(19)
(11)EP 2 536 814 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
29.04.2020 Bulletin 2020/18

(21)Application number: 11743007.4

(22)Date of filing:  15.02.2011
(51)International Patent Classification (IPC): 
C11D 3/00(2006.01)
(86)International application number:
PCT/US2011/024907
(87)International publication number:
WO 2011/100746 (18.08.2011 Gazette  2011/33)

(54)

IMPROVED CATALYST FOR ESTERAMINE PRODUCTION

VERBESSERTER KATALYSATOR ZUR ESTERAMINHERSTELLUNG

CATALYSEUR AMÉLIORÉ UTILISABLE EN VUE DE LA PRODUCTION D'ESTER AMINE


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 15.02.2010 US 304713 P

(43)Date of publication of application:
26.12.2012 Bulletin 2012/52

(73)Proprietor: Stepan Company
Northfield, Illinois 60093 (US)

(72)Inventors:
  • NEPRAS, Marshall J.
    Burlington, Wisconsin 53105 (US)
  • LUXEM, Franz J.
    Palatine, Illinois 60074 (US)
  • ZAPOROWSKI, Leonard F.
    Chicago, Illinois 60630 (US)
  • EISENBERG, David
    Northbrook, Illinois 60062 (US)

(74)Representative: Schnappauf, Georg et al
ZSP Patentanwälte PartG mbB Hansastraße 32
80686 München
80686 München (DE)


(56)References cited: : 
US-A- 2 989 499
US-A- 5 637 743
US-A- 5 908 946
US-A1- 2006 167 144
US-A1- 2010 016 163
US-B1- 6 458 173
US-A- 4 690 783
US-A- 5 637 743
US-A1- 2002 025 915
US-A1- 2009 169 677
US-B1- 6 458 173
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    BACKGROUND OF THE INVENTION



    [0001] The presently described technology relates generally to a method for producing esteramines through esterification processing between alkanolamines and fatty acids. More specifically, the present technology provides methods for decreasing the reaction time and/or lowering the reaction temperature needed to react alkanolamines and fatty acids through utilization of a zinc catalyst which is zinc oxide, zinc carbonate, zinc diphosphinate, zinc triflate or zinc stearate.

    [0002] Esterification reactions of alkanolamines with carboxylic acids or fatty acids have traditionally been catalyzed with an acid catalyst, such as, for example, phosphorous acid, sulfuric acid, or the starting carboxylic acid itself. Such acid catalysts have several drawbacks, including a very slow reaction time.

    [0003] Sodium or potassium alkoxides (e.g., methoxides), in general, are also used with alkyl esters for transesterification reaction processing. Such processes are seriously inhibited, however, by moisture and/or acidic impurities. These types of alkoxides also produce resultant transesterified products that, in many instances, exhibit the viscosity of a gel, due to side reactions. Potassium hydroxide is often used to catalyze the reaction between triglycerides and triethanolamine. However, the reaction is still very slow and is believed by those skilled in the art to be due, in part, to the potassium hydroxide immediately reacting with acidic impurities during reaction processing to generate water and other potassium salts, which may, or may not, be of any use as catalysts.

    [0004] Titanium catalysts, sold commercially under the brand name TYZOR® have also been used to catalyze the reaction of triethanolamine and fatty acid. Such titanium catalysts, however, also have several drawbacks. In particular, titanium catalysts tend to form titanium precipitates in solution. Residual titanium catalysts can also interfere with product stability and result in a poorly colored product that may require further bleaching. In addition, when titanium catalysts are used with triethanolamine and fatty acid, the resulting ratios of monester, diester and triester esteramines are not in line with established product specifications. Further, it is known that the activity of titanium catalysts are negatively impacted by amines in the absence of carboxylic acids. This effect is a hindrance when a carboxylic acid feed is replaced by an alkyl ester feed, such as methylester, in conducting the reaction to produce the esteramine.

    [0005] In view of the above drawbacks, there is a need for an improved catalyst that can decrease the esterification reaction time for the reaction between alkanolamines and fatty acids. There is also a need for a catalyst that can produce an esteramine product that is storage stable, has a good color, and has ratios of monoester, diester and triester esteramines that meet existing product specifications for esteramines.

    [0006] US 5,637,743 describes a cationic surfactant compound comprising, in the form of a quaternary ammonium salt, a product of condensation between, on the one hand a fraction of saturated or unsaturated fatty acids, or of derivatives of said acids chosen from the group comprising esters, anhydrides and acid chlorides, and on the other hand at least one tertiary amine.

    [0007] US 6,458,173 describes a poly(hydroxy-carboxylic acid)amide or -ester derivative of a specific formula and the use thereof as a fuel additive acting as a detergent and as a lubricity additive in fuel compositions.

    BRIEF SUMMARY OF THE INVENTION



    [0008] In one aspect, the presently described technology provides a method for decreasing the reaction time between an alkanolamine and a fatty acid to produce esteramines, the method comprising:

    providing an alkanolamine;

    providing a fatty acid;

    reacting the alkanolamine and the fatty acid in the presence of a divalent zinc catalyst to form at least one esteramine;

    wherein the zinc catalyst is zinc oxide, zinc carbonate, zinc diphosphinate, zinc triflate or zinc stearate.



    [0009] In accordance with at least one embodiment of the present technology, the esterification reaction can proceed to completion substantively faster than, and in some cases twice as fast as when conventional catalysts are used.

    [0010] Suitable alkanolamines include, for example, ethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, alkyldiethanolamines, alkyldiisopropanolamines, dialkylmonoethanolamines, dialkylmonoisopropanolamines, and combinations thereof. Preferred alkanolamines for the presently described technology are dimethylethanolamine (DMEA) methydiethanolamine (MDEA) and triethanolamine (TEA). Examples of suitable fatty acids include stearic acid, tallow fatty acid, derivatives thereof, and combinations thereof.

    [0011] The divalent zinc catalyst is added in a usable form to the reaction mixture so that the zinc can be soluble in order for homogeneous catalysis to occur. In some embodiments of the present technology, the divalent zinc catalyst is in the form of zinc oxide, zinc carbonate, or zinc diphosphinate.

    [0012] In one embodiment of the present technology, the zinc diphosphinate catalyst is formed in situ.

    [0013] In another embodiment of the present technology, the reacting occurs at a temperature within the range of 60°C to 300°C, preferably 130° to 190°C.

    [0014] In another embodiment of the present technology, the method occurs in the presence of an inert atmosphere, preferably nitrogen.

    [0015] In another embodiment of the present technology, the fatty acid is an alkyl acid having from 2 to 30 carbon atoms, preferably 5 to 25 carbon atoms.

    [0016] In another embodiment of the present technology, the zinc catalyst is present in an amount greater than 1 ppm based on the total weight of the reactants.

    [0017] In another embodiment of the present technology, the zinc catalyst is present in an amount of 20 ppm to 5000 ppm based on the total weight of the reactants, preferably 100 ppm to 200 ppm based on the total weight of the reactants.

    [0018] In another embodiment of the present technology, the alkanolamine and fatty acid are present in a molar ratio of 0.5/1 to 3/1, where the alkanolamine represents the denominator in the ratio.

    [0019] The resulting esteramines produced by the method of the present technology can be derivitized with a quaternizing agent, such as, for example, methyl chloride or dimethyl sulfate in order to produce a fabric softener or anti-static agent. Other quaternizing agents can also be used, such as epichlorohydrin, or derivatives thereof, such as 3-chloro-2-hydroxypropanesulfonate, sodium salt.

    DETAILED DESCRIPTION OF THE INVENTION



    [0020] The presently described technology relates generally to a method for producing esteramines through the esterification reaction of alkanolamines and fatty acids. More specifically, the present technology provides a method for decreasing the reaction time between alkanolamines (e.g., triethanolamine) and fatty acids.

    [0021] The presently described technology utilizes a divalent zinc catalyst selected from the group consisting of zinc oxide, zinc carbonate, zinc diphosphinate, zinc triflate and zinc stearate, in at least one esterification reaction to produce an esteramine. By divalent zinc is meant zinc in its +2 oxidation state. The divalent zinc is added in a usable form to the reaction mixture so that the zinc can become soluble in order for homogeneous catalysis to occur. For starting reaction mixtures of fatty acid and alkanolamine, the zinc catalyst can be added in the form of zinc oxide, zinc carbonate or zinc triflate. If stearic acid is used as the fatty acid the zinc oxide is then rapidly converted to zinc distearate. Zinc diphosphinate can also be used as the catalyst. Zinc diphosphinate can be made in situ or, alternatively from a separate reaction of zinc oxide and phosphinic acid. Zinc carbonate or zinc triflate can also be used.

    [0022] It has been surprisingly found that the divalent zinc catalyst used in the present technology can unexpectedly improve esterification speed/reaction time. For example, when the divalent zinc catalyst as specified above is used in accordance with at least one embodiment of the present technology, the esterification reaction can proceed to completion, on average, twice as fast as when other catalysts are used in place of the divalent zinc catalyst as specified above when compared on a molar basis.

    [0023] In accordance with one or more embodiments of the present technology, the divalent zinc catalysts used in the present technology can also visually improve the color of the resultant esteramine materials such that a subsequently quaternized material can be of improved color also. This can, for example, make an additional bleaching step unnecessary when producing products according to the present technology.

    [0024] In accordance with some embodiments of the present technology, the divalent zinc catalysts used in the present technology can produce esteramine products that are free of precipitates and that also have superior storage stability compared to esteramine products prepared by using other catalysts.

    [0025] A further advantage of the divalent zinc catalysts used in the present technology is that, with respect to the reaction of triethanolamine and fatty acid, the resulting mole ratios of monoester, diester and triester esteramines in the final product mixture are consistent with the established product specifications for esteramines that were obtained from the well established Bronsted acid catalysis.

    [0026] As is well known, when triethanolamine is the starting amine and is made to react with carboxylic acids, the resulting esteramines are composed of a mixture of monoesterified, diesterified, and triesterified esteramines. This mixture is made possible due to the fact that triethanolamine contains three identical alcohols, each of which can react with a fatty acid to generate the ester bonds. When the divalent zinc catalyst used in the present technology is employed instead of a traditional acid or base catalyst, the final product mixtures have an identical mixture composition of monoester, diester and triester esteramines, as compared to mixtures obtained from traditional Bronsted catalysts, yet the overall esterification reaction proceeds at a much faster rate.

    [0027] Similarly, when methyldiethanolamine is the starting amine and made to react with a carboxylic acid, the resulting esteramines are composed of a mixture of monoesterified and diesterified esteramines. This mixture is made possible due to the fact that methyl diethanolamine contains two identical alcohols, each of which can react with a fatty acid to generate the ester bonds. When the divalent zinc catalyst used in the present technology is employed instead of a traditional Bronsted acid catalyst, the final product mixtures have an identical composition mixture of monoester and diester esteramines compared to mixtures obtained from traditional Bronsted catalysts, but the overall esterification reaction proceeds at a much faster rate.

    [0028] When dimethylmonoethanolamine is the starting amine, the resulting esteramine is the monoesterified esteramine because the lone alcohol can react with a fatty acid to generate the ester bond. When the divalent zinc catalyst used in the present technology is employed instead of a traditional Bronsted acid catalyst, the esterification reaction proceeds at a much faster rate.

    [0029] In accordance with some embodiments of the present technology, the divalent zinc catalysts used in the present technology are also surprisingly active in the presence of moisture and/or acidic materials, which may be present in feedstocks utilized for reaction processing.

    [0030] Another advantage of the divalent zinc catalyst used in the present technology is that it does not become deactivated by amines. The problem with Bronsted acid catalysis in the presence of amines is that the acids quickly become deactivated due to proton transfer from the acid to the nitrogen on the amine. The strong nature of the acid catalysts, as compared to the weaker carboxylic acids, causes them to lose their proton preferentially to the amine, thus preventing strong acid proton availability for catalysis. This transfer makes the proton largely unavailable to perform any catalysis on the moieties which are crucial to the esterification reaction. On the other hand, catalysis by metals is possible and the metals are known to be coordinated Lewis acids. Surprisingly, divalent zinc is an effective catalyst and does not become deactivated by amines. This development is a surprise, since amines are known to coordinate to divalent zinc, or metal ions in general, but this apparently does not significantly hinder the catalysis of the esterification reaction for zinc. Without being bound by theory, it is believed that divalent zinc can act as a Lewis acid without changing the pH of the reaction media. Divalent zinc catalysts are therefore superior to protic acids, because: 1) divalent zinc may induce multiple positive charges into reactants, while a proton can induce only a single positive charge, 2) divalent zinc can exist in neutral media not just acidic solutions, which can minimize unwanted side reactions, and 3) divalent zinc can coordinate to several electron donor atoms simultaneously, whereas a proton usually coordinates to only one donor atom.

    [0031] Suitable starting fatty acids for the present technology can be, for example, any alkyl acid having from 2 to 30, alternatively from 5 to 25 carbon atoms, and can be saturated or unsaturated or partially hydrogenated.

    [0032] Suitable alkanolamines include, for example, ethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, alkyldiethanolamines, alkyldiisopropanolamines, dialkyl monoethanolamines, dialkylmonoisopropanolamines, and combinations thereof. The alkyl groups in the alkanolamines may contain from 1 to 30 carbon atoms, and can be saturated or unsaturated, linear, cyclic, or aromatic. Preferred alkanolamines for the present technology include methyldiethanolamine and triethanolamine.

    [0033] Preferably, the combined catalyst and starting materials including the alkanolamines and fatty acids can be heated to a temperature of from 60°C to 300°C, preferably from 130°C to 190°C. In accordance with some embodiments of the present technology, the esterification reaction can be conducted within one preferred temperature range. In accordance with some other embodiments of the present technology, the esterification reaction can be conducted within a first preferred temperature range for a period of time, and then within another preferred temperature range for another period of time, and there can be two or more such periods.

    [0034] Preferably, the molar ratio of alkanolamine and fatty acids, where the alkanolamine is in the denominator of the ratio, can be from 0.5/1 to 3/1, alternatively 1.5/1 to 2.0/1, alternatively 1.7/1 to 2.0/1, alternatively 1.7/1 to 1.75/1, alternatively 1.88/1 to 1.92/1.

    [0035] The divalent zinc catalysts used in the present technology can be added either before or after the reaction temperature has been reached. The amount of catalyst contained in the reaction mixture should be an effective amount of divalent zinc metal greater than 1 ppm and calculated from the total weight of reactants, preferably from 20 ppm to 5000 ppm by weight, most preferably at 100 ppm to 200 ppm. Usually, but not necessarily, the reaction occurs in the presence of an inert atmosphere such as, but not limited to, nitrogen.

    [0036] In some embodiments of the present technology, when the starting material requires, a vacuum system can be attached to the reaction system in order to remove, for example, volatile alcohols, products, or by-products during the course of the esterification reaction.

    [0037] The divalent zinc catalyst used in the present technology is an improved or superior catalyst for the esterification reaction of alkanolamines with fatty carboxylic acids. It has also been surprisingly observed that the divalent zinc catalyst used in the present technology is also affected by the structure of the alkanolamines, during the course of the esterificationreactions, thus, a relative reactivity scale is as follows: polyolalkylamine >>> triolalkylamine >> diolalkylamine > monoalkanolamine. Without being bound by theory it is believed that the divalent zinc is chelated by the alkanolamines, in such a way, as to better facilitate the esterification reactions. In addition, it is also believed that the zinc catalyst could be used to catalyze the esterification reaction of (1) fatty or carboxylic acids with alcohols, or (2) fatty alkyl esters or methyl esters with alcohols.

    [0038] The present technology will be better understood by reference to the following examples. These examples are provided to describe specific embodiments of the invention and to demonstrate aspects of the present technology. By providing these specific examples, the inventors do not limit the scope of the invention.

    EXAMPLES


    EXAMPLE 1A:


    TEA/FATTY ACID BASED ESTERAMINE SYNTHESIS WITH ZINC DERIVED FROM ZNO



    [0039] Tallow fatty acid (1740.9 g, MW=272.0, 6.400 mole) was placed into the large 3-liter resin kettle reactor at 87°C, under a blanket of nitrogen with 2.1709 g of Anox 20. The zinc oxide (Sunsmart, lot#189, 0.3575 g) was added to the fatty acid. This amount of ZnO gave a pre-reaction Zinc concentration of 125 ppm. Triethanolamine (TEA), 554.2795 g (MW = 149.19, 3.7149 mole) was added to the flask, and the mole ratio of fatty acid/TEA was calculated to be 1.72/1. The nitrogen was regulated and subsurface sparged at a rate of 175 ml/min. The mixture was stirred. A vacuum was used to remove the excess oxygen, with the application of 11 kPa (80 mmHg) vacuum followed by nitrogen release; this cycle was applied twice. The mixture was heated until a temperature of 180°C was reached. The majority of the water was condensed at atmospheric pressure with the help of an air cooled condenser, before 150°C was reached. At 150°C, the vacuum was applied at 11 kPa (83 mmHg). Samples of crude esteramine were collected at intervals and titrated for residual fatty acid with a visual phenolphthalein endpoint using 0.1002N KOH/Methanol. The expected free fatty acid range was 0.11-0.08 mEq/g. The reaction reached completion 0.75 hour after the temperature of 180°C was reached.

    REFERENCE EXAMPLE 1B (not according to the invention):


    TEA/FATTY ACID BASED ESTERAMINE SYNTHESIS WITHOUT ZINC



    [0040] Tallow fatty acid (1733.7 g, MW=272.0, 6.374 mole) was placed into the large 3-liter resin kettle reactor at 87°C, under a blanket of nitrogen with 2.1609 g of Anox 20. Triethanolamine (TEA), 551.9269 g (MW = 149.19, 3.6995 mole) was added to the flask, and the mole ratio of fatty acid/TEA was calculated to be 1.72/1. The nitrogen was regulated and subsurface sparged at a rate of 175ml/min. The mixture was stirred. A vacuum was used to remove the excess oxygen, with the application of 11 kPa (80 mmHg) vacuum followed by nitrogen release; this cycle was applied twice. The mixture was heated until a temperature of 180°C was reached. The majority of the water was condensed at atmospheric pressure with the help of an air cooled condenser before 150°C was reached. At 150°C, a vacuum was applied at 11 kPa (83 mmHg). Samples of crude esteramine were collected at intervals and titrated for residual fatty acid with a visual phenolphthalein endpoint using 0.1002N KOH/Methanol. The expected free fatty acid range was 0.11-0.08 mEq/g. The reaction reached completion 1.37 hours after the temperature of 180°C was reached.

    EXAMPLE 2A:


    TEA/FATTY ACID BASED ESTERAMINE SYNTHESIS WITH ZINC DERIVED FROM ZINC TRIFLATE



    [0041] Tallow fatty acid, 332.3 g (MW=272.0, 1.222 mole) was placed into a small 4-neck round bottom flask, under a blanket of nitrogen. Triethanolamine (TEA), 95.9 g (MW = 149.19, 0.643 mole) was added to the flask, and the mole ratio of fat/TEA was calculated to be 1.90/1. The mixture was stirred. The temperature of the mixture was increased to 130°C, at which point, zinc triflate 98% (Aldrich, MW=363.51, 0.2501 g, 0.000688 mole) was added to the reactor, which was then sealed under nitrogen. The pre-reaction zinc content was calculated to be 105 ppm. The nitrogen was subsurface sparged at a rate of 200 ml/min. The mixture was heated until a temperature of 170°C was reached. At 156°C, the rapid evolution of water was observed, and the water was condensed with the help of an air cooled condenser. Samples of crude esteramine were collected at intervals and titrated for residual fatty acid with a visual phenolphthalein endpoint using 0.1000N KOH/Methanol. The final expected free fatty acid goal was 0.05 mEq/g. The reaction reached completion 5.3 hours after heating began.

    REFERENCE EXAMPLE 2B (not according to the invention):


    TEA/FATTY ACID BASED ESTERAMINE SYNTHESIS WITH PHOSPHOROUS ACID CATALYST



    [0042] Tallow fatty acid, 327.2 g (MW=272.0, 1.203 mole) was placed into a small 4-neck round bottom flask, under a blanket of nitrogen. Triethanolamine(TEA), 94.5 g (MW = 149.19, 0.633 mole) was added to the flask, and the mole ratio of fatty acid/TEA was calculated to be 1.90/1. The mixture was stirred. The temperature of the mixture was increased to 130°C, at which point, phosphorous acid (MW=82.00, 0.2329 g, 0.002840 mole) was added to the reactor, which was then sealed under nitrogen. The nitrogen was subsurface sparged at a rate of 200 ml/min. The mixture was heated until a temperature of 170°C was reached. The water was condensed with the help of an air cooled condenser. Samples of crude esteramine were collected at intervals and titrated for residual fatty acid with a visual phenolphthalein endpoint using 0.1000N KOH/Methanol. The final expected free fatty acid goal was 0.05 mEq/g. The reaction reached completion 6.1 hours after heating began.

    EXAMPLE 3:


    TEA/FATTY ACID BASED ESTERAMINE SYNTHESIS WITH ZINC DERIVED FROM ZINC STEARATE



    [0043] Tallow fatty acid (410.2 g, MW=272.0, 1.508 mole) was placed into a small 4-neck round bottom flask at 85°C, under a blanket of nitrogen. Triethanolamine (TEA), 118.42 g (MW = 149.19, 0.7937 mole) was added to the flask, and the mole ratio of fatty acid/TEA was calculated to be 1.90/1. The mixture was stirred and heated to 130°C, at which point, zinc stearate (Sigma-Aldrich, technical grade, 0.5334 g, 0.0008435 mole, MW=632.33) was added and the reactor was sealed under nitrogen. This amount gave a pre-reaction Zinc concentration of 104 ppm. The nitrogen was regulated and subsurface sparged at a rate of 200 ml/min. The mixture was heated until a temperature of 170°C was reached. The water was condensed with the help of an air cooled condenser. Samples of crude esteramine were collected at intervals and titrated for residual fatty acid with a visual phenolphthalein endpoint using 0.1000N KOH/Methanol. The final expected free fatty acid goal was 0.06 mEq/g. The reaction reached completion 4.5 hours after Tmax was reached.

    EXAMPLE 4A:


    MDEA/FATTY ACID BASED ESTERAMINE SYNTHESIS WITH ZINC DERIVED FROM ZINC STEARATE



    [0044] Tallow fatty acid (839.0 g, 3.05 mole) was placed into a round bottom flask at 100°C, under a blanket of nitrogen. Methyldiethanolamine (220.7 g, 1.91 mole) was added to the flask. The zinc stearate was added at a loading level of 1000 ppm. This amount gave a pre-reaction Zinc concentration of about 100 ppm. The mixture was stirred and heated until a temperature of 190°C was reached. The nitrogen was regulated and subsurface sparged at a rate of between 150 ml/min and 200 ml/min. The water was condensed with the help of an air cooled condenser. A vacuum of 21.3 kPa (160 mmHg) was applied when the batch acid value reached 0.35 mEq/g or less. Samples of crude esteramine were collected at intervals and titrated for residual fatty acid with a visual phenolphthalein endpoint using 0.1000N KOH/Methanol. The final expected free fatty acid goal was 0.07 mEq/g. The reaction reached completion 2.25 hours after Tmax was reached. With phosphorous acid as the catalyst the reaction reached completion 4.67 hours after Tmax was reached. This represents a 51.8% reduction in reaction time as compared to standard.

    REFERENCE EXAMPLE 4B (not according to the invention):


    MDEA/FATTY ACID BASED ESTERAMINE SYNTHESIS WITH PHOSPHOROUS ACID CATALYST



    [0045] Tallow fatty acid (194.0 g, 0.71 mole) was placed into a round bottom flask at 75°C, under a blanket of nitrogen. Methyldiethanolamine (50.5 g, 0.42 mole) was added to the flask. The phosphorous acid was added at a loading level of 500 ppm. The mixture was stirred and heated until a temperature of 175°C was reached. The nitrogen was regulated and subsurface sparged at a rate of between 150 ml/min and 200 ml/min. The pressure was one atmosphere. The water was condensed with the help of an air cooled condenser. A sample of crude esteramine was collected one hour after Tmax was reached, then titrated for residual fatty acid with a visual phenolphthalein endpoint using 0.1000N KOH/Methanol. The one hour acid value was 0.294 mEq/g and will be used as the baseline for this study: Percent performance was equal to 1.00 units and set as the standard for comparison.

    REFERENCE EXAMPLE 4C (not according to the invention):


    MDEA/FATTY ACID BASED ESTERAMINE SYNTHESIS WITH ZINC DERIVED FROM ZINC ACETATE



    [0046] Tallow fatty acid (195.9 g, 0.71 mole) was placed into a round bottom flask at 75°C, under a blanket of nitrogen. Methyldiethanolamine (51.5 g, 0.43 mole) was added to the flask. The zinc acetate was added at a loading level of 270 ppm. The mixture was stirred and heated until a temperature of 175°C was reached. The nitrogen was regulated and subsurface sparged at a rate of between 150 ml/min and 200 ml/min. The pressure was one atmosphere. The water was condensed with the help of an air cooled condenser. A sample of crude esteramine was collected one hour after Tmax was reached, then titrated for residual fatty acid with a visual phenolphthalein endpoint using 0.1000N KOH/Methanol. The one hour acid value was 0.405 mEq/g: Percent performance was equal to 0.62 units if compared to the rate of the phosphorous acid catalyst reaction.

    EXAMPLE 4D:


    MDEA/FATTY ACID BASED ESTERAMINE SYNTHESIS WITH ZINC DERIVED FROM ZINC OXIDE



    [0047] Tallow fatty acid (198.8 g, 0.72 mole) was placed into a round bottom flask at 75°C, under a blanket of nitrogen. Methyldiethanolamine (52.2 g, 0.44 mole) was added to the flask. The zinc oxide was added at a loading level of 120 ppm. The mixture was stirred and heated until a temperature of 175°C was reached. The nitrogen was regulated and subsurface sparged at a rate of between 150 ml/min and 200 ml/min. The pressure was one atmosphere. The water was condensed with the help of an air cooled condenser. A sample of crude esteramine was collected one hour after Tmax was reached, then titrated for residual fatty acid with a visual phenolphthalein endpoint using 0.1000N KOH/Methanol. The one hour acid value was 0.291 mEq/g: Percent performance was equal to 1.01 units if compared to the rate of the phosphorous acid catalyst reaction.

    EXAMPLE 4E:


    MDEA/FATTY ACID BASED ESTERAMINE SYNTHESIS WITH ZINC DERIVED FROM ZINC OXIDE



    [0048] Tallow fatty acid (198.0 g, 0.72 mole) was placed into a round bottom flask at 75°C, under a blanket of nitrogen. Methyldiethanolamine (51.9 g, 0.44 mole) was added to the flask. The zinc oxide was added at a loading level of 960 ppm. The mixture was stirred and heated until a temperature of 175°C was reached. The nitrogen was regulated and subsurface sparged at a rate of between 150 ml/min and 200 ml/min. The pressure was one atmosphere. The water was condensed with the help of an air cooled condenser. A sample of crude esteramine was collected one hour after Tmax was reached, then titrated for residual fatty acid with a visual phenolphthalein endpoint using 0.1000N KOH/Methanol. The one hour acid value was 0.274 mEq/g: Percent performance was equal to 1.07 units if compared to the rate of the phosphorous acid catalyst reaction.

    EXAMPLE 4F:


    MDEA/FATTY ACID BASED ESTERAMINE SYNTHESIS WITH ZINC DERIVED FROM ZINC OXIDE



    [0049] Tallow fatty acid (799.5 g, 2.91 mole) was placed into a round bottom flask at 75°C, under a blanket of nitrogen. Methyldiethanolamine (209.5 g, 1.76 mole) was added to the flask. The zinc oxide was added at a loading level of 2200 ppm. The mixture was stirred and heated until a temperature of 175°C was reached. The nitrogen was regulated and subsurface sparged at a rate of between 150 ml/min and 200 ml/min. The pressure was one atmosphere. The water was condensed with the help of an air cooled condenser. A sample of crude esteramine was collected one hour after Tmax was reached, then titrated for residual fatty acid with a visual phenolphthalein endpoint using 0.1000N KOH/Methanol. The one hour acid value was 0.145 mEq/g: Percent performance was equal to 1.51 units if compared to the rate of the phosphorous acid catalyst reaction.

    REFERENCE EXAMPLE 5 (not according to the invention):


    DMEA/METHYL ESTER BASED ESTERAMINE SYNTHESIS WITH SODIUM METHYLATE CATALYST



    [0050] A mixture of dimethylethanolamine (DMEA, 44.6 g, 0.50 mole) and 30% sodium methylate in methanol (1.1 g) was added to a 4-neck flask fitted with a nitrogen sparge, a distillation column, a thermocouple, and a mechanical stirrer. The mixture was heated to 130°C after which a C12/C14 mixed fatty methyl ester (89.2 g, 0.40 mole) was added. This mixture was heated to 155°C and held there for 2 hrs. Conversion to the esteramine was determined by proton NMR to be 84%. Solids were observed.

    REFERENCE EXAMPLE 6 (not according to the invention):


    DMEA/METHYL ESTER BASED ESTERAMINE SYNTHESIS WITH ZINC ACETATE CATALYST



    [0051] A mixture of dimethylethanolamine (DMEA, 68.3 g, 0.77 mole), C12/C14 mixed fatty methyl ester (90.5 g, 0.41 mole), and zinc acetate (0.44 g) was added to a 4-neck flask fitted with a nitrogen sparge, a distillation column, a thermocouple, and a mechanical stirrer. The mixture was heated gradually to 180°C over 4 hrs and held at 180°C for 1.5 hrs. Conversion, as indicated by proton NMR, was 92%. The next day the mixture was reheated to 180°C and held for 2 hours, the conversion, by proton NMR, was determined to be > 99%. No solids were observed.

    REFERENCE EXAMPLE 7 (not according to the invention):


    DMEA/METHYL ESTER BASED ESTERAMINE SYNTHESIS WITH TITANIUM CATALYST



    [0052] A mixture of dimethylethanolamine (DMEA, 114.5 g, 1.29 mole), C12/C14 mixed fatty methyl ester (270 g, 1.21 mole), and Vertec 2000, a titanium catalyst (0.27 g) was added to a 4-neck flask fitted with a nitrogen sparge, a distillation column, a thermocouple, and a mechanical stirrer. The mixture was heated from 140°C to 152°C over 5 hrs. Conversion to the esteramine was determined by proton NMR to be 24%.

    REFERENCE EXAMPLE 8 (not according to the invention):


    DMEA/METHYL ESTER BASED ESTERAMINE SYNTHESIS WITH SODIUM ACETATE CATALYST



    [0053] A mixture of dimethylethanolamine (DMEA, 116 g, 1.30 mole), C12/C14 mixed fatty methyl ester (236 g, 1.06 mole), and sodium acetate catalyst (0.72 g) was added to a 4-neck flask fitted with a nitrogen sparge, a distillation column, a thermocouple, and a mechanical stirrer. The mixture was heated to 147°C for 5 hrs. Conversion to the esteramine was determined by proton NMR to be 11%.

    REFERENCE EXAMPLE 9 (not according to the invention):


    TEA/METHYL ESTER BASED ESTERAMINE SYNTHESIS WITH TETRABUTYL TITANATE CATALYST



    [0054] A mixture of triethanolamine (TEA, 125 g, 0.84 mole), soft tallow methyl ester (379.2 g, 1.30 mole), tetrabutyl titanate (0.86 g), and Anox 20 anti-oxidant was added to a 4-neck flask fitted with a nitrogen sparge, a thermocouple, and a mechanical stirrer.The mixture was heated to 170°C for 3 hrs. No methanol was observed in the overhead, which indicated a minimal conversion.

    [0055] Selected example summaries are listed, as follows, in table form:
    Table I
    Example NumberTemperature as TmaxCatalyst UsedReaction Time, HoursAlkanolamine Used *
    1A 180°C Zn+2 0.75 TEA
    1B (reference) 180°C - 1.37 TEA
    2A 170°C Zn+2 5.3 TEA
    2B (reference) 170°C Phosphorous acid 6.1 TEA
    3 170°C Zn+2 4.5 TEA
    * Where TEA stands for Triethanolamine
    Table II
    Example NumberTemperature as TmaxCatalyst UsedRelative Reaction Performance

    Alkanolamine Used **
    4B (reference) 175°C Phosphorous acid 1.00 MDEA
    4C (reference) 175°C Zn+2 0.62 MDEA
    4D 175°C Zn+2 1.01 MDEA
    4E 175°C Zn+2 1.07 MDEA
    4F 175°C Zn+2 1.51 MDEA


    Numbers larger than 1.00 are faster reaction rates.
    ** Where MDEA stands for Methyldiethanolamine.


    [0056] The invention is now described in such full, clear, concise and exact terms as to enable any person skilled in the art to which it pertains, to practice the same. It is to be understood that the foregoing describes preferred embodiments of the invention and that modifications may be made therein without departing from the scope of the invention as set forth in the appended claims.


    Claims

    1. A method for decreasing the reaction time between an alkanolamine and a fatty acid to produce esteramines, the method comprising:

    providing an alkanolamine;

    providing a fatty acid;

    reacting the alkanolamine and the fatty acid in the presence of a divalent zinc catalyst to form at least one esteramine;

    wherein the zinc catalyst is zinc oxide, zinc carbonate, zinc diphosphinate, zinc triflate or zinc stearate.


     
    2. The method of claim 1, wherein the alkanolamine is selected from the group consisting of ethanolamine, diethanolamine, triethanolamine, triisopropanolamine, alkyldiethanolamines, alkyldiisopropanolamines, isopropanolamine, diisopropanolamine, dialkylmonoethanolamines, dialkylmonoisopropanolamines, and combinations thereof.
     
    3. The method of claim 1, wherein the zinc diphosphinate catalyst is formed in situ.
     
    4. The method of claim 1, wherein the reacting occurs at a temperature within the range of 60°C to 300°C, preferably 130° to 190°C.
     
    5. The method of claim 1, wherein the method occurs in the presence of an inert atmosphere, preferably nitrogen.
     
    6. The method of claim 1, wherein the fatty acid is an alkyl acid having from 2 to 30 carbon atoms, preferably 5 to 25 carbon atoms.
     
    7. The method of claim 1, wherein the zinc catalyst is present in an amount greater than 1 ppm based on the total weight of the reactants.
     
    8. The method of claim 1, wherein the zinc catalyst is present in an amount of 20 ppm to 5000 ppm based on the total weight of the reactants, preferably 100 ppm to 200 ppm based on the total weight of the reactants.
     
    9. The method of claim 1, wherein the alkanolamine and fatty acid are present in a molar ratio of 0.5/1 to 3/1, where the alkanolamine represents the denominator in the ratio.
     


    Ansprüche

    1. Verfahren zum Verringern der Reaktionszeit zwischen einem Alkanolamin und einer Fettsäure zum Herstellen von Esteraminen, wobei das Verfahren umfasst:

    Bereitstellen eines Alkanolamins,

    Bereitstellen einer Fettsäure,

    Umsetzen des Alkanolamins und der Fettsäure in der Gegenwart eines divalenten Zink-Katalysators zum Ausbilden mindestens eines Esteramins,

    wobei der Zink-Katalysator Zinkoxid, Zinkcarbonat, Zinkdiphosphinat, Zinktriflat oder Zinkstearat ist.


     
    2. Verfahren nach Anspruch 1, wobei das Alkanolamin aus der Gruppe ausgewählt ist, bestehend aus Ethanolamin, Diethanolamin, Triethanolamin, Triisopropanolamin, Alkyldiethanolaminen, Alkyldiisopropanolaminen, Isopropanolamin, Diisopropanolamin, Dialkylmonoethanolaminen, Dialkylmonoisopropanolaminen und Kombinationen davon.
     
    3. Verfahren nach Anspruch 1, wobei der Zinkdiphosphinat-Katalysator in situ gebildet wird.
     
    4. Verfahren nach Anspruch 1, wobei das Umsetzen bei einer Temperatur innerhalb des Bereichs von 60°C bis 300°C, vorzugsweise 130° bis 190°C, erfolgt.
     
    5. Verfahren nach Anspruch 1, wobei das Verfahren in der Gegenwart einer inerten Atmosphäre, vorzugsweise Stickstoff, erfolgt.
     
    6. Verfahren nach Anspruch 1, wobei die Fettsäure eine Alkylsäure mit 2 bis 30 Kohlenstoffatomen, vorzugsweise 5 bis 25 Kohlenstoffatomen, ist.
     
    7. Verfahren nach Anspruch 1, wobei der Zink-Katalysator in einer Menge von mehr als 1 ppm, basierend auf dem Gesamtgewicht der Reaktanten, vorhanden ist.
     
    8. Verfahren nach Anspruch 1, wobei der Zink-Katalysator in einer Menge von 20 ppm bis 5000 ppm, basierend auf dem Gesamtgewicht der Reaktanten, vorzugsweise 100 ppm bis 200 ppm, basierend auf dem Gesamtgewicht der Reaktanten, vorhanden ist.
     
    9. Verfahren nach Anspruch 1, wobei das Alkanolamin und die Fettsäure in einem Molverhältnis von 0,5/1 bis 3/1 vorhanden sind, wobei das Alkanolamin den Nenner in dem Verhältnis repräsentiert.
     


    Revendications

    1. Procédé pour raccourcir la durée de la réaction entre une alcanolamine et un acide gras pour produire des esteramines, le procédé comprenant :

    la fourniture d'une alcanolamine ;

    la fourniture d'un acide gras ;

    la réaction de l'alcanolamine et de l'acide gras en présence d'un catalyseur au zinc divalent pour former au moins une esteramine ;

    dans lequel le catalyseur au zinc est de l'oxyde de zinc, du carbonate de zinc, du diphosphinate de zinc, du triflate de zinc ou du stéarate de zinc.


     
    2. Procédé selon la revendication 1, dans lequel l'alcanolamine est choisie dans le groupe constitué de l'éthanolamine, de la diéthanolamine, de la triéthanolamine, de la triisopropanolamine, des alkyldiéthanolamines, des alkyldiisopropanolamines, de l'isopropanolamine, de la diisopropanolamine, des dialkylmonoéthanolamines, des dialkylmonoisopropanolamines et des combinaisons de celles-ci.
     
    3. Procédé selon la revendication 1, dans lequel le catalyseur au diphosphinate de zinc est formé in situ.
     
    4. Procédé selon la revendication 1, dans lequel la réaction a lieu à une température dans la plage de 60 °C à 300 °C, de préférence de 130° à 190 °C.
     
    5. Procédé selon la revendication 1, dans lequel le procédé a lieu en présence d'une atmosphère inerte, de préférence d'azote.
     
    6. Procédé selon la revendication 1, dans lequel l'acide gras est un acide alkylique comportant de 2 à 30 atomes de carbone, de préférence de 5 à 25 atomes de carbone.
     
    7. Procédé selon la revendication 1, dans lequel le catalyseur au zinc est présent en une quantité supérieure à 1 ppm sur la base du poids total des réactifs.
     
    8. Procédé selon la revendication 1, dans lequel le catalyseur au zinc est présent en une quantité de 20 ppm à 5 000 ppm sur la base du poids total des réactifs, de préférence de 100 ppm à 200 ppm sur la base du poids total des réactifs.
     
    9. Procédé selon la revendication 1, dans lequel l'alcanolamine et l'acide gras sont présents en un rapport molaire de 0,5/1 à 3/1, où l'alcanolamine représente le dénominateur dans le rapport.
     






    Cited references

    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description