Methods for producing polyaspartic acids in the presence of methanesulfonic acid

• US 10,233,286 B2
• Filed: 09/08/2014
• Issued: 03/19/2019
• Est. Priority Date: 09/16/2013
• Status: Active Grant

• Current Assignee: BASF SE
• Original Assignee: BASF SE
• Inventors: Detering, Jurgen, Turkoglu, Gazi, Fehringer, Dietrich
• Primary Examiner(s): Boyer, Charles I
• Application Number:
  US15/022,037
• Publication Number:
  US 20160229956A1
• Time in Patent Office: 1,653 Days
• CPC Class Codes: C08G 2230/00 Compositions for preparing biodegradable polymers
• CPC Class Codes: C08G 69/04 Preparatory processes
• CPC Class Codes: C08G 69/10 Alpha-amino-carboxylic acids polysuccinimides C08G73/1092
• CPC Class Codes: C08G 73/1092 Polysuccinimides
• CPC Class Codes: C08G 73/14 Polyamide-imides
• CPC Class Codes: C11D 3/0036 Soil deposition preventing compositions; Antiredeposition agents
• CPC Class Codes: C11D 3/3719 Polyamides or polyimides
• CPC Class Codes: Y02W 10/37 using solar energy

Abstract

The present invention relates to methods for producing polyaspartic acids with a weight-average molecular weight (Mw) of from 6,000 to 15,000 g/mol. The invention also relates to polyaspartic acids which can be obtained by the method according to the invention, to a composition containing the polyaspartic acids, and to the use thereof as scale inhibitors, dispersants and as an additive in dishwashing agents, detergents or cleaning agents.

Claims

1. A method for producing polyaspartic acids with a weight-average molecular weight (Mw) of 6000 to 15 000 g/mol, comprising the following steps:

(i) polycondensation of

(a) aspartic acid in the presence of

(b) 1 to 15 mol % of methanesulfonic acid, based on the amount of aspartic acid used in (a)

at a temperature of 170°

C. to 230°

C. for a time period of 1 minute to 50 hours;

(ii) subsequent hydrolysis of the polycondensates with addition of a base; and

(iii) optional acidification of the salt of polyaspartic acid obtained in (ii) with mineral acids or acidic ion exchangers, and

wherein the polycondensation step further comprises the addition of water.

2. The method according to claim 1, wherein 2 to 13 mol % of methanesulfonic acid are used in step (i) (b), based on the amount of aspartic acid used in (a).

3. The method according to claim 1, wherein 3 to 10 mol % of methanesulfonic acid are used in step (i) (b), based on the amount of aspartic acid used in (a).

4. The method according to claim 1, wherein the polycondensation in step (i) is carried out at a temperature of 190°

C. to 220°

C.

5. The method according to claim 1, wherein the quotient of weight-average molecular weight (Mw) to number-average molecular weight (Mn) of the polyaspartic acid produced is not greater than 3.

6. The method according to claim 5, wherein the quotient is not greater than 2.5.

7. The method according to claim 1, wherein the base used in step (ii) is selected from the group consisting of aqueous sodium hydroxide solution, aqueous potassium hydroxide solution, calcium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, ammonia and ammonium hydroxide.

8. The method according to claim 1, wherein the mineral acid used in step (iii) is sulfuric acid or hydrochloric acid.

9. A polyaspartic acid obtainable by the method according to claim 1.

10. A composition comprising the polyaspartic acid according to claim 9.

11. The composition according to claim 10, wherein the composition is a dishwashing composition, a detergent composition or a cleaning composition.

12. A dishwashing composition comprising

(a) 1-20% by weight polyaspartic acid according to claim 9;

(b) 0-50% by weight complexing agents;

(c) 0.1-80% by weight builders and/or co-builders;

(d) 0.1-20% by weight non-ionic surfactants;

(e) 0-30% by weight bleach, bleach activators and bleach catalysts;

(f) 0-8% by weight enzymes; and

(g) 0-50% by weight additives.

13. A solid detergent composition or cleaning composition comprising

(A_F) 0.1 to 20% by weight polyaspartic acid according to claim 9,

(B_F) 1 to 50% by weight surfactants,

(C_F) 0.1 to 70% by weight builders, co-builders and/or complexing agents,

(D_F) 0 to 30% by weight bleach system, and

(E_F) 0.1 to 70% by weight detergent or cleaning ingredients.

14. A liquid or gel-like detergent composition and cleaning composition comprising

(A_L) 0.1 to 20% by weight polyaspartic acid according to claim 9,

(B_L) 1 to 80% by weight surfactants,

(C_L) 0.1 to 50% by weight builders, co-builders and/or complexing agents,

(D_L) 0 to 20% by weight bleach system,

(E_L) 0.1 to 60% by weight detergent or cleaning ingredients, and

(F_L) 0 to 98.7% by weight water.

15. A scale inhibitor and/or dispersant which comprises the polyaspartic acid according to claim 9.

16. A scale inhibitor and/or dispersant in water-conducting systems which comprises the polyaspartic acid according to claim 9.

17. An additive in dishwashing agents, detergents or cleaning agents which comprises the polyaspartic acid according to claim 9.

18. The additive according to claim 17, wherein the dishwashing agent is for machine dishwashing.

19. The method according to claim 3, wherein the polycondensation in step (i) is carried out at a temperature of 200°

C. to 220°

C. for 1 hour to 15 hours.

20. The dishwashing composition as claimed in claim 12, wherein the composition comprises

(a) 1-20% by weight said polyaspartic acid;

(b) 3-50% by weight complexing agents;

(c) 0.1-80% by weight builders and/or co-builders;

(d) 0.5-10% by weight non-ionic surfactants;

(e) 0.1-30% by weight bleach, bleach activators and bleach catalysts;

(f) 0-8% by weight enzymes; and

(g) 0-50% by weight additives.