Dispersions Of Polymeric Oil Additives

Abstract

The invention provides dispersions comprising I) at least one oil-soluble polymer effective as a cold flow improver for mineral oils, II) at least one organic, water-immiscible solvent, III) a dispersant comprising, based on the total amount of dispersant, a) 10-90% by weight of a salt of an ethercarboxylic acid and b) 90-10% by weight of a nonionic surfactant, IV) water and V) at least one organic, water-miscible solvent.

Claims

1. A dispersion comprising an organic phase dispersed in an aqueous phase, in which a) the dispersed organic phase comprises at least one oil-soluble polymer effective as a cold flow improver for mineral oils as component I) and at least one organic, water-immiscible solvent as component II), b) the continuous aqueous phase comprises water as component IV) and at least one organic, water-miscible solvent as component V), wherein the dispersion contains c) 0.5% to 12% by weight of a dispersant as component III), which, based on the total amount of dispersant, comprises i) 5-95% by weight of a salt of an ethercarboxylic acid and ii) 95-5% by weight of a nonionic surfactant having an HLB value measured according to Griffin of greater than 7.

2. The dispersion according to claim 1, in which the cold flow improver I is selected from the group consisting of i) copolymers of ethylene and ethylenically unsaturated esters, ethers and/or alkenes, ii) homo- or copolymers of C.sub.10-C.sub.30-alkyl-bearing esters, amides and/or imides of ethylenically unsaturated carboxylic acids, iii) ethylene copolymers grafted with ethylenically unsaturated esters and/or ethers, iv) homo- and copolymers of higher olefins, and v) condensation products of phenols bearing at least one alkyl radical and aldehydes and/or ketones.

3. The dispersion according to claim 1, in which the cold flow improver I) comprises a copolymer of ethylene and vinyl ester.

4. The dispersion according to claim 1, in which the cold flow improver I) is a homo- or copolymer of an ester, amide and/or imide of at least one ethylenically unsaturated dicarboxylic acid containing at least one C.sub.10-C.sub.30-alkyl radical.

5. The dispersion according to claim 1, in which the cold flow improver is an ethylene copolymer grafted with an ethylenically unsaturated ester and/or ether, where the ethylene copolymer is an ethylene-vinyl ester copolymer.

6. The dispersion according to claim 5, wherein the ethylenically unsaturated ester is a C.sub.10-C.sub.30-alkyl-bearing ester of acrylic acid and/or methacrylic acid.

7. The dispersion according to claim 1, in which the cold flow improver is a homo- and copolymer of -olefins having 3 to 30 carbon atoms.

8. The dispersion according to claim 1, in which the cold flow improver is a condensation product of at least one phenol bearing at least one alkyl radical and at least one aldehyde or ketone.

9. The dispersion according to claim 8, in which the condensation product conforms to the formula (6) ##STR00005## in which R.sup.14 is C.sub.1- to C.sub.100-alkyl, C.sub.2- to C.sub.100-alkenyl, OC.sub.1- to OC.sub.100-alkyl, OC.sub.2- to OC.sub.100-alkenyl, C(O)OC.sub.1- to C(O)OC.sub.100-alkyl, C(O)OC.sub.2- to C(O)OC.sub.100-alkenyl, OC(O)C.sub.1- to OC(O)C.sub.100-alkyl or OC(O)C.sub.2- to OC(O)C.sub.100-alkenyl, and n is a number from 2 to 250.

10. The dispersion according to claim 1, in which the salt of an ethercarboxylic acid has been prepared by neutralization of at least one ethercarboxylic acid with at least one base of the alkali metals or alkaline earth metals or an amine.

11. The dispersion according to claim 1, in which the ethercarboxylic acid conforms to the formula (7)
R.sup.15(OC.sub.xH.sub.2x).sub.yOCH.sub.2COOH(7) in which R.sup.15 is a linear or branched alkyl or alkenyl group having 4 to 24 carbon atoms, an alkylaryl group wherein the alkyl radical has 1 to 24 carbon atoms, or an aryl group, x is the number 2 and/or 3 and y is a number from 0 to 20.

12. The dispersion according to claim 10, in which the amine is an alkanolamine.

13. The dispersion according to claim 12, in which the alkanolamine is a primary, secondary or tertiary amine bearing at least one alkyl radical substituted by a hydroxyl group.

14. The dispersion according to claim 12, in which the alkanolamine conforms to the formula (9):
NR.sup.16R.sup.17R.sup.18(9) in which R.sup.16 is a hydrocarbyl radical which bears at least one hydroxyl group and has 1 to 10 carbon atoms and R.sup.17, R.sup.18 are independently hydrogen, an optionally substituted hydrocarbyl radical having 1 to 50 carbon atoms.

15. The dispersion according to claim 10, in which the amine is a heterocyclic compound comprising a cycle which has 5 to 7 ring members and comprises not only a nitrogen atom but also an oxygen atom, and which bears, on the nitrogen atom, an alkyl radical having 1 to 4 carbon atoms or a group of the formula (10)
(BO).sub.pR.sup.19(10) in which B is an alkylene radical having 2 or 3 carbon atoms, and p is 1 or 2, and R.sup.19 is hydrogen or a group of the formula BNH.sub.2.

16. The dispersion according to claim 1, in which the nonionic surfactant is selected from the group consisting of a) 1- to 80-tuply ethoxylated C.sub.8- to C.sub.20-alkanol, C.sub.8- to C.sub.12-alkylphenol, C.sub.8- to C.sub.20 fatty acid, C.sub.8- to C.sub.20 fatty acid amide, b) copolymers of ethylene oxide and propylene oxide, and c) partial esters of polyols with fatty acids.

17. The dispersion according to claim 1, in which the nonionic surfactant conforms to the structural formulae (11) to (14) ##STR00006## in which R.sup.20 is an aliphatic hydrocarbyl radical having 5 to 29 carbon atoms and R.sup.21 is an aliphatic hydrocarbyl radical having 1 to 6 carbon atoms.

18. The dispersion according to claim 1, in which the weight ratio between ethercarboxylic salt and nonionic surfactant is between 1:10 and 10:1.

19. The dispersion according to claim 1, in which the dispersant (III) further comprises an anionic, cationic and/or zwitterionic coemulsifier (VI).

20. The dispersion according to claim 1, in which the water-miscible solvent (V) has a relative permittivity .sub.r of at least 3.

21. The dispersion according to claim 1, wherein the organic, water-miscible solvent (V) is selected from the group consisting of alcohols, glycols, poly(glycols), acetates, ketones and lactones.

22. The dispersion according to claim 1, comprising 5%-60% by weight of an oil-soluble polymer (I) effective as a cold flow improver for mineral oils.

23. The dispersion according to claim 1, comprising 5-40% by weight of water-immiscible solvent (II).

24. The dispersion according to claim 1, comprising 20-80% by weight of a continuous phase of water (IV) and at least one organic, water-miscible solvent (V).

25. The dispersion according to claim 1, in which the continuous phase contains between 10% and 90% by weight of water (IV) and between 90% and 10% by weight of the organic, water-miscible solvent (V), based on the total amount of the continuous phase.

26. The dispersion according to claim 1, in which the pH of the dispersion is above 6.0, measured as a 1% dilution in water.

27. The dispersion according to claim 1, in which a rheology-modifying substance that generates a yield point is added, which is a water-soluble polymer.

28. A process for producing a dispersion comprising an organic phase dispersed in an aqueous phase, in which a) the dispersed organic phase comprises at least one oil-soluble polymer effective as a cold flow improver for mineral oils as component I) and at least one organic, water-immiscible solvent as component II), b) the continuous aqueous phase comprises water as component IV) and at least one organic, water-miscible solvent as component V), wherein the dispersion contains c) 0.5% to 12% by weight of a dispersant as component III), which, based on the total amount of dispersant, comprises i) 5-95% by weight of a salt of an ethercarboxylic acid and ii) 95-5% by weight of a nonionic surfactant having an HLB value measured according to Griffin of greater than 7, by converting constituents I, II, III, IV and V to a dispersion by mixing with stirring at temperatures above 50 C.

29. A process for producing a dispersion according to claim 28, by using a solution of the oil-soluble polymer (I) effective as a cold flow improver for mineral oils in the organic, water-immiscible solvent (II).

30. A process for producing a dispersion according to claim 28, by adding a mixture of constituents I and II to a mixture of water (IV), the organic, water-miscible solvent (V) and the dispersant (III) at temperatures between 30 C. and 100 C., so as to form an oil-in-water dispersion.

31. A process for producing a dispersion according to claim 28, by homogenizing constituents I), II) and III) and then adding a mixture of constituents IV and V at temperatures between 30 C. and 100 C., so as to form an oil-in-water dispersion.

32. A process for producing a dispersion according to claim 28, by subjecting the mixture of the constituents to shear.

33. (canceled)

34. A process for improving the cold flow properties of crude oil, heating oil, bunker oil, residue oil and mineral oil that contains at least one residue oil, by adding a dispersion comprising an organic phase dispersed in an aqueous phase, in which a) the dispersed organic phase comprises at least one oil-soluble polymer effective as a cold flow improver for mineral oils as component I) and at least one organic, water-immiscible solvent as component II), b) the continuous aqueous phase comprises water as component IV) and at least one organic, water-miscible solvent as component V), wherein the dispersion contains c) 0.5% to 12% by weight of a dispersant as component III), which, based on the total amount of dispersant, comprises i) 5-95% by weight of a salt of an ethercarboxylic acid and ii) 95-5% by weight of a nonionic surfactant having an HLB value measured according to Griffin of greater than 7, to a paraffinic mineral oil and products produced therefrom.

Description

EXAMPLES

[0228] Production of the Dispersions, Variant A

[0229] The amounts of cold flow improver and ethercarboxylic acid specified in table 2 were dissolved/homogenized at 80-85 C. in the organic, water-immiscible solvent (xylene, Solvent Naphtha). After addition of an amount of the base equimolar to the ethercarboxylic acid (as a 10% aqueous solution), the mixture was stirred at 80-85 C. for a further 30 minutes, forming an inverse emulsion (W/O). Subsequently, a mixture of the remaining amount of water, the organic, water-miscible solvent and the nonionic surfactant was added, forming a white, low-viscosity dispersion (O/W). If the pH of this dispersion (as a 1% dilution in water) was less than 6, further base was used to adjust it to a pH of >6. Table 2 shows the total amounts of base added to the dispersions and the pH of the dispersion established thereby. After cooling to 50 C., the dispersion was subjected to shear with an Ultra-Turrax T45 with G45M tool at 21 500 rpm for 2 minutes.

[0230] Production of Dispersions, Variant B

[0231] The amounts of the starting materials specified in table 2 were metered into a beaker and heated to 80-85 C. If the pH of this dispersion (as a 1% dilution in water) was less than 6, further base was used to adjust it to a pH >6 (as for variant A, table 2 shows the total amounts of base added to the dispersions and the pH values of the dispersions established thereby). This was followed by stirring at this temperature by means of a magnetic stirrer for 1 hour. After cooling to 50 C., the dispersion was subjected to shear with an Ultra-Turrax T45 with G45M tool at 21 500 rpm for 2 minutes.

TABLE-US-00001 TABLE 1 Starting materials used: Cold flow PPD 1 Poly(stearyl acrylate) with K value of 32 (measured according to improver Fikentscher in 5% toluenic solution) PPD 2 Behenyl acrylate-grafted (in a weight ratio of 4:1) ethylene-vinyl acetate copolymer having a vinyl acetate content of 28% by weight and an MFI.sub.190 of 7 g/10 minutes. PPD 3 Stearyl acrylate-grafted (in a weight ratio of 3:1) ethylene-vinyl acetate copolymer having a vinyl acetate content of 28% by weight and an MFI.sub.190 of 7 g/10 minutes. PPD 4 Behenyl alcohol-esterified copolymer of maleic anhydride and C.sub.20-24--olefin, acid number 38 mg KOH/g and weight-average molecular weight Mw of 10 000 g/mol PPD 5 Behenyl alcohol-esterified copolymer of maleic anhydride and C.sub.20-24--olefin, acid number 9 mg KOH/g and weight-average molecular weight Mw 11 500 g/mol PPD 6 Ethylene-vinyl acetate copolymer having a vinyl acetate content of 25% by weight and a weight-average molecular weight Mw of 100 000 g/mol (measured by means of GPC in THF against poly(styrene) standards) PPD 7 C.sub.20/24-Alkylphenol-formaldehyde resin having a weight-average molecular weight Mw of 5400 g/mol (measured by means of GPC in THF against poly(styrene) standards) Ether- ECS 1 Isotridecanol + 7 EO-ethercarboxylic acid carboxylic ECS 2 Lauryl alcohol + 5 EO-ethercarboxylic acid acids ECS 3 Oleyl alcohol + 8 EO-ethercarboxylic acid ECS 4 Oleyl alcohol + 10 EO-ethercarboxylic acid Bases DEA diethanolamine TEA triethanolamine KOH KOH TEM triethylamine Nonionic NiS 1 Isotridecanol ethoxylated with 15 mol of ethylene oxide; HLB 15.4 surfactants NiS 2 Isotridecanol ethoxylated with 2.5 mol of ethylene oxide; HLB 8.2 NiS 3 Tri-sec-butylphenol ethoxylated with 30 mol of ethylene oxide; HLB 16 NiS 4 NC.sub.12/24-Acyl-N-methylglucamide; HLB 11.5 NiS 5 (C) Coconut fatty alcohol alkoxylated with 4 mol of ethylene oxide and 4 mol of propylene oxide, HLB 6.0 Water- MEG monoethylene Water- Xyl: xylene miscible glycol immiscible organic DEG diethylene organic SN: Solvent Naphtha solvent glycol solvent (aromat. solvent EtOH ethanol mixture with boiling IPA isopropanol range 185-215 C.) GLY glycerol W water OA 1 (C) behenic acid OA 2 (C) Mixture of 1 part by weight of polycyclic carboxylic acids (main constituents: abietic acid, neoabietic acid, dehydroabietic acid, palustric acid, pimaric acid and levopimaric acid) and 3 parts by weight of tall oil fatty acid having a fatty acid content of 98%.

[0232] The dispersions were each characterized after shear. Viscosity and yield point were determined with a plate-cone viscometer having a diameter of 35 mm, a cone angle of 4 and a shear rate of 100 s.sup.1. The yield point was determined according to DIN EN ISO 3219. The particle sizes and distributions of the dispersions were determined by means of dynamic light scattering (with an instrument of the Mastersizer 2000 type; Malvern Instruments). Melt indices (MFI.sub.190) of the polymers used were determined according to DIN 53735 at 190 C. with an applied force of 2.16 kg.

TABLE-US-00002 TABLE 2 Composition of the dispersions (amount in g) Hydrophobic Ethercarboxylic Nonionic Hydrophilic Production Example PPD solvent (II) acid Base surfactant Water solvent (V) pH variant 1 PPD 4 (20) SN (10) ECS 3 (1.8) TEA (1.0) NiS 2 (2.0) (38) MEG (28) 7.91 A 2 PPD 3 (30) SN (20) ECS 1 (1.8) TEA (0.5) NiS 1 (2.0) (25) MEG (21) 7.37 A 3 PPD 3 (25) SN (17) ECS 1 (2.7) DEA (0.5) NiS 1 (5.0) (27) DEG (23) 6.86 A 4 PPD 5 (20) SN (20) ECS 1 (1.8) DEA (0.5) NiS 1 (2.0) (30) MEG (30) 7.99 A 5 PPD 1 (24) Xyl (16) ECS 4 (1.8) TEA (1.0) NiS 1 (2.0) (32) MEG (23) 7.90 A 6 PPD 4 (20) SN (10) ECS 1 (2.7) TEA (1.0) NiS 1 (2.5) (27) MEG (37) 6.95 A 7 PPD 4 (20) SN (10) ECS 1 (2.7) TEA (1.0) NiS 1 (2.0) (27) MEG (37) 6.34 B 8 PPD 3 (25) SN (17) ECS 1 (1.8) TEA (0.5) NiS 2 (2.0) (20) MEG (34) 7.52 A 9 PPD 1 (20) Xyl (20) ECS 1 (1.8) TEA (1.0) NiS 1 (2.0) (24) MEG (31) 8.01 A 10 PPD 5 (20) SN (20) ECS 1 (1.8) DEA (0.5) NiS 1 (2.0) (22) MEG (34) 8.89 B 11 PPD 3 (25) SN (17) ECS 1 (1.8) TEA (0.5) NiS 2 (2.0) (20) MEG (34) 7.38 B 12 PPD 6 (20) SN (30) ECS 1 (3.9) TEA (0.7) NiS 1 (2.9) (27) MEG (15) 7.31 A 13 PPD 7 (15) SN (20) ECS 2 (4.0) DEA (2.0) NiS 4 (2.5) (18) DEG (40) 7.26 B 14 PPD 4 (17) SN (16) ECS 1 (1.8) TEA (1.0) NiS 1 (2.0) (28) MEG (18) 8.30 A PPD 3 (12) 15 PPD 4 (30) SN (15) ECS 2 (3.0) TEA (1.0) NiS 1 (2.0) (28) MEG (35) 6.72 A 16 PPD 6 (20) SN (30) ECS 4 (3.0) KOH (0.4) NiS 4 (1.8) (30) GLY (15) 7.60 B 17 PPD 2 (25) SN (17) ECS 4 (2.5) TEM (0.8) NiS 4 (1.5) (25) DEG (30) 9.12 A 18 PPD 2 (24) SN (16) ECS 1 (2.7) TEA (1.0) NiS 3 (5.0) (30) MEG (21) 7.95 A 19 PPD 2 (25) SN (17) ECS 3 (1.8) TEA (0.5) NiS 4 (3.0) (30) DEG (25) 7.42 A 20 PPD 4 (15) SN (15) ECS 4 (1.5) TEA (1.0) NiS 2 (2.5) (37) GLY (28) 7.14 B 21 (C) PPD 3 (25) SN (17) ECS 1 (1.8) TEA (0.5) NiS 5 (2.5) (25) MEG (25) 8.02 A 22 (C) PPD 6 (20) SN (30) OA 1 (2.5) KOH (0.8) NiS 1 (2.0) (23) MEG (23) 7.45 A 23 (C) PPD 4 (30) SN (18) OA 2 (2.5) DEA (1.0) NiS 1 (2.0) (26) MEG (25) 7.31 A

TABLE-US-00003 TABLE 3 Properties of the dispersions Dispersion from Viscosity example Stability Pour point @ 10 C. Yield point 1 >7 days 30 C. 44 mPas <10 mPa 2 >7 days 36 C. 371 mPas <10 mPa 3 >7 days 36 C. 467 mPas <10 mPa 4 >7 days 45 C. 168 mPas <10 mPa 5 >7 days 45 C. 110 mPas <10 mPa 6 >7 days <50 C. 157 mPas <10 mPa 7 >7 days <50 C. 127 mPas <10 mPa 8 >7 days <50 C. 624 mPas 42 mPa 9 >7 days <50 C. 145 mPas <10 mPa 10 >7 days <50 C. 259 mPas <10 mPa 11 >7 days 39 C. 306 mPas <10 mPa 12 >7 days 36 C. 940 mPas 62 mPa 13 >7 days 19 C. 241 mPas <10 mPa 14 >7 days 39 C. 209 mPas <10 mPa 15 >7 days 33 C. 582 mPas 35 mPa 16 >7 days 36 C. 205 mPas <10 mPa 17 >7 days <50 C. 614 mPas 39 mPa 18 >7 days 33 C. 745 mPas 50 mPa 19 >7 days 36 C. 102 mPas <10 mPa 20 >7 days 36 C. 116 mPas <10 mPa 21 (C) inhomogeneous n.a. n.a. n.a. 22 (C) >7 days 18 C. 2017 mPas 540 mPa 23 (C) >7 days 24 C. 1760 mPas 306 mPa

[0233] Efficacy as Pour Point Depressant

[0234] The testing of the efficacy of the dispersions of the invention and the solutions in aromatic solvents that were used for their production was undertaken in various crude oils and residue oils. Pour points were determined according to DIN ISO 3016. The proportions in the crude oils of saturated hydrocarbons (aliphatics), aromatic hydrocarbons (aromatics), resins and asphaltenes were determined by means of a combination of thin-layer chromatography and flame ionization detection in accordance with IP 469 (latroscan analysis).

TABLE-US-00004 TABLE 5 Characterization of the crude oils Crude oil Pour point Aliphatics Aromatics Resins Asphaltenes A 21 C. 57.0% 21.3% 18.0% 3.7% B 24 C. 67.0% 13.5% 16.6% 2.9%

TABLE-US-00005 TABLE 4 Efficacy of the dispersions in crude oil A Example Additive Dosage rate Pour point 24 Example 2 300 ppm 12 C. 25 Example 5 300 ppm 9 C. 26 Example 17 300 ppm 15 C. 27 (C) PPD 1, 24% in xylene 300 ppm 6 C. 28 (C) PPD 2, 25% in Solvent Naphtha 300 ppm 15 C. 29 (C) PPD 3, 30% in Solvent Naphtha 300 ppm 12 C.

TABLE-US-00006 TABLE 5 Efficacy of the dispersions in crude oil B Example Additive Dosage rate Pour point 30 Example 2 200 ppm 9 C. 31 Example 6 200 ppm 6 C. 32 Example 10 200 ppm 6 C. 33 (C) Example 23 (C) 135 ppm 12 C. 34 (C) PPD 3, 30% in Solvent Naphtha 200 ppm 9 C. 35 (C) PPD 4, 20% in Solvent Naphtha 200 ppm 12 C. 36 (C) PPD 5, 20% in Solvent Naphtha 200 ppm 9 C.

[0235] The experiments show that the superior stability and improved cold properties and also the performance of the dispersions of the invention result to a crucial degree from the presence of ethercarboxylic salts. In addition, they show that the efficacy of the active ingredients formulated in the form of the dispersions of the invention is at least equal to and in various cases even superior to the solutions of the corresponding active ingredients in organic solvents.