WO2012177121A1

WO2012177121A1 - Novel liquid curing agents and surfactants

Info

Publication number: WO2012177121A1
Application number: PCT/NL2012/000040
Authority: WO
Inventors: Alexander Maslow; Alexander Schoolen; Erik Alexander Bijpost
Original assignee: Holland Novochem Technical Coatings B.V.
Priority date: 2011-06-23
Filing date: 2012-06-25
Publication date: 2012-12-27
Also published as: NL1038883C2; CN103764712B; NL1039698A; NL1039698C2; EP2723795A1; CN103764712A

Abstract

A liquid acting as curing agent and/or surface active compound, comprising a stoichiometric amount of an alkylated polyamine (A) and a substituted phenol (B) wherein R in said alkylated polyamine (A) preferably represents a linear or branched C1-C24 alkyl or alkylaryl chain, and wherein in said substituted phenol (B), X and Y may have several meanings; B is most preferably catechol or salicylic acid.

Description

Title: Novel liquid curing agents and surfactants

Jntroduc ion

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 . 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 oneself against particles, dust and vapours .

Patent WO2010/146030 describes an elegant liquid

composition in which fatty (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 mentioned criteria.

Fatty (poly) amines are widely applied as curing agent for epoxy-based coating systems. Though carboxylic acids, such as salicylic acid, at low amounts are known to accelerate and/or to optimize curing reactions, they have yet not been reported to act as curing agent at higher concentrations at room temperature. Another objective of this invention is to prepare a curing agent, based on fatty (poly) amines and carboxylic acids, for example epoxy-containing products. Invention:

Applicant has surprisingly found that fatty (poly) amines can be liquefied upon mixing stoichiometric amounts of

substituted phenols, in particular hydroxybenzoic acids, such as salicylic acid. The resulting mixtures appeared even to be stable and liquid at temperatures around 0 °C for a long period of time. The products dissolve very easily in water and are usually very high foaming. Depending on the concentration the foams can be stable for several days.

The liquids acting as curing agent and/or surface active composition comprise stoichiometric amount of:

• An alkylated polyamine having formula (A)

And a substituted phenol having formula

B

Preferably the R group in said alkylated polyamine (A) represents a linear or branched CI - 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) , alkylaryl ( (CH₂) _m (aryl) , poly(aryl), 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 (C) , with the formula R' NHR", wherein R' and R" 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

substituted phenol (B) as well.

In all cases, the said substituted phenol (B) consists of X = COOH, carboxylate, OH, NH₂, N0₂, S0₃H, COOR, Cl, Br, F, I, alkyl, alkenyl, ether, ketone (COR) or aldehyde (CHO) and Y = H, COOH, carboxylate, OH, NH₂, N0₂, S0₃H, COOR, Cl, Br, F, I, alkyl, alkenyl, ether, ketone (COR) or aldehyde (CHO) .

In a preferred embodiment, the substituted phenol (B) is catechol or salicylic acid.

Moreover, upon applying stoichiometric ratios of fatty (poly) amine and substituted phenols, excellent curing of epoxy-based systems and the like can be obtained. The

exceptional curing properties of fatty (poly) amines- substituted phenols products will be claimed in an independent patent parallel to the underlying patent.

In addition, Applicant found that i.e. pour point

depressants, solvents and compatiblisers , can contribute to easier processing the starting materials, but are definitely not necessary to maintain the properties of the reacted fatty (poly) amine composition.

Apart from fatty (poly) amines Applicant found that fatty alkyl secondary amines, such as di (octadecyl) amine, a typical decomposition product of octadecylamine , can be liquefied as well upon mixing with substituted phenols.

It is obvious for those-skilled-in-the arts that the invention 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 by-product in the production of amines. Description:

Fatty (poly) amines, such as alkylpropylenediamines , commercially available under brand names Duomeen, Dinoramax etc, are solid at room temperature. Proper handling usually can only occur upon warming up the product. At high temperature decomposition can take place, usually with release of ammonia. 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 (temporarily) the nucleophilic properties of the amine functionality. Commonly carboxylic acids are used for this purpose. Substituted phenols can transfer a proton to an amine as well, but are mainly explored in fundamental studies (see for example J. Phys . Chem. B,

2008, 112 (25), 7748-7759) . US 2703765 claims that small

(catalytic) amounts of substituted benzoic acids, such as salicylic acid, can act as curing agent for both epoxy- and amine-aldehyde resins. However, these acids have never been published as stabilizer for fatty (poly) amines .

Applicant found that substituted phenols, such as salicylic acid, can form stable liquids with fatty

(poly) amines , such as cocopropylenediamine , when mixed in more or less stoichiometric ratios. FT-IR spectroscopic studies showed that amide formation, a typical reaction between carboxylic acid and amine, does not occur, even after storage at 60 °C for a long period of time.

The exceptional stability is believed to originate from the formation of stable six-ring type of hydrogen bond

products via both the propylene diamine functionality,

and/or the substituted phenol, for example,

and the accompanying intermolecular exchange of protons .

The present invention more specifically relates to a liquid acting as curing agent and/or surface active

composition, comprising a stoichiometric amount of:

• An alkylated polyamine having formula (A)

• And a substituted phenol having formula (B]

B Preferably, R in said alkylated polyamine (A) represents a linear or branched CI - C24 alkyl or alkylaryl chain, more preferably is R = C6-C18 linear alkyl chain, especially R = C8-C14 linear alkyl chain.

In the polyamine having formula (A) is n = 0 to 10.

The amino groups in polyamine (A) are preferably

connected via linear alkyl ((CH₂)_m), branched alkyl ((CH₂)_m), alkylaryl ( (CH₂) _m (aryl) , poly(aryl), alkylene or poly (alkylene) groups, more preferably via linear alkyl ((CH₂)_m) with m = 1 to 10, expediently via a propylene group ((CH₂)₃) . In a preferred embodiment of the present composition is the alkylated polyamine (A) dodecylpropylenediamine, or

alkyldipropylenetriamine .

In said substituted phenol (B) have X and Y preferably the following meanings :

• X = COOH, carboxylate, OH, NH₂, N0₂, S0₃H, COOR, CI, Br, F, I, alkyl, alkenyl, ether, ketone (COR) or aldehyde (CHO) ;

• Y = H, COOH, carboxylate, OH, NH₂, N0₂, S0₃H, COOR, CI, Br, F, I, alkyl, alkenyl, ether, ketone (COR) or aldehyde (CHO) ,

more preferably X = COOH, carboxylate, or OH and Y = H, COOH, carboxylate, OH, NH₂, N0₂, S0₃H, COOR, CI, Br, F, I, alkyl, alkenyl, ether, ketone (COR) or aldehyde (CHO) .

In a preferred embodiment is said substituted phenol (B) catechol or salicylic acid, more preferably salicylic acid.

In a liquid, according to the invention acting as curing agent and/or surface active compound consisting of alkylated polyamine (A) and substituted phenol (B) is the molar ratio of A to B preferably 0.8 to 1.2, more preferably 1.2 to 0.8, especially 1 to 1.

An expedient embodiment of a composition according to the invention is a liquid acting as curing agent and/or surface active composition consisting of 50 - 99% by weight of

dodecylpropylenediamine and 1 - 50% by weight of salicylic acid.

Preferably such a composition contains 60 - 70% by weight of dodecylpropylenediamine and 30 - 40% by weight of salicylic acid.

In the present composition may the substituted phenol (B) at least partially be replaced by a hydroxylated thiophene, hydroxylated pyridine, hydroxylated pyrrole, hydroxylated furan, hydroxylated polycyclic hydrocarbon or hydroxylated substituted polycyclic hydrocarbon; said hydroxylated

thiophene, hydroxylated pyridine, hydroxylated pyrrole, hydroxylated furan, hydroxylated polycyclic hydrocarbon or hydroxylated substituted polycyclic hydrocarbon may further comprise a carboxylic acid or carboxylate group.

The invention also relates to a liquid composition, comprising: Bisalkylated amine

Substituted phenol

B

The bisalkylated amine (C) is preferably a bis (fatty alkyl) amine with saturated, unsaturated, linear and/or

branched C6-C24 alkyl chains or mixtures thereof; more

preferably a bis (fatty alkyl) amine with C14-C20 saturated linear alkyl chains.

In said substituted phenol (B) have X and Y preferably the following meanings:

• Y = H, COOH, carboxylate, OH, NH₂, N0₂, S0₃H, COOR, CI, Br,

F, I, alkyl, alkenyl, ether, ketone (COR) or aldehyde (CHO) ,

more preferably is X = COOH, carboxylate, or OH and Y = H,

COOH, carboxylate, OH, NH₂, N0₂, S0₃H, COOR, CI, Br, F, I, alkyl, alkenyl, ether, ketone (COR) or aldehyde (CHO) .

A liquid, according to the invention, consists

expediently of bis (alkylated) amine (C) and substituted phenol (B) in a molar ratio 0.6 to 1.4, more specifically a molar ratio 1.4 to 0.6, especially a molar ratio of C to B of 1 to

1.

In the present composition may the substituted phenol (B) at least partially be replaced by a hydroxylated thiophene, hydroxylated pyridine, hydroxylated pyrrole, hydroxylated furan, hydroxylated polycyclic hydrocarbon or hydroxylated substituted polycyclic hydrocarbon, and may said hydroxylated thiophene, hydroxylated pyridine, hydroxylated pyrrole, hydroxylated furan, hydroxylated polycyclic hydrocarbon or hydroxylated substituted polycyclic hydrocarbon further comprise a carboxylic acid or carboxylate group.

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 its spirit and scope, as will be apparent to those skilled- in-the-arts .

Cocopropylene diamine (Duomeen CD - Akzo Nobel Surface Chemistry) is molten at 40 °C. 50 grams Duomeen CD is

transferred into a glass beaker, equipped with a magnetic stirring bar, followed by slow addition of 27 grams salicylic acid (1 : 1 molar ratio) . 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. Under all conditions, the liquid product remains stable optically.

In another experiment, 50 grams Duomeen CD is molten and transferred into a glass beaker, equipped with a magnetic stirring bar. Then slowly 21 grams catechol (99%, Acros

Organics) is added (1 : 1 molar ratio) whilst continuously stirring the mixture. Finally a clear yellow solution is obtained, which has been subjected to several storage tests. In each case a stable product remained, except at 4 °C due to solidification (solidification point of approximately 8 °C) .

In addition, 65 grams cocopropylene triamine (Triameen C - Akzo Nobel Surface Chemistry) is thoroughly mixed with 35 grams salicylic acid. A hazy stable liquid is obtained and remains stable at room temperature over a long period of time.

In another experiment, 65 grams tallowdipropylene triamne (Triameen YT - Akzo Nobel Surface Chemistry, melting range 15- 25 °C) is combined with 35 grams salicylic acid. After

thoroughly mixing, a hazy liquid remains. The mixture appears to be stable a 4 °C for many weeks.

Moreover, 40 grams Di (octadecyl) amine (obtained by decomposition of octadecylamine , average molecular weight 540 g/mol, melting point 55 °C) and 10 grams salicylic acid (1 : 1 molar ratio) is mixed thoroughly . A hazy liquid is obtained and remains stable at room temperature .

Claims

1. A liquid acting as curing agent and/or surface active composition, comprising a stoichiometric amount of:

• An alkylated polyamine having formula (A)

R. NH

• And a substituted phenol having formula (B)

B

2. Composition according to Claim 1, wherein R in said alkylated polyamine (A) represents a linear or branched CI C24 alkyl or alkylaryl chain.

3. Composition according to Claim 1 or 2 , wherein R = C6-C18 linear alkyl chain.

4. Composition according to one or more of the Claims 1-3, wherein R = C8-C14 linear alkyl chain.

5. Composition according to one or more of the Claims 1-4, wherein n - 0 to 10.

6. Composition according to one or more of the Claims 1-5, wherein the amino groups in polyamine (A) are connected via linear alkyl ((CH₂)_m), branched alkyl ((CH₂ ) m ) , alkylaryl

( (CH₂) m (ary1 ) , poly(aryl), alkylene or poly (alkylene) groups.

7. Composition according to one or more of the Claims 1-6, wherein the amino groups in polyamine (A) are connected via linear alkyl ((CH₂)_m) with m = 1 to 10.

8. Composition according to one or more of the Claims 1-7, wherein the amino groups in polyamine (A) are connected via a propylene group ((CH₂)₃).

9. Composition according to one or more of the Claims 1-8, wherein the alkylated polyamine ( A) is

dodecylpropylenediamine .

10. Composition according to one or more of the Claims 1-9, wherein the alkylated polyamine (A) is

alkyldipropylenetriamine .

11. Composition according to one or more of the claims 1-10, wherein the alkylated polyamine is the corresponding polymer of (A) .

12. Composition according to one or more of the Claims 1-11, wherein in said substituted phenol ( B ) :

• X = COOH, carboxylate, OH, NH₂, N0₂, S0₃H, COOR, Cl, Br, F, I, alkyl, alkenyl, ether, ketone (COR) or aldehyde (CHO) ;

• Y = H, COOH, carboxylate, OH, NH₂, N0₂, S0₃H, COOR, Cl, Br, F, I, alkyl, alkenyl, ether, ketone (COR) or aldehyde (CHO) .

13. Composition according to one or more of the Claims 1-12 wherein X = COOH, carboxylate, or OH and Y = H, COOH,

carboxylate, OH, NH₂, N0₂, S0₃H, COOR, Cl, Br, F, I, alkyl, alkenyl, ether, ketone (COR) or aldehyde (CHO) .

14. Composition according to one or more of the Claims 1-13 wherein said substituted phenol ( B ) is catechol or salicylic acid.

15. Composition according to one or more of the Claims 1-14, wherein substituted phenol (B) is salicylic acid.

16. A liquid, according to one or more Claims 1-15, acting as curing agent and/or surface active compound consisting of alkylated polyamine (A) and substituted phenol (B) wherein the molar ratio of A to B is 0.8 to 1.2.

17. A liquid according to one or more Claims 1-16, consisting of alkylated polyamine (A) and substituted phenol (B) wherein the molar ratio of A to B is 1.2 to 0.8.

18. A liquid according to one or more Claims 1-17, consisting of alkylated polyamine (A) and substituted phenol (B) wherein the molar ratio of A to B is 1 to 1.

19. A liquid acting as curing agent and/or surface active composition consisting of 50 - 99% by weight of

dodecylpropylenediamine and 1 - 50% by weight of salicylic acid.

20. Composition according to claim 19, wherein the mixture contains 60 - 70% by weight of dodecylpropylenediamine and 30 - 40% by weight of salicylic acid.

21. Composition according to one or more of the Claims 1-20, wherein the substituted phenol (B) is at least partially replaced by a hydroxylated thiophene, hydroxylated pyridine, hydroxylated pyrrole, hydroxylated furan, hydroxylated

polycyclic hydrocarbon or hydroxylated substituted polycyclic hydrocarbon .

22. Composition according to Claim 21, wherein said

hydroxylated thiophene, hydroxylated pyridine, hydroxylated pyrrole, hydroxylated furan, hydroxylated polycyclic

hydrocarbon or hydroxylated substituted polycyclic hydrocarbon further comprise a carboxylic acid or carboxylate group.

23. A liquid composition, comprising:

• Bisalkylated amine (C) , with the formula R'NHR" and

• Substituted phenol (B)

B

24. Composition according to Claim 23, wherein the

bisalkylated amine (C) is bis (fatty alkyl) amine with

saturated, unsaturated, linear and/or branched C6-C24 alkyl chains or mixtures thereof .

25. Composition according to Claim 23-24, wherein the

bisalkylated amine (C) is bis (fatty alkyl) amine with C14-C20 saturated linear alkyl chains .

26. Composition according to one or more of the Claims 23-25, wherein in said substituted phenol (B) :

• X = COOH, carboxylate, OH, NH₂, N0₂, S0₃H, COOR, CI, Br, F, I, alkyl, alkenyl, ether, ketone (COR) or aldehyde (CHO) ; · Y = H, COOH, carboxylate, OH, NH₂, N0₂, S0₃H, COOR, Cl, Br,

F, I, alkyl, alkenyl, ether, ketone (COR) or aldehyde (CHO) .

27. Composition according to one or more of the Claims 23-26, wherein X = COOH, carboxylate, or OH and Y = H, COOH,

28. Composition according to one or more of the Claims 23-27, wherein substituted phenol (B) is catechol or salicylic acid.

29. Composition according to one or more of the Claims 23-28, wherein substituted phenol (B) is salicylic acid.

30. A liquid, according to one or more Claims 23-29, consisting of bis (alkylated) amine (C) and substituted phenol (B) in a molar ratio 0.6 to 1.4.

31. A liquid, according to one or more Claims 23-30,

consisting of bis (alkylated) amine and substituted phenol (B) in a molar ratio 1.4 to 0.6.

32. A liquid according to one or more Claims 23-31, consisting of bis (alkylated) amine (C) and substituted phenol (B) wherein the molar ratio of A to B is 1 to 1.

33. Composition according to one or more of the Claims 23-32, wherein the substituted phenol (B) is at least partially replaced by a hydroxylated thiophene, hydroxylated pyridine, hydroxylated pyrrole, hydroxylated furan, hydroxylated

polycyclic hydrocarbon or hydroxylated substituted polycyclic hydrocarbon .

34. Composition according to Claim 33, wherein said