阅读说明：本技术 具有末端聚氧化丁烯嵌段的烷氧基化聚亚烷基亚胺或烷氧基化多胺 (Alkoxylated polyalkyleneimines or alkoxylated polyamines having terminal polyoxybutylene blocks ) 是由 B·卢多尔夫 S·艾伯特 S·夏拉 F·许尔斯科特 M·杰克逊 K·布莱斯 R·奇尔顿 于 2020-03-10 设计创作，主要内容包括：本发明涉及根据通式(I)的烷氧基化聚亚烷基亚胺或烷氧基化多胺,其中各变量E、R、B、y和z如下所定义。本发明还涉及一种制备这类烷氧基化聚亚烷基亚胺或烷氧基化多胺的方法以及这类化合物在例如化妆品配制剂中的用途。[式I](The invention relates to alkoxylated polyalkyleneimines or alkoxylated polyamines according to the general formula (I) wherein the variables E, R, B, y and z are defined as follows. The invention also relates to a method for producing said alkoxylated polyalkyleneimines or alkoxylated polyamines and to the use of said compounds, for example in cosmetic formulations. [ formula I ]])

1. an alkoxylated polyalkyleneimine or an alkoxylated polyamine of the general formula (I):

wherein each variable is defined as follows:

r represents identical or different linear or branched C₂-C₁₂Alkylene or an ether alkyl unit of the following formula (III):

wherein each variable is defined as follows:

R¹⁰、R¹¹、R¹²denotes the same or different linear or branched C₂-C₆Alkylene, and

d is an integer of 0 to 50;

b represents the extension of the alkoxylated polyalkyleneimines by branching,

y and z are each an integer of 0 to 150,

e represents identical or different alkyleneoxy units of formula (II):

wherein each variable is defined as follows:

R¹represents 1, 2-butylene and/or 1, 2-isobutylene;

R²represents hydrogen and/or C₁-C₂₂Alkyl and/or C₇-C₂₂Aralkyl group;

m is an integer of at least 20;

n is an integer of at least 3.

2. The alkoxylated polyalkyleneimine or alkoxylated polyamine according to claim 1, wherein R represents the same or different linear or branched C₂-C₁₂Alkylene, preferably R is ethylene, propylene or hexamethylene.

3. An alkoxylated polyalkyleneimine or alkoxylated polyamine according to claim 1 or 2 wherein within formula (II) the variables are each as defined below:

R¹represents 1, 2-butylene;

R²represents hydrogen and/or C₁-C₄Alkyl, preferably hydrogen, methyl and/or ethyl, most preferably hydrogen;

m is an integer from 20 to 50, preferably from 20 to 40, more preferably from 21 to 28, in particular from 22 to 25;

n is an integer from 3 to 20, preferably from 4 to 12, more preferably from 4 to 8, in particular from 4 to 7.

4. Alkoxylated polyalkyleneimine or alkoxylated polyamine according to any of claims 1 to 3, wherein the molecular weight (Mw) of the polyalkyleneimine backbone or polyamine backbone is from 50 to 10000g/mol, preferably 500-5000g/mol, more preferably 600-1000 g/mol.

5. The alkoxylated polyalkyleneimine according to any of claims 1 to 4, wherein each of the variables is defined as follows:

r is ethylene or propylene, preferably ethylene;

the sum y + z is an integer from 9 to 120, preferably from 10 to 20.

6. The alkoxylated polyalkyleneimine according to claim 5, wherein

R is ethylene or propylene, preferably ethylene;

the sum y + z is an integer from 9 to 120, preferably from 10 to 20;

R¹represents 1, 2-butylene;

R²represents hydrogen and/or C₁-C₄Alkyl, preferably hydrogen, methyl and/or ethyl, most preferably hydrogen;

m is an integer from 20 to 50, preferably from 20 to 40, more preferably from 21 to 28, in particular from 22 to 25;

n is an integer from 3 to 20, preferably from 4 to 12, more preferably from 4 to 8, in particular from 4 to 7.

7. The alkoxylated polyalkyleneimine according to claim 5 or 6, wherein each of the variables is defined as follows:

r is ethylene

The sum of y + z is an integer from 10 to 20;

R¹represents 1, 2-butylene;

R²represents hydrogen;

m is an integer of 22 to 25;

n is an integer of 4 to 7.

8. The alkoxylated polyamine according to any one of claims 1 to 4, wherein

y and z are both 0 and are each,

r represents identical or different linear or branched C₂-C₁₂Alkylene or an etheralkyl unit according to formula (III) wherein

d is 1 to 5, and

R¹⁰、R¹¹、R¹²independently selectFrom linear or branched C₃-C₄An alkylene group.

9. The alkoxylated polyamine according to claim 8, wherein

R¹Represents 1, 2-butylene;

R²represents hydrogen and/or C₁-C₄Alkyl, preferably hydrogen, methyl and/or ethyl, most preferably hydrogen;

m is an integer from 20 to 50, preferably from 20 to 40, more preferably from 21 to 28, in particular from 22 to 25;

n is an integer from 3 to 20, preferably from 4 to 12, more preferably from 4 to 8, in particular from 4 to 7.

10. The alkoxylated polyamine according to claim 8 or 9, wherein

R is a linear hexamethylene group;

R¹represents 1, 2-butylene;

R²represents hydrogen;

m is an integer of 22 to 25;

n is an integer of 4 to 7.

11. Alkoxylated polyalkyleneimine or alkoxylated polyamine according to any of claims 1 to 10, wherein up to 100% of the nitrogen atoms present in the alkoxylated polyalkyleneimine or alkoxylated polyamine are quaternized, preferably the degree of quaternization of the nitrogen atoms present in the alkoxylated polyalkyleneimine or alkoxylated polyamine is from 10 to 95%.

12. Use of the alkoxylated polyalkyleneimines or alkoxylated polyamines according to any of claims 1 to 11 in cosmetic formulations, as breakers for crude oil emulsions, in pigment dispersions for inkjet inks, in formulations for electroplating, in cement compositions.

13. A process for the preparation of an alkoxylated polyalkyleneimine or an alkoxylated polyamine according to any of claims 1 to 11, wherein the polyalkyleneimine backbone or polyamine backbone is first reacted with ethylene oxide and then with butylene oxide to obtain the corresponding alkoxylated compound.

14. The process according to claim 13, wherein the polyalkyleneimine or polyamine backbone is reacted with at least 20 moles of ethylene oxide and then with at least 3 moles of butylene oxide per mole of N-H functional groups in the polyalkyleneimine or polyamine.

15. A process according to claim 13 or 14, wherein additionally a quaternized alkoxylated polyalkyleneimine or alkoxylated polyamine is present.

Examples

The following abbreviations are used in the examples:

EO ethylene oxide

BUO butylene oxide

Polyethyleneimine with PEI600 average molecular weight of 600g/mol

xEO/NH x moles ethylene oxide/mole NH functional groups

y BUO/NH y moles butylene oxide/mole NH functional groups

Synthesizing:

example 1: polyethyleneimine, with a molecular weight of 600g/mol, alkoxylated with 24 mol of ethylene oxide and 4 mol of 1, 2-butylene oxide per NH function.

Step 1a) A polyethyleneimine having a molecular weight of 600g/mol, alkoxylated with 1 mol of ethylene oxide per NH function

A5L autoclave was charged with 665.0g of polyethyleneimine having an average molecular weight of 600g/mol and 33.3g of water. The reactor was purged 3 times with nitrogen and heated to 110 ℃. 680.5g of ethylene oxide were added over 13 hours. To complete the reaction, the reaction mixture was allowed to post-react for 5 hours. Water and volatile compounds were removed under vacuum (20 mbar) at 90 ℃. A highly viscous yellow oil (1340.0g, pH: 11.05 (5% in water)) was obtained.

Step 1b) polyethyleneimine having a molecular weight of 600g/mol, alkoxylated with 24 mol of ethylene oxide per NH function

The product from step 1a) (101.3g) and 5.1g of potassium hydroxide (50% in water) were placed in a 2L autoclave. The mixture was heated to 120 ℃ under vacuum (<10 mbar) and stirred for 2 hours to remove water. The reactor was purged 3 times with nitrogen and the mixture was heated to 140 ℃. 1178.3g of ethylene oxide were added over 8 hours. To complete the reaction, the mixture was allowed to post-react for 3 hours. Volatile compounds were removed in vacuo. 1275.0g of a beige solid are obtained.

Step 1c) A polyethyleneimine having a molecular weight of 600g/mol alkoxylated with 24 mol of ethylene oxide and 4 mol of butylene oxide per NH function

The product from step 1b) (577.0g) and 0.6g of potassium hydroxide (50% in water) were placed in a 2L autoclave. The mixture was heated to 120 ℃ under vacuum (<10 mbar) and stirred for 2 hours to remove water. The reactor was purged 3 times with nitrogen and the mixture was heated to 140 ℃. 156.2g of butylene oxide were added over 2 hours. To complete the reaction, the mixture was allowed to post-react for 5 hours. Volatile compounds were removed in vacuo at 90 ℃. 704.0g of a light brown oil were obtained (cloud point: 43 ℃ C. (1% in water)).

Example 2: polyethyleneimine having a molecular weight of 600g/mol, alkoxylated with 24 mol of ethylene oxide and 6 mol of 1, 2-butylene oxide per NH function.

Step 2c) A polyethyleneimine having a molecular weight of 600g/mol alkoxylated with 24 mol of ethylene oxide and 6 mol of butylene oxide per NH function

The product from example 1, step 1b) (536.8g) and 0.8g of potassium hydroxide (50% in water) were placed in a 2L autoclave. The mixture was heated to 120 ℃ under vacuum (<10 mbar) and stirred for 2 hours to remove water. The reactor was purged 3 times with nitrogen and the mixture was heated to 140 ℃. 217.5g of butylene oxide were added over 2 hours. To complete the reaction, the mixture was allowed to post-react for 5 hours. Volatile compounds were removed in vacuo at 90 ℃. 735.0g of a light brown oil were obtained (cloud point: 27 ℃ C. (1% in water)).

Comparative example 3(CE 3): polyethyleneimine, with a molecular weight of 600g/mol, alkoxylated with 4 moles of 1, 2-butylene oxide and 24 moles of ethylene oxide per NH function.

Step 3a) A polyethyleneimine having a molecular weight of 600g/mol alkoxylated with 1 mol of 1, 2-butylene oxide per NH function

A2L autoclave was charged with 430.0g of polyethyleneimine having an average molecular weight of 600g/mol and 21.5g of water. The reactor was purged 3 times with nitrogen and heated to 120 ℃. 721.1g of 1, 2-butylene oxide were added over 11 hours. To complete the reaction, the reaction mixture was allowed to post-react for 10 hours. Water and volatile compounds were removed under vacuum (20 mbar) at 90 ℃ for 3 hours. A highly viscous yellow oil (1151g) was obtained.

Step 3b) polyethyleneimine having a molecular weight of 600g/mol alkoxylated with 4 mol of 1, 2-butylene oxide per NH function

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

Step 3c) alkoxylation of a polyethyleneimine having a molecular weight of 600g/mol by 4 mol of 1, 2-butylene oxide and 24 mol of ethylene oxide per NH function

The product from step 3b) (232.0g) and 3.15 potassium hydroxide (50% in water) were placed in a 2L autoclave. The mixture was heated to 120 ℃ under vacuum (<10 mbar) and stirred for 2 hours to remove water. The reactor was purged 3 times with nitrogen and the mixture was heated to 140 ℃. 740.0g of ethylene oxide were added over 16 hours. To complete the reaction, the mixture was allowed to post-react for 5 hours. Volatile compounds were removed in vacuo. 974.0g of a beige solid are obtained.

Examples of use in laundry detergents

After the addition, the pH is readjusted to the pH of the washing solution without additives.

Standard colorimetric measurements were used to obtain values for L, a, and b for each stain before and after washing. According to ASTM standards: d4265-14, calculating the Stain Removal Index (SRI) from the values of L, a and b.

In the following examples, the ingredients in the cleaning compositions are expressed in weight percent relative to the cleaning composition.

The following laundry detergent compositions are prepared by mixing the listed ingredients in a conventional manner known to those skilled in the art.

Example (b):

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

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

Comparative example CE 3: PEI600+4BuO/NH +24EO/NH

The above examples were added as additives to detergent compositions shown in Table 1, and used as laundry detergents using a bottle type detergency tester shown in Table 2.

Table 1: detergent composition

Dodecyl benzene sulfonate	6,9g
		C12C14 fatty alcohol ether sulfate (2EO), sodium salt, 70% aqueous solution	11,3g
KOH	To pH 8,5
		C13C15 oxo alcohol ethoxylate (7EO)	1,0g
1, 2-propanediol	6,0g
		Ethanol	2,0g
Water (W)	To 100g

Table 2: 2000ppm detergent was used with 25ppm additive. 30 ℃, hardness: 1 mM.

As can be seen from Table 2, by using the detergent compositions containing the compounds of the present invention having a terminal polyoxybutylene block (examples 1 and 2), stains can be removed more effectively (higher SRI value) than the composition of comparative example 3 containing polyoxybutylene in which polyoxybutylene is not a terminal block but polyoxybutylene is in a different position in each alkoxylated compound.

Illustrative examples of specific cleaning compositions are provided below. Alkoxylated polyalkyleneimines or alkoxylated polyamines according to the present invention, for example the specific compounds as described above with respect to examples 1 or 2, are added to those illustrative examples of cleaning compositions in suitable amounts known to those skilled in the art.

Illustrative examples, hand dishwashing compositions:

illustrative examples, water-soluble laundry detergent unit dose pouches:

a water-soluble unit dose laundry detergent pouch comprising a water-soluble film based on polyvinyl alcohol or a polyvinyl alcohol copolymer, preferably wherein the film is a blend of polyvinyl alcohol homopolymer and/or polyvinyl alcohol copolymer and the liquid laundry detergent comprises:

illustrative examples, liquid laundry detergent compositions:

illustrative examples, free-flowing solid particulate laundry detergent compositions: