ALKOXYLATED POLYALKYLENE IMINES OR ALKOXYLATED POLYAMINES WITH A TERMINAL POLYBUTYLENE OXIDE BLOCK

Abstract

The present invention relates to an alkoxylated polyalkylene imine or an alkoxylated polyamine according to the general formula (I) (I), in which the variables E, R, B, y and z are defined below. The present invention further relates to a process for preparing such alkoxylated polyalkylene imines or alkoxylated polyamines as well as to the use of such compound within, for example, cosmetic formulations.

##STR00001##

Claims

1. An alkoxylated polyalkylene imine or alkoxylated polyamine of the general formula (I) ##STR00021## in which the variables are each defined as follows: R represents identical or different, linear or branched C.sub.2-C.sub.12 alkylene radicals or an etheralkyl unit of the following formula (III): ##STR00022##  in which the variables are each defined as follows:  R.sup.10, R.sup.11, R.sup.12 represent identical or different, linear or branched C.sub.2-C.sub.6-alkylene radicals and  d is an integer having a value in the range of 0 to 50; B represents a continuation of the alkoxylated polyalkylene imine by branching; y and z are each an integer having a value in the range of 0 to 150, E represents identical or different alkylenoxy units of the formula (II) ##STR00023##  in which the variables are each defined as follows: R.sup.1 represents 1,2-butylene or 1,2-isobutylene; R.sup.2 represents hydrogen, C.sub.1-C.sub.22-alkyl or C.sub.7-C.sub.22 aralkyl; m is an integer having a value of at least 20; n is an integer having a value of at least 3.

2. The alkoxylated polyalkylene imine or alkoxylated polyamine according to claim 1, wherein R represents identical or different, linear or branched C.sub.2-C.sub.12-alkylene radicals.

3. The alkoxylated polyalkylene imine or alkoxylated polyamine according to claim 1, wherein within formula (II) the variables are each defined as follows: R.sup.1 represents 1,2-butylene; R.sup.2 represents hydrogen or C.sub.1-C.sub.4-alkyl; m is an integer having a value in the range of 20 to 50; n is an integer having a value in the range of 3 to 20.

4. The alkoxylated polyalkylene imine or alkoxylated polyamine according to claim 1, wherein the weight average molecular weight (Mw) of the polyalkylene imine backbone or of the polyamine backbone, determined by gel permeation chromatography, lies in the range of 50 to 10 000 g/mol.

5. The alkoxylated polyalkylene imine according to claim 1, wherein the variables are each defined as follows: R is ethylene or propylene; the sum of y+z is an integer having a value in the range of 9 to 120.

6. The alkoxylated polyalkylene imine according to claim 5, wherein R is ethylene or propylene; the sum of y+z is an integer having a value in the range of 10 to 20; R.sup.1 represents 1,2-butylene; R.sup.2 represents hydrogen or C.sub.1-C.sub.4-alkyl; m is an integer having a value in the range of 20 to 50; n is an integer having a value in the range of 3 to 20.

7. The alkoxylated polyalkylene imine according to claim 5, wherein the variables are each defined as follows: R is ethylene the sum of y+z is an integer having a value in the range of 10 to 20; R.sup.1 represents 1,2-butylene; R.sup.2 represents hydrogen; m is an integer having a value in the range of 22 to 25; n is an integer having a value in the range of 4 to 7.

8. The alkoxylated polyamine according to claim 1, wherein y and z are both 0, R represents identical or different, linear or branched C.sub.2-C.sub.12 alkylene radicals or an etheralkyl unit according to formula (III), wherein d is from 1 to 5, and R.sup.10, R.sup.11, R.sup.12 are independently selected from linear or branched C.sub.3 to C.sub.4 alkylene radicals.

9. The alkoxylated polyamine according to claim 8, wherein R.sup.1 represents 1,2-butylene; R.sup.2 represents hydrogen or C.sub.1-C.sub.4-alkyl; m is an integer having a value in the range of 20 to 50; n is an integer having a value in the range of 3 to 20.

10. The alkoxylated polyamine according to claim 8, wherein R is linear hexamethylene; R.sup.1 represents 1,2-butylene; R.sup.2 represents hydrogen; m is an integer having a value in the range of 22 to 25; n is an integer having a value in the range of 4 to 7.

11. The alkoxylated polyalkylene imine or alkoxylated polyamine according to claim 1, wherein up to 100% of the nitrogen atoms present in the alkoxylated polyalkylene imine or alkoxylated polyamine are quaternized, and the degree of quaternization of the nitrogen atoms present in the alkoxylated polyalkylene imine or alkoxylated polyamine lies in the range of 10% to 95%.

12. Use of the alkoxylated polyalkylene imine or alkoxylated polyamine according to claim 1 in cosmetic formulations, as crude oil emulsion breaker, in pigment dispersions for ink jet inks, formulations for electro plating, in cementitious compositions.

13. A process for preparing an alkoxylated polyalkylene imine or an alkoxylated polyamine according to claim 1, wherein a polyalkylene imine backbone or a polyamine backbone is first reacted with ethylene oxide and then with butylene oxide in order to obtain the respective alkoxylated compounds.

14. A process according to claim 13 in which per mol of N—H functionalities in the polyalkylene imine or polyamine the polyalkylene imine backbone or polyamine backbone is reacted with at least 20 moles ethylene oxide and then with at least 3 moles butylene oxide.

15. A process according to claim 13, in which the alkoxylated polyalkylene imine or the alkoxylated polyamine is additionally quaternized.

Description

EXAMPLES

[0151] In the examples, the following abbreviations are used:

EO ethylene oxide
BUO butylene oxide
PEI600 polyethylene imine with an average molecular weight of 600 g/mol
x EO/NH x mole ethylene oxide per mole of NH-functionality
y BUO/NH y mole butylene oxide per mole of NH-functionality

Synthesis:

Example 1

[0152] polyethylene imine, molecular weight 600 g/mol, alkoxylated with 24 mole ethylene oxide and 4 mole 1,2-butylene oxide per NH functionality.

[0153] Step 1a) polyethylene imine, molecular weight 600 g/mol, alkoxylated with 1 mole ethylene oxide per NH functionality

[0154] A 5 l autoclave was charged with 665.0 g of a polyethylenimine with an average molecular weight of 600 g/mol and 33.3 g water. The reactor was purged three times with nitrogen and heated to 110° C. 680.5 g ethylene oxide were added within 13 hours. To complete the reaction, the reaction mixture was allowed to post-react for 5 hours. Water and volatile compounds were removed in vacuo (20 mbar) at 90° C. A highly viscous yellow oil (1340.0 g, pH: 11,05 (5% in water)) was obtained.

[0155] Step 1b) polyethylene imine, molecular weight 600 g/mol, alkoxylated with 24 mole ethylene oxide per NH functionality

[0156] Product from step 1a) (101.3 g) and 5.1 g potassium hydroxide (50% in water) was placed in a 2 l autoclave. The mixture was heated under vacuum (<10 mbar) to 120° C. and stirred for 2 hours to remove water. The reactor was purged three times with nitrogen and the mixture was heated to 140° C. 1178.3 g ethylene oxide were added within 8 hours. To complete the reaction, the mixture was allowed to post-react for 3 hours. Volatile compounds were removed in vacuo. 1275.0 g of a light brown solid were obtained.

[0157] Step 1c) polyethylene imine, molecular weight 600 g/mol, alkoxylated with 24 mole ethylene oxide and 4 mole butylene oxide per NH functionality

[0158] Product from step 1b) (577.0 g) and 0.6 g potassium hydroxide (50% in water) was placed in a 2 l autoclave. The mixture was heated under vacuum (<10 mbar) to 120° C. and stirred for 2 hours to remove water. The reactor was purged three times with nitrogen and the mixture was heated to 140° C. 156.2 g butylene oxide were added within 2 hours. To complete the reaction, the mixture was allowed to post-react for 5 hours. Volatile compounds were removed in vacuo at 90° C. 704.0 g of a light brown oil were obtained (cloud point 43° C. (1% in water)).

Example 2

[0159] polyethylene imine, molecular weight 600 g/mol, alkoxylated with 24 mole ethylene oxide and 6 mole 1,2-butylene oxide per NH functionality.

[0160] Step 2c) polyethylene imine, molecular weight 600 g/mol, alkoxylated with 24 mole ethylene oxide and 6 mole butylene oxide per NH functionality

[0161] Product from example 1, step 1b) (536.8 g) and 0.8 g potassium hydroxide (50% in water) was placed in a 2 l autoclave. The mixture was heated under vacuum (<10 mbar) to 120° C. and stirred for 2 hours to remove water. The reactor was purged three times with nitrogen and the mixture was heated to 140° C. 217.5 g butylene oxide were added within 2 hours. To complete the reaction, the mixture was allowed to post-react for 5 hours. Volatile compounds were removed in vacuo at 90° C. 735.0 g of a light brown oil were obtained (cloud point 27° C. (1% in water)).

Comparative Example 3 (CE3)

[0162] polyethylene imine, molecular weight 600 g/mol, alkoxylated with 4 mole 1,2-butylene oxide and 24 mole ethylene oxide per NH functionality.

[0163] Step 3a): polyethylene imine, molecular weight 600 g/mol, alkoxylated with 1 mole 1,2-butylene oxide per NH functionality

[0164] A 2 l autoclave was charged with 430.0 g of a polyethylenimine with an average molecular weight of 600 g/mol and 21.5 g water. The reactor was purged three times with nitrogen and heated to 120° C. 721.1 g 1,2-butylene oxide were added within 11 hours. To complete the reaction, the reaction mixture was allowed to post-react for 10 hours. Water and volatile compounds were removed in vacuo (20 mbar) at 90° C. for 3 hours. A highly viscous yellow oil (1151.0 g) was obtained.

[0165] Step 3b): polyethylene imine, molecular weight 600 g/mol, alkoxylated with 4 mole 1,2-butylene oxide per NH functionality

[0166] Product from step 3a) (345.3 g) and 4.23 g potassium hydroxide (50% in water) was placed in a 2 l autoclave. The mixture was heated under vacuum (<10 mbar) to 120° C. and stirred for 2 hours to remove water. The reactor was purged three times with nitrogen and the mixture was heated to 140° C. 648.9 g 1,2-butylene oxide were added within 11 hours. To complete the reaction, the mixture was allowed to post-react for 10 hours. Volatile compounds were removed in vacuo. 995.0 g of a yellow viscous oil were obtained.

[0167] Step 3c): polyethylene imine, molecular weight 600 g/mol, alkoxylated with 4 mole 1,2-butylene oxide and 24 mole ethylene oxide per NH functionality

[0168] Product from step 3b) (232.0 g) and 3.15 g potassium hydroxide (50% in water) was placed in a 2 l autoclave. The mixture was heated under vacuum (<10 mbar) to 120° C. and stirred for 2 hours to remove water. The reactor was purged three times with nitrogen and the mixture was heated to 140° C. 740.0 g ethylene oxide were added within 16 hours. To complete the reaction, the mixture was allowed to post-react for 5 hours. Volatile compounds were removed in vacuo. 974.0 g of a light brown solid were obtained.

Examples for the Use in Laundry Detergents

[0169] Technical stains PC-S-94, w-20D and PC-S-132 were purchased from CFT (Center for Testmaterials, The Netherlands). The stains were washed for 30 min in a launder-o-meter (manufactured by SDL Atlas) at 30° C. using per canister 500 mL of washing solution, 20 metal balls and ballast fabrics. The washing solution contained 2000 ppm of detergent composition (table 1). Water hardness was 1 mM (Ca2+:Mg2+ was 4:1). Additives were added to the washing solution of each canister separately and in the amount as detailed below. After addition the pH value was re-adjusted to the pH value of washing solution without additive.

[0170] Standard colorimetric measurement was used to obtain L*, a* and b* values for each stain before and after the washing. From L*, a* and b* values the stain removal index (SRI) was calculated according to ASTM Designation: D4265-14.

[0171] In the following examples, the individual ingredients within the cleaning compositions are expressed as percentages by weight of the cleaning compositions.

[0172] The following laundry detergent compositions are prepared by traditional means known to those of ordinary skill in the art by mixing the listed ingredients.

Examples

Example 1: PEI600+24 EO/NH+4 BuO/NH

Example 2: PEI600+24 EO/NH+6 BuO/NH

Comparative Example CE3: PEI600+4 BuO/NH+24 EO/NH

[0173] The examples above are added as additives to the detergent composition as shown in table 1 and employed as a laundry detergent using a launder-o-meter as shown in table 2.

TABLE-US-00001 TABLE 1 Detergent Dodecylbenzenesulfonate 6.9 g C12C14-fatty alcohol 11.3 g ethersulfate (2 EO), sodium salt, 70% aqueous solution KOH to pH 8.5 C13C15-oxo alcohol 1.0 g ethoxylate (7 EO) 1,2 Propylenglykol 6.0 g Ethanol 2.0 g water to 100 g

TABLE-US-00002 TABLE 2 2000 ppm detergent have been used together with 25 ppm of additive. 30° C., hardness: 1 mM. Stain Stain Stain Average of PCS-132/ PCS-94/ wfk20D/ three stains/ Additive [SRI] [SRI] [SRI] [SRI] none 22.9 26.1 23.8 24.3 Example 1 28.7 38.8 45.6 37.7 Example 2 28.5 41.1 50.9 40.1 CE3 25.6 34.7 30.9 30.4

[0174] As can be seen from table 2, stains can be removed more efficiently (higher SRI values) by employing a detergent composition containing compounds according to the present invention (examples 1 and 2) having a terminal polybutylene oxide block, compared to a composition containing comparative example 3 instead, wherein the polybutylene oxide block is not a terminal block, but the polybutylene oxide block is at a different position within the respective alkoxylated compound.

[0175] In the following, illustrative examples for specific cleaning compositions are provided. The alkoxylated polyalkylene imines or alkoxylated polyamines according to the present invention, for example, the specific compounds as described above in the context of examples 1 or 2, are added to those illustrative examples of cleaning compositions in a suitable amount known to a person skilled in the art.

[0176] Illustrative Example, Hand Dish Washing Compositions:

TABLE-US-00003 Ingredient Composition 1 Composition 2 (active wt %) (wt %) (wt %) C.sub.12-13AE.sub.0.6S anionic 21.5% 21.2% surfactant (Avg. branching: 33.44%) C.sub.12-14 dimethyl amine  7.2% — oxide CAP-betaine —  7.0% (Empigen BS/PG3) Alcohol ethoxylate —  0.5% nonionic surfactant (Neodol 91/8) Ethanol  1.9%  1.9% NaCl  0.7%  0.7% Na-citrate   1%   1% Polypropyleneglycol 0.55% 0.55% (MW2000) Water + minor Balance Balance ingredients (perfume, to 100% to 100% dye, preservatives) pH (at 10% product 9.0 9.0 concentration in demineralized water—with NaOH/ HCl trimming)

[0177] Illustrative Example, Water-Soluble Laundry Detergent Unit Dose Pouch:

[0178] A water-soluble unit dose laundry detergent pouch comprising a polyvinyl alcohol or polyvinyl alcohol copolymer-based water-soluble film, preferably wherein the film is a blend of polyvinyl alcohol homopolymers and/or polyvinyl alcohol copolymers, and a liquid laundry detergent comprising:

TABLE-US-00004 Composition Ingredient (active wt %) 3 (wt % Linear C.sub.9-C.sub.15 alkylbenzene sulfonic acid   15-25 C.sub.12-15 ethoxylated alkyl sulphate with an   5-20 average degree of ethoxylation of 3 C.sub.12-14 fatty alcohol ethoxylate having an   2-10 average degree of ethoxylation of 7 Citric Acid  0.5-2 Fatty acid   4-10 Chelants  0.5-2.5 Cleaning polymers (selected from CMC,   4-10 polyester terephthalate (preferably anionically modified), amphiphilic graft copolymer, ethoxylated polyethyleneimine or a mixture thereof) Enzymes (selected from amylase, protease, 0.01-1 lipase, xyloglucanase or a mixture thereof) Brightener 49 0.05-1 Structurant (preferably hydrogenated castor 0.05-0.5 oil) Solvent system (selected from propanediol,   10-30 glycerol, ethanol, dipropyleneglycol, tripropyleneglycol, polyetheyleneglycol, polypropyleneglycol) Water   5-15 Perfume  0.5-2 Perfume capsule  0.5-2 Aesthetic dye, opacifier or a mixture thereof  0.5-2 Mono-ethanolamine, NaOH or mixture   5-15 thereof Other laundry adjuncts/minors (incl. to 100 preservatives, antioxidants)

[0179] Illustrative Example, Liquid Laundry Detergent Compositions:

TABLE-US-00005 Ingredient Composition 4 Composition 5 Composition 6 (active wt %) (wt %) (wt %) (wt %) C.sub.12-.sub.14AE.sub.1-3S 13 8.3 10 C.sub.11-.sub.13LAS 3 5.5 6.5 Neodol  ® 25-7 1.4 4 7 alcohol Citric acid 0 2 1.7 Boric acid 0 2 1.9 C.sub.12-.sub.18 fatty acid 1.5 1.2 1.3 Na-DTPA 0.06 0.2 0.4 Propylene glycol 0 1.2 2.5 Calcium chloride 0 0 0.06 Silicone emulsion 0 0.0025 0.0025 Monoethanolamine 0.096 0.096 0.096 NaOH Up to pH 8 Up to pH 8 Up to pH 8 Tinosan  ® HP100 0.25 0.25 0.25 Perfume 0.15 0.15 0.35 microcapsule Hydrogenated 0.12 0.12 0.12 castor oil Brightener 0 0.06 0.06 Protease 0 0 0.45 Amylase 0 0 0.08 Dye 0 0.002 0.002 Neat perfume oil 0 0.6 0.6 Water to 100 to 100 to 100

[0180] Illustrative Example, Solid Free-Flowing Particulate Laundry Detergent Composition:

TABLE-US-00006 Ingredient Composition 7 (wt %) Anionic detersive surfactant (such as from 8 wt % to 15 wt % alkyl benzene sulphonate, alkyl ethoxylated sulphate and mixtures thereof) Non-ionic detersive surfactant (such as from 0.1 wt % to 4 wt % alkyl ethoxylated alcohol) Cationic detersive surfactant (such as from 0 wt % to 4 wt % quaternary ammonium compounds) Other detersive surfactant (such as from 0 wt % to 4 wt % zwiterionic detersive surfactants, amphoteric surfactants and mixtures thereof) Carboxylate polymer (such as co- from 0.1 wt % to 4 wt % polymers of maleic acid and acrylic acid and/or carboxylate polymers comprising ether moieties and sulfonate moieties) Polyethylene glycol polymer (such as a from 0 wt % to 4 wt % polyethylene glycol polymer compris- ing polyvinyl acetate side chains) Polyester soil release polymer (such as from 0 wt % to 2 wt % Repel-o-tex and/or Texcare polymers) Cellulosic polymer (such as from 0.5 wt % to 2 wt % carboxymethyl cellulose, methyl cellulose and combinations thereof) Other polymer (such as care polymers) from 0 wt % to 4 wt % Zeolite builder and phosphate builder from 0 wt % to 4 wt % (such as zeolite 4A and/or sodium tripolyphosphate) Other co-builder (such as sodium citrate from 0 wt % to 3 wt % and/or citric acid) Carbonate salt (such as sodium from 0 wt % to 20 wt % carbonate and/or sodium bicarbonate) Silicate salt (such as sodium silicate) from 0 wt % to 10 wt % Filler (such as sodium sulphate and/or from 10 wt % to 70 wt % bio-fillers) Source of hydrogen peroxide (such as from 0 wt % to 20 wt % sodium percarbonate) Bleach activator (such as tetraacetyl- from 0 wt % to 8 wt % ethylene diamine (TAED) and/or nonanoyloxybenzenesulphonate (NOBS)) Bleach catalyst (such as oxaziridinium- from 0 wt % to 0.1 wt % based bleach catalyst and/or transition metal bleach catalyst) Other bleach (such as reducing bleach from 0 wt % to 10 wt % and/or pre-formed peracid) Photobleach (such as zinc and/or from 0 wt % to 0.1 wt % aluminium sulphonated phthalocyanine) Chelant (such as ethylenediamine-N'N'- from 0.2 wt % to 1 wt % disuccinic acid (EDDS) and/or hydroxyethane diphosphonic acid (HEDP)) Hueing agent (such as direct violet 9, from 0 wt % to 1 wt % 66, 99, acid red 50, solvent violet 13 and any combination thereof) Brightener (C.I. fluorescent brightener from 0.1 wt % to 0.4 wt % 260 or C.I. fluorescent brightener 351) Protease (such as Savinase, Savinase from 0.1 wt % to 0.4 wt % Ultra, Purafect, FN3, FN4 and any combination thereof) Amylase (such as Termamyl, Termamyl from 0 wt % to 0.2 wt % ultra, Natalase, Optisize, Stainzyme, Stainzyme Plus and any combination thereof) Cellulase (such as Carezyme and/or from 0 wt % to 0.2 wt % Celluclean) Lipase (such as Lipex, Lipolex, from 0 wt % to 1 wt% Lipoclean and any combination thereof) Other enzyme (such as xyloglucanase, from 0 wt % to 2 wt % cutinase, pectate lyase, mannanase, bleaching enzyme) Fabric softener (such as montmorillonite from 0 wt % to 15 wt % clay and/or polydimethylsiloxane (PDMS)) Flocculant (such as polyethylene oxide) from 0 wt % to 1 wt % Suds suppressor (such as silicone and/or from 0 wt % to 4 wt % fatty acid) Perfume (such as perfume microcapsule, from 0.1 wt % to 1 wt % spray-on perfume, starch encapsulated perfume accords, perfume loaded zeolite, and any combination thereof) Aesthetics (such as coloured soap rings from 0 wt % to 1 wt % and/or coloured speckles/noodles) Miscellaneous balance to 100 wt %