CN1067713C - Composite additive for gasoline - Google Patents

Abstract

The present invention relates to a gasoline addictive composition which comprises at least one kind of polyisobutene succinimideand at least one kind of polyether which has the number average molecular weight of 500 to 5000 and is obtained by the homopolymerization or the copolymerization of an epoxy compound with the carbon number of 2 to 8, wherein the number average molecular weight of polyisobutylene is 400 to 200. The composition has a favorable purification effect to an air throttle, a nozzle, an air intake valve, etc. of a gasoline engine, and can also inhibit the generation of deposition on the positions. The composition can also save oil consumption, and reduce the discharge amount of hydrocarbon compounds and carbon monoxide.

Description

Composite additive for gasoline

The present invention relates to a kind of composite additive for gasoline, more particularly, is a kind of composite additive for gasoline that is used to reduce and prevent the settling formation of gasoline engine intake system and prime the fuel system.

At present, the electronically-controlled fuel injection engine is used widely in automotive industry.The nozzle bore of this engine is very tiny, is easy to be deposited thing and stops up, and causes that fuel feeding is smooth, problems such as automobile stall, cold starting difficulty and deterioration of emission.In addition, the intake valve of the electronic fuel injection engine of life-time service surface can generate settling, causes cylinder seal not tight, and motor performance descends.

For addressing this problem, CN1167136A discloses a kind of multi-function gasoline additives composition, and it comprises thinner that (A) is a large amount of and (B) carries oil in right amount; (C) at least a purification agent and/or anti-deposition agent; (D) at least a oxidation inhibitor and/or metal passivator; (E) at least a rust-preventive agent; (F) at least a demulsifying agent, wherein component (C) is polyolefinic succinimide imide and/or polyolefin amide, and/or polyetheramine, and polyolefine is the polyisobutene of molecular weight 800 ~ 1200, the test method that this patent application is adopted is a non-standard method, is difficult to judge the quality of this prescription from the gained data.

CN1108683A discloses a kind of gasoline composite additive and preparation method thereof, and it comprises (A) allyl butyrate imide; (B) alkylphenol; (C) benzotriazole derivative; (D) thiadiazoles derivative; (E) solubility promoter of low mass molecule alcohol and oil lighting end solvent.This additive can improve the detergency of gasoline, improves stabilization of gasoline.

EP0654524A2 discloses a kind of composite additive for gasoline, and it comprises (A) at least a ester; (B) at least a detergent-dispersant additive that is selected from mono butonediimide, two succimide, alkylamine or benzylamine; (C) 100 ℃ of viscosity are 3 ~ 35mm ²The lubricating oil of/s.The ester number lattice of using in this prescription are more expensive, be difficult to obtain.

The objective of the invention is to based on prior art, overcome its defective, a kind of composite additive for gasoline that the settling of parts such as valve, intake valve and nozzle is had good peace and quiet effect is provided.

Composite additive for gasoline provided by the invention comprises following component:

(a) at least a two succimides of polyisobutenyl that are selected from the polyisobutenyl mono butonediimide of structure formula I or are selected from the structure formula II.

(b) at least a number-average molecular weight that is selected from is 500 ~ 5000, is the polyethers that 2 ~ 8 epoxy compounds homopolymerization or copolymerization obtain by carbon number. Wherein, R ₁For number-average molecular weight is 400 ~ 2000 polyisobutene, R ₂For containing the alkylidene group of 2 ~ 4 carbon atoms, m is 1 ~ 8 positive integer.

Wherein, R ₃And R ₃' be that identical or different number-average molecular weight is 400 ~ 2000 polyisobutene, R ₄For containing the alkylidene group of 2 ~ 4 carbon atoms, n is 1 ~ 7 positive integer.

Said polyisobutenyl succimide dispersion agent is a kind of effective detergent-dispersant additive, generally is earlier polyisobutene and maleic anhydride to be reacted, and products therefrom makes with the polyamines reaction again.If obtain mono butonediimide, then the mol ratio of thiazolinyl maleic anhydride and polyamines is 1: 1; If obtain two succimides, then the mol ratio of thiazolinyl maleic anhydride and polyamines is 2: 1.

Consider the oil soluble of polyisobutene succinimide, R in structure formula I and (II) ₁, R ₃And R ₃' represented polyisobutene should have suitable molecular weight ranges, for example, number-average molecular weight can be 400 ~ 2000, and is preferred 600 ~ 1500, preferably 800 ~ 1200.

Said polyamines shown in structure formula I or structure formula II, R ₂Or R ₄For containing the alkylidene group of 2 ~ 4 carbon atoms, m is 1 ~ 8 positive integer, preferred 2 ~ 5 positive integer.N is 1 ~ 7 positive integer, preferred 2 ~ 4 positive integer.For example, said polyamines can be quadrol, propylene diamine, butanediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine etc., preferred diethylenetriamine, triethylene tetramine and tetraethylene pentamine, preferably triethylene tetramine and tetraethylene pentamine.

The consumption of said polyisobutenyl succimide in gasoline is generally 10 ~ 2000, preferred 30 ~ 1000ppm.

Said polyethers is by C ₂~ C ₈Epoxy compounds under the effect of initiator Fatty Alcohol(C12-C14 and C12-C18) or alkylphenol, obtain by homopolymerization or copolymerization mode, reaction formula is expressed as follows:

Wherein ROH is C ₂~ C ₁₈Fatty Alcohol(C12-C14 and C12-C18) or C ₂~ C ₆Alkylphenol, R ₁, R ₂, R ₃, R ₄Be H or C ₁~ C ₆Alkyl, preferred H or C ₁~ C ₄Alkyl, as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl etc., R ₁, R ₂, R ₃, R ₄Can be the same or different, but their carbon number sum is not more than 6, preferably is not more than 4.N is the polymerization degree, can be 3 ~ 120, and under such polymerization degree, the number-average molecular weight of polyethers is 500 ~ 5000, preferred 800 ~ 3000.The consumption of said polyethers in gasoline is generally 40～800ppm, preferred 50～600ppm.

In addition, in the composite additive for gasoline provided by the invention, can also add additives such as oxidation inhibitor, rust-preventive agent, emulsion splitter, the over-all properties of gasoline is further improved.

Said oxidation inhibitor can be the mixture of amine type oxidation inhibitor, phenol type antioxidant or their arbitrary proportions.Wherein amine type oxidation inhibitor is selected from dialkyl diphenylamine, alkylphenylenediaminin, or its mixture, as di-iso-octyldiphenylamine, two sec-butyl pentanoic, diisooctyl Ursol D, di-sec-butyl-p-phenyl enediamine etc., phenol type antioxidant is selected from 2,6-ditertbutylparacresol, 2,6 di-t-butyl mixed phenols, 2,4,6-tri-tert-butyl phenol etc.The consumption of said oxidation inhibitor in gasoline is generally 5 ~ 20ppm.

Said rust-preventive agent is C ₁₂~ C ₅₄Dimeracid or a kind of or its mixture in the trimer acid, be generally 5 ~ 50ppm as the dimeracid or the consumption of trimer acid in gasoline of compounds such as talloleic acid, oleic acid, linolic acid.

Said emulsion splitter is the mixture of alkylphenol formaldehyde resin polyoxyethylene polyoxy propyl ether and polyoxyethylene glycol, and ratio of mixture is 1: 0.5 ~ 2.The consumption of said emulsion splitter in gasoline is generally 5～200ppm.

Except that said components, can also add other additive as required in the composite additive for gasoline provided by the invention, as deicing agent, octane promoter, antistatic agent etc.

In case of necessity, also can add lube cut in the composition provided by the invention as carrying oil.The existence of carrying oil can promote dissolving each other of each binder component.The suitable oil that carries can be that 100 ℃ of viscosity are 3 ~ 30mm ²/ s, preferred 5 ~ 20mm ²The synthetic oil of/s or mineral oil can be by the common process productions of various production lubricating oil, as solvent dewaxing, refining, the catalytic dewaxing of alditol, and technology such as hydrofinishing, as 150SN, 250SN, 500SN neutral oil, polyolefin oil, ester class wet goods.The consumption that carries oil can be 0 ~ 8 times of additive total amount, preferred 2 ~ 6 times.

Composition provided by the invention can be with using behind the organic solvent diluting or preserving.This class organic solvent can be benzene,toluene,xylene, ethylbenzene, propyl benzene, trimethylbenzene, pentane, hexane, heptane, octane, decane, hexanaphthene, pentamethylene, N, dinethylformamide, ether, propyl ether, methyl-propyl ether, kerosene etc., preferred toluene, dimethylbenzene, ethylbenzene.These solvents can be used alone, but also also mix together, and the consumption of solvent can be to carry 1 ~ 2 times of weight of oil.

Composite additive for gasoline provided by the invention can join respectively in the gasoline, also can make mixture with ordinary method, be about to component (a) and (b) and other component and mix, stirring gets final product, can be heated to 40 ~ 60 ℃ in case of necessity, make it mix more evenly.If the adding thinner then can mix the solid additive component operation of being more convenient for so earlier again with other component with the thinner dissolving.

Compositions of additives provided by the invention can be used for the doped fuel or the white gasoline of various explained hereafter, also can be used for diesel oil.

Composite additive for gasoline provided by the invention compared with prior art has following advantage owing to adopted new prescription:

(1) said composition not only has good peace and quiet effect to positions such as petrolic carburettor, butterfly, nozzle and intake valves, also can suppress the formation of settling at these positions.For example, use can to make average spray nozzle clogging after the said composition and descend 14 ~ 19% than before using, settling generates relative quantity and descends about 20 ~ 30 at dosage during for 600ppm.

(2) use said composition can save the quantity discharged of hydrocarbon polymer in automobile fuel consumption, the minimizing tail gas.For example, after the use said composition, the carbon monoxide purification rate can reach 13 ~ 52%, and the hydrocarbon polymer purification rate can reach 9 ~ 45%, and oil consumption reduces about 7%.

The invention will be further described below by implementing.

Example 1

Composite additive for gasoline contains:

(1) 12 gram number-average molecular weight is 640 polyisobutene mono butonediimide (T151, Suzhou specialty oil products factory product);

(2) 8 gram number-average molecular weights are 1020 polyethylene oxides;

Example 2

Composite additive for gasoline contains:

(1) 14 gram number-average molecular weight is 1520 polyisobutene mono butonediimide;

(2) 6 gram number-average molecular weights are 2950 poly(propylene oxide)s;

Example 3

Composite additive for gasoline contains:

(1) 15 gram number-average molecular weight is 1270 the two succimides (T154, Jinzhou petrochemical plant product) of polyisobutene;

(2) 15 gram number-average molecular weights are 2080 polybutylene oxide;

(3) 70 gram 150SN lubricating oil.

Example 4

Composite additive for gasoline contains:

(1) 14 gram number-average molecular weight is 1120 polyisobutene mono butonediimide;

(2) 14 gram number-average molecular weights are 2030 poly(propylene oxide);

(3) 65 grams 500 SN lubricating oil;

(4) 2 gram 2,6 ditertiary butyl p cresol oxidation inhibitor.

(5) 2.7 gram dimeracid rust-preventive agent (chemical plant, Mudanjiang product).

(6) 2.3 gram alkylphenol formaldehyde resin polyoxyethylene polyoxy propyl ether and 1: 1 mixture of polyoxyethylene glycol are as emulsion splitter.

Example 5

Composite additive for gasoline contains:

(1) 14 gram number-average molecular weight is 1120 polyisobutene mono butonediimide;

(2) 6 gram number-average molecular weights are 990 polybutylene oxides;

(3) 75 gram 500SN lubricating oil;

(4) 1 gram di-iso-octyldiphenylamine oxidation inhibitor;

(5) 2 gram dimeracid rust-preventive agent.

(6) 2 gram alkylphenol formaldehyde resin polyoxyethylene polyoxy propyl ether and 1: 2 mixture of polyoxyethylene glycol are as emulsion splitter.

Example 6

Composite additive for gasoline contains:

(1) 20 gram number-average molecular weight is 1550 the two succimides of polyisobutene;

(2) 10 gram number-average molecular weights are 2030 poly(propylene oxide)s;

(3) 31 gram 150SN lubricating oil;

(4) 1.5 grams 2,6-di-t-butyl mixed phenol oxidation inhibitor;

(5) 2 gram dimeracid rust-preventive agent;

(6) 1.5 gram alkylphenol formaldehyde resin polyoxyethylene polyoxy propyl ether and 2: 1 mixture of polyoxyethylene glycol are as emulsion splitter.

Example 7

This example illustrates that compositions of additives provided by the invention is to suppressing the effect of spray nozzle clogging.Test oil is 93 ^#White gasoline, test method are U.S. Coordinating Research Council (CRC) method.Test-results sees Table 1.

Table 1

The additive source	Dosage, ppm	Test temperature, ℃	Test pressure, KPa	Average spray nozzle clogging rate, %
Blank example 1 example 2 examples 3 examples 4 examples 5 examples 6	- 250 150 800 600 600 600	160	2.8	20.4 6.6 4.6 1.5 3.5 4.1 5.2

Example 8

This example illustrates that compositions of additives provided by the invention is to suppressing the effect that settling generates on intake valve.Manufactured and designed intake valve settling analogue experiment installation with reference to automotive air intake valve principle of work.Gasoline is sprayed onto on the heated deposited tube through oil nozzle, can calculate settling weight according to the changes in weight before and after the deposited tube test, investigates peace and quiet effect in view of the above.Test-results sees Table 2.Test conditions: test oil 93 ^#The combustion gas in 60 minutes of 180 ℃ of test periods of white gasoline deposited tube temperature was than 1: 15

Table 2

The additive source	Dosage, ppm	Settling generates relative quantity
			Blank		100
Example 1	600	78
			Example 2	400	82
Example 3	800	70
			Example 4	800	64
Example 5	600	68
			Example 6	600	75

Example 9

This example illustrates the rust-proof effect of compositions of additives provided by the invention, and test method is the ASTM D655 method of American Association of Motor Vehicle Manufacturers (AAMA) regulation.Test-results sees Table 3

Test oil:＞90 ℃ gasoline alkylate

Test temperature: 38 ℃

Test period: 5 hours

Water: synthetic sea water

Table 3

The additive source	Rod iron surface corrosion situation	The result
			Example 4 examples 5 examples 6	Three of two 0.5*0.5 rust spots of no rust spot 0.5*0.5 rust spot	By by passing through

Example 10

This example illustrates the demulsification of compositions of additives provided by the invention.Test oil is a catalytically cracked gasoline, and test method is ASTM D1094, and test-results sees Table 4.

Table 4

The additive source	Interface rating	Separate evaluation	The result
				Example 4 examples 5 examples 6	1b 1b 1b	2 2 2	By by passing through

Example 11

This example is the road test of keeping a public place clean that the compositions of additives of use-case 4 preparations carries out.Test method is ASTM D5500, and instruction carriage is Audi 100 2.6E, the road test of keeping a public place clean program:

Low speed 64KM 12 circles

Middling speed 134KM 24 circles

High speed 450KM 82 circles

Add up to 648KM 118 circle accumulation 16000KM

Test oil is the 93# white gasoline, and with the HITEC4940 agent as a comparison that ethyl corporation is produced, the nozzle test-results sees Table 5, and the intake valve test-results sees Table 6,1 ^#~ 6 ^#Be cylinder numbers.

Table 5

Additive	Actual service life	The spray nozzle clogging rate, %
									1 #	2 #	3 #	4 #	5 #	6 #	On average
		Example 4	15946	1.06	4.27	1.85	2.44	1.78	1.93	2.22
HITEC4940	15822	5.05	5.60	5.82	5.11	4.89	5.20	5.28

Table 6

Additive	Intake valve settling weight, mg
								1 #	2 #	3 #	4 #	5 #	6 #	On average
	Example 4	453.8	402.7	959.2	225.3	1303.4	610.6
HITEC4940	777.1	534.1	739.1	1075.5	247.5	674.3	674.6

Example 12

This example is for cleaning road test, and the composition for preparing with example 3 is an additive, and instruction carriage is Audi100 2.6E, and test oil is 93 ^#White gasoline, test are divided into nozzle cleaning and intake valve cleans, and test-results sees Table 7:

Table 7

	The nozzle cleaning road test	Intake valve cleans road test
			Additive concentration, ppm	1200	12000
Actual service life, Km	2500	600
			Before the test	Average spray nozzle clogging rate, 13.29%	Average deposition thing weight, the 887.2mg/ valve
After the test	Average spray nozzle clogging rate, 0.53%	Average deposition thing weight, the 25.9mg/ valve
			Cleaning rate, %	96	97

Example 13

This example is the investigation of hydrocarbon polymer and carbonoxide quantity discharged in the oil consumption of automobile behind the compositions of additives of use-case 4 preparation in the actual motion and the tail gas.Table 8 is the operation result according to the vehicle of Chengdu environmental protection " idling method " adjustment.

Table 8

The vehicle license number	Distance travelled before the test, Km	The test run mileage, Km	Idling speed r/min		Carbon monoxide, %	The carbon monoxide purification rate, %	Hydrocarbon polymer, ppm	The hydrocarbon polymer purification rate, %	The kilometer oil consumption, L	The oil consumption reduced rate, %
Alto, Xi'an river A45444	73531	1178			Before the test	892	4.6	13	200	15	- -	-
			After the test	1120	4.0	170
			Liberation bread river A95346	61910	1172	Before the test	878		5.2				21	320	9	- -	-
After the test	1100	4.1				290
Chang'an, Chongqing river A09740	34457	1383				Before the test	901	5.7	52	600	45	7.20 6.68		7.22
			After the test	1160	2.7	330

Annotate: 1. purification rate=(observed value before adding-interpolations back observed value)/add preceding observed value * 100%

2. rate of economizing gasoline=(fuel consumption per hundred kilometers before adding-interpolations back fuel consumption per hundred kilometers)/add preceding fuel consumption per hundred kilometers * 100%

3. the above-mentioned bolt vehicle operative norm that is subjected to: carbon monoxide 4.5%, hydrocarbon polymer 1200ppm.

Claims (7)

1. A gasoline additive composition is characterized in that it comprises the following components: (a) at least one polyisobutenyl monosuccinimide selected from structural formula (I) or polyisobutenyl bis-succinimide selected from structural formula (II); (b) at least one polyether selected from the number average molecular weight of 500 to 5000, obtained by homopolymerization or copolymerization of epoxy compounds with a carbon number of 2 to 8, wherein the amount ratio of (a) and (b) is 1: 1～7:3; Structural formulas (I) and (II) are respectively:

Wherein, _R1 is polyisobutylene with a number average molecular weight of 400-2000, _R2 is an alkylene group containing 2-4 carbon atoms, and m is a positive integer of 1-8; Wherein, R ₃ and R ₃ ′ are the same or different polyisobutylenes with a number average molecular weight of 400-2000, R ₄ is an alkylene group containing 2-4 carbon atoms, and n is a positive integer of 1-7. 2. The composition according to claim 1, characterized in that said polyisobutene in (I) and (II) has a number average molecular weight of 600-1500. 3. The composition according to claim 1, characterized in that m in (I) is a positive integer of 3-5. 4. The composition according to claim 1, characterized in that n in (II) is a positive integer of 2-4. 5. The composition according to claim 1, characterized in that said polyether in component (b) is a homopolymer or copolymer of epoxy compounds containing 2 to 6 carbon atoms. 6. The composition according to claim 1 or 5, characterized in that the polyether in said component (b) is a homopolymer or copolymer of ethylene oxide, propylene oxide or butylene oxide. 7. The composition according to claim 1, characterized in that said polyether in component (b) has a number average molecular weight of 800-3000.