of time.

Performance tests with novel polvamines

The curing properties of the novel polyamines have been examined as follows. An 10 equimolar ratio of hydrogenated bis-phenol A bis glycidyl ether and polyamine is thoroughly mixed in a 20 ml. glass vessel. Afterwards the mixture is allowed to stand for 10 minutes and applied on a carbon steel Q-panel (90 micron layer). The treated surfaces are allowed to cure at room temperature. The obtained materials are subjected to scratch tests, adhesive strength and flexibility. For comparison the corresponding untreated polyamine has been studied as well.

15 Hydrogenated bis-phenol A bis glycidyl ether with aromatic sulphonic acids show rapid curing: within 4 hours tackiness could be observed. The resulting coating is glossy and scratch resistant. Phosphate esters and long chain carboxylic acids appeared to cure at similar rate as the untreated polyamine with hydrogenated bis-phenol A bis glycidyl ether. However, flow properties are easier to adjust.

20 The performance towards corrosion protection in an aggressive aqueous media has been studied in urea ammonium nitrate, applying the method described in WO 01/71062. The three neutralized fatty (poly)amines are dosed as such in an amount of 50 mg per 1000 grams of urea ammonium nitrate. The loss of metal weight of the unwelded metal coupon is determined after 24 hours and compared with the untreated sample. The blank sample shows a corrosion rate of 25 190 mpy. The dodecylsulphonate, organic phosphate ester and long chain carboxylic acid containing product showed a rate of, respectively, 2, 4 and 15 mpy. This clearly show that the novel fatty (poly)amines are capable of creating protective films under severe aqueous conditions.

1039557

Claims

A stable, liquid, solvent-free composition, with hardening, corrosion-inhibiting and surfactant properties, based on a fatty amine and an acidic compound, comprising: • an alkylated polyamine of formula (A) fKk R \ ^ N N N \

The composition of claim 1, wherein components A, and B, C and D are present in stoichiometric amounts. 25

A composition according to claim 1 or 2, wherein R in the alkylated polyamine (A) represents a linear or branched C 1 -C 24 alkyl or alkylaryl chain.

4. Composition according to one or more of claims 1-3, wherein R = C 6 -C 18 linear alkyl chain.

The composition of any one of claims 1-4, wherein R = C8 -C14 linear alkyl chain.

The composition of any one of claims 1-5, wherein n = 0 to 10.

The composition of any one of claims 1 to 6, wherein the amino groups in the polyamine (A) are connected via linear alkyl ((CH 2) m). branched alkyl ((CH2) m), alkylaryl ((CH2) m (aryl), poly (aryl), alkylene or poly (alkylene) groups.

The composition of any one of claims 1-7, wherein the amino groups in the polyamine (A) are connected via linear alkyl ((CH 2) m) with m = 1 to 10.

The composition of any one of claims 1 to 8, wherein the amino groups in the polyamine (A) are connected via a propylene group ((CH 2) 3). 10

The composition of any one of claims 1 to 9, wherein the alkylated polyamine (A) is dodecyl propylene diamine.

10. Jn * A • and at least one compound selected from 1. a substituted aromatic sulfonic acid of formula (B) selected from: i) a benzene sulfonic acid of formula B1 "" O'50 "" "o 20 ii) a naphthalene sulfonic acid of formula B2 R 'Vyvso3H 25 kAk (B2) and iii) a polycondensed naphthalene sulfonic acid of formula B3 R'v) 30> ^ n ^ Vso3h kk ^ k R \) rYVs ° 3H 35 kk ^ k * / ( b3) 1039557 2. an organic phosphate ester of formula (C) O 5 11 R "0 | OR" / rM OR "10 3) a fatty carboxylic acid of formula (D) O (D) 15 wherein R is an alkyl or aryl group R 1 represents an alkyl, alkylene, aryl, carboxyl, alkenyl, ether, ketone, aldehyde, OH, NH 2, NO 2, SO 3 H, Cl, Br, F, I group;

11. A composition according to any one of claims 1-10, wherein the alkylated polyamine (A) alkyl is dipropylene triamine.

The composition of any one of claims 1 to 11, wherein the alkylated polyamine is the corresponding polymer of (A).

The composition of any one of claims 1 to 12, wherein the alkylated polyamine (A) further comprises one or more ethoxy or propoxy groups.

14. A composition according to any one of claims 1-13, wherein the substituted aromatic sulfonic acid of formula (B) contains a single aromatic, preferably benzene or naphthalene group, or a polycyclic aromatic hydrocarbon group.

A composition according to any one of claims 1-14, wherein the substituted aromatic sulfonic acid of formula (B) is a polycondensed, preferably formaldehyde-condensed, naphthalene sulfonic acid. 30

The composition of any one of claims 14 to 15, wherein the sulfonic acids further have one or more substituents R 'selected from the groups linear alkyl ((CH2) m), branched alkyl ((CH2) m), alkylaryl (( CH 2) m (aryl), alkylene or poly (alkylene) groups, COOH, carboxylate, OH, NH 2, NO 2, SO 3 H, COOR, Cl, Br, F, J, alkyl, alkenyl, ether, ketone (COR) or aldehyde ( CHO), or a mixture thereof.

The composition of any one of claims 14 to 16, wherein the sulfonic acid is dodecyl benzene sulfonic acid.

A composition according to any one of claims 1-13, wherein the organic phosphate esters of formula (C) one or more substituents R 'selected from the groups H, linear alkyl ((CH 2) m), branched alkyl (( CH 2) m), alkylaryl ((CH 2) m (aryl), (poly) aryl, alkylene or poly (alkylene) groups, or a mixture thereof.

The composition of claim 18, wherein the organic phosphate ester further comprises polyethoxy or polypropoxy chains.

A composition according to any one of claims 18-19, wherein the organic phosphate ester is a mixture of mono- and di-2-ethylhexyl phosphate ester.

R 11 represents H, or an alkyl, aryl or alkylene group; R111 represents H, or an alkyl, aryl or alkylene group.

A composition according to any one of claims 1-13, wherein the long chain carboxylic acids of formula (D) comprise at least 7 carbon atoms and substituent R '' can be selected from H, linear alkyl ((CH 2) m), branched alkyl ((CH2) m), unsaturated alkyl ((CH2) (CH = CH) 1.3 (CH2)), alkylaryl ((CH2) m (aryl), poly (aryl), alkylene or poly (alkylene) groups, or Mixtures thereof.

The composition of claim 21, wherein the carboxylic acid is neodecanoic acid.

23. Liquid composition according to one or more of claims 1-22, with hardening, corrosion-inhibiting and / or surface-active properties, consisting of alkylated polyamine (A) and aromatic sulfonic acid (B) or organic phosphate ester (C) or carboxylic acid with long chain (D) wherein the molar ratio of A to B, or C or D, 0.5-1.5 to 1.5 is -0.5.

24. Liquid composition according to one or more of claims 1-23, consisting of alkylated polyamine (A) and aromatic sulfonic acid (B) or organic phosphate ester (C) or long chain carboxylic acid (D) wherein the molar ratio of A to B, or C or D is 0.8-1.2 to 1.2 - 0.8.

25. Liquid composition according to one or more of claims 1-24, consisting of alkylated polyamine (A) and aromatic sulfonic acid (B), and / or organic phosphate ester (C) and / or long-chain carboxylic acid (D).

Liquid composition according to claim 25, wherein the liquid composition further comprises short-chain carboxylic acid and / or substituted phenol compounds or mixtures thereof.

27. A method for liquefying a fatty polyamine to obtain a solvent-free, stable, fatty polyamine composition by mixing an alkylated polyamine of formula (A) with stoichiometric amounts of at least one compound of formula (B), ( C) or (D) as defined in claims 1 to 26.

28. Method for protecting surfaces, such as steel, carbon steel, stainless steel, polyethylenes, polypropylenes, polyacrylates, polyesters, wood, aluminum, ceramics and glass, in a very efficient and long-lasting manner, by applying a mixture comprising: 5-95% by weight of glycidyl ether, and / or glycidyl ester-containing resins and / or epoxidized olefin compounds, and / or oxetane group (s) containing compound and • 5-95% by weight of curing agent comprising • 40-99% by weight of alkylated polyamine A) 20. and 1-60% by weight of aromatic sulfonic acid (B) or organic phosphate ester (C) or long-chain carboxylic acid (D) as defined in claims 1 to 26.

29. A method according to claim 28, wherein a mixture is applied which comprises 5-95% by weight of glycidyl ether, and / or glycidyl ester-containing resins and / or epoxidized olefin compounds, and / or oxetane group (s) containing compounds. % of a curing agent according to claims 1 to 25 comprising • 40-99% by weight of alkylated polyamine (A) • and 1-60% by weight of aromatic sulfonic acid (B), and / or organic phosphate ester (C) 30 and / or long chain carboxylic acid (D), as defined in claims 1 to 26.

The method of any one of claims 28 to 29, wherein the epoxy resin is a reaction product of a hydroxyl-containing compound with epichlorohydrin, cycloaliphatic epoxy, phenolic epoxy, Novolac epoxy, epoxy terminated, epoxidized cardanol resin / epoxidized cashew nut caps, or mixtures thereof.

31. A method according to any one of claims 28-30, wherein the epoxy resin is an epoxidized organosilane or siloxane, silicone epoxy resins, or mixtures thereof.

The method of any one of claims 28 to 31, wherein the epoxidized olefin is epoxidized unsaturated natural oil or its corresponding fatty acids, or mixtures thereof. 10

The method of any one of claims 28 to 32, wherein the epoxidized olefin is epoxidized polydiene oligomer and / or epoxidized polydiene polymer.

34. A method according to one or more of claims 28-33 for inhibiting corrosion by using a composition according to one or more of claims 1-25 in a corrosive aqueous liquid.

The method of claim 34, wherein the corrosion inhibition is achieved by using 1 to 500 ppm of the composition as defined in claims 1 to 20 by 26 based on the weight of the aqueous liquid. 1039557