JP2001040377A - Fuel oil additive and fuel oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fuel oil additive which is excellent in cleaning properties in the combustion chamber of an internal combustion engine by using, as the additive, a copolymer essentially comprising units derived from a prim-amino- containing (meth)acrylate monomer and an alkyl (meth)acrylate. SOLUTION: This fuel additive is a copolymer prepared by using a prim- amino-containing (meth)acrylate monomer [e.g. aminoethyl (meth)acrylate] and an alkyl (meth)acrylate [e.g. n-butyl(meth)acrylate] as essential comonomers. The alkyl (meth)acrylate preferably has a 4-18C alkyl group. The copolymer preferably has a glass transition point (Tg) of 30 deg.C or lower, a primary amine value of 1-500, and a number average mol.wt. of 300-50,000. Preferably, the copolymer contains 5-99 wt.% units derived from the prim-amino-containing (meth)acrylate monomer. An ethylenically unsaturated monomer (e.g. a styrene compound) in an amount of 0-5 wt.% may be copolymerized into the polymer. The amount of the copolymer added to a fuel oil is preferably 50-10,000 ppm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fuel oil additive, and more particularly, to a fuel oil additive having excellent solubility in fuel oil, and particularly excellent cleanliness in a combustion chamber of a gasoline engine or a diesel engine.

[0002]

2. Description of the Related Art Deposits such as sludge and deposits in a fuel system or a combustion chamber of an internal combustion engine have a bad effect on engine performance, exhaust gas and the like. For this reason, various additives are added to fuel oil such as gasoline for the purpose of removing sludge and deposit, preventing adhesion, and purifying.

For example, polyetheramine-based fuel oil additives are disclosed in JP-B-56-48556, JP-A-3-229797 and JP-A-6-322381. Further, JP-A-8-199179 discloses a urethane fuel oil additive. However, under the severe operating conditions in which acceleration and deceleration are frequent, the fuel oil additive described above has a sufficient effect of cleaning the intake system but not a sufficient effect of cleaning the combustion chamber.

[0004]

Accordingly, it is an object of the present invention to provide a fuel oil additive having excellent cleanliness of the fuel system and combustion chamber of an internal combustion engine even under frequent and severe operating conditions. is there.

[0005]

As a result of intensive studies to achieve the above object, it has been found that a specific primary amino group-containing poly (meth) acrylate exhibits excellent cleanliness, and the present invention has been achieved. . That is, the present invention is a fuel oil additive comprising a polymer having a primary amino group-containing (meth) acrylate monomer (A-1) and an alkyl (meth) acrylate (A-2) as essential constitutional units.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, these will be described in detail. As the monomer (A-1) used in the present invention, a primary aminoalkyl (meth) acrylate [for example, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, aminobutyl (meth) acrylate];
Amino (poly) alkylene glycol mono (meth) acrylate [eg, aminoethoxy (meth) acrylate, aminopropoxy (meth) acrylate, aminobutoxy (meth) acrylate, aminopolybutylene glycol mono (meth) acrylate, aminopolypropylene glycol mono (Meth) acrylate, amino polyethylene glycol mono (meth) acrylate] and the like. These primary amino group-containing monomers may be used alone or in combination of two or more. Of these, primary aminopolyalkylene glycol monomethacrylate is preferred, and primary aminopolypropylene glycol monomethacrylate is particularly preferred.

The content of (A-1) in the polymer is usually 5
-99% by weight, preferably 5-80% by weight.

Alkyl (meth) acrylate (A-2)
Examples thereof include an alkyl (meth) acrylate having 1 to 30 carbon atoms, and specifically, an alkyl (1 to 3 carbon atoms)
(Meth) acrylate [methyl (meth) acrylate,
Ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate], alkyl (4 to 18 carbon atoms) (meth) acrylate [n-
Butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, 2-ethyloctyl (meth) acrylate, Dodecyl (meth) acrylate], alkyl (19 to 19 carbon atoms)
30) (meth) acrylates. Of these, alkyl (meth) acrylates having 4 to 18 carbon atoms are preferred. The content of (A-2) in the polymer is usually 1 to 95% by weight, preferably 20 to 95% by weight.

The polymer of the present invention comprises (A-1), (A-
In addition to 2), an ethylenically unsaturated monomer (B) can be copolymerized. Examples of the ethylenically unsaturated monomer (B) include styrene compounds [styrene, α-methylstyrene, vinyltoluene, etc.], unsaturated dicarboxylic esters [dibutyl fumarate, di-2-ethylhexyl fumarate, maleic acid] And the like, unsaturated nitriles [acrylonitrile, methacrylonitrile, etc.], vinyl esters [vinyl acetate, vinyl propionate, etc.], and mixtures of two or more of these. The content of (B) in the polymer is usually 0 to 5% by weight, preferably 0 to 5% by weight.
3% by weight.

The number-average molecular weight of the polymer is usually from 300 to 50,000 in view of the detergency effect and solubility in fuel oil.
0, preferably 500 to 10,000, particularly preferably 1000 to 5,000. 1 of the polymer
The secondary amine value is usually 1 to 500, preferably 3 to 400 from the viewpoint of affinity with sludge.

As a method for producing the monomer (A-1), the primary amino group of hydroxyamine is protected with an acid or a ketone, and then esterified with (meth) acrylic acid. There is a method of removing the protecting group by a decomposition method or the like.
Specific examples of the protecting group include p-toluenesulfonic acid, methyl ethyl ketone, methyl isobutyl ketone, and the like.

The production of the polymer is carried out by using a predetermined amount of (A-1)
(A-2) If necessary, (B) can be obtained in the presence of a radical polymerization initiator by any known method such as bulk polymerization, solution polymerization, suspension polymerization, etc. In this method, the solvent is removed after the solution polymerization in a solvent.

Examples of the radical polymerization initiator include known azo initiators and organic peroxide initiators. Representative examples include azobisisobutyronitrile, azobisdimethylvaleronitrile, di-ter
t-butyl peroxide, tert-butyl perbenzoate and the like. These may be used alone or in combination of two or more.

In the above polymerization reaction, a known chain transfer agent may be used if necessary. As a chain transfer agent,
Octyl mercaptan, dodecyl mercaptan, butyl alcohol, hexyl alcohol, ethylene glycol, glycerin and the like can be mentioned.

Solvents optionally used in the above polymerization reaction include aromatic solvents such as toluene and xylene; aliphatic solvents such as methyl isobutyl ketone and butyl acetate; alcohols such as butanol and isopropyl alcohol; At least one kind of mixed solvent is used.

The polymer of the present invention can be used for various fuel oils, for example, petroleum fractions, alcohols, LNG, vegetable oils, etc., all of which can be used as fuels for internal combustion engines.
In particular, when added to gasoline for internal combustion engines, it exhibits extremely excellent performance in the cleanliness of the fuel system and combustion chamber of the gasoline engine. The amount of the polymer of the present invention added to the fuel oil is not particularly limited, but is preferably 5 to 5 parts by weight of the fuel oil.
It is 0 ppm or more and 10,000 ppm or less. 50pp
m, the effect of addition is not sufficient, and 10,000 ppm
No effect is observed even if the value exceeds.

The fuel oil to which the polymer of the present invention has been added may optionally contain other additives such as an antioxidant, a metal detergent, an ashless detergent, a corrosion inhibitor and the like. it can.

[0018]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

The meanings of the abbreviations of the raw materials used in the examples and comparative examples are as follows. [Monomer (A-1)] EAMMA: aminoethyl methacrylate (amine value: 435) EAPMMA: aminopolypropylene glycol monomethacrylate (amine value: 328.1) EABMMA: aminopolybutylene glycol monomethacrylate (amine value: 218. 3) EAEMMA: amino polyethylene glycol monomethacrylate (amine value: 279.1) [monomer (B)] BMA: butyl methacrylate RMA: lauryl methacrylate DMA: dodecyl methacrylate

Examples 1 to 9 33.3 parts of xylene was charged into a pressure-resistant reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet, and air in the reaction vessel was replaced with nitrogen gas. It was heated to reflux. After the heating reflux, the container was closed and the temperature was raised to 175 ° C.
Then, 4 parts of dicumyl peroxide as a polymerization initiator,
And a mixture of the monomers in the amounts shown in Table 1 was added dropwise over 1.5 hours under pressure. After aging for 1 hour at the same temperature, the mixture was cooled to 130 ° C. 180 ° C under normal pressure
Xylene was distilled off while the temperature was raised to 180 ° C., and when the temperature reached 180 ° C., the pressure was switched to reduced pressure. After reaching 2000 Pa, distillation was performed for 1.5 hours. I got Table 2 shows the number average molecular weight of the obtained sample. The number average molecular weight was measured using GPC under the following conditions. Apparatus: Waters Column: Ultra Styra Gel Linear 2 Measurement temperature: 25 ° C Sample solution: 0.25% by weight THF solution Solution injection amount: 200 μl Detector: Refractive index detector The molecular weight calibration curve uses standard polystyrene. Created.

Comparative Example 1 A pressure-resistant reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet was charged with 33.3 parts of xylene, and the air in the reaction vessel was replaced with nitrogen gas. did. After the heating reflux, the container was closed and the temperature was raised to 175 ° C.
Then, 4 parts of dicumyl peroxide as a polymerization initiator,
And the monomer of the amount shown in Table 1 was dripped under pressure over 1.5 hours. After further aging for 1 hour at the same temperature,
Cooled to 30 ° C. The xylene was distilled off while the temperature was raised to 180 ° C. under normal pressure, and when the temperature reached 180 ° C., the pressure was switched to reduced pressure.
After cooling to room temperature, Comparative Sample 1 of the polymer of the present invention was obtained.
Table 2 shows the number average molecular weight of the obtained sample. The number average molecular weight was measured using GPC under the same conditions as in the examples.

[0022]

[Table 1]

The effects of cleanliness by the samples obtained in Examples 1 to 9 and Comparative Examples 1 and 2 were evaluated by an engine test, and the results are shown in Table 2.

Evaluation Test 1 A fuel injection type unused passenger car having a total displacement of 1800 cc was prepared, and only the following gasoline was used using only gasoline.
After repeating the running mode for 30 minutes in the cycle for 120 hours, the amount of deposit adhering to the intake valve was measured. Running mode: idling (1 minute) → 1500 rpm (15 minutes) → 2700 rpm (10 minutes) → stop (4 minutes) Then, install the intake valve without removing the deposit, and use the gasoline added with 200 ppm of each sample as described above. The running mode of 30 minutes per cycle shown was repeated for 48 hours. After the test, the amount of deposit adhering to the intake valve was measured, and the difference between the amount of gasoline to which 200 ppm of the sample was added and the amount of deposit before use was determined to evaluate the intake system deposit cleanliness.

Evaluation Test 2 A fuel-injection type unused car having a total displacement of 1800 cc was prepared, and operated at 1800 rpm for 120 hours using gasoline added with 200 ppm of each sample.
The amount of deposit adhering to the combustion chamber was measured, and the difference from the amount of deposit adhering to the combustion chamber when operating only with gasoline was determined.

[0026]

[Table 2]

[0027]

The fuel oil additive of the present invention exerts an excellent effect on the cleanliness of the intake system deposit and especially the combustion chamber deposit. In particular, it exerts an extremely excellent effect on the cleanliness of the combustion chamber deposit.

Claims (6)

[Claims] 1. A primary amino group-containing (meth) acrylate monomer (A-1) and an alkyl (meth) acrylate (A
-2) a fuel oil additive comprising a polymer having essential structural units. 2. The polymer according to claim 1, wherein (A-2) is an alkyl (meth) acrylate having an alkyl group having 4 to 18 carbon atoms, and the glass transition point (Tg) of the polymer is 30 ° C. or lower. Fuel oil additive. 3. The fuel oil additive according to claim 1, wherein (A-1) is contained in the polymer in an amount of 5 to 99% by weight. 4. A polymer having a number average molecular weight of 300 to 5
The fuel oil additive according to any one of claims 1 to 3, which has a molecular weight of 000. 5. The fuel oil additive according to claim 1, wherein the polymer has a primary amine value of 1 to 500. 6. A fuel oil composition comprising the additive according to claim 1 and gasoline or light oil.