This invention relates to polyetheramines based on 1 ,3-dialcohols, in particular to polyethera- mine mixtures obtainable by the alkoxylation and amination of 1 ,3-dialcohols.

Due to the increasing popularity of easy-care fabrics made of synthetic fibers as well as the ever increasing energy costs and growing ecological concerns of detergent users, the once popular hot water wash has now taken a back seat to washing fabrics in cold water. Many commercially available laundry detergents are even advertised as being suitable for washing fabrics at 40°C or 30°C or even at room temperature. To achieve satisfactory washing result at such low temperatures, results comparable to those obtained with hot water washes, the demands on low- temperature detergents are especially high.

It is known to include certain additives in detergent compositions to enhance the detergent power of conventional surfactants so as to improve the removal of grease stains at temperatures of 60°C and below.

WO 86/07603 discloses that detergent composition comprising an aliphatic amine compound, in addition to at least one synthetic anionic and/or nonionic surfactant, are known and have led to improved cleaning results even at low wash temperatures. These compounds are said to con- tribute to the improvement of the washing performance of the detergent at lower temperatures. Also, the use of linear, alkyl-modified (secondary) alkoxypropylamines in laundry detergents to improve cleaning at low temperatures is known (WO90/03423). These known laundry detergents, however, are unable to achieve satisfactory cleaning when laundry is washed at cold temperatures.

Furthermore, the use of linear, primary polyoxyalkyleneamines (e.g., Jeffamine® D-230) to stabilize fragrances in laundry detergents and provide longer lasting scent is also known (WO2009/065738). Also, the use of high-moleculer-weight (molecular weight of at least about 1000), branched, trifunctional, primary amines (e.g., Jeffamine® T-5000 polyetheramine) to suppress suds in liquid detergents is known (WO01/76729).

Additionally, WO 201 1/087793 reads on etheramine mixtures comprising at least 10wt% of an alkoxylated monoether amine based on polyhydric alcohols containing 2 to 4 hydroxyl groups as the starting compound. A process for the manufacture of these etheramine mixtures is also disclosed. These products find an application as a curing agent or as a raw material in the synthesis of polymers. There is a continuous need for cleaning compositions that remove grease stains from fabrics and other soiled materials, as grease stains are challenging stains to remove. Conventional cleaning compositions directed to grease removal frequently utilize various amine compounds which tend to show strong negative impacts on whiteness. As a consequence there is still a continual need for improved amine compositions which provide improved grease removal from fabrics and other soiled materials and at the same time do not negatively impact the clay cleaning.

It was an object of the present invention to provide compounds which would improve the wash- ing performance of detergents at low temperatures, i.e. at temperatures as low as 30°C or even lower.

This goal was achieved with an etheramine mixture comprising at least 90% by weight, based on the total weight of the etheramine mixture, of an amine of Formula (I) and/or (II),

Formula (II) wherein R1-R12 are independently selected from H, alkyl, cycloalkyl, aryl, alkylaryl, or arylalkyl, wherein at least one of R1-R6 and at least one of R7-R12 is different from H, wherein A1-A9 are independently selected from linear or branched alkylenes having 2 to 18 carbon atoms, preferably 2-10 carbon atoms, most preferably 2-5 carbon atoms, wherein Z1-Z4 are independently selected from OH or NH2, wherein at least one of Z1-Z2 and at least one of Z3-Z4 is NH2, and wherein the sum of x+y is in the range of about 2 to about 200, wherein x>1 and y>1 ; and xi + yi is in the range of about 2 to about 200, preferably 2-20, most preferaby 2-10, wherein xi>1 and yi≥1.

Preferably, the sum of x and y is in the range of 2 to 20, more preferably in the range of 2 to 10, even more preferably in the range of 3 to 8 and even more preferably in the range of 4 to 6. Preferably, the sum of xi and yi is in the range of 2 to 20, more preferably in the range of 2 to 10, even more preferably in the range of 3 to 8 and even more preferably in the range of 2 to 4.

In a preferred embodiment, the etheramine mixture comprises at least 95% by weight, based on the total weight of the etheramine mixture, of the amine of Formula (I) and/or (I I).

In another preferred embodiment, A1-A9 are independently selected from the group consisting of ethylene, propylene, or butylene, preferably each of A1-A9 is propylene.

In Formula (I) or (I I), Ri, R2, R5, F S, R7, Rs, R11 , and R12 are H and R3, R ₄ , R9, and R10 are independently selected from C1 -16 alkyl or aryl.

Preferably, in Formula (I) or (I I), Ri, R2, R5, R6, R7, Rs, R11 , and R12 are H and R3, R ₄ , R9, and R10 are independently selected from a butyl group, an ethyl group, a methyl group, a propyl group, or a phenyl group.

Even more preferably, in Formula (I) or (I I), R3 and R9 are each an ethyl group, Ri, R2, R5, R6, R ₇ , Rs, R11 , and R12 are each H, R4 and R10 are each a butyl group .

The polyetheramine of Formula (I) or Formula (I I) has a weight average molecular weight of about 290 to about 1000 grams/mole, preferably, of about 300 to about 700 grams/mole, even more preferably of about 300 to about 450 grams/mole.

The etheramine mixture comprising at least 90% by weight, based on the total weight of the etheramine mixture, of an etheramin of Formula (I) and/or (I I) is obtainable by a process com- prising the following steps: a) the reaction of 1 ,3-diols of Formula (III) with C2-C18 alkylene oxides, wherein the molar ratio of 1 ,3- diol to C2-C18 alkylene oxides is in the range of 1 :2 to 1 :10,

Formula (III)

with Ri-F¾ are independently of one another H, alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl and at least one group selected from R1-R6 IS different from H,

b) the amination of the alkoxylated 1 , 3- diols with ammonia.

In a preferred embodiment, this etheramine mixture comprising at least 95% by weight, based on the total weight of the etheramine mixture, of the obtained etheramine.

In a preferred embodiment the molar ratio of 1 ,3- diol to C2-C18 alkylene oxides is in the range of 1 :3 to 1 :8, even more preferably in the range of 1 :4 to 1 :6. Preferably the C2-C18 alkylene oxides are selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide or a mixture thereof, even more preferably C2-C18 alkylene oxide is propylene oxide.

Preferably in the 1 ,3-diol of Formula (III) Ri, R2, R5, R6 are H and R3, R ₄ are C1 -16 alkyl or aryl.

The 1 ,3-diol of Formula (III) is preferably selected from the group consisting of 2-butyl-2-ethyl- 1 ,3-propanediol, 2-methyl-2-propyl-1 ,3-propanediol, 2-methyl-2-phenyl-1 ,3-propanediol, 2,2- dimethyl-1 ,3-propandiol, 2-ethyl-1 ,3-hexandiol. Step a): alkoxylation

Substituted 1 ,3 diols (Formula III ) are synthesized according WO10026030, WO10026066, WO09138387, WO09153193, W010010075.

Suitable 1 ,3-diols (Formula III) are for example: 2, 2-dimethyl-1 ,3-propane diol, 2-butyl-2-ethyl- 1 ,3-propane diol, 2-pentyl-2-propyl-1 ,3-propane diol, 2-(2-methyl)butyl-2-propyl-1 ,3-propane diol, 2,2, 4-trimethyl-1 ,3-propane diol, 2, 2-diethyl-1 ,3-propane diol, 2-methyl-2-propyl-1 ,3- propane diol, 2-ethyl-1 ,3-hexane diol, 2-phenyl-2-methyl-1 ,3-propane diol, 2-methyl-1 ,3-propane diol, 2-ethyl-2-methyl-1 ,3 propane diol, 2,2-dibutyl-1 ,3-propane diol, 2,2-di(2-methylpropyl)-1 ,3- propane diol, 2-isopropyl-2-methyl-1 ,3-propane diol, etc.

Preferred 1 ,3-diols are 2-butyl-2-ethyl-1 ,3-propanediol, 2-methyl-2-propyl-1 ,3-propanediol, 2- methyl-2-phenyl-1 ,3-propanediol.

Alkoxylated 1 ,3-diols are obtained by reaction of 1 ,3-diols (Formula III) with alkylene oxides and can be affected according to general alkoxylation procedures known in the art. The alkoxylated 1 ,3-diols may be prepared in a known manner by reaction of 1 ,3-diols with alkylene oxides. Suitable alkylene oxides are C2-C18 alkylene oxides like ethylene oxide, propylene oxide, butylene oxide, pentene oxide, hexene oxide, decene oxide, dodecene oxide etc. Preferred C2-C18 alkylene oxides are ethylene oxide, propylene oxide, butylene oxide or a mixture thereof.

The 1 ,3-diols are reacted with one single alkylene oxide or combinations of two or more different alkylene oxides. Using two or more different alkylene oxides, the resulting polymer can be obtained as a block-wise structure or a random structure.

The molar ratio of molar ratio of 1 ,3- diol to C2-C18 alkylene oxides at which the alkoxylation reaction is carried out lies in the range of 1 :2 to 1 :10, preferably in the range of 1 :3 to 1 :8, even more preferably in the range of 1 :4 to 1 :6.

This reaction is undertaken generally in the presence of a catalyst in an aqueous solution at a reaction temperature from about 70 to about 200°C and preferably from about 80 to about 160°C. This reaction may be affected at a pressure of up to about 10 bar, and in particular up to about 8 bar.

Examples of suitable catalysts are basic catalysts such as alkali metal and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal alkoxides, in particular sodium and potassium Ci-C4-alkoxides, such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, alkali metal and alkaline earth metal hydrides such as sodium hydride and calcium hydride, and alkali metal carbonates such as sodium carbonate and potassium carbonate. Preference is given to alkali metal hydroxides, particular preference being given to potassium hydroxide and sodium hydroxide. Typical use amounts for the base are from 0.05 to 10% by weight, in particular from 0.1 to 2% by weight, based on the total amount of polyalkyleneimine and alkylene oxide. Alkoxylation with x+y C2-C18 alkylene oxides leads to structures as drawn in Formula IV and/or Formula V

Formula (IV)

Formula (V)

wherein R1-R12 are independently selected from H, alkyl, cycloalkyl, aryl, alkylaryl, or arylalkyl, wherein at least one of R1-R6 and at least one of R7-R12 is different from H,

wherein A1-A9 are independently selected from linear or branched alkylenes having 2 to 18 carbon atoms, preferably 2-10 carbon atoms, most preferably 2-5 carbon atoms,

and wherein the sum of x+y is in the range of about 2 to about 200, wherein x>1 and y≥1 ; and xi

+ yi is in the range of about 2 to about 200, preferably 2-20, most preferaby 2-10, wherein xi>1

Step b): amination

Amination of the alkoxylated 1 ,3-diols leads to new structures with Formula I and/or (II):

Formula (I)

Formula (II)

wherein R1-R12 are independently selected from H, alkyl, cycloalkyl, aryl, alkylaryl, or arylalkyl, wherein at least one of R1-R6 and at least one of R7-R12 is different from H,

wherein A1-A9 are independently selected from linear or branched alkylenes having 2 to 18 carbon atoms, preferably 2-10 carbon atoms, most preferably 2-5 carbon atoms,

wherein Z1-Z4 are independently selected from OH or NH2, wherein at least one of Z1-Z2 and at least one of Z3-Z4 is NH2, and wherein the sum of x+y is in the range of about 2 to about 200, wherein x>1 and y≥1 ; and xi + yi is in the range of about 2 to about 200, preferably 2-20, most preferaby 2-10, wherein xi>1 and yi≥1.

Polyetheramines according to Formula (I) and/or (II) are obtained by reductive amination of the alkoxylated 1 ,3-diol mixture (Formula IV and V) with ammonia in presence of hydrogen and a catalyst containing nickel. Suitable catalysts are described in WO 201 1/067199 A1 and in WO201 1/067200 A1 , and in EP0696572 B1. Preferred catalysts are supported copper-, nickel- and cobalt-containing catalysts, wherein the catalytically active material of the catalysts, before the reduction thereof with hydrogen, comprises oxygen compounds of aluminium, of copper, of nickel and of cobalt, and in the range from 0.2 to 5.0% by weight of oxygen compounds of tin, calculated as SnO. Other preferred catalysts are supported copper-, nickel- and cobalt- containing catalysts, wherein the catalytically active material of the catalysts, before the reduc- tion thereof with hydrogen, comprises oxygen compounds of aluminium, of copper, of nickel, of cobalt and of tin, and in the range from 0.2 to 5.0% by weight of oxygen compounds of yttrium, of lanthanum, of cerium and/or of hafnium, each calculated as Y2O3, La203, Ce203 and Hf203 respectively. Another preferred catalyst is a zirconium, copper, nickel catalyst, wherein the catalytically active composition comprises from 20 to 85 % by weight of oxygen-containing zirconium compounds, calculated as Zr02, from 1 to 30% by weight of oxygen-containing compounds of copper, calculated as CuO, from 30 to 70 % by weight of oxygen-containing compounds of nickel, calculated as NiO, from 0.1 to 5 % by weight of oxygen-containing compounds of aluminium and/ or manganese, calculated as AI203 and Mn02 respectively. For the reductive amination step as well supported as non-supported catalyst can be used. The supported catalyst e.g. is obtained by deposition of the metallic components of the catalyst compositions onto support materials known to those skilled in the art, using techniques which are well-known in the art including without limitation, known forms of alumina, silica, charcoal, carbon, graphite, clays, mordenites; and molecular sieves, to provide supported catalysts as well. When the catalyst is supported, the support particles of the catalyst may have any geometric shape, for example the shape of spheres, tablets or cylinders in a regular or irregular version.

The process can be carried out in a continuous or discontinuous mode, e.g. in an autoclave, tube reactor or fixed-bed reactor. The reactor design is also not narrowly critical. The feed thereto may be upflowing or downflowing, and design features in the reactor which optimize plug flow in the reactor may be employed.

Byproducts which contain secondary or tertiary amino functions may be formed under amination reaction conditions. Secondary amines are e.g. obtained from a reaction of a fully or partially aminated diol with another fully and/or partially aminated diol. Tertiary amines are formed e.g. via a reaction of a secondary amine with another fully or partially aminated diol.

The degree of amination is between 50 to 100%, preferably from 60 to 100% and more preferably from 70-100% and even more preferably from 90 to 100% .

The degree of amination is calculated from the total amine value (AZ) divided by sum of the total acetylables value (AC) and tertiary amine value(tert. AZ) multiplicated by 100: (Total AZ: (AC+tert. AZ)x100).

The total amine value (AZ) is determined according to DIN 16945.

The total acetylables value (AC) is determined according to DIN 53240.

The secondary and tertiary amine are determined according to ASTM D2074-07.

The hydroxyl value is calculated from (total acetylables value + tertiary amine value)- total amine value. In another preferred embodiment, the etheramines of the invention can also be further reacted with an acid. The acid may be selected from the group consisting of citric acid, lactic acid, sulfuric acid, methanesulfonic acid, hydrogen chloride, phosphoric acid, formic acid, acetic acid, propionic acid, valeric acid, oxalic acid, succinic acid, adipic acid, sebacic acid, glutaric acid, glucaric acid, tartaric acid, malic acid, benzoic acid, salicylic acid, phthalic acid, oleic acid, stea- ric acid and mixtures thereof. In an alternative embodiment, the etheramines of the invention may, in protonated form, have a surfactant as a counter ion, as obtained from e.g. linear alkyl benzene sulphonic acid.

Tertiary dialkyl-substituted polyether amines can be prepared from the respective primary poly- ether amines by reductive amination. Typical procedures involve the use of formaldehyde or other alkylaldehydes like ethanal, 1 -propanal or 1 -butanal in the presence of a hydrogen donor such as formic acid or the in the presence of hydrogen gas and a transition metal containing catalyst.

Alternatively, dialky-substituted tertiary polyether amines can be obtained by reacting a polyeth- er alcohol with a dialkylamine like e.g. dimethylamine in the presence of a suitable transition metal catalyst, preferably in the additional presence of hydrogen and under continuous removal of the reaction water.

Applications: The inventive etheramine mixtures may be used used in personal care, especially in shampoo and body wash formulations.

They may also be used as curing agent for epoxy resins or as a reactant in the production of polymers but also in polyurethanes, polyureas, epoxy resins, polyamides.

The inventive polyetheramines have proved to be effective for removal of stains, particularly grease, from soiled material. Besides, cleaning compositions with inventive polyetheramines also do not have the cleaning negatives seen with conventional, amine cleaning compositions for hydrophilic bleachable stains, such as coffee, tea, wine, or particulates. Additionally, for stain removal from white fabric, cleaning compositions with inventive polyetheramines do not cause the whiteness negatives that commercially available, amine cleaning compositions cause.

A further advantage of cleaning compositions comprising the inventive polyetheramines is their ability to remove grease stains in cold water cleaning solutions, via pretreatment of the grease stain outside the washing machine, followed by cold water washing. Without being limited by theory, cold water solutions have the effect of causing greases to harden or solidify, making greases more resistant to removal, especially from fabric. Cleaning compositions with with etheramine mixtures according to Formula (I) and/or (II) however, are surprisingly effective when used in pretreatment followed by cold water cleaning. As used herein the phrase "cleaning composition" includes compositions and formulations designed for cleaning soiled material. Such compositions include but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, laundry prewash, laundry pretreat, laundry additives, spray products, dry cleaning agent or composition, laundry rinse additive, wash additive, post- rinse fabric treatment, ironing aid, unit dose formulation, delayed delivery formulation, liquid hand dishwashing composition, detergent contained on or in a porous substrate or nonwoven sheet, automatic dish-washing agent, hard surface cleaner, and other suitable forms that may be apparent to one skilled in the art in view of the teachings herein.. Such compositions may be used as a pre-laundering treatment, a post-laundering treatment, may be added during the rinse or wash cycle of the laundering operation, or used in homecare cleaning applications. The cleaning compositions may have a form selected from liquid, powder, single-phase or multiphase unit dose, pouch, tablet, gel, paste, bar, or flake. The cleaning compositions described herein may include from about 0.1 % to about 10%, in some examples, from about 0.2% to about 5%, and in other examples, from about 0.5% to about 3%, by weight the composition, of an amine-terminated polyalkylene glycol of Formula I and/or II.

The inventive etheramine mixtures are effective for removal of stains, particularly grease, from soiled material. Cleaning compositions containing the amine-terminated polyalkylene glycols of the invention also do not exhibit the cleaning negatives seen with conventional amine- containing cleaning compositions on hydrophilic bleachable stains, such as coffee, tea, wine, or particulates. Additionally, unlike conventional amine-containing cleaning compositions, the amine-terminated polyalkylene glycols of the invention do not contribute to whiteness negatives on white fabrics.

A further advantage of cleaning compositions containing the inventive etheramine mixture is their ability to remove grease stains in cold water, for example, via pretreatment of a grease stain followed by cold water washing. Without being limited by theory, it is believed that cold water washing solutions have the effect of hardening or solidifying grease, making the grease more resistant to removal, especially on fabric. Cleaning compositions containing the amine- terminated polyalkylene glycols of the invention are surprisingly effective when used as part of a pretreatment regimen followed by cold water washing. Surfactant System

The cleaning compositions comprise a surfactant system in an amount sufficient to provide desired cleaning properties. In some embodiments, the cleaning composition comprises, by weight of the composition, from about 1 % to about 70% of a surfactant system. In other embod- iments, the liquid cleaning composition comprises, by weight of the composition, from about 2% to about 60% of the surfactant system. In further embodiments, the cleaning composition comprises, by weight of the composition, from about 5% to about 30% of the surfactant system. The surfactant system may comprise a detersive surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, am- pholytic surfactants, and mixtures thereof. Those of ordinary skill in the art will understand that a detersive surfactant encompasses any surfactant or mixture of surfactants that provide cleaning, stain removing, or laundering benefit to soiled material.

Adjunct Cleaning Additives The cleaning compositions of the invention may also contain adjunct cleaning additives. Suitable adjunct cleaning additives include builders, structurants or thickeners, clay soil removal/anti- redeposition agents, polymeric soil release agents, polymeric dispersing agents, polymeric grease cleaning agents, enzymes, enzyme stabilizing systems, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, brighteners, dyes, hueing agents, dye transfer inhibiting agents, chelating agents, suds supressors, softeners, and perfumes.

Methods of Use

The present invention includes methods for cleaning soiled material. As will be appreciated by one skilled in the art, the cleaning compositions of the present invention are suited for use in laundry pretreatment applications, laundry cleaning applications, and home care applications.

Such methods include, but are not limited to, the steps of contacting cleaning compositions in neat form or diluted in wash liquor, with at least a portion of a soiled material and then optionally rinsing the soiled material. The soiled material may be subjected to a washing step prior to the optional rinsing step.

For use in laundry pretreatment applications, the method may include contacting the cleaning compositions described herein with soiled fabric. Following pretreatment, the soiled fabric may be laundered in a washing machine or otherwise rinsed. Machine laundry methods may comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry cleaning composition in accord with the invention. An "effective amount" of the cleaning composition means from about 20g to about 300g of product dissolved or dispersed in a wash solution of volume from about 5L to about 65L. The water temperatures may range from about 5°C to about 100°C. The water to soiled material (e.g., fabric) ratio may be from about 1 :1 to about 20:1 . In the context of a fabric laundry composition, usage levels may also vary depending not only on the type and severity of the soils and stains, but also on the wash water temperature, the volume of wash water, and the type of washing machine (e.g., top-loading, front- loading, top-loading, vertical-axis Japanese-type automatic washing machine).

The cleaning compositions herein may be used for laundering of fabrics at reduced wash temperatures. These methods of laundering fabric comprise the steps of delivering a laundry cleaning composition to water to form a wash liquor and adding a laundering fabric to said wash liquor, wherein the wash liquor has a temperature of above 0°C to about 20°C, or to about 15 °C, or to about 10 °C. The fabric may be contacted to the water prior to, or after, or simultaneous with, contacting the laundry cleaning composition with water.

Another method includes contacting a nonwoven substrate impregnated with an embodiment of the cleaning composition with soiled material. As used herein, "nonwoven substrate" can comprise any conventionally fashioned nonwoven sheet or web having suitable basis weight, caliper (thickness), absorbency, and strength characteristics. Non-limiting examples of suitable commercially available nonwoven substrates include those marketed under the tradenames SON- TARA® by DuPont and POLYWEB® by James River Corp.

Hand washing methods, and combined handwashing with semiautomatic washing machines, are also included.

Machine Dishwashing Methods

Methods for machine-dishwashing or hand dishwashing soiled dishes, tableware, silverware, or other kitchenware, are included. One method for machine dishwashing comprises treating soiled dishes, tableware, silverware, or other kitchenware with an aqueous liquid having dissolved or dispensed therein an effective amount of a machine dishwashing composition in accord with the invention. By an effective amount of the machine dishwashing composition it is meant from about 8g to about 60g of product dissolved or dispersed in a wash solution of volume from about 3L to about 10L.

One method for hand dishwashing comprises dissolution of the cleaning composition into a receptacle containing water, followed by contacting soiled dishes, tableware, silverware, or other kitchenware with the dishwashing liquor, then hand scrubbing, wiping, or rinsing the soiled dishes, tableware, silverware, or other kitchenware. Another method for hand dishwashing comprises direct application of the cleaning composition onto soiled dishes, tableware, silverware, or other kitchenware, then hand scrubbing, wiping, or rinsing the soiled dishes, tableware, silverware, or other kitchenware. In some examples, an effective amount of cleaning composition for hand dishwashing is from about 0.5 ml. to about 20 ml. diluted in water.

Packaging for the Compositions

The cleaning compositions described herein can be packaged in any suitable container including those constructed from paper, cardboard, plastic materials, and any suitable lami- nates. An optional packaging type is described in European Application No. 94921505.7.

Multi-Compartment Pouch Additive

The cleaning compositions described herein may also be packaged as a multi-compartment cleaning composition. Synthesis Examples Example 1

1 mol 2-Butyl-2-ethyl-1 ,3-propane diol + 4 mol propylene oxide, aminated a) 1 mol 2-Butyl-2-ethyl-1 ,3-propane diol + 4 mol propylene oxide

In a 2 I autoclave 322,6 g 2-Butyl-2-ethyl-1 ,3-propane diol and 7,9 g KOH (50 % in water) were mixed and stirred under vacuum (<10 mbar) at 120°C for 2 h. The autoclave was purged with nitrogen and heated to 140°C. 467,8 g propylene oxide was added in portions within 6 h. To complete the reaction, the mixture was allowed to post-react for additional 5 h at 140°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80°C. The catalyst potassium hydroxide was removed by adding 2,3 g synthetic magnesium silicate (Macrosorb MP5plus, Ineos Silicas Ltd.), stirring at 100°C for 2 h and filtration.

A yellowish oil was obtained (772,0 g, hydroxy value: 248,5 mgKOH/g). b) 1 mol 2-Butyl-2-ethyl-1 ,3-propane diol + 4 mol propylene oxide, aminated In a 9 I autoclave 600 g of the resulting diol mixture from example 1 -a, 1250 g THF and 1500 g ammonia were mixed in presence of 200 ml of a solid catalyst as described in EP0696572B1. The catalyst containing nickel, cobalt, copper, molybdenum and zirconium was in the form of 3x3 mm tables. The autoclave was purged with hydrogen and the reaction was started by heating the autoclave. The reaction mixture was stirred for 18 h at 205°C, the total pressure was maintained at 270 bar by purging hydrogen during the entire reductive amination step. After cooling down the autoclave the final product was collected, filtered, vented of excess ammonia and stripped in a rotary evaporator to remove light amines and water. A total of 560 grams of a low-color etheramine mixture was recovered. The analytical results thereof are shown in Table 1 .

Table 1 .

Example 2

1 mol 2,2,4-Trimethyl-1 ,3-propane diol + 4 mol propylene oxide, aminated a) 1 mol 2,2,4-Trimethyl-1 ,3-propane diol + 4 mol propylene oxide

327,3 g molten 2,2,4-Trimethyl-1 ,3-pentane diol and 8,5g KOH (50% in water) were dewatered for 2 h at 80°C and <10 mbar in a 2 I autoclave. The autoclave was purged with nitrogen and heated to 140°C. 519,4 g propylene oxide was added in portions within 6 h. To complete the reaction, the mixture was allowed to post-react for additional 5 h at 140°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80°C. The catalyst was removed by adding 2,5 g Macrosorb MP5plus, stirring at 100°C for 2 h and filtration. A yellowish oil was obtained (825,0 g, hydroxy value: 172,3 mgKOH/g). b) 1 mol 2,2,4-Trimethyl-1 ,3-propane diol + 4 mol propylene oxide, aminated

In a 9 I autoclave 700 g of the resulting diol mixture from example 2-a, 1000 ml. THF and 1500 g Ammonia were mixed in presence of 200 ml of a solid catalyst as described in EP0696572B1. The catalyst containing nickel, cobalt, copper, molybdenum and zirconium was in the form of 3x3 mm tables. The autoclave was purged with hydrogen and the reaction was started by heating the autoclave. The reaction mixture was stirred for 15 h at 205°C, the total pressure was maintained at 280 bar by purging hydrogen during the entire reductive amination step. After cooling down the autoclave the final product was collected, filtered, vented of excess ammonia and stripped in a rotary evaporator to remove light amines and water. A total of 670 grams of a low-color etheramine mixture was recovered. The analytical results thereof are shown in Table 2.

Table 2.

Example 3

1 mol 2,2-Diethyl-1 ,3-propane diol + 4 mol propylene oxide, aminated a) 1 mol 2,2-Diethyl-1 ,3-propane diol + 4 mol propylene oxide

197,4 g molten 2,2-diethyl-1 ,3-propane diol and 5,4 g KOH (50% in water) were dewatered for 2 h at 80°C and <10 mbar in a 2 I autoclave. The autoclave was purged with nitrogen and heated to 140°C. 346,4 g propylene oxide was added in portions within 4 h. To complete the reaction, the mixture was allowed to post-react for additional 5 h at 140°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80°C. The catalyst was removed by adding 1 ,6 g Macrosorb MP5plus, stirring at 100°C for 2 h and filtration.

A yellowish oil was obtained (530,0 g, hydroxy value: 267,8 mgKOH/g). b) 1 mol 2,2-Diethyl-1 ,3-propane diol + 4 mol propylene oxide, aminated

In a 9 I autoclave 500 g of the resulting diol mixture from example 3-a, 1200 ml THF and 1500 g Ammonia were mixed in presence of 200 ml of a solid catalyst as described in EP0696572B1. The catalyst containing nickel, cobalt, copper, molybdenum and zirconium was in the form of 3x3 mm tables. The autoclave was purged with hydrogen and the reaction was started by heat- ing the autoclave. The reaction mixture was stirred for 15 h at 205°C, the total pressure was maintained at 270 bar by purging hydrogen during the entire reductive amination step. After cooling down the autoclave the final product was collected, filtered, vented of excess ammonia and stripped in a rotary evaporator to remove light amines and water. A total of 470 grams of a low-color etheramine mixture was recovered. The analytical results thereof are shown in Table 3.

Table 3.

Example 4

1 mol 2-Methyl-2-propyl-1 ,3-propandiol + 4 mol propylene oxide, aminated a) 1 mol 2-Methyl-2-propyl-1 ,3-propandiol + 4 mol propylene oxide

198,3 g molten 2-methyl-2-propyl-1 ,3-propanediol and 5,5 g KOH (50% in water) were de- watered for 2 h at 80°C and <10 mbar in a 2 I autoclave. The autoclave was purged with nitrogen and heated to 140°C. 348,0 g propylene oxide was added in portions within 4 h. To complete the reaction, the mixture was allowed to post-react for additional 5 h at 140°C. The reac- tion mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80°C. The catalyst was removed by adding 1 ,6 g Macrosorb MP5plus, stirring at 100°C for 2 h and filtration.

A yellowish oil was obtained (520,0 g, hydroxy value: 308,1 mgKOH/g). b) 1 mol 2-Methyl-2-propyl-1 ,3-propandiol + 4 mol propylene oxide, aminated

In a 9 I autoclave 500 g of the resulting diol mixture from example 4-a, 1200 ml THF and 1500 g ammonia were mixed in presence of 200 ml of a solid catalyst as described in EP0696572B1. The catalyst containing nickel, cobalt, copper, molybdenum and zirconium was in the form of 3x3 mm tables. The autoclave was purged with hydrogen and the reaction was started by heating the autoclave. The reaction mixture was stirred for 15 h at 205°C, the total pressure was maintained at 270 bar by purging hydrogen during the entire reductive amination step. After cooling down the autoclave the final product was collected, filtered, vented of excess ammonia and stripped in a rotary evaporator to remove light amines and water. A total of 470 grams of a low-color etheramine mixture was recovered. The analytical results thereof are shown in Table 4.

Table 4.

Example 5

1 mol 2-Ethyl-1 ,3-hexane diol + 4 mol propylene oxide, aminated a) 1 mol 2-Ethyl-1 ,3-hexane diol + 4 mol propylene oxide

A 2 I autoclave was charged with 290,6 g molten 2-Ethyl-1 ,3-hexane diol and 7,5 g KOH (50% in water). The mixture was dewatered for 2 h at 90°C and <10 mbar. The autoclave was purged with nitrogen and heated to 140°C. 461 ,1 g propylene oxide was added in portions within 4 h. To complete the reaction, the mixture was stirred for additional 5 h at 140°C. The reaction mix- ture was stripped with nitrogen and volatile compounds were removed in vacuo at 80°C. The catalyst was removed by adding 2,3 g Macrosorb MP5plus, stirring at 100°C for 2 h and filtration.

A yellowish oil was obtained (745,0 g, hydroxy value: 229,4 mgKOH/g). b) 1 mol 2-Ethyl-1 ,3-hexane diol + 4 mol propylene oxide, aminated

In a 9 I autoclave 750 g of the resulting diol mixture from example 5-a, 950 ml THF and 1500 g Ammonia were mixed in presence of 200 ml of a solid catalyst as described in EP0696572B1. The catalyst containing nickel, cobalt, copper, molybdenum and zirconium was in the form of 3x3 mm tables. The autoclave was purged with hydrogen and the reaction was started by heating the autoclave. The reaction mixture was stirred for 15 h at 205°C, the total pressure was maintained at 270 bar by purging hydrogen during the entire reductive amination step. After cooling down the autoclave the final product was collected, filtered, vented of excess ammonia and stripped in a rotary evaporator to remove light amines and water. A total of 710 grams of a low-color etheramine mixture was recovered. The analytical results thereof are shown in Table 5. Table 5.

Example 6

1 mol 2-Phenyl-2-methyl-1 ,3-propane diol + 4 mol propylene oxide, aminated a) 1 mol 2-Phenyl-2-methyl-1 ,3-propane diol + 4 mol propylene oxide

A 2 I autoclave was charged with 298,4 g 2-Phenyl-2-methyl-1 ,3-propane diol and 7,1 g KOH (50% in water) and heated to 120°C. The mixture was dewatered for 2 h at 120°C and <10 mbar. The autoclave was purged with nitrogen and heated to 140°C. 408,6 g propylene oxide was added in portions within 4 h. To complete the reaction, the mixture was stirred for additional 5 h at 140°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80°C. The catalyst was removed by adding 2,1 g Macrosorb MP5plus, stirring at 100°C for 2 h and filtration.

A yellowish oil was obtained (690,0 g, hydroxy value: 266,1 mgKOH/g). b) 1 mol 2-Phenyl-2-methyl-1 ,3-propane diol + 4 mol propylene oxide, aminated

In a 9 I autoclave 600 g of the resulting diol mixture from example 6-a, 1 100 ml THF and 1500 g Ammonia were mixed in presence of 200 ml of a solid catalyst as described in EP0696572B1. The catalyst containing nickel, cobalt, copper, molybdenum and zirconium was in the form of 3x3 mm tables. The autoclave was purged with hydrogen and the reaction was started by heating the autoclave. The reaction mixture was stirred for 15 h at 205°C, the total pressure was maintained at 270 bar by purging hydrogen during the entire reductive amination step. After cooling down the autoclave the final product was collected, filtered, vented of excess ammonia and stripped in a rotary evaporator to remove light amines and water. A total of 570 grams of a low-color etheramine mixture was recovered. The analytical results thereof are shown in Table 6.

Table 6.

Example 7

1 mol 2,2-Dimethyl-1 ,3-propane diol+ 4 mol propylene oxide, aminated a) 1 mol 2,2-Dimethyl-1 ,3-propane diol+ 4 mol propylene oxide

A 2 I autoclave was charged with 208,3 g 2,2-Dimethyl-1 ,3-propane diol and 1 ,34 g potassium tert.-butylate and heated to 120°C. The autoclave was purged with nitrogen and heated to 140°C. 464 g propylene oxide was added in portions within 6 h. To complete the reaction, the mixture was stirred for additional 5 h at 140°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80°C. The catalyst was removed by adding 1 ,1 g Macrosorb MP5plus, stirring at 100°C for 2 h and filtration.

A light yellowish oil was obtained (650,0 g, hydroxy value: 308,6 mgKOH/g). b) 1 mol 2, 2-Dimethyl-1 ,3-propane diol+ 4 mol propylene oxide, aminated

In a 9 I autoclave 500 g of the resulting diol mixture from example 6-a, 1200 ml THF and 1500 g Ammonia were mixed in presence of 200 ml of a solid catalyst as described in EP0696572B1. The catalyst containing nickel, cobalt, copper, molybdenum and zirconium was in the form of 3x3 mm tables. The autoclave was purged with hydrogen and the reaction was started by heating the autoclave. The reaction mixture was stirred for 15 h at 205°C, the total pressure was maintained at 280 bar by purging hydrogen during the entire reductive amination step. After cooling down the autoclave the final product was collected, filtered, vented of excess ammonia and stripped in a rotary evaporator to remove light amines and water. A total of 450 grams of a low-color etheramine mixture was recovered. The analytical results thereof are shown in Table 7.

Table 7.

Example 8: 1 mol 2-butyl-2-ethyl-1 ,3-propanediol + 5.6 mol propylene oxide, aminated a) 1 mol 2-butyl-2-ethyl-1 ,3-propanediol + 5.6 mol propylene oxide

In a 2 I autoclave 313.1 g 2-Butyl-2-ethyl-1 ,3-propanediol and 3.8 g KOH (50 % in water) were mixed and stirred under vacuum (<10 mbar) at 120°C for 2 h. The autoclave was purged with nitrogen and heated to 140°C. 635.6 g propylene oxide was added in portions within 6 h. To complete the reaction, the mixture was allowed to post-react for additional 5 h at 140°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80°C. The catalyst was removed by adding 50.9 g water and 8.2 g phosphoric acid (40 % in water) stirring at 100°C for 0.5 h and dewatering in vacuo for 2 hours. After filtration 930.0 g of light yellowish oil was obtained (hydroxy value: 190 mgKOH/g). b) 1 mol 2-butyl-2-ethyl-1 ,3-propanediol + 5.6 mol propylene oxide, aminated

The amination of 8a (1 mol 2-butyl-2-ethyl-1 ,3-propanediol + 5.6 mole propylene oxide) was conducted in a tubular reactor (length 500 mm, diameter 18 mm) which had been charged with 15 mL of silica (3x3 mm pellets) followed by 70 ml. (74 g) of the catalyst precursor (containing oxides of nickel, cobalt, copper and tin on gama-A Os, 1.0-1 .6 mm split - prepared according to WO 2013/072289 A1 ) and filled up with silica (ca. 15 mL).

The catalyst was activated at atmospheric pressure by being heated to 100 °C with 25 Nl/h of nitrogen, then 3 hours at 150 °C in which the hydrogen feed was increased from 2 to 25 Nl/h, then heated to 280 °C at a heating rate of 60 °C per hour and kept at 280 °C for 12 hours.

The reactor was cooled to 100 °C, the nitrogen flow was turned off and the pressure was increased to 120 bar. The catalyst was flushed with ammonia at 100 °C, before the temperature was increased to 206 °C and the alcohol feed was started with a WHSV of 0.19 kg/liter ^* h (molar ratio ammonia/alcohol = 55:1 , hydrogen/alcohol = 1 1 ,6:1 ). The crude material was collected and stripped on a rotary evaporator to remove excess ammonia, light weight amines and reaction water to afford 8 b (1 mol 2-butyl-2-ethyl-1 ,3-propanediol + 5.6 mole propylene oxide, aminat- ed). The analytical data of the reaction product is shown in Table 8.

Table 8.

Use as additives in laundry detergents

Technical stain swatches of blue knitted cotton containing Beef Fat, Pork Fat, Sausage Fat, Chicken Fat, Bacon Graese and Napolina Olive Oil were purchased from Warwick Equest Ltd. and washed in conventional western European washing machines (Miele Waschmaschine Softronic W 2241 ), selecting a 59 min washing cycle without heating and using 75 g of liquid detergent composition LA1 (table 9) together with or without 1.25 g of polyetheramine additive and some hydrochloric acid to readjust the pH after addition of the polyetheramine. The pH of 75 g of LA1 (Tab. 9) in 1 L water should be at pH = 8.3. Water hardness was 2.5 mM (Ca ²⁺ : Mg ²⁺ was 3:1 ). 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 level was calculated.

Stain removal from the swatches was calculated as follows:

Stain Removal Index AEinitiai - AE _waS hed X 100

(SRI) =

AE initial

AEinitiai = Stain level before washing

AEwashed = Stain level after washing

Four replicates for each stain type have been carried out. Given below are the averaged values. Stain level corresponds to the amount of grease on the fabric. The stain level of the fabric before the washing (AEinmai) is high, in the washing process stains are removed and the stain level after washing is smaller (AEwashed).. The better the stains have been removed the lower the value for AEwashed will be and the higher the difference will be to AEinitiai. Therefore the value of stain removal index increases with better washing performance. Table 9: liquid detergent composition LA1

¹ Linear alkylbenenesulfonate having an average aliphatic carbon chain length C1 1 -C12 supplied by Stepan, Northfield Illinois, USA

2 AE3S is C12-15 alkyl ethoxy (3) sulfate supplied by Stepan, Northfield, Illinois, USA

³ AE9 is C12-14 alcohol ethoxylate, with an average degree of ethoxylation of 9, supplied by Huntsman, Salt Lake City, Utah, USA

⁴ Nl 45-7 is C14-15 alcohol ethoxylate, with an average degree of ethoxylation of 7, supplied by Huntsman, Salt Lake City, Utah, USA

5 Random graft copolymer is a polyvinyl acetate grafted polyethylene oxide copolymer having a polyethylene oxide backbone and multiple polyvinyl acetate side chains. The molecular weight of the polyethylene oxide backbone is about 6000 and the weight ratio of the polyethylene oxide to polyvinyl acetate is about 40 to 60 and no more than 1 grafting point per 50 ethylene oxide units.

⁶ A compound having the following general structure: bis((C2H50)(C2H40)n)(CH3)-N+-CxH2x- N+-(CH3)-bis((C2H50)(C2H40)n), wherein n = from 20 to 30, and x = from 3 to 8, or sulphated or sulphonated variants thereof

⁷ Polyethyleneimine (MW = 600) with 20 ethoxylate groups per -NH

⁸ Proteases may be supplied by Genencor International, Palo Alto, California, USA (e.g. Pura- fect Prime®) or by Novozymes, Bagsvaerd, Denmark (e.g. Liquanase®, Coronase®).

9 Natalase®, Mannaway® are all products of Novozymes, Bagsvaerd, Denmark.

¹⁰ Suitable chelants are, for example, diethylenetetraamine pentaacetic acid (DTPA) supplied by Dow Chemical, Midland, Michigan, USA or Hydroxyethane di phosphonate (HEDP) or diethy- lene triamine penta(methyl phosphonic) acid supplied by Solutia, St Louis, Missouri, USA;

¹¹ Fluorescent Brightener 1 is Tinopal® AMS, Fluorescent Brightener 2 supplied by Ciba Spe- cialty Chemicals, Basel, Switzerland

Washing Test 1 : Initial water temperature at 24 °C

A: liquid detergent composition LA1 (table 8) without additional polyetheramine additive

B: liquid detergent composition LA1 (table 8) with polyetheramine (2-Aminomethylethyl)-omega- (2-aminomethylethoxy)-poly(oxy(methyl-1 ,2-ethandiyl)), sold under the trade name Polyetheramine® D 230 or JEFFAMINE® D-230. C: liquid detergent composition LA1 (table 8) with polyetheramine of Example 1

D: liquid detergent composition LA1 (table 8) with polyetheramine of Example 4

E: liquid detergent composition LA1 (table 8) with polyetheramine of Example 6

Washing Test 2: Initial water temperature at 25 °C Stain A B C

Sausage

Fat 64.6 66.6 73.6

Chicken Fat 63.0 65.9 74.4

Bacon

Grease 67.1 72.0 75.5

A: liquid detergent composition LA1 (table 8) without additional polyetheramine additive

B: liquid detergent composition LA1 (table 8) with Polyetheramine® D230

C: liquid detergent composition LA1 (table 8) with polyetheramine of Example 5

The superior grease cleaning effect obtained with the addition of the claimed 1 ,3 propandiol- based polyetheramine compounds is clearly shown.

Washing Test 3: Initial water temperature at 24.5 °C

A: liquid detergent composition LA1 (table 8) without additional polyetheramine additive

B: liquid detergent composition LA1 (table 8) with polyetheramine of example 7

Washing Test 4: Initial water temperature at 18°C

Technical stain swatches of blue knitted cotton containing Beef Fat, Pork Fat and Chicken Fat were purchased from Warwick Equest Ltd. and washed in conventional western European washing machines (Miele Waschmaschine Softronic W 2241 ), selecting a 59 min washing cycle without heating (wash at 18 °C) and using 75 g of liquid detergent composition LA1 (see Table 9) together with or without 0.75 g of etheramine additive and some hydrochloric acid to readjust the pH. The pH of 75 g of LA1 (Tab. 9) in 1 L water should be at pH = 8.3.

A: liquid detergent composition LA1 (see Table 9) without additional etheramine additive B: liquid detergent composition LA1 (see Table 9) with polyetheramine of example 8.

C: liquid detergent composition LA1 (see Table 9) with polyetheramine (2-Aminomethylethyl)- omega-(2-aminomethylethoxy)-poly(oxy(methyl-1 ,2-ethandiyl)), sold under the trade name Polyetheramine® D 230 or JEFFAMINE® D-230

The cleaning composition with the etheramine according to the invention (see Washing Test 4B) shows superior grease cleaning effects over the detergent composition without etheramines (see Washing Test 4A) and also shows superior grease cleaning effects over the cleaning composition with the etheramine of the comparative example (Washing Test 4C).

Application tests

In the following examples, the individual ingredients within the cleaning compositions are ex- pressed as percentages by weight of the cleaning compositions.

Example I: Comparative Grease Stain Removal from NA Laundry Detergent Compositions

The following laundry detergent compositions are prepared by traditional means known to those of ordinary skill in the art by mixing the listed ingredients. Composition A is a conventional pre- mium laundry detergent that uses Baxxodur® EC301 comprising a linear amine-terminated pol- yalkylene glycol with the structure of Formula A.

Formula A Detergent compositions B and C each contain an etheramine mixture comprising 2-Butyl-2- ethyl-1 ,3-propane diol + 2,0 propylene oxide/OH, aminated, preparation of polyetheramine described in Example 1 (Formula B).

Formula B

Liquid Liquid Liquid

Detergent Detergent Detergent A B C

(wt%) (wt%) (wt%)

AES C12-15 alkyl ethoxy (1.8) sulfate 10.9 10.9 10.9

Alkyl benzene sulfonate ² 1 .56 1 .56 1 .56

Sodium formate 2.66 2.66 2.66

Sodium hydroxide 0.21 0.21 0.21

Monoethanolamine (MEA) 1 .65 1 .65 1 .65

Diethylene glycol (DEG) 4.10 4.10 4.10

AE9 ³ 0.40 0.40 0.40

C16AE7 3.15 3.15 3.15

Baxxodur EC301 1 .04 — —

Polyetheramine ¹¹ 1 .04 2.30

Chelant ⁴ 0.18 0.18 0.18

Citric Acid 1 .70 1 .70 1 .70

C12-18 Fatty Acid 1 .47 1 .47 1 .47

Borax 1 .19 1 .19 1 .19

Ethanol 1 .44 1 .44 1 .44

Ethoxylated Polyethyleneimine ¹ 1 .35 1 .35 1 .35

A compound having the following general structure:

bis((C2H ₅ 0)(C2H ₄ 0)n)(CH3)-N ⁺ -CxH2x-N ⁺ -(CH3)- bis((C2H ₅ 0)(C2H ₄ 0)n), wherein n = from 20 to 30, and x

= from 3 to 8, or sulphated or sulphonated variants

thereof 0.40 0.40 0.40

1 ,2-Propanediol 2.40 2.40 2.40

Protease (54.5 mg active/g) ⁹ 0.89 0.89 0.89

Mannanase: Mannaway® (25.6 mg active/g) ⁵ 0.04 0.04 0.04

Amylase: Natalase® (29 mg active/g) ⁵ 0.14 0.14 0.14

Fluorescent Whitening Agents ¹⁰ 0.10 0.10 0.10

Water, perfume, dyes & other components Balance

1 . Polyethyleneimine (MW = 600) with 20 ethoxylate groups per -NH.

2. Linear alkylbenzenesulfonate having an average aliphatic carbon chain length C11-C12 supplied by Stepan, Northfield, Illinois, USA 3. AE9 is C12-13 alcohol ethoxylate, with an average degree of ethoxylation of 9, supplied by Huntsman, Salt Lake City, Utah, USA

4. Suitable chelants are, for example, diethylenetetraamine pentaacetic acid (DTPA) supplied by Dow Chemical, Midland, Michigan, USA or Hydroxyethane di phosphonate (HEDP) supplied by Solutia, St Louis, Missouri, USA Bagsvaerd, Denmark

5. Natalase®, Mannaway® are all products of Novozymes, Bagsvaerd, Denmark.

6. Proteases may be supplied by Genencor International, Palo Alto, California, USA (e.g.

Purafect Prime®) or by Novozymes, Bagsvaerd, Denmark (e.g. Liquanase®, Coronase®).

10. Suitable Fluorescent Whitening Agents are for example, Tinopal® AMS, Tinopal® CBS-X, Sulphonated zinc phthalocyanine Ciba Specialty Chemicals, Basel, Switzerland

1 1 . 2-Butyl-2-ethyl-1 ,3-propane diol + 2,0 propylene oxide/OH, aminated, preparation of poly- etheramine described in Example 1 .

Technical stain swatches of CW120 cotton containing US clay, Frank's® Hot Sauce, hamburger grease, Italian dressing, and make up were purchased from Empirical Manufacturing Co., Inc (Cincinnati). The swatches were washed in a Whirlpool® front loader washing machine, using 6 grains per gallon water hardness and washed at 100 degrees Fahrenheit. The total amount of liquid detergent used in the test was 49 grams.

Image analysis was used to compare each stain to an unstained fabric control. Software converted images taken into standard colorimetric values and compared these to standards based on the commonly used Macbeth Colour Rendition Chart, assigning each stain a colorimetric value (Stain Level). Eight replicates of each were prepared.

Stain removal from the swatches was measured as follows:

Stain Removal Index AEinmai - E _waS hed X 100

(SRI) =

AE initial

AEinitiai = Stain level before washing

AEwashed = Stain level after washing Stain removal index scores for each stain were calculated and are listed in the table below:

These results illustrate the surprising grease removal benefit of an etheramine compound comprising compounds of Formula I and/or ll(as used in Compositions B and C), as compared to a linear polyalkylene glycol with terminal primary amines (Composition A).

Example II: Comparative Grease Removal from Laundry Cleaning Powder Composition

The following laundry detergent compositions are prepared by traditional means known to those of ordinary skill in the art by mixing the listed ingredients. Composition A is a conventional pre- mium laundry detergent that contains no amine-terminated polyalkylene glycol compound. Composition B is a laundry detergent that uses Baxxodur®EC301 , a linear amine-terminated polyalkylene glycol (see Formula A above).

Composition C is a detergent that uses a polyetheramine comprising 2-Butyl-2-ethyl-1 ,3- propane diol + 2,0 propylene oxide/OH, aminated, preparation of polyetheramine described in Example 1 (Formula B above). Powder Powder Powder

Detergent Detergent Detergen

A B C

(wt%) (wt%) (wt%)

Linear alkylbenzenesulfonate ¹ 8.2 8.2 8.2

AE3S ² 1 .9 1 .9 1 .9

Zeolite A ³ 1 .8 1 .8 1 .8

Citric Acid 1 .5 1 .5 1 .5

Sodium Carbonate ⁵ 29.7 29.7 29.7

Silicate 1 .6R (Si0 ₂ :Na ₂ 0) ⁴ 3.4 3.4 3.4

Soil release agent ⁶ 0.2 0.2 0.2

Acrylic Acid/Maleic Acid Copolymer ⁷ 2.2 2.2 2.2

Carboxymethylcellulose 0.9 0.9 0.9

Protease - Purafect® (84 mg active/g) ⁹ 0.08 0.08 0.08

Amylase - Stainzyme Plus® (20 mg active/g) ⁸ 0.16 0.16 0.16

Lipase - Lipex® (18.00 mg active/g) ⁸ 0.24 0.24 0.24

Cellulase - Celluclean™ (15.6 mg active/g) ⁸ 0.1 0.1 0.1

Baxxodur EC301 — 1 .0 —

Polyetheramine ¹⁰ — — 1 .0

TAED 3.26 3.26 3.26

Percarbonate ¹² 14.1 14.1 14.1

Na salt of Ethylenediamine-N,N'-disuccinic acid, (S,S) isomei

(EDDS) ¹³ 2.19 2.19 2.19

Hydroxyethane di phosphonate (HEDP) ¹⁴ 0.54 0.54 0.54

MgS0 ₄ 0.38 0.38 0.38

Perfume 0.38 0.38 0.38

Suds suppressor agglomerate ¹⁵ 0.04 0.04 0.04

Sulphonated zinc phthalocyanine (active) ¹⁶ 0.0012 0.0012 0.0012

Sulfate/ Water & Miscellaneous Balance Balance Balance

1. Linear alkylbenzenesulfonate having an average aliphatic carbon chain length Cn-

Ci2 supplied by Stepan, Northfield, Illinois, USA

AE3S is C12-15 alkyl ethoxy (3) sulfate supplied by Stepan, Northfield, Illinois, USA Zeolite A is supplied by Industrial Zeolite (UK) Ltd, Grays, Essex, UK

1 .6R Silicate is supplied by Koma, Nestemica, Czech Republic 5. Sodium Carbonate is supplied by Solvay, Houston, Texas, USA

6. Soil release agent is Repel-o-tex® PF, supplied by Rhodia, Paris, France

7. Acrylic Acid/Maleic Acid Copolymer is molecular weight 70,000 and acrylate:maleate ratio 70:30, supplied by BASF, Ludwigshafen, Germany

8. Savinase®, Natalase®, Stainzyme®, Lipex®, Celluclean™, Mannaway® and

Whitezyme® are all products of Novozymes, Bagsvaerd, Denmark.

9. Proteases may be supplied by Genencor International, Palo Alto, California, USA (e.g. Purafect Prime®) or by Novozymes, Bagsvaerd, Denmark (e.g. Liquanase®, Coronase®).

10. 2-Butyl-2-ethyl-1 ,3-propane diol + 2,0 propylene oxide/OH, aminated, preparation of polyetheramine described in Example 1

11. TAED is tetraacetylethylenediamine, supplied under the Peractive® brand name by Clariant GmbH, Sulzbach, Germany

12. Sodium percarbonate supplied by Solvay, Houston, Texas, USA

13. Na salt of Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer (EDDS) is supplied by Octel, Ellesmere Port, UK

14. Hydroxyethane di phosphonate (HEDP) is supplied by Dow Chemical, Midland, Michigan, USA

15. Suds suppressor agglomerate is supplied by Dow Corning, Midland, Michigan, USA

16. Fluorescent Brightener 1 is Tinopal® AMS, Fluorescent Brightener 2 is Tinopal® CBS-X, Sulphonated zinc phthalocyanine and Direct Violet 9 is Pergasol® Violet BN- Z all supplied by Ciba Specialty Chemicals, Basel, Switzerland

Technical stain swatches of cotton CW120 containing bacon grease, burnt butter, dirty motor oil, hamburger grease, Italian dressing, lipstick, margarine, pizza sauce, taco grease were purchased from Empirical Manufacturing Co., Inc (Cincinnati). The stained swatches were washed in conventional western European washing machines (Meile®) using 14 grains per gallon hardness, selecting the cotton cycle at 30°C, using 80 g of each of the respective detergent compositions. Image analysis was used to compare each stain to an unstained fabric control. Soft- ware converted images taken into standard colorimetric values and compared these to standards based on the commonly used Macbeth Colour Rendition Chart, assigning each stain a colorimetric value (Stain Level). Eight replicates of each were prepared. The stain removal index was then calculated according to the formula shown above. Key results are summarized in the following table:

These results illustrate the surprising grease removal benefit of the polyetheramine compound comprising compounds of Formula I and/or II (as used in Composition C), as compared to a linear polyalkylene glycol with terminal primary amines (Composition B) and a conventional (nil- polyetheramine) powdered detergent, especially on difficult-to-remove, high-frequency consumer stains like hamburger grease and taco grease.

Example III: Comparative Grease Removal from WE Laundry Liquid Compositions

The following laundry detergent compositions are prepared by traditional means known to those of ordinary skill in the art by mixing the listed ingredients. Composition A is a conventional premium laundry detergent that contains no amine-terminated polyalkylene glycol compound.

Composition B is a detergent that uses a polyetheramine comprising two terminal primary amines and two alkyl branches (specifically, 2-Butyl-2-ethyl-1 ,3-propane diol + 2,0 propylene oxide/OH, aminated, preparation of polyetheramine described in Example 1 Formula B above). WE WE

Liquid Liquid

HDL HDL

A B

(wt%) (wt%)

AE3S ⁴ 2.6 2.6

Alkyl benzene sulfonate ³ 7.5 7.5

Sodium formate/Calcium formate 0.4 0.4

Sodium hydroxide 3.7 3.7

Monoethanolamine (MEA) 0.3 0.3

Diethylene glycol (DEG) 0.8 0.8

AE9 ⁶ 0.4 0.4

AE7 ⁵ 4.4 4.4

Polyetheramine ¹¹ — 1 .0

Chelant ⁷ 0.3 0.3

Citric Acid 3.2 3.2

C12-18 Fatty Acid 3.1 3.1

Ethanol 2.0 2.0

Ethoxylated Polyethylenimine ¹ 1 .5 1 .5

Amphiphilic polymer ² 0.5 0.5

A compound having the following general

structure: bis((C2H ₅ 0)(C ₂ H ₄ 0)n)(CH3)-N ⁺ -

CxH2x-N ⁺ -(CH ₃ )-bis((C2H ₅ 0)(C2H ₄ 0)n), wherein n = from 20 to 30, and x = from 3 to 8, or

sulphated or sulphonated variants thereof 1 .0 1 .0

1 ,2-Propanediol 3.9 3.9

Protease (40.6 mg active/g) ⁹ 0.6 0.6

Amylase: Stainzyme® (15 mg active/g) ⁸ 0.2 0.2

Fluorescent Whitening Agents ¹⁰ 0.1 0.1

Water, perfume, dyes & other components Balance

Polyethyleneimine (MW = 600) with 20 ethoxylate groups per -NH.

Random graft copolymer is a polyvinyl acetate grafted polyethylene oxide copolymer having a polyethylene oxide backbone and multiple polyvinyl acetate side chains. The molecular weight of the polyethylene oxide backbone is about 6000 and the weight ratio of the polyethylene oxide to polyvinyl acetate is about 40 to 60 and no more than 1 grafting point per 50 ethylene oxide units.

3. Linear alkylbenzenesulfonate having an average aliphatic carbon chain length C11-C12 supplied by Stepan, Northfield, Illinois, USA

4. AE3S is C12-15 alkyl ethoxy (3) sulfate supplied by Stepan, Northfield, Illinois, USA

5. AE7 is C12-15 alcohol ethoxylate, with an average degree of ethoxylation of 7, supplied by Huntsman, Salt Lake City, Utah, USA

6. AE9 is C12-13 alcohol ethoxylate, with an average degree of ethoxylation of 9, supplied by Huntsman, Salt Lake City, Utah, USA

7. Suitable chelants are, for example, diethylenetetraamine pentaacetic acid (DTPA) supplied by Dow Chemical, Midland, Michigan, USA or Hydroxyethane di phosphonate (HEDP) supplied by Solutia, St Louis, Missouri, USA Bagsvaerd, Denmark

8. Savinase®, Natalase®, Stainzyme®, Lipex®, Celluclean™, Mannaway® and Whitezyme® are all products of Novozymes, Bagsvaerd, Denmark.

9. Proteases may be supplied by Genencor International, Palo Alto, California, USA (e.g.

Purafect Prime®) or by Novozymes, Bagsvaerd, Denmark (e.g. Liquanase®, Coronase®).

10. Suitable Fluorescent Whitening Agents are for example, Tinopal® AMS, Tinopal® CBS-X, Sulphonated zinc phthalocyanine Ciba Specialty Chemicals, Basel, Switzerland

1 1 . 2-Butyl-2-ethyl-1 ,3-propane diol + 2,0 propylene oxide/OH, aminated, preparation of poly- etheramine described in Example 1 .

Technical stain swatches of cotton CW120 containing bacon grease, burnt butter, dirty motor oil, hamburger grease, Italian dressing, lipstick, margarine, pizza sauce, taco grease were purchased from Empirical Manufacturing Co., Inc (Cincinnati). The stained swatches were washed in conventional western European washing machines (Miele®) using 14 grains per gallon hard- ness, selecting the cotton cycle at 30°C, using 80 g of each of the respective detergent composition. Image analysis was used to compare each stain to an unstained fabric control. Software converted images taken into standard colorimetric values and compared these to standards based on the commonly used Macbeth Colour Rendition Chart, assigning each stain a colorimetric value (Stain Level). Eight replicates of each were prepared. The stain removal index was then calculated according to the formula shown above. Key results are summarized in the following table:

These results illustrate the surprising grease removal benefit of an etheramine mixture comprising compounds of Formula I and/or II (as used in Composition B), as compared to a conven- tional (nil-polyetheramine) liquid detergent, especially on difficult-to-remove, high-frequency consumer stains like hamburger grease and taco grease.

Example IV: Comparative Grease Removal in a Powder Additive.

The following laundry detergent compositions are prepared by traditional means known to those of ordinary skill in the art by mixing the listed ingredients. Composition A is a powder additive that contains no amine-terminated polyalkylene glycol compound. Composition B is a powder additive that uses a polyetheramine comprising 2-Butyl-2-ethyl-1 ,3-propane diol + 2,0 propylene oxide/OH, aminated, preparation of polyetheramine described in Example 1 Formula B above).

Technical stain swatches were purchased from Warwick Equest Ltd. and washed in conven- tional western European washing machines (Ariston Hotpoint), selecting the cotton cycle at 30°C, using 80 g of a marketed commercial liquid detergent composition (i.e., Ariel Liquid Ac- tilift) and 30g of powder additive, Composition A, which contains no amine-terminated poly- alkylene glycol compound, or Composition B , a powder additive that uses a polyetheramine comprising 2-Butyl-2-ethyl-1 ,3-propane diol + 2,0 propylene oxide/OH , aminated, preparation of polyetheramine described in Example 1 , Formula B above).

Image analysis was used to compare each stain to an unstained fabric control. Software converted images taken into standard colorimetric values and compared these to standards based on the commonly used Macbeth Colour Rendition Chart, assigning each stain a colorimetric value (Stain Level). Eight replicates of each were prepared. The stain removal index was then calculated according to the formula above.

Statistical significance on a 95% confidence level was calculated using standard statistical methods (Student's t-test) and is shown with an "s" nest to the stain removal index.

Key results are summarized in the following tables:

1. Mannaway, from Novozymes (Denmark), 4mg active enzyme per gram.

2. Celluclean, from Novozymes (Denmark), 15.6mg active enzyme per gram.

3. 2-Butyl-2-ethyl-1 ,3-propane diol + 2,0 propylene oxide/OH, aminated, preparation of polyetheramine described in Example 1 4. TAED is tetraacetylethylenediamine, supplied under the Peractive® brand name by Clari- ant GmbH, Sulzbach, Germany

5. Sodium percarbonate supplied by Solvay, Houston, Texas, USA

6. AE7 is C-14-15 alcohol ethoxylate, with an average degree of ethoxylation of 7, supplied by Huntsman, Salt Lake City, Utah, USA

7. NOBS is sodium nonanoyloxybenzenesulfonate, supplied by Future Fuels, Batesville, Arkansas, USA

8. Suitable Fluorescent Whitening Agents are for example, Tinopal® AMS, Tinopal® CBS-X,

Sulphonated zinc phthalocyanine Ciba Specialty Chemicals, Basel, Switzerland

These results illustrate the surprising grease removal benefit of an etheramine mixture comprising compounds of Formula I and/or II (as used in Composition B) compared to conventional WE liquid detergent that does not contain branched amine-terminated polyakylene glycols, in 30 C Miele wash cycle. Application of the amines as hardener in epoxy systems

Example 1 :

Preparation of the reaction resin molding material and investigation of reactivity profile

The compared formulations were prepared by mixing of stoichiometric amounts of amine with a liquid epoxy resin based on bisphenol-A-diglycidyl ether (EEW 182).

The rheological measurements for investigating the reactivity profile of the amines with epoxy resins were carried out at a shear stress controlled plate-plate rheometer (MCR 301 , Anton Paar) with a plate diameter of 15 mm and a gap distance of 0.25 mm at different temperatures.

Analysis 1 : Comparison of the time to reach a viscosity of 10000 mPa ^* s at a defined tempera- tur: The measurement was carried out using the before mentioned rheometer at different temperatures (10°C, 23°C, 75°C) (rotating). Comparison of gel time: The measurement was carried out using the before mentioned rheometer at different temperatures (10°C, 23°C, 40°C, 75°C) (rotating-oscillating). The gel time is given by the insection of loss modulus (G") and storage modulus (G').

A: polyetheramine (2-Aminomethylethyl)-omega-(2-aminomethylethoxy)-poly(oxy(me thyl-1 ,2- ethandiyl)), sold under the trade name Polyetheramine® D 230 or JEFFAMINE® D-230

B: Pol etheramine with the following structure, sold under the tradename XTJ568®:

n = 2,5

C: Poly[oxy(methyl-1 , 2-ethanediyl)], a-hydro^-(2-aminomethylethoxy)-, ether with 2-ethyl-2- (hydroxymethyl)-1 ,3-propanediol (3:1 ), CAS-Nr.: 39429-51 -3, sold under the trade name Polyetheramine T 403 or JEFFAMINE T-403 D: 2-Butyl-2-ethyl-1 ,3-propane diol + 2,0 propylene oxide/OH, aminated, synthesis described in example 1

E: 2-Butyl-2-ethyl-1 ,3-propane diol + 2,0 propylene oxide/OH, aminated, synthesis described in example 1 , second batch

F: 1 mol 2-butyl-2-ethyl-1 ,3-propanediol + 1 .0 mole propylene oxide, aminated, synthesis described in comparative example 1

G: 2, 2-Dimethyl-1 ,3-propane diol+ 2 PO/ OH, aminated, synthesis described in comparative example 7 Example 2

Exothermic profile of reaction resin molding material and glas temperatures of the cured ther- mosets

The DSC-measurements of the curing reaction of the amines with a liquid epoxy resin based on bisphenol-A-diglycidyl ether (EEW 182) for determination of onset temperature (T ₀ ), exotherm (ΔΕ) as well as glas temperature (T _g ) was carried out according to ASTM D 3418.

Analysis 2a) Temperature program for the DSC-measurements: 0°C -> 5K/min 180°C -> 30min 180°C -» 20K/min 0°C -» 20K/min 220°C.

A: polyetheramine (2-Aminomethylethyl)-omega-(2-aminomethylethoxy)-poly(oxy(me thyl-1 ,2- ethandiyl)), sold under the trade name Polyetheramine® D 230 or JEFFAMINE® D-230

B: Pol etheramine with the following structure, sold under the tradename XTJ568®:

n = 2,5

C: Poly[oxy(methyl-1 , 2-ethanediyl)], a-hydro^-(2-aminomethylethoxy)-, ether with 2-ethyl-2- (hydroxymethyl)-l ,3-propanediol (3:1 ), CAS-Nr.: 39429-51 -3, sold under the trade name Polyetheramine® D 230 or JEFFAMINE® D-230. D: 2-Butyl-2-ethyl-1 ,3-propane diol + 2,0 propylene oxide/OH, aminated, synthesis described in example 1

E: 2-Butyl-2-ethyl-1 ,3-propane diol + 2,0 propylene oxide/OH, aminated, synthesis described in example 1 , second batch

F: 1 mol 2-butyl-2-ethyl-1 ,3-propanediol + 1 .0 mole propylene oxide, aminated, synthesis described in comparative example 1

G: 2, 2-Dimethyl-1 ,3-propane diol+ 2 PO/ OH, aminated, synthesis described in comparative example 7 Results:

D; E and G show a longer open time at 23°C compared to F, the time to reach 10.000 mPas is significantly longer. On the other hand, at 75°C, D and E show a faster overall curing which are measured by the gel time. This is an advantage for the workability of the epoxy systems because the reactive components are usually mixed at ambient temperature and cured at higher temperatures later.

D and E show similiar Tgs compared to F. This means we have a better reactivity profile with similar thermomechanical properties.