NEW MIXTURES FOR IMPROVING THE STABILITY OF ADDITIVE PACKAGES

Abstract

Mixtures of certain olefin-carboxylic acid copolymers (A) with at least one additive with detergent action, preferably at least one quaternary nitrogen compound (B), and optionally further fuel additives, are useful for improving the stability of additive packages for fuels, especially fuel oils and gasoline fuels.

Claims

1. (canceled)

2. The process according to claim 16, wherein monomer (Aa) is maleic acid anhydride.

3. The process according to claim 16, wherein monomer (Ab) is one or more linear or branched 1-alkene.

4. The process according to claim 16, wherein no (Ac) and (Ad) are present in the copolymer.

5. The process according to claim 16, wherein compound (B) is of the formula
.sup.+NR.sup.1R.sup.2R.sup.3R.sup.4A.sup. in which A.sup. stands for an anion, and R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 independently of another are an organic residue with from 1 to 100 carbon atoms, substituted or unsubstituted, and R.sup.5 additionally may be a substituted or unsubstituted cycloalkyl or aryl residue bearing 5 to 20 carbon atoms.

6. The process according to claim 16, wherein nitrogen compounds (B) are obtainable by addition of a compound which comprises at least one oxygen- or nitrogen-containing group reactive with an anhydride and additionally al least one quaternizable amino group onto a polycarboxylic anhydride compound and subsequent quaternization in the presence of an acid or in an acid-free manner, in the absence of free acid, or with a carboxylic ester.

7. The process according to claim 16, wherein the nitrogen compound (B) is of formula ##STR00008## wherein in this formula PIB stands for a polyisobutenyl residue having a number average molecular weight M.sub.n of from 550 to 2300 g/mol, R stands for an C.sub.1-alkyl or hydroxy-C.sub.1- to C.sub.4-alkyl, and A.sup. stands for an anion.

8. The process according to claim 16, wherein the nitrogen compound (B) is of formula ##STR00009## wherein in this formula PIB stands for a polyisobutenyl residue having a number average molecular weight M.sub.n of from 550 to 2300 g/mol, and R stands for a hydroxy-C.sub.1- to C.sub.4-alkyl.

9. The process according to claim 16, wherein the nitrogen compound (B) is of formula ##STR00010## wherein in this formula PIB stands for a polyisobutenyl residue having a number average molecular weight M.sub.n of from 550 to 2300 g/mol, R stands for an C.sub.1- to C.sub.4-alkyl or hydroxy-C.sub.1- to C.sub.1-alkyl, and A.sup. stands for an anion.

10. The process according to claim 16, wherein the nitrogen compound (B) is of formula ##STR00011## wherein in this formula R.sup.a stands for C.sub.1-C.sub.20-alkyl, R.sup.b stands for a hydroxy-C.sub.1- to C.sub.4-alkyl, and A.sup. stands for an anion.

11. The process according to claim 16, wherein the nitrogen compound (B) is of formula ##STR00012## wherein in this formula X.sub.i for i=1 to n and 1 to in are independently of another selected from the group consisting of CH.sub.2CH.sub.2O, CH(CH.sub.3)CH.sub.2O, CH.sub.2C(CH.sub.3).sub.2O, C(CH.sub.3).sub.2CH.sub.2O, CH.sub.2CH(C.sub.2H.sub.5)O, CH(C.sub.2H.sub.5)CH.sub.2O and CH(CH.sub.3)CH(CH.sub.3)O, m and n independently of another are positive integers, with the proviso that the sum (m+n) is from 2 to 50, R stands for an C.sub.1- to C.sub.4-alkyl, and A.sup. stands for an anion.

12. The process according to claim 16, wherein the nitrogen compound (B) is of formula ##STR00013## wherein in this formula R.sup.a and R.sup.b independently of another stand for C.sub.1-C.sub.20-alkyl or hydroxy-C.sub.1- to C.sub.4-alkyl, and A.sup. stands for an anion.

13. The process according to claim 16, wherein the polyisobutenylsuccinimide (G) is of formula ##STR00014## wherein in this formula PIB stands for a polyisobutenyl residue having a number average molecular weight M.sub.n of from 550 to 2300 g/mol, and n stands for a positive integer of from 2 to 6.

14. The process according to claim 16, wherein (A) is applied to the fuel additive package comprising (B) or (G) with at least one dehazer as additive component (C) selected from the group consisting of (C1) alkoxylation copolymers of ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and/or other oxides; and (C2) alkoxylated phenol formaldehyde resins.

15. The process according to claim 16, wherein (A) is applied to the fuel additive package comprising (B) or (G) with at least one organic nitrate as additive cetane number improver (D).

16. A process for improving the stability of additives with detergent action in fuel additive packages, the process comprising: applying at least olefin-carboxylic acid copolymers (A) with a number-average molecular weight M.sub.n of from 0.5 to 10 kDa (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard), obtainable by in a first reaction (I), copolymerizing (Aa) at least one ethylenically unsaturated mono- or dicarboxylic acid or derivative thereof, (Ab) at least one -olefin having from at least 2 up to and including 30 carbon atoms, (Ac) optionally at least one further aliphatic or cycloaliphatic olefin which has at least 4 carbon atoms and is different than (Ab), and (Ad) optionally one or more further copolymerizable monomers other than monomers (Aa), (Ab), and (Ac), selected from the group consisting of (Ada) vinyl esters, (Adb) vinyl ethers, (Adc) (meth)acrylic esters of alcohols having at east 5 carbon atoms, (Add) allyl alcohols or ethers thereof, (Ade)N-vinyl compounds selected from the group consisting of vinyl compounds of heterocycles containing at least one nitrogen atom, N-vinylamides, and N-vinyllactams, (Adf) ethylenically unsaturated aromatics, (Adg) ,-ethylenically unsaturated nitriles, (Adh) (meth)acrylamides, and (Adi) allylamines followed by in a second optional reaction (II) partly or fully hydrolyzing and/or saponifying anhydride or carboxylic ester functionalities present in a copolymer obtained from (I), the second reaction Met) being run at least when the copolymer obtained from reaction (I) does not comprise any free carboxylic functionalities; to a fuel additive package comprising at least one additive with detergent action selected from the group consisting of quaternary nitrogen compounds (B), and polyisobutenylsuccinimides (G).

17. The process according to claim 16, Wherein (Aa) is at least one ethylenically unsaturated dicarboxylic acid.

18. The process according to claim 5, wherein A.sup. is a carboxylate R.sup.5COO.sup. or a carbonate R.sup.5OCOO.sup.; R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 independently of another are an unsubstituted, linear or branched alkyl, alkenyl, or hydroxyalkyl residue with 1 to 100 carbon atoms; and R.sup.5 additionally may be a substituted or unsubstituted cycloalkyl or aryl residue bearing 5 to 12 carbon atoms.

19. The process according to claim 7, wherein PIB is a polyisobutenyl residue having a number average molecular weight M.sub.n of from 750 to 1300 g/mol, R is methyl or 2-hydroxypropyl, and A.sup. is acetate, salicylate, or methyloxalate.

20. The process according to claim 9, wherein PIB is a polyisobutenyl residue having a number average molecular weight M.sub.n of from 750 to 1300 g/mol, R is methyl, and A.sup. is salicylate or methyloxalate.

21. The process according to claim 12, wherein R.sup.a is a C.sub.1-C.sub.20-alkyl, R.sup.b is a hydroxy-C.sub.1- to C.sub.4-alkyl, and A.sup. is a C.sub.12-C.sub.100-alkyl- and -alkenyl succinic acid.

Description

EXAMPLES

[0272] Additive Formulations (Given in Weight %) (Gasoline Additive Formulation)

TABLE-US-00001 Example 1 (Comparative) 2 (Inventive) 3 (Inventive) Detergent .sup.a) 26.65 26.60 26.56 Carrier Oil .sup.b) 14.73 14.71 14.69 Quaternary Detergent .sup.c) 9.40 9.39 9.38 Oleic Acid .sup.d) 10.97 10.96 10.94 Solvesso 150 31.98 31.93 31.88 2-Ethylhexanol 6.27 6.26 6.25 Component (A) .sup.e) 0.16 0.31 .sup.a) Detergent Polyisobutene amine, molecular weight approx. 1000 g/mol, commercially available as KEROCOM PIBA 03 from BASF .sup.b) Carrier oil: C.sub.13-alkanol propoxylate according to WO 00/02978, molecular weight Mn approx. 1300 g/mol .sup.c) Quaternary Ammonium Salt Detergent: Reaction product of n-hexadecyldimethylamine with propylene oxide, with hydrolyzed polyisobutenyl succinic acid as counterion as described in EP 3004294 B1, Synthetic Example 6 (applied as 50 wt % solution in 2-ethylhexanol). .sup.d) Oleic acid as friction modifier .sup.e) Hydrolyzed copolymer of a mixture of C.sub.20 to C.sub.24 alpha-olefins with maleic acid anhydride, Mn: 1500 g/mol, Mw: 3200 g/mol, applied as 40% solution in Solvesso, as described in EP 3099720 B1, Synthetic Example 2.

[0273] Application Tests

[0274] 100 ml of the formulations 1 to 3 were stored at 20 C. for a period of 3 days.

[0275] 1) The samples were examined for their turbidity immediately after storage (FIG. 1, from left to right) with the result as follows: [0276] Example 1 (most turbid)>Example 2 (less turbid)>Example 3 (least turbid)

[0277] 2) Afterwards the samples were allowed to warm up to room temperature and were examined for their turbidity (FIG. 2, from left to right) with the result as follows: [0278] Example 1 (slightly turbid)>Example 2 (clear)>Example 3 (clear)

[0279] Since the formulation of Example 1 exhibits a turbidity even after storage at 20 C. for 3 days which remains after warming to room temperature it fails the stability criterion. In contrast, the formulations of Examples 2 and 3 remain stable at 20 C. for more than 8 weeks.

[0280] Additive Formulations (Given in Weight Amount) (Diesel Additive Formulation)

TABLE-US-00002 Example 4 (Comparative) 5 (Inventive) Quaternary Detergent (B) .sup.a) 21.9 21.9 Tall oil fatty acid 8.8 8.8 Antifoam (Si containing) 1.8 1.8 Dehazer 1.8 1.8 2-Ethylhexyl nitrate 65.7 64.8 Component (A) .sup.b) 0.9 .sup.a) Detergent Polyisobutene succinid acid converted with DMAPA and PO, molecular weight approx. 1200 g/mol, see WO 2012/004300 Ex 1, 50% polymer content in 50% solvent .sup.b) Hydrolyzed copolymer of a mixture of C.sub.20 to C.sub.24 alpha-olefins with maleic acid anhydride, Mn: 1500 g/mol, Mw: 3200 g/mol, as described in EP 3099720 B1, Synthetic Example 2.

[0281] Application Tests

[0282] 100 ml of the formulations 4 and 5 were stored at 30 C. for a period of 7 days. The samples were examined for their turbidity after this storage period: [0283] Example 4 (turbid, sediments) [0284] Example 5 (not turbid, no sediments)

[0285] Since the comparative formulation of Example 4 exhibits sediments and turbidity after storage at 30 C. for 7 days, it is clearly less stable than Example 5 according to the invention.