Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
  • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
  • C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
  • C07C209/12—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/62—Quaternary ammonium compounds
  • C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms

Definitions

• the present invention is directed towards a method of preparing quaternary fatty ammonium polyalkoxylates having two symmetrical or nearly symmetrical alkoxylate chains in a one-pot alkoxylation reaction, the products obtained using this method, surfactant compositions comprising these products and their uses.
• alkoxylated fatty ammonium compounds belong to the class of cationic surfactants and are widely used for various applications, including fabric softening (see US 5,574,179, US 6,004,913), shampoos and hair conditioning (US 4,744,977, US 6,322,778, US 7,951,762), surface cleaners, e.g. household, car, etc.
• the method of the invention comprises a unique series of alkoxylation steps performed in a one pot reaction, which allows rigorous control of the degree of alkoxylation and thus the chain length distribution of the obtained quaternary fatty ammonium polyalkoxylates, while eliminating production of wasteful and hazardous side products.
• the method of the invention includes a three-step alkoxylation reaction which is performed under strict anhydrous conditions in a one-pot reaction and thus without the need for isolating and/or purifying intermediate products.
• the final quaternary fatty ammonium polyalkoxylates are characterized by a controlled structural composition having a symmetrical or nearly symmetrical distribution of long-chain alkoxylate substituents, i.e. through symmetrical extension the polyalkoxylates have two alkoxylate chains of equal length.
• the polyalkoxylates of the invention are thus of high purity and there is no need for any further purification.
• the present invention is directed towards a method for preparing a quaternary fatty ammonium polyalkoxylate having two symmetrical or nearly symmetrical alkoxylate chains (i.e. having two alkoxylate chains of equal length) in a one-pot reaction comprising the steps of (a) providing a fatty amine, (b) adding 2 to 4 Mol equivalents of a first alkylene oxide under anhydrous conditions and allowing alkoxylation to occur to obtain a symmetrical tertiary fatty amine ⁇ , ⁇ -alkoxylate, (c) adding at least 4 Mol equivalents, preferably 4 to 60 Mol equivalents of a second alkylene oxide under anhydrous conditions in the presence of a basic catalyst and allowing chain extension (of the symmetrical tertiary fatty amine N,N- alkoxylate obtained in step (b)) to occur to obtain a symmetrical tertiary fatty amine N,N- polyalkoxylate, (d) lowering the pH
• the quaternary fatty ammonium polyalkoxylate having 2 symmetrical alkoxylate chains is a quaternary fatty ammonium polyalkoxylate of formula I [RiR 2 R 3 N + -
• Ri is a linear or branched, saturated or unsaturated, aliphatic or aromatic, substituted or unsubstituted C(6-24) hydrocarbon radical or a mixture thereof,
• R 2 is a group of formula -CHR a -CHR b -0-(CHR a -CHR b -0) n H and R 3 is a group of formula - CHR c -CHR d -C CHR c -CHR d -OVH, n and m are an integer of from 4 to 60, e.g. 4 to 40, preferably 4 to 20, more preferably 5 to 15, most preferably 5 to 10, with the proviso that n and m are either the same integer or integers differing by 1 or 2,
• R a , Rb, R c , Rd, R e , Rf are independently of each other H or Me,
• p 0 or 1
• X is a counterion selected from the group consisting of species generated from a mineral acid or organic acid, in a one-pot reaction comprising the steps of:
• R 2 is a group of formula -CHR a -CHR b -0-(CHR a - CHR b -0) consentH and R 3 is a group of formula -CHR c -CHR d -0-(CHR c -CHR d -0) m H, groups R a , R b , R c , Ra are as defined above, and n and m are the same and an integer selected from 0, 1 or 2,
• step (c) adding at least 4 Mol equivalents, preferably 4 to 60 Mol equivalents of a second alkylene oxide under anhydrous conditions in the presence of a basic catalyst and allowing chain extension (of the tertiary fatty amine ⁇ , ⁇ -alkoxylate obtained in step (b)) to occur to obtain a tertiary fatty amine ⁇ , ⁇ -polyalkoxylate of formula III RiR 2 R 3 N, wherein R 1 is as defined above, R 2 is a group of formula -CHR a -CHRb-0-(CHR a -CHR b -0) n H and R 3 is a group of formula groups R a , R b , R c , R d are as defined above, and n and m are an integer of from 4 to 60, e.g. 4 to 40, preferably 4 to 20, more preferably 5 to 15, most preferably 5 to 10, with the proviso that n and m are either the same integer or integers differing by
• step (d) lowering the pH of the reaction mixture obtained in step (c) to a pH of 7 or less, preferably a pH of 2 to 4, and
• first and second and third alkylene oxide are independently of each other EO or PO, more preferably EO, and R a , R b , R c , Ra, e , R f are H.
• the fatty amine is a (C6-24)alkyl- or (C6-24)alkenylamine, preferably oleylamine.
• Typical embodiments of the various steps of the present methods include that the fatty amine in step (a) is dried in vacuo at a temperature of from 40° to 140°C, preferably 80° to 140°C, prior to subjecting it to step (b), that step (b) is performed at a pressure of 2.5 bar or less, that the basic catalyst in step (c) is selected from alkaline salts and alkali metal alkoxylates such as NaH, NaOH, NaOEt, NaOMe, KH, KOH, KOtBu, KOEt, CaO, CaH, Ca(OH) 2 ,Ca(OCH(CH 3 ) 2 ) 2 , preferably NaOH and KOH, and that the mineral acid or organic acid used in step (d) are preferably selected from hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, ace
• the present invention includes quaternary fatty ammonium polyalkoxylates of formula [RiR 2 R 3 N + -CHR e -CHRrO-(CHR e -CHR r O) p H] X " obtained according to a method of the invention, which distinguish themselves from the prior art by the designed symmetry of the alkoxylate chains R 2 and R 3 , as well as compositions comprising a quaternary fatty ammonium polyalkoxylate of formula [RiR 2 R 3 N -CHR e -CHR r O-(CHR e -
• the present invention also includes a surfactant composition comprising one or more quaternary fatty ammonium polyalkoxylates having two symmetrical alkoxylate chains (i.e.
• a surfactant composition wherein the one or more quaternary fatty ammonium polyalkoxylates are of formula I [R 1 R 2 R 3 N + -CHR e -CHRf-0-(CHR e -CHRrO) p H] X " , wherein Ri is a linear or branched, saturated or unsaturated, aliphatic or aromatic, substituted or unsubstituted C(6-24) hydrocarbon radical or a mixture thereof, R 2 is a group of formula -CHR a -CHR b -0-(CHR a - CHR b -0) ordinH and R 3 is a group of formula -CHR c -CHR d -0-(CHR c -CHR d -0) m H, n and m are an integer of from 4 to 60, e.g.
• n and m are either the same integer or integers differing by 1 or 2
• groups R a , R b , R c , R d are independently of each other H or Me, p is 0 or 1
• X is a counterion selected from the group consisting of species generated from a mineral acid or organic acid.
• the present invention also includes the use of a quaternary fatty ammonium polyalkoxylate of formula [RiR 2 R 3 N + -CHR e -CHRrO-(CHR e -CHRrO) p H] X " as obtained according to a method of the invention as softeners in fabric care, in personal care products, as deposit dispersants, and in agrochemical formulations.
• Figure 1 Structure of an exemplary quaternary, nearly symmetrical POE (8-10) C(9-22) fatty ammonium polyalkoxylate.
• Figure 2 13 C NMR of quaternized oleylamine of Example 1 (A) and comparative tertiary product (B).
• a representative structure is shown in Figure 1.
• the methods comprise the steps of (i) alkoxylating a primary fatty amine under anhydrous conditions in the absence of a catalyst using a suitable alkoxylation agent to obtain a symmetrical tertiary fatty amine N,N- alkoxylate, (ii) extending the N,N-alkoxylate groups by reacting the tertiary fatty amine ⁇ , ⁇ -alkoxylate with a suitable alkoxylation agent in the presence of a basic catalyst (under controlled temperature and pressure conditions) to obtain a symmetrical tertiary fatty amine ⁇ , ⁇ -polyalkoxylate, and (iii) reacting the symmetrical tertiary fatty amine ⁇ , ⁇ -polyalkoxylate with a suitable alkoxylation agent under neutral to acidic conditions to obtain the desired quaternary fatty ammonium polyalkoxylate.
• the present invention is directed towards a method of preparing quaternary fatty ammonium polyalkoxylates having 2 symmetrical alkoxylate chains in a one- pot reaction under anhydrous conditions comprising the steps of:
• step (b) adding 2 to 4 Mol equivalents of a first alkylene oxide under anhydrous conditions (and in the absence of a catalyst) and allowing alkoxylation to occur to obtain a symmetrical tertiary fatty amine N,N-alkoxylate, (c) adding at least 4 Mol equivalents, preferably 4 to 60 Mol equivalents, of a second alkylene oxide under anhydrous conditions in the presence of a basic catalyst and allowing chain extension (of the symmetrical tertiary fatty amine ⁇ , ⁇ -alkoxylate obtained in step (b)) to occur to obtain a symmetrical tertiary fatty amine N,N-polyalkoxylate,
• step (d) lowering the pH of the reaction mixture obtained in step (c) to a pH of 7 or less, preferably a pH of 2 to 4, and
• the obtained product may be used in situ or stored without any further purification.
• the quaternary fatty ammonium polyalkoxylate having 2 symmetrical alkoxylate chains has the formula I
• Ri is a linear or branched, saturated or unsaturated, aliphatic or aromatic, substituted or unsubstituted C(6-24) hydrocarbon radical or a mixture thereof,
• R 2 is a group of formula -CHR a -CHR b -0-(CHR a -CHR b -0) n H and R 3 is a group of formula - CHR e -CHR d -O- CHR c -CHR d -O ⁇ H,
• n and m are 4 to 60, e.g. 4 to 40, preferably 4 to 20, more preferably 5 to 15, most preferably 5 to 10, with the proviso that n and m are either the same integer or integers differing by 1 or 2,
• R a , Rb, R c , Rd, R e , R f are independently of each other H or Me, p is 0, 1, 2, 3 or 4, preferably 0 or 1, and X is a counterion selected from the group consisting of species generated from a mineral acid or organic acid, preferably a mineral acid.
• X is a counterion selected from the group consisting of species generated from a mineral acid or organic acid, preferably a mineral acid.
• R a , 3 ⁇ 4, R c , 3 ⁇ 4, R e , R f are H.
• the term "symmetrical" in context with the quaternary fatty ammonium polyalkoxylates of the invention indicates that the alkoxylation methods of the invention are performed under rigorous control of the degree of alkoxylation such that the alkoxylate chain substituents R 2 and R 3 of the tertiary fatty amine alkoxylate compounds obtained in steps (b) and (c) are symmetrically extended, i.e. the alkoxylate chains are of equal length. It is understood that the alkoxylate chains may be differing by one or two monomer units and thus may be fully or nearly symmetrical.
• n and m are either the same integer (in the case of symmetrical alkoxylate chains) or integers differing by 1 or 2 (in the case of nearly symmetrical alkoxylate chains).
• n and m are either the same integer (in the case of symmetrical alkoxylate chains) or integers differing by 1 or 2 (in the case of nearly symmetrical alkoxylate chains).
• Such a quaternary fatty ammonium polyalkoxylate of the invention having two symmetrical ethoxylate chains is herein also designated POE (4-60) C(6-24) fatty ammonium polyalkoxylate of the invention (i.e. with POE (4-60) indicating that the length of the two polyoxyethyelene (POE) chains is an integer from 4 to 60 and C(6-24) defining the hydrocarbon chain length of the fatty amine to be an integer from 6 to 24).
• POE polyoxyethyelene
• the compounds of the invention are hereinafter referred to as being symmetrical, which includes the term "nearly symmetrical".
• the symmetrical tertiary fatty amine ⁇ , ⁇ -alkoxylate obtained in step (b) is a compound of formula II RiR 2 R 3 N, wherein
• Ri is a linear or branched, saturated or unsaturated, aliphatic or aromatic, substituted or unsubstituted C(6-24) hydrocarbon radical or a mixture thereof
• R 2 is a group of formula -CHR a -CHR b -0-(CHR a -CHR b -0) admirH
• R 3 is a group of formula - CHR c -CHR d -0-(CHR c -CHR d -0) m H
• n and m are an integer selected from 0, 1 or 2, preferably 0 or 1
• R a , 3 ⁇ 4, R c , R d are independently of each other H or Me.
• a compound of formula II may be represented by the following structural formula:
• R a , R b , R c , R d are H.
• the symmetrical tertiary fatty amine ⁇ , ⁇ -polyalkoxylate obtained in step (c) is a compound of formula III RiR 2 R 3 N, wherein
• Ri is a linear or branched, saturated or unsaturated, aliphatic or aromatic, substituted or unsubstituted C(6-24) hydrocarbon radical or a mixture thereof,
• R 2 is a group of formula -CHR a -CHR b -0-(CHR a -CHR b -0) n H
• R 3 is a group of formula - CHR c -CHR d -0-(CHR c -CHR d -0) m H
• n and m are an integer of from 4 to 60, e.g. 4 to 40, preferably 4 to 20, more preferably 5 to 15, most preferably 5 to 10, with the proviso that n and m are either the same integer or integers differing by 1 or 2,
• R a , Rb, R c , Rd are independently of each other H or Me.
• a compound of formula III may be represented by the following structural formula:
• R a , R b , R c , Ra are H.
• the obtained product may be used in situ or stored without any further purification.
• one-pot reaction refers to a reaction comprising a series of steps that may be performed in a single reaction vessel.
• One-pot procedures are particularly desirable as they eliminate the need for isolation (e.g., purification) of intermediates while typically reducing the production of waste materials (e.g., solvents, impurities, side reaction products).
• waste materials e.g., solvents, impurities, side reaction products.
• Other advantages include ease of handling and typically reduction of overall reaction time.
• anhydrous refers to a water content of less than 1%, in particular less than 0.1%, preferably less than 0.05%, but does not exclude the possibility of the presence of some minor amounts of water arising from the reaction itself, such as water of crystallization arising from the catalyst.
• alkylene oxide refers to (Ci-C 6 )alkyl oxiranes such as ethylene oxide (EO), propylene oxide (PO) and butylene oxide (BO), preferably EO and PO, more preferably EO.
• alkoxylated as used herein in combination with fatty amine refers to the product obtained when a fatty amine has been reacted with at least one alkylene oxide, resulting in a fatty amine carrying as a substituent the corresponding ring opened reaction product of the at least one alkylene oxide.
• the alkylene oxide-substituent may consist of one or more alkylene oxide units that are linked via ether bonds.
• the first, second and third alkylene oxide used in steps (b), (c) and (e) may be the same or different, preferably they are the same, more preferably they are EO.
• m and n in compounds of formula I or III are an integer of from 4 to 60, e.g. 4 to 40, preferably 5 to 15, more preferably 5 to 10, most preferably about 8. It is understood, that the symmetry of the two alkoxylate chains indicates that m and n are either the same integer or integers differing by 1 or 2.
• the fatty amines that are used in the present methods as starting material are not limited and may be any one of animal based oils and fats derived from beef tallow, fish oil, lanolin, etc.; plant based oils and fats derived from coconut oil, palmoil, soybeanoil, etc.; synthetic fatty acid alkyl esters derived from a-olefins by means of using an oxo-synthesis method.
• the fatty amine is a primary amine of the formula 3 ⁇ 4- ⁇ 2 , wherein Ri is a linear or branched, saturated or unsaturated, aliphatic or aromatic, substituted or unsubstituted C(6-24) hydrocarbon radical or a mixture of different linear or branched, saturated or unsaturated, aliphatic or aromatic, substituted or unsubstituted C(6-24) hydrocarbon radicals.
• saturated refers to an alkyl fatty amine, which is a hydrocarbon radical having a fully saturated aliphatic or alicyclic backbone, i.e., with no double bonds.
• unsaturated refers to "the state in which not all of the available valence bonds along an alkyl chain are satisfied" (Hawley's Condensed Chemical Dictionary, 1 151 , 14th Edition, 2002, by John Wiley & Sons, Inc.). More specifically, the term “unsaturated” in reference to a fatty amine refers to an alkenyl fatty amine, which is a hydrocarbon radical having at least one double bond, preferably 1 to 3 double bonds in the hydrocarbon chain 3 ⁇ 4.
• substituted in reference to a fatty amine refers to substitution of the hydrocarbon chain Ri by groups selected from hydroxy, oxo, carboxyl, amino, Cl-C6-alkyl, Cl-C6-alkenyl and Cl-C6-alkoxyhydroxyl, and the like.
• the fatty amines are unsubstituted.
• Ri is a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having from 6 to 24 carbon atoms, preferably 12 to 24 carbon atoms, more preferably 12 to 20 carbon atoms.
• alkyl- or alkenyl-fatty groups of the fatty amines for use as starting materials in the methods of the invention include, but are not limited to, hexyl, heptyl, n-octyl, p-tert. octyl, n-nonyl-, p-tert.
• fatty amine also includes commercially available fatty amines such as Armeen® amines (available from Akzo Chemicals, Chicago, III.) such as Akzo's Armeen C, Armeen O, Armeen OL, Armeen T, Armeen HT, Armeen S and Armeen SD, wherein the letter designation relates to the fatty group, such as coco, oleyl, tallow, or stearyl groups, or Genamin® amines (available from Clariant) having e.g. stearyl, tallow fat or oleyl moieties.
• Suitable fatty amines can also be prepared from corresponding fatty acids or fatty alcohols according to methods well known in the art of organic synthesis.
• any amines derived from other specifically recited fatty alcohols and fatty acids are contemplated as well.
• Combinations of two or more fatty amines, and combinations of one or more fatty amines and one or more other lipid compounds also are contemplated.
• fatty amines comprising one or more double bonds may exist as cis- or trans-isomer or mixtures thereof.
• the skilled person will understand that unless stated specifically all isomeric structures (in pure form or as mixtures) are contemplated herein. Unless stated otherwise, structures as shown herein are only representative for all isomers.
• the fatty amine used as starting material is dried in vacuo at elevated temperatures.
• the term "under anhydrous conditions" includes drying the starting fatty amine to a water content of less than 1%, in particular less than 0.1%, preferably less than 0.05%, which is typically achieved by drying in vacuo at a temperature of from 40° to 140°C, preferably 80° to 140°C, for at least 15 minutes, preferably between 15 to 90 minutes before subjecting it to an alkoxylation reaction according to step (b).
• step (b) is performed by adding the alkylene oxide gradually to the dried fatty amine (to control the exothermicity and pressure build-up of the reaction). In another embodiment, step (b) is conducted at a pressure of 2.5 bar or less to control production of potential side products, preferably at a pressure between 1.0 and 2.5 bar.
• the temperature of the alkoxylation steps, i.e. during addition of the first, second and third alkylene oxide, is typically less than 150°C, such as 100 to 150°C, preferably 120 to 150°C.
• the addition of the basic catalyst and the neutralization step with the mineral or organic acid is typically performed at 60 to 80°C.
• alkoxylation in step (c) is performed using a basic catalyst.
• the term "basic catalyst” includes any catalysts which are basic or alkaline, preferably a basic salt of the alkali metals of Group I of the Periodic Table, e.g., sodium, potassium, rubidium, and cesium, or a basic salt of certain alkaline earth metals of Group II of the Periodic Table, e.g., calcium, strontium, barium, magnesium.
• Typical basic catalysts include alkaline salts and alkali metal alkoxylates such as NaH, NaOH, NaOEt, NaOMe, KH, KOH, KOtBu, KOEt, CaO, CaH, Ca(OH) 2 ,Ca(OCH(CH 3 ) 2 ) 2 , and mixtures thereof.
• the basic catalyst used in step (c) is KOH or NaOH,
• the catalysts may be employed at concentrations of about 0.01 wt% to about 1.5 wt%, preferably about 0.01 wt% to about 1.0 wt%, more preferably about 0.05 wt% to about 0.5 wt%, most preferably about 0.05 wt% to about 0.25 wt%, typically about 0.1 wt% based on the amount of fatty amine used.
• step (c) is carried out by first adding the basic catalyst, preferably at ambient temperature, and subsequently adding the second alkylene oxide, preferably at elevated temperatures.
• the pH in step (d) is lowered by using a mineral acid or organic acid, preferably a mineral acid.
• mineral acid refers to hydrochloric acid, hydrobromic acid, nitric acid, phosphoric acid, sulfuric acid, boric acid, hydrofluoric acid, perchloric acid, and the like, preferably hydrochloric acid, phosphoric acid, sulfuric acid, more preferably hydrochloric acid.
• organic acid includes, but is not limited to, formic acid, acetic acid, propionic acid, butyric or isobutyric acid, 2-ethylhexanoic acid, mono- or di- or trichloroacetic acid, mono- or di- or trifluoroacetic acid, a- or ⁇ - or ⁇ - chlorobutyric acid, lactic acid, glycolic acid, pyruvic acid, glyoxalic acid, acrylic acid and like monocarboxylic acids, methanesulfonic acid, toluenesulfonic acid and like sulfonic acids, oxalic acid, succinic acid, adipic acid, tartaric acid, citric acid and like polycarboxylic acids, preferably formic, acid acetic acid, lactic acid, 2-ethylhexanoic acid.
• the mineral acid or organic acid of choice may be used in an amount of less than 5 wt%, preferably less than 3 wt%, more preferably less than 2 wt%.
• the mineral acid may be used from 0.01 to 5 wt%, more preferably from 0.01 to 3 wt%, most preferably from 0.1 to 2 wt%, based on the amount of catalyst used.
• the present invention is directed towards a method for preparing a quaternary fatty ammonium polyalkoxylate of formula I [RiR 2 R 3 N + -CHR e -CHR f - 0-(CHR e -CHRrO) p H] X having 2 symmetrical alkoxylate chains, wherein
• Ri is a linear or branched, saturated or unsaturated, aliphatic or aromatic, substituted or unsubstituted C(6-24) hydrocarbon radical or a mixture thereof,
• R 2 is a group of formula -CHR a -CHR b -0-(CHR a -CHR b -0) n H and R 3 is a group of formula - CHR c -CHR d -0-(CHR c -CHR d -0) m H, n and m are an integer of from 4 to 60, e.g. 4 to 40, preferably 4 to 20, more preferably 5 to 15, most preferably 5 to 10, with the proviso that n and m are either the same integer or integers differing by 1 or 2,
• R a , Rb, R c , Rd, R e , Rf are independently of each other H or Me,
• p is 0 or 1
• X is a counterion selected from the group consisting of species generated from a mineral acid or organic acid, in a one-pot reaction comprising the steps of:
• R a , R , R c , Ra are as defined above, and n and m are the same and are an integer selected from 0, 1 or 2,
• step (c) adding at least 4 Mol equivalents, preferably 4 to 60 Mol equivalents of a second alkylene oxide, which is selected from EO or PO, preferably EO, under anhydrous conditions in the presence of a basic catalyst and allowing chain extension (of the tertiary fatty amine N,N- alkoxylate obtained in step (b)) to occur to obtain a tertiary fatty amine N,N- polyalkoxylate of formula III RiR 2 R 3 N, wherein Ri is as defined above, R 2 is a group of formula -CHR a -CHR b -0-(CHR a -CHR b -0) n H and R 3 is a group of formula -CHR c -CHRa- 0-(CHRc-CHRd-0) m H, groups R a , Rb, R c , 3 ⁇ 4 are as defined above, and n and m are an integer of from 4 to 60, e.g. 4 to 40
• step (d) lowering the pH of the reaction mixture obtained in step (c) to a pH of 7 or less, preferably a pH of 2 to 4, and
• the reaction mixture is subjected to an afterstirring time of typically up to 4 hours, preferably 0.5 to 2 hours, more preferably 1 hour, to allow for full conversion and complete reduction of pressure, thereby avoiding the formation of PEG sideproducts.
• the quaternary fatty ammonium polyalkoxylates obtained by the methods of the invention are characterized by a well-defined structural composition, which is indicated by having 2 symmetrical alkoxylate chains, and thus can be distinguished from corresponding polyalkoxylated compounds of the prior art, which typically show a statistical distribution of polyalkoxylate chains.
• step (b) replaces the two acidic H atoms in a symmetrical way by one or two hydroxyalkyl units under anhydrous conditions
• step (c) allows to extend the hydroxyalkyl units in a symmetrical way in the presence of a basic catalyst under anhydrous conditions
• step (e) is used for selectively quaternizing the tertiary alkoxylated fatty amine, i.e. without obtaining chain extension of the nearly symmetrical alkoxylate chains obtained in the first and second alkoxylation.
• the quaternary fatty ammonium polyalkoxylates of the invention may be used singly, or in combination with one another to form mixtures and/or in admixture with other components and additives to form compositions suitable for the intended use.
• the invention is also directed towards a surfactant composition comprising quaternary fatty ammonium polyalkoxylates of the invention having two symmetrical alkoxylate chains as defined above. More specifically, typically at least 90%, preferably at least 95%, more preferably at least 98% of the quaternary fatty ammonium polyalkoxylates of the invention have symmetrical alkoxylate chains.
• the surfactant composition of the present invention comprise quaternary fatty ammonium polyalkoxylates with two symmetrical alkoxylate chains of the formula [R 1 R 2 R 3 N + -CHR e -CHRrO-(CHR e -CHR r O) p H] X " as defined above, i.e. wherein 3 ⁇ 4 is a linear or branched, saturated or unsaturated, aliphatic or aromatic, substituted or unsubstituted C(6-24) hydrocarbon radical or a mixture thereof,
• R 2 is a group of formula -CHR a -CHR b -0-(CHR a -CHR b -0) n H and R 3 is a group of formula -
• n and m are an integer of from 4 to 60, e.g. 4 to 40, preferably 4 to 20, more preferably 5 to 15, most preferably 5 to 10, with the proviso that n and m are either the same integer or integers differing by 1 or 2,
• R a , Rb, R c , Rd, R e , R f are independently of each other H or Me, p is 0 or 1 , and
• the surfactant composition of the invention comprises one or more fatty ammonium polyalkoxylates of the invention having two symmetrical alkoxylate chains in an amount of 0.001 to 99.99 %, preferably 50.0 to 99.99%.
• the surfactant composition of the present invention comprises quaternary fatty ammonium polyalkoxylates with two symmetrical alkoxylate chains of the formula [RiR 2 R 3 N + -CHR e -CHR r O-(CHR e -CHRrO) p H] X " as defined above, wherein R a , R b ,
• R c , Ra, R e , R f are H.
• the mineral acid is selected from hydrochloric acid, hydrobromic acid, nitric acid, phosphoric acid, sulfuric acid, boric acid, hydrofluoric acid, perchloric acid
• the organic acid is selected from formic acid, acetic acid, 2- ethylhexanoic acid, lactic acid.
• Other components that may or may not be present in the surfactant compositions of the invention include, but are not limited to, nonionic, cationic or anionic surfactants (in amounts typically used for the intended application).
• Optional additives include, but are not limited to, pH adjusting agents and pH buffers including organic and inorganic salts; non-aqueous solvents, perfumes, perfume carriers, optical brighteners, coloring agents such as dyes and pigments, opacifying agents, hydrotropes, antifoaming agents, viscosity modifying agents such as thickeners, enzymes, anti-spotting agents, anti-oxidants, anti-corrosion agents as well as others not specifically elucidated here.
• the quaternary fatty ammonium polyalkoxylates of the invention may be used in combination with a biocidal agent, such as dodecylguanidine hydrochloride; methylene bis (thiocyanate); n-alkyl dimethylbenzylammonium chloride; glutaraldehyde; 2,2-dibromo-3-nitrilo propionamide; 5-chloro-2-methyl-4-isothiazolin-3-one; 2-methyl-4-isothiazolin-3-one; or 2- bromo-2-nitropropane-l,3-diol; sodium or calcium hypochlorite; sodium bromide; P-bromo-p- nitrostyrene; oxazolidines; chromated copper arsenate; zinc pyrithione; copper pyrithione; a carbamate; a halohydantoin; dinonylsulfosuccinate; sodium
• the present invention is also directed towards uses of the polyalkoxylates of the invention (or compositions thereof) in various applications and endproducts. They may be used as softeners, for example in detergent formulations, such as liquid and powdered laundry detergents, liquid and sheet fabric softeners. Thus, the present invention also contemplates detergent formulations comprising a compound of the invention.
• a further application includes their use in personal care products such as liquid cleansing products, conditioning bars, oral care products, hair care products, cosmetics, and the like.
• personal care products such as liquid cleansing products, conditioning bars, oral care products, hair care products, cosmetics, and the like.
• the present invention also contemplates personal care products comprising a compound of the invention.
• the compounds of the invention are particularly efficient in deposit control applications, especially in preventing (or removing) organic or inorganic attachment to surfaces of any article and subsequent biofilm formation and any corrosion effects, which may be found in various environments including biological, medical, commercial (textiles), industrial (food, paper, transport industries, construction, metal, chemical, oil and gas, power, petrochemical), and other processing operations.
• Their use may be for example in hard and soft surface detergents, sanitizers and disinfectants, especially for cleaning surfaces contaminated with e.g. of gram positive and/or gram negative bacteria.
• Surfaces to be treated include (i) soft surfaces having a softer, highly flexible material such as fabric, carpet, leather, paper, wood, rubber, hair, and skin, and (ii) hard surfaces such as glazed and unglazed tile, porcelain, ceramics as well as stone including marble, granite, concrete, and other stones surfaces; composite materials, glass; metals and metal alloys; synthetic or natural polymers, such as plastics e.g. PE (polyethylene), PP (polypropylene), PA (polyamides), PVC (polyvinylchloride), polyester, vinyl; fiberglass, Formica, Corian and other hard surfaces known to the industry. Specific nonlimiting examples of such surfaces can be found in e.g.
• water handling/processing industries include plumbing, tubing, and support components involved with water handling, sewerage discharges, paper pulping operations, re-circulating water systems (such as air conditioning systems, a cooling water systems, and the like), and in other water bearing, handling, processing, and collection systems.
• Other surfaces that have contacts with water may be found in household environment and include in particular surfaces found in washrooms (e.g. shower stalls, bathtubs and bathing appliances, toilets, bidets, drains, wall and flooring surfaces and the like), in kitchens (e.g. cabinets and countertop surfaces, walls and floor surfaces), etc.
• washrooms e.g. shower stalls, bathtubs and bathing appliances, toilets, bidets, drains, wall and flooring surfaces and the like
• kitchens e.g. cabinets and countertop surfaces, walls and floor surfaces
• industries or environments where surfaces may be found include e.g.
• the present invention also contemplates deposit control formulations comprising a compound of the invention.
• the compounds of the invention may be used as additives in agrochemical formulations to promote penetration of an agrochemically active compound(s) of choice into the plant and thereby enhance the activity of the active compound(s).
• the compounds of the invention may be able to increase wettability of the formulation and thus lead to a better distribution of the spray coating on the surface of the plant, which will increase the availability of the active compound (which have to penetrate into the plant to be able to unfold their systemic activity evenly throughout the plant).
• agrochemical formulations comprising at least one agrochemically active compound and at least one compound of the invention.
• the agrochemically active compound may be a biocidal compound, i.e. a chemical substance capable of killing or inhibiting growth, division, reproduction, or spread of microorganisms, such as bacteria, algae, and fungi used in the field of agriculture (which includes any type of intensive cultivation of land).
• biocidal compounds include e.g. pesticides, such as for example herbicides, insecticides, fungicides, plant growth regulators, rodenticides, algicides, moluscicides and miticides, as well as antimicrobials, such as for example germicides, antibiotics, antibacterials, antivirals, antifungals, antiprotozoals and antiparasites.
• agrochemical formulations may include as agrochemically active ingredient a pesticide, such as glufosinate (salts), glyphosate (salts), paraquat, diquat, dicamba, fomesafen, imazethapyr, imazaquin, imazapyr, propamocarb, clopyralyd and bentazone and the like.
• a pesticide such as glufosinate (salts), glyphosate (salts), paraquat, diquat, dicamba, fomesafen, imazethapyr, imazaquin, imazapyr, propamocarb, clopyralyd and bentazone and the like.
• the agrochemically active compound may be a fertilizer, preferably a partially water-soluble fertilizer, for example a foliar fertilizer, such as urea or foliar macro- or microelement fertilizer, including chelates.
• a fertilizer preferably a partially water-soluble fertilizer, for example a foliar fertilizer, such as urea or foliar macro- or microelement fertilizer, including chelates.
• Suitable agrochemical formulations may also include a combination of agrochemically active compounds, such as a combination of herbicides, insecticides and fungicides, and, if desired, fertilizers.
• agrochemically active compounds such as a combination of herbicides, insecticides and fungicides, and, if desired, fertilizers. Examples of suitable agrochemicals and mixtures of agrochemicals are listed in standard works of reference and will be known to the skilled person.
• an agrochemical formulation is a water-based formulation, preferably in form of a soluble concentrate formulation.
• compositions for use in the methods of the invention are preferably corrosion-resistant Hastelloy® types, glass or ceramic as materials.
• Example 1 Preparation of a quaternized (POE 8.5 oleylamine 1.
• thermo-jacket Attached to a circulation thermostat
• thermocouple is charged with 534g distilled oleylamine (e.g. Genamin OL 100D, Clariant MW 267.56, 2 mol).
• the oleylamine was vacuum dried for approx. 30 minutes at 130°C until water content is below 0.05%.
• the reactor was heated to about 150°C, and 176g ethylene oxide (MW 44.06 g/mol, 4 mol) was added. After the ethylene oxide has been consumed, stirring was continued for additional 30 minutes whilst cooling down to 90°C. Then the mixture was charged with 2.24g potassium hydroxide (50% aq. solution).
• the mixture was vacuum dried for approx. 30 minutes at 130°C.
• the temperature was raised to 150°C and 1320g of ethylene oxide (30 mol) was fed to the reactor.
• the reaction temperature at this point was 145°C.
• stirring was continued for additional 30 minutes whilst cooling down to 60°C.
• 231.2g of hydrochloric acid (32%) was added to the mixture to achieve a pH of 3.
• the mixture was vacuum dried for 1 hour at 130°C until the water content was below 0.05%.
• the reactor was heated to 140°C, and 88g of ethylene oxide was added. After the reaction is completed, an afterstirring time of one hour is applied.
• the final pH of the product (10% in deionised water) was approx. 8.5.
• the product obtained was a homogeneous, odourless, slightly brownish, clear solution.
• the yield was approx. 92%.
• Analysis of structure and purity by 13 C-NMR showed that the total 18 mol of ethylene oxide were distributed symmetrically between the two chain, giving a ratio of alkyleneoxide units of the three substituents of 8.5 : 8.5 : 1.
• the amine value (which indicates the total amount of amines expressed by the number of milligrams of KOH equivalent to the hydrochloric acid required to neutralize one gram of a sample) of an aliquot (i.e. prior to quatemization) was ca.
• Example 2 Comparative example of tertiary fatty amine (as described in DE-A-20 52 321):
• thermo-jacket Attached to a circulation thermostat
• thermocouple is charged with 534g distilled oleylamine (e.g. Genamin OL 100D, Clariant MW 267.56, 2 mol).
• 534g distilled oleylamine e.g. Genamin OL 100D, Clariant MW 267.56, 2 mol
• 36g of deionised water (10 mol) is added.
• the mixture became viscous whilst stirring.
• the reactor was evacuated for approx. 30 minutes at room temperature. Upon heating the mixture became fluid again.
• 70°C 160g ethylene oxide (MW 44.06 g/mol, 3.6 mol) was added. After additional 120g ethylene oxide the mixture started foaming and became viscous again.
• Example 3 Characterization (a) 13 C-NMR: The assignment of the peaks and thus proof of structure was confirmed by comparing C- NMR data of the quaternary oleylamine of Example 1 ( Figure 2: A) with the tertiary amine of the comparative Example 2 ( Figure 2: B). Major differences were observed in the range of 45 to 75 ppm, while aliphatic peaks (0 to 35 ppm) were in agreement for both compounds. As expected, one difference was found for the terminal C-atom of a PEG unit (peaks at 72.6 and 61.5 ppm). The low intensity of these peaks for the compound of Example 1 indicated an equimolar concentration, while the much higher intensity for the tertiary compound indicated a higher concentration.
• Example 1 The compound of Example 1 was subjected to the evaluation of the aerobic biodegradability in aqueous media according to OECD 30 IF. The results are shown in Table 1 in comparison to three reference compounds. The compounds of the invention showed high biodegradability of typically > 60%.
• the surface active biocide (didecyldimethylammonium chloride) showed a profound biocidal effect at a concentration of 30 ppm and 100 ppm. It induced a reduction in the live germ count by a factor of 10 5 in the test germs Pseudomonas aeruginosa ATCC 15442 (gram negative) and Staphylococcus aureus ATCC 6538 (gram positive) within both 30 and 60 minutes. After 24 hours the number of remaining germ colonies had again increased by a factor of 10 4 .
• compound 1 could effectively and safely prevent biofilm formation of Pseudomonas putida in the same range as the two commercially available reference products.

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