ETHERAMINES BASED ON 1,3-DIALCOHOLS

Abstract

An etheramine mixture comprising of at least one amine selected from the group consisting of amine of Formula (I) and amine of Formula (II) wherein R.sub.1-R.sub.12 are independently selected from H, alkyl, cycloalkyi, aryl, alkylaryl, or arylalkyi, 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, and wherein Z.sub.1-Z.sub.3 are linear CH.sub.2CH.sub.2CH.sub.2NH.sub.2.

##STR00001##

Claims

1. An etheramine mixture comprising of at least one amine selected from the group consisting of amine of Formula (I) and amine of Formula (II), ##STR00005## 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, and wherein Z.sub.1-Z.sub.3 are linear CH.sub.2CH.sub.2CH.sub.2NH.sub.2.

2. The etheramine mixture according to claim 1, wherein the etheramine mixture comprises at least 90% by weight, based on a total weight of the etheramine mixture, of an amine of Formula (I) and/or (II).

3. The etheramine mixture according to claim 1, wherein in said amine of Formula (I) or Formula (II), R.sub.1, R.sub.2, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.11, and R.sub.12 are H and R.sub.3, R.sub.4, R.sub.9, and R.sub.10 are independently selected from C1-16 alkyl or aryl.

4. The etheramine mixture according to claim 1, wherein in said amine of Formula (I) or Formula (II), R.sub.1, R.sub.2, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.11, and R.sub.12 are H and R.sub.3, R.sub.4, R.sub.9, and R.sub.10 are independently selected from a butyl group, an ethyl group, a methyl group, a propyl group, or a phenyl group.

5. The etheramine mixture according to claim 1, wherein in said amine Formula (I) or Formula (II), R.sub.3 and R.sub.9 are each an ethyl group, R.sub.1, R.sub.2, R.sub.5 R.sub.6, R.sub.7, R.sub.8, R.sub.11, R.sub.12 are each H, R.sub.4 and R.sub.10 are each a butyl group.

6. The etheramine mixture according to claim 1, wherein the amine of Formula (I) or Formula (II) has a weight average molecular weight of about 150 to about 1000 grams/mol.

7. The etheramine mixture according to claim 1, wherein the amine of Formula (I) or Formula (II) is reacted with an acid.

8. A method of using the etheramine mixture of claim 1, the method comprising using said etheramine mixture in personal care.

9. A method of using the etheramine mixture of claim 1, the method comprising using said etheramine mixture in shampoo and body wash formulations.

10. A method of using the etheramine mixture of claim 1, the method comprising using said etheramine mixture as a curing agent for epoxy resins or as a reactant in the production of polymers.

11. A method of using the etheramine mixture of claim 1, the method comprising using said etheramine mixture in polyurethanes, polyureas, and as thermoplastic polyamide adhesives.

12. A process of production of etheramine mixtures according to claim 1 by cyanoethylation of a diol of Formula (III), ##STR00006## wherein R.sub.1-R.sub.6 are independently selected from H, alkyl, cycloalkyl, aryl, alkylaryl, or arylalkyl.

Description

EXAMPLES

[0080] .sup.1H-NMR and .sup.13C-NMR measurements were carried out in CDCl.sub.3 with a Bruker 400 MHz spectrometer.

[0081] Unless specified otherwise herein, 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) multiplied by 100:

(Total AZ:(AC+tert. AZ)100).

[0082] The total amine value (AZ) is determined according to DIN 53176.

[0083] The total acetylables value (AC) is determined according to DIN 53240.

[0084] The secondary+tertiary amine value is determined according to ASTM D2074.

[0085] The tertiary amine value is determined according to ASTM D2074.

[0086] The primary amines value is calculated as follows: primary amine value=AZsecondary+tertiary amine value.

[0087] Primary amine in % of total amine is calculated as follows:

[0088] Primary amine in %=((AZsecondary+tertiary amine value)/AZ)*100

[0089] The hydroxyl value is calculated from (total acetylables value+tertiary amine value)total amine value.

[0090] All percentages are presented as percentage based on weight unless otherwise indicated.

Example 1a

1 mol 2-butyl-2-ethyl-1,3-propanediol+2.0 mol acrylonitrile

[0091] In a 4-neck glass vessel with reflux condenser, nitrogen inlet, thermometer, and dropping funnel 216.3 g molten 2-butyl-2-ethyl-1,3-propanediol and 3.1 g tetrakis(2-hydroxyethyl)ammonium hydroxide (50% in water) was charged at 50 C. The temperature was increased to 60 C. and 171.9 g acrylonitrile was added dropwise within 1.0 h. During the addition the temperature was allowed to rise to 70 C. The reaction mixture was stirred at 60 C. for 3 h and filtered and volatile compounds were removed in vacuo. 353.0 g of a orange liquid was obtained. .sup.1H-NMR in CDCl.sub.3 showed complete conversion of acrylonitrile.

Example 1b

1 mol 2-butyl-2-ethyl-1,3-propanediol+2.0 mol acrylonitrile, hydrogenated

[0092] The nitrile was continuously hydrogenated in a tubular reactor (length 500 mm, diameter 18 mm) filled with a splitted cobalt catalyst prepared as described in EP636409. At a temperature of 110 C. and a pressure of 160 bar, 15.0 g of a solution of the nitrile in THF (20%), 24.0 g of ammonia and 16 norm litre (NL) of hydrogen were passed through the reactor per hour. The crude material was collected and stripped on a rotary evaporator to remove excess ammonia, light weight amines and THF to afford the hydrogenated product. .sup.1H and .sup.13C-NMR analysis showed full conversion of the nitrile. The analytical data by means of titration is summarized in table 1.

TABLE-US-00001 TABLE 1 Total Tertiary Primary amine- Total Secondary amine- Amine value acetylables and tertiary value Degree of value mg value amine mg amination in % of total KOH/g mg KOH/g mg KOH/g KOH/g in % amine 408.3 408.7 1.87 1.78 99.5 99.5

Example 2a

1 mol 2-butyl-2-ethyl-1,3-propanediol+1.2 mol acrylonitrile

[0093] In a 4-neck glass vessel with reflux condenser, nitrogen inlet, thermometer, and dropping funnel 240.4 g molten 2-butyl-2-ethyl-1,3-propanediol and 3.5 g tetrakis(2-hydroxyethyl)ammonium hydroxide (50% in water) was charged at 50 C. The temperature was increased to 60 C. and 95.5 g acrylonitrile was added dropwise within 1.0 h at 60-70 C. The reaction mixture was stirred at 60 C. for 3 h and filtered and volatile compounds were removed in vacuo. 372.0 g of a light yellow liquid was obtained. .sup.1H-NMR in CDCl.sub.3 showed complete conversion of acrylonitrile.

Example 2b

1 mol 2-butyl-2-ethyl-1,3-propanediol+1.2 mol acrylonitrile, hydrogenated

[0094] The nitrile was continuously hydrogenated in a tubular reactor (length 500 mm, diameter 18 mm) filled with a splitted cobalt catalyst prepared as described in EP636409. At a temperature of 110 C. and a pressure of 160 bar, 15.0 g of a solution of the nitrile in THF (20%), 24.0 g of ammonia and 16 NL of hydrogen were passed through the reactor per hour. The crude material was collected and stripped on a rotary evaporator to remove excess ammonia, light weight amines and THF to afford the hydrogenated product. .sup.1H and .sup.13C-NMR analysis showed full conversion of the nitrile. The analytical data by means of titration is summarized in table 2.

TABLE-US-00002 TABLE 2 Total Tertiary amine- Total Secondary amine- Primary value acetylables and tertiary value Degree of Amine value mg value amine mg amination in % of total KOH/g mg KOH/g mg KOH/g KOH/g in % amine 278.8 501.5 1.8 1.4 55.4 99.4

Example 3a

1 mol 2-ethyl-1,3-hexanediol+2.0 mol acrylonitrile

[0095] In a 4-neck glass vessel with reflux condenser, nitrogen inlet, thermometer, and dropping funnel 197.4 g 2-ethyl-1,3-hexanediol and 3.2 g tetrakis(2-hydroxyethyl)ammonium hydroxide (50% in water) was charged at 50 C. The temperature was increased to 60 C. and 186.2 g acrylonitrile was added dropwise within 1.0 h at 60-70 C. The reaction mixture was stirred at 60 C. for 3 h and filtered and volatile compounds were removed in vacuo. 375.0 g of a dark yellow liquid was obtained. .sup.1H-NMR in CDCl.sub.3 showed complete conversion of acrylonitrile.

Example 3b

1 mol 2-ethyl-1,3-hexanediol+2.0 mol acrylonitrile, hydrogenated

[0096] The nitrile was continuously hydrogenated in a tubular reactor (length 500 mm, diameter 18 mm) filled with a splitted cobalt catalyst prepared as described in EP636409. At a temperature of 110 C. and a pressure of 160 bar, 15.0 g of a solution of the nitrile in THF (20%), and 16 NL of hydrogen were passed through the reactor per hour. The crude material was collected and stripped on a rotary evaporator to remove excess ammonia, light weight amines and THF to afford the hydrogenated product. .sup.1H and .sup.13C-NMR analysis showed full conversion of the nitrile. The analytical data by means of titration is summarized in table 3.

TABLE-US-00003 TABLE 3 Total Tertiary amine- Total Secondary amine- Primary value acetylables and tertiary value Degree of Amine value mg value amine mg amination in % of total KOH/g mg KOH/g mg KOH/g KOH/g in % amine 376.4 471.3 15.8 1.8 79.6 95.8

Comparative Example 1a

1 mol 2-butyl-2-ethyl-1,3-propandiol+5.6 mol propylene oxide

[0097] In a 2 I autoclave 1286.7 g 2-Butyl-2-ethyl-1,3-propane diol and 15.5 g KOH (50% in water) were mixed and stirred under vacuum (<10 mbar) at 90 C. for 2 h. The autoclave was purged with nitrogen and heated to 140 C. 2612.0 g propylene oxide was added within 26 h. To complete the reaction, the mixture was allowed to post-react for additional 10 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 211.0 g water and 33.9 g phosphoric acid (40% in water) stirring at 100 C. for 0.5 h and dewatering in vacuo for 2 hours. After filtration 3901.0 g of a light yellowish oil was obtained (hydroxy value: 190 mgKOH/g).

Comparative Example 1b

1 mol 2-butyl-2-ethyl-1,3-propandiol+5.6 mol propylene oxide, aminated

[0098] The amination of 2-butyl-2-ethyl-1,3-propanediol+2,8 PO/OH (1) was conducted in a tubular reactor (length 500 mm, diameter 18 mm) which had been charged with 15 mL of silica (33 mm pellets) followed by 70 mL (74 g) of the catalyst precursor (containing oxides of nickel, cobalt, copper and tin on gama-Al.sub.2O.sub.3, 1,0-1,6 mm splitprepared according to WO 2013/072289 A1) and filled up with silica (ca. 15 mL).

[0099] After catalyst activation the alcohol was aminated at a WHSV of 0.19 kg/liter*h (molar ratio ammonia/alcohol=55:1, hydrogen/alcohol=11,6:1) at 206 C. The crude material was collected and stripped on a rotary evaporator to remove excess ammonia, light weight amines and reaction water to afford aminated 1. The analytical data of the reaction product is shown below.

TABLE-US-00004 Total Secondary Tertiary Primary amine- Total and tertiary amine- Hydroxyl Degree of Amine value 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 222.92 231.50 2.57 0.31 8.89 96.16 98.85

[0100] 2. Use as Additives in Laundry Detergent

[0101] Technical stain swatches of blue knitted cotton containing Beef Fat, Pork Fat, Chicken Fat and Bacon Grease were purchased from Warwick Equest Ltd. The stains were washed for 30 min in a launder-o-meter (manufactured by SDL Atlas) at room temperature using per canister 500 mL of washing solution, 20 steel balls (weight of 1 ball is 1 g) and ballast fabrics. The washing solution contained 5000 ppm of detergent composition DC1 (table 1). Water hardness was 2.5 mM (Ca.sup.2+:Mg.sup.2+ molar ratio 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.

[0102] 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 were calculated as color difference E (calculated according to DIN EN ISO 11664-4) between stain and untreated fabric. Stain removal from the swatches was calculated as follows:

[00001]$\mathrm{Stain}.Math..Math.\mathrm{Removal}.Math..Math.\mathrm{Index}.Math..Math.\left(\mathrm{SRI}\right)=\frac{.Math..Math.E_{\mathrm{inital}}-.Math..Math.E_{\mathrm{washed}}}{.Math..Math.E_{\mathrm{initial}}}100$

[0103] E.sub.initiail=Stain level before washing

[0104] E.sub.washed=Stain level after washing

[0105] Stain level corresponds to the amount of grease on the fabric. The stain level of the fabric before the washing (E.sub.initiail) ishigh, in the washing process stains are removed and the stain level after washing is smaller (E.sub.washed). The better the stains have been removed the lower the value for E.sub.washed will be and the higher the difference will be to E.sub.initial. Therefore, the value of stain removal index increases with better washing performance.

TABLE-US-00005 TABLE 4 Detergent composition DC1 Ingredients of liquid detergent composition DC1 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+CxH2xN+(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

[0106] Washing Test 1:

TABLE-US-00006 SRI, SRI, SRI, SRI, additive/ Beef Pork Chicken Bacon Additive [g] Fat Fat Fat Grease without additive 27.2 24.9 25.5 39.3 Comparitive example 1b 0.0375 41.0 36.9 40.4 51.0 Example 1b 0.0375 43.0 42.5 44.5 60.0

[0107] Washing Test 2

TABLE-US-00007 SRI, SRI, additive/ SRI, SRI, Chicken Bacon Additive [g] Beef Fat Pork Fat Fat Grease without additive 27.8 27.4 22.8 37.5 Example 3b 0.0375 36.9 37.3 34.9 52.2