阅读说明：本技术 制备烷氧基化聚乙烯亚胺的方法 (Process for preparing alkoxylated polyethyleneimines ) 是由 H·蒂尔克 T·W·霍尔科姆 A·D·格林 A·J·帕瑞 J·贝内特 R·J·卡斯韦尔 于 2019-07-30 设计创作，主要内容包括：本发明涉及一种制备乙氧基化聚乙烯亚胺的方法、乙氧基化聚乙烯亚胺及其应用。(The invention relates to a method for preparing ethoxylated polyethyleneimine, the ethoxylated polyethyleneimine and application thereof.)

1. Process for the preparation of an ethoxylated polyethyleneimine by reacting at least one Polyethyleneimine (PEI) with at least one ethylene oxide EO, wherein in a first step (1) the Polyethyleneimine (PEI) is reacted with ethylene oxide EO in an amount of less than 1 molar equivalent per PEI and subsequently in a second step (2) the product of step (1) is reacted with a further amount of ethylene oxide EO in the presence of a basic catalyst C, and wherein in step (1) ethylene oxide EO is added in an amount of 0.01 to 0.85 ethylene oxide units per NH group of the Polyethyleneimine (PEI) and wherein the Polyethyleneimine (PEI) has a molecular weight Mw (before ethoxylation) in the range of 1000-, mainz, germany) was calibrated.

2. The method according to claim 1, wherein the Polyethyleneimine (PEI) has a molecular weight Mw (before ethoxylation) in the range of 1300-.

3. The method according to claim 1, wherein the Polyethyleneimine (PEI) has a molecular weight Mw (prior to ethoxylation) in the range of 1600-, preferably 1800-, 2200-, more preferably 1900-, 2100g/mol, as determined by Gel Permeation Chromatography (GPC) with 1.5 wt.% aqueous formic acid as eluent and crosslinked polyhydroxyethyl methacrylate as stationary phase (TSKgel GMPWXL column) and calibrated by using an RI detector and a Pullulan standard (PSS GmbH, Mainz, Germany).

4. The process according to any one of claims 1 to 3, wherein the ethylene oxide EO is added in step (1) in an amount of from 0.1 to 0.7 ethylene oxide units per NH group of the Polyethyleneimine (PEI), more preferably from 0.1 to 0.5 ethylene oxide units per NH group of the Polyethyleneimine (PEI).

5. The method according to any one of claims 1 to 4, wherein the sum of the amounts of ethylene oxide EO added in steps (1) and (2) lies in the range of 15 to 40 ethylene oxide units per NH group of the Polyethyleneimine (PEI), preferably 20 to 40 ethylene oxide units per NH group of the Polyethyleneimine (PEI), more preferably 25 to 35 ethylene oxide units per NH group of the Polyethyleneimine (PEI).

6. The process according to any one of claims 1 to 5, wherein the basic catalyst C is selected from basic catalysts containing alkaline earth metals.

7. Process according to any one of claims 1 to 6, wherein the basic catalyst C is selected from LiOH, NaOH, KOH, CsOH and mixtures thereof, preferably a mixture comprising KOH, more preferably KOH.

8. Process according to any one of claims 1 to 7, in which the basic catalyst C is added in an amount of from 0.05 to 0.3% by weight, preferably from 0.15 to 0.25% by weight, relative to the Ethoxylated Polyethyleneimine (EPEI).

9. Process according to any one of claims 1 to 8, wherein the temperature during the first step (1) is in the range of from 90 to 180 ℃, preferably 100-.

10. The process according to any one of claims 1 to 9, wherein the temperature during the second step (2) is in the range of 100 ℃ and 250 ℃, preferably 120 ℃ and 180 ℃.

11. The process according to any of claims 1 to 10, wherein in the first step (1) additionally 1 to 50 wt. -%, preferably 1 to 25 wt. -%, more preferably 2 to 18 wt. -% of water relative to the unreacted Polyethyleneimine (PEI) is added.

12. The process according to any one of claims 1 to 11, wherein the product obtained after step (2) is treated with a bleaching agent.

13. The method according to claim 12, wherein said bleaching agent is selected from the group consisting of borates, hypochlorites and borohydrides.

14. Ethoxylated polyethyleneimine obtainable by the process according to any one of claims 1 to 13.

15. Use of an ethoxylated polyethyleneimine obtainable by the process according to any one of claims 1 to 14 in a liquid laundry formulation.

Examples

Polymer synthesis:

example 1: synthesis of ethoxylated PEI P.1

To a 2 liter autoclave was added 35.0g of a completely dehydrated and CO-free according to the procedure described in US 2010/0216949₂The PEI 2000. Then by adding 6.1g H₂O PEI2000 was made as a 15 wt% aqueous solution. The vessel was purged 3 times with a nitrogen pressure of up to 5 bar and finally rendered inert with a nitrogen pad of 2 bar. The temperature was equilibrated at 100 ℃ and then 26.0g of ethylene oxide were fed in over 6 hours and reacted further for 1 hour. To the product PEI2000+0.7EO/NH was added 4.9g of 50 wt% aqueous KOH and stirred. The mixture was then stripped of water at 120 ℃ and 10 mbar for 2 hours. The temperature is raised to 130 ℃ and the container is flushed with 2 bar nitrogenThe vessel was inert, 1158g of ethylene oxide were fed in over 12 hours at a total pressure of from about 3.5 bar (initial pressure) to about 8 bar (pressure at the end of the EO feed) and the postreaction was carried out for at least 3 hours. The sample was then purged with nitrogen to strip any residual EO, vented from the reactor and stripped of water and any residual EO under vacuum (20 mbar, 90 ℃). 1226g of a light tan solid are obtained.

Example 2: synthesis of ethoxylated PEI P.2

To a 2 liter autoclave was added 508.5g of a completely dehydrated and CO-free according to the procedure described in US 2010/0216949₂The PEI 2000. Then by adding 89.7g H₂O PEI2000 was made as an 85 wt% aqueous solution. The vessel was purged 3 times with a nitrogen pressure of up to 5 bar and finally rendered inert with a nitrogen pad of 2 bar. The temperature was equilibrated at 100 ℃ and then 261g of ethylene oxide were fed in over 6 hours and reacted further for 1 hour. The product PEI2000+0.5EO/NH was then purged with nitrogen to strip any residual EO, vented from the reactor and stripped of water and any residual EO. 53.0g of this material was charged to a clean and empty 2 liter autoclave. 4.8g of 50% by weight aqueous KOH solution were then introduced and stirred with PEI2000+0.5 EO/NH. The mixture was then stripped of water at 120 ℃ and 10 mbar for 2 hours. The temperature was then raised to 130 ℃, the vessel was made inert with a nitrogen blanket of 2 bar, 1150g of ethylene oxide were fed in over 12 hours at a total pressure of about 3.5 bar (initial pressure) to about 8 bar (pressure at the end of the EO feed) and the post-reaction was carried out for at least 3 hours. The sample was then purged with nitrogen to strip any residual EO, vented from the reactor and stripped of water and any residual EO under vacuum (20 mbar, 90 ℃). 1223g of a light tan solid are obtained.

Example 3: synthesis of ethoxylated PEI P.3

To a 2 liter autoclave was added 500.0g of a completely dehydrated and CO-free according to the procedure described in US 2010/0216949₂The PEI 2000. Then by adding 88.3g H₂O PEI2000 was made as an 85 wt% aqueous solution. The vessel was purged 3 times with a nitrogen pressure of up to 5 bar and finally rendered inert with a nitrogen pad of 2 bar. The temperature was equilibrated at 100 ℃ and then 52.0g of ethylene oxide were fed in over 6 hours and reacted further for 1 hour. The product PEI2000+0 was then purged with nitrogen.1EO/NH to strip any residual EO, the reactor is vented and stripped of water and any residual EO. 36.0g of this material was charged to a clean and empty 2 liter autoclave. 4.5g of 50% by weight aqueous KOH solution were then introduced and stirred with PEI2000+0.1 EO/NH. The mixture was then stripped of water at 120 ℃ and 10 mbar for 2 hours. The temperature was then raised to 130 ℃, the vessel was made inert with a nitrogen blanket of 1 bar, 1084g of ethylene oxide were fed in over 12 hours at a total pressure of about 3.5 bar (initial pressure) to about 8 bar (pressure at the end of the EO feed) and the post-reaction was carried out for at least 3 hours. The sample was then purged with nitrogen to strip any residual EO, vented from the reactor and stripped of water and any residual EO under vacuum (20 mbar, 90 ℃). 1142g of a light tan solid are obtained.

Example 4: synthesis of ethoxylated PEI P.4

A2 liter autoclave was charged with 35.0g of PEI 2000. No pre-treatment according to the procedure described in US 2010/0216949 was performed. Instead, the vessel was purged directly 3 times with a nitrogen pressure of up to 5 bar and finally rendered inert with a nitrogen pad of 2 bar. The temperature was equilibrated at 100 ℃ and then 18.0g of ethylene oxide was added over 6 hours and the reaction was further continued for 1 hour. To the product PEI2000+0.5EO/NH was added 4.8g of 50 wt% aqueous KOH and stirred. The mixture was then stripped of water at 120 ℃ and 10 mbar for 2 hours. The temperature was then raised to 130 ℃, the vessel was made inert with a nitrogen blanket of 2 bar, 1150g of ethylene oxide were fed in over 12 hours at a total pressure of about 3.5 bar (initial pressure) to about 8 bar (pressure at the end of the EO feed) and the post-reaction was carried out for at least 3 hours. The sample was then purged with nitrogen to strip any residual EO, vented from the reactor and stripped of water and any residual EO under vacuum (20 mbar, 90 ℃). 1217g of a light brown-yellow solid were obtained.

Example 5: synthesis of ethoxylated PEI P.5

To a 2 liter autoclave was added 34.5g of a completely dehydrated and CO-free according to the procedure described in US 2010/0216949₂PEI 5000. Then by adding 2.1g H₂O PEI5000 was made into a 5 wt% aqueous solution. The vessel was purged 3 times with a nitrogen pressure of up to 5 bar and finally rendered inert with a nitrogen pad of 2 bar. The temperature was equilibrated at 100 ℃ and then supplied over 6 hours8.0g of ethylene oxide were added and the reaction was further continued for 1 hour. To the product PEI5000+0.2EO/NH was added 4.4g of 50 wt% aqueous KOH and stirred. The mixture was then stripped of water at 120 ℃ and 10 mbar for 2 hours. The temperature was maintained at 120 ℃, the vessel was made inert with a nitrogen blanket of 2 bar, 1049g of ethylene oxide were fed in over 12 hours at a total pressure of about 3.5 bar (initial pressure) to about 8 bar (pressure at the end of the EO feed) and the post-reaction was carried out for at least 3 hours. The sample was then purged with nitrogen to strip any residual EO, vented from the reactor and stripped of water and any residual EO under vacuum (20 mbar, 90 ℃). 1102g of a light brown-yellow solid are obtained.

Comparative example 1: synthesis of ethoxylated PEI CP.1

To a 2 liter autoclave was added 300.0g of a completely dehydrated and CO-free according to the procedure described in US 2010/0216949₂The PEI800 of (1). Then by adding 82.0g H₂O PEI800 was made into an 85 wt% aqueous solution. The vessel was purged 3 times with a nitrogen pressure of up to 5 bar and finally rendered inert with a nitrogen pad of 2 bar. The temperature was equilibrated at 100 ℃ and then 246g of ethylene oxide were fed in over 6 hours and reacted further for 1 hour. The product PEI800+0.8EO/NH was then purged with nitrogen to strip any residual EO, the reactor was vented and stripped of water and any residual EO. 55.0g of this material was charged to a clean and empty 2 liter autoclave. Then 3.8g of 50% by weight aqueous KOH solution were introduced and stirred with PEI800+0.8 EO/NH. The mixture was then stripped of water at 120 ℃ and 10 mbar for 2 hours. The temperature was then raised to 130 ℃, the vessel was made inert with a nitrogen blanket of 2 bar, 900g of ethylene oxide were fed in over 12 hours at a total pressure of about 3.5 bar (initial pressure) to about 8 bar (pressure at the end of the EO feed) and the post-reaction was carried out for at least 3 hours. The sample was then purged with nitrogen to strip any residual EO, vented from the reactor and stripped of water and any residual EO under vacuum (20 mbar, 90 ℃). 961g of a light tan solid are obtained.

Comparative example 2: synthesis of ethoxylated PEI CP.2

To a 2 liter autoclave was added 300.0g of a completely dehydrated and CO-free according to the procedure described in US 2010/0216949₂The PEI800 of (1). Then by adding 82.0g H₂O PEI800 was made into an 85 wt% aqueous solution.The vessel was purged 3 times with a nitrogen pressure of up to 5 bar and finally rendered inert with a nitrogen pad of 2 bar. The temperature was equilibrated at 100 ℃ and then 154g of ethylene oxide were fed in over 6 hours and reacted further for 1 hour. The product PEI800+0.5EO/NH was then purged with nitrogen to strip any residual EO, the reactor was vented and stripped of water and any residual EO. 52.2g of this material was charged to a clean and empty 2 liter autoclave. 4.4g of 50% by weight aqueous KOH solution were then introduced and stirred with PEI800+0.5 EO/NH. The mixture was then stripped of water at 120 ℃ and 10 mbar for 2 hours. The temperature was then raised to 130 ℃, the vessel was made inert with a nitrogen blanket of 2 bar, 1040g of ethylene oxide were fed in over 12 hours at a total pressure of about 3.5 bar (initial pressure) to about 8 bar (pressure at the end of the EO feed) and the post-reaction was carried out for at least 3 hours. The sample was then purged with nitrogen to strip any residual EO, vented from the reactor and stripped of water and any residual EO under vacuum (20 mbar, 90 ℃). 1110g of a light brown-yellow solid are obtained.

Comparative example 3: synthesis of ethoxylated PEI CP.3

To a 2 liter autoclave was added 500.0g of a completely dehydrated and CO-free according to the procedure described in US 2010/0216949₂The PEI 2000. Then by adding 88.3g H₂O PEI2000 was made as an 85 wt% aqueous solution. The vessel was purged 3 times with a nitrogen pressure of up to 5 bar and finally rendered inert with a nitrogen pad of 2 bar. The temperature was equilibrated at 100 ℃ and then 461g of ethylene oxide were fed in over 6 hours and reacted further for 1 hour. The product PEI2000+0.9EO/NH was then purged with nitrogen to strip any residual EO, the reactor was vented and stripped of water and any residual EO. 60.0g of this material was charged to a clean and empty 2 liter autoclave. 4.3g of a 50% by weight aqueous KOH solution were then introduced and stirred with PEI2000+0.9 EO/NH. The mixture was then stripped of water at 120 ℃ and 10 mbar for 2 hours. The temperature is then raised to 130 ℃, the vessel is rendered inert with a nitrogen blanket of 2 bar, 1011g of ethylene oxide are fed in over 12 hours at a total pressure of about 3.5 bar (initial pressure) to about 8 bar (pressure at the end of the EO feed) and the postreaction is carried out for at least 3 hours. The sample was then purged with nitrogen to strip any residual EO, vented from the reactor and stripped of water and any residual EO under vacuum (20 mbar, 90 ℃). To obtainTo 1094g of a light tan solid. Comparative example 4: synthesis of ethoxylated PEI CP.4

To a 2 liter autoclave was added 50.0g of a completely dehydrated and CO-free according to the procedure described in US 2010/0216949₂The PEI 2000. The vessel was purged 3 times with a nitrogen pressure of up to 5 bar and finally rendered inert with a nitrogen pad of 2 bar. The temperature was equilibrated at 100 ℃ and then 6.9g of 50% by weight KOH in water was added and stirred. Water was stripped from the mixture at 130 ℃ and 10 mbar for 2 hours. The temperature was maintained at 130 ℃, the vessel was made inert with a nitrogen blanket of 2 bar, 1025g of ethylene oxide were fed in over 12 hours at a total pressure of about 3.5 bar (initial pressure) to about 8 bar (pressure at the end of the EO feed) and the post-reaction was carried out for at least 3 hours. The sample was then purged with nitrogen to strip any residual EO, vented from the reactor and stripped of water and any residual EO under vacuum (20 mbar, 90 ℃). 1098g of a light brown-yellow solid are obtained.

Comparative example 5: synthesis of ethoxylated PEI CP.5

To a 2 liter autoclave was charged 495.0g of a completely dehydrated and CO-free according to the procedure described in US 2010/0216949₂The PEI 2000. Then by adding 87.4g H₂O PEI2000 was made as an 85 wt% aqueous solution. The vessel was purged 3 times with a nitrogen pressure of up to 5 bar and finally rendered inert with a nitrogen pad of 2 bar. The temperature was equilibrated at 100 ℃ and then 335g of propylene oxide were fed in over 6 hours and further reacted for 1 hour. The product PEI2000+0.5PO/NH was then purged with nitrogen to strip any residual PO, vented from the reactor and stripped of water and any residual PO. 53.0g of this material was charged to a clean and empty 2 liter autoclave. 4.4g of 50% by weight aqueous KOH solution were then introduced and stirred with PEI2000+0.5 PO/NH. The mixture was then stripped of water at 120 ℃ and 10 mbar for 2 hours. The temperature was then raised to 130 ℃, the vessel was made inert with a nitrogen blanket of 2 bar, 1038g of ethylene oxide were fed in over 12 hours at a total pressure of about 3.5 bar (initial pressure) to about 8 bar (pressure at the end of the EO feed) and the post-reaction was carried out for at least 3 hours. The sample was then purged with nitrogen to strip any residual EO, vented from the reactor and stripped of water and any residual EO under vacuum (20 mbar, 90 ℃). 1100.9g of a light tan solid were obtained. Comparative example 6: synthetic ethoxyBasic PEI CP.6

To a 2 liter autoclave was added 34.5g of a completely dehydrated and CO-free according to the procedure described in US 2010/0216949₂PEI 5000. Then by adding 1.9g H₂O PEI5000 was made into a 5 wt% aqueous solution. The vessel was purged 3 times with a nitrogen pressure of up to 5 bar and finally rendered inert with a nitrogen pad of 2 bar. The temperature was equilibrated at 100 ℃ and then 35.0g of ethylene oxide was fed in over 6 hours and further reacted for 1 hour. To the product PEI5000+0.9EO/NH was added 4.4g of 50 wt% aqueous KOH and stirred. The mixture was then stripped of water at 120 ℃ and 10 mbar for 2 hours. The temperature was maintained at 120 ℃, the vessel was made inert with a nitrogen blanket of 2 bar, 1022g of ethylene oxide were fed in over 12 hours at a total pressure of about 3.5 bar (initial pressure) to about 8 bar (pressure at the end of the EO feed) and the post-reaction was carried out for at least 3 hours. The sample was then purged with nitrogen to strip any residual EO, vented from the reactor and stripped of water and any residual EO under vacuum (20 mbar, 90 ℃). 1085g of a light tan solid are obtained.

Comparative example 7: synthesis of ethoxylated PEI CP.7

A2 liter autoclave was charged with 350.0g of PEI 2000. No pre-treatment according to the procedure described in US 2010/0216949 was performed. Instead, by adding 14.0g H₂O PEI2000 was made as a 96 wt% aqueous solution. The vessel was purged 3 times with a nitrogen pressure of up to 5 bar and finally rendered inert with a nitrogen pad of 2 bar. The temperature was equilibrated at 120 ℃ and then 323g of ethylene oxide was fed in over 6 hours and reacted further for 10 hours. The product PEI2000+0.9EO/NH was then purged with nitrogen to strip any residual EO, the reactor was vented and stripped of water and any residual EO. 36.0g of this material was charged to a clean and empty 2 liter autoclave. To the product PEI2000+0.9EO/NH was added 4.0g of 50 wt% aqueous KOH and stirred. The mixture was then stripped of water at 100 ℃ and 10 mbar for 2 hours. The temperature was then raised to 120 ℃, the vessel was made inert with a nitrogen blanket of 2 bar, 951g of ethylene oxide were fed in over 18 hours at a total pressure of about 3.5 bar (initial pressure) to about 8 bar (pressure at the end of the EO feed) and the post-reaction was allowed to proceed for a further 12 hours. The sample was then purged with nitrogen to strip any residual EO from the reactionThe vessel was vented and the water and any residual EO were stripped under vacuum (20 mbar, 90 ℃). 990g of a light tan solid were obtained.

Polymer characterization

Molecular weights were determined by Gel Permeation Chromatography (GPC). The conditions used were 1.5% by weight aqueous formic acid as eluent and crosslinked polyhydroxyethyl methacrylate as stationary phase of polyethyleneimine material; or 0.05% by weight of potassium trifluoroacetate in Hexafluoroisopropanol (HFIP) as eluent and crosslinked polystyrene/divinylbenzene as stationary phase of the final ethoxylated polyethyleneimine. In the case of polyethyleneimine feedstocks, the molecular weights were obtained by calibration using an RI detector and a pulullan standard (PSS GmbH, Mainz, germany). In the case of the end product ethoxylated polyethyleneimine, a MALLS detector was used and the absolute weight average molecular weight was obtained.

Analytical data for PEI ethoxylates are summarized in table 1.

TABLE 1A composition and physicochemical characterization of PEI ethoxylates

TABLE 1b composition and physicochemical characterization of PEI ethoxylates (continent)

Additionally, 800g/mol raw material and about 20 EO/NH (M) based on PEI_w9900 g/mol) of a commercially available PEI ethoxylateHP20(BASF SE, Ludwigshafen, Germany) was used for comparison.

Determined by Gel Permeation Chromatography (GPC) with 1.5 wt% aqueous formic acid as eluent and crosslinked polyhydroxyethyl methacrylate as stationary phase (TSKgel GMPWXL column); RI detector and Pullulan standard (PSS GmbH, Mainz, Germany).

Determined by Gel Permeation Chromatography (GPC), with 0.05 wt% potassium trifluoroacetate in Hexafluoroisopropanol (HFIP) as eluent and crosslinked polystyrene/divinylbenzene as stationary phase (PL HFIPGel column); MALLS detector.

The data in table 1 clearly show that the process of the invention, which is characterized by the application of strong underhydroxyethylation (< 0.9EO/NH in the first reaction step), results in a significantly higher weight average molecular weight (by comparing polymers p.1-P.4 with cp.3 and p.5 with cp.6) compared to the slight underhydroxyethylation known in the art (0.9 EO/NH in the first reaction step). It can also be seen that the maximum weight average molecular weight is achieved for the PEI2000 feedstock if 0.5 of the under-hydroxyethylation of EO/NH is applied. The presence of water and/or the pretreatment of PEI before the strongly under-hydroxyethylation does not seem to be important for the process of the invention (P.2 vs. P.4), however the pretreatment may additionally lead to a better physical appearance of the product (color, odor; as described in US 2010/0216949). The reason for the higher weight average molecular weight observed with strong underhydroxyethylation was not due to fewer by-products (confirmed by GPC), and was therefore assumed to be due to the higher polydispersity of the PEG chains attached to the PEI core. The higher polydispersity of the attached PEG chains leads to higher weight average molecular weight of the final macromolecule while maintaining the same molecular composition (PEI: EO ratio), thus leading to new materials with new properties in applications (see below). The data in table 1 also show that this one-step process (cp.4) does not give high molecular weights at all, since the catalyst KOH appears to react with EO itself, thus leading in this case to a large amount of by-Products (PEG) (GPC confirmation). Thus, it can be concluded that the lower limit of the underhydroxyethylation process is clearly defined by the amount of catalyst (e.g. KOH) added to the system: the amount of hydroxyethyl groups added in the first reaction step before the second step is started should be the same or higher than the amount of KOH added at a later point in time. Furthermore, the data in table 1 show that strong under-alkoxylation with propylene oxide (cp.5) also does not lead to higher molecular weights due to the limited reactivity of the attached secondary hydroxyl groups.

Application test:

viscosity:

to determine the effect of the polymer on the viscosity of the liquid laundry formulations, 1.45 wt.% PEI ethoxylate was formulated in each case into a liquid detergent containing a fixed concentration of 0.75 wt.% HASE thickening polymer (formulation f.1) or 1.05 wt.% HASE thickening polymer (formulation f.2). The pH was adjusted to pH 7.5 with 50 wt% aqueous NaOH in both cases. The formulation was stirred with a magnetic stirrer for 2 hours and then stored without mechanical agitation for another 24 hours. The viscosity of the samples was then measured using a rotational rheometer Rheolab QC (Anton Paar, Ostfildern, Germany) at room temperature (25 ℃) in spindle CC27 or DG42 (depending on the absolute viscosity). The measurements were carried out at shear rates of 0-12001/s. Table 1 shows the composition of the final formulation and Table 2 summarizes the resulting viscosity at a shear rate of 201/s.

TABLE 2 composition of liquid laundry formulations

All data are% by weight active ingredient, independent of the corresponding product form.

TABLE 3 viscosity of liquid laundry formulations

Linear standard deviation of the method used was +/-10mPa · s, obtained from measurements of 3 identical formulations.

The data in table 3 show that all PEI ethoxylates (used in laundry detergents to enhance cleaning performance) result in some reduction in the viscosity of the liquid laundry formulations due to adverse interactions with the thickening system. Therefore, more thickener is required in all cases to maintain the viscosity at the initial level, which is generally not preferred. However, the data in table 3 also clearly show that the PEI ethoxylates of the present invention based on the strong underhydroxyethylation method exhibit a much less detrimental effect on the formulation viscosity than non-inventive polymers based on only a slight underhydroxyethylation (either based on using propylene oxide instead of ethylene oxide, or based on PEI with Mw outside the scope of the present invention as a starting material), thus resulting in significantly higher viscosities of laundry formulations. The effect of the method of the invention on viscosity can be seen when comparing polymers with the same PEI core size (PEI 2000: P.1-P.4 vs. CP.3-CP.5; and PEI 5000: P.5 vs. CP.6). If applied to low molecular weight PEI starting materials, strong underhydroxyethylation did not result in improved viscosity (PEI 800: CP.2 vs. CP.1). It is also seen that higher molecular weights generally result in higher formulation viscosities, thus PEI5000 based samples result in higher viscosities than PEI2000 based samples and the latter result in higher viscosities than PEI800 based samples. Thus, the reason for the improved properties of the polymers of the invention seems to be the higher molecular weight of the attached PEG chains due to their higher polydispersity while maintaining the initial chemical composition (PEI: EO ratio).

Primary cleaning performance:

to determine the primary detergency, the cleaning performance on round red pottery stains on polyester fabrics (Warwick Equest, Consett, UK) was measured by measuring the color difference (Δ E) between the stain and the unstained white fabric after washing using a reflectometer (Datacolor SF600 plus). The smaller the difference, the better the cleaning performance of the corresponding liquid laundry detergent. 4 round red pottery stains were used in 1 test and each test was repeated 3 times, thus giving a total of 12 wash stains per test condition to calculate the average Δ E value. Table 3 shows the composition of the laundry detergent, table 4 shows the wash test conditions and table 5 summarizes the resulting cleaning performance data (Δ E). Table 5 also shows the normalized cleaning performance Δ Δ Ε (i.e., the poor performance of a laundry detergent comprising the corresponding PEI ethoxylate versus a laundry detergent without any PEI ethoxylate). The greater the Δ Δ E value, the greater the positive contribution of the corresponding PEI ethoxylate to cleaning performance.

TABLE 4 composition of liquid laundry detergents

All data are% by weight active ingredient, independent of the corresponding product form.

TABLE 5 Wash conditions for evaluation of Primary detergency

Test fabrics were rinsed with 12 ° fH water (2 times) after the wash test and then dried overnight at ambient room temperature before being measured with a reflectometer.

TABLE 6 washing test results

The data in Table 6 show that the polymers P.1-P.3 of the invention are based onHP20) exhibited the same primary cleaning performance as compared to the other. The cleaning performance was also at least the same as compared to the non-inventive polymer cp.3 (prepared via slight underhydroxyethylation), but the adverse effect on viscosity was significantly lower (see table 3). The inventive polymer p.5 (based on PEI5000 raw material) which exhibits very high viscosity when implemented in laundry formulations still exhibits significant cleaning benefits, but its cleaning performance ratioHP20 was slightly worse. The conclusion from this is an improved viscosity (relative to that ofHP20) and the same cleaning performance can be optimized by using a composition based on strong underhydroxyethylation and based on PEI2000 cores of PEI ethoxylates of the present invention. Simply increasing the molecular weight of PEI ethoxylates by increasing the EO chain length (CP.7: 50 EO/NH) is also not useful because the method changes the molecular composition (lower PEI: EO ratio) and thus results in (EO/EO ratio) relative to the benchmarkHP20) significantly reduced cleaning performance.

PEI ethoxylates having high molecular weight, especially those based on PEI2000 and PEI5000 materials, are preferred ingredients in laundry detergents because of their relative preference to those based on PEI2000 and PEI5000 materialsThe higher molecular weight of HP20 (due to the larger PEI core size (2000/5000 vs 800) and longer EO chains (30-35 vs about 20)) generally resulted in higher viscosity. PEI core size (>5000g/mol) or EO chain length(s) ((EO)>A further increase of 40 EO/NH) results in a significant decrease in cleaning performance and therefore the process is not suitable. In contrast, the process of the invention via strong underhydroxyethylation (samples P.1 to P.5) allows a significant increase in molecular weight without changing the chemical composition. The molecular weight increase further improves the viscosity of the laundry formulation, while the constant chemical composition ensures consistent cleaning performance.