COMPOSITION, METHOD AND USE

Abstract

A quaternary ammonium salt of formula (I): wherein X is a linking group; Y is O, NH or NR.sup.1 wherein R.sup.1 is H or an optionally substituted hydrocarbyl group; Q.sup.+ is a moiety that includes a quaternary ammonium cation; A.sup. is an anion; R.sup.2 is an optionally substituted alkylene group; R.sup.3 is hydrogen or an optionally substituted hydrocarbyl group; and n is 0 or a positive integer; provided that n is not 0 when R.sup.3 is hydrogen.

##STR00001##

Claims

1. A quaternary ammonium salt of formula (I): ##STR00016## wherein X is a linking group; Y is O, NH or NR.sup.1 wherein R.sup.1 is H or an optionally substituted hydrocarbyl group; Q.sup.+ is a moiety that includes a quaternary ammonium cation; A.sup. is an anion; R.sup.2 is an optionally substituted alkylene group; R.sup.3 is hydrogen or an optionally substituted hydrocarbyl group; and n is 0 or a positive integer; provided that n is not 0 when R.sup.3 is hydrogen.

2. A composition comprising a quaternary ammonium salt of formula (I): ##STR00017## wherein X is a linking group; Y is O, NH or NR.sup.1 wherein R.sup.1 is H or an optionally substituted hydrocarbyl group; Q.sup.+ is a moiety that includes a quaternary ammonium cation; A.sup. is an anion; R.sup.2 is an optionally substituted alkylene group; R.sup.3 is hydrogen or an optionally substituted hydrocarbyl group; and n is 0 or a positive integer; provided that n is not 0 when R.sup.3 is hydrogen.

3. (canceled)

4. A method of improving the performance of an engine, the method comprising combusting in the engine a fuel composition comprising as an additive a quaternary ammonium salt of formula (I): ##STR00018## wherein X is a linking group; Y is O, NH or NR.sup.1 wherein R.sup.1 is H or an optionally substituted hydrocarbyl group; Q.sup.+ is a moiety that includes a quaternary ammonium cation; A.sup. is an anion; R.sup.2 is an optionally substituted alkylene group; R.sup.3 is hydrogen or an optionally substituted hydrocarbyl group; and n is 0 or a positive integer; provided n is not 0 when R.sup.3 is hydrogen.

5. The salt according to claim 1 wherein the quaternary ammonium salt additive is prepared by reacting: (a) a hydrocarbyl substituted dicarboxylic acid or anhydride thereof; with (b) an alcohol of formula R.sup.3(OR.sup.2).sub.nOH; (c) a reactive alcohol or amine including a tertiary amino group; and (d) a quaternising agent.

6. The salt according to claim 1 wherein X is an optionally substituted alkylene or arylene group and R.sup.4 is an optionally substituted hydrocarbyl group.

7. The salt according to claim 1 wherein n is 0 and R.sup.3 is an optionally substituted alkyl or alkenyl group having 4 to 40 carbon atoms.

8. The salt according to claim 1 wherein each R.sup.2 is ethylene or propylene.

9. The salt according to claim 8 wherein R.sup.3 is hydrogen and n is at least 1.

10. The salt according to claim 8 wherein R.sup.3 is an optionally substituted alkyl group having 4 to 40 carbon atoms and n is from 1 to 40.

11. The salt according to claim 1 wherein Q.sup.+ is a group having the formula: ##STR00019## wherein R.sup.5 is an optionally substituted alkylene, arylene or alkenylene group and each of R.sup.6, R.sup.7 and R.sup.8 is independently an optionally substituted hydrocarbyl group.

12. The salt according to claim 11 wherein R.sup.5 is an optionally substituted alkylene group having 1 to 6 carbon atoms, R.sup.6 is C.sub.1 to C.sub.6 alkyl, R.sup.7 is C.sub.1 to C.sub.6 alkyl and R.sup.8 is an unsubstituted C.sub.1 to C.sub.6 alkyl group or a hydroxy substituted C.sub.1 to C.sub.40 alkyl group.

13. The salt according to claim 1 wherein A.sup. is a carboxylate anion.

14. The salt according to claim 1 wherein the quaternary ammonium salt additive is prepared by reacting: (a) an optionally substituted succinic acid or anhydride thereof; (b) an alcohol of formula H(OR.sup.2).sub.nOH or R.sup.3OH; (c) a reactive alcohol including a tertiary amino group; and (d) a quaternising agent.

15. The salt according to claim 1 wherein the quaternary ammonium salt additive is prepared by reacting: (a) a succinic acid or anhydride thereof substituted with a C.sub.20 to C.sub.24 alkyl or alkenyl group; (b) a polypropylene glycol or butanol; (c) dimethylaminopropanol; and a quaternising agent selected from the group consisting of: methyl salicylate, dimethyl oxalate and a hydrocarbyl epoxide in combination with an acid.

16. The composition according to claim 2 wherein the composition is a lubricating composition.

17. The composition according to claim 2 wherein the composition is a gasoline fuel composition.

18. The composition according to claim 17 wherein the gasoline fuel composition comprises one or more further detergents selected from the group consisting of: a) carrier oils b) acylated nitrogen compounds which are the reaction product of a carboxylic acid-derived acylating agent and an amine c) hydrocarbyl-substituted amines wherein the hydrocarbyl substituent is substantially aliphatic and contains at least 8 carbon atoms d) mannich base additives comprising nitrogen-containing condensates of a phenol, aldehyde and primary or secondary amine e) aromatic esters of a polyalkylphenoxyalkanol; and f) quaternary ammonium salts.

19. The composition according to claim 17 wherein the gasoline fuel composition comprises a mixture of two or more quarternary ammonium salt additives.

20. (canceled)

21. The method according to claim 4 wherein the engine is a direct injection spark ignition engine.

22. The method according to claim 4 which achieves keep clean performance.

23. The method according to claim 4 which achieves clean up performance.

24. The method according to claim 4 which combats injector deposits.

25. The method according to claim 24 wherein the deposits are internal injector deposits.

26. The method according to claim 4 which achieves an improvement in performance of one or more of: improved fuel economy reduced maintenance less frequent overhaul or replacement of injectors improved driveability improved power; or improved acceleration

Description

EXAMPLE 1

[0380] Additive A1, an additive of the invention was prepared as follows:

[0381] A mixture of alkenes having 20 to 24 carbon atoms was heated with 1.2 molar equivalents of maleic anhydride. On completion of the reaction excess maleic anhydride was removed by distillation. The anhydride value of the substituted succinic anhydride product was measured as 2.591 mmolg.sup.1.

[0382] This product was then heated with one molar equivalent of polypropylene glycol having a number average molecular weight of 425, and the reaction was monitored by FTIR.

[0383] The resultant material was reacted with one molar equivalent dimethyl aminopropanol at 140 C. in xylene and the reaction monitored until constant acid valve and FTIR spectra were obtained. Volatiles were then removed in vacuo to afford a mixed diester.

[0384] This mixed diester product was reacted with 1.5 molar equivalents of butylene oxide, 6 molar equivalents of water and one molar equivalents of acetic acid at 60 C. in toluene for 6 hours. Volatiles were removed in vacuo to provide the quaternary ammonium salt A1.

[0385] Additive A2 was prepared using a method analogous to that used to prepare additive A1 except that tripropylene glycol was used in place of polypropylene glycol.

[0386] Additive A3 was prepared using a method analogous to that used to prepare additive A1 except that polyethylene glycol having a number average molecular weight of 400 was used in place of the polypropylene glycol.

[0387] Additive A4 was prepared using a method analogue to that used to prepare additive A1 except that in the last step the diester was reacted with one molar equivalent of dimethyl oxalate in place of the butylene oxide/acetic acid.

[0388] Additive A5 was prepared using a method analogous to the preparation of additive A2 except in the last step the diester was reacted with one molar equivalent of dimethyl oxalate in place of the butylene oxide/acetic acid.

[0389] Additive A6 was prepared using a method analogous to that used in the preparation of additive A3 except in the last step the diester was reacted with one molar equivalent of dimethyl oxalate in place of the butylene oxide/acetic acid.

[0390] Additive A7 was prepared using a method analogous to that used to prepare additive A1 except that in the last step 1 molar equivalent of methyl salicylate was used as the quaternising agent.

[0391] Additive A8 was prepared using a method analogous to the preparation of additive A2 except that in the last step 1 molar equivalents of methyl salicylate was used as the quaternising agent.

[0392] Additive A9 was prepared using a method analogous to that used in the preparation of additive A3 except that in the last step 1 molar equivalents of methyl salicylate was used as the quaternising agent.

[0393] The reagents used in the preparation of additives A1 to A9 are summarised in the table below and further additives prepared from polyisobutenyl substituted succinic acid derivatives and other amines, alcohols and quaternising agents are also listed in table 1. Compounds A10 to A15 were prepared by methods analogous to those described in relation to compounds A1 to A9.

TABLE-US-00001 TABLE 1 Succinic anhydride Quaternising Example No substituent Alcohol Amine agent A1 C20-24 Poly(propylene N,N- Butylene oxide + glycol) Mn425 dimethylamino acetic acid propanol A2 C20-24 Poly(propylene N,N- Butylene oxide + glycol) Mn425 dimethylamino acetic acid propanol A3 C20-24 Poly(ethylene N,N- Butylene oxide + glycol) Mn400 dimethylamino acetic acid propanol A4 C20-24 Poly(propylene N,N- Dimethyl oxalate glycol) Mn425 dimethylamino propanol A5 C20-24 tri(propylene N,N- Dimethyl oxalate glycol) dimethylamino propanol A6 C20-24 Poly(ethylene N,N- Dimethyl oxalate glycol) Mn400 dimethylamino propanol A7 C20-24 Poly(propylene N,N- Methyl Salicylate glycol) Mn425 dimethylamino propanol A8 C20-24 tri(propylene N,N- Methyl Salicylate glycol) dimethylamino propanol A9 C20-24 Poly(ethylene N,N- Methyl Salicylate glycol) Mn400 dimethylamino propanol A10 1000PIB Poly(ethlylene N,N- Methyl Salicylate glycol) 600 dimethylamino propylamine A11 1000PIB Tridecanol.(PO).sub.15 N,N- 1,2 dimethylamino epoxydodecane + propanol acetic acid A12 1000PIB Poly(propylene N,N- Butylene oxide + glycol) Mn425 dimethylamino acetic acid propanol A13 1000PIB Tridecanol.(PO).sub.15 N,N- Styrene oxide + dimethylamino acetic acid propanol A14 550PIB tri(propylene N,N- Methyl Salicylate glycol) dimethylamino propanol A15 1000PIB tri(propylene N,N- Methyl Salicylate glycol) dimethylamino propanol Tridecanol.(PO).sub.15 is the reaction product of a C.sub.13 alkanol and an average of 15 moles of propylene oxide per molecule.

EXAMPLE 2

[0394] Additive A15 was dosed into a gasoline base fuel and tested according to the following procedure:

[0395] The GDI test procedure uses an engine that has been proposed as a CEC industry standard test engine.

[0396] The test engine is the VW EA111 1,4 L TSI (CAVE) engine with 132 kW, representing the Skoda version of the EA111 engine family

[0397] The test procedure is performed with new 6-hole injectors, type 03C906036E/F. The injector run-in procedure is performed at high load for 4 hours.

[0398] The test procedure is a steady state test at an engine speed of 2000 rpm and a constant torque of 56 Nm (=5 bar mean effective pressure).

[0399] The engine is run on a base fuel (ULG95) for a 48 hour dirty up phase and then a 24 hour clean up phase using the base fuel+105 mg/kg of additive.

[0400] Nozzle coking is measured as change of injection timing. Due to nozzle coking, the hole diameter of the injector holes is reduced and the injection time adjusted by the Engine Control Unit (ECU) accordingly. The injection time in milliseconds is a direct readout from the ECU via ECU control software.

[0401] The results of the test are shown in FIG. 1.