CA2152240A1 - Alkoxylation product mixtures having a narrow alkoxyl distribution - Google Patents
Alkoxylation product mixtures having a narrow alkoxyl distributionInfo
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- CA2152240A1 CA2152240A1 CA002152240A CA2152240A CA2152240A1 CA 2152240 A1 CA2152240 A1 CA 2152240A1 CA 002152240 A CA002152240 A CA 002152240A CA 2152240 A CA2152240 A CA 2152240A CA 2152240 A1 CA2152240 A1 CA 2152240A1
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- alkoxylation
- product mixture
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/10—Saturated ethers of polyhydroxy compounds
- C07C43/11—Polyethers containing —O—(C—C—O—)n units with ≤ 2 n≤ 10
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2654—Aluminium or boron; Compounds thereof
-
- 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
- C11D1/66—Non-ionic compounds
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Detergent Compositions (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Polyethers (AREA)
Abstract
The invention relates to alkoxylation product mixtures of the formula I having a narrow alkoxyl distribution (I) where R is the radical of an organic compound containing at least one active hydrogen atom, m is an integer from 1 up to the number of active hydrogen atoms in the organic compound, x and y in each case are the average molar number of ethylene oxide or propylene oxide units and independently of one another are an integer from 2 to 10 and the individual alkoxylation units of the alkoxyla-tion product mixture in each case at most have a degree of alkoxylation of 18% by weight.
The invention further relates to a process for their preparation, and their use.
The invention further relates to a process for their preparation, and their use.
Description
HOECHST AKTIENGESELLSCHAFT HOE 94/F 169 Dr. KI
Description Alkoxylation product mixtures having a narrow alkoxyl distribution The invention relates to alkoxylation product mixtures having a narrow alkoxyl distribution, and also to a process for the preparation of the~e alkoxylation product mixtures and to their use.
Alkoxylates have great importance, for example as inter-mediates for derivatizations and as nonionic components in industrial and cosmetic detergents and cleaners. They are additionally employed in a multiplicity of applica-tion areas as emulsifiers, dispersants and the like. In these areas, the alkoxylates desired are frequently those which have a narrow distribution of the alkoxylation homologs.
The still unpublished German Patent Application with the reference P 4341576.8 describes ethoxylates having a narrow homolog distribution. A process for the ethoxyla-tion of compounds cont~;n;ng active hydrogen atoms in the presence of specific alkaline earth metal salts of alkyl-or alkenylsuccinic acid monoesters as catalysts is additionally described.
EP-A-0 133 715 describes alkoxylation product mixtures which are obtained by reaction of an organic compound containing at least one active hydrogen atom with an epoxide, such as ethylene oxide or propylene oxide, the product mixture cont~;n;ng an alkoxylation unit which i~
20-40% by weight of the mixture.
It has been shown, however, that the alkoxylation product mixtures known from the prior art only have limited biodegradability. With regard to increased environmental con~ciousne~s, however, particular attention is being directed even at the characteristic of biodegradability .
in the case of detergents and cleaners.
The object was thus to make available alkoxylation product mixtures which are distinguished by good biodegradability.
It has been shown that this object can be achieved by the provision of alkoxylation product mixtures having a narrow alkoxyl distribution.
The invention relate~ to alkoxylation product mixtures of the formula I having a narrow alkoxyl distribution CH~
R - (CH2 - CH2 - 0)~ - (CH - CH2 ~ )r H (I) where R is the radical of an organic compound containing at least one active hydrogen atom, m is an integer from 1 up to the number of active hydrogen atoms in the organic compound, x and y in each case are the average molar number of ethylene oxide or propylene oxide units and independently of one another are an integer from 2 to 10 and the individual alkoxylation units of the alkoxyla-tion product mixture in each case at most have a degree of alkoxylation of 18% by weight.
Formula I, m is preferably a number from 1 to 3 and particularly preferably equal to 1. The values x and y in formula I are, independently of one another, preferably a number from 2 to 6, and y is particularly preferably a number from 2 to 4.
Preferred alkoxylation product mixtures of the formula I
are those in which m = 1 and x and y independently of one another are an integer from 2 to 6.
Particularly preferred alkoxylation product mixtures of the formula I are those in which m = 1, x and y are independent of one another and x is a number from 2 to 6 2l522~ o -and y is a number from 2 to 4.
The radical R in formula I is derived from organic compounds having at least one active hydrogen atom, for example from compounds containing hydroxyl groups, amine compounds and acid compounds such as fatty acids.
Preferably, the radical R is derived from compounds cont~;n;ng hydroxyl groups, for example from alcohols, amino alcohols, perfluoroalkyl alcohols, glycols, glycol monoethers, phenols or kresols, alcohols being particu-larly preferred. They can originate from a native sourceor from synthetic processes, and be straight-chain or branched, saturated or unsaturated and mono- or poly-valent, for example oxo alcohols or fatty alcohols.
In particular, monovalent, straight-chain or branched, saturated or unsaturated C8-C18-alcohols or mixtures thereof are employed, for example mixtures of C12 and C14-alcohol (C12~14). Specific examples of the particu-larly preferred alcohols which may be mentioned are:
non~nol, isononyl alcohol, decanol, undecanol, isounde-canol, lauryl alcohol, isotridecyl alcohol, stearylalcohol, coconut fatty alcohol and mixtures thereof, and also 2-ethylhexanol, 2-hexyldecanol and 2-octyldecanol.
In formula I, R is consequently particularly preferably a monovalent, ~traight-chain or branched, saturated or unsaturated C8-C18-alkoxy group or mixtures thereof.
Preferred alkoxylation products of the formula I are therefore those in which m = 1, x and y independently of one another are a number from 2 to 6 and R is a mono-valent, straight-chain or branched, saturated or unsatu-rated C8-C18-alkoxy group or mixtures thereof.
Particularly preferred alkoxylation products of the formula I are those in which m = 1, x and y are indepen-dent of one another, x is a number from 2 to 6 and y is a number from 2 to 4 and R is a monovalent, straight-chain or branched, saturated or unsaturated C8-C18-alkoxy group or mixtures thereof.
- - 21 ~2240 The invention addltlonally relates to a process for the preparatlon of alkoxylatlon product mlxtures accordlng to the formula I comprlslng the process steps - reactlon of an organlc compound contalning at least one actlve hydrogen atom wlth ethylene oxlde ln a molar ratlo of 2 to 10 mol of ethylene oxlde per mole of actlve hydrogen ln the compound to be ethoxylated ln the presence of at least one alkallne earth metal salt of the alkyl- or alkenylsucclnlc acid monoester of the formulae (II) and ~III) below as catalyst R3 - CH - COO - (CH2CH2O)n-R (M2+) ¦ (II) _ __ H2 COO - ( CH2CH2o ) n~R4 ( M2+ ) ¦ (III) where R3 8 30 alkyl or C8 to C30-alkenyl n ls an lnteger from 0 to 6, R4 ls Cl to C18-alkyl or C3 to C18-alkenyl or hydrogen lf n = 1 or ~ 1, M ls Ba, Ca or Sr and z ls a number from 0.9 to 1.8, - then addltlon of a base to the ethoxylate product mlxture obtalned and addltlon of propylene oxlde.
, 4a The reactlon of the organic compound containlng at lest one actlve hydrogen atom wlth ethylene oxlde ln the presence of at least one alkallne earth metal salt of the alkyl- or alkenylsucclnic acid hemiester is customarily carried out at a temperature from 60 to 200C, preferably 100 to 180C, and a pressure of approximately 0.5 to 6 bar, the ethylene oxide being metered in ln portlons or continuously. The amount of ethylene oxide added is 2 to 10 mol, preferably 2 to 8 mol and in particular 2 to 6 mol, per mole of active hydrogen in the compound to be ethoxylated. The ethoxylation product mixture obtained can in general be reacted again without prior separation of the catalyst.
The alkaline earth metal salts of alkyl- and/or alkenyl-succinic acid hemiesters to be used (in this case these are positional isomers which in general are present in the mixture) are known and are commercially available, for example as ~HOSTACOR (~ = registered trademark of Hoechst). In the formulae II and III, R3 is preferably a Cg to C20-alkyl or a Cg to C20-alkenyl, n i~ preferably a number from O to 3, Rl is preferably a C1 to Cl2-alkyl or a C3 to Cl2-alkenyl and can preferably also be the hydro-gen atom if n = 1 or ~ 1 and z is preferably a number from 1 to 1.3 and particularly preferably 1. For reasons of expediency, M is preferably Ca. For z c 1, besides M
protons can additionally be present as further counter-ions. The alkenyl groups preferably have 1 to 3 doublebonds. The alkyl and alkenyl groups can be straight or branched. Alkyl and alkenyl can also be present in the form of mixtures, for example in the form of a mixture of Cl2 and Cl4-alkyl (Cl2/14-alkyl) or C12 and C14 alkenyl (Cl2/l4-alkenyl) or of Cl2 and Cl4-alkyl and -alkenyl groups. Of the alkaline earth metal salts to be used of the succinic acid hemiester substituted by an alkyl or an alkenyl group, those substituted by an alkenyl group are preferred, that is R3 in the formulae (II) and (III) is preferably one of the alkenyl group~ mentioned. The radical R4, on the other hand, is preferably one of the alkyl groups mentioned. Examples of alkyl and alkenyl radicals are thus methyl, propyl, butyl, isobutyl, octyl, octenyl, decyl, decenyl, dodecyl (lauryl), dodecenyl, oleyl, octadecadienyl, octadecatrienyl and tallow fatty alkyl.
It was found that a still higher activity with respect to . 2l522qo catalytic activity and narrow homolog distribution is achieved if the ethoxylation is carried out in the presence of at least one succinic acid monoester salt of the formulae (II) and (III), of which 10 to 70%, prefer-ably 30 to 60%, of its titratable alkalinity has beenneutralized by an inorganic acid which forms poorly water-soluble salts with the cations Ba, Ca and Sr.
Preferred mineral acids are sulfuric acid (H2S04) and sulfurous acid (H2S03) as well as phosphoric acid (H3P04) and phosphorous acid (H3P03).
The amount of the alkaline earth metal salt of the alkyl-or alkenylsuccinic acid hemiester to be employed in the ethoxylation can vary within wide limits and is in general 0.1 to 5% by weight, preferably 0.5 to 3% by weight, based on the weight of the organic compound having at least one active hydrogen atom to be alkoxylated. The catalyst is added to the compound to be alkoxylated in the amount indicated. It can also be produced in situ, for example by first adding to the compound to be alkoxylated a defined amount of a barium, calcium or strontium oxide, carbonate or hydroxide, the hydroxides being preferred, and adding the stoichiometric amount of substituted succinic anhydride compound adjusted to this, resulting from the formulae (II) and (III), and then drying, optionally under reduced pres-sure, whereupon the reaction is begun with the ethoxyla-tion. The in-situ variant can also include the part neutralization described.
The alkaline earth metal salts of the alkyl- or alkenyl-succinic acid hemiesters have a high catalytic activityand lead in a relatively short reaction time to a vir-tually complete conversion and to a high yield. The ethoxylate consequently has a narrow homolog distribution and only a small content of the starting compound to be ethoxylated.
The ethoxylated product mixture obtained after the 21S224~
ethoxylation i8 treated, for further catalysis, with a base and the mixture is then optionally dried. Prefer-ably, the ethoxylate product mixture is treated with an aqueous alkali metal hydroxide solution or an alkali metal alkoxide as a base. The aqueous alkali metal hydroxide solution employed is preferably a sodium hydroxide solution. Alkali metal alkoxides of C1-C4-alcohols, preferably methanol or ethanol, are furthermore used. Drying is customarily carried out at a temperature of 70 - 150C, preferably 80 - 120C, and under a reduced pressure of 10 - 100 mbar, preferably 10 - 30 mbar.
The amount of the base employed is proportioned such that an alkali number of 1 - 5 results in the crude final product.
The propylene oxide is added to the optionally dried ethoxylation product mixture. This addition is custo-marily carried out over a period of 1 - 10 h, at a temperature of 100 - 150C, preferably 110 - 140C, the propylene oxide being metered in in portions or con-tinuously. The amount of propylene oxide is in general 2 to 10 mol, preferably 2 to 6 mol and in particular 2 to 4 mol, per mole of active hydrogen in the compound to be alkoxylated. If appropriate, the alkoxylation product mixture is then neutralized with a Cl-C10-carboxylic acid, straight-chain, aliphatic C1-C3-carboxylic acids and branched, aliphatic CB-ClO-carboxylic acids preferably being used in this case. The alkoxylation product mixture obtained can in general be further used without prior separation of the catalysts.
The alkoxylation product mixtures according to the invention have a narrow homolog distribution and are distinguished by a particularly good biodegradability. In their capacity as low-foaming surfactants, they can be employed in cleaners, for example liquid detergentsl liquid cleaners, machine dishwashing liquids/powders ana';
bottle cleaners. They can also be used as dispersants or 21522~0 wetting agents.
The invention is now illustrated in greater detail by examples.
The homolog distribution of the alcohol alkoxylates obtained in the examples was determined by means of capillary gas chromatography after prior derivatization (silylation of the OH end groups of the alcohol block alkoxylates using (CH3)3SiCl). As a measure of the homo-log distribution, the so-called Q value according to the equation Q = n* x p2 is given, in which n* is the average number of ethylene oxide and propylene oxide molecules added to the organic starting compound containing at least one active hydrogen atom (mean degree of alkoxyla-tion) and p is the percentage by weight of the most highly occurring alkoxylation homologs in % by weight.
This Q value, as is known, is in particular a good st~n~rd if these are alkoxylates having an essentially identical average degree of alkoxylation. Higher values of Q indicate a more selective alkylation and an alkoxy-late having a narrower homolog distribution.
The biodegradability was determined in the modified Sturmtest in accordance with OECD guideline 301B, in which the substances were tested over a period of 29 days on an unadapted activated sludge.
Examples Preparation of c12-cl4-fattY alcohol-ethylene oxide/propylene oxide block alkoxylates Example 1 1st stage:
194 g (1.00 mol) of a C12/14-alcohol mixture were initially introduced into a stirable pressure reactor.
After the customary flll~h;ng of the reaction space with nitrogen, the mixture was heated to 90C and stirred under reduced pressure for 1 hour in order to lower the -g water content to ~0.10% by weight. 2.9 g of the catalyst 1 were then added and a total of 251 g of ethylene oxide (5.7 mol) were metered in at 150 - 160C in a period of 5 hours.
To react the epoxide completely, the mixture was addi-tionally stirred at 150 - 160C for 1 hour.
2nd stage:
Description Alkoxylation product mixtures having a narrow alkoxyl distribution The invention relates to alkoxylation product mixtures having a narrow alkoxyl distribution, and also to a process for the preparation of the~e alkoxylation product mixtures and to their use.
Alkoxylates have great importance, for example as inter-mediates for derivatizations and as nonionic components in industrial and cosmetic detergents and cleaners. They are additionally employed in a multiplicity of applica-tion areas as emulsifiers, dispersants and the like. In these areas, the alkoxylates desired are frequently those which have a narrow distribution of the alkoxylation homologs.
The still unpublished German Patent Application with the reference P 4341576.8 describes ethoxylates having a narrow homolog distribution. A process for the ethoxyla-tion of compounds cont~;n;ng active hydrogen atoms in the presence of specific alkaline earth metal salts of alkyl-or alkenylsuccinic acid monoesters as catalysts is additionally described.
EP-A-0 133 715 describes alkoxylation product mixtures which are obtained by reaction of an organic compound containing at least one active hydrogen atom with an epoxide, such as ethylene oxide or propylene oxide, the product mixture cont~;n;ng an alkoxylation unit which i~
20-40% by weight of the mixture.
It has been shown, however, that the alkoxylation product mixtures known from the prior art only have limited biodegradability. With regard to increased environmental con~ciousne~s, however, particular attention is being directed even at the characteristic of biodegradability .
in the case of detergents and cleaners.
The object was thus to make available alkoxylation product mixtures which are distinguished by good biodegradability.
It has been shown that this object can be achieved by the provision of alkoxylation product mixtures having a narrow alkoxyl distribution.
The invention relate~ to alkoxylation product mixtures of the formula I having a narrow alkoxyl distribution CH~
R - (CH2 - CH2 - 0)~ - (CH - CH2 ~ )r H (I) where R is the radical of an organic compound containing at least one active hydrogen atom, m is an integer from 1 up to the number of active hydrogen atoms in the organic compound, x and y in each case are the average molar number of ethylene oxide or propylene oxide units and independently of one another are an integer from 2 to 10 and the individual alkoxylation units of the alkoxyla-tion product mixture in each case at most have a degree of alkoxylation of 18% by weight.
Formula I, m is preferably a number from 1 to 3 and particularly preferably equal to 1. The values x and y in formula I are, independently of one another, preferably a number from 2 to 6, and y is particularly preferably a number from 2 to 4.
Preferred alkoxylation product mixtures of the formula I
are those in which m = 1 and x and y independently of one another are an integer from 2 to 6.
Particularly preferred alkoxylation product mixtures of the formula I are those in which m = 1, x and y are independent of one another and x is a number from 2 to 6 2l522~ o -and y is a number from 2 to 4.
The radical R in formula I is derived from organic compounds having at least one active hydrogen atom, for example from compounds containing hydroxyl groups, amine compounds and acid compounds such as fatty acids.
Preferably, the radical R is derived from compounds cont~;n;ng hydroxyl groups, for example from alcohols, amino alcohols, perfluoroalkyl alcohols, glycols, glycol monoethers, phenols or kresols, alcohols being particu-larly preferred. They can originate from a native sourceor from synthetic processes, and be straight-chain or branched, saturated or unsaturated and mono- or poly-valent, for example oxo alcohols or fatty alcohols.
In particular, monovalent, straight-chain or branched, saturated or unsaturated C8-C18-alcohols or mixtures thereof are employed, for example mixtures of C12 and C14-alcohol (C12~14). Specific examples of the particu-larly preferred alcohols which may be mentioned are:
non~nol, isononyl alcohol, decanol, undecanol, isounde-canol, lauryl alcohol, isotridecyl alcohol, stearylalcohol, coconut fatty alcohol and mixtures thereof, and also 2-ethylhexanol, 2-hexyldecanol and 2-octyldecanol.
In formula I, R is consequently particularly preferably a monovalent, ~traight-chain or branched, saturated or unsaturated C8-C18-alkoxy group or mixtures thereof.
Preferred alkoxylation products of the formula I are therefore those in which m = 1, x and y independently of one another are a number from 2 to 6 and R is a mono-valent, straight-chain or branched, saturated or unsatu-rated C8-C18-alkoxy group or mixtures thereof.
Particularly preferred alkoxylation products of the formula I are those in which m = 1, x and y are indepen-dent of one another, x is a number from 2 to 6 and y is a number from 2 to 4 and R is a monovalent, straight-chain or branched, saturated or unsaturated C8-C18-alkoxy group or mixtures thereof.
- - 21 ~2240 The invention addltlonally relates to a process for the preparatlon of alkoxylatlon product mlxtures accordlng to the formula I comprlslng the process steps - reactlon of an organlc compound contalning at least one actlve hydrogen atom wlth ethylene oxlde ln a molar ratlo of 2 to 10 mol of ethylene oxlde per mole of actlve hydrogen ln the compound to be ethoxylated ln the presence of at least one alkallne earth metal salt of the alkyl- or alkenylsucclnlc acid monoester of the formulae (II) and ~III) below as catalyst R3 - CH - COO - (CH2CH2O)n-R (M2+) ¦ (II) _ __ H2 COO - ( CH2CH2o ) n~R4 ( M2+ ) ¦ (III) where R3 8 30 alkyl or C8 to C30-alkenyl n ls an lnteger from 0 to 6, R4 ls Cl to C18-alkyl or C3 to C18-alkenyl or hydrogen lf n = 1 or ~ 1, M ls Ba, Ca or Sr and z ls a number from 0.9 to 1.8, - then addltlon of a base to the ethoxylate product mlxture obtalned and addltlon of propylene oxlde.
, 4a The reactlon of the organic compound containlng at lest one actlve hydrogen atom wlth ethylene oxlde ln the presence of at least one alkallne earth metal salt of the alkyl- or alkenylsucclnic acid hemiester is customarily carried out at a temperature from 60 to 200C, preferably 100 to 180C, and a pressure of approximately 0.5 to 6 bar, the ethylene oxide being metered in ln portlons or continuously. The amount of ethylene oxide added is 2 to 10 mol, preferably 2 to 8 mol and in particular 2 to 6 mol, per mole of active hydrogen in the compound to be ethoxylated. The ethoxylation product mixture obtained can in general be reacted again without prior separation of the catalyst.
The alkaline earth metal salts of alkyl- and/or alkenyl-succinic acid hemiesters to be used (in this case these are positional isomers which in general are present in the mixture) are known and are commercially available, for example as ~HOSTACOR (~ = registered trademark of Hoechst). In the formulae II and III, R3 is preferably a Cg to C20-alkyl or a Cg to C20-alkenyl, n i~ preferably a number from O to 3, Rl is preferably a C1 to Cl2-alkyl or a C3 to Cl2-alkenyl and can preferably also be the hydro-gen atom if n = 1 or ~ 1 and z is preferably a number from 1 to 1.3 and particularly preferably 1. For reasons of expediency, M is preferably Ca. For z c 1, besides M
protons can additionally be present as further counter-ions. The alkenyl groups preferably have 1 to 3 doublebonds. The alkyl and alkenyl groups can be straight or branched. Alkyl and alkenyl can also be present in the form of mixtures, for example in the form of a mixture of Cl2 and Cl4-alkyl (Cl2/14-alkyl) or C12 and C14 alkenyl (Cl2/l4-alkenyl) or of Cl2 and Cl4-alkyl and -alkenyl groups. Of the alkaline earth metal salts to be used of the succinic acid hemiester substituted by an alkyl or an alkenyl group, those substituted by an alkenyl group are preferred, that is R3 in the formulae (II) and (III) is preferably one of the alkenyl group~ mentioned. The radical R4, on the other hand, is preferably one of the alkyl groups mentioned. Examples of alkyl and alkenyl radicals are thus methyl, propyl, butyl, isobutyl, octyl, octenyl, decyl, decenyl, dodecyl (lauryl), dodecenyl, oleyl, octadecadienyl, octadecatrienyl and tallow fatty alkyl.
It was found that a still higher activity with respect to . 2l522qo catalytic activity and narrow homolog distribution is achieved if the ethoxylation is carried out in the presence of at least one succinic acid monoester salt of the formulae (II) and (III), of which 10 to 70%, prefer-ably 30 to 60%, of its titratable alkalinity has beenneutralized by an inorganic acid which forms poorly water-soluble salts with the cations Ba, Ca and Sr.
Preferred mineral acids are sulfuric acid (H2S04) and sulfurous acid (H2S03) as well as phosphoric acid (H3P04) and phosphorous acid (H3P03).
The amount of the alkaline earth metal salt of the alkyl-or alkenylsuccinic acid hemiester to be employed in the ethoxylation can vary within wide limits and is in general 0.1 to 5% by weight, preferably 0.5 to 3% by weight, based on the weight of the organic compound having at least one active hydrogen atom to be alkoxylated. The catalyst is added to the compound to be alkoxylated in the amount indicated. It can also be produced in situ, for example by first adding to the compound to be alkoxylated a defined amount of a barium, calcium or strontium oxide, carbonate or hydroxide, the hydroxides being preferred, and adding the stoichiometric amount of substituted succinic anhydride compound adjusted to this, resulting from the formulae (II) and (III), and then drying, optionally under reduced pres-sure, whereupon the reaction is begun with the ethoxyla-tion. The in-situ variant can also include the part neutralization described.
The alkaline earth metal salts of the alkyl- or alkenyl-succinic acid hemiesters have a high catalytic activityand lead in a relatively short reaction time to a vir-tually complete conversion and to a high yield. The ethoxylate consequently has a narrow homolog distribution and only a small content of the starting compound to be ethoxylated.
The ethoxylated product mixture obtained after the 21S224~
ethoxylation i8 treated, for further catalysis, with a base and the mixture is then optionally dried. Prefer-ably, the ethoxylate product mixture is treated with an aqueous alkali metal hydroxide solution or an alkali metal alkoxide as a base. The aqueous alkali metal hydroxide solution employed is preferably a sodium hydroxide solution. Alkali metal alkoxides of C1-C4-alcohols, preferably methanol or ethanol, are furthermore used. Drying is customarily carried out at a temperature of 70 - 150C, preferably 80 - 120C, and under a reduced pressure of 10 - 100 mbar, preferably 10 - 30 mbar.
The amount of the base employed is proportioned such that an alkali number of 1 - 5 results in the crude final product.
The propylene oxide is added to the optionally dried ethoxylation product mixture. This addition is custo-marily carried out over a period of 1 - 10 h, at a temperature of 100 - 150C, preferably 110 - 140C, the propylene oxide being metered in in portions or con-tinuously. The amount of propylene oxide is in general 2 to 10 mol, preferably 2 to 6 mol and in particular 2 to 4 mol, per mole of active hydrogen in the compound to be alkoxylated. If appropriate, the alkoxylation product mixture is then neutralized with a Cl-C10-carboxylic acid, straight-chain, aliphatic C1-C3-carboxylic acids and branched, aliphatic CB-ClO-carboxylic acids preferably being used in this case. The alkoxylation product mixture obtained can in general be further used without prior separation of the catalysts.
The alkoxylation product mixtures according to the invention have a narrow homolog distribution and are distinguished by a particularly good biodegradability. In their capacity as low-foaming surfactants, they can be employed in cleaners, for example liquid detergentsl liquid cleaners, machine dishwashing liquids/powders ana';
bottle cleaners. They can also be used as dispersants or 21522~0 wetting agents.
The invention is now illustrated in greater detail by examples.
The homolog distribution of the alcohol alkoxylates obtained in the examples was determined by means of capillary gas chromatography after prior derivatization (silylation of the OH end groups of the alcohol block alkoxylates using (CH3)3SiCl). As a measure of the homo-log distribution, the so-called Q value according to the equation Q = n* x p2 is given, in which n* is the average number of ethylene oxide and propylene oxide molecules added to the organic starting compound containing at least one active hydrogen atom (mean degree of alkoxyla-tion) and p is the percentage by weight of the most highly occurring alkoxylation homologs in % by weight.
This Q value, as is known, is in particular a good st~n~rd if these are alkoxylates having an essentially identical average degree of alkoxylation. Higher values of Q indicate a more selective alkylation and an alkoxy-late having a narrower homolog distribution.
The biodegradability was determined in the modified Sturmtest in accordance with OECD guideline 301B, in which the substances were tested over a period of 29 days on an unadapted activated sludge.
Examples Preparation of c12-cl4-fattY alcohol-ethylene oxide/propylene oxide block alkoxylates Example 1 1st stage:
194 g (1.00 mol) of a C12/14-alcohol mixture were initially introduced into a stirable pressure reactor.
After the customary flll~h;ng of the reaction space with nitrogen, the mixture was heated to 90C and stirred under reduced pressure for 1 hour in order to lower the -g water content to ~0.10% by weight. 2.9 g of the catalyst 1 were then added and a total of 251 g of ethylene oxide (5.7 mol) were metered in at 150 - 160C in a period of 5 hours.
To react the epoxide completely, the mixture was addi-tionally stirred at 150 - 160C for 1 hour.
2nd stage:
2.4 g of a 50% strength aqueous NaOH solution were added to the C12/14-alcohol ethoxylate pre~ent in the reactor from the 1st ~tage and the mixture was then dried at 90C
for 2 hours under a reduced pressure of 20 mbar.
A total of 232 g of propylene oxide (4.0 mol) were then metered in at 120 - 130C in a period of 5 hours.
To react the epoxide completely, the mixture was addi-tionally stirred at 135C for 1 hour.
It was then neutralized using isononanoic acid.
Catalygt 1 i8 a compound of the formula (II), where R3 is iso-Cl2-alkenyl, R4 is isobutyl, n is O, M is Ca and z is 1 and this alkenylsuccinic acid hemiester calcium salt was partially neutralized using 0.4 times the stoichiometric amount of H2SO4 neces~ary for neutralization of the alkalinity (as a 25% strength by weight aqueous solution).
At 20C, the final product is a ~lightly turbid, low viscosity liquid with a turbidity point of 32C (measured in a 1% strength aqueous solution according to DIN 53917).
The pH of a 1% ~trength aqueous solution is 6.6; an OH
number (corr.) of 89 i~ obtained. The Q value is 2450.
Table 1 contains the homolog distribution of the alcohol alkoxylates prepared.
21522~
In testing the biodegradability, the alcohol alkoxylates prepared attained the threshold value required in the context of the 29-day experimental period of a degree of degradation greater than or equal to 60% by weight within 10 days after exceeding the 10% by weight limit (= start of the degradation phase) and were therefore classified as easily biodegradable. At a test concentration of 7 mg/l, the alcohol alkoxylates were degraded to 100% by weight after 22 days. Table 2 contains the data for the biodegradability of the alcohol alkoxylates.
Table 1: Homolog distribution of the fatty alcohol-ethylene oxide (EO)/propylene oxide (PO) block alkoxylate EO+PO 1 2 3 4 5 6 7 8 9 10 11 15 number ~ by 1.8 2.3 2.8 3.9 6.4 10.5 15.1 17.5 17.1 13.3 9.2 weight Table 2: Biodegradability of the fatty alcohol-EO/PO
block alkoxylate Test concentration 7 ~mg/L]
Biodegradation after 6 d 35 ~%]
after 14 d 86 ~%]
after 22 d 100 ~%]
after 29 d 100 ~%]
Example 2 l~t stage:
194 g (1.00 mol) of a Cl2/l4-alcohol mixture was initially introduced into a stirable pressure reactor. After the customary flu~hing of the reaction ~pace with nitrogen, the mixture was heated to 90C and stirred under reduced pressure for 1 hour in order to lower the water content to ~ 0.10% by weight.
2.9 g of the catalyst 2 were then added and a total of 97 g of ethylene oxide (2.2 mol) were metered in at 150 - 160C in a period of 3 hours. To react the epoxide completely, it was additionally stirred at 150 - 160C
for 1 hour.
2nd stage:
2.0 g of a 50% strength aqueous NaOH solution were added to the C12/14-alcohol ethoxylate present in the reactor from the 1st stage and the mixture was then dried at 90C
for 2 hours under a reduced pres~ure of 20 mbar.
A total of 232 g of propylene oxide (4.0 mol) were then metered in at 120 - 130C in a period of 5 hours. To react the epoxide completely, the mixture was addi-tionally stirred at 135C for 1 hour.It was then neutralized with isononanoic acid.
At 20C, the final product is a slightly turbid, low-viscosity liquid having a turbidity point of 27C in butyldiglycol/water (measured according to DIN 53917).
The pH of a 1% strength aqueous solution is 7.1; an OH
number (corr.) of 112 is obtained. The Q value is 1220.
Table 3 contains the homolog distribution of the alcohol alkoxylates prepared.
In testing the biodegradability, the alcohol alkoxylates prepared attained the threshold value of a degree of degradation greater than or equal to 60% by weight required in the context of the 29-day experimental period within 10 days after exceeding the 10% by weight limit (=
start of the degradation phase) and were therefore classified as easily biodegradable. At a test concentra-tion of 7 mg/l, the alcohol alkoxylates were degraded to 100% by weight after 29 days. Table 4 contains the data for the biodegradability of the alcohol alkoxylates.
Catalyst 2 is a compound of the formula (II), where R3 is iso-C12-alkenyl, R4 i8 c12/14-alkyl, n is O, M is Ca and z is 1 and this alkenylsuccinic acid hemiester calcium Ralt was partially neutralized using 0.4 times the stoichiometric amount of H2S04 necessary for the neutralization of the alkalinity (as a 25% strength by weight solution).
Table 3: Homolog distribution of the fatty alcohol-ethylene oxide (E0)/propylene oxide (P0) block alkoxylate number % by 7.0 9.5 11.2 11.8 13.6 14.0 13.2 9.4 6.1 2.7 1.7 1 0 weight Table 2: Biodegradability of the fatty alcohol-E0/P0 block alkoxylate Test concentration 7 [mg/L]
Biodegradation after 6 d 29 [%]
after 14 d 64 [%]
after 22 d 90 [%]
after 29 d 100 [%]
for 2 hours under a reduced pressure of 20 mbar.
A total of 232 g of propylene oxide (4.0 mol) were then metered in at 120 - 130C in a period of 5 hours.
To react the epoxide completely, the mixture was addi-tionally stirred at 135C for 1 hour.
It was then neutralized using isononanoic acid.
Catalygt 1 i8 a compound of the formula (II), where R3 is iso-Cl2-alkenyl, R4 is isobutyl, n is O, M is Ca and z is 1 and this alkenylsuccinic acid hemiester calcium salt was partially neutralized using 0.4 times the stoichiometric amount of H2SO4 neces~ary for neutralization of the alkalinity (as a 25% strength by weight aqueous solution).
At 20C, the final product is a ~lightly turbid, low viscosity liquid with a turbidity point of 32C (measured in a 1% strength aqueous solution according to DIN 53917).
The pH of a 1% ~trength aqueous solution is 6.6; an OH
number (corr.) of 89 i~ obtained. The Q value is 2450.
Table 1 contains the homolog distribution of the alcohol alkoxylates prepared.
21522~
In testing the biodegradability, the alcohol alkoxylates prepared attained the threshold value required in the context of the 29-day experimental period of a degree of degradation greater than or equal to 60% by weight within 10 days after exceeding the 10% by weight limit (= start of the degradation phase) and were therefore classified as easily biodegradable. At a test concentration of 7 mg/l, the alcohol alkoxylates were degraded to 100% by weight after 22 days. Table 2 contains the data for the biodegradability of the alcohol alkoxylates.
Table 1: Homolog distribution of the fatty alcohol-ethylene oxide (EO)/propylene oxide (PO) block alkoxylate EO+PO 1 2 3 4 5 6 7 8 9 10 11 15 number ~ by 1.8 2.3 2.8 3.9 6.4 10.5 15.1 17.5 17.1 13.3 9.2 weight Table 2: Biodegradability of the fatty alcohol-EO/PO
block alkoxylate Test concentration 7 ~mg/L]
Biodegradation after 6 d 35 ~%]
after 14 d 86 ~%]
after 22 d 100 ~%]
after 29 d 100 ~%]
Example 2 l~t stage:
194 g (1.00 mol) of a Cl2/l4-alcohol mixture was initially introduced into a stirable pressure reactor. After the customary flu~hing of the reaction ~pace with nitrogen, the mixture was heated to 90C and stirred under reduced pressure for 1 hour in order to lower the water content to ~ 0.10% by weight.
2.9 g of the catalyst 2 were then added and a total of 97 g of ethylene oxide (2.2 mol) were metered in at 150 - 160C in a period of 3 hours. To react the epoxide completely, it was additionally stirred at 150 - 160C
for 1 hour.
2nd stage:
2.0 g of a 50% strength aqueous NaOH solution were added to the C12/14-alcohol ethoxylate present in the reactor from the 1st stage and the mixture was then dried at 90C
for 2 hours under a reduced pres~ure of 20 mbar.
A total of 232 g of propylene oxide (4.0 mol) were then metered in at 120 - 130C in a period of 5 hours. To react the epoxide completely, the mixture was addi-tionally stirred at 135C for 1 hour.It was then neutralized with isononanoic acid.
At 20C, the final product is a slightly turbid, low-viscosity liquid having a turbidity point of 27C in butyldiglycol/water (measured according to DIN 53917).
The pH of a 1% strength aqueous solution is 7.1; an OH
number (corr.) of 112 is obtained. The Q value is 1220.
Table 3 contains the homolog distribution of the alcohol alkoxylates prepared.
In testing the biodegradability, the alcohol alkoxylates prepared attained the threshold value of a degree of degradation greater than or equal to 60% by weight required in the context of the 29-day experimental period within 10 days after exceeding the 10% by weight limit (=
start of the degradation phase) and were therefore classified as easily biodegradable. At a test concentra-tion of 7 mg/l, the alcohol alkoxylates were degraded to 100% by weight after 29 days. Table 4 contains the data for the biodegradability of the alcohol alkoxylates.
Catalyst 2 is a compound of the formula (II), where R3 is iso-C12-alkenyl, R4 i8 c12/14-alkyl, n is O, M is Ca and z is 1 and this alkenylsuccinic acid hemiester calcium Ralt was partially neutralized using 0.4 times the stoichiometric amount of H2S04 necessary for the neutralization of the alkalinity (as a 25% strength by weight solution).
Table 3: Homolog distribution of the fatty alcohol-ethylene oxide (E0)/propylene oxide (P0) block alkoxylate number % by 7.0 9.5 11.2 11.8 13.6 14.0 13.2 9.4 6.1 2.7 1.7 1 0 weight Table 2: Biodegradability of the fatty alcohol-E0/P0 block alkoxylate Test concentration 7 [mg/L]
Biodegradation after 6 d 29 [%]
after 14 d 64 [%]
after 22 d 90 [%]
after 29 d 100 [%]
Claims (10)
1. An alkoxylation product mixture of the formula I
having a narrow alkoxyl distribution (I) where R is the radical of an organic compound con-taining at least one active hydrogen atom, m is an integer from 1 up to the number of active hydrogen atoms in the organic compound, x and y in each case are the average molar number of ethylene oxide or propylene oxide units and independently of one another are an integer from 2 to 10 and the indivi-dual alkoxylation units of the alkoxylation product mixture in each case at most have a degree of alkoxylation of 18% by weight.
having a narrow alkoxyl distribution (I) where R is the radical of an organic compound con-taining at least one active hydrogen atom, m is an integer from 1 up to the number of active hydrogen atoms in the organic compound, x and y in each case are the average molar number of ethylene oxide or propylene oxide units and independently of one another are an integer from 2 to 10 and the indivi-dual alkoxylation units of the alkoxylation product mixture in each case at most have a degree of alkoxylation of 18% by weight.
2. An alkoxylation product mixture as claimed in claim 1, wherein in formula I m = 1 and x and y indepen-dently of one another are a number from 2 to 6.
3. An alkoxylation product mixture as claimed in claim 1 or 2, wherein in formula I m = 1, x and y are independent of one another and x is a number from 2 to 6 and y is a number from 2 to 4.
4. An alkoxylation product mixture as claimed in one or more of claims 1 to 3, wherein R in formula I is a straight-chain or branched, saturated or unsaturated C8-C18-alkoxy group or mixtures thereof.
5. An alkoxylation product as claimed in one or more of claims 1 to 4, wherein in formula I m = 1, x and y are independent of one another and x is a number from 2 to 6 and y is a number from 2 to 4 and R is a monovalent, straight-chain or branched, saturated or unsaturated C8-C18-alkoxy group or mixtures thereof.
6. A process for the preparation of alkoxylation pro-duct mixtures as claimed in one or more of claims 1 to 5, comprising the process steps - reaction of an organic compound containing at least one active hydrogen atom with ethylene oxide in a molar ratio of 2 to 10 mol of ethylene oxide per mole of active hydrogen in the compound to be ethoxylated in the presence of at least one alkaline earth metal salt of the alkyl- or alkenylsuccinic acid monoester of the formulae (II) and (III) below as catalyst (II) (III) where R3 is C8 to C30-alkyl or C8 to C30-alkenyl, n is an integer from 0 to 6, R4 is C1 to C18-alkyl or C3 to C18-alkenyl or hydro-gen if n = 1 or > 1, M is Ba, Ca or Sr and z is a number from 0.9 to 1.8, - then addition of a base to the ethoxylate product mixture obtained and addition of propylene oxide.
7. The process as claimed in claim 6, wherein ethylene oxide and propylene oxide are each employed in an amount from 2 to 6 mol per mole of active hydrogen in the organic compound to be alkoxylated.
8. The process as claimed in claim 6 or 7, wherein an aqueous sodium hydroxide solution is added to the ethoxylate product mixture as a base for further catalysis.
9. The process as claimed in one of claims 6 to 8, wherein the mixture obtained after addition of the base to the ethoxylate product mixture is dried at a temperature of 70 to 150°C and under a reduced pressure of 10 - 100 mbar.
10. The use of the alkoxylation product mixture as claimed in one or more of claims 1 to 5 as low-foaming surfactants, dispersants or wetting agents.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4421576A DE4421576A1 (en) | 1994-06-21 | 1994-06-21 | Alkoxylation product mixtures with a narrow alkoxyl distribution |
| DEP4421576.2 | 1994-06-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2152240A1 true CA2152240A1 (en) | 1995-12-22 |
Family
ID=6521067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002152240A Abandoned CA2152240A1 (en) | 1994-06-21 | 1995-06-20 | Alkoxylation product mixtures having a narrow alkoxyl distribution |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0688755A1 (en) |
| JP (1) | JPH08176047A (en) |
| CA (1) | CA2152240A1 (en) |
| DE (1) | DE4421576A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6680286B1 (en) | 2000-11-14 | 2004-01-20 | Sanyo Chemical Industries, Ltd. | Detergent composition comprising a quaternary ammonium salt of a carboxyl containing polymer |
| US7175996B1 (en) * | 1999-10-14 | 2007-02-13 | Applied Molecular Evolution | Methods of optimizing antibody variable region binding affinity |
| US11634642B2 (en) | 2017-07-14 | 2023-04-25 | Basf Se | Biodegradable surfactant |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1120457B1 (en) * | 1998-09-29 | 2013-07-03 | Sanyo Chemical Industries, Ltd. | Surfactant, process for producing the same, and detergent composition |
| CN100381547C (en) * | 1998-09-29 | 2008-04-16 | 三洋化成工业株式会社 | Anionic surfactant and detergent composition containing same |
| JP3635064B2 (en) * | 1998-09-29 | 2005-03-30 | 三洋化成工業株式会社 | Method for producing nonionic surfactant |
| JP4633243B2 (en) * | 2000-10-26 | 2011-02-16 | 三洋化成工業株式会社 | Bleach cleaning composition |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL134504C (en) * | 1965-06-28 | |||
| BE787398A (en) * | 1971-08-10 | 1973-02-12 | Basf Ag | OXALCOYL ALCOHOLS AND DETERGENT PREPARATIONS CONTAINING THEM AS ANTI-FOAMS |
| US4207421A (en) * | 1977-11-21 | 1980-06-10 | Olin Corporation | Biodegradable, alkali stable, non-ionic surfactants |
| US4223164A (en) * | 1979-07-02 | 1980-09-16 | Conoco, Inc. | Ethoxylation with strontium bases |
| AU570489B2 (en) | 1983-07-05 | 1988-03-17 | Union Carbide Corporation | Alkoxylation using calcium catalysts |
| DE3812168A1 (en) * | 1988-04-12 | 1989-10-26 | Henkel Kgaa | USE OF ERDALCALISALCES OF POLYCARBONE ACID MONESTERS AS CATALYSTS FOR ALKOXYLATION |
| DE4341576A1 (en) * | 1993-12-07 | 1995-06-08 | Hoechst Ag | Process for the preparation of alkoxylates using ester compounds as a catalyst |
-
1994
- 1994-06-21 DE DE4421576A patent/DE4421576A1/en not_active Withdrawn
-
1995
- 1995-06-12 EP EP95109012A patent/EP0688755A1/en not_active Withdrawn
- 1995-06-20 CA CA002152240A patent/CA2152240A1/en not_active Abandoned
- 1995-06-20 JP JP7153615A patent/JPH08176047A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7175996B1 (en) * | 1999-10-14 | 2007-02-13 | Applied Molecular Evolution | Methods of optimizing antibody variable region binding affinity |
| US6680286B1 (en) | 2000-11-14 | 2004-01-20 | Sanyo Chemical Industries, Ltd. | Detergent composition comprising a quaternary ammonium salt of a carboxyl containing polymer |
| US11634642B2 (en) | 2017-07-14 | 2023-04-25 | Basf Se | Biodegradable surfactant |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0688755A1 (en) | 1995-12-27 |
| JPH08176047A (en) | 1996-07-09 |
| DE4421576A1 (en) | 1996-01-04 |
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| FZDE | Discontinued |