Dialkyl-polyalkylamine compositions, process for their preparation and their use

Abstract

The application relates to compositions comprising di-fatty-alkyl or -alkenyl polyalkylamines of the general formula (I) or (II), to a process for their preparation which involves a cyanoethylation step and a hydrogenation step, and their use as demulsifiers for oil-in-water emulsions, corrosion inhibitor, fuel additive, anti-scaling agent, asphalt additive, enhanced oil recovery agent for oil-wells, cutting-oil additive, and anti-static agent. The product show good performance combined with a favourable viscosity profile. ##STR00001##

Claims

1. Di-fatty-alkyl(ene) polyalkylamine composition which comprises a mixture of polyalkylamines selected from products with formulae (I) and (II), ##STR00005## wherein each R is, independent of the other R, an alkyl or alkylene moiety with 8-22 carbon atoms, n and z are independent of each other either 0, 1, 2, or 3, and when z>0 then o and p are independent of each other either 0, 1, 2, or 3, or derivatives thereof, whereby said mixture comprises a) a total of at least 3% by weight of branched compounds of formula (I) with at least one of n and z>=1 and products of formula (II) with n>=1, and b) a total of at least 5% by weight of products of formula (I) with n and z=0, and compounds of formula (II) with n=0.

2. Polyalkylamines composition according to claim 1 comprising a total of at least 4% w/w of branched compounds of formula (I) with at least one of n and z<>0 and compounds of formula (II) with n<>0.

3. Polyalkylamines composition according to claim 1 comprising at least 5% by weight of products of formulae (I) and (II) with a linear structure with n is 0 in formulae (I) and (II) and z is 0 in formula (I).

4. Polyalkylamines composition of claim 1 comprising derivatives of di-fatty-alkyl(ene) polyalkylamines, wherein the derivatives are alkoxylates which are optionally methylated.

5. Polyalkylamines composition of claim 1 comprising derivatives of di-fatty-alkyl(ene) polyalkylamines, wherein the derivatives are methylated.

6. A process for making the polyalkylamines compositions of claim 1 wherein a di-fatty-alkyl(ene) alkyldiamine is reacted in two or more cycles whereby each cycle comprises a cyanoethylation step and a subsequent hydrogenation step.

7. A process of claim 6 wherein an acidic catalyst is used during the cyanoethylation steps.

8. A process of claim 6 wherein the reaction temperature during a later cyanoethylation step is higher than the temperature in an earlier cyanoethylation step.

9. A process of claim 6 wherein more than 1 mole of acrylonitrile is used per mole of the starting polyamine.

10. A process for making the polyalkylamines compositions of claim 1 wherein a di-fatty-alkyl(ene) alkyldiamine is subjected to a cyanoethylation step and a subsequent hydrogenation step, whereby in the cyanoethylation step at least 2 mole of acrylonitrile is used per mole of di-fatty-alkyl(ene) alkyldiamine and an acidic catalyst is used.

11. A process of claim 10 wherein the product is subjected to one or more further cycles comprising a cyanoethylation and subsequent hydrogenation step.

12. A process according to claim 6 wherein one or more solvents selected from C.sub.1-4 alcohol and C.sub.2-4 dials is present in the cyanoethylation step.

13. A process of claim 12 wherein the amount of solvent is from 0.1 to 50% by weight of the liquid reaction mixture.

14. A process to make the derivatives of claim 4 wherein a di-fatty-alkyl(ene) alkyldiamine is reacted in two or more cycles whereby each cycle comprises a cyanoethylation step and a subsequent hydrogenation step, with an additional step wherein the di-fatty-alkyl(ene) polyalkylamines are methylated, alkoxylated, or both.

15. A method comprising adding the di-fatty-alkyl(ene) polyalkylamine composition of claim 1 to an oil-in-water emulsion.

16. A method comprising adding the di-fatty-alkyl(ene) polyalkylamine composition of claim 1 to a formulation, wherein the formulation is suitable for use as a corrosion inhibitor, a fuel additive, an anti-scaling agent, an asphalt additive, an enhanced oil recovery agent for oil-wells, a cutting-oil additive, and an anti-static agent.

17. Polyalkylamines composition according to claim 1 comprising a total of at least 5% w/w of branched compounds of formula (I) with at least one of n and z<>0 and compounds of formula (II) with n<>0.

18. Polyalkylamines composition according to claim 1 comprising a total of at least 6% w/w of branched compounds of formula (I) with at least one of n and z<>0 and compounds of formula (II) with n<>0.

19. Polyalkylamines composition according to claim 1 comprising a total of at least 10% w/w of branched compounds of formula (I) with at least one of n and z<>0 and compounds of formula (II) with n<>0.

20. Polyalkylamines composition according to claim 1 comprising a total of at least 20% w/w of branched compounds of formula (I) with at least one of n and z<>0 and compounds of formula (II) with n<>0.

Description

EXPERIMENTAL

(1) Duomeen 2HT is available from AkzoNobel.

(2) Other chemicals were sourced from SigmaAldrich, unless indicated differently.

Example 1

(3) A fully branched product with 4 amine functions was prepared using a 1 L glass reactor with turbine stirrer to which chemicals can be dosed using a Prominent Gamma/L membrane pump and which was thermostatted using a Lauda K6KP heating bath.

(4) Raw Materials

(5) TABLE-US-00001 Intake Molw. Intake Chemical Supplier (g) (g/mol) (mol) Duomeen 2HT AkzoNobel 342.0 566 0.604 Hydrochloric acid (36%) J T Baker 3.06 36.5 0.014 Water Tap 1.12 18.0 0.062 Isopropanol J T Baker 34.2 60.1 0.569 Sodium carbonate Acros As needed, see text Acrylonitrile Acros 81.5 53.1 1.299 Raney Cobalt CatAlloy As needed, see text Ammonia Air products As needed, see text
Procedure & Results

(6) The cyano-ethylation step is performed by charging the reactor with Duomeen 2HT, isopropanol (co-catalyst and solvent for the dicyano-product that is formed), water, and HCl, and subsequent dosing, in approximately three hours, of the acrylonitrile. Reaction pathway:

(7) ##STR00003##
wherein HT stands for hydrogenated tallow.

(8) After a conversion of 80% the reaction rate was so slow that the reaction was stopped. Vacuum was applied to the reactor the temperature was increased to 110 C. to remove the acrylonitrile, water & IPA. The product was washed and neutralized in two steps with 4% Na.sub.2CO.sub.3 solution to remove all HCl, and subsequently hydrogenated using the same equipment. Reaction pathway:

(9) ##STR00004##

(10) Thereto the stirred reactor containing the dicyano-product was charged with a conventional Raney Cobalt catalyst, such as A-7000 ex Johnson Matthey or Acticat1100 ex CatAlloy, and subsequently heated to 130 C. while sparging with nitrogen, to remove traces of acrylonitrile and water. Then the reactor was charged with ammonia (13-14 barg) while kept at a temperature of 105 C. Then the reactor was heated to 150 C., and hydrogen was added to maintain a pressure of 49 barg. After completion of the reaction, the temperature was lowered to 80 C. and remaining hydrogen and ammonia were flushed out using nitrogen.

(11) The resulting composition was analyzed using GC-MS and found to contain >70% of the product 2HTY of formula (II) with n=1, as well as more than 14% w/w of the linear product (HT).sub.2N(CH.sub.2).sub.3NH(CH.sub.2).sub.3NH.sub.2, a little starting product (HT).sub.2N(CH.sub.2).sub.3NH.sub.2, and some unidentified further alkylamines.

Example 2A and 2B

(12) A mixture of linear and branched product (Tetrameen 2HTb) was prepared by the two cycle procedure wherein the cyano-ethylation and the hydrogenation steps above were repeated. The 0.6 mole of the Duomeen 2HT was combined with 0.65 mole of acrylonitrile and reacted in the first cyano-ethylation step. After hydrogenation, the triamine was combined with another 0.65 mole of acrylonitrile and reacted. At the end of each cyano-ethylation step, NMR was used to analyze the reaction mixture and to determine if one mole of acrylonitrile had reacted per mole of starting material. If the reaction was found to be too low, some additional acrylonitrile was dosed and after 1 hour the analysis was repeated. This cycle was repeated till the desired reaction was obtained. The final product was analyzed using GC-MS applying the following conditions

(13) TABLE-US-00002 Gas chromatograph TRACE ULTRA GC Interscience MS system ISQ GC-MS Column Fused silica WCOT, 20 m 0.32 mm ID stationary phase Sil 5 CB, 100% polydimethyl-siloxane, cross-linked film thickness 0.12 m Carrier gas Helium flow 2 ml/min. Temperatures injector 275 C. column initial: 200 C. during 1 min rate: 20 C./min final: 310 C. during 15 min Injection volume 1 l, approx. 250 mg sample in 10 ml cyclohexane

(14) In the examples no additional acrylonitrile had to be added after the first cyanoacrylation step which was conducted at a temperature of 85 C. and 75 C., for examples 2a and 2b respectively. In the second cyanoacrylation step the temperature was 85 and 80 C., for examples 2a and 2b respectively. In example 2a an additional amount of 0.025 mole of acrylonitrile was needed to complete the second cyanoacrylation step while in example 2b an additional amount of 0.12 mole of acrylonitrile was added before the addition of 0.60 mole of acrylonitrile was achieved. The highest amount of branching was observed in the sample 2a that was highest in temperature.

(15) It was confirmed that the off-white products, which were pasty/viscous liquids at room temperature, contained more than 13.8% w/w of branched product of formula (I) with one or more of n and z>=1, and also contained more than 14% w/w of the linear product with n=z=0.

Examples 3-5

(16) To a commercial lubricant (Talusia HR70, which is overbased and comprises CaCO.sub.3, from Total LubeMarine), 5 wt % of the 2HTb of example 2a, 2HTY, or a 50/50 blend of 2HTY and 2HTb was added and thoroughly blended, followed by neutralization of 50 BN points of the lubricant composition with 95% sulfuric acid, in order to simulate the phenomenon of neutralization of the composition to be closer to real conditions of use of the lubricating composition in a marine engine.

(17) In this process the amines together with the overbased detergents neutralizes the sulfuric acid. The generated sulfate ions become the counterions of the positively charged ammonium groups and/or react with the calcium of the CaCO.sub.3 to form gypsum, CaSO.sub.4.

(18) Measurements of the viscosity (Pa.Math.s) at 40 C. of the three acidized blends of lubricant and alkylpolyamines, as prepared above, were performed by measuring the viscosity at a shear rate of 0.05 s1 as displayed in the tables. All measurements were performed at 40 C. on an AR-G2 rheometer from TA-instruments.

(19) TABLE-US-00003 TABLE 1 Viscosity Product Pa .Math. s 2HTb 0.3639 2HTY 0.3838 50/50 of 2HTb/2HTY 0.3561

(20) All of these samples show an acceptable viscosity.

Comparative Examples A-C

(21) Acidized blends of a commercial mono-oleyl tripropylenetetramine of AkzoNobel (Tetrameen OV) and a commercial mono-tallow tripropylenetetramine of AkzoNobel (Tetrameen T) in lubricant, prepared as described for Examples 3-5, were analyzed for its viscosity and compared with the viscosity of the 2HTb blend and lubricant only.

(22) TABLE-US-00004 TABLE 2 Viscosity Product Pa .Math. s Tetrameen OV 0.8061 Tetrameen T 2.705 2HTb 0.3639 Base oil 0.2695

(23) The results show that Tetrameen OV and Tetrameen T resulted in an unacceptable viscosity of the acidized blend.

Comparative Examples D-F

(24) Acidized blends of a commercial di-hydrogenated tallow dipropylenetriamine of AkzoNobel (Triameen 2HT) and a commercial di-hydrogenated tallow propylenediamine of AkzoNobel (Duomeen 2HT) in lubricant, prepared as described for Examples 3-5, whereby the amount of the triamine was increased to 6.2% w/w and the amount of Duomeen was increased to 8% w/w to achieve the same total base number, were analyzed for its viscosity and compared with the viscosity of the blends of comparative example A-C. The viscosity (Pa.Math.s) at a shear rate of 0.05 s1 was found to be between the viscosity for Tetrameen OV and Tetrameen T, so again showing an undesired high viscosity.

Mental Example 6

(25) In this example the compounds of Examples 1, 2a and 2b are used as demulsifiers for oil-in-water emulsions, corrosion inhibitor, fuel additive, anti-scaling agent, asphalt additive, enhanced oil recovery agent for oil-wells, cutting-oil additive, and anti-static agent. They show the typical performance, but also a viscosity profile which is surprising for di-fatty-alkyl(ene) polyalkylamines with this molecular weight.