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US-20260125620-A1 - AMPHOTERICALLY-MODIFIED TRIALKYLENE TETRAMINE ETHOXYLATES FOR IMPROVED STAIN REMOVAL OF LAUNDRY DETERGENTS

US20260125620A1US 20260125620 A1US20260125620 A1US 20260125620A1US-20260125620-A1

Abstract

Disclosed herein are amphoterically-modified trialkylene tetramine ethoxylates, their manufacture and their use in detergent formulations.

Inventors

  • Holger Tuerk
  • SUSANNE CARINA ENGERT
  • Alexander Michael HAYDL

Assignees

  • BASF SE

Dates

Publication Date
20260507
Application Date
20221118
Priority Date
20211129

Claims (20)

  1. 1 . Amphoterically-modified trialkylene tetramine ethoxylates (A) of general formula (I) wherein each R 1 is individually the same or different and selected from the group consisting of C 1 -C 4 -alkyl, H and a free electron pair, wherein at least 50% of all R 1 are C 1 -C 4 -alkyl, EO is —CH 2 —CH 2 —O, each Y is individually the same or different and selected from the group consisting of SO 3 − and H, wherein at least 30% of all Y are SO 3 − , each x is individually the same or different and in a range of from 5 to 50 and n is selected from the group consisting of 1, 2 and 3, and wherein n is 1, 2 or 3, at least 80% of R 1 are C 1 -C 4 -alkyl and the ratio of R 1 to Y is on average from 1.0:1.0 to 1.0:0.8 when R 1 is C 1 -C 4 -alkyl and Y is SO 3 − .
  2. 2 . The amphoterically-modified trialkylene tetramine ethoxylates (A) according to claim 1 , wherein n is 1 and at least 90% of all R 1 are methyl.
  3. 3 . The amphoterically-modified trialkylene tetramine ethoxylates (A) according to claim 1 , wherein n is 1, at least 90% of all R 1 are methyl and x is in a range of from 15-30.
  4. 4 . A mixture of compounds comprising at least one amphoterically-modified trialkylene tetramine ethoxylate (A) according to claim 1 , and at least one isomeric compound according to formula (II) wherein each R 1 is individually the same or different and selected from the group consisting of C 1 -C 4 -alkyl, H and a free electron pair, wherein at least 50% of all R 1 are C 1 -C 4 -alkyl, EO is —CH 2 —CH 2 —O, each Y is individually the same or different and selected from the group consisting of SO 3 − and H, wherein at least 30% of all Y are SO 3 − , each x is individually the same or different and in a range of from 5 to 50, and n is selected from the group consisting of 1, 2 and 3.
  5. 5 . The mixture according to claim 4 comprising an amphoterically-modified trialkylene tetramine ethoxylate (A) according to formula (I) and compounds according to formula (II) in a total molar ratio in a range of from 10:1 or higher.
  6. 6 . The mixture comprising a compound according to claim 4 , wherein said mixture additionally comprises the sulfate of an alkali metal and/or an amine.
  7. 7 . The mixture according to claim 6 , wherein said mixture additionally comprises the sulfate salt of an alkanolamine.
  8. 8 . A process for making amphoterically-modified trialkylene tetramine ethoxylates (A) according to claim 1 , said process comprising (e) providing a diamine selected from the group consisting of 1,2-ethylene diamine, 1,4-butylene diamine, 1,6-hexamethylene diamine and mixtures thereof (f) cyanoethylating said diamine with acrylonitrile in a ratio from 1:1 to 1:2.5, followed by hydrogenation, to obtain trialkylene tetramines with 1, 2 and 3 repeating units, (g) optionally purifying the trialkylene tetramines from step (b), (h) ethoxylating said trialkylene tetramines from step b or c, and (i) at least partially quaternizing and transsulfating with a di-C 1 -C 4 -alkyl sulfate.
  9. 9 . The process according to claim 8 , wherein the purifying (g) is performed to obtain trialkylene tetramines with 1, 2 and 3 repeating units, or mixtures thereof, with a purity of at least 50 wt %.
  10. 10 . The process according to claim 8 , wherein the at least partially quaternizing in step (i) is performed with dimethyl sulfate,
  11. 11 . The process according to claim 8 , wherein the transsulfating is performed with sulfuric acid as a catalyst.
  12. 12 . The process according to claim 8 , wherein the transsulfating in step (i) is performed quantitatively with a yield of at least 80% and a slightly cationic or net neutral polymer is obtained.
  13. 13 . The process according to claim 8 , wherein said process includes the subsequent step of neutralizing the sulfuric acid with a base selected from the group consisting of alkali metal hydroxides and amines.
  14. 14 . The process according to claim 13 , wherein the base for neutralizing the sulfuric acid is selected from the group consisting of alkanolamines.
  15. 15 . The process according to claim 8 , wherein the ethoxylating in step (h) is performed in two sub-steps: (i) converting with up to one mole of ethylene oxide per N—H function followed by (ii) converting with more ethylene oxide under alkaline catalysis.
  16. 16 . Amphoterically-modified trialkylene tetramine ethoxylates (A), obtained by a process according to claim 8 .
  17. 17 . A method of using amphoterically-modified trialkylene tetramine ethoxylates (A) according to claim 1 , wherein the method comprises using the amphoterically-modified trialkylene tetramine ethoxylates (A) in laundry applications.
  18. 18 . A laundry formulation, comprising at least one of the amphoterically-modified trialkylene tetramine ethoxylates (A) according to claim 1 .
  19. 19 . The amphoterically-modified trialkylene tetramine ethoxylates (A) of general formula (I) of claim 1 , wherein each R 1 is individually the same or different and selected from the group consisting of C 1 -C 4 -alkyl, H and a free electron pair, wherein at least 80% of all R 1 are C 1 -C 4 -alkyl, each Y is individually the same or different and selected from the group consisting of SO 3 − and H, wherein at least 50% of all Y are SO 3 − , each x is individually the same or different and in a range of from 10 to 40 and n is 1.
  20. 20 . The process according to claim 8 , wherein the purifying (g) is performed to obtain trialkylene tetramines with 1, 2 and 3 repeating units, or mixtures thereof, with a purity of at least 75 wt %.

Description

The present invention relates to certain amphoterically-modified ethoxylated oligoamines, their manufacture and use. In the following, oligo-/polypropyleneimine is also abbreviated “PPI”, oligo-/polyethyleneimine is also abbreviated “PEI”. Furthermore, in the following, ethylene oxide is sometimes referred to as “EO” and propylene oxide is sometimes referred to as “PO”. Alkoxylated oligo- and polyalkyleneimines, especially alkoxylated oligo- and polyethyleneimines, are well known as additives for various applications, such as laundry detergents (e.g., EP3301154, EP3167034 and EP112593), additives for cementitious binder systems (WO2016187085), or hard surface cleaners (EP2961819). In case of utilization within laundry applications, benefits on both primary cleaning and secondary cleaning performance have been mentioned. In contrast, modified oligo- and polyalkyleneimine alkoxylates are less common. EP2662436 describes cationic alkoxylated polyethyleneimines in combination with bleach boosters for automatic dish wash applications. Both hydrophobically- and amphoterically-modified polyalkyleneimines for detergent compositions are described in WO2004020563. Laundry compositions containing alkoxylated and optionally further cationically- or amphoterically-modified polyalkyleneimines bearing at least 6 N-atoms per molecule are described in EP2961821 for example. More specifically oligo- and polypropyleneimines exhibiting at least 6 N-atoms per molecule, modified and unmodified, are disclosed which led to benefits in soil removal and contribute to improved whiteness. Any impact on the rheology of the detergents has not been mentioned. In addition, EP3039109 and EP3039057 describe predominantly ethoxylated and optionally further amphoterically-modified oligo- and polyalkyleneimines with low melting points. Due to the incorporation of at least one mol of a C3 to C5 alkylene oxide into the polyalkoxylate chains, mainly based on ethylene oxide, polymers with low melting points can be obtained being favorable for their preparation process. Any benefits in terms of application performance in comparison to identical polymers based solely on ethylene oxide and thus higher melting points have not been mentioned. Furthermore, EP1198492 describes zwitterionic (i.e., amphoterically-modified) alkoxylated polyamines with improved thermal stability, used as additives for laundry detergents. In general, the amphoteric modification of the materials has been obtained by a combination of independent quaternization and sulfation steps, wherein the sulfation has been carried out with a sulfation agent such as chlorosulfonic acid. The use of chlorosulfonic acid has the disadvantage that salt is obtained which may lead to corrosion; furthermore, methanol is a by-product, which is classified as toxic. The described zwitterionic polyamines have a net anionic charge, i.e., the number of anionic groups exceeds the number of cationic groups by at least 20%, preferably by at least 50%. As one example, experimental example no. 4 of said document may be cited. An improved benefit on cleaning performance and a positive impact on the viscosity of the detergents has not been mentioned. The process of manufacturing alkoxylated and further amphoterically-modified oligo- and polyalkyleneimines is in principle already known in literature. As mentioned before, the manufacturing process of alkoxylated zwitterionic polyamines, wherein the alkoxylates have been quarternized with a modification agent (1) and sulfatized using a different modification agent (2) (e.g., chlorosulfonic acid), are described in EP1198492. The obtained structures have a net anionic charge. WO2001029112 describes a process for the sulfation of alkoxylated quarternized polyamines using sulfur trioxide as sulfation agent, allowing high sulfation degrees. The described structures also possess a net anionic charge. A process based on a combination of alkoxylation, quaternization and transsulfation starting from tertiary aminoalcohols has been described in EP1309546. The process includes the reaction of a tertiary amine with a sulfation precursor (e.g., dialkyl sulfate) forming an admixture comprising a quarternized amine and a sulfating species. The hydroxyl species has then been sulfated under acidic conditions. More specifically, the preparation of alkoxylated, quaternized and fully sulfated oligo- and polyalkyleneimines has been disclosed, by using auxiliary amines. The obtained polymers did not contain any free hydroxyl groups anymore, i.e., all groups have been converted into sulfate groups. Therefore, the net charge of the described polymers has been anionic. Another process based on a combination of alkoxylation, quaternization and transsulfation without the use of auxiliary amines has been described in WO200424858. The process includes the reaction of a tertiary amine in the backbone of an alkoxylated oligo- or polyamine with a sulfation precursor (e.g., dialkyl sulfate) formi