Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/001—Softening compositions
  • C11D3/0015—Softening compositions liquid
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/645—Mixtures of compounds all of which are cationic
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
  • C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
  • C11D1/526—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 are polyalkoxylated
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/62—Quaternary ammonium compounds

Definitions

• the invention relates to new formulations comprising esterquats and amides, and their use in detergent, fabric softening, dryer sheets, personal care and cleaners.
• the invention also relates to an improved process for making these formulations where unreacted fatty acid used in the esterification step is reacted with an amine to form the amide in situ. This improved process offers the advantages of reducing total reaction time, providing an amide that stabilizes the formulation and eliminating free fatty acid that can hurt the stability of the formulation.
• compositions containing quaternary ammonium salts having at least one long chain esterified hydrocarbyl group are widely known for their use in laundry (for example, fabric softeners, dryer sheets, softergents, detergents), cleaner and personal care applications. These esterquats are known for their efficacy in cleaning and softening applications, but it is also widely recognized that the esterquat formulations that were previously known suffered from hydrolytic stability problems. These problems may bring limitations to their use in aqueous formulations and can be problematical even in solid formulations, if the product is used in an aqueous environment and breaks down before the esterquat has a chance to act on the target surface.
• esterquats quaternary ammonium salts having at least one long chain esterified hydrocarbyl group
• esterquats are typically formed by reacting an alkanolamine with a fatty acid.
• the fatty acid reacts with the OH group forming an ester amine and releasing water.
• the ester amine can then be quaternized as is known in the art.
• One potential lengthy step in this process is the esterification reaction, which can take more than 24 hours to fully react the alkanolamine with a stoichiometric amount of fatty acid.
• the amount of time needed to complete the reaction is directly correlated with the cost of the process. Two approaches are commonly used in such situations in order to decrease the time and therefore the cost of the process. The first is the use of excess fatty acid.
• the esterification reaction follows the common pattern where the concentration of the reactants asymptotically approaches zero. Thus, the majority of the starting material is consumed in the early stages of the reaction whereas the last percentages of starting material take comparatively longer to react. However, stopping the reaction before it reaches completion again leads to the presence of unreacted fatty acid, which as previously discussed is problematical.
• the invention is a composition of matter comprising an esterquat and an amide and having salts of primary fatty amines present in an amount no greater than 5 percent of the esterquat, by weight.
• the esterquat corresponds to the following formula:
• A is independently at each occurrence [CH 2 ]_-[CYR 3 ] m -CYR 3 H; Y is independently at each occurrence H, OH, N(R ) 2 or QT; Q is independently at each occurrence -O-C(O)-; -C(O)-O-; O-C(O)-O-; NR 4 C(O)-; -C(O)NR 4 -; (O-CH 2 -CHR 3 ) p -O-C(O)-; or (O-CH 2 -CHR 3 ) p -C(O)-O-
• T is independently at each occurrence a C 5 -C 35 alkyl group
• R 1 is independently at each occurrence a C,-C 4 alkyl group, or an aryl group having 6-12 carbons, optionally substituted with an alkyl group, or an hydroxyalkyl group having 2 to 6 carbons
• R 2 is independently at each occurrence R 1 or A;
• R 3 is independently at each occurrence H or R 1 ;
• R 4 is independently at each occurrence H or R 1 or a C,-C 4 hydroxyalkyl group;
• n is independently at each occurrence a number equal to 1 or greater;
• m is independently at each occurrence a number from 0 to 5;
• p is independently at each occurrence a number from 1 to 10; with the proviso that at least one Y is QT and at least one Q contains an ester group.
• J is independently at each occurrence -(CH 2 -CHR 5 -O)_-R 6 or -C n ,H (2n , +1 . x) (OR 8 ) x ;
• Z is independently at each occurrence J or [-P-N(J)(J)] ;
• P is independently at each occurrence -C 2 . 12 hydrocarbyl or -C n .H (2n , .x) (R 9 ) x -;
• R 5 is independently at each occurrence H or a C 1 4 alkyl
• R 6 is independently at each occurrence H, C 1 20 alkyl or (-C(O)R 7 ) ;
• R 7 is independently at each occurrence a C 5.35 alkyl
• R 8 is independently at each occurrence R 6 or (-CH 2 -CHR 5 -O) a -R 6 ;
• R 9 is independently at each occurrence -OR 8 or -N(R 8 )(R 8 ) ;
• a is independently at each occurrence 0 to 30;
• x is independently at each occurrence 0 to 6;
• m' is independently at each occurrence 0 to 10;
• n' is independently at each occurrence 2 to 6; with the proviso that there is at least one (-C(O)R 7 ) present and connected directly to a nitrogen atom.
• the invention comprises an improved esterification reaction, or indeed, an improvement for any reaction that uses a fatty acid and which would benefit from the removal of unreacted or excess fatty acid.
• the improved process of the invention is suitable for those reactions that comprise reacting a species having a reactive H (typically OH or NH groups) with a fatty acid.
• esterification reaction comprising contacting an alkanolamine having reactive OH groups with a fatty acid to convert at least a portion of the reactive OH groups into esters
• the esterification reaction is allowed to continue for a period of time and then an amine is added to react with at least a portion of the fatty acid which has not yet reacted with the alkanolamine.
• Similar procedures could be used for example in a reaction of an amine with a fatty acid to form an amide, wherein after a period of time a second amine is added which reacts faster than the first amine to quickly eliminate the unreacted or excess fatty acid.
• Suitable amines in such a process will corresponds to the formula: (J)(J)N[-P-N(Z)] m ,-(J) where: J is independently at each occurrence -(CH 2 -CHR 5 -O) a -R 6 or -C_,H (2n , +1.x) (OR 8 ) x ;
• Z is independently at each occurrence J or [-P-N(J)(J)]
• P is independently at each occurrence -C 2 12 hydrocarbyl or -C_,H (2n , x) (R 9 ) x -;
• R 5 is independently at each occurrence H or a C 1 4 alkyl;
• R 6 is independently at each occurrence H, C, 20 alkyl or (-C(O)R 7 ) ;
• R 7 is independently at each occurrence a C 5.35 alkyl
• R 8 is independently at each occurrence R 6 or (-CH 2 -CHR 5 -O) a -R 6 ;
• R 9 is independently at each occurrence -OR 8 or
• a third aspect of the invention is a process of improving the concentratibility or hydrolytic stability of an esterquat based fabric softener composition, comprising including an amount of an amide to the composition, wherein the amide is defined as above and may be formed in situ or added separately.
• Yet another aspect of the invention is the use of the compositions described above, whether or not made by using the process described above, in detergents, softergents, fabric softeners, dryer sheets, cleaners or personal care applications.
• esterquats suitable for use in the present invention correspond to the following formula:
• X is a softener compatible anion
• A is independently at each occurrence [CH 2 ] n - [CYR 3 ] m -CYR 3 H
• Y is independently at each occurrence H, OH, N(R 4 ) 2 or QT
• Q is independently at each occurrence -O-C(O)-; -C(O)-O-; O-C(O)-O-; NR 4 C(O)-; -C(O)NR 4 -; (O-CH 2 -CHR 3 ) p -O-C(O)-; or (O-CH 2 -CHR 3 ) p -C(O)-O-
• T is independently at each occurrence a C--C 35 alkyl group
• R 1 is independently at each occurrence a C,-C 4 alkyl group, or an aryl group having 6 to 12 carbons, optionally substituted with an alkyl group, or an hydroxyal
• esterquat is intended to be within the scope of this invention.
• the present invention is suitable for any species having an ester group connected, to a quaternized nitrogen atom. It is possible, however, that the esterquat may have two or more nitrogen atoms, may have two or more ester groups, may be alkoxylated (for example by random or block addition of one or more of ethylene oxide, propylene oxide or butylene oxide), may have free OH groups which have not been esterified, may have three short chain (C ) hydrocarbyl groups or only one. It is preferred that when p is present that it is not greater than 3.
• the T group(s) can be selected from saturated and unsaturated species and may be straight or branched, and can be long or short, although the range of C 7.23 is preferred.
• the esterquats for use in the present invention can be purchased, or be synthesized by any means known to those skilled in the art, as the particular process used is not important in this aspect of the invention.
• the process involves first esterifying an alkanolamine and then totally or partially quatemizing the esterification product. Any reaction conditions conducive to forming an ester can be used. These conditions tend to be at a temperature of from 50°C to 300°C, and at a pressure of from 0.01 atm to about 10 atm. These reactions may be conducted under a blanket of inert gas such as nitrogen.
• the fatty acid chosen to esterify the alkanolamine can be selected from any C 6.36 fatty acid capable of reacting with an OH group.
• fatty acid shall be understood to mean those compounds corresponding to the formula: R 7 C(O)OH where R 7 is a C 5.35 alkyl group. It is preferred that the fatty acid have from 6 to 24 carbons.
• the hydrocarbyl chain of the fatty acid can be linear or branched, saturated or unsaturated. The following list demonstrates some alkanolamines which can be esterified
• RadiacidTM 406 is a material consisting primarily of partially hydrogenated C 16 -C 18 fatty acids
• RadiacidTM 409 is a material consisting primarily of fully saturated C 16 -C 18 fatty acids
• RadiacidTM 600 is a material consisting primarily of C 12 -C 16 fatty acids (topped coconut);
• RadiacidTM 626 is a material consisting primarily of C 6 -C 16 fatty acids (coconut);
• the following list demonstrates some of the fatty acids which can be used, either alone or in combination with other fatty acids, to esterify the alkanolamine which can then be quaternized to some degree and used in the compositions of the invention: valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, and the branched (for example isovaleric acid) or unsaturated isomers (for example oleic acid) thereof.
• valeric acid caproic acid
• caprylic acid capric acid
• lauric acid myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, and the branched (for example isovaleric acid) or unsaturated isomers (for example oleic acid) thereof.
• this list is exemplary and not exhaustive, and the person of ordinary skill
• Quaternization of alkanolamine esters to make the final esterquat product is also a known process, and in general any of the many teachings on this subject are applicable in this invention. It is conceived that the quaternization will involve the reaction of the alkanolamine ester with a composition corresponding to the formula R 1 X, where R and X are as described above. The quaternization reaction is preferably carried out at the ratio of from 0.1 to 20 moles of R'X per mole of esterified alkanolamine. The temperature is typically from 30°C to 150°C, and at a pressure of from 1 to 50 bars. Suitable quaternizing agents include alkyl halides, dialkyl sulfates, and trialky phosphates.
• Some preferred alky halides are methyl chloride, ethyl chloride, benzyl chloride, methyl bromide, and ethyl bromide.
• Preferred dialkyl sulfates include dimethyl sulfate and diethyl sulfate.
• Preferred trialkyl phosphates include trimethyl phosphate and triethyl phosphate. As is known in the art, it may be advantageous to carry out the quaternization reaction in the presence of a defoaming agent and/or an additive to lower the melting point of the reaction mixture.
• Commonly known materials include water, isopropanol, propanediol, dipropylene glycol, polyethylene glycol, polypropylene glycol, alkoxylated fatty acids and alcohols having more than three carbons in the alkyl chain, glycol ether solvents, diether solvents, tetrahydrofuran, methanol, ethanol, hexanediol, and acetone.
• J is independently at each occurrence -(CH 2 -CHR 5 -O) a -R 6 or -C n ,H (Zn . +1.x) (OR 8 ) x ; Z is independently at each occurrence J or [-P-N(J)(J)]; P is independently at each occurrence - C 2 .
• R 5 is independently at each occurrence H or a C, .4 hydrocarbyl
• R 6 is independently at each occurrence H, C 1 20 alkyl or (-C(O)R 7 );
• R 7 is independently at each occurrence a C 5.3 _ alkyl;
• R 8 is independently at each occurrence R 6 or (-CH 2 -CHR 5 -O) a -R 6 ;
• R 9 is independently at each occurrence -OR 8 or -N(R 8 )(R 8 );
• a is independently at each occurrence 0 to 30;
• x is independently at each occurrence 0 to 6;
• m' is independently at each occurrence 0 to 10;
• n' is independently at each occurrence 2 to 6; with the proviso that there is at least one (-C(O)R 7 ) present and connected directly to a nitrogen atom.
• R 7 can be saturated or unsaturated, straight or branched, and can be long or short, although the range of C 723 is preferred. It should be noted that R 7 may be the same as T in the esterquat but is not necessarily so. It is preferred that R 5 be H or a C 1 2 hydrocarbyl; R 6 be -C(O)C 6 . 19 ; x be either 0 or 1 ; P is a C 26 hydrocarbyl group; a be from 0 to 10, and m' be from 0 to 5.
• the amides suitable for use in the present invention can be purchased commercially, or be made according to methods known by those skilled in the art, such as the ones described in the following references: The Aikanolamines Handbook published by The Dow Chemical Company (Form No. 111-1159-88R-SAI) and the references cited therein; Houben-Weyl, Methoden der Organischen Chemie, band 6, Thieme 1952, Surfactant Science Series Vol. 1 , Nonionic Surfactants, M. Schick, and McKenna, Arthur L., Fatty amides: synthesis, properties, reactions, and applications, Witco Chemical Corporation, Humko Chemical Division, 1982. More preferably the amides can be made in situ in the esterification reaction mixture.
• the amide is not made in situ (that is, it is purchased or synthesized separately), it is added to the finished quaternized alkanolamine ester, however, it can be added at any stage in the synthesis of the alkanolamine esterquat. If added before the synthesis is complete it should be understood, that a portion of the amide might be reacted as a side reaction with the intended reaction, which may or may not cause problems depending on the intended application.
• suitable amides which can be used in the current invention can be made from the amines and acids listed below and which can optionally be further alkoxylated with EO, PO or BO. These examples are exemplary only and are not meant to be exhaustive:
• MAE MIPA, MEA, Dimethylamine, TETA, TEPA, AEEA, DEA, DIPA, EDA, DETA, RadiacidTM406, RadiacidTM 409, RadiacidTM 600, and RadiacidTM 626.
• the amide be formed in situ. This can be done simply by adding an amine to the esterification reaction at a point where there is still unreacted fatty acid in the reaction mixture. Thus, this can be done under the same reaction conditions as the esterification reaction, or alternatively, as the reaction mixture is cooled as is typically done prior to quaternization. It should be understood that if the amide is formed prior to or during quaternization, then some of the amide might also be quaternized. As should be readily understood by those skilled in the art, when the amide is formed in situ with the esterified alkanolamine, then T will be the same as R 7 , as both T and R 7 will be the residual portion of the same fatty acid.
• J is independently at each occurrence -(CH 2 -CHR 5 -O) a -R 6 or -C n ,H (2n , +1.x) (OR 8 ) x ;
• Z is independently at each occurrence J or [-P-N(J)(J)];
• P is independently at each occurrence - C 2 . 12 hydrocarbyl or -C n ,H (2n , .x) (R 9 ) x -;
• R 5 is independently at each occurrence H or a C, .4 hydrocarbyl;
• R 6 is independently at each occurrence H, C. .2 . alkyl or
• R 7 is independently at each occurrence a C 535 alkyl
• R 8 is independently at each occurrence R 6 or (-CH 2 -CHR 5 -O) a -R 6
• R 9 is independently at each occurrence -OR 8 or -N(R 8 )(R 8 );
• a is independently at each occurrence 0-30;
• x is independently at each occurrence 0 to 6;
• m' is independently at each occurrence 0 to 10;
• n' is independently at each occurrence 2 to 6; with the proviso that there is at least one H connected directly to a nitrogen atom which is capable of reacting with a fatty acid to form an amide.
• the amount of fatty acid that was present in the reaction mixture is of course reduced as it reacts with the amine. It is preferred that the amine be added in such a quantity that there is less than 10 percent fatty acid, more preferably 5 percent or 1 percent fatty acid and most preferably, essentially no free fatty acid left in the final reaction mixture.
• the term "in situ” means only that the amide is formed in the presence of the reaction product (for example an alkanolamine ester) with the fatty acid (or fatty acid mixture) which was used to react
• the reaction product for example an alkanolamine ester
• the fatty acid or fatty acid mixture
• amides from acids and amines is generally known and well- described in the public literature. For example amines and acid can be reacted at low temperatures, for example,-10°C to 25°C, to form ammonium salts, which can then be converted to amides (and water) at higher temperatures, for example up to 250°C. Of course, it is also known that the ammonium salt formation occurs also at higher temperatures and can be followed at once by the amide formation.
• the choice of the initial temperature depends on the volatility of the amine; once the ammonium salt formed, the heating can start.
• the in situ formation of amides can be conveniently combined with the conditions of the esterification (or other reaction of a reactive H with a fatty acid for example amidation reaction) step.
• the esterification reaction After the esterification reaction has come to a certain point, where a certain amount of unreacted acid is left, which can be estimated from the kinetics of that particular esterification reaction and which can be determined by chemical analysis (for example by titration), the selected amine can be directly introduced into the reaction mixture and the process can be continued as if it was an esterification.
• the composition of the present invention may include more than one esterquat, or more than one amide. It may also contain other ingredients used in fabric softeners, detergents, cleaners, or personal care formulations. These are well known in the art and include things such as enzymes and enzyme stabilizers, dispersing agents, optical brighteners, suds suppressers, non-esterquat fabric softeners, non-esterquat surfactants such as cationic, anionic, nonionic, amphoteric, zwitterionic surfactants , thickening agents, viscosity control agents, pH modifiers, colorants, perfumes, preservatives, bactericides, germicides, fungicides, and antistatic agents.
• enzymes and enzyme stabilizers include things such as enzymes and enzyme stabilizers, dispersing agents, optical brighteners, suds suppressers, non-esterquat fabric softeners, non-esterquat surfactants such as cationic, anionic, nonionic, amphoteric, zwit
• compositions of the present invention especially those in which the amide is made in situ such that there little, if any, free fatty acid in the formulation, exhibit improved hydrolytic stability and can be concentrated in an aqueous solution to a much higher level than previously observed.
• Aqueous fabric softeners made with a composition of the present invention can be concentrated such that the aqueous formulation comprises 20 percent, 25 percent, 30 percent 35 percent or even 40 percent by weight esterquat.
• the formulations are improved as they are more hydrolytically stable and may demonstrate improved viscosity profiles.
• the esterquat and the amide can be chosen to make the formulation even more suitable for a particular application.
• the target application was as a fabric softener then it is possible to use an amide (or to use an amine which reacts with the fatty acid to form an amide) which is known to have fabric softening properties, in order to get an extra benefit.
• diesterquats are generally considered to have better fabric softening properties than monoester or triesterquats, and so the reactants and reaction conditions should be chosen so as to optimize the production of diesters when the target application is fabric softening.
• RadiacidTM 409 was mixed with DMAPD in a mole ratio of 2. The pressure was decreased to 200 mbar. Then the temperature was raised to 200°C within typically one hour, while the pressure was gradually decreased to 20 mbar. The reaction mixture was kept at 175°C/20 mbar during 7 hours, after which the reaction was stopped. The residual acid content was then 9.1 weight percent, determined by titration.
• the esteramine thus obtained, was solved in 20 weight percent acetone at 95°C in an appropriate pressure vessel. Then 1.5 moles of MeCI per mole of esteramine were added and the mixture kept at 95°C/5 to 4 barg during 2 hours. Next the reactor was discharged removing the excess of MeCI and the solvent, leaving a solid material. From titration analysis of residual amine it was found that the esteramine was quaternized for 100 percent (residual Nitrogen determination by perchloric acid titration).
• Example 1 The procedure of Example 1 was repeated with a mole ratio acid: DMAPD of 2 and with a esterification reaction time of 12 hours, resulting in a residual acid content of 5.7 weight percent.
• Example 1 The procedure of Example 1 was repeated with a mole ratio acid: DMAPD of 2.3 and with a esterification reaction time of 8 hours, resulting in a residual acid content of 15 weight percent.
• Example 2 The esterification procedure of Example 1 was repeated with a mole ratio acid: DMAPD of 2. The reaction mixture was kept at 175°C/20 mbar during 8 hours, after which the residual acid content was 8.4 weight percent. Then the vacuum was interrupted and the temperature decreased to 170°C. DEA was added in an amount of 3 weight percent. The temperature was raised again to 200°C and the pressure decreased to 20 mbar. The mixture was kept for an hour under these conditions, after which the residual acid content was 0.8 weight percent. The final product contained about 10 weight percent amide.
• DMAPD mole ratio acid
• Example 4 provides superior hydrolytic stability and has a lower viscosity when formulated at any concentration in water and consequently it can be concentrated to a higher degree than the comparative examples. This is in addition to the benefit of reduced reaction time.
• RadiacidTM 409 was mixed with MDEA in a mole ratio of 1.6. The pressure was decreased to 200 mbar. Then the temperature was raised to 200°C, while the pressure was gradually decreased to 20 mbar. The reaction mixture was kept at 200°C/20 mbar for 1 hour, after which the reaction was stopped. The residual acid content was then 7.9 weight percent.
• the esteramine thus obtained, was dissolved in 20 weight percent acetone at 95°C in an appropriate pressure vessel. Then 1.5 moles of MeCI per mole of esteramine were added and the mixture kept at 95°C/6 to 4 bar gauge during 8 hours. Next the reactor was discharged removing the excess MeCI and the solvent, leaving a solid material. From analysis of residual amine it was found that the esteramine was quaternized for 100 percent.
• Example 7 (comparative) The procedure of Example 6 was repeated with a mole ratio acid:MDEA of 1.6 and with a esterification reaction time of 18.5 hours, resulting in a residual acid content of 1.0 weight percent.
• Example 6 The esterification procedure of Example 6 was repeated with a mole ratio acid:MDEA of 1.6. The reaction mixture was kept at 200°C/20 mbar for 1 hour, after which the residual acid content was 7.7 weight percent. Then the vacuum was interrupted and the temperature decreased to 170°C. DEA was added in an amount of 2.8 weight percent. The temperature was raised again to 200°C and the pressure decreased to 20 mbar. The mixture was kept for an hour under these conditions, after which the residual acid content was 0.2 weight percent. The final product contained about 10 weight percent amide.
• MDEA mole ratio acid:MDEA
• the esteramine/amide mixture thus obtained, was dissolved in 20 weight percent acetone at 95°C in an appropriate pressure vessel. Then 1.5 moles of MeCI per mole of esteramine were added and the mixture kept at 95°C/6 to 4 bar gauge for 8 hours. Next the reactor was discharged removing the excess MeCI and the solvent, leaving a solid material. From analysis of residual amine it was found that the esteramine was 100 percent quaternized.
• Example 10 The procedure of Example 6 was repeated with a mole ratio acid: MDEA of 2 and with a esterification reaction time of 2 hours, resulting in a residual acid content of 8.8 weight percent.
• Example 10 The procedure of Example 6 was repeated with a mole ratio acid: MDEA of 2 and with a esterification reaction time of 2 hours, resulting in a residual acid content of 8.8 weight percent.
• Example 8 The procedure of Example 8 was repeated with a mole ratio acid: MDEA of 2, with a esterification reaction time of 2 hours, resulting in a residual acid content of 8.8 weight percent, with 3.2 weight percent DEA addition, resulting in a final residual acid content of 0.4 weight percent and an amide content of about 11 weight percent.
• MDEA mole ratio acid
• Example 11 The procedure of Example 8 was repeated with a mole ratio acid: MDEA of 2, with a esterification reaction time of 2 hours, resulting in a residual acid content of 8.8 weight percent, with 3.2 weight percent DEA addition, resulting in a final residual acid content of 0.4 weight percent and an amide content of about 11 weight percent.
• the esterquats products of Examples 6 to 10 were dispersed in water in different concentrations and the viscosities measured. At the same time, a 5 weight percent dispersion in water was kept at 50°C/pH 4, after 4 weeks the hydrolysis of the esterquat was measured. The results are in the Table II.
• RadiacidTM 406 was mixed with TEA in a mole ratio of 1.6. The pressure was decreased to 200 mbar. Then the temperature was raised to 200°C, while the pressure was gradually decreased to 20 mbar. The reaction mixture was kept at 200°C/20 mbar during 2.5 hours, after which the reaction was stopped. The residual acid content was then 2.9 weight percent.
• the esteramine thus obtained, was heated to 70°C. Then, carefully, 0.9 moles of DMS per mole of esteramine was added and the mixture kept at 90°C for 2 hours. From analysis of residual amine it was found that the DMS was fully converted and the esteramine quaternized for 90 percent.
• Example 14 The procedure of Example 12 was repeated with a mole ratio acid: TEA of 1.7 and with a esterification reaction time of 1 hour, resulting in a residual acid content of 6.2 weight percent.
• Example 14 The procedure of Example 12 was repeated with a mole ratio acid: TEA of 1.7 and with a esterification reaction time of 1 hour, resulting in a residual acid content of 6.2 weight percent.
• Example 12 The esterification procedure of Example 12 was repeated with a mole ratio acid.TEA of 1.7.
• the reaction mixture was kept at 200°C/20 mbar during 1 hour, after which the residual acid content was 8.2 weight percent.
• the vacuum was interrupted and the temperature decreased to 170°C.
• DEA was added in an amount of 3 weight percent.
• the temperature was raised again to 200°C and the pressure decreased to 20 mbar.
• the mixture was kept for an hour under these conditions, after which the residual acid content was 0.3 weight percent.
• the final product contained about 10 weight percent amide.
• Example 10 The procedure of Example 10 was repeated where 3.2 percent DEA was replaced by DIPA, resulting in a final residual acid content of 1.5 percent and an amide content of about 10 percent. At the same time a 5 weight percent dispersion in water was kept at 50°C/pH 4, after 4 weeks the hydrolysis of the esterquat was measured to be 56 percent, which is far better than the one of the comparative Example 9.
• DEA can be replaced by equivalent amounts of other amines such as MEA, MIPA, DIPA, AEEA, EDA, DETA, TETA, or TEPA.
• DMAPD, MDEA or TEA can be replaced with other tertiary di- and trialkanolamines can be used, such as DEA-1 PO, DEA-1 BO, MEA-2PO, TIPA, MDIPA, MAE-1 PO, MAE-1 BO and alkoxylated tertiary di- and trialkanolamines.
• tertiary mo/7oalkanolamines like DMAE and DMAP and their alkoxylates, can also be used. It should be noted that these monoalkanoiamines may have applications in detergents, especially if esterified with fatty acids having shorter chain lengths such as RadiacidTM 600 or RadiacidTM 626.
• Example 17 (amide formation)
• RadiacidTM 406 was mixed with DEA in a mole ratio of 1. The pressure was decreased to 200 mbar. Then the temperature was raised to 200°C, while the pressure was gradually decreased to 20 mbar. The reaction mixture was kept at 200°C/20 mbar for 1 hour, after which the reaction was stopped. The residual acid content of the DEA amide was then 0.6 weight percent.
• Example 13 The TEA esterquat of Example 13 was molten together with the DEA amide of Example 17 (10:1 weight ratio). This mixture was dispersed in water (20 weight percent).
• Example 20 The TEA esteramine of Example 13 was molten together with the DEA amide of Example 17 and this mixture quaternized with DMS as described in Example 12. The resulting esterquat was dispersed in water (20 weight percent).
• Example 20 The TEA esteramine of Example 13 was molten together with the DEA amide of Example 17 and this mixture quaternized with DMS as described in Example 12. The resulting esterquat was dispersed in water (20 weight percent).
• RadiacidTM 406 was mixed with TEA in a mole ratio of 1.7. The pressure was decreased to 200 mbar. Then the temperature was raised to 200°C, while the pressure was gradually decreased to 20 mbar. The reaction mixture was kept at 200°C/20 mbar for a time long enough to esterify more than 99 weight percent of the fatty acid, after which the reaction was stopped. The residual acid content was then 0.5 weight percent.
• the esteramine thus obtained, was heated to 70°C. Then carefully 0.9 moles of DMS per mole of esteramine was added and the mixture kept at 90°C for 2 hours. From analysis of residual amine it was found that the DMS was fully converted and the esteramine 90 percent quaternized. This mixture was dispersed in water (20 weight percent).
• Example 17 was molten and was added to the molten product of Example 20 such that the ratio of product of Example 17 to the product of Example 20 is 6:100. The obtained mixture was dispersed in water (20 weight percent).
• Example 22
• RadiacidTM 406 was mixed with DETA in a mole ratio of 2 to 1. The pressure was decreased to 200 mbar. Then the temperature was raised to 175°C, while the pressure was gradually decreased to 20 mbar. The reaction mixture was kept at 175°C/20 mbar for 4 hours. The residual acid content of the DETA amide was then 7.5 weight percent.
• DEA was added in an amount of about 3 weight percent to the product of Example 23 at a temperature of 60°C to 70°C. The temperature was raised again to 175°C and the pressure decreased to 20 mbar. The mixture was kept for two hours under these conditions, after which the residual acid content was 0.9 weight percent. The final product contained about 10 weight percent of DEA-amide.
• Example 25 In appropriate equipment the product of Example 23 was ethoxylated with EO in a mole ration of 1 to 3 in presence of KOH catalyst in about 2.5 hours at a temperature of 120°C and at a pressure of 3 to 5 atmosphere. The product was then neutralized with low amounts of acetic acid.
• Example 23 In appropriate equipment the product of Example 23 can be alkoxylated during about two hours with BO without the presence of a catalyst in a mole ratio of 1 to 1 and then ethoxylated with EO in a mole ratio of 1 to 2.5 in presence of KOH catalyst in about 2.5 hours. The product can then be neutralized with low amounts of acetic acid. This product could then be mixed with product of Example 20 in a ratio described in Example 29 and then be formulated in an aqueous medium as described in Example 29 to lead to a 30 weight percent active formulation having a viscosity at 25°C of less than 100 mPa-s
• Example 10 The procedure of Example 10 was repeated with a mole ratio acid: MDEA+1 PO of 2 and with an esterification time of 8.5 hours, resulting in a residual acid content of 8.6 weight percent. DEA was added in an amount of about 3 weight percent and then the temperature was raised again to 200°C and the pressure decreased to 20 mbar. The mixture was kept for an hour under these conditions, after which the residual acid content was 0.4 weight percent. The final product contained about 10 weight percent amide.
• Example 4 The exact procedure of Example 4 was repeated but with one exception.
• the RadiacidTM 409 was replaced by RadiacidTM 406.
• the final product contains 0.8 weight percent of residual acid and about 10 weight percent amide.
• Example 23 to 25 have been molten and mixed with molten products of Examples 13, 14, 20, 27 and 28 in a ratio of 2:1 and then formulated in warm water (containing sufficient amount of hydrochloric acid to fully neutralize the various DETA amides) at either 20 percent concentration or 30 percent concentration.
• 0.5 weight percent CaCI 2 was systematically added at the end of the formulation in order to decrease the viscosity of the final mixture which was measured at 25 C (mPa-s). Results are reported in the table below.

Applications Claiming Priority (3)

Publications (1)

Family

ID=22424539

Family Applications (1)

Country Status (3)

Families Citing this family (3)

Family Cites Families (5)

• 2000
  • 2000-03-24 EP EP00916661A patent/EP1171558A1/de not_active Withdrawn
  • 2000-03-24 WO PCT/US2000/007970 patent/WO2000058427A1/en not_active Application Discontinuation
  • 2000-03-24 AU AU37731/00A patent/AU3773100A/en not_active Abandoned

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events