CA2127644A1 - Process for the continuous preparation of polyhydroxyfatty amides from n-alkylpolyhydroxyamines and alkyl esters of fatty acids - Google Patents
Process for the continuous preparation of polyhydroxyfatty amides from n-alkylpolyhydroxyamines and alkyl esters of fatty acidsInfo
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- CA2127644A1 CA2127644A1 CA002127644A CA2127644A CA2127644A1 CA 2127644 A1 CA2127644 A1 CA 2127644A1 CA 002127644 A CA002127644 A CA 002127644A CA 2127644 A CA2127644 A CA 2127644A CA 2127644 A1 CA2127644 A1 CA 2127644A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
Abstract
Abstract of the disclosure Process for the continuous preparation of polyhydroxy-fatty amides from N-alkylpolyhydroxyamines and alkyl esters of fatty acids In the process according to the invention, an N-alkyl-polyhydroxyamine, for example N-methylglucamine, is reacted with an alkyl ester of a fatty acid and in the presence of a basic catalyst. The reaction is carried out continuously in at least two, preferably in two or three, stirred tanks arranged in a cascade, under defined conditions in each stirred tank. Polyhydroxy-fatty amides, for example N-methyl fatty glucamides, are obtained continuously in high yield and purity with the process according to the invention.
Description
2 1 2 ~
HOECHST AKTIENGESELLSCHAFT HOE 93~F 918 Dr.GL-nu Werk Gendorf : '' Process for the continuous preparation of polyhydroxy fatty amides from N-alkylpolyhydroxyamines and alkyl esters of fatty acids Description The invention relates to a pr~cess for the continuou~
preparation of polyhydroxy-fatty amides by reaction of N-alkylpolyhydroxyamines with alkyl esters of fatty acids in the presence of basic catalystsO
Polyhydroxy-fatty amides are valuable surface-active compounds which are usable in many ways. Thus, for example, they can be used as such or in a mixture:with : anionic, cationic and/or nonionic surfactants as cleaning agents, detergents, textile treatment compositions and the like, that is in the form of solid products (for example as powders, grains or granules), solutions, dispersions, emulsions, pastes and the like. Since polyhydroxy-fatty amides are also readily biodegradable and can be prepared from renewable raw materials, they have achieved greater Lmportance recently.
~20 The polyhydroxy-fatty amides in question are generally :~ compounds of the formula R-CO-NR'-Z, in which R is a hydrocarbon radical having about 5 to 30 carbon atoms, preferably 8 to 18 carbon atoms, R~ is hydrogen, alkyl or hydroxyalkyl having up to prefera~ly 6 carbon atoms and : 25 Z is a linear polyhydroxyhydrocarbon radical having at least three O~ groups, which can also be alkoxylated, preferably a sugar alcohol radical. The preferred polyhydroxy-fatty amides therefore correspond to the formula below 2 ~ & L :~
Rl -N-CO--R2 I
fH2 (CHOH)n in which R1 is a short-chain al]kyl or hydroxyl, R2 is a fatty alkyl and n is preferably 3 or 4. The compounds having n = 4, which are particularly preferred, are termed glycamides and, in the case of glucose, are termed hexose radical glucamides.
:The preparation of polyhydroxy-fatty amides is generally carried out by reacting an N-alkylpolyhydroxy2mine (for ex~mple N-alkylglucamine) with an alkyl ester of a fatty : 10 acid in the prese~ce of basic compounds as catalystO The reaction equation below with N-methylglucamine and methyl la-lrate is intended to illustrate this in more detail:
C~3-N--~ + C11H23COCH3 , CH3-I-CO-C11}I23 ~ CH3 1 ~2 CH2 (C~O~) 4 (CBO~) 4 Such a process, for example, is described in the publica-::~tions WO 92/06071, WO 92/06072, WO 92/06073, WO g2/08687 ~` 15 and WO 93/03004.
:
According to the known processes for the preparation ofpolyhydroxy-fatty amides, the N-alkylglucamine and the : alkyl ester of the fatty acid are reacted in a molar ratio of essentially 1:1 in the prese.nce of a basic cataly~t selected from the group comprising the alkali metal alkoxides and alkali metal hydroxides at a temperature below 135C (cf. e.g. WO 92/06073, pa~e 10, ~ ~ 2 '~
HOECHST AKTIENGESELLSCHAFT HOE 93~F 918 Dr.GL-nu Werk Gendorf : '' Process for the continuous preparation of polyhydroxy fatty amides from N-alkylpolyhydroxyamines and alkyl esters of fatty acids Description The invention relates to a pr~cess for the continuou~
preparation of polyhydroxy-fatty amides by reaction of N-alkylpolyhydroxyamines with alkyl esters of fatty acids in the presence of basic catalystsO
Polyhydroxy-fatty amides are valuable surface-active compounds which are usable in many ways. Thus, for example, they can be used as such or in a mixture:with : anionic, cationic and/or nonionic surfactants as cleaning agents, detergents, textile treatment compositions and the like, that is in the form of solid products (for example as powders, grains or granules), solutions, dispersions, emulsions, pastes and the like. Since polyhydroxy-fatty amides are also readily biodegradable and can be prepared from renewable raw materials, they have achieved greater Lmportance recently.
~20 The polyhydroxy-fatty amides in question are generally :~ compounds of the formula R-CO-NR'-Z, in which R is a hydrocarbon radical having about 5 to 30 carbon atoms, preferably 8 to 18 carbon atoms, R~ is hydrogen, alkyl or hydroxyalkyl having up to prefera~ly 6 carbon atoms and : 25 Z is a linear polyhydroxyhydrocarbon radical having at least three O~ groups, which can also be alkoxylated, preferably a sugar alcohol radical. The preferred polyhydroxy-fatty amides therefore correspond to the formula below 2 ~ & L :~
Rl -N-CO--R2 I
fH2 (CHOH)n in which R1 is a short-chain al]kyl or hydroxyl, R2 is a fatty alkyl and n is preferably 3 or 4. The compounds having n = 4, which are particularly preferred, are termed glycamides and, in the case of glucose, are termed hexose radical glucamides.
:The preparation of polyhydroxy-fatty amides is generally carried out by reacting an N-alkylpolyhydroxy2mine (for ex~mple N-alkylglucamine) with an alkyl ester of a fatty : 10 acid in the prese~ce of basic compounds as catalystO The reaction equation below with N-methylglucamine and methyl la-lrate is intended to illustrate this in more detail:
C~3-N--~ + C11H23COCH3 , CH3-I-CO-C11}I23 ~ CH3 1 ~2 CH2 (C~O~) 4 (CBO~) 4 Such a process, for example, is described in the publica-::~tions WO 92/06071, WO 92/06072, WO 92/06073, WO g2/08687 ~` 15 and WO 93/03004.
:
According to the known processes for the preparation ofpolyhydroxy-fatty amides, the N-alkylglucamine and the : alkyl ester of the fatty acid are reacted in a molar ratio of essentially 1:1 in the prese.nce of a basic cataly~t selected from the group comprising the alkali metal alkoxides and alkali metal hydroxides at a temperature below 135C (cf. e.g. WO 92/06073, pa~e 10, ~ ~ 2 '~
- 3 ~
lines 3 to 12~. In detail, the procedure is carried out in such a way that the secondary glucamine, the alkyl ester o~ the fatty acid, the basic catalyst compound and a solvent are mixed together and the mixture is refluxed until the desired degree of convexsion, whereupon the fatty acid glucamide is isolated rom the reaction product, if ne~essary with vacuum treatment (cf. e.g. WO
92/06073, Examples I to V). This process delivers a relatively high conversion rate of the N-alkylpoly-hydroxyamine used and the resulting N-methylglucamide is also relatively pure, but, inter alia, it exhibits the disadvantages o discontinuous procedures. Although in the publications mentioned reference is made to the fact that the process described can also be carried out continuously, nothing further is stated~ in particular with respect to apparatus setup, procedure, reaction conditions and the like (cf. e.g. WO 92~06073, page 10, lines 3 to 12).
The present invention now provides a continuous process for the preparation of polyhydroxy-fatty amides. Starting from C1 to C4 alkyl esters of fatty acid~, preferably from methyl esters of fatty acids, a high degree of conversion of the N-alkylpolyhydroxyamine used is to be achieved and the resulting polyhydroxy-fatty amide is to be very pure, that is it is to contain the particularly undesirable by-products, i.e. cyclic polyhydroxy compounds, only in a very small amount.
The process according to the invention for the continuous preparation of polyhydroxy-fatty amides by reaction of N-alkylpolyhydroxyamine and C1 to C4 alkyl ester of fattyacid in the presence of basic catalysts comprises con-tinuously carrying out the reaction in at least two stirred tanks arranged in a cascade and during this carrying out the procedure in such a way that (in the steady state~
a) in the first stirred tank a temperature of 6 0 to 120C, preferably 65 to 95C, is maintained and a ~ ~ 2 i~
,~ - 4 -residence time is maintained (with retention of the Cl to C4 alcohol present) such that a single-phase liquid reaction mixture is obtained, b) the single-phase liquid reaction mixture entering into the second and further stirred tanks is held in each case at a temperature of 60 to 100C, preferably 65 to 90C, and for a residence time such that in ea~h tank a higher conversion rate in each case of N-alkyl-polyhydroxyamine to polyhydroxy-fatty amide i6 obtained, C, to C4 alcohol present in the second stirred tank and in the further stirred tanks being distilled off under vacuum, and that c) the polyhydroxy-fatty amide i6 isolated from the reaction mixture leaving the last stirred tank.
The process according to the invention is preferably carried out in two or three stirred tanks arranged in a cascade. When the procedure is carried out in two stirred tanks arranged in a cascade, it is preferably carried out in such a way that (i~ the steady state) a) the N-alkylpolyhydroxyamine~ the Cl to C4 alkyl ester of the fatty acid in an amount of 1 to 1~5 mol, preferably 1 to 1.1 mol, per mole of N-alkyl-polyhydroxyamine and an alkali metal alkoxide or an alkali metal hydroxide or a mixture thereof as basic catalyst in an amount of 0.01 to 0.15 mol, preferably 0.05 to 0.1 molr per mole of N-alkylpolyhydroxyamine and in the foxm of a 5 to 50% strength by weight, preferably 20 to 40% strength by weight, methanolic solution are continuously and simultaneously fed to the first stirred tankr and in the tank a temperature of 60 to 120~C, preferably 65 to 95Cr is maintained and a residence time is maintained (with retention of the C1 to C4 alcohol present) such that a single-phase liquid reaction mixture is obtainedr b) the single-phase liquid reaction mixture leaving the first stirred tank and entering the second stirred tank is kept in the second stirred tank at a tempera-ture of 60 to 100Cr preferably 65 to 90Cr and under 21 ~ ~ 6'~ ~
, 5 vacuum, generally a vacuum of 5 to 150 mbar, prefer-ably 10 to 50 mbar, and for a residence time such that 80 to 98 mol% of the N-alkylpolyhydroxyamine, prefer-ably 85 to 95 mol%, are reacted, essentially all of the C, to C4 alcohol present being distilled off, and that c) the polyhydroxy-fatty amide is isolated from the reaction mixture leaving the second reaction tank.
According to another preferred embodiment in two stirred tanks arranged in a cascade, the procedure is carried out in such a way that in a first step (a1), the N~alkyl-polyhydroxyamine is reacted with alkali metal alkoxide or alkali metal hydroxide or with a mixture thereof in an amount of 0.01 to 0.15 mol, preferably 0~05 to 0 1 mol, per mole of N-alkylpolyhydroxyamine to prepare an essen-tially anhydrous mixture essentially comprising N-alkyl-polyhydroxyamine and the alkali metal salt of N-alkyl-polyhydroxyamine formed and functioning as catalyst. This mixture and alkyl ester of fatty acid in an amou~t of 1 20 to 1.5 mol, preferably 1 to 1.1 mol, per mole of the N-alkylpolyhydroxyamine used to prepare the mixture are then continuously and simultaneously fed to the first stirred tank. The reaction in the first and second tanks is then continued a~ described above.
When the process a~cording to the invention is carried out in three stirred tanks arranged in a cascade, the procedure is preferably carried out in such a way that (in the steady state) a) the N-alkylpolyhydroxyamine, the C1 to C4 alkyl ester of the fatty acid in an amount of 1 to 1.5 mol, preferably 1 to 1.1 mol, per mole of ~-alkyl-polyhydroxyamine and an alkali metal alkoxide or an alkali metal hydroxide or a mixture thereof as basic catalyst in an amount of 0.01 to 0.15 mol, preferably 0.05 to 0.1 mol, per mole of N-alkylpolyhydroxyamine and in the form of a S to 50% strength by weight, preferably 20 to ~0% strength by weight, methanolic , . , . - .- - . ..... ..
2~ 2'~L~4~
solution are continuously and simultaneously fed to the first stirred tank, and in the tank a temperature of 60 to 120C, preferably 65 to 95~C, is maintained and a residence time is maintained (with retention of the C1 to C4 alcohol present) such that a single-phass liquid reaction mixture is obtained, b) the single-phase liguid rPacti~n mixture leaving the first stirred tank and entering the second stirred tank is kept in the second stirred tank at a tempera-ture of 60 to 100C, preferably 65 to 90C, and under ~acuum, generally a vacuum of 50 to 600 mbar, prefer-ably 100 to 500 mbar, and for a residence time such that 80 to 95 mol% of the N-alkylpolyhydroxyamine, preferably 85 to 93 mol%, are reacted, the C1 to C4 alcohol present being distilled off down to a residual amount of 0.1 to 20% by weight, preferably 0.5 .to 5%
by weight, based on solid product, c) the single-phase liquid reaction mixture leaving the second stirred tank and entering the third stirred tank is kept in the third stirred tank at a tempera-ture of 60 to 100C, preferably 65 to 90DC, and under vacuum, generally a vacuum of 5 to 100 mbar, prefer-ably 10 to 50 mbar, and for a residence time such that 93 to 99 mol% of the N-alkylpolyhydroxyamine, prefer-ably 95 to 98 mol%, are reacted, essentially all of the Cl to C4 alcohol present being distilled off, and that d) the polyhydroxy-fatty amide is isolated from the reaction mixture leaving the third stirred tank.
.
The embodiment described above, in which an essentially anhydrous mixture of essentially N-alkylpolyhydroxy-amine and alkali metal salt of N-alkylpolyhydroxyamine : functioning as catalyst is first prepared, is also a further preferred process variant in the case of three stirred tanks.
Since it is the aim of the process according to the invention to keep as low as possible a temperature even 2 .12 7 ~
in the first stirred tank and constantly to have present a single-phase liquid reaction mixture (a hom~geneous phase or clear solution) (that is that still unreacted N-alkylpolyhydroxyamine is present completely dissolved), it can be necessary under some circumstances to introduce further alcohol (methanol) as solvent additionally to the alcohol liberated by the amidat:ion reaction. This amount of additional alcohol which is fed to the first, and frequently also the second stirred tank is in total generally 0.5 to 20 mol, preferably 1 to 10 mol, per mole of the N-alkylpolyhydroxyamine fed to the first tank.
The mixture described of N-alkylpolyhydroxyamine and an alkali metal salt thereof in a catalytic amount is preferably fed to the first stirred tank in the form of a flowing melt at about 125 to 135DC. The preparation of the mixture, in detail, is preferably carried out in a manner such that the N-alkylpolyhydroxyamine and the alkali metal compound are each used in the form of a 10 to 60% strength by weight, preferably 15 to 50% strength by weight, aqueous solution (the N-alkylpolyhydroxy-amine, because of the type of its preparation, generally arises in the form of the said solutions), the two solutions are mixed together, preferably at room tempera-ture, and the aqueous mixture (total solution) is dried by removing the water. The solvent water is preferably removed until only at most 0.5% by weight of water is still present, preferably at most 0.2 to 0.3% ~y weight, based on the dry (dehydrated) mixture. The dehydration is preferably achieved by distilling off the water under vacuum from the said aqueous total solution at about 90 to 135C. The dehydration can be carried out with the aid o~ conventional thin-film evaporators, falling film evaporators or stripping apparatuses. It is assumed that the mixture obtained after the removal of water essenti-ally comprises, as the main constituent, the N-alkyl-polyhydroxyamine used and alkali metal salt, which has been formed, of N-alkylpol~vhydroxyamine, in which case still other ~urther basic ~alkaline) alkali metal com-~ : ~12 ~8~
pounds can be present, likewise acting as catalyst, such as unreacted alkali metal starting compound and/or modifications thereof, for example alkali metal oxideO
This product (mixture) is solid at room temperature, is a more or less liquid melt at 115 to 135C and generally only contains the abovementioned residual amount of water of at most 0.5% by~weight, preferably at most 0.2 to 0.3%
by weight, based on the weight of the product.
It has proved to be advantageous if a viscosity lowering ayent is introduced in the first or second stirred tank or in both, preferably only in the second. Such agents are preferably ethylene glycol, propylene glycol or C8 to Cl8 fatty alcohols, or ethoxylates thereof having 1 to 5 ethylene oxide units, ethylene glycol, propylene glycol or a mixture thereof being preferred. The amount can bevaried in broad ranges. It is generally 1 to 50?~ by weight, preferably 2 to 30% by weight, based on solid product.
The initiation of the continuous reaction according to the invention, that is the preparation of a single-phase liquid start mixture in the first stirred tank, can be carried out in diverse ways. ThUs, the ester of the fatty acid can be introduced, heated to reaction temperature and the alkali metal compound and the N-alkylpolyhydroxy-amine and, if required, methanol can be introduced intothe heated ester, whereupon the mixture is kept at reaction temperature (without removal of the solvent) until the sought-after single-phase liquid reaction mixture is obtained. The said components can also be placed into the first tank in a differant sequence. If desired, all the said components can be introduced into the first stirred tank and kept at reaction temperature until the initially disperse reaction mixture has the sought-after appearance.
The reaction according to the invention is carried out at atmospheric pressure or the pressure which establishes itselE in the stirred tank, apart from the vacuum described for the more rapid discharge of the alcohol from the reaction mixture. As already mentioned, in each subsequent stirred tank, a higher amount of polyhydroxy-fatty amide is reacted than in the preceding tank. It isalso preferred to carry out the reaction in each sub-sequent stirred tank at a temperature at most equal to (that is no higher than) that in the preceding tank and preferably at a somewhat lower temperature (expediently 1 to 5C). The homogeneous li~lid product, solid at room temperature, in the last stirred tank essentially comprises polyhydroxy-fatty amide, unreacted N-alkyl polyhydroxyamine and the viscosity-decreasing liquid which may have been used. Generally, the resulting product is taken up in additional liquid (solvent) and/or water, by which means not only is a rapid cooling achieved, but also a product is obtained which flows readily at room temperature and thus is easily handleable. The polyhydroxy-fatty amide can also be converted into the form of flakes, grains, granules or powders.
The process according to the invention has a series of advantages. The linear polyhydroxy-fatty amide is obtained in virtually quantitative yield. It only con-tains very slightly interfering by-products such as cyclic polyhydroxy compounds. It is thus possible by the process according to the invention to prepare polyhydroxy-fatty amides in high yield (space-time yield) and in high purity. The linear fatty amide (melt) is slightly yellow colored, therefore has the desired good color. The process according to the invention is continu-ous and can be carried out in stirred tanks which are simple in terms of apparatus. A further essential advant-age results therefrom, that is that the reaction can be carried out optimally with respect to automation, control and maintenance of constant reaction conditions, which is obviously of great importance for uniform product quality. A further essential advantage is that, in the "' - 10 -steady state phase of the reaction, even the alcohol formed in the reaction is frequently sufficient as solvent and complete homogeneity is always present. This ensures a high reaction rate and simultaneously the high degree of conversion and the high purity of the product The clear homogeneous reaction mixture permits relatively low reaction temperatures from the beginning, which in turn has a favorable effect on the purity of the polyhydroxy-fatty amide.
The following can further be stated below on the basic compounds to be used in the process according to the invention and on the N alkylpolyhydroxyamine and on the alkyl ester of the fatty acid: the basic compounds are preferably alkali metal compounds in the form of alkali metal alkoxides and/or alkali metal hydroxides. The alkali metal alkoxides are preferably alkali metal Cl to C4-alkoxides, the Cl to C3-alkoxides beinq pre~erred. The alkali metal methylate is particularly preferred. The alkali metal is preferably sodium or potassium. The alkali metal hydroxides are preferably sodium hydroxide and potassium hydroxide.
The starting compounds N-alkylpolyhydroxyamine and al~yl esters of fatty acids are likewise known compounds and commercially available. They are furthermore extensively 25 described in the publication WO 92/06073 mentioned at the outset, which is incorporated herein by reference. The N-alkylpolyhydroxyamines can contain alkyl radicals and polyhydroxy radicals of the most varied type. As regards the polyhydroxy portion, this preferably originates from polyhydroxy compounds selected from the group comprising the reducing sugars or reducing sugar derivatives.
Preferred reducing sugar compounds are the mono-saccharides, preferably pentoses and hexoses, and the oligosaccharides, preferably disaccharides and tri-accharides. Examples of monosaccharides are fructose, glucose, galactose, mannose, sorbose and talose as -- 2~l27~i1,,~
hexoses and arabinose, ribose and xylose as pentoses. Of the monosaccharides, the hexoses are preferred. Examples of oligosaccharides (polysaccharides) are lactose, maltose, maltotriose and the like. Of the oligosacchar-ides, the disaccharides are preferred. Particularlypreferred polyhydroxy compounds are the (reducing) hexoses, in particular glucose. ~he alkyl radical in the N-monoalkylpolyhydroxyamine can alternatively be a hydroxyalkyl radical, for example -C~2C~2OH. It is prefer-ably a Cl to C4-alkyl, for example methyl, ethyl, propyl or isopr~pyl. Preferred N-alkylpolyhydroxyamines are therefore the N-C1 to C3-glycamines, preferably of fructose, gluco e, galactose, mannose, sorbose or talose or mixtures thereof. Particularly preferred N-alkylpoly-hydroxyamines are the N-Cl to C3 glucamines, N-methyl-glucamine being very particularly preferred.
The alkyl esters of fatty acids are preferably C1 to C4 alkyl esters of fatty acids, methyl, ethyl, propyl or isopropyl being preferred. The methyl esters of fatty acids are particularly preferred. The fatty acid radical (the acyl group) generally has 6 to 24 carbon atoms, preferably 8 to 18 carbon atoms. It can be saturated or unsaturated (preferably monounsaturated to triunsatur-ated). Examples which can be mentioned are the acyl radicals of caprylic, capric, lauric, palmitic, stearic and oleic acids, as well as coconut acyl, tallow acyl, preferably hardened tallow acyl, and the like. The fatty acid radical is frequently a mixture of two or more acyl groups, for example C,2 and Cl~-acyl (Cl2/l4), Cl6 and Cl9-acyl (C16/l8) or C12 to Cl8-acyl.
The inventlon will now be described in more detail with reference to examples.
Examples 1 to 5 These examples were carried out in two stirred tanks arranged in a cascade. The abbreviation "MW" used below . ~ .
~ ~ 2'~
denotes molecular weight.
Example l ~.
Product feed to the first tank~
1.00 mol of N-methylglucamine (MW = 195) 1.00 mol of the methyl ester of Cl2~,4-fatty acid tMW =
220) 0.05 mol of sodium methylate (MM = 541 in the form of a 30% strength by weight methanolic solution Product feed to the seco~d tank: .
0.50 mol of propylene glycol (MM = 76), that is 10% by weight (based on solid product) .
Procedure:
In order to start the continuous preparation of N-methyl~
glucamide, 3 mol of the methyl ester Of Cl2/l4 fatty acid are first introduced into the first stirred tank and heated to about 95C. 3 mol of flowing, that is heated to about 130C, N-methylglucamine and then 0.15 mol of sodium methylate in the form of a 30% strength by weight methanolic solution are introduced into the heated ester.
~ 20 ~he mixture is kept at about 95C and at the pressure : which is established until a single-phase liquid (clear homogeneous) reaction mixture is obtained. As soon as this mixture is present in the first stirred tank, the continuous op~ration begins, that is continuously and simultaneously, per hour, the products specified abo~e under "product feed to the first tank~' are ft_d to the first tank, maintaining the temperaturst mentioned of . about 95C. The clear homogeneous reaction mixturet leaving the first tank and entering the second tank (the two tanks o the cascade are filled and in the steady state) shows a degree of conversion of 82.2 mol%, based on N-methylglucamine. The mean residence time in the first tank iB 1 . 9 hours. In the second stirxed tank, the reaction mixture is held at 90C and a vacuum of 22 mbar, the methanol being distilled off. The propylene glycol J~
amount specified above is continuously added per hour to the second tank to decrease the viscosity of the reaction mixture in the second tank. The mean residence time in the second tank, in which the amidation reaction pro-ceeds, is 2.1 hours. The clear product leaving the secondtank exhibits a conversion rate of 94.5 mol%, based on N-methylglucamine.
Example 2 Product $eed to the ~irst tank:
1.00 mol of N-methylglucamine 1.10 mol of methyl laurate (MW = 214) 0.05 mol of sodium methylate as in Example 1 10.00 mol of methanol (MW z 32) Product feed to the second tank: none Example 3 Product feed to the first tank:
1.00 mol of N-methylglucamine containing 0.07 mol of catalyst 1.06 mol of methyl ester of Cl2/l4-fatty acid (MW = 220) 2.00 mol of methanol Product feed to the second tank:
0.50 mol of propylene glycol (10% by w~ight) -.
:
The mixture of N-methylglucamine and 0.07 mol of catalyst was prepared in such a manner that 1 mol of N-methyl-glucamine and 0.07 mol of NaO~ were each mixed in theform of a 35~ strength by weight aqueous solution and the total solution was dehydrated with the aid of a thin-film evaporator at up to 130C and a vacuum of 50 mbar down to 0.3% by weight residual water. The mixture is fed to the first tank as a melt (about 130C).
~ L~L 3 r Example 4 Product feed to the first tank-1.00 mol of N-methylglucamine 1.10 mol of methyl stearate (~ - 298) 0.03 mol of sodium methylate as in Example 1 Product feed to the second tank:
1.1 mol of propylene glycol (20% by weight) Example 5 .. ..
Product feed to the first tank:
1.00 mol of ~-methylfructamine 1030 mol of methyl ester of Cl2/~4-fatty acid (MW = 220 0.15 mol of sodium methylate as in Example 1 20.00 mol of methanol ' Product feed to the second tank:
0.50 mol of propylene glycol (10% by weight) Examples 2 to 5 were carried out similarly to Example 1.
Examples 6 to 8 These examples were carried ou~ in three stirred tanks arranged in a cascade. ~he abbreviation MM used below also denotes molecular weight here.
Example 6 ! ' I ' Product feed to the first tank:
1.00 mol of N-methylglucamine 1.06 mol of methyl ester of C,2/,4-fatty acid (MW - 220) 0.07 mol of sodium methyla~e in the form of a 30%
strength by weight methanolic solution 2.00 mol of methanol : .
~2~
Product feed to the second tank:
0.50 mol of propylene glycol t10% by weight) Procedure-In order to start the continuous preparation of N methyl-glucamide, the procedure is followed as in Example 1, atemperature of 87C being established and maintained. As soon as the described reaction mixture is present in the first stirred tank, the continuous operation begins, that is the products specified above under "produc~ feed to the first tank~ are continuously and simultaneously fed to the first tank per hour, maintaining the temperature mentioned of about 87C. The clear homogeneous reaction mixture leaving the first tank and entering into the second tank (the three tanks of the cascade are filled and in the steady state) shows a conversion rate of 77~4 mol%, based on N-methylglucamine. The mean residence time in the first tank is 1.6 hours. In the second stirred tank, the reaction mixture is kept at 80C and a vacuum of 165 mbar, the methanol being distilled off down to a residual content of 0.95g by weight, based on solid product. The propylene glycol amount specified above is continuously added per hour to the second tank to decrease the viscosity of the reaction mixture in the second tank. The mean residence time in the second tank, in which the amidation reaction proceeds, is 1.9 hours.
The single-phase liquid reaction mixture leaving the second tank and entering into the third tank shows a conversion rate of 93.0 mol~, based on N-m~thylglucamine.
In the third stirred tank, the reaction mixture is kept at 80C and a vacuum of 26 mbar, methanol being further distilled off. The mean residence time in the third stirred tank, in which the amidation reaction pxoceeds further, is 2 hours. The clear product leaving the third tank shows a conversion rate o ~8 mol%, based on N-methylglucamine.
Example 7 Product feed to the first tank-1.00 mol of N-methylglucamine 1.00 mol of methyl stearate (MW = 298) 0.03 mol of sodium methylate as in Example 6 Product feed to the second tank.
1.2 mol of propylene glycol (20% by weight) Example 8 Product feed to the first tank:
1.O mol of N-methylglucamine containing 0.15 mol of -catalyst 1.3 mol of methyl ester of Cl2~14-fatty acid (MM = 220) 20.0 mol of methanol Pxoduct feed to the second tank:
0,5 mol of propylene glycol (10% by weight) . . .
The mixture of N-methylglucamine and 0~15 mol of catalyst was prepared in such a manner that 1 mol of N-methylgluc-amine and 0.15 mol of NaO~ were each mixed in solid form and the mixture was fused. It is fed in this form to the first tank.
.
~xamples 7 and 8 were carried out similarly to Example 6, in Example 7, in the second stixred tank, the methanol being distilled off down to a residual content of 1.4% by weight, based on solid product, and in Example 8, down to 20~ by weight, based on solid product (that is, the solid content in the reaction mixture).
Results of Examples 1 to 8:
The degree of conversion achieved of the N-alkylpoly-hydroxyamine used is very high in all examples. The linear polyhydroxy-fatty amide obtained is very pure. The - ~12~
content of cyclic compounds is .in the range from less than 200 ppm to at most 1000 ppm (the determination was carried out by quantitative thin-layer chromatoqraphy).
The polyhydroxy-fatty amide also contains only a very 1 5 little residllal methanol, since the alcohol is removed aa completely as possible by distillation in the second tank (in the case of two stirred tanks) or in the third tank (in the case of three stirred tanks3O
In the table below, the degree of conversion in percent, based on ~-alkylpolyhydroxyamine used, which was obtained in Examples 1 to 8, is summarized. The table also contains the procedural characteristics of Examples 2 to 5 and 7 and 8 and, for the sake of completeness, also those of the ~xamples 1 and 6 described in detail~ The following abbreviations are used in the table:
"RT" for residence time in hours "DC" for the said degree of conversion.
Table . . .
fir~lt t~nk second tanX I third tllnk I
l l l l l I l l l I
I Elcu~pl~ I nc I RT I DC I C I R~ I mbur I DC I C I R~ I Jnbsr I DC
+ ~- I i I I I ~ . .1 1 1 1 20 1 1 1 95 1 1.9 1 82.2 I go 1 2.1 1 22 1 94.5 1 -- I -- l -- l --+ + ~ +
2 167 1 1.1 ! 65.4 1 97 1 1.9 1 46 1 86.6 1 -- I -- l -- l -- I
+ + ~ + + + + ~ ~ i 3 187 1 1.6 1 77.4 1 80 1 2.0 1 23 1 93.9 1 -- I -- l -- l --4 1 120 1 0.25 1 70.4 1 loo 1 0.25 1 98 1 85.1 1 -- I -- l -- l --+------ --+--~ __ _+_____~_____+_____~_____+_____~_____ i :
1 5 1 60 1 1.3 1 65.3 1 60 1 3.2 1 105 1 88.1 1 -- I -- I -- I -- I
2 5 1 6 1 87 1 1.6 1 77.4 1 80 1 1.9 1 165 1 93.0 1 80 1 2.0 1 26 1 98.0 1 ~______f____~____~_____~_____~_____~_____~_____~_____+_____~___--+------i : .
7 1 120 1 0.25 1 70.4 1 loo 1 0.25 1 436 1 85.0 1 loo 1 0.25 1 29 1 93.3 1 ~______+____~____~_____ +_--------~---- --~----------+----------+----------t-----~ ----------+----------'1 1 8 1 60 1 1.3 1 6s.3 1 60 1 2.6 1 600 1 8s.~ 1 60 1 3.3 1 94 1 97.5 1'. '. I ' ~ L ~ I I I ! ' ' .
lines 3 to 12~. In detail, the procedure is carried out in such a way that the secondary glucamine, the alkyl ester o~ the fatty acid, the basic catalyst compound and a solvent are mixed together and the mixture is refluxed until the desired degree of convexsion, whereupon the fatty acid glucamide is isolated rom the reaction product, if ne~essary with vacuum treatment (cf. e.g. WO
92/06073, Examples I to V). This process delivers a relatively high conversion rate of the N-alkylpoly-hydroxyamine used and the resulting N-methylglucamide is also relatively pure, but, inter alia, it exhibits the disadvantages o discontinuous procedures. Although in the publications mentioned reference is made to the fact that the process described can also be carried out continuously, nothing further is stated~ in particular with respect to apparatus setup, procedure, reaction conditions and the like (cf. e.g. WO 92~06073, page 10, lines 3 to 12).
The present invention now provides a continuous process for the preparation of polyhydroxy-fatty amides. Starting from C1 to C4 alkyl esters of fatty acid~, preferably from methyl esters of fatty acids, a high degree of conversion of the N-alkylpolyhydroxyamine used is to be achieved and the resulting polyhydroxy-fatty amide is to be very pure, that is it is to contain the particularly undesirable by-products, i.e. cyclic polyhydroxy compounds, only in a very small amount.
The process according to the invention for the continuous preparation of polyhydroxy-fatty amides by reaction of N-alkylpolyhydroxyamine and C1 to C4 alkyl ester of fattyacid in the presence of basic catalysts comprises con-tinuously carrying out the reaction in at least two stirred tanks arranged in a cascade and during this carrying out the procedure in such a way that (in the steady state~
a) in the first stirred tank a temperature of 6 0 to 120C, preferably 65 to 95C, is maintained and a ~ ~ 2 i~
,~ - 4 -residence time is maintained (with retention of the Cl to C4 alcohol present) such that a single-phase liquid reaction mixture is obtained, b) the single-phase liquid reaction mixture entering into the second and further stirred tanks is held in each case at a temperature of 60 to 100C, preferably 65 to 90C, and for a residence time such that in ea~h tank a higher conversion rate in each case of N-alkyl-polyhydroxyamine to polyhydroxy-fatty amide i6 obtained, C, to C4 alcohol present in the second stirred tank and in the further stirred tanks being distilled off under vacuum, and that c) the polyhydroxy-fatty amide i6 isolated from the reaction mixture leaving the last stirred tank.
The process according to the invention is preferably carried out in two or three stirred tanks arranged in a cascade. When the procedure is carried out in two stirred tanks arranged in a cascade, it is preferably carried out in such a way that (i~ the steady state) a) the N-alkylpolyhydroxyamine~ the Cl to C4 alkyl ester of the fatty acid in an amount of 1 to 1~5 mol, preferably 1 to 1.1 mol, per mole of N-alkyl-polyhydroxyamine and an alkali metal alkoxide or an alkali metal hydroxide or a mixture thereof as basic catalyst in an amount of 0.01 to 0.15 mol, preferably 0.05 to 0.1 molr per mole of N-alkylpolyhydroxyamine and in the foxm of a 5 to 50% strength by weight, preferably 20 to 40% strength by weight, methanolic solution are continuously and simultaneously fed to the first stirred tankr and in the tank a temperature of 60 to 120~C, preferably 65 to 95Cr is maintained and a residence time is maintained (with retention of the C1 to C4 alcohol present) such that a single-phase liquid reaction mixture is obtainedr b) the single-phase liquid reaction mixture leaving the first stirred tank and entering the second stirred tank is kept in the second stirred tank at a tempera-ture of 60 to 100Cr preferably 65 to 90Cr and under 21 ~ ~ 6'~ ~
, 5 vacuum, generally a vacuum of 5 to 150 mbar, prefer-ably 10 to 50 mbar, and for a residence time such that 80 to 98 mol% of the N-alkylpolyhydroxyamine, prefer-ably 85 to 95 mol%, are reacted, essentially all of the C, to C4 alcohol present being distilled off, and that c) the polyhydroxy-fatty amide is isolated from the reaction mixture leaving the second reaction tank.
According to another preferred embodiment in two stirred tanks arranged in a cascade, the procedure is carried out in such a way that in a first step (a1), the N~alkyl-polyhydroxyamine is reacted with alkali metal alkoxide or alkali metal hydroxide or with a mixture thereof in an amount of 0.01 to 0.15 mol, preferably 0~05 to 0 1 mol, per mole of N-alkylpolyhydroxyamine to prepare an essen-tially anhydrous mixture essentially comprising N-alkyl-polyhydroxyamine and the alkali metal salt of N-alkyl-polyhydroxyamine formed and functioning as catalyst. This mixture and alkyl ester of fatty acid in an amou~t of 1 20 to 1.5 mol, preferably 1 to 1.1 mol, per mole of the N-alkylpolyhydroxyamine used to prepare the mixture are then continuously and simultaneously fed to the first stirred tank. The reaction in the first and second tanks is then continued a~ described above.
When the process a~cording to the invention is carried out in three stirred tanks arranged in a cascade, the procedure is preferably carried out in such a way that (in the steady state) a) the N-alkylpolyhydroxyamine, the C1 to C4 alkyl ester of the fatty acid in an amount of 1 to 1.5 mol, preferably 1 to 1.1 mol, per mole of ~-alkyl-polyhydroxyamine and an alkali metal alkoxide or an alkali metal hydroxide or a mixture thereof as basic catalyst in an amount of 0.01 to 0.15 mol, preferably 0.05 to 0.1 mol, per mole of N-alkylpolyhydroxyamine and in the form of a S to 50% strength by weight, preferably 20 to ~0% strength by weight, methanolic , . , . - .- - . ..... ..
2~ 2'~L~4~
solution are continuously and simultaneously fed to the first stirred tank, and in the tank a temperature of 60 to 120C, preferably 65 to 95~C, is maintained and a residence time is maintained (with retention of the C1 to C4 alcohol present) such that a single-phass liquid reaction mixture is obtained, b) the single-phase liguid rPacti~n mixture leaving the first stirred tank and entering the second stirred tank is kept in the second stirred tank at a tempera-ture of 60 to 100C, preferably 65 to 90C, and under ~acuum, generally a vacuum of 50 to 600 mbar, prefer-ably 100 to 500 mbar, and for a residence time such that 80 to 95 mol% of the N-alkylpolyhydroxyamine, preferably 85 to 93 mol%, are reacted, the C1 to C4 alcohol present being distilled off down to a residual amount of 0.1 to 20% by weight, preferably 0.5 .to 5%
by weight, based on solid product, c) the single-phase liquid reaction mixture leaving the second stirred tank and entering the third stirred tank is kept in the third stirred tank at a tempera-ture of 60 to 100C, preferably 65 to 90DC, and under vacuum, generally a vacuum of 5 to 100 mbar, prefer-ably 10 to 50 mbar, and for a residence time such that 93 to 99 mol% of the N-alkylpolyhydroxyamine, prefer-ably 95 to 98 mol%, are reacted, essentially all of the Cl to C4 alcohol present being distilled off, and that d) the polyhydroxy-fatty amide is isolated from the reaction mixture leaving the third stirred tank.
.
The embodiment described above, in which an essentially anhydrous mixture of essentially N-alkylpolyhydroxy-amine and alkali metal salt of N-alkylpolyhydroxyamine : functioning as catalyst is first prepared, is also a further preferred process variant in the case of three stirred tanks.
Since it is the aim of the process according to the invention to keep as low as possible a temperature even 2 .12 7 ~
in the first stirred tank and constantly to have present a single-phase liquid reaction mixture (a hom~geneous phase or clear solution) (that is that still unreacted N-alkylpolyhydroxyamine is present completely dissolved), it can be necessary under some circumstances to introduce further alcohol (methanol) as solvent additionally to the alcohol liberated by the amidat:ion reaction. This amount of additional alcohol which is fed to the first, and frequently also the second stirred tank is in total generally 0.5 to 20 mol, preferably 1 to 10 mol, per mole of the N-alkylpolyhydroxyamine fed to the first tank.
The mixture described of N-alkylpolyhydroxyamine and an alkali metal salt thereof in a catalytic amount is preferably fed to the first stirred tank in the form of a flowing melt at about 125 to 135DC. The preparation of the mixture, in detail, is preferably carried out in a manner such that the N-alkylpolyhydroxyamine and the alkali metal compound are each used in the form of a 10 to 60% strength by weight, preferably 15 to 50% strength by weight, aqueous solution (the N-alkylpolyhydroxy-amine, because of the type of its preparation, generally arises in the form of the said solutions), the two solutions are mixed together, preferably at room tempera-ture, and the aqueous mixture (total solution) is dried by removing the water. The solvent water is preferably removed until only at most 0.5% by weight of water is still present, preferably at most 0.2 to 0.3% ~y weight, based on the dry (dehydrated) mixture. The dehydration is preferably achieved by distilling off the water under vacuum from the said aqueous total solution at about 90 to 135C. The dehydration can be carried out with the aid o~ conventional thin-film evaporators, falling film evaporators or stripping apparatuses. It is assumed that the mixture obtained after the removal of water essenti-ally comprises, as the main constituent, the N-alkyl-polyhydroxyamine used and alkali metal salt, which has been formed, of N-alkylpol~vhydroxyamine, in which case still other ~urther basic ~alkaline) alkali metal com-~ : ~12 ~8~
pounds can be present, likewise acting as catalyst, such as unreacted alkali metal starting compound and/or modifications thereof, for example alkali metal oxideO
This product (mixture) is solid at room temperature, is a more or less liquid melt at 115 to 135C and generally only contains the abovementioned residual amount of water of at most 0.5% by~weight, preferably at most 0.2 to 0.3%
by weight, based on the weight of the product.
It has proved to be advantageous if a viscosity lowering ayent is introduced in the first or second stirred tank or in both, preferably only in the second. Such agents are preferably ethylene glycol, propylene glycol or C8 to Cl8 fatty alcohols, or ethoxylates thereof having 1 to 5 ethylene oxide units, ethylene glycol, propylene glycol or a mixture thereof being preferred. The amount can bevaried in broad ranges. It is generally 1 to 50?~ by weight, preferably 2 to 30% by weight, based on solid product.
The initiation of the continuous reaction according to the invention, that is the preparation of a single-phase liquid start mixture in the first stirred tank, can be carried out in diverse ways. ThUs, the ester of the fatty acid can be introduced, heated to reaction temperature and the alkali metal compound and the N-alkylpolyhydroxy-amine and, if required, methanol can be introduced intothe heated ester, whereupon the mixture is kept at reaction temperature (without removal of the solvent) until the sought-after single-phase liquid reaction mixture is obtained. The said components can also be placed into the first tank in a differant sequence. If desired, all the said components can be introduced into the first stirred tank and kept at reaction temperature until the initially disperse reaction mixture has the sought-after appearance.
The reaction according to the invention is carried out at atmospheric pressure or the pressure which establishes itselE in the stirred tank, apart from the vacuum described for the more rapid discharge of the alcohol from the reaction mixture. As already mentioned, in each subsequent stirred tank, a higher amount of polyhydroxy-fatty amide is reacted than in the preceding tank. It isalso preferred to carry out the reaction in each sub-sequent stirred tank at a temperature at most equal to (that is no higher than) that in the preceding tank and preferably at a somewhat lower temperature (expediently 1 to 5C). The homogeneous li~lid product, solid at room temperature, in the last stirred tank essentially comprises polyhydroxy-fatty amide, unreacted N-alkyl polyhydroxyamine and the viscosity-decreasing liquid which may have been used. Generally, the resulting product is taken up in additional liquid (solvent) and/or water, by which means not only is a rapid cooling achieved, but also a product is obtained which flows readily at room temperature and thus is easily handleable. The polyhydroxy-fatty amide can also be converted into the form of flakes, grains, granules or powders.
The process according to the invention has a series of advantages. The linear polyhydroxy-fatty amide is obtained in virtually quantitative yield. It only con-tains very slightly interfering by-products such as cyclic polyhydroxy compounds. It is thus possible by the process according to the invention to prepare polyhydroxy-fatty amides in high yield (space-time yield) and in high purity. The linear fatty amide (melt) is slightly yellow colored, therefore has the desired good color. The process according to the invention is continu-ous and can be carried out in stirred tanks which are simple in terms of apparatus. A further essential advant-age results therefrom, that is that the reaction can be carried out optimally with respect to automation, control and maintenance of constant reaction conditions, which is obviously of great importance for uniform product quality. A further essential advantage is that, in the "' - 10 -steady state phase of the reaction, even the alcohol formed in the reaction is frequently sufficient as solvent and complete homogeneity is always present. This ensures a high reaction rate and simultaneously the high degree of conversion and the high purity of the product The clear homogeneous reaction mixture permits relatively low reaction temperatures from the beginning, which in turn has a favorable effect on the purity of the polyhydroxy-fatty amide.
The following can further be stated below on the basic compounds to be used in the process according to the invention and on the N alkylpolyhydroxyamine and on the alkyl ester of the fatty acid: the basic compounds are preferably alkali metal compounds in the form of alkali metal alkoxides and/or alkali metal hydroxides. The alkali metal alkoxides are preferably alkali metal Cl to C4-alkoxides, the Cl to C3-alkoxides beinq pre~erred. The alkali metal methylate is particularly preferred. The alkali metal is preferably sodium or potassium. The alkali metal hydroxides are preferably sodium hydroxide and potassium hydroxide.
The starting compounds N-alkylpolyhydroxyamine and al~yl esters of fatty acids are likewise known compounds and commercially available. They are furthermore extensively 25 described in the publication WO 92/06073 mentioned at the outset, which is incorporated herein by reference. The N-alkylpolyhydroxyamines can contain alkyl radicals and polyhydroxy radicals of the most varied type. As regards the polyhydroxy portion, this preferably originates from polyhydroxy compounds selected from the group comprising the reducing sugars or reducing sugar derivatives.
Preferred reducing sugar compounds are the mono-saccharides, preferably pentoses and hexoses, and the oligosaccharides, preferably disaccharides and tri-accharides. Examples of monosaccharides are fructose, glucose, galactose, mannose, sorbose and talose as -- 2~l27~i1,,~
hexoses and arabinose, ribose and xylose as pentoses. Of the monosaccharides, the hexoses are preferred. Examples of oligosaccharides (polysaccharides) are lactose, maltose, maltotriose and the like. Of the oligosacchar-ides, the disaccharides are preferred. Particularlypreferred polyhydroxy compounds are the (reducing) hexoses, in particular glucose. ~he alkyl radical in the N-monoalkylpolyhydroxyamine can alternatively be a hydroxyalkyl radical, for example -C~2C~2OH. It is prefer-ably a Cl to C4-alkyl, for example methyl, ethyl, propyl or isopr~pyl. Preferred N-alkylpolyhydroxyamines are therefore the N-C1 to C3-glycamines, preferably of fructose, gluco e, galactose, mannose, sorbose or talose or mixtures thereof. Particularly preferred N-alkylpoly-hydroxyamines are the N-Cl to C3 glucamines, N-methyl-glucamine being very particularly preferred.
The alkyl esters of fatty acids are preferably C1 to C4 alkyl esters of fatty acids, methyl, ethyl, propyl or isopropyl being preferred. The methyl esters of fatty acids are particularly preferred. The fatty acid radical (the acyl group) generally has 6 to 24 carbon atoms, preferably 8 to 18 carbon atoms. It can be saturated or unsaturated (preferably monounsaturated to triunsatur-ated). Examples which can be mentioned are the acyl radicals of caprylic, capric, lauric, palmitic, stearic and oleic acids, as well as coconut acyl, tallow acyl, preferably hardened tallow acyl, and the like. The fatty acid radical is frequently a mixture of two or more acyl groups, for example C,2 and Cl~-acyl (Cl2/l4), Cl6 and Cl9-acyl (C16/l8) or C12 to Cl8-acyl.
The inventlon will now be described in more detail with reference to examples.
Examples 1 to 5 These examples were carried out in two stirred tanks arranged in a cascade. The abbreviation "MW" used below . ~ .
~ ~ 2'~
denotes molecular weight.
Example l ~.
Product feed to the first tank~
1.00 mol of N-methylglucamine (MW = 195) 1.00 mol of the methyl ester of Cl2~,4-fatty acid tMW =
220) 0.05 mol of sodium methylate (MM = 541 in the form of a 30% strength by weight methanolic solution Product feed to the seco~d tank: .
0.50 mol of propylene glycol (MM = 76), that is 10% by weight (based on solid product) .
Procedure:
In order to start the continuous preparation of N-methyl~
glucamide, 3 mol of the methyl ester Of Cl2/l4 fatty acid are first introduced into the first stirred tank and heated to about 95C. 3 mol of flowing, that is heated to about 130C, N-methylglucamine and then 0.15 mol of sodium methylate in the form of a 30% strength by weight methanolic solution are introduced into the heated ester.
~ 20 ~he mixture is kept at about 95C and at the pressure : which is established until a single-phase liquid (clear homogeneous) reaction mixture is obtained. As soon as this mixture is present in the first stirred tank, the continuous op~ration begins, that is continuously and simultaneously, per hour, the products specified abo~e under "product feed to the first tank~' are ft_d to the first tank, maintaining the temperaturst mentioned of . about 95C. The clear homogeneous reaction mixturet leaving the first tank and entering the second tank (the two tanks o the cascade are filled and in the steady state) shows a degree of conversion of 82.2 mol%, based on N-methylglucamine. The mean residence time in the first tank iB 1 . 9 hours. In the second stirxed tank, the reaction mixture is held at 90C and a vacuum of 22 mbar, the methanol being distilled off. The propylene glycol J~
amount specified above is continuously added per hour to the second tank to decrease the viscosity of the reaction mixture in the second tank. The mean residence time in the second tank, in which the amidation reaction pro-ceeds, is 2.1 hours. The clear product leaving the secondtank exhibits a conversion rate of 94.5 mol%, based on N-methylglucamine.
Example 2 Product $eed to the ~irst tank:
1.00 mol of N-methylglucamine 1.10 mol of methyl laurate (MW = 214) 0.05 mol of sodium methylate as in Example 1 10.00 mol of methanol (MW z 32) Product feed to the second tank: none Example 3 Product feed to the first tank:
1.00 mol of N-methylglucamine containing 0.07 mol of catalyst 1.06 mol of methyl ester of Cl2/l4-fatty acid (MW = 220) 2.00 mol of methanol Product feed to the second tank:
0.50 mol of propylene glycol (10% by w~ight) -.
:
The mixture of N-methylglucamine and 0.07 mol of catalyst was prepared in such a manner that 1 mol of N-methyl-glucamine and 0.07 mol of NaO~ were each mixed in theform of a 35~ strength by weight aqueous solution and the total solution was dehydrated with the aid of a thin-film evaporator at up to 130C and a vacuum of 50 mbar down to 0.3% by weight residual water. The mixture is fed to the first tank as a melt (about 130C).
~ L~L 3 r Example 4 Product feed to the first tank-1.00 mol of N-methylglucamine 1.10 mol of methyl stearate (~ - 298) 0.03 mol of sodium methylate as in Example 1 Product feed to the second tank:
1.1 mol of propylene glycol (20% by weight) Example 5 .. ..
Product feed to the first tank:
1.00 mol of ~-methylfructamine 1030 mol of methyl ester of Cl2/~4-fatty acid (MW = 220 0.15 mol of sodium methylate as in Example 1 20.00 mol of methanol ' Product feed to the second tank:
0.50 mol of propylene glycol (10% by weight) Examples 2 to 5 were carried out similarly to Example 1.
Examples 6 to 8 These examples were carried ou~ in three stirred tanks arranged in a cascade. ~he abbreviation MM used below also denotes molecular weight here.
Example 6 ! ' I ' Product feed to the first tank:
1.00 mol of N-methylglucamine 1.06 mol of methyl ester of C,2/,4-fatty acid (MW - 220) 0.07 mol of sodium methyla~e in the form of a 30%
strength by weight methanolic solution 2.00 mol of methanol : .
~2~
Product feed to the second tank:
0.50 mol of propylene glycol t10% by weight) Procedure-In order to start the continuous preparation of N methyl-glucamide, the procedure is followed as in Example 1, atemperature of 87C being established and maintained. As soon as the described reaction mixture is present in the first stirred tank, the continuous operation begins, that is the products specified above under "produc~ feed to the first tank~ are continuously and simultaneously fed to the first tank per hour, maintaining the temperature mentioned of about 87C. The clear homogeneous reaction mixture leaving the first tank and entering into the second tank (the three tanks of the cascade are filled and in the steady state) shows a conversion rate of 77~4 mol%, based on N-methylglucamine. The mean residence time in the first tank is 1.6 hours. In the second stirred tank, the reaction mixture is kept at 80C and a vacuum of 165 mbar, the methanol being distilled off down to a residual content of 0.95g by weight, based on solid product. The propylene glycol amount specified above is continuously added per hour to the second tank to decrease the viscosity of the reaction mixture in the second tank. The mean residence time in the second tank, in which the amidation reaction proceeds, is 1.9 hours.
The single-phase liquid reaction mixture leaving the second tank and entering into the third tank shows a conversion rate of 93.0 mol~, based on N-m~thylglucamine.
In the third stirred tank, the reaction mixture is kept at 80C and a vacuum of 26 mbar, methanol being further distilled off. The mean residence time in the third stirred tank, in which the amidation reaction pxoceeds further, is 2 hours. The clear product leaving the third tank shows a conversion rate o ~8 mol%, based on N-methylglucamine.
Example 7 Product feed to the first tank-1.00 mol of N-methylglucamine 1.00 mol of methyl stearate (MW = 298) 0.03 mol of sodium methylate as in Example 6 Product feed to the second tank.
1.2 mol of propylene glycol (20% by weight) Example 8 Product feed to the first tank:
1.O mol of N-methylglucamine containing 0.15 mol of -catalyst 1.3 mol of methyl ester of Cl2~14-fatty acid (MM = 220) 20.0 mol of methanol Pxoduct feed to the second tank:
0,5 mol of propylene glycol (10% by weight) . . .
The mixture of N-methylglucamine and 0~15 mol of catalyst was prepared in such a manner that 1 mol of N-methylgluc-amine and 0.15 mol of NaO~ were each mixed in solid form and the mixture was fused. It is fed in this form to the first tank.
.
~xamples 7 and 8 were carried out similarly to Example 6, in Example 7, in the second stixred tank, the methanol being distilled off down to a residual content of 1.4% by weight, based on solid product, and in Example 8, down to 20~ by weight, based on solid product (that is, the solid content in the reaction mixture).
Results of Examples 1 to 8:
The degree of conversion achieved of the N-alkylpoly-hydroxyamine used is very high in all examples. The linear polyhydroxy-fatty amide obtained is very pure. The - ~12~
content of cyclic compounds is .in the range from less than 200 ppm to at most 1000 ppm (the determination was carried out by quantitative thin-layer chromatoqraphy).
The polyhydroxy-fatty amide also contains only a very 1 5 little residllal methanol, since the alcohol is removed aa completely as possible by distillation in the second tank (in the case of two stirred tanks) or in the third tank (in the case of three stirred tanks3O
In the table below, the degree of conversion in percent, based on ~-alkylpolyhydroxyamine used, which was obtained in Examples 1 to 8, is summarized. The table also contains the procedural characteristics of Examples 2 to 5 and 7 and 8 and, for the sake of completeness, also those of the ~xamples 1 and 6 described in detail~ The following abbreviations are used in the table:
"RT" for residence time in hours "DC" for the said degree of conversion.
Table . . .
fir~lt t~nk second tanX I third tllnk I
l l l l l I l l l I
I Elcu~pl~ I nc I RT I DC I C I R~ I mbur I DC I C I R~ I Jnbsr I DC
+ ~- I i I I I ~ . .1 1 1 1 20 1 1 1 95 1 1.9 1 82.2 I go 1 2.1 1 22 1 94.5 1 -- I -- l -- l --+ + ~ +
2 167 1 1.1 ! 65.4 1 97 1 1.9 1 46 1 86.6 1 -- I -- l -- l -- I
+ + ~ + + + + ~ ~ i 3 187 1 1.6 1 77.4 1 80 1 2.0 1 23 1 93.9 1 -- I -- l -- l --4 1 120 1 0.25 1 70.4 1 loo 1 0.25 1 98 1 85.1 1 -- I -- l -- l --+------ --+--~ __ _+_____~_____+_____~_____+_____~_____ i :
1 5 1 60 1 1.3 1 65.3 1 60 1 3.2 1 105 1 88.1 1 -- I -- I -- I -- I
2 5 1 6 1 87 1 1.6 1 77.4 1 80 1 1.9 1 165 1 93.0 1 80 1 2.0 1 26 1 98.0 1 ~______f____~____~_____~_____~_____~_____~_____~_____+_____~___--+------i : .
7 1 120 1 0.25 1 70.4 1 loo 1 0.25 1 436 1 85.0 1 loo 1 0.25 1 29 1 93.3 1 ~______+____~____~_____ +_--------~---- --~----------+----------+----------t-----~ ----------+----------'1 1 8 1 60 1 1.3 1 6s.3 1 60 1 2.6 1 600 1 8s.~ 1 60 1 3.3 1 94 1 97.5 1'. '. I ' ~ L ~ I I I ! ' ' .
Claims (10)
1. A process for the continuous preparation of polyhydroxy-fatty amide by reaction of N-alkylpoly-hydroxyamine and C1 to C4 alkyl ester of fatty acid in the presence of basic catalysts, which comprises continuously carrying out the reaction in at least two stirred tanks arranged in a cascade and carrying it out in this case in such a way that a) in the first stirred tank a temperature of 60 to 120°C is maintained and a residence time is maintained such that a single-phase liquid reaction mixture is obtained, b) the single-phase liquid reaction mixture enter-ing into the second and further stirred tanks is held in each case at a temperature of 60 to 100°C and for a residence time such that in each tank a higher conversion rate in each case of N-alkylpolyhydroxyamine to polyhydroxy-fatty amides is obtained, C1 to C4 alcohol present in the second stirred tank and in the further stirred tanks being distilled off under vacuum, and that c) the polyhydroxy-fatty amide is isolated from the reaction mixture leaving the last stirred tank.
2. The process as claimed in claim 1, wherein the reaction is carried out in two stirred tanks arranged in a cascade and is carried out in this case in such a way that a) the N-alkylpolyhydroxyamine, the C1 to C4 alkyl ester of the fatty acid in an amount of 1 to 105 mol per mole of N-alkylpolyhydroxyamine and an alkali metal alkoxide or an alkali metal hydroxide or a mixture thereof as basic cata-lyst in an amount of 0.01 to 0.15 mol per mole of N-alkylpolyhydroxyamine and in the form of a 5 to 50% strength by weight methanolic solution are continuously and simultaneously fed to the first stirred tank, and in the tank a temperature of 60 to 120°C is maintained and a residence time is maintained such that a single-phase liquid reaction mixture is obtained, b) the single-phase liquid reaction mixture leav-ing the first stirred tank and entering the second stirred tank is kept in the second stirred tank at a temperature of 60 to 100°C
and under vacuum and for a residence time such that 80 to 98 mol% of the N-alkylpolyhydroxy-amine are reacted, essentially all of the C1 to C4 alcohol being distilled off, and that c) polyhydroxy-fatty amide is isolated from the reaction mixture leaving the second reaction tank.
and under vacuum and for a residence time such that 80 to 98 mol% of the N-alkylpolyhydroxy-amine are reacted, essentially all of the C1 to C4 alcohol being distilled off, and that c) polyhydroxy-fatty amide is isolated from the reaction mixture leaving the second reaction tank.
3. The process as claimed in claim 1, wherein the reaction is carried out in two stirred tanks arranged in a cascade and is carried out in this case in such a way that a1) the N-alkylpolyhydroxyamine is first reacted with an alkali metal alkoxide or an alkali metal hydroxide or with a mixture thereof in an amount of 0.01 to 0.15 mol per mole of N-alkyl-polyhydroxyamine to prepare an essentially anhydrous mixture essentially comprising N-alkylpolyhydroxyamine and catalyst and a2) the mixture prepared in step a1) and the C1 to C4 alkyl ester of fatty acid in an amount of 1 to 1.5 mol per mole of N-alkylpolyhydroxyamine used in step a1) are continuously and simul-taneously fed to the first stirred tank and in the tank a temperature of 60 to 120°C is main-tained and a residence time is maintained so that a single-phase liquid reaction mixture is obtained, b) the single-phase liquid reaction mixture leaving the first stirred tank and entering the second stirred tank is kept in the second stirred tank at a temperature of 60 to 100°C
and under vacuum and for a residence time such that 80 to 98 mol% of the N-alkylpolyhydroxy-amine are reacted, essentially all of the C1 to C4 alcohol being distilled off, and that c) the polyhydroxy-fatty amide is isolated from the reaction mixture leaving the second reac-tion tank.
and under vacuum and for a residence time such that 80 to 98 mol% of the N-alkylpolyhydroxy-amine are reacted, essentially all of the C1 to C4 alcohol being distilled off, and that c) the polyhydroxy-fatty amide is isolated from the reaction mixture leaving the second reac-tion tank.
4. The process as claimed in claim 1, wherein the reaction is carried out in three stirred tanks arranged in a cascade and is carried out in this case in such a way that a) the N-alkylpolyhydroxyamine, the C1 and C4 alkyl ester of the fatty acid in an amount of 1 to 1.5 mol per mole of N-alkypolyhydroxyamine and an alkali metal alkoxide or an alkali metal hydroxide or a mixture thereof as basic cata-lyst in an amount of 0.01 to 0.15 mol per mole of N-alkylpolyhydroxyamine and in the form of a 5 to 50% strength by weight methanolic solution are continuously and simultaneously fed to the first stirred tank, and in the tank a temperature of 60 to 120°C is maintained and a residence time is maintained such that a single-phase liquid reaction mixture is obtained, b) the single-phase liquid reaction mixture leav-ing the first stirred tank and entering the second stirred tank is kept in the second stirred tank at a temperature of 60 to 100°C
and under vacuum and for a residence time such that 80 to 95 mol% of the N-alkylpolyhydroxy-amine are reacted, the C1 to C4 alcohol present being distilled off down to a residual amount of 0.1 to 20% by weight based on solid product, c) the single-phrase liquid reaction mixture leaving the second stirred tank and entering the third stirred tank is kept in the third stirred tank at a temperature of 60 to 100°C
and under vacuum and for a residence time such that 93 to 99 mol% of the N-alkylpolyhydroxy-amine are reacted, essentially all of the C1 to C4 alcohol present being distilled off, and that d) the polyhydroxy-fatty amide is isolated from the reaction mixture leaving the third stirred tank.
and under vacuum and for a residence time such that 80 to 95 mol% of the N-alkylpolyhydroxy-amine are reacted, the C1 to C4 alcohol present being distilled off down to a residual amount of 0.1 to 20% by weight based on solid product, c) the single-phrase liquid reaction mixture leaving the second stirred tank and entering the third stirred tank is kept in the third stirred tank at a temperature of 60 to 100°C
and under vacuum and for a residence time such that 93 to 99 mol% of the N-alkylpolyhydroxy-amine are reacted, essentially all of the C1 to C4 alcohol present being distilled off, and that d) the polyhydroxy-fatty amide is isolated from the reaction mixture leaving the third stirred tank.
5. The process as claimed in claim 1, wherein the reaction is carried out in three stirred tanks arranged in a cascade and is carried out in this case in such a way that a1) the N-alkylpolyhydroxyamine is first reacted with an alkali metal alkoxide or an alkali metal hydroxide or with a mixture thereof in an amount of 0.01 to 0.15 mol per mole of N-alkyl-polyhydroxyamine to prepare an essentially anhydrous mixture essentially comprising N-alkylpolyhydroxyamine and catalyst and a2) the mixture prepared in step a1) and the C1 to C4 alkyl ester of fatty acid in an amount of 1 to 1.5 mol per mole of N-alkylpolyhydroxyamine used in step a1) are continuously and simul-taneously fed to the first stirred tank and in the tank a temperature of 60 to 120°C is main-tained and a residence time is maintained such that a single-phase liquid reaction mixture is obtained, b) the single-phase liquid reaction mixture leav-ing the first stirred tank and entering the second stirred tank is kept in the second stirred tank at a temperature of 60 to 100°C
and under vacuum and for a residence time such that 80 to 95 mol% of the N-alkylpolyhydroxy-amine are reacted, the C1 to C4 alcohol present being distilled off down to a residual amount of 0.1 to 20% by weight based on solid product, c) the single-phase liquid reaction mixture leaving the second stirred tank and entering the third stirred tank is kept in the third stirred tank at a temperature of 60 to 100°C
and under vacuum and for a residence time such that 93 to 99 mol% of the N-alkylpolyhydroxy-amine have reacted, essentially all of the C1 to C4 alcohol present being distilled off, and that d) the polyhydroxy-fatty amide is isolated from the reaction mixture leaving the third stirred tank.
and under vacuum and for a residence time such that 80 to 95 mol% of the N-alkylpolyhydroxy-amine are reacted, the C1 to C4 alcohol present being distilled off down to a residual amount of 0.1 to 20% by weight based on solid product, c) the single-phase liquid reaction mixture leaving the second stirred tank and entering the third stirred tank is kept in the third stirred tank at a temperature of 60 to 100°C
and under vacuum and for a residence time such that 93 to 99 mol% of the N-alkylpolyhydroxy-amine have reacted, essentially all of the C1 to C4 alcohol present being distilled off, and that d) the polyhydroxy-fatty amide is isolated from the reaction mixture leaving the third stirred tank.
6. The process as claimed in claims 1 to 5, wherein methanol is fed to the first stirred tank in an amount of 0.5 to 20 mol per mole of the N-alkyl-polyhydroxyamine fed to the first stirred tank.
7. The process as claimed in claims 3 and 5, wherein the mixture prepared in step a1) is fed to the first stirred tank in the form of a flowing melt.
8. The process as claimed in one or more of claims 1 to 7, wherein a viscosity-decreasing agent selected from the group comprising ethylene glycol, propylene glycol or C8 to C18 fatty alcohols or ethoxylates thereof having 1 to 5 ethylene oxide units is fed to the second stirred tank in an amount of 1 to 50% by weight, based on solid product.
9. The process as claimed in one or more of claims 1 to 7, wherein ethylene glycol, propylene glycol or a mixture thereof as a viscosity-decreasing agent is fed to the second stirred tank in an amount of 1 to 50% by weight, based on solid product.
10. The process as claimed in one or more of claims 1 to 9, wherein the N-alkylpolyhydroxyamine used is N-methylglucamine, the alkyl ester of the fatty acid used is a methyl ester of the fatty acid, the alkali metal alkoxide used is potassium methylate or sodium methylate and the alkali metal hydroxide used is potassium hydroxide or sodium hydroxide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4322874.7 | 1993-07-09 | ||
| DE4322874A DE4322874C2 (en) | 1993-07-09 | 1993-07-09 | Process for the continuous production of polyhydroxy fatty acid amides from N-alkyl polyhydroxy amines and fatty acid alkyl esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2127644A1 true CA2127644A1 (en) | 1995-01-10 |
Family
ID=6492334
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002127644A Abandoned CA2127644A1 (en) | 1993-07-09 | 1994-07-08 | Process for the continuous preparation of polyhydroxyfatty amides from n-alkylpolyhydroxyamines and alkyl esters of fatty acids |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0633244B1 (en) |
| JP (1) | JPH07145124A (en) |
| BR (1) | BR9402665A (en) |
| CA (1) | CA2127644A1 (en) |
| DE (2) | DE4322874C2 (en) |
| MX (1) | MX9405240A (en) |
Cited By (16)
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|---|---|---|---|---|
| US5731461A (en) * | 1996-01-03 | 1998-03-24 | Condea Vista Company | Surfactant composition and process for producing same |
| US5750749A (en) * | 1996-02-09 | 1998-05-12 | Condea Vista Company | Polyhydroxy-fatty amide surfactant composition and method of preparing same |
| CN103827079A (en) * | 2011-09-13 | 2014-05-28 | 花王株式会社 | Method for producing N-acylamino triol |
| EP2736877B1 (en) | 2011-07-28 | 2015-09-16 | Unilever PLC, a company registered in England and Wales under company no. 41424 | Amino acid salt containing compositions |
| EP2736879B1 (en) | 2011-07-28 | 2015-11-18 | Unilever PLC, a company registered in England and Wales under company no. 41424 of | General method for preparing fatty acyl amido based surfactants |
| EP2737039B1 (en) | 2011-07-28 | 2016-03-30 | Unilever PLC | Fatty acyl amido based surfactant concentrates |
| US9303143B2 (en) | 2012-10-09 | 2016-04-05 | Clariant International Ltd. | Dispersing agent from renewable raw materials for binding agent-free pigment preparations |
| CN104910035B (en) * | 2014-03-11 | 2017-03-15 | 南京理工大学 | A kind of method that hydroxyalkyl amide is catalyzed and synthesized with supported solid |
| CN107001239A (en) * | 2014-11-13 | 2017-08-01 | 科莱恩国际有限公司 | The continuation method of surfactant is prepared in tubular reactor |
| US10772324B2 (en) | 2012-11-03 | 2020-09-15 | Clariant International Ltd. | Aqueous adjuvant-compositions |
| US10813862B2 (en) | 2012-05-30 | 2020-10-27 | Clariant International Ltd. | Use of N-methyl-N-acylglucamines as solubilizers |
| US10864275B2 (en) | 2012-05-30 | 2020-12-15 | Clariant International Ltd. | N-methyl-N-acylglucamine-containing composition |
| US10920080B2 (en) | 2015-10-09 | 2021-02-16 | Clariant International Ltd. | N-Alkyl glucamine-based universal pigment dispersions |
| US10961484B2 (en) | 2015-10-09 | 2021-03-30 | Clariant International Ltd. | Compositions comprising sugar amine and fatty acid |
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| US11425904B2 (en) | 2014-04-23 | 2022-08-30 | Clariant International Ltd. | Use of aqueous drift-reducing compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19519705A1 (en) * | 1995-05-30 | 1996-12-05 | Hoechst Ag | Concentrated solutions of polyhydroxyalkylamines and their use |
| DE202014010355U1 (en) | 2014-11-13 | 2015-05-06 | Clariant International Ltd. | Low-VOC coalescents for aqueous dispersions |
| DE202014010366U1 (en) | 2014-11-24 | 2015-05-15 | Clariant International Ltd. | Use of polyhydroxy fatty acid amides to improve the wet abrasion resistance of aqueous dispersions |
| DE102014017368A1 (en) | 2014-11-24 | 2015-05-28 | Clariant International Ltd. | Use of polyhydroxy fatty acid amides to improve the wet abrasion resistance of aqueous emulsion paints |
| DE102015212507A1 (en) * | 2015-07-03 | 2017-01-05 | Clariant International Ltd. | Process for the synthesis of aliphatic and aromatic amides |
| EP3858961A1 (en) | 2020-01-28 | 2021-08-04 | The Procter & Gamble Company | Cleaning product |
| EP3858965B1 (en) | 2020-01-28 | 2022-05-11 | The Procter & Gamble Company | Cleaning product |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5194639A (en) * | 1990-09-28 | 1993-03-16 | The Procter & Gamble Company | Preparation of polyhydroxy fatty acid amides in the presence of solvents |
| WO1992008687A1 (en) * | 1990-11-09 | 1992-05-29 | The Procter & Gamble Company | Process for preparing n-alkyl polyhydroxy amines in amine and amine/water solvents and fatty acid amides therefrom |
| US5188769A (en) * | 1992-03-26 | 1993-02-23 | The Procter & Gamble Company | Process for reducing the levels of fatty acid contaminants in polyhydroxy fatty acid amide surfactants |
| DE4235783A1 (en) * | 1992-10-23 | 1994-04-28 | Basf Ag | Process for the preparation of N-alkanoyl-polyhydroxyalkylamines |
-
1993
- 1993-07-09 DE DE4322874A patent/DE4322874C2/en not_active Expired - Fee Related
-
1994
- 1994-07-05 EP EP94110458A patent/EP0633244B1/en not_active Expired - Lifetime
- 1994-07-05 DE DE59405684T patent/DE59405684D1/en not_active Expired - Fee Related
- 1994-07-08 JP JP6157591A patent/JPH07145124A/en not_active Withdrawn
- 1994-07-08 CA CA002127644A patent/CA2127644A1/en not_active Abandoned
- 1994-07-08 BR BR9402665A patent/BR9402665A/en not_active Application Discontinuation
- 1994-07-08 MX MX9405240A patent/MX9405240A/en unknown
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| US5847210A (en) * | 1996-01-03 | 1998-12-08 | Condea Vista Company | Process for producing surfactant composition |
| US5731461A (en) * | 1996-01-03 | 1998-03-24 | Condea Vista Company | Surfactant composition and process for producing same |
| US5750749A (en) * | 1996-02-09 | 1998-05-12 | Condea Vista Company | Polyhydroxy-fatty amide surfactant composition and method of preparing same |
| EP2736879B1 (en) | 2011-07-28 | 2015-11-18 | Unilever PLC, a company registered in England and Wales under company no. 41424 of | General method for preparing fatty acyl amido based surfactants |
| EP2736879B2 (en) † | 2011-07-28 | 2019-07-03 | Unilever PLC, a company registered in England and Wales under company no. 41424 of | General method for preparing fatty acyl amido based surfactants |
| EP2737039B1 (en) | 2011-07-28 | 2016-03-30 | Unilever PLC | Fatty acyl amido based surfactant concentrates |
| EP2736877B1 (en) | 2011-07-28 | 2015-09-16 | Unilever PLC, a company registered in England and Wales under company no. 41424 | Amino acid salt containing compositions |
| CN103827079A (en) * | 2011-09-13 | 2014-05-28 | 花王株式会社 | Method for producing N-acylamino triol |
| EP2757090A4 (en) * | 2011-09-13 | 2015-03-04 | Kao Corp | Method for producing n-acylamino triol |
| CN103827079B (en) * | 2011-09-13 | 2016-09-14 | 花王株式会社 | The manufacture method of N-acyl amino triol |
| EP2757090A1 (en) * | 2011-09-13 | 2014-07-23 | Kao Corporation | Method for producing n-acylamino triol |
| US10864275B2 (en) | 2012-05-30 | 2020-12-15 | Clariant International Ltd. | N-methyl-N-acylglucamine-containing composition |
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| CN104910035B (en) * | 2014-03-11 | 2017-03-15 | 南京理工大学 | A kind of method that hydroxyalkyl amide is catalyzed and synthesized with supported solid |
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| CN107001239B (en) * | 2014-11-13 | 2020-02-21 | 科莱恩国际有限公司 | Continuous process for preparing surfactants in a tubular reactor |
| CN111217717A (en) * | 2014-11-13 | 2020-06-02 | 科莱恩国际有限公司 | Continuous process for preparing surfactants in a tubular reactor |
| US10112889B2 (en) * | 2014-11-13 | 2018-10-30 | Clariant International Ltd. | Continuous process for producing a surfactant in a tube reactor |
| CN107001239A (en) * | 2014-11-13 | 2017-08-01 | 科莱恩国际有限公司 | The continuation method of surfactant is prepared in tubular reactor |
| US10920080B2 (en) | 2015-10-09 | 2021-02-16 | Clariant International Ltd. | N-Alkyl glucamine-based universal pigment dispersions |
| US10961484B2 (en) | 2015-10-09 | 2021-03-30 | Clariant International Ltd. | Compositions comprising sugar amine and fatty acid |
| US11220603B2 (en) | 2016-05-09 | 2022-01-11 | Clariant International Ltd. | Stabilizers for silicate paints |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9402665A (en) | 1995-05-02 |
| DE59405684D1 (en) | 1998-05-20 |
| EP0633244A3 (en) | 1996-03-06 |
| EP0633244B1 (en) | 1998-04-15 |
| JPH07145124A (en) | 1995-06-06 |
| DE4322874C2 (en) | 1995-07-20 |
| EP0633244A2 (en) | 1995-01-11 |
| MX9405240A (en) | 1995-01-31 |
| DE4322874A1 (en) | 1995-01-12 |
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