JPH05504985A - Gasoline fuel for internal combustion engines - Google Patents

Abstract

A gasoline detergent to reduce the formation of deposits in a spark ignition combustion engine comprises a mixture of a polyolefine polyamine, the number average molecular weight of the polyolefine being above 1000, and a hydrocarbon oil in the form of a mineral oil having a viscosity in the range of 200 to 1000 cSt at 40 DEG C.

Description

[Detailed description of the invention] 10. The claim that the viscosity of the mineral oil is within the range of 400 to 800 cSt at 40°C. The invention according to any one of 1 to 9.

11. The additive is 0.2 to 3 parts by weight of polyolefin polymer per 1 part by weight of hydrocarbon oil. The invention according to any one of claims 1 to 10, comprising reamin.

12. Polyolefin containing 0.5 to 1.1 parts by weight of additives per 1 part by weight of hydrocarbon oil The invention according to claim 11, comprising a polyamine.

13. The weight of the additive based on the weight of gasoline petroleum fuel is 20-20009Pl Claims 1.2 and 4, and their subsidiary claims, within the scope of The invention according to any one of items 5 to 12.

The invention according to claim 13, wherein the it range is 50 to 500 ppm.

15. Claim 3 and its attachments, wherein the solvent is a hydrocarbon or an oxygen-containing hydrocarbon. The invention according to any one of the accompanying claims 5-12.

Engraving (no changes to the content) Specification Gasoline fuel for internal combustion engines The present invention relates to the use of additives in gasoline fuels for internal combustion engines.

The increase in traffic density on roads is mostly due to the partially burned or unburned portion of motor vehicle fuel. accompanied by air pollution. Incomplete combustion of petroleum hydrocarbons and residual lubricating oil mist Important factors that cause the generation of dust are impurities and the air intake system of spark ignition engines. The occurrence of an overly rich mixture caused by deposits in the evaporator.

The engine crank chamber collects blow-by gas from the suction point of the carburetor or its air filter. The gas is degassed by recirculation to the Therefore, the oil build-up in the crank chamber The strike part passes through the carburetor to the engine, where it is largely destroyed by combustion. It will be done. However, some of the oil mist is deposited on the inner surface of the vaporizer. modern high efficacy Rate vaporizers have very precise channels and bores and a high rate of gasoline atomization and metering. It is a complex structure containing precisely calibrated nozzles. These spirits in the vaporizer Even small amounts of residue in dense control equipment, nozzles and channels can reduce vaporizer effectiveness. rate, resulting in undesirable changes in the proportions of the components in the fuel/air mixture. The combustion of fuel in a carburetor engine is not as complete as when the carburetor is clean. . As mentioned above, the exhaust gases therefore contain unburned and partially burned hydrocarbon residues. . At the same time, there is an unfavorable shift in the ratio of carbon monoxide to carbon dioxide in the exhaust gas. ie, if the vaporizer becomes fouled, the carbon monoxide rate increases.

Therefore, keep the internal combustion engine clean and prevent the occurrence of deposits on the large mouth valve and in the carburetor part. to prevent deposits and deposits present in the vaporizer if it has already been contaminated. A method that generates a cleaning effect by including an appropriate additive in the fuel that washes away dirt and grime. It was desirable to find a law.

The technology overcomes the above limitations through the use of detergent additives in gasoline petroleum fuels. contains many suggestions for For example, GB-A-1410788 is a carbo The patent specification describes the use of various amine derivatives of aminated polyolefin acids. describes the use of fins, such as aminated polyisobutylene: GB-A-1 346765, US-A-3438757, US-A-3565804; US -A-3574576+ and US-A-4022589゜Those with the above specifications describes the use of aminated polyolefins in mixtures with certain hydrocarbon oils. ing. For example, CB-A-1346765 is composed of polyamine and mineral oil components. describes the use of substances that do not produce It is stated that mineral oil components with viscosity can also be present. US-A-4 022589 is polybutenamine and 250-500 SUS at 100°F. It describes the use of viscous paraffinic hydrocarbon oil.

The present invention uses a combination of a polyamine of a defined molecular weight and a hydrocarbon oil of a defined viscosity. Concerning business.

One aspect of the present invention is to provide a spark ignition internal combustion engine for controlling fuel in the engine. Addition in gasoline petroleum fuels to reduce the tendency to form deposits during use The additive is an oil-soluble polyolefin polyamine, the polyolefin has a number average molecular weight greater than 500, and 200 to 1000 C3 at 40°C. hydrocarbon oils in the form of mineral oils with viscosities within the range of t.

A second aspect of the invention comprises a mixture of mainly gasoline petroleum fuel and minor amounts of said additives. It is a composition.

A third aspect of the present invention provides that the above-mentioned additive for use in gasoline petroleum fuel is It is a liquid concentrate containing a solution in a solvent.

A fourth aspect of the invention includes using a gasoline petroleum fuel containing said additive. How to reduce the tendency for deposits to form in spark ignition internal combustion engines It is.

As shown in the examples herein, the present invention is applied to spark ignition engines. is surprisingly effective in reducing the tendency for deposits to form within the For example, on the intake system e.g. inlet valves, fuel injectors, carburetors and manifolds. Has a tendency to cheat.

Features of the invention are discussed in more detail below.

As mentioned above, such materials are known in the art. Preferably Polyolefin polyamine is a nitrogen or at least one olefin polymer chain bonded to one or both carbon atoms Two. For example, polyamine has a general structural formula: % formula % (In the formula, R' is hydrogen or a polyolefin, and at least one R1 is a polyolefin And: R2 is alkylene with 1 to 8 carbon atoms; R'' is hydrogen or 1 to 6 carbon atoms; is an alkyl having a carbon atom; X is O~5; R1, R2 and R3 are each independently branched or linearly linked as appropriate) You can have it.

R1 is, for example, polyethylene, polypropylene, polybutylene, polyisobutylene , polyethylene/polypropylene, or polyethylene/polyα-methylstyrene can be. Particular preference is given to polyisobutylene.

Polyolefin polyamines are olefin polymers as indicated above for R1. and a polyamine. Such polyamines are For example, it can have 2 to 12 nitrogen atoms and 2 to 40 carbon atoms. So These include, for example, polyalkylene polyamines and substituted polyamines, including alkylene diamines. Can be derived from alkylene polyamines. Preferably the alkylene is 2 ~6 carbon atoms, more preferably 2-3 carbon atoms between the nitrogen atoms. So Specific examples of polyamines such as primary and secondary low molecular weight aliphatic polyamines include For example, ethylenediamine, diethylenetriamine, triethylenetetramine, Pyrenediamine, butylenediamine, trimethyltrimethylenediamine, tetra Methylenediamine, diaminopentane or pentamethylenediamine, hexamethylene Diamine, heptamethylene diamine, noamino octane, decamethylene diamine and higher homologs of up to 18 carbon atoms. Ethylenediamine is preferred Yes.

The number average molecular weight of polyolefin of polyolefin polyamine is determined by vapor phase osmotic pressure method. more measured. Preferably it is 900 or more, more preferably 100 It is within the range of 0-5000, most preferably within the range of 1200-2500.

Polyolefin polyamines can be prepared by methods described in the art, e.g. The manufacturing process is achieved by halogenating the fins and reacting the resulting halide with polyamine. Lukotcatekill. Example 1fUS-A-3275554 and UDE-A-21250 See 39. Furthermore, US-A-4832702 contains polybutene or polyisobutyne. Hydroformylation and the resulting oxo product are subjected to a 7-Nitz reaction or under hydrogenation conditions. Its preparation by subjecting it to amination is described.

This includes distillate oils, residual oils and products obtained from conversion processes. it is one or that Contains the above hydrocarbons. Preferably the mineral oil is an oil obtained from the residue of petroleum distillation. For example, it is a high viscosity lubricating oil. Preferably, the viscosity of the mineral oil is 400 to 80 degrees centigrade at 40 tons. It is within the range of TiStokes (c5t).

劃-金 Preferably, the additive is 0.2 to 11 parts of 3 parts I per part by weight of hydrocarbon oil, more preferably or 0.5 to 1.1 parts by weight of polyolefin polyamine.

In the first, second and fourth aspects of the present invention, based on the weight of gasoline petroleum fuel, The weight of the additive is preferably in the range of 20 to 2000 ppm, more preferably It is within the range of 50 to 500Pp11.

When the present invention is a concentrate, the solvent for it may be, for example, a hydrocarbon or It can be an oxygen-containing hydrocarbon. Examples of hydrocarbons are alkanes or aromatic carbons Hydrogen such as benzene and xylene. Examples of oxygen-containing hydrocarbons are butanol, These are pentanol and hexanol. The concentration of additives in the concentrate is It can be varied within wide limits depending on requirements and restrictions. Generally, it is 5 to 90 weight For example, the amount may be in the range of 10 to 70% by weight.

Other additive ingredients Other additives may be used in combination with the additives of the present invention in the practice of the present invention. can. Examples include di(fatty acid amides) of aliphatic polyamines, e.g. Amine di(oleic acid amide), dipropylenetriamine di(stearic acid) amide), di(valmitic acid amide) of diethylenetriamine, diethylenedia Mine di(valmitic acid amide) and triethylenetetramine di(undecane) acid amide).

Other examples are carboxylic acid derivatives of polyamines with 1 to 6 nitrogen atoms per molecule; For example, hydroxyamines such as ethanolamines, isopropionolamines, etc. Polyamines such as polyamines and tetraethylenepentamine stearic acid, isostearic acid and undecanoic acid esters, and tallow oil It is an acid derivative.

Other additives that can be included are plasticizer esters such as adipate esters and mixtures thereof. co-existing ingredients such as antioxidants, lead scavengers, ignition improvers and metal deactivators. Ru. Such other additives include, for example, 50 to 500 PPω (heavy V weight) in the fuel. can exist within the range of

fuel The fuels used are hydrocarbons such as straight paraffin, branched paraffin, and olefin. It is a composition containing fins, aromatic hydrocarbons, and naphthenic hydrocarbons. The example is about 21 ．． An initial boiling point of 1°C (70°F) and an end point of approximately 232°C (450°F) (ASTMD -86). The fuel components can be processed by any of the conventional refining and blending methods. You can get more. Synthetic fuels are also included.

The additives of the present invention can be optionally added in a mixed confinement or separately using conventional fuel additive injection methods. can be added to the fuel in the following order: Preferably the additive is according to the third aspect of the invention Added as a concentrate.

Example The invention is then described in detail in the following examples using the following additive components = A: Amination of polyisobutylene with a number average molecular weight of 1300 with ethylenediamine Polyisobutylene polyamine produced by.

B: Contains mineral oil in the form of a high viscosity lubricating oil obtained from the residues of petroleum distillation, Table 1 A hydrocarbon oil with the properties shown in it.

C: Polyisobutylene with a number average molecular weight of 900 is aminated with ethylenediamine. Polyisobutylene polyamine produced by

Hydrocarbon oils including mineral oils having the properties shown in Table D2.

E: Other hydrocarbon oil having the properties shown in Table ■.

Additives containing D or E as a component do not fall within the definition of additives in the present invention. It would be recognized that

Driving under normal conditions, 350 to 500 miles per day. approximately 1 hour between engine switch-off and restart at low ambient temperature. There was a cooling period. At the end of the test, remove the engine's 7 cylinder head and turn it upside down. I made it. The ease with which a valve descends from the cylinder head under its own weight or vice versa Used as a measure of sticking effectiveness; passes if the valve descends easily without resistance to movement. If the valve did not lower easily, a failure was recorded. Specific examples is as follows, and all percentages are by weight based on the weight of fuel.

Example 1 Additive composition is A228PPm, B200ppm and diisodecyl adipate 1 A pass was recorded when it contained 52 ppra. The concentration of B passes the valve sticking test. considered to correspond to the minimum amount for

Example 2 When the additive composition contains 200 ppm A and 400 ppm E, borderline Passing was recorded.

Example 3 The additive composition contains C300ppm, 8200ppm and adipic acid diisodecyl A pass was recorded when the test sample contained 500 ppm. The concentration of B is sufficient to pass the valve sticking test. was considered the minimum amount for

Example 4 A failure is recorded when the additive composition contains 500 ppm CC and 500 ppm E. It was.

Example 5 A pass is recorded when the additive composition contains 230 ppm A and 8230 ρρm. Ta.

Example 6 A failure is recorded when the additive composition contains CC500pp and E500ppta It was done.

Example 7 A failure is recorded when the additive composition contains C300ρpi+ and D300PP1m. recorded.

Example 8 The additive composition includes C300Ppffl, B500ρpH and adipic acid diisodecyl A pass was recorded when the sample contained 200p-.

The above results show that the additive composition of the present invention (as in Example 1) has low processing power for detergency. The need for a hydrocarbon oil of high efficiency (see Example 2) and the use of Additive B It can be concluded that it has an advantageous effect compared to the use of additive E or additive E. Ru.

We acknowledge that in the examples, esters were not considered to have a significant effect. Should. The test engines in Examples 1-6 were General Motors (Ge) neral Motors) L 6 L engine, and in Examples 7 and 8. The test conducted was a VW Boxer engine test.

Example 9 In other tests, carburetor deposits in a BMW 325 engine were tested with additives A and B. The following results were obtained: Deposit (Mg) No additives 199 420 volume ppm I 08 500 volume ppI1158 620 volume ppta 9 Similar tests were also performed on the tetraethylenetetramine derivative of isostearic acid (IS AT) was used in the additive combination and the following results were obtained: 350 50 2.8 400 50 0.6 500 50 8, 2 The test is run for 100 hours under variable conditions.

Engraving (no changes to the content) abstract Spark ignition gasoline cleaner that reduces the formation of deposits in internal combustion engines. The cleaning agent is a polyolefin polyamine, and the number average molecular weight of the polyolefin is is approximately 1000, and the viscosity is within the range of 200-1000 cSt at 40°C. This includes mixtures with hydrocarbon oils in the form of mineral oils.

Heisei Year Month Day

Claims (15)

[Claims] 1. The additive is an oil-soluble polyolefin polyamine, and the polyolefin is 50% with a number average molecular weight greater than 0, and between 200 and 1000 cSt at 40°C. Spark ignition oils containing hydrocarbon oils in the form of mineral oils with viscosities within the range Reduces the tendency for deposits to form in internal combustion engines during the use of fuel in said engines The use of additives in gasoline petroleum fuels to 2. A mixture of a large proportion of gasoline petroleum fuel and a small amount of the additive according to claim 1. A composition comprising. 3. A gas containing the additive according to claim 1 in the form of a solution in a solvent therefor. Liquid concentrate used in Solin petroleum fuel. 4. comprising using a gasoline petroleum fuel containing the additive according to claim 1. , to reduce the tendency for deposits to form in spark ignition internal combustion engines. Law. 5. Polyolefin polyamines contain nitrogen atoms of alkylene groups connecting amine nitrogen atoms. at least one olefinic polyolefin bonded to elementary atoms and/or carbon atoms; The invention according to any one of claims 1 to 4, having a mer chain. 6. The polyolefin polyamine has a general structural formula: R12N-R2-(NR2)x -NR32 (in the formula, R1 is hydrogen or a polyolefin, and at least one R1 is a polyolefin And; R2 is alkylene with 1 to 8 carbon atoms; R3 is hydrogen or 1 to 6 carbon atoms; is an alkyl having a carbon atom; x is 0 to 5; R1, R2 and R3 are each independently branched or linearly linked as appropriate) The invention according to claim 5. 7. Polyisobutylene in which polyolefin polyamine is aminated with ethylenediamine The invention according to claim 6, which is tyrene. 8. Claim 1, wherein the polyolefin has a number average molecular weight of 1000 to 5000. The invention according to any one of -7. 9. Claim 8, wherein the polyolefin has a number average molecular weight of 1200 to 2500. The invention described in . 10. Claims wherein the viscosity of the mineral oil is within the range of 400 to 800 cSt at 40°C. The invention according to any one of 1 to 9. 11. The additive is 0.2 to 3 parts by weight of polyolefin polymer per 1 part by weight of hydrocarbon oil. The invention according to any one of claims 1 to 10, comprising reamin. 12. Polyolefin containing 0.5 to 1.1 parts by weight of additives per 1 part by weight of hydrocarbon oil The invention according to claim 11, comprising a polyamine. 13. Additive weight based on the weight of gasoline petroleum fuel is 20-2000 ppm Claims 1, 2, and 4, and the claims appended thereto, within the scope of The invention according to any one of items 5 to 12. 14. The invention according to claim 13, wherein the range is 50 to 500 ppm. 15. Claim 3 and its appendices, wherein the solvent is a hydrocarbon or an oxygen-containing hydrocarbon. The invention according to any one of the accompanying claims 5-12.