Tertiary amine surfactant production process

Abstract

Processes for producing surfactants and surfactant compositions are provided. Additionally, specific surfactants and compositions thereof and their use in a wide variety of applications, such as all-purpose cleaning agents, are provided.

Description

[Technical field]

[0001] The present invention relates to a process for producing tertiary amine surfactants. The present invention further relates to individual embodiments of the surfactants and surfactant compositions. [Background technology]

[0002] Surfactants are compounds that reduce the surface tension between two phases, particularly between two liquids. Surfactants are generally organic amphiphilic compounds, i.e. compounds that contain both hydrophobic and hydrophilic groups. Such compounds are used, for example, as detergents, wetting agents, foaming agents, emulsifiers, and dispersing agents.

[0003] N-alkylamino surfactants are promising amphoteric surfactants. These surfactants have an amine moiety as a polar head group. They exhibit low critical micelle concentrations (CMC) and provide low values ​​of surface tension at the CMC.

[0004] Being a commodity, surfactants are produced on a large scale and there is a pressing need to develop direct and sustainable catalytic methods to obtain fully biobased environmentally friendly alternatives, especially in the context of a biobased economy. Despite the clear potential of N-alkylamino compounds, there is a relative lack of selective catalytic methods to obtain these compounds via the direct functionalization of unprotected amino compounds such as secondary amines.

[0005] Typically, N-alkylation of secondary amines has been carried out using stoichiometric methods such as reductive amination of aldehydes with complexing salts or nucleophilic substitution with alkyl halides. One method described in the art involves the reductive amination of fatty aldehydes with secondary amines in the presence of elemental hydrogen.

[0006] JP 62-149647 A describes the reductive amination of n-dodecanal with morpholine in the presence of a heterogeneous catalyst selected from palladium, platinum, Raney copper, and Raney nickel at temperatures between 150 and 250° C. and a molecular hydrogen pressure of 5 bar.

[0007] Selective N-monoalkylation of secondary amines under mild conditions remains challenging. For example, the use of alkyl halides can lead to exhaustive alkylation (peralkylation) of the nitrogen center to quaternary ammonium salts. Summary of the Invention [Problem to be solved by the invention]

[0008] There remains a need to provide surfactants in high yields under environmentally beneficial conditions, particularly using bio-renewable starting materials, i.e., materials available in nature, via biological processes, and / or materials available via chemical processes from materials available in nature. Additionally, a need exists for novel surfactants. [Means for solving the problem]

[0009] The present invention relates to a compound represented by the general formula (I) [ka] (In the formula, R 1 is C5~C 17 -Alkyl and C5-C 17 -alkenyl, R 2 and R 3 are independently selected from C1-C8-alkyl and C3-C8-alkenyl, each of which may be optionally substituted with one or more substituents selected from hydroxy, C1-C8-alkoxy, amino, C1-C8-alkylamino, thio and C1-C8-alkylthio groups; or R2 and R 3 form a 5- or 6-membered heterocycle together with the nitrogen atom to which they are attached, and may be optionally substituted with one or more substituents selected from a hydroxy group, a C1-C8 alkoxy group, an amino group, a C1-C8 alkylamino group, a thio group, and a C1-C8 alkylthio group. A process for producing a tertiary amine surfactant or a salt thereof comprising: The process is carried out according to the general formula (II) [ka] (In the formula, R 1 is defined as above) The aldehyde of General formula (III) [ka] (In the formula, R 2 and R 3 is defined as above) With secondary amines, reductive amination in the presence of molecular hydrogen and a heterogeneous catalyst comprising an element from Group 10 of the Periodic Table of the Elements; The reductive amination is carried out in a feed operation in which a secondary amine of general formula (III) is provided and an aldehyde of general formula (II) is metered therein, Reductive amination is - at least a molecular hydrogen pressure in the range of 1 bara to less than 40 bara, preferably in the range of more than 1 bara to less than 30 bara, and - At temperatures ranging from 25 to 70°C, Provide a process to be implemented. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The process allows high yields under mild reaction conditions.Moreover, the aldehyde of formula (II) and the secondary amine of formula (III) are typically available in nature, available through biological processes, and / or available through chemical processes from materials available in nature.Overall, the process thus allows surfactants to be obtained in an environmentally friendly manner.

[0011] The process for the production of tertiary amine surfactants of general formula (I) comprises the reductive amination of aldehydes of general formula (II) with secondary amines of general formula (III): [ka] R 1 is C5~C 17 -Alkyl and C5-C 17 -alkenyl and may be linear or branched. 1 is an alkenyl group, R 1 R can be monounsaturated or polyunsaturated. 1 is preferably C7 to C 15 -Alkyl and C7-C 15 -alkenyl, more preferably C7-C 13 -Alkyl and C7-C 13 -alkenyl, most preferably C7-C 11 -Alkyl and C7-C 11 -alkenyl.

[0012] In a particularly preferred embodiment, R 1 is C8-, C9-, or C 11 -alkyl, especially C- or C 11 or R 1 is C9~C 17 -alkenyl, particularly C9-alkenyl.

[0013] The aldehyde of general formula (II) is aliphatic aldehyde.Suitable aldehyde of general formula (II) includes octanal, nonanal, decanal, undecanal, dodecanal, tetradecanal, hexadecanal, 2-ethylhexanal, and citral, particularly citral and dodecanal.Citral is understood as a mixture of two geometric isomers, particularly geranial (citral A) and neral (citral B).

[0014] R 2 and R 3 may be independently selected from C1-C8-alkyl and C3-C8-alkenyl, each of which may be linear or branched. 2 and R 3 are independently selected from optionally substituted C1-C8-alkyl, especially C1-C6-alkyl and optionally substituted C1-C4-alkyl, in particular optionally substituted methyl, optionally substituted ethyl, optionally substituted n-propyl and optionally substituted n-butyl. In a preferred embodiment, R 2 is an optionally substituted C1-C3 alkyl, in particular a C1-C3 alkyl substituted with a hydroxy group, and R 3 is optionally substituted C1-C3-alkyl, in particular methyl. In a particularly preferred embodiment, R 2 is hydroxyethyl, and R 3 is methyl.

[0015] R 2 and R 3 may each independently be optionally substituted with one or more substituents, for example 1 to 3 substituents, selected from a hydroxy group, a C1-C8 alkoxy group, an amino group, a C1-C8 alkylamino group, a thio group, and a C1-C8 alkylthio group, in particular a hydroxy group.

[0016] In a preferred embodiment, R 2 and R 3 is R2 and R 3 is taken together with the nitrogen atom to which it is attached to form a 5- or 6-membered heterocycle, such as a pyrrolidinyl, piperidinyl, morpholinyl or 8-oxa-3-azabicyclo[3.2.1]octanyl group. The heterocycle may be saturated or unsaturated, preferably saturated. The heterocycle may be optionally substituted with a hydroxy group, a C1-C8-alkoxy group, an amino group, a C1-C8-alkylamino group, a thio group or a C1-C8-alkylthio group.

[0017] Suitable secondary amines of general formula (III) include pyrrolidine, piperidine, morpholine, 8-oxa-3-azabicyclo[3.2.1]octane, and N-methylethanolamine.

[0018] The molar ratio of the total amount of aldehydes of general formula (II) to the total amount of secondary amines of general formula (III) is preferably within the range of 0.8:1 to 1.3:1, more preferably 0.9:1 to 1.2:1, and most preferably 0.95:1 to 1.15:1.

[0019] The reductive amination is carried out in the presence of a heterogeneous catalyst comprising an element from group 10 of the periodic table of the elements. The element from group 10 may be selected from nickel (Ni), palladium (Pd), and platinum (Pt). Preferably, the element from group 10 is selected from nickel (Ni), platinum (Pt), and palladium (Pd), more preferably platinum (Pt) and palladium (Pd), and in particular palladium (Pd).

[0020] The metal can be used as is or can be applied to a support. Preferred supports are selected from aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide, and activated carbon. Particularly preferred are supported metals. Preferred supports are activated carbon, aluminum oxide, and titanium dioxide. Of these, a particularly preferred support is activated carbon. Of these, a particularly preferred hydrogenation catalyst is palladium on activated carbon.

[0021] In a preferred embodiment, the heterogeneous catalyst is selected from Raney nickel and palladium on activated carbon, in particular palladium on activated carbon (Pd / C). When the heterogeneous catalyst is palladium on activated carbon, the catalyst may include a binder such as polytetrafluoroethylene (PTFE).

[0022] The reductive amination is carried out at a molecular hydrogen pressure in the range of at least 1 bara to less than 40 bara, preferably at least 1 bara to less than 35 bara, in particular in the range of more than 1 bara to 30 bara. Preferably, the molecular hydrogen pressure is in the range of 3 to 30 bara, more preferably 3 to 25 bara, most preferably 4 to 21 bara. A molecular hydrogen pressure of more than 1 bara advantageously allows for shorter reaction times, thus increasing the process efficiency.

[0023] On the other hand, if the molecular hydrogen pressure is too high, the aldehyde does not participate in the reductive amination but is reduced to the corresponding alcohol, which is extremely difficult to separate from the reaction mixture. Therefore, operating at a molecular hydrogen pressure within the claimed range allows for high selectivity and high efficiency of the process.

[0024] The reductive amination is carried out at a temperature of 25 to 70° C. Preferably, the temperature is in the range of 25 to 65° C., more preferably 30 to 60° C., and most preferably 40 to 50° C. A temperature within this range allows the reductive amination reaction to proceed at an appropriate rate under mild conditions.

[0025] Reductive amination is typically carried out in the presence of a solvent, which can provide benefits to the reductive amination reaction, such as improved solubility of hydrogen, reduced viscosity of the reaction mixture, improved mixing efficiency, and improved heat transfer.

[0026] In one embodiment, the reductive amination is carried out at a pressure of 18 to 38 MPa. 1 / 2 Within the range of 25 to 37 MPa 1 / 2 , more preferably 26 to 36 MPa 1 / 2 , and most preferably 30 to 36 MPa1 / 2 Specifically, 32-35MPa 1 / 2 The reaction is carried out in the presence of a solvent having a Hildebrand solubility parameter δ in the range of δ=1.0 to 1.0. Solvents with a Hildebrand solubility parameter δ in this range have been found to allow high solubility of both the starting material and the resulting surfactant. The solvent can be in the form of a single solvent or a mixture of two or more solvents. The Hildebrand solubility parameter δ is used as an indicator of solubility since it provides a numerical estimate of the degree of interaction between compounds. Compounds with similar δ values ​​are likely to be miscible.

[0027] The Hildebrand solubility parameter δ is well known in the literature. The table below provides exemplary solvents and their Hildebrand solubility parameters from Barton, Allan FM (1983), Handbook of Solubility Parameters and Other Cohesion Parameters, CRC Press.

[0028] [Table 1]

[0029] The Hildebrand solubility parameter δ of a solvent mixture can be determined by volume averaging the Hildebrand values ​​of the individual solvents. For example, the Hildebrand solubility parameter of a mixture of 2 parts ethanol and 1 part water is: δ = ((2 × 26.2 MPa 1 / 2 +48.0MPa 1 / 2 ) / 3)=33.5MPa 1 / 2 It can be calculated as:

[0030] Selection of a solvent having a Hildebrand solubility parameter δ within the above range ensures that the solvent has suitable solubility characteristics for the secondary amine of general formula (III) and that the reductive amination reaction proceeds at an appropriate rate.

[0031] In a preferred embodiment, the solvent comprises a protic solvent and / or an aprotic solvent containing an ether moiety, in particular a protic solvent. A protic solvent is one that provides a proton (H + ) is understood to be a solvent that can donate a proton to the solute.

[0032] Preferably, the solvent comprises at least one protic solvent selected from water and an aliphatic alcohol. Preferred aliphatic alcohols include methanol, ethanol, and isopropanol, in particular ethanol. More preferably, the solvent comprises an aliphatic alcohol or a mixture of an aliphatic alcohol and water. In another preferred embodiment, the solvent is a mixture of an aliphatic alcohol and water in a volume ratio ranging from 1:1 to 4:1, preferably from 1.25:1 to 3:1, and most preferably from 1.5:1 to 2:1. In a particularly preferred embodiment, the solvent is a mixture of ethanol and water in a volume ratio ranging from 1:1 to 4:1, preferably from 1.25:1 to 4:1, more preferably from 1.5:1 to 2:1, and most preferably from 1.5:1 to 2:1. When the solvent is composed of a mixture of different solvents, the volume of the mixture may be less than the sum of the volumes of the individual solvents. This phenomenon is known as "volume shrinkage". It may occur, for example, when the solvent is composed of an aliphatic alcohol and water. Volume ratios are understood to relate to the ratio of the individual solvent volumes before mixing, ie, ignoring any volumetric shrinkage that may occur due to mixing.

[0033] In another embodiment, the solvent comprises at least one aprotic solvent containing an ether moiety, such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, or tetrahydropyran, particularly tetrahydrofuran. In one embodiment, the solvent is tetrahydrofuran.

[0034] In a further embodiment, the solvent comprises at least one aprotic solvent containing an ether moiety and at least one protic solvent. For example, the solvent may comprise a mixture of tetrahydrofuran and at least one protic solvent, particularly water or an alcohol. In a preferred embodiment, the solvent is a mixture of tetrahydrofuran and water or ethanol, particularly a mixture of tetrahydrofuran and water.

[0035] Additionally, preferred solvents may prevent the development of two separate liquid phases during reductive amination, which can occur due to the liberation of water as a co-product during the reaction.

[0036] The reductive amination is preferably carried out at a solvent dilution ratio of less than 5.0 L / kg. The term solvent dilution ratio as used herein means the total volume of solvent relative to the total weight of the aldehyde of general formula (II) and the secondary amine of general formula (III). The term "total volume of solvent" includes the initial volume of solvent and the solvent volume added throughout the reductive amination. The solvent volume added throughout the reductive amination is, for example, the solvent volume contained in the solution of reactants metered in during the feeding operation process. It is understood that the "total volume of solvent" takes into account volumetric shrinkage.

[0037] Preferably, the reductive amination is carried out at a solvent dilution ratio of at most 5.0 kg / L, even at most 3.5 kg / L. Typically, the reductive amination is carried out at a solvent dilution ratio of 1.0 to 4.5 kg / L, more preferably 1.0 to 3.5 kg / L. Concentrations of the aldehyde of general formula (II) and the secondary amine of general formula (III) within this range allow efficient reaction of the secondary amine with the aldehyde with high selectivity. More dilute reaction mixtures result in poor space-time yields, while in some cases of over-concentrated reaction mixtures the benefit of the solvent may be minimized.

[0038] The process of the present invention can be carried out in any reactor, such as an autoclave, suitable for maintaining the pressure of molecular hydrogen within the desired range at the desired temperature.

[0039] The process of the invention is carried out in a feed operation in which a secondary amine of general formula (III) is provided (i.e. initially charged) and an aldehyde of general formula (II) is metered thereto. The reductive amination can take place in the presence of a solvent. Providing a secondary amine of general formula (III) is understood to also include providing a solution of a secondary amine of general formula (III). Similarly, metering an aldehyde of general formula (II) thereto also includes metering a solution of an aldehyde of general formula (II) thereto. The solvent contained in the solution of the secondary amine of general formula (III) and the solvent contained in the solution of the aldehyde of general formula (II) together constitute the solvent in the presence of which the reductive amination takes place. The solvents contained in the two solutions may be identical or different. In the latter case, the solvent in the presence of which the reductive amination takes place is a mixture of solvents.

[0040] In general, the aldehyde of general formula (II) is added at a constant feed rate. This allows to avoid undesirable side reactions. On the one hand, this prevents the reduction of the aldehyde to the corresponding alcohol, and obtains the tertiary amine surfactant of general formula (I) with higher selectivity, while avoiding the difficult removal of the corresponding alcohol. On the other hand, this prevents the formation of aldehyde dimers by aldol condensation of the aldehyde itself. This also allows higher selectivity, and also prevents the formation of dimeric surfactants with less favorable properties.

[0041] The reaction product obtained in the process of the present invention may be purified by typical means such as filtering the reaction mixture to remove the heterogeneous catalyst, followed by evaporation of the solvent from the filtrate to obtain a crude material. A suitable additional solvent, in particular ethanol, may be added prior to filtration to fully dissolve the reaction product in the resulting reaction mixture. The crude material may be further purified, for example by distillation.

[0042] The surfactant can be a non-ionic compound of general formula (I) or an external salt of a compound of general formula (I). The "external salt" can be obtained under acidic conditions. In one embodiment, the process comprises neutralizing a tertiary amine surfactant of general formula (I) with an acid. Thus, a salt of the tertiary amine surfactant of general formula (I) is obtained. The acid can be selected from organic acids and mineral acids.

[0043] Suitable mineral acids include hydrochloric acid, sulfuric acid, amidosulfuric acid, and phosphoric acid. Preferably, the mineral acid is selected from hydrochloric acid and sulfuric acid.

[0044] Suitable organic acids include carboxylic acids, sulfonic acids, carbonic acids, organic phosphonic acids, and aminocarboxylic acids. Preferably, the organic acid is selected from carboxylic acids, most preferably from formic acid, acetic acid, oxalic acid, propionic acid, hydroxypropionic acid, lactic acid, malic acid, maleic acid, succinic acid, tartaric acid, citric acid, aconitic acid, and glutamic acid.

[0045] Neutralization of the tertiary amine surfactant of general formula (I) with an acid is typically carried out at room temperature, i.e. 25°C, and under atmospheric pressure. Neutralization is typically carried out in a solvent, preferably in a solvent as described above. The neutralized reaction product can be purified by typical means, such as evaporating the solvent to obtain a crude material, which can be further purified, for example, by recrystallization.

[0046] In one embodiment, the aldehyde of general formula (II) and / or the secondary amine of general formula (III), in particular the aldehyde of general formula (II), are biobased compounds. In this embodiment, the process makes it possible to obtain surfactants in a particularly environmentally friendly manner.

[0047] Radiocarbon and isotope ratio mass spectrometry analyses can be used to determine the biobased content of a material. For example, ASTM International has established a standard method for assessing the biobased content of a material. The ASTM method is referred to as ASTM-D6866.

[0048] The application of ASTM-D6866 to determining the "biobased content" of a material is based on the same concept as radiocarbon dating, but does not use age equations. The analysis is based on the amount of radiocarbon ( 14 This is done by deriving the ratio of the amount of radiocarbon (C) present in the sample to that of a modern reference standard. The ratio is reported as a percentage in "pMC" (percent modern carbon). When the material being analyzed is a mixture of modern radiocarbon and fossil carbon (which does not contain any radiocarbon), the pMC value obtained correlates directly to the amount of biomass material present in the sample.

[0049] Modern reference standards used in radiocarbon dating are NIST standards of known radiocarbon content that roughly correspond to the year 1950 AD. The year 1950 AD was chosen because it represents a time prior to thermonuclear weapons testing, where each explosion introduced large amounts of excess radiocarbon (referred to as "bomb carbon") into the atmosphere. The 1950 AD reference represents 100 pMC.

[0050] Further details on the assessment of materials to determine whether they are bio-based or not can be found, for example, in WO 2007 / 095262 A2.

[0051] The surfactants of general formula (I) are preferably at least partially biodegradable, preferably at least 20%, more preferably at least 60% within 28 days according to OECD 301 (all percentages in wt.-% based on the total solids content).

[0052] The process avoids the deleterious extensive aldol condensation of the aldehyde itself to form aldehyde dimers, allowing for higher selectivity, but it is believed that dimerization cannot be avoided entirely. It is believed that small amounts of dimeric surfactants can favorably affect important surfactant properties such as foam volume, wetting time, surface tension, and contact angle.

[0053] The present invention therefore relates to a surfactant composition comprising a surfactant of general formula (I) as defined above in an amount of at least 90 wt.-% based on the weight of the surfactant composition, or a salt thereof, and a surfactant of general formula (IV) in an amount of 0.01 to 5.0 wt.-% based on the weight of the surfactant composition [ka] (In the formula, R 2 and R 3 is defined as above, and R 4 is C 10 ~C 34 -Alkyl and C 10 ~C 34 -alkenyl, where R 4 The number of carbon atoms in R 1 The number of carbon atoms in R 4 The number of carbon atoms in the R 1 For example, R 1 (This is twice the number of carbon atoms in the or a salt thereof, The surfactant composition further provides that the compound of general formula (IV) is preferably obtained via reductive amination of an aldehyde dimer obtained from the self-aldol condensation of an aldehyde of formula (II) as defined above and a secondary amine of general formula (III) as defined above.

[0054] In one embodiment, the surfactant composition comprises the compound of general formula (IV) in an amount of 0.01 to 4.5 wt.-%, preferably 0.05 to 4.5 wt.-%, more preferably 0.1 to 4.0 wt.-%, and most preferably 0.5 to 3.0 wt.-%, based on the weight of the surfactant composition.

[0055] In one embodiment, the surfactant composition comprises the surfactant of general formula (I) in an amount of at least 93 wt.-%, preferably at least 94 wt.-%, more preferably at least 95 wt.-%, such as at least 96 wt.-%, or at least 97 wt.-%, based on the weight of the surfactant composition.

[0056] The surfactant composition may further comprise by-products of the process of the present invention, such as unreacted starting materials or by-products, such as alcohols. Preferably, the surfactant composition comprises less than 5 wt.-%, more preferably less than 4 wt.-%, and most preferably less than 3 wt.-% of compounds other than the surfactant of general formula (I) and the compound of general formula (IV).

[0057] Preferably, the surfactant composition is obtained according to the process of the present invention. The surfactant composition may be mixed with further ingredients to obtain surfactants for a wide variety of applications, including detergents, as described in detail below.

[0058] In another embodiment, the present invention further comprises a surfactant of general formula (I) as defined above or a salt thereof and a surfactant of general formula (IV) [ka] (In the formula, R 2 and R 3 is defined as above, and R 4 is C 10 ~C 34 -Alkyl and C 10 ~C 34 -alkenyl, provided that 4 The number of carbon atoms in R 1 The number of carbon atoms in R 4 The number of carbon atoms in the R 1 For example, R 1 (This is twice the number of carbon atoms in the or a salt thereof, the weight ratio of the total amount of the surfactant of general formula (I) and its salt to the total amount of the compound of general formula (IV) and its salt is within the range of 15:1 to 10,000:1, preferably 20:1 to 1,000:1, more preferably 25:1 to 100:1, for example, 25:1 to 75:1; The compound of general formula (IV) is preferably obtained via reductive amination of an aldehyde dimer obtained from the self-aldol condensation of an aldehyde of formula (II) as defined above, and a secondary amine of general formula (III) as defined above, providing a surfactant composition.

[0059] In the process of the present invention, the surfactant of general formula (I) is obtained together with a small amount of the compound of general formula (IV) as a by-product.Preferably, the compound of general formula (IV) contained in the surfactant composition of the present invention is derived from the self-aldol condensation product of the aldehyde (II) used in the process of the present invention.The compound of general formula (IV) can be obtained in enriched form from the crude reaction product of the process of the present invention, for example, via distillation.The ratio of the surfactant of general formula (I) and the compound of general formula (IV) can be determined via gas chromatography (after silylation) or via gas chromatography-mass spectrometry (GC-MS).

[0060] The present invention further comprises: - 2-[(3,7-dimethyloctyl)(methyl)amino]ethanol, - 1-(3,7-dimethyloctyl)pyrrolidine, 3-dodecyl-8-oxa-3-azabicyclo[3.2.1]octane, 3-nonyl-8-oxa-3-azabicyclo[3.2.1]octane, and - 3-(3,7-dimethyloctyl)-8-oxa-3-azabicyclo[3.2.1]octane, or a salt thereof.

[0061] These compounds are obtainable by the process of the present invention.

[0062] The present invention further provides compositions comprising at least one compound of the present invention.

[0063] The present invention further provides the use of the compound of the present invention or the composition of the present invention as surfactant.The surfactant and composition of the present invention, which is understood to include the surfactant composition of the present invention, can be used as surfactant in a wide variety of applications, including detergents such as granular laundry detergents, liquid laundry detergents, liquid dishwashing detergents, and in a wide variety of formulations such as all-purpose cleaning agents, liquid soaps, shampoos, shower gels, liquid scouring agents, etc.In addition, the compound and composition of the present invention can be used as surfactant in institutional and industrial cleaning formulations such as kitchen cleaners, industrial laundry detergents, vehicle cleaners, disinfectant cleaners, etc.In addition, the compound and composition of the present invention can be used as adjuvant in pesticide formulations such as pesticide formulations.

[0064] The compounds and compositions of the present invention find particular use as surfactants in detergents, particularly laundry detergents and hand dishwashing products. These generally contain several ingredients other than the compounds of the present invention. The compositions typically contain the compounds of the present invention in a total amount of 0.1-15 wt.-% based on the weight of the composition. Typical compositions are well known to those skilled in the art.

[0065] Laundry detergents typically contain other surfactants of anionic, nonionic, amphoteric, or cationic type, builders such as phosphates, aminocarboxylates, and zeolites, organic cobuilders such as polycarboxylates, bleaching agents and their activators, foam control agents, enzymes, anti-greying agents, optical brighteners, and stabilizers.

[0066] Liquid laundry detergents generally contain the same ingredients as granular laundry detergents, but generally contain less builder. In addition, liquid detergent formulations often contain hydrotropic materials. All-purpose cleaning agents may contain other surfactants, builders, suds suppressors, hydrotropes, and solubilizing alcohols.

[0067] Builders may be included in amounts up to 90% by weight, preferably about 5-35% by weight, to enhance cleaning action. Examples of common inorganic builders are phosphates, polyphosphates, alkali metal carbonates, silicates, and sulfates. Examples of organic builders are polycarboxylates, aminocarboxylates, such as ethylenediaminetetraacetate, nitrilotriacetate, hydroxycarboxylates, citrates, succinates, and substituted and unsubstituted alkane di- and polycarboxylic acids.

[0068] Another type of builder useful in granular and built liquid laundry agents includes various substantially water-insoluble materials capable of reducing water hardness, for example by an ion exchange process. In particular, the complex sodium aluminosilicates known as Type A zeolites are useful for this purpose.

[0069] Laundry detergents may also contain bleaching agents, such as per compounds, such as perborate, percarbonate, persulfate, and organic peroxyacids. Formulations containing per compounds may also contain stabilizers, such as magnesium silicate, sodium ethylenediaminetetraacetate, and sodium salts of phosphonic acids. Additionally, bleach activators can be used to increase the efficiency of inorganic persalts at lower wash temperatures. Particularly useful for this purpose are substituted carboxylic acid amides, such as tetraacetylethylenediamine, substituted carboxylic acids, such as isononyloxybenzenesulfonate, and sodium cyanamide.

[0070] Examples of suitable hydrotropic substances are the alkali metal salts of benzene, toluene, and xylene sulfonic acid, the alkali metal salts of formic acid, citric acid, and succinic acid, urea, mono-, di-, and triethanolamine. Examples of solubilizing alcohols are ethanol, isopropanol, mono- or polyethylene glycol, monopropylene glycol, and ether alcohols.

[0071] Examples of suds suppressors are high molecular weight fatty acid soaps, paraffinic hydrocarbons, and silicon-containing defoamers. In particular, hydrophobic silica particles having adsorbed silicon are effective suds suppressors in such laundry detergent formulations.

[0072] Examples of known enzymes useful in laundry detergents are proteases, amylases, cellulases, mannanases, and lipases, among others. Preferred are enzymes that have their optimum performance under the conditions for which the detergent is designed.

[0073] A large number of optical brighteners have been described in the literature. In laundry detergent formulations, derivatives of diaminostilbene disulfonates and substituted distyrylbiphenyls are particularly suitable.

[0074] As anti-greying agents, preferably organic water-soluble colloids are used, examples being water-soluble polyanionic polymers such as polymers and copolymers of acrylic and maleic acid, cellulose derivatives such as carboxymethylcellulose, methyl and hydroxyethylcellulose.

[0075] In addition to one or more of the other surfactants and other detergent composition components mentioned above, laundry detergent compositions typically include one or more inert components. By way of example, the balance of a liquid detergent composition is typically an inert solvent or diluent, most commonly water.

[0076] The hand dishwashing product may contain, in addition to the compounds obtained by the process of the present invention, other surfactants of the anionic, nonionic, amphoteric, or cationic type, solvents, diamines, carboxylic acids or their salts, polymeric suds stabilizers, enzymes, builders, fragrances, and / or chelating agents.

[0077] Suitable solvents include diols, polymeric glycols, and mixtures thereof. Preferred diols include propylene glycol, 1,2 hexanediol, 2-ethyl-1,3-hexanediol, and 2,2,4-trimethyl-1,3-pentanediol.

[0078] Polymeric glycols containing ethylene oxide (EO) and propylene oxide (PO) groups may also be included in the present invention. These materials are formed by adding blocks of ethylene oxide moieties to the ends of polypropylene glycol chains. A preferred polymeric glycol is a polypropylene glycol having an average molecular weight in the range of 1,000 to 5,000 g / mol. When a polymeric glycol is present, it may be beneficial to include either a diol and / or an alkali metal inorganic salt, such as sodium chloride, to obtain satisfactory physical stability. The preferred amount of diol to provide physical stability is within the ranges found above.

[0079] Further suitable solvents include glycols or alkoxylated glycols, ethers and diethers having 4 to 14 carbon atoms, preferably 6 to 12 carbon atoms, aromatic alcohols, alkoxylated aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, linear C1 to C5 alcohols, alkoxylated linear C1 to C5 alcohols, C8 to C 14 Alkyl and cycloalkyl hydrocarbons and halohydrocarbons, C6-C 16 glycol ethers, as well as mixtures thereof.

[0080] Suitable alkoxylated glycols are methoxyoctadecanol and / or ethoxyethoxyethanol. Suitable aromatic alcohols include benzyl alcohol. Suitable aliphatic branched alcohols include 2-ethylbutanol and / or 2-methylbutanol. Suitable alkoxylated aliphatic branched alcohols include 1-methylpropoxyethanol and / or 2-methylbutoxyethanol. Suitable linear C1-C5 alcohols include methanol, ethanol, and / or propanol.

[0081] Hand dishwashing compositions typically contain 0.01 to 20 wt.-% of a solvent, based on the total weight of the composition. The solvent may be used in combination with an aqueous liquid carrier, such as water, or may be used without any aqueous liquid carrier present.

[0082] The hand dishwashing composition may further comprise one or more diamines.

[0083] The composition preferably comprises 0.1 to 15 wt.-% of at least one diamine, based on the total weight of the composition.

[0084] Suitable diamines include organic diamines having pK1 and pK2 in the range of 8.0 to 11.5, such as 1,3-bis(methylamine)-cyclohexane (pKa=10-10.5), 1,3-propanediamine (pK1=10.5, pK2=8.8), 1,6-hexanediamine (pK1=11, pK2=10), 1,3-pentanediamine (pK1=10.5, pK2=8.9), and 2-methyl-1,5-pentanediamine (Dytek A) (pK1=11.2, pK2=10.0). The pKa values ​​referred to herein may be obtained from references such as "Critical Stability Constants: Volume 2, Amines" by Smith and Martel, Plenum Press, NY and London, 1975. The pKa of the diamine is specifically shown in an all-aqueous solution at 25° C. and an ionic strength of 0.1 to 0.5M.

[0085] Other preferred materials are primary diamines having two primary amino groups with an alkylene spacer in the C4 to C8 range.

[0086] The composition according to the invention may comprise a linear or cyclic carboxylic acid or salt thereof. When the acid or salt thereof is present and linear, it preferably contains 1 to 6 carbon atoms, whereas when the acid is cyclic, it preferably contains more than 3 carbon atoms. The linear or cyclic carbon-containing chain of the carboxylic acid or salt thereof may be substituted with a substituent selected from the group consisting of hydroxyl groups, ester groups, ether groups, aliphatic groups having 1 to 6, more preferably 1 to 4, carbon atoms, and mixtures thereof.

[0087] Preferred carboxylic acids are those selected from the group consisting of salicylic acid, maleic acid, acetylsalicylic acid, 3-methylsalicylic acid, 4-hydroxyisophthalic acid, dihydroxyfumaric acid, 1,2,4-benzenetricarboxylic acid, pentanoic acid, and their salts and mixtures thereof. When the carboxylic acid is present in salt form, the cation of the salt is preferably selected from alkali metals, alkaline earth metals, monoethanolamine, diethanolamine, or triethanolamine, and mixtures thereof.

[0088] The carboxylic acid or salt thereof is preferably present in an amount of from 0.1% to 5 wt.%, based on the total weight of the composition.

[0089] The composition may include a polymeric suds stabilizer that provides increased suds volume and suds duration without sacrificing the oily soil removal ability of the liquid detergent composition. Suitable polymeric suds stabilizers include homopolymers of (N,N-di(C1-C8 alkyl)amino)(C1-C8) alkyl acrylate esters and copolymers thereof.

[0090] The molecular weight of the polymeric suds stabilizer is preferably in the range of 1,000 to 2,000,000 g / mol, most preferably 20,000 to 500,000 g / mol. The polymeric suds stabilizer may be present in the form of a salt, for example, a citrate, sulfate, or nitrate salt of an (N,N-dimethylamino) alkyl acrylate ester. One preferred polymeric suds stabilizer is an (N,N-dimethylamino) alkyl acrylate ester. The polymeric suds stabilizer is preferably present in an amount of 0.01% to 15 wt.-% based on the total weight of the composition.

[0091] Suitable builders include aluminosilicate materials, silicates, polycarboxylates, and fatty acid materials such as ethylene-diaminetetraacetate, sequestering agents such as aminopolyphosphonates, especially ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylene-phosphonic acid. Phosphate builders can also be used, although they are less preferred for obvious environmental reasons.

[0092] Suitable polycarboxylate builders include citric acid, preferably in water-soluble salt form, and succinic acid derivatives.Specific examples include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate, 2-tetradecenyl succinate.Succinate builders are preferably used in their water-soluble salt form, including sodium, potassium, ammonium, and alkanolammonium salts.Other suitable polycarboxylates are oxodisuccinate and the mixture of tartrate monosuccinic acid and tartrate disuccinic acid described in U.S. Pat. No. 4,663,071.

[0093] Suitable fatty acid builders include saturated and unsaturated C 10 ~ 18 Fatty acids and even the corresponding soaps are mentioned. Preferred saturated species have 12 to 16 carbon atoms in the alkyl chain. A preferred unsaturated fatty acid is oleic acid. Other preferred builder systems for liquid compositions are dodecenyl succinic acid and citric acid.

[0094] The builder is preferably present in an amount of from 0.5% to 50 wt.-%, more preferably from 5 to 25 wt.-%, based on the total weight of the composition.

[0095] Suitable enzymes include those selected from cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases, or mixtures thereof. The enzymes may be present in an amount of 0.0001% to 5 wt.-% active enzyme based on the total weight of the composition.

[0096] In that case, preferred proteolytic enzymes are selected from the group consisting of Alcalase® (Novo Industri A / S), BPN', Protease A and Protease B (Genencor), and mixtures thereof. Protease B is most preferred. Preferred amylase enzymes include TERMAMYL®, DURAMYL®, and the amylase enzymes described in WO 9418314 to Genencor International and WO 9402597 to Novo.

[0097] Suitable chelating agents include iron and / or manganese chelating agents. Such chelating agents can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents, and mixtures thereof. Suitable aminocarboxylates include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilo-tri-acetate, ethylenediaminetetrapropionate, triethylenetetraminehexaacetate, diethylenetriaminepentaacetate, and ethanoldiglycine, their alkali metal, ammonium, and substituted ammonium salts, and mixtures thereof. Suitable aminophosphonates include ethylenediaminetetrakis(methylenephosphonate). Suitable polyfunctionally substituted aromatic chelating agents include dihydroxydisulfobenzenes, such as 1,2-dihydroxy-3,5-disulfobenzene. The chelating agents can be present in an amount of 0.00015% to 15 wt.-% based on the weight of the composition.

[0098] The present invention is explained in further detail by the examples which follow. EXAMPLES

[0099] General information Reductive amination of aldehydes with secondary amines was carried out in a 300 mL autoclave at temperatures between 25-50° C. and hydrogen pressures between 5-10 bar according to Table 1 below.

[0100] Analyses were performed via gas chromatography (after silylation) or via gas chromatography-mass spectrometry (GC-MS) and structures were confirmed by nuclear magnetic resonance (NMR) spectroscopy.

[0101] Example 1 Palladium on carbon black (10 wt.-%, 1.9 g) was added to a solution of pyrrolidine (99%, 10 g) and dodecanal (95%, 29 g) in tetrahydrofuran (100 mL) in an autoclave. The reaction vessel was closed and then purged with nitrogen gas (3 times at 5 bar). Stirring (700 rpm) was applied with an initial hydrogen gas pressure of 5 bar. The reaction mixture was warmed to 25° C. and the hydrogen pressure was maintained at 5 bar.

[0102] The reaction mixture was stirred under these conditions for 12 h, then cooled to room temperature and purged with nitrogen gas (3 times at 5 bar).The catalyst was then filtered off and the solvent was removed by evaporation to give the crude material as a liquid (purity: 71%, 35 g, yield: 75%).

[0103] Example 2 Example 2 was carried out similarly to Example 1 as shown in Table 1.

[0104] Example 3 Palladium on carbon black (10 wt.-%, 1 g) was added to a solution of morpholine (99%, 10 g) in ethanol (90 mL) in an autoclave. The reaction vessel was closed and then purged with nitrogen gas (3 times at 5 bar). Stirring (700 rpm) was applied with an initial hydrogen gas pressure of 5 bar. The reaction mixture was warmed to 40° C. Dodecanal (95%, 25 g) was then continuously metered into the reaction mixture as a solution in ethanol (20 mL) over a period of 5 h. The temperature (40° C.) and hydrogen pressure (5 bar) were maintained.

[0105] After complete addition of the aldehyde solution, the reaction mixture was stirred at a temperature of 40° C. and 5 bar hydrogen pressure for 1 h, then cooled to room temperature and purged with nitrogen gas (3 times at 5 bar).The catalyst was then filtered off and the solvent was removed by evaporation to give the crude material as a colorless liquid (purity: 91%, 29 g, yield: 91%).

[0106] Example 4 Palladium on carbon black (10 wt.-%, 1.5 g) was added to a solution of pyrrolidine (99%, 15 g) in a mixture of ethanol (50 mL) and water (40 mL) in an autoclave. The reaction vessel was closed and then purged with nitrogen gas (3 times at 5 bar). Stirring (700 rpm) was applied with an initial hydrogen gas pressure of 5 bar. The reaction mixture was warmed to 40° C. Dodecanal (95%, 45 g) was then metered continuously into the reaction mixture as a solution in ethanol (20 mL) over a period of 5 h. The temperature (40° C.) and hydrogen pressure (5 bar) were maintained.

[0107] After complete addition of the aldehyde solution, the reaction mixture was stirred at a temperature of 40° C. and 5 bar hydrogen pressure for 1 h, then cooled to room temperature and purged with nitrogen gas (3 times at 5 bar). The catalyst was then filtered off and the solvent removed by evaporation to give the crude material as a yellow liquid (purity: 89%, 46 g, yield: 80%). Distillation (5 mbar, 140-150° C.) gave the product as a colorless liquid (purity: 99%, 30 g, yield: 59%).

[0108] Examples 5 to 8 As shown in Table 1, Examples 5 to 8 were carried out in the same manner as Example 4.

[0109] Example 9 Palladium on carbon black (10 wt.-%, 1.5 g) was added to a solution of N-methylethanolamine (100%, 15 g) and dodecanal (95%, 43 g) in a mixture of ethanol (70 mL) and water (40 mL) in an autoclave. The reaction vessel was closed and then purged with nitrogen gas (3 times at 5 bar). Stirring (700 rpm) was applied with an initial hydrogen gas pressure of 20 bar. The reaction mixture was warmed to 50° C. and the hydrogen pressure was maintained at 20 bar.

[0110] The reaction mixture was stirred under these conditions for 6 h, then cooled to room temperature and purged with nitrogen gas (3 times at 5 bar).The catalyst was then filtered off and the solvent was removed by evaporation to give the crude material as a liquid (purity: 93%, yield: 88%).

[0111] [Table 2]

[0112] Example 10 - Salt Form of Example 1 The crude N-dodecylpyrrolidine obtained in Example 1 (71%, 10 g) was dissolved in tetrahydrofuran (50 mL). Concentrated aqueous hydrochloric acid (37%) was added to the solution until a pH value of 1 was reached. The reaction mixture was stirred at room temperature for 12 h. Afterwards, the solvent was removed by evaporation and the crude material was recrystallized from heptane / toluene (19:1) at 75° C. (purity: 82%, 10 g, yield: 84%).

Claims

1. General formula (I) 【Chemistry 1】 (In the formula, R １ is C ５ ~C １７ -Alkyl and C ５ ~C １７ -alkenyl, R ２ and R ３ is C １ ~C ８ -Alkyl and C ３ ~C ８ -alkenyl, where C １ ~C ８ -Alkyl and C ３ ~C ８ -Alkenyl is each a hydroxy group, C １ ~C ８ -Alkoxy group, amino group, C １ ~C ８ -Alkylamino group, thio group, and C １ ~C ８ -alkylthio groups, Or R ２ and R ３ form a 5- or 6-membered heterocycle together with the nitrogen atom to which they are attached; １ ~C ８ -Alkoxy group, amino group, C １ ~C ８ -Alkylamino group, thio group, and C １ ~C ８ -alkylthio groups, A process for producing a tertiary amine surfactant or a salt thereof comprising: The process comprises the steps of: 【Chemistry 2】 (In the formula, R １ is defined as above) with an aldehyde of the general formula (III) 【Chemistry 3】 (In the formula, R ２ and R ３ is defined as above) With the secondary amine, reductive amination in the presence of molecular hydrogen and a heterogeneous catalyst comprising an element from Group 10 of the Periodic Table of the Elements; the reductive amination is carried out in a feed operation in which a secondary amine of general formula (III) is provided and an aldehyde of general formula (II) is metered therein; and The reductive amination is carried out at a pressure of molecular hydrogen ranging from at least 1 bara to less than 40 bara and at a temperature ranging from 25 to 70°C.

2. R １ C ７ ~C １７ - alkyl, in particular C ８ -, C ９ - or C １１ -alkyl, or R １ C ９ ~C １７ -alkenyl, particularly C ９ -alkenyl.

3. R ２ is optionally substituted C １ ~C ３ - C substituted with alkyl, particularly hydroxyl groups １ ~C ３ -alkyl and R ３ is optionally substituted C １ ~C ３ 3. The process according to claim 1 or 2, wherein - alkyl, in particular methyl.

4. R ２ and R ３ together with the nitrogen atom to which they are attached form a pyrrolidinyl group, a piperidinyl group, a morpholinyl group, or a 8-oxa-3-azabicyclo[3.2.1]octanyl group, each of which is optionally substituted.

5. The process according to any one of claims 1 to 4, wherein the group 10 elements are selected from palladium, platinum and nickel, preferably palladium and platinum, in particular palladium.

6. 6. The process of claim 5, wherein the heterogeneous catalyst is palladium on activated carbon.

7. The process is carried out by using a solvent, specifically a pressure of 18 to 38 MPa. １／２ The process of any one of claims 1 to 6, carried out in the presence of a solvent having a Hildebrand solubility parameter δ in the range of

8. 8. The process of claim 7, wherein the solvent comprises a protic solvent and / or an aprotic solvent containing an ether moiety.

9. 9. The process of claim 8, wherein the solvent is selected from aliphatic alcohols and mixtures of aliphatic alcohols and water.

10. 10. The process according to any one of claims 7 to 9, wherein the solvent dilution ratio is less than 5.0 L / kg, where the solvent dilution ratio is the total volume of solvent to the total weight of the aldehyde of general formula (II) and the secondary amine of general formula (III).

11. A process according to any one of claims 1 to 10, which comprises neutralising a tertiary amine surfactant of general formula (I) with an acid.

12. The process according to any one of claims 1 to 11, wherein the aldehyde of general formula (II) and / or the secondary amine of general formula (III) are bio-based compounds.

13. A surfactant or salt thereof of the general formula (I) according to any one of claims 1 to 4 in an amount of at least 90 wt.-% based on the weight of the surfactant composition, and a surfactant of the general formula (IV) in an amount of 0.01 to 5.0 wt.-% based on the weight of the surfactant composition 【Chemistry 4】 or a salt thereof, R ２ and R ３ is defined as above, and R ４ is C １０ ~C ３４ -Alkyl and C １０ ~C ３４ -alkenyl, where R ４ The number of carbon atoms in R １ The surfactant composition according to claim 1, wherein the number of carbon atoms in the

14. below 2-[(3,7-dimethyloctyl)(methyl)amino]ethanol, 1-(3,7-dimethyloctyl)pyrrolidine, 3-dodecyl-8-oxa-3-azabicyclo[3.2.1]octane, 3-nonyl-8-oxa-3-azabicyclo[3.2.1]octane, and 3-(3,7-dimethyloctyl)-8-oxa-3-azabicyclo[3.2.1]octane, or a salt thereof.

15. A composition comprising at least one compound according to claim 14.

16. 16. Use of a compound according to claim 15 or a composition according to claim 13 or 14 as a surfactant.

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