JPH04114089A - Fuel oil additive and fuel oil - Google Patents

Abstract

PURPOSE:To obtain the additive having excellent solubility in fuel oil and heat resistance, not sludging and cleaning dispersibility, comprising a specific polyether compound, an amine-based N and an oxyalkylene group-containing compound or a polyamine. CONSTITUTION:The objective additive comprising (A) a polyether compound shown by the formula (R<1> and R<2> are H, 1-26C hydrocarbon or 2-22C acyl; A<1> and A<2> are 2-18C alkylene; m and n are 1-50; R<3> and R<4> are 1-4C alkyl) and having <=30wt.% (preferably <=25wt.%) oxyethylene group content based on the whole molecular weight and (B) an amine-based N and an oxyalkylene group-containing compound or a polyamine.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a fuel oil additive comprising a polyether compound and an amine compound.

[Conventional technology]

Conventionally, many compounds have been disclosed as detergents and dispersants for fuel oils such as gasoline and diesel oil.

For example, carboxylic acid dispersants (Japanese Patent Publication No. 49-45.7)
No. 71), amine dispersant (JP-A No. 62-241,
No. 992, U.S. Patent No. 4,568.358, Japanese Patent Publication No. 61-500,268), amine oxide-based dispersants (Japanese Patent Application Laid-open No. 62-223,295), polymer-based dispersants (Special Publication No. 48-42.685).

Furthermore, detergent-dispersing agents comprising two or more components are also disclosed. For example, monopolymer-based dispersants and amine-based dispersants (JP-A-62-240,379).

Amine-based dispersant and polyoxyalkylene glycol monoalkyl ether (JP-A-62-68,891)
, a mixture of an amine dispersant and a polyphenol compound or an alkylphenol (JP-A-61-276.89)
4, Japanese Patent Application Laid-Open No. 1987-87,706), etc.

Further, as an example of a mixture, JP-A-47. -34,506 Publication, JP-A-53-42,202, Special Publication 1986-
500,960, etc.

[Problem to be solved by the invention]

The following characteristics are required for fuel oil detergent and dispersants.

1) Dissolves in fuel oil.

2) Has sludge dispersibility.

3) The additive itself does not turn into sludge.

4) Excellent heat resistance.

Conventional fuel oil detergent and dispersants do not fully satisfy these conditions.

An object of the present invention is to provide a fuel oil additive that satisfies these conditions.

[Means to solve the problem]

The present invention is a fuel oil additive comprising (a) a polyether compound represented by general formula (1) and (b) a compound or polyamine having an aminic nitrogen atom and an oxyalkylene group.

(However, R1 and R2 are hydrogen atoms, hydrocarbon groups having 1 to 26 carbon atoms, or acyl groups having 2 to 22 carbon atoms, A1 and A2
is an alkylene group having 2 to 18 carbon atoms, and m and n are 1 to 50.
R'' and R4 are alkyl groups having 1 to 4 carbon atoms, and the content of oxyethylene groups is 30% by weight or less of the total molecular weight. It's oil.

In the compound represented by general formula (1) as component (a),
Hydrocarbon groups having 1 to 26 carbon atoms represented by R1 and R2 include methyl group, ethyl group, propyl group, isopropyl group, allyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, impentyl group. , hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group.

Dodecyl group, intridecyl group, tetradecyl group.

hexadecyl group, isohexadecyl group, octadecyl group, isooctadecyl group, oleyl group, linole group, octyldodecyl group, tocosyl group, decyltetradecyl group,
Examples include hexadecyl group, benzyl group, cresyl group, butylphenyl group, dibutylphenyl group, octylphenyl group, nonylphenyl group, dodecylphenyl group, dioctylphenyl group, dinonylphenyl group, and styrenated phenyl group. In addition, examples of acyl groups having 2 to 22 carbon atoms include acetic acid, propionic acid, butyric acid, isobutyric acid, caprylic acid, 2-
Ethylhexanoic acid, nonanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, isopalmitic acid, margaric acid, stearic acid.

There are acyl groups derived from isostearic acid, arachidic acid, behenic acid, undecylenic acid, palmitoleic acid, oleic acid, linoleic acid, lylinic acid, erucic acid, benzoic acid, hydroxybenzoic acid, cinnamic acid, gallic acid, and the like.

The alkylene group having a carbon number of up to 18 represented by A1 and A2 includes an ethylene group, a propylene group, a butylene group,
Examples include tetramethylene group, octylene group, dodecylene group, tetradecyl group, hexadecyl group, octadecyl group, styrene group, etc. A1 and A20 are oxyalkylene groups to which alkylene oxide or tetrahydrofuran is added by ring opening.

m and n are the numbers of oxyalkylene groups, and at least one each is required; however, if m and n exceed 50, the viscosity of the compound increases and it becomes difficult to remove the catalyst used in the reaction during production. The preferred range of m and n is 1-40.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R3 and R4 include methyl group, ethyl group, propyl group, isopropyl group, allyl group, butyl group, isobutyl group, and tert-butyl group.

The polyether compound of general formula (1) can be easily obtained by subjecting a bisphenol derivative to an addition reaction with an alkylene oxide and, if necessary, further etherifying or esterifying the compound.

This polyether compound needs to be soluble in fuel oil, and for this reason the content of oxyethylene groups is not more than 30% by weight, preferably not more than 25% by weight of the total molecular weight.

Examples of the compound or polyamine having an aminic nitrogen atom and an oxyalkylene group as component (b) include compounds represented by the following formulas (2) to (4).

Rs(OA')aX (NHR')bNH2(2)(R
' is a hydrogen atom, a hydrocarbon group having 1 to 26 carbon atoms or an acyl group having 2 to 22 carbon atoms, A1 is an alkylene group having 2 to 18 carbon atoms, and a is 0 to 100. X is -(OA') c-1-
0CH, (OA') d -rukylene group, b is O-6, A
4 and A5 are alkylene groups having 2 to 18 carbon atoms, C and d are 0
~5. ) In formula (2), R5 has 1 to 2 carbon atoms;
The hydrocarbon group of 6 and the acyl group having 2 to 22 carbon atoms are represented by formula (1)
It is the same as that exemplified for R' and R2, and A3A4,
A' is the same as that exemplified for A1 and A2 in formula (1).

Examples of the alkylene group having 2 to 8 carbon atoms in R6 include ethylene group, propylene group, trimethylene group, butylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, and octamethylene group.

The total number of oxyalkylene groups of a, c, and d is 100 from the viewpoint of ease of catalyst removal during production and solubility in fuel oil.
The following are preferred.

Examples of NHR' in (NHRl)bNH include an ethyleneimino group, a propyleneimino group, a butyleneimino group, a tetramethyleneimino group, and an octamethyleneimino group.

In the compound of formula (2), X is -OCR, (OA')
In the case of d-, it can be produced by the following reaction.

R” (OAff)ao H0CH2C120H(OAff)
' ) d (N HR' ) b N Hz +2
N a OH → R5 (○A') aOcH2 (○A')
d(NHR')bNH2+2NaC1 In the compound of formula (2), when X is other than the compound, it can be produced by a known method.

The alkylene group having a prime number of 2 to 8 is the same as that exemplified for R6 in formula (2).

The total number of oxyalkylene groups of e, g, h, and i is 1 from the viewpoint of ease of catalyst removal during production and solubility in fuel oil.
00 or less is preferable. It is for the same reason that f is limited to 70 or less.

(R', R9, R'''0, R11 are hydrogen atoms, carbon number 1
~26 hydrocarbon group or C2-22 acyl group,
A6, A7, A8, and A' are alkylene groups having 2 to 18 carbon atoms, e, g, h, and i are o to 5o, R@ is an alkylene group having 2 to 8 carbon atoms, and f is 0 to 70. ) The hydrocarbon groups and acyl groups represented by R7, R9, RID, R'' are the same as those exemplified for R1 in formula (1), and the hydrocarbon groups and acyl groups represented by A', A', A8, and A9 have 2 to 2 carbon atoms. 18
The alkylene groups are the same as those exemplified for A1 and A2 in formula (1), and the alkylene groups represented by R1 (A10, A11,
A", A13 is an alkylene group having 2 to 18 carbon atoms, R",
R1'3 is a hydrocarbon group having 1 to 26 carbon atoms, j, m
, H is 1 to 5o, and ■ is 1 to 1O. ) The alkylene group having 2 to 18 carbon atoms represented by A'', A''2, A13 is A1, A2 of formula (1).
The hydrocarbon group having 1 to 26 carbon atoms in R'' and Rl 3 is the same as that exemplified in R1 of formula (1).

The total number of oxyalkylene groups jl + kl + m + n is 1 from the viewpoint of ease of catalyst removal during production and solubility in fuel oil.
00 or less is preferable. l is limited to 10 or less because
This is because the condensation reaction of alkanolamine with methylene chloride or formaldehyde becomes difficult.

The ratio of component (a) and component (b) in the present invention is 100
: 1 to 1:1OO (weight ratio), preferably 20
:1 to 1:20.

The fuel oil additive consisting of components (a) and (b) of the present invention can be added to fuel oils such as gasoline and diesel oil by a 5 to 20% additive.
oooPPIll, preferably 10-10, OOOpp
m is added.

〔Effect of the invention〕

The fuel oil additive of the present invention has excellent solubility in fuel oil and heat resistance, does not turn into sludge itself, and exhibits excellent cleaning and dispersion properties for internal combustion engines from low to high temperatures.

〔Example〕

The present invention will be explained below with reference to Examples. In addition, % means weight %.

Example 1 Table 2 shows the results of thermal stability and anti-sludge tests conducted on additives using the components of the invention and comparison shown in Table 1.

Test conditions Temperature: 160±56C Time: 16 hours Container: Stainless steel petri dish with diameter of 50rIn and height of 15mm Sample collection amount: 0.8g Equipment: Hot air circulation constant temperature bath () Iigh-Temp
.

0ven, HPS-222, Tabai Espec Co., Ltd.
Test method: 0.8 g of a sample was accurately weighed into the above-mentioned container, and this was left in an apparatus set at the above-mentioned temperature for 16 hours to examine thermal stability (volatile residue) and anti-sludge properties.

The anti-sludge property was determined by leaving the container at room temperature for 1 hour after the test, adding 20 mfl of n-hexane, letting it stand for 30 minutes, and then discarding the contents, which was repeated twice. The presence or absence of sludge was visually determined.

Table 2 shows that the fuel oil additive of the present invention has excellent anti-sludge properties, has a volatile residue equivalent to that of the comparative product, and has excellent thermal stability.

Example 2 An engine test was conducted by adding the composition of Table 2 to gasoline.

1) Test engine: VG-20 type (manufactured by Nissan Motor Corporation) 2) Engine operating conditions ■Idle 1 minute ■1 v
500 r -p -m, intake negative pressure 200+++a
Hg 30 minutes ■ 2,700r, p-11y intake negative pressure 300mmHg 20 minutes ■ Engine stopped
200 cycles were performed continuously for 9 minutes, with the above steps (1) to (2) being one cycle.

3) Test gasoline JIS K2202. No. 1 gasoline physical density (g/cgi", 15℃) Vapor pressure (Kgf/cm", 37.8℃) 10% distillation temperature ('C) 50% distillation temperature ('C) 90% distillation temperature (℃) 0, 7534 0.665 52, 0 99, 5 141, 5 Real gum (mg/100m Q) 14) Evaluation method 120 ppm of each of the compositions in Table 2 was added to gasoline, and the test was performed under the above operating conditions. The weight of each intake valve was measured to determine the average weight of deposits attached to each intake valve.

The results are shown in Table 3. In addition, test results for the case without additives are also shown.

Table 3 shows that the fuel oil additive of the present invention has excellent detergency and dispersibility.

Example 3 The same test as in Example 2 was conducted using gasoline with no additives added, and an engine with contaminated intake valves was tested. The test was conducted under the same conditions as in Example 2 except that the operating conditions were changed from 200 cycles to 20 cycles. Additionally, additive-free gasoline was also tested. Average deposit weight before test is 0.4
It was 3g/piece.

The test results are shown in Table 4, and by adding a relatively large amount of the additive of the present invention to gasoline, the average deposit weight of contaminated intake valves was reduced and cleaned even in a short period of 20 cycles. I understand that.

Claims (1)

[Claims] 1. A fuel oil additive comprising (a) a polyether compound represented by general formula (1) and (b) a compound or polyamine having an aminic nitrogen atom and an oxyalkylene group. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) (However, R^1 and R^2 are hydrogen atoms, carbon numbers 1 to 26
hydrocarbon group or acyl group having 2 to 22 carbon atoms, A^1
and A^2 are alkylene groups having 2 to 18 carbon atoms, m and n are 1
~50, R^3 and R^4 are alkyl groups having 1 to 4 carbon atoms, and the content of oxyethylene groups is 30% by weight or less of the total molecular weight. ) 2. A fuel oil containing the fuel oil additive according to claim 1.