POLY-LYSINE DERIVATIVE STABILIZE SOLID-BASED COMPOSITIONS COMPRISING ONE OR MORE SALTS

Abstract

Described herein is a polymeric stabilizing agent selected from poly-lysine derivatives obtained by process including heating an aqueous lysine solution to boiling, increasing a temperature of the aqueous lysine solution to a reaction temperature in the range of about 105° C. to about 180° C., and keeping the reaction temperature in the range of about 105° C. to about 180° C. until a melt viscosity of the reaction mixture is in the range of about 350 mPa*s to about 6,500 mPa*s, and (ii) an amine number in the range of about 100 mg KOH/g to about 500 mg KOH/g is achieved. The process also includes adding alkyl-carboxylic acid or alkenyl-carboxylic acid in amounts of 2.5 mol % to 10 mol %, and increasing or keeping the reaction temperature in the range of about 105° C. to about 180° C. until number of free alkyl-carboxylic acid or alkenyl-carboxylic acid is ≤9% by weight.

Claims

1. A polymeric stabilizing agent selected from poly-lysine derivatives obtained by a process comprising the steps of: I. heating an aqueous lysine solution to boiling; II. increasing a temperature of the aqueous lysine solution to a reaction temperature in the range of about 105° C. to about 180° C.; III. keeping the reaction temperature in the range of about 105° C. to about 180° C. until; i. a melt viscosity of the reaction mixture is in the range of about 350 mPa*s to about 6,500 mPa*s when measured at 160° C. and ii. an amine number in the range of about 100 mg KOH/g to about 500 mg KOH/g is achieved; IV. optionally, releasing a vacuum applied; V. adding alkyl-carboxylic acid or alkenyl-carboxylic acid in amounts of 2.5 mol % to 10 mol %, relative to a theoretical amount of poly-lysine in the reaction mixture; and VI. increasing or keeping the reaction temperature in the range of about 105° C. to about 180° C. until number of free alkyl-carboxylic acid or alkenyl-carboxylic acid is 9% by weight, relative to the total weight of the reaction mixture, wherein vacuum is applied in step (a), (b), and/or (c), and water is removed continuously during the process.

2. A storage-stable solid-based composition comprising: I. a liquid phase comprising components A and B, one or more salts, optionally component C, and optionally at least one additional solvent, wherein component B comprises at least one solvent in which component A is soluble, wherein component C is selected from at least one additional compound, wherein the at least one additional solvent is immiscible with component B, and wherein component A and at least one salt of the one or more salts are soluble in component B, and II. component D comprising at least one solid compound, wherein component D is dispersed in the liquid phase, wherein component A comprises at least one poly-lysine derivative obtained by a process comprising the steps of: (a) heating an aqueous lysine solution to boiling, (b) increasing a temperature of the aqueous lysine solution to a reaction temperature in the range of about 105° C. to about 180° C., (c) keeping the reaction temperature in the range of about 105° C. to about 180° C. until: i. a melt viscosity of the reaction mixture is in the range of about 350 mPa*s to about 6,500 mPa*s when measured at 160° C., and ii. an amine number in the range of about 100 mg KOH/g to about 500 mg KOH/g is achieved, (d) optionally, releasing a vacuum applied, (e) adding alkyl-carboxylic acid or alkenyl-carboxylic acid in amounts of 2.5 mol % to 10 mol %, relative to a theoretical amount of poly-lysine in the reaction mixture (f) increasing or keeping the reaction temperature in the range of about 105° C. to about 180° C. until number of free alkyl-carboxylic acid or alkenyl-carboxylic acid is 9% by weight, relative to the total weight of the reaction mixture, wherein vacuum is applied in step (a), (b) and/or (c) and water is removed continuously during the process.

3. The storage-stable solid-based composition of claim 2, wherein the one or more salts in the liquid phase are soluble in component B or a solvent miscible with component B at 20° C. and 101.3 kPa until the saturation concentration is achieved.

4. The storage-stable solid-based composition of claim 2, wherein the one or more salts in the liquid phase (1) are soluble in the at least one additional solvent at 20° C. and 101.3 kPa until the saturation concentration is achieved.

5. The storage-stable solid-based composition of claim 2, wherein at least one salt of the one or more salts dissociates in the liquid phase into ions, wherein both the cation and the anion are hydrophilic.

6. The storage-stable solid-based composition of claim 2, wherein at least one salt of the one or more salts in the liquid phase dissociates in the liquid phase into ions, wherein the cation or the anion is amphiphilic.

7. The storage-stable solid-based composition of claim 2, wherein the liquid phase and/or component D comprises at least one agrochemically active compound.

8. The storage-stable solid-based composition of claim 2, wherein at least one of the solid compounds in component D is selected from agrochemically active compounds insoluble in component B.

9. The storage-stable solid-based composition of claim 2, wherein the composition is stable at 20° C. and/or 54° C. for 14 days.

10. A method for production of a solid-based composition according to claim 2, the method comprising mixing in no specified order in one or more steps components A, B, optionally C, component D, and one or more salts which are soluble in component B or a solvent miscible with component B.

11. The method of claim 11, wherein the pH is adjusted of both the composition and/or solution comprising component A and the composition and/or solution comprising at least one salt soluble in component B or a solvent miscible with component B, before the composition and/or solution comprising component A and the composition and/or solution comprising at least one salt soluble in component B or a solvent miscible with component B are mixed with each other.

12. The method of claim 10 further comprising the steps of: I. providing a solution (1) of poly-lysine functionalized with fatty acid(s) by mixing at least components A and B, and optionally adjusting to pH of the solution (1), and II. providing a liquid (2) by mixing in no specified order in one or more steps one or more salts in at least one solvent, and optionally adjusting the pH of the liquid (2), and III. providing a solid-based composition (3) by dispersing component D in a dispersing medium comprising at least one dispersant in which component D is insoluble, and IV. mixing at least the solution (1) and the solid-based composition (3) and optionally the liquid (2).

13. A method of producing a tank-mix, the method comprising diluting the storage-stable composition of claim 2 with soft and/or hard water, wherein the water optionally comprises fertilizer.

14. A method of stabilizing a solid-based composition, the method comprising the steps of adding to the solid-based composition at least one poly-lysine derivative obtained by a process comprising the steps of: (a) heating an aqueous lysine solution to boiling; (b) increasing a temperature of the aqueous lysine solution to a reaction temperature in the range of about 105° C. to about 180° C.; (c) keeping the reaction temperature in the range of about 105° C. to about 180° C. until: i. a melt viscosity of the reaction mixture is in the range of about 350 mPa*s to about 6,500 mPa*s when measured at 160° C.; and ii. an amine number in the range of about 100 mg KOH/g to about 500 mg KOH/g is achieved; (d) optionally, releasing a vacuum applied; (e) adding alkyl-carboxylic acid or alkenyl-carboxylic acid in amounts of 2.5 mol % to 10 mol %, relative to a theoretical amount of poly-lysine in the reaction mixture; and (f) increasing or keeping the reaction temperature in the range of about 105° C. to about 180° C. until number of free alkyl-carboxylic acid or alkenyl-carboxylic acid is ≤9% by weight, relative to the total weight of the reaction mixture, wherein vacuum is applied in step (a), (b), and/or (c), and water is removed continuously during the process.

15. A method to increase storage-stability of a solid-based composition comprising one or more salts, the method comprising the step of adding at least one poly-lysine derivative to the solid-based composition, wherein at least one poly-lysine derivative is obtained by a process comprising the steps of: (a) heating an aqueous lysine solution to boiling, (b) increasing a temperature of the aqueous lysine solution to a reaction temperature in the range of about 105° C. to about 180° C., (c) keeping the reaction temperature in the range of about 105° C. to about 180° C. until: i. a melt viscosity of the reaction mixture is in the range of about 350 mPa*s to about 6,500 mPa*s when measured at 160° C., and ii. an amine number in the range of about 100 mg KOH/g to about 500 mg KOH/g is achieved; (d) optionally, releasing a vacuum applied; (e) adding alkyl-carboxylic acid or alkenyl-carboxylic acid in amounts of 2.5 mol % to 10 mol %, relative to a theoretical amount of poly-lysine in the reaction mixture; (f) increasing or adding the reaction temperature in the range of about 105° C. to about 180° C. until number of free alkyl-carboxylic acid or alkenyl-carboxylic acid is ≤9% by weight, relative to the total weight of the reaction mixture, wherein vacuum is applied in step (a), (b), and/or (c), and water is removed continuously during the process, and wherein the solid-based composition comprises at least one solvent miscible with the one or more salts.

Description

EXAMPLES

Example 1—General Process for Synthesis of Poly-Lysine Derivative

[0509]

TABLE-US-00001 Initial charge 500 g Lysine solution 50% in water, 1.25 g sodium hypophosphite feed 1: 2000 g Lysine solution 50% in water feed 2: . . . g alkyl-carboxylic acid or alkenyl-carboxylic acid

[0510] The initial charge is started to be heated. At an internal temperature of 100° C., feed 1 is started to be added to the boiling initial charge. After 45 minutes the internal temperature of 160° C. should be achieved. The internal temperature of the reaction mixture (i.e reaction temperature) is to be kept at this temperature at the following. Feed 1 is added within 5 hours to the reaction mixture.

[0511] After having added the whole feed 1, the pressure within the reaction system is to be reduced to 780 mbar within 35 minutes.

[0512] Within further 35 minutes, the pressure within the reaction system is to be further reduced to 725 mbar. The reaction mixture is to be kept at 160° C. and 725 mbar for additional 2 hours and 20 minutes.

[0513] During the whole time, evaporating water is distilled of.

[0514] The K-value is to be checked during the reaction several times. For this purpose, the vacuum is to be released to collect a sample and is to be applied again immediately after collecting the probe.

[0515] The K-value is to be determined by measurement of kinematic viscosity via Ubbelohde-viscosimeter (DIN 51562-3).

[0516] The amine number is to be checked after achieving the target K-value by potentiometric titration of the reaction mixture at 20° C. and 101.3 kPa with trifluoromethanesulfonic acid: amount of KOH in mg equals 1 g amine-comprising substance.

[0517] The molecular weight, viscosity and PDI are determined.

[0518] After reaching the target K-value and amine number, vacuum is to be released and feed 2 is to be added to the reaction mixture within 10 minutes.

[0519] Immediately after finishing the addition of feed 2, pressure within the reaction system is to be reduced to 725 mbar and the internal temperature of the reaction mixture is to be kept at 160° C. for another 4 hours. During this time, evaporating water is distilled of.

[0520] The weight-average molecular weight of the resulting poly-lysine derivative is to be determined by size exclusion chromatography (SEC or GPC) using hexafluoro iso-propanol with 0.055% of trifluoro acetic acid potassium salt as an eluent at 35° C. Signal calibration is done using a PMMA standard from the company PSS with molecular weights from 800 g/mol to 2,200,000 g/mol. Signal detection is performed by UV/Vis and refractive index sensors. Typically, 50 μL of sample having a concentration of 1.5 mg/mL are injected onto the column setup (1.sup.st precolumn 8 mm inner diameter, 5 cm length; separation column one 7.5 mm inner diameter, 30 cm length; separation column two 7.5 mm inner diameter, 30 cm length) with a flow rate of 0.85 mL/min. Afterwards the internal pressure is to be set to atmospheric pressure and the temperature is to be reduced to 120° C. The product obtained is diluted with water to a concentration of about 30% and the pH is adjusted with lactic acid to a pH value of about 8.

Example 2

[0521]

TABLE-US-00002 Initial charge 500 g Lysine solution 50% in water, 1.25 g sodium hypophosphite feed 1: 2000 g Lysine solution 50% in water feed 2: 120.8 g Oleic acid

[0522] The procedure described in example 1 was conducted until the poly-lysine reached a K value of 11; the poly-lysine had a Mw of 6,990 g/mol, Mn of 2,720 g/mol, and a PDI of 2.6. The amine number was 422, melt viscosity 3,280 mPa*s (measured with Epprecht viscosimeter at 140° C.), melt viscosity 1,000 mPa*s (measured with Epprecht viscosimeter at 160° C.).

[0523] Then feed 2 was introduced into the reaction mixture as described in example 1; the resulting poly-lysine oleate had a K-value of 14.9, an amine number of 315 mg KOH/g, Mw of 46,200 g/mol, Mn of 6,740 g/mol and a PDI of 6.9. Free acid was 2.1% relative to the total weight of the poly-lysine derivative (solid matter). The pH of the poly-lysine oleate solution was 8.3.

Example 3

[0524]

TABLE-US-00003 Initial charge 500 g Lysine solution 50% in water, 1.25 g sodium hypophosphite feed 1: 2000 g Lysine solution 50% in water feed 2: 120.8 g Oleic acid

[0525] The procedure described in example 1 was conducted until the poly-lysine reached a K value of 12.3; the poly-lysine had a Mw of 17,100 g/mol, Mn of 4,910 g/mol, and a PDI of 3.5. The amine number was 391, melt viscosity 6,320 mPa*s (measured with Epprecht viscosimeter at 140° C.), melt viscosity 2,240 mPa*s (measured with Epprecht viscosimeter at 160° C.).

[0526] Then feed 2 was introduced as described in example 1; the resulting poly-lysine oleate had a K-value of 15.1, an amine number of 321 mg KOH/g, Mw of 49,700 g/mol, Mn of 7,420 g/mol and a PDI of 6.7. The pH of the poly-lysine oleate solution was 8.5.

Example 4

[0527]

TABLE-US-00004 Initial charge 500 g Lysine solution 50% in water, 1.25 g sodium hypophosphite feed 1: 2000 g Lysine solution 50% in water feed 2: 362.4 g Oleic acid

[0528] The procedure described in example 1 was conducted until the poly-lysine reached a K value of 11; the poly-lysine had a Mw of 12,900 g/mol, Mn of 3,920 g/mol, and a PDI of 3.3. The amine number was 422, melt viscosity 3,280 mPa*s (measured with Epprecht viscosimeter at 140° C.), melt viscosity 1,000 mPa*s (measured with Epprecht viscosimeter at 160° C.).

[0529] Then feed 2 was introduced as described in example 1; the resulting poly-lysine oleate had an amine number of 221 mg KOH/g, Mw of 44,000 g/mol, Mn of 6,500 g/mol and a PDI of 6.8. Free acid was 2.4% relative to the total weight of the poly-lysine derivative (solid matter). The pH of the poly-lysine-oleate solution was 8.0.

Example 5

[0530]

TABLE-US-00005 Initial charge 500 g Lysine solution 50% in water, 1.25 g sodium hypophosphite feed 1: 2000 g Lysine solution 50% in water feed 2: 85.67 g Lauric acid

[0531] The procedure described in example 1 was conducted until the poly-lysine reached a K-value of 12; the poly-lysine had a Mw of 22,700 g/mol, Mn of 5,850 g/mol, and a PDI of 3.9. The amine number was 391, melt viscosity 6,320 mPa*s (measured with Epprecht viscosimeter at 140° C.), melt viscosity 2,240 mPa*s (measured with Epprecht viscosimeter at 160° C.).

[0532] Then feed 2 was introduced into the reaction mixture as described in example 1; the resulting poly-lysine laurate had a K-value of 16.2, an amine number of 313 mg KOH/g, Mw of 81,400 g/mol, Mn of 9,340 g/mol and a PDI of 8.7. Free acid was 2.7% relative to the total weight of the poly-lysine derivative (solid matter). The pH of the poly-lysine laurate solution was 8.8.

Example 6

[0533]

TABLE-US-00006 Initial charge 500 g Lysine solution 50% in water, 1.25 g sodium hypophosphite, 212.5 g mPEG (Mw = 5000 g/mol, Pluriol A 5010E) feed 1: 2000 g Lysine solution 50% in water feed 2: 120.8 g Oleic acid

[0534] The procedure described in example 1 was conducted until the poly-lysine reached a K-value of 12; the poly-lysine had a Mw of 13,900 g/mol, Mn of 3,000 g/mol, and a PDI of 4.7. The amine number was 395, melt viscosity 1,280 mPa*s (measured with Epprecht viscosimeter at 140° C.), melt viscosity 360 mPa*s (measured with Epprecht viscosimeter at 160° C.).

[0535] Then feed 2 was introduced into the reaction mixture as described in example 1; the resulting poly-lysine-oleate-mPEG had a K-value of 16.1, an amine number of 276 mg KOH/g, Mw of 34,400 g/mol, Mn of 7,450 g/mol and a PDI of 4.6. Free acid was 1.8% relative to the total weight of the poly-lysine derivative (solid matter). The pH of the poly-lysine-oleate-mPEG solution was 9.

Example 7—Comparative Example: Synthesis of Poly-Lysine Oleate Based on Basodrill™ S 100

[0536] An aqueous solution of poly-lysine (9.934 kg) having a K value of 11 (Mw=17.100 g/mol, trade name Basodrill™ S100 by BASF) was dosed into the reactor. Successively water was removed from the solution at 160° C. Then oleic acid (Edenor™ T105, 0.71 kg) was added to the reaction mixture and water was removed from the reaction mixture at 160° C. for 240 min. The reaction had to be stopped due to too high viscosity of the melt.

Example 8: Storage Stability of Solid-Based Formulation

[0537] Particle size distributions in example 8-11 were determined by CIPAC method MT 46-accelerated storage procedure.

[0538] The following concentrated solid-based composition was prepared:

[0539] Component D: 25% w/w azoxystrobin

[0540] Component A+B: 2.5% w/w poly-lysine oleate (5% oleic acid) in water—calculated to 100% active

[0541] Liquid comprising salt was added, wherein the liquid comprised Castoroil ethoxylate+Calciumdodecyl-benzenesulfonate (Agnique CSO 30+Agnique ABS 70 C) 2.5% in the concentrated solid-based composition, calculated to 100% active, wherein Agnique CSO 30: Agnique ABS 70 C was 3:1.

[0542] Then add water up to 100%. The concentrated solid-based composition was milled by wet comminution and evaluated.

[0543] Note: if sheer-sensitive salts are used, milling may take place before addition of said salts.

[0544] Particle Size Stability of the solid-based composition:

TABLE-US-00007 μm start dx10 0.72 dx50 1.55 dx90 3.41 14 days/RT dx10 0.77 dx50 1.85 dx90 3.94 14 days/54° C. dx10 0.81 dx50 2.05 dx90 4.89

[0545] The concentrated solid-based composition was diluted to give a spray-mix: 5% w/w concentrated solid-based composition+95% w/w CIPAC D water (hard water).

[0546] Suspensibility was determined by CIPAC method MT 161.

[0547] Suspensibility test in the spray solution CIPAC D water:

TABLE-US-00008 start Blooming homogenous suspensibility after 30 min 92.29% 14 days/RT blooming homogenous suspensibility after 30 min 93.73% 14 days/54° C. blooming homogenous suspensibility after 30 min  84.1%

Example 9: Storage Stability of Solid-Based Formulation

[0548] The following concentrated solid-based composition was prepared:

[0549] Component D: 25% w/w azoxystrobin

[0550] Component A+B: 2.5% w/w poly-lysine oleate (5% oleic acid) in water—calculated to 100% active

[0551] A solution comprising salt was added, wherein the solution comprised 62% Glyphosate IPA-Salt in water. The concentrated solid-based composition comprised 40% Glyphosate IPA-salt (calculated to 100% active).

[0552] The solid-based composition was milled by wet comminution and evaluated.

[0553] Particle Size Stability of the concentrated solid-based composition

TABLE-US-00009 start dx10 0.67 dx50 1.47 dx90 3.17 14 days/RT dx10 0.697 dx50 1.500 dx90 3.180 14 days/54° C. dx10 0.71 dx50 1.54 dx90 3.25

[0554] The concentrated solid-based composition was diluted to give a spray-mix: 5% w/w concentrated solid-based composition+95% w/w CIPAC D water (hard water).

[0555] Suspensibility was determined by CIPAC method MT 161.

[0556] Suspensibility test in the spray mix:

TABLE-US-00010 start blooming homogenous Suspensibility after 30 min 89.18% 14 days/RT blooming homogenous Suspensibility after 30 min 88.32% 14 days/54° C. blooming homogenous Suspensibility after 30 min 88.67%

Example 10: Storage Stability of Solid-Based Formulation

[0557] The following concentrated solid-based composition (SC) was prepared:

[0558] Component D: 20% w/w azoxystrobin

[0559] Component A+B: 2.5% w/w poly-lysine oleate (5% oleic acid) in water—calculated to 100% active

[0560] Component C: 0.86% w/w defoamer

[0561] Add water up to 100% w/w; the SC was milled by wet comminution.

[0562] An emulsion comprising salt was prepared, wherein the emulsion comprised 25% w/w Oxyfluorofen, 53% w/w Agnique AMD 10 (solvent), 10% w/w Solvesso 200 ND (Co-Solvent), 10% w/w Agnique CSO 35 and 2% Agnique ABS 70C.

[0563] The SC and the emulsion were mixed in various ratios and the particle size of component D was determined.

[0564] Mixture matrix and particle size stability at room temperature (the particle size was determined before storage and after storage for 2 weeks at room temperature):

TABLE-US-00011 Particle Size dx50 Ratios constant: Initial vs. SC:emulsion RT after 2 w [μm] 1:1 1.67 2:1 1.61 3:1 1.74 4:1 1.77 5:1 1.9 6:1 2.05 7:1 2.23

[0565] The compositions comprising various ration SC: emulsion were diluted to give a spray-mix: 5% w/w composition+95% w/w of either CIPAC D water (hard water) or CIPAC B water (soft water).

[0566] The spray-mixes comprising either CIPAC D or B were evaluated according to CIPAC method MT 161.

[0567] CIPAC B (Soft Water):

TABLE-US-00012 Ratios SC:emulsion Residue [g] 1:1 0.13 2:1 0.13 3:1 0.13 4:1 0.34 5:1 0.76 6:1 0.76 7:1 0.67

[0568] CIPAC D (Hard Water):

TABLE-US-00013 Ratios SC:emulsion Residue [g] 1:1 0.66 2:1 0.56 3:1 0.13 4:1 0.12 5:1 0.11 6:1 0.1 7:1 0.11

[0569] A small residue [g] value in comparison to the amount of component D present in the spray-mix indicates a homogenous distribution of component D within the spray-mix

Example 11: Storage Stability of Solid-Based Formulation

[0570] The following concentrated solid-based composition was prepared:

[0571] Component D: 25% w/w azoxystrobin

[0572] Component A+B: 2.5% w/w poly-lysine oleate (5% oleic acid) in water—calculated to 100% active

[0573] A solution 1 comprising salt was added, wherein the solution 1 comprised 62% Glyphosate IPAS-alt in water. The concentrated solid-based composition comprised 40% Glyphosate IPA-salt (calculated to 100% active).

[0574] The solid-based composition was milled by wet comminution and evaluated.

[0575] A solution 2 comprising salt was prepared, wherein the solution comprised Fertilzer NPK 10-34-0 and 40% w/w water (product used: Ammonium polyphosphate solution from BASF North America).

[0576] The concentrated solid-based composition was diluted to give a spray-mix: 5% w/w concentrated solid-based composition+10-95% solution 2+0-85% w/w of either CIPAC D water (hard water) or CIPAC B water (soft water).

[0577] Formulation 1:

[0578] 85% CIPAC water B or D

[0579] 10% solution 2

[0580] 5% concentrated solid-based composition

[0581] CIPAC water and solution 2 were mixed before the concentrated solid-based composition was added.

[0582] Evaluation of the formulation was done according to CIPAC method MT 161: Suspension was not stable within 30 minutes at room temperature, due to settling of component D.

[0583] Formulation 2:

[0584] 0-75% CIPAC water B or D

[0585] 20-95% solution 2

[0586] 5% concentrated solid-based composition

[0587] CIPAC water and solution 2 were mixed before the concentrated solid-based composition was added.

[0588] Evaluation of the formulation was done according to CIPAC method MT 161: Suspension kept homogenous within 30 minutes at room temperature—no settling occurred.