POLYETHERAMINES BASED ON 1,3-DIALCOHOLS

Abstract

This invention relates to polyetheramines based on 1,3-dialcohols, in particular to 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),

##STR00001##

wherein R.sub.1-R.sub.12 are independently selected from H, alkyl, cycloalkyl, aryl, alkylaryl, or arylalkyl, wherein at least one of R.sub.1-R.sub.6 and at least one of R.sub.7-R.sub.12 is different from H, wherein A.sub.1-A.sub.9 are independently selected from linear or branched alkylenes having 2 to 18 carbon atoms, wherein Z.sub.1-Z.sub.4 are independently selected OH, CH.sub.2CH.sub.2CH.sub.2NH.sub.2, NH.sub.2, NHR′ or NR′R″, wherein the degree of amination is <50%, wherein R′ and R″ are independently selected from alkylenes having 2-6 carbon atoms, and wherein the sum of x+y is in the range of from 2 to 200, wherein x≧1 and y≧1; and x.sub.1+y.sub.1 is in the range of from 2 to 200.

Claims

1. An etheramine mixture comprising at least 90% by weight, based on the total weight of the etheramine mixture, of an amine of at least one of Formula (I) and (II), ##STR00006## 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 one of linear or branched alkylenes having 2 to 18 carbon atoms, wherein Z1-Z4 are independently selected from OH, CH2CH2CH2NH2, NH2, NHR′ or NR′R″, wherein the degree of amination is <50%, wherein R′ and R″ are independently selected from alkylenes having 2 to 6 carbon atoms, and wherein the sum of x+y is in the range of from 2 to 200, wherein x≧1 and y≧1; and x1+y1 is in the range of from 2 to 200.

2. The etheramine mixture according to claim 1, wherein 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 (II).

3. The etheramine mixture according to claim 1, wherein in said polyetheramine of Formula (I) or Formula (II), x+y is in the range of from 2 to 20.

4. The etheramine mixture according to claim 1, wherein in said polyetheramine of Formula (I) or Formula (II), x+y is in the range of from 3 to 20.

5. The etheramine mixture according to claim 1, wherein in said polyetheramine of Formula (I) or Formula (II), the degree of amination lies in the range of 30% to <50%.

6. The etheramine mixture according to claim 1, wherein in said polyetheramine of Formula (I) or Formula (II), A1-A9 are independently selected from the group consisting of ethylene, propylene, and butylene.

7. The etheramine mixture according to claim 1, wherein in said polyetheramine of Formula (I) or Formula (II), each of A1-A9 is propylene.

8. The etheramine mixture according to claim 1, wherein in said polyetheramine of Formula (I) or Formula (II), R1, R2, R5, R6, R7, R8, R11, and R12 are H and R3, R4, R9, and R10 are independently selected from C1-16 alkyl or aryl.

9. The etheramine mixture according to claim 1, wherein in said polyetheramine of Formula (I) or Formula (II), R1, R2, R5, R6, R7, R8, R11, and R12 are H and R3, R4, R9, and R10 are independently selected from a butyl group, an ethyl group, a methyl group, a propyl group, or a phenyl group.

10. The etheramine mixture according to claim 1, wherein in said polyetheramine Formula (I) or Formula (II), R3 and R9 are each an ethyl group, R1, R2, R5 R6, R7, R8, R11, R12 are each H, R4 and R10 are each a butyl group.

11. The etheramine mixture according to claim 1, wherein the polyetheramine of each of Formula (I) and Formula (II) has a weight average molecular weight of about 290 to about 1000 grams/mole.

12. The etheramine mixture according to claim 1, wherein the polyetheramine of each of Formula (I) and Formula (II) is reacted with an acid.

13. A process for the manufacture of an etheramine mixture comprising at least 90% by weight, based on the total weight of the etheramine mixture, of an etheramine of at least one of Formula (I) and (II) comprising the following steps: a) reacting a 1,3-diol 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, ##STR00007## wherein R1-R6 are independently of one another H, alkyl, cycloalkyl, aryl, alkylaryl, or arylalkyl and at least one group selected from R1-R6 is different from H, followed by one of: b1) aminating the alkoxylated 1, 3-diols with ammonia, and b2) reductive cyanoethylation of the alkoxylated 1, 3-diols.

14. The process according to claim 12, wherein the molar ratio of 1,3-diol to C2-C18 alkylene oxides is in the range of 1:3 to 1:8.

15. The process according to claim 12, wherein the molar ratio of 1,3-diol to C2-C18 alkylene oxides is in the range of 1:4 to 1:6.

16. The process according to claim 12, wherein the C2-C18 alkylene oxides are selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and a mixture thereof.

17. The process according to claim 12, wherein the C2-C18 alkylene oxide is propylene oxide.

18. The process according to claim 12, wherein the 1,3-diol of formula (III) is 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, and 2-ethyl-1,3-hexandiol.

19. The process according to claim 12, wherein the amination is carried out in the presence of copper-, nickel- or cobalt-containing catalyst.

20. The process according to claim 18, wherein the catalytically active material of the catalysts, before the reduction thereof with hydrogen, comprises oxygen compounds of aluminum, 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.

21. A composition for use in at least one of personal care, shampoo, and body wash formulations, the composition comprising the etheramine mixture of claim 1.

22. A composition for use as a curing agent, the composition comprising the etheramine mixture of claim 1.

23. A composition for use as a reactant in the production of polymers, the composition comprising the etheramine of claim 1.

24. A composition for use in at least one of polyurethanes, polyureas, and thermoplastic polyamide adhesives, the composition comprising the etheramine of claim 1.

Description

METHODS OF USE

[0074] 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.

[0075] 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.

[0076] 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 20 g to about 300 g of product dissolved or dispersed in a wash solution of volume from about 5 L to about 65 L. 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).

[0077] 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.

[0078] 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 SONTARA® by DuPont and POLYWEB® by James River Corp.

[0079] Hand washing methods, and combined handwashing with semiautomatic washing machines, are also included.

Machine Dishwashing Methods

[0080] 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 8 g to about 60 g of product dissolved or dispersed in a wash solution of volume from about 3 L to about 10 L.

[0081] 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

[0082] The cleaning compositions described herein can be packaged in any suitable container including those constructed from paper, cardboard, plastic materials, and any suitable laminates. An optional packaging type is described in European Application No. 94921505.7.

Multi-Compartment Pouch Additive

[0083] The cleaning compositions described herein may also be packaged as a multi-compartment cleaning composition.

EXAMPLES

Example 1a: 1 Mol 2-Butyl-2-Ethyl-1,3-Propanediol+5.6 Mole Propylene Oxide

[0084] In a 2 l autoclave 313.1 g 2-Butyl-2-ethyl-1,3-propane diol 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 a light yellowish oil was obtained (hydroxy value: 233 mgKOH/g).

Example 1b: 1 Mol 2-Butyl-2-Ethyl-1,3-Propanediol+5.6 Mole Propylene Oxide, Partially Aminated (32% Amination Degree)

[0085] The amination of (1a) was conducted in a tubular reactor (length 500 mm, diameter 18 mm) which had been charged with 15 mL of silica (3×3 mm pellets) followed by 70 mL (74 g) of the catalyst precursor (containing oxides of nickel, cobalt, copper and tin on gamma-Al.sub.2O.sub.3, 1.0-1.6 mm split—prepared according to WO 2013/072289 A1) and filled up with silica (ca. 15 mL).

[0086] 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.

[0087] The catalyst was flushed with ammonia at 100° C., before the temperature was increased to 175° C. and the alcohol feed was started with a WHSV of 0.44 kg/liter*h (molar ratio ammonia/alcohol=27:1, hydrogen/alcohol=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 the aminated material. The analytical data of the reaction product is shown in Table 1.

TABLE-US-00001 TABLE 1 Properties of reaction product of Example 1b. Total Secondary Tertiary Primary amine- Total and tertiary amine- Hydroxyl Grade of Amine value acetylatables amine value value value amination in % of total mg KOH/g mg KOH/g mg KOH/g mg KOH/g mg KOH/g in % amine 75.87 237.00 0.16 0.00 161.13 32.01 99.79

Use as Additives in Laundry Detergents

[0088] Technical stain swatches of blue knitted cotton containing Beef Fat, Pork Fat, Sausage Fat, Chicken Fat and Bacon Grease 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 1.125 g of polyetheramine additive and some hydrochloric acid to readjust the pH after addition of the polyetheramine. (pH of 75 g of LA1 (Tab. 2) in 1 L water should be at pH=8.3.) Water hardness was 2.5 mM (Ca.sup.2+:Mg.sup.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.

[0089] Stain removal from the swatches was calculated as follows:

[00001]$\mathrm{Stain}.Math..Math.\mathrm{Removal}.Math..Math.\mathrm{Index}.Math..Math.\left(S.Math..Math.R.Math..Math.I\right)=\frac{\left(\Delta .Math..Math.E_{\mathrm{initial}}-\Delta .Math..Math.E_{\mathrm{washed}}\right)}{\Delta .Math..Math.E_{\mathrm{initial}}}\times 100$$\Delta .Math..Math.E_{\mathrm{initial}}=\mathrm{Stain}.Math..Math.\mathrm{level}.Math..Math.\mathrm{before}.Math..Math.\mathrm{washing}$$\Delta .Math..Math.E_{\mathrm{washed}}=\mathrm{Stain}.Math..Math.\mathrm{level}.Math..Math.\mathrm{after}.Math..Math.\mathrm{washing}$

[0090] ΔE is calculated as CIE 1976 color difference according to DIN EN ISO 11664-4 (June 2012). ΔE.sub.initial is calculated with L*, a*, b* values measured on fabric without stain and the L*, a*, b* values measured on the greasy stain before washing. ΔE.sub.washed is calculated with L*, a*, b* values measured on fabric without stain and the L*, a*, b* values measured on the greasy stain after washing. Standard colorimetric measurement was used to obtain L*, a* and b* values.

[0091] 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 (ΔE.sub.initial) is high, in the washing process stains are removed and the stain level after washing is smaller (ΔE.sub.washed). The better the stains have been removed the lower the value for ΔE.sub.washed Will be and the higher the difference will be to ΔE.sub.initial. Therefore the value of stain removal index increases with better washing performance.

TABLE-US-00002 TABLE 2 liquid detergent composition LA1 Ingredients of liquid detergent composition LA1 percentage by weight Alkyl Benzene sulfonate.sup.1 7.50% AE3S.sup.2 2.60% AE9.sup.3 0.40% NI 45-7.sup.4 4.40% Citric Acid 3.20% C1218 Fatty acid 3.10% Amphiphilic polymer.sup.5 0.50% Zwitterionic dispersant.sup.6 1.00% Ethoxylated Polyethyleneimine.sup.7 1.51% Protease.sup.8 0.89% Enymes.sup.9 0.21% Chelant.sup.10 0.28% Brightener.sup.11 0.09% Solvent 7.35% Sodium Hydroxide 3.70% Fragrance & Dyes 1.54% Water, filler, stucturant To Balance .sup.1Linear alkylbenenesulfonate having an average aliphatic carbon chain length C11-C12 supplied by Stepan, Northfield Illinois, USA .sup.2AE3S is C12-15 alkyl ethoxy (3) sulfate supplied by Stepan, Northfield, Illinois,USA .sup.3AE9 is C12-14 alcohol ethoxylate, with an average degree of ethoxylation of 9, supplied by Huntsman, Salt Lake City, Utah, USA .sup.4NI 45-7 is C14-15 alcohol ethoxylate, with an average degree of ethoxylation of 7, supplied by Huntsman, Salt Lake City, Utah, USA .sup.5Random 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. .sup.6A compound having the following general structure: bis((C2H5O)(C2H4O)n)(CH3)—N+—CxH2x—N+—(CH3)-bis((C2H5O)(C2H4O)n), wherein n = from 20 to 30, and x = from 3 to 8, or sulphated or sulphonated variants thereof .sup.7Polyethyleneimine (MW = 600) with 20 ethoxylate groups per—NH .sup.8Proteases may be supplied by Genencor International, Palo Alto, California, USA (e.g. Purafect Prime ®) or by Novozymes, Bagsvaerd, Denmark (e.g. Liquanase ®, Coronase ®). .sup.9Natalase ®, Mannaway ® are all products of Novozymes, Bagsvaerd, Denmark. .sup.10Suitable chelants are, for example, diethylenetetraamine pentaacetic acid (DTPA) supplied by Dow Chemical, Midland, Michigan, USA or Hydroxyethane di phosphonate (HEDP) or diethylene triamine penta(methyl phosphonic) acid supplied by Solutia, St Louis, Missouri, USA; .sup.11Fluorescent Brightener 1 is Tinopal ® AMS, Fluorescent Brightener 2 supplied by Ciba Specialty Chemicals, Basel, Switzerland

TABLE-US-00003 Washing Test 1: Initial water temperature at 22° C. Stain SRI for A SRI for B Beef Fat 72.9 78.0 Pork Fat 68.8 73.8 Bacon Grease 68.6 72.9 A: liquid detergent composition LA1 (see Table 2) without additional etheramine additive B: liquid detergent composition LA1 (see Table 2) with (1 mol 2-butyl-2-ethyl-1,3-propanediol + 5.6 mole propylene oxide, partially aminated (32% amination degree)) as described in example 1b.