JP4550195B2 - Fuel oil additive and fuel oil composition - Google Patents

Description

【００２７】
ａ１−１：メタノールのプロピレンオキサイド２モル付加物のメタクリレート
ａ１−２：イソブタノールのエチレンオキサイド２モル付加物のメタクリレート
ａ１−３：ｎ−ブタノールのエチレンオキサイド２モル付加物のメタク
リレート
ａ１−４：メタノールのプロピレンオキサイド３モル付加物のメタク
リレート
ａ１−５：イソプロピルアルコールのプロピレンオキサイド２モル付
加物のメタクリレート
ａ２−１：ジエチルアミノエチルメタクリレート
ａ２−２：モルホリノエチルメタクリレート
ｃ１：ブタノールのエチレンオキサイド２モル付加物
ｃ２：エチルメチルベンゼン
【００２８】
実施例１〜９、比較例１〜２で得られた試料による清浄性の効果を、エンジン試験評価を行い、その結果を表２に示す。
【００２９】
総排気量１８００ｃｃの燃料インジェクション式未使用の乗用車を用意し、ガソリンのみを用いて以下に示す１サイクル３２分の走行モードを１２０時間繰り返した後、吸気弁に付着したデポジット量を測定した。
走行モード；アイドリング（１分）→１５００ｒｐｍ（１７分）→２７００ｒｐｍ （１０分）→停止（４分）
次いでデポジットを取り除くことなく吸気弁を取り付け、各試料２００ｐｐｍ添加したガソリンを用いて、上記に示す１サイクル３２分の走行モードを４８時間繰り返した。試験後、吸気弁に付着したデポジット量を測定し、試料２００ｐｐｍ添加したガソリンを使用前のデポジット量との差を求め吸気系デポジット清浄性の評価とした。
【００３０】
評価試験２
総排気量１８００ｃｃの燃料インジェクション式未使用の乗用車を用意し、各試料２００ｐｐｍ添加したガソリンを用いて回転数１８００ｒｐｍで１００時間稼働後、燃焼室に付着したデポジット量を測定し、ガソリンのみで稼働した場合に燃焼室に付着したデポジット量との差を求めた。
【００３１】
【表２】

【００３２】
【発明の効果】
本発明の燃料油添加剤は吸気系デポジットおよび特に燃焼室デポジットの清浄性に優れた効果を発揮する。特に燃焼室デポジットの清浄性に極めて優れた効果を発揮する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a fuel oil additive, and more particularly to a fuel oil additive that is excellent in solubility in fuel oil and particularly excellent in cleanliness in a combustion chamber of a gasoline engine or a diesel engine.
[0002]
[Prior art]
If deposits such as sludge and deposits are generated in the fuel system and combustion chamber of the internal combustion engine, the engine function is deteriorated and exhaust gas is adversely affected. 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.
[0003]
For example, JP-A-56-48556, JP-A-3-229797, JP-A-6-322381 and the like disclose polyetheramine fuel oil additives. JP-A-8-199179 discloses a urethane fuel oil additive. However, the nitrogen-containing fuel oil additive as described above has a sufficient intake system cleaning effect under severe operating conditions where acceleration and deceleration are frequent, but the combustion chamber cleaning effect is not sufficient.
[0004]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a fuel oil additive excellent in cleanliness of a fuel system and a combustion chamber of an internal combustion engine even under frequent and severe operating conditions.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the inventors have found that a specific polymethacrylate exhibits excellent cleanliness, and have reached the present invention.
That is, the present invention comprises a polymer (A) containing 75% by weight or more of methacrylate (a1) as a structural unit and having a solubility parameter (SP value) of 8.5 to 12.5, and the number of (A) In differential thermogravimetric measurement, the average molecular weight is 300 to 5000, and the temperature is increased from 30 ° C. at 10 ° C./min. And a fuel oil composition comprising the additive and fuel oil.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, these will be described in detail.
[0007]
As the methacrylate (a1), alkyl (1 to 16 carbon atoms) methacrylate [methyl methacrylate, ethyl methacrylate, normal propyl methacrylate, isopropyl methacrylate, normal butyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate, normal hexyl methacrylate, cyclohexyl methacrylate, 2 -Ethylhexyl methacrylate, normal octyl methacrylate, isodecyl methacrylate, normal decyl methacrylate, normal dodecyl methacrylate, isododecyl methacrylate, etc.], aralkyl (carbon number 7-12) methacrylate [benzyl methacrylate, etc.], hydroxyl group-containing alkyl (carbon number) 2-3) Methacrylate [2-hydroxyethyl methacrylate Acrylate, 2-hydroxypropyl methacrylate, etc.], ether group-containing methacrylate [1 to 3 moles of alkylene oxide (2 to 4 carbon atoms) adduct methacrylate to 1 to 10 carbon atoms of alcohol [butanol ethylene oxide 1 to 3 moles] Adduct methacrylate, Butanol propylene oxide 1-3 mol adduct methacrylate, Methanol ethylene oxide 1-3 mol adduct methacrylate, Methanol propylene oxide 1-3 mol adduct methacrylate, 2-ethylhexanol Ethylene oxide 1-2 mol adduct methacrylate and the like]] and the like.
Of (a1), an ether group-containing methacrylate is preferable, and an ethylene oxide 1-3 mole adduct of an alcohol having 1 to 4 carbon atoms is particularly preferable.
[0008]
The content of (a1) in the polymer (A) is usually 75% by weight or more, preferably 85% by weight or more.
[0009]
It is preferable that a polymer (A) contains the monomer (a2) containing nitrogen as a structural unit. Examples of the nitrogen-containing monomer (a2) include nitrogen-containing alkyl methacrylate [diethylaminoethyl methacrylate, pyrrolidoethyl methacrylate, morpholinoethyl methacrylate, etc.], nitrogen, ether group-containing methacrylate [addition of 1 to 3 mol of propylene oxide of morpholine. Methacrylate, morpholine ethylene oxide 1-3 mol adduct methacrylate, morpholine butylene oxide 1-3 mol adduct methacrylate, 2-pyrrolidinone propylene oxide 1-3 mol adduct methacrylate, 2-pyrrolidinone Of 1 to 3 mol adduct of ethylene oxide, methacrylate of 1 to 3 mol of butylene oxide of 2-pyrrolidinone, and 1 to 3 mol of adduct of ethylene oxide of piperidine Methacrylate, propylene oxide 1-3 mol adduct methacrylate, piperidine butylene oxide 1-3 mol adduct methacrylate, propylene oxide 1-3 mol adduct methacrylate, monoethanolamine ketiminate, monoethanolamine methacrylate And the like, and the like, and the like, and the like.
Among (a2), nitrogen and ether group-containing methacrylates are preferable.
Particularly preferred are methacrylates of propylene oxide 1 to 3 mol adduct of monoethanolamine ketiminate, and methacrylates of ethylene oxide adduct of monoethanolamine ketiminate.
[0010]
The content of (a2) in the polymer is usually 25% by weight or less, preferably 15% by weight or less.
[0011]
The polymer (A) can contain another ethylenically unsaturated monomer (B) as a constituent unit in addition to (a1) and (a2).
Examples of (B) include styrene compounds [styrene, α-methylstyrene, vinyltoluene, etc.], unsaturated dicarboxylic acid esters [dibutyl fumarate, di-2-ethylhexyl fumarate, dibutyl maleate, etc.], unsaturated Nitriles [acrylonitrile, methacrylonitrile, etc.], vinyl esters [vinyl acetate, vinyl propionate, etc.], vinyl pyrrolidone, and mixtures of two or more of these.
[0012]
Content of (B) in a polymer (A) is 0 to 4 weight% normally, Preferably it is 0 to 2 weight%.
[0013]
The number average molecular weight of the polymer (A) is 300 to 5,000, preferably 300 to 3,000, particularly preferably 500 to 2,000. If it is less than 300 or more than 5,000, the cleaning effect is insufficient, and the solubility in fuel oil is insufficient.
The rate of thermal decomposition residue at 200 ° C. in the differential thermogravimetric measurement at 30 ° C. to 10 ° C./min (final temperature 600 ° C.) is 25 to 75% by weight, preferably 35 to 65% by weight. It is. If the amount is less than 25% by weight, the arrival efficiency of the additive with respect to the deposit is poor, and the performance is not exhibited. If the amount exceeds 75% by weight, the additive itself is deposited, which has an adverse effect. The thermal decomposition residue rate at 300 ° C. is 3% by weight or less, preferably 1% by weight or less. If it exceeds 3% by weight, the additive itself deposits, which has an adverse effect.
[0014]
The fuel oil additive of the present invention may further contain a carrier oil having an SP value of 8.5 to 12.5, a boiling point or decomposition point of 120 to 300 ° C., and an HLB of 0.8 to 10.9. preferable.
Specific examples of carrier oils include alkylene oxide adducts of alcohols having 1 to 6 carbon atoms [butanol ethylene oxide 2 mol adduct, butanol propylene oxide 5 mol adduct, methanol propylene oxide 5 mol adduct, etc.], Examples include aromatic solvents having 7 to 10 carbon atoms [toluene, xylene, ethylmethylbenzene, diethylbenzene, butylbenzene and the like].
[0015]
It is preferable that the metal content in (A) is 2 ppm or less for each metal, and the halogen content is 10 ppm or less.
Since the metal and the halogen act as a negative catalyst with respect to the automobile exhaust gas treatment catalyst, the above small content is preferable.
Metals and halogens are attributed to the catalyst used at the time of raw material synthesis such as ether group-containing methacrylate. Examples of means for removing these include filtration using a normal adsorbent and the like, and purification of raw materials by distillation.
[0016]
As a method for producing the polymer (A), a predetermined amount of (a1) and, if necessary, (a2) and (B), in the presence of a radical polymerization initiator, bulk polymerization, solution polymerization, suspension polymerization, etc. Any known method may be used, but it is preferably a method in which the solvent is removed after solution polymerization in an organic solvent.
[0017]
Examples of the radical polymerization initiator include known azo initiators and organic peroxide initiators. Illustrative examples include azobisisobutyronitrile, azobisdimethylvaleronitrile, di-tert-butyl peroxide, tert-butyl perbenzoate, dimethylazobisisobutyrate, and the like. These may be used alone or in combination of two or more. In the differential thermogravimetric measurement, it is preferable to use an initiator having a residual weight at 300 ° C. of 3% or less.
[0018]
In the above polymerization reaction, a known chain transfer agent may be used as necessary. Examples of the chain transfer agent include octyl mercaptan, dodecyl mercaptan, butyl alcohol, hexyl alcohol, ethylene glycol, glycerin and the like.
[0019]
Solvents used in the above solution polymerization 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; and mixed solvents of two or more of these Is mentioned.
[0020]
The fuel oil additive comprising the polymer (A) of the present invention can be used for various fuel oils such as petroleum fractions, alcohols, LNG, vegetable oils and the like that can be used as fuels for internal combustion engines. .
In particular, when it is added to gasoline that satisfies the conditions (i) to (viii) or light oil having a sulfur content of 0.05% by weight or less, it exhibits extremely excellent performance in cleanliness of the engine fuel system and combustion chamber.
(I) 35% or less of total aromatic compounds based on unleaded gasoline total amount (ii) 0-5% by volume of benzene based on unleaded gasoline total amount
(Iii) 0 to 25% of toluene based on the total amount of unleaded gasoline
(Iv) 0 to 15% by volume of C8 aromatic compound based on the total amount of unleaded gasoline
(V) 0 to 15% by volume of C9 aromatic compound based on the total amount of unleaded gasoline
(Vi) 0 to 15% by volume of aromatic compounds having 10 or more carbon atoms based on the total amount of unleaded gasoline
(Vii) Sum of aromatic compounds having 9 carbon atoms and aromatic compounds having 10 or more carbon atoms based on the total amount of unleaded gasoline / total amount of toluene and aromatic compounds having 8 carbon atoms based on the total amount of unleaded gasoline
(Viii) When two or more alkyl-substituted aromatic compounds based on the total amount of unleaded gasoline are 0, or when two or more alkyl-substituted aromatic compounds based on the total amount of unleaded gasoline are not 0, monoalkyl-substituted aromatics based on the total amount of unleaded gasoline / 2 The amount of the alkyl-substituted aromatic compound is 1 or more and the amount of the polymer of the present invention added to the fuel oil is not particularly limited, but is preferably 50 ppm to 10,000 ppm with respect to the fuel oil. If it is less than 50 ppm, the effect of addition is not sufficient, and even if it exceeds 10,000 ppm, the effect is not improved.
[0021]
In addition, other additives such as an antioxidant, a metal detergent, an ashless detergent, a corrosion inhibitor and the like can be blended in the fuel oil to which the polymer of the present invention is added, as necessary.
[0022]
【Example】
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to these.
[0023]
Examples 1-9
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 n-butanol, and the air in the reaction vessel was replaced with nitrogen gas, followed by heating to reflux. After heating and refluxing, the container was sealed, heated to 100 ° C., and then a mixture of 4 parts of dimethylazobisisobutyrate as a polymerization initiator and an amount of monomers shown in Table 1 was added under pressure. It was added dropwise over 1.5 hours. Furthermore, after aging at the same temperature for 1 hour, it was cooled to 80 ° C. N-Butanol was distilled off under reduced pressure at 80 ° C., and after reaching 2000 Pa, distillation was performed for 1.5 hours, followed by cooling to room temperature to obtain samples 1 to 7 of the polymer of the present invention. Further, in the case of Examples containing carrier oil, after the n-butanol was distilled off, a predetermined amount of carrier oil was added, and the mixture was stirred at 80 ° C. for 1 hour to be uniform and then cooled to room temperature. 8 and 9 were obtained. The number average molecular weight of the obtained sample is shown in Table 1. The number average molecular weight was measured using GPC under the following conditions.
Apparatus: Waters column: Ultra Styl gel linear Measurement temperature: 25 ° C
Sample solution: 0.25 wt% THF solution injection amount: 200 μl
Detector: Refractive index detector The molecular weight calibration curve was prepared using standard polystyrene.
Differential thermogravimetry was performed by increasing the temperature from 30 ° C. to 600 ° C. at a rate of 10 ° C./min and measuring the weight change.
[0024]
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, and then heated and refluxed. After heating and refluxing, the vessel was sealed and heated to 175 ° C., and then 4 parts of dicumyl peroxide as a polymerization initiator and the amount of monomers shown in Table 1 were added under pressure for 1.5 hours. And dripped. Further, after aging for 1 hour at the same temperature, the mixture was cooled to 130 ° C. The xylene was distilled off while raising the temperature to 180 ° C. under normal pressure, and when the temperature reached 180 ° C., the pressure was changed to reduced pressure. Comparative sample 1 was obtained. The number average molecular weight of the obtained sample is shown in Table 1. The number average molecular weight was measured using GPC under the same conditions as in the examples.
[0025]
Comparative Example 2
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, and then heated and refluxed. After heating and refluxing, the vessel was sealed and the temperature was raised to 145 ° C., and then 0.5 parts of dicumyl peroxide as a polymerization initiator and the amount of monomers shown in Table 1 were added under pressure to 1.5 parts. It was added dropwise over time. Further, after aging for 1 hour at the same temperature, the mixture was cooled to 130 ° C. The xylene was distilled off while raising the temperature to 180 ° C. under normal pressure, and when the temperature reached 180 ° C., the pressure was changed to reduced pressure. Comparative sample 2 was obtained. The number average molecular weight of the obtained sample is shown in Table 1. The number average molecular weight was measured using GPC under the same conditions as in the examples.
[0026]
[Table 1]

[0027]
a1-1: methacrylate of propylene oxide 2 mol adduct of methanol a1-2: methacrylate of ethylene oxide 2 mol adduct of isobutanol a1-3: methacrylate of ethylene oxide 2 mol adduct of n-butanol a1-4: methanol Propylene oxide 3-mole adduct methacrylate a1-5: isopropyl alcohol propylene oxide 2-mole adduct methacrylate a2-1: diethylaminoethyl methacrylate a2-2: morpholinoethyl methacrylate c1: butanol ethylene oxide 2-mole adduct c2: Ethylmethylbenzene 【0028】
The cleanliness effect of the samples obtained in Examples 1 to 9 and Comparative Examples 1 and 2 was evaluated by an engine test, and the results are shown in Table 2.
[0029]
A fuel injection type unused passenger car having a total displacement of 1800 cc was prepared, and the following travel mode of 32 cycles per cycle was repeated for 120 hours using only gasoline, and the amount of deposit adhered to the intake valve was measured.
Driving mode: Idling (1 minute) → 1500 rpm (17 minutes) → 2700 rpm (10 minutes) → Stop (4 minutes)
Next, the intake valve was attached without removing the deposit, and the running mode of 32 minutes per cycle was repeated for 48 hours using gasoline added with 200 ppm of each sample. After the test, the amount of deposit adhering to the intake valve was measured, and the difference between the amount of deposit of 200 ppm of the sample and the amount of deposit before use was determined to evaluate the intake system deposit cleanliness.
[0030]
Evaluation test 2
A fuel injection type unused passenger car with a total displacement of 1800 cc was prepared, and after operating for 100 hours at 1800 rpm with gasoline added with 200 ppm of each sample, the amount of deposit adhered to the combustion chamber was measured, and it was operated only with gasoline. In this case, the difference from the deposit amount adhering to the combustion chamber was obtained.
[0031]
[Table 2]

[0032]
【The invention's effect】
The fuel oil additive of the present invention exhibits an excellent effect on the cleanliness of the intake system deposit and particularly the combustion chamber deposit. In particular, it exhibits an extremely excellent effect on the cleanliness of the combustion chamber deposit.

Claims (6)

  The polymer (A) contains 75% by weight or more of the methacrylate (a1) as a structural unit and has a solubility parameter (SP value) of 8.5 to 12.5, and the number average molecular weight of (A) is 300 to For fuel oil, the residual weight at 200 ° C. is 25 to 75% and the residual weight at 300 ° C. is 3% or less in the differential thermogravimetric measurement at 5000 at 30 ° C. to 10 ° C./min. Additive.   The additive for fuel oil according to claim 1, wherein (A) contains a monomer (a2) containing nitrogen as a structural unit.   The fuel oil according to claim 1 or 2, further comprising a carrier oil having an SP value of 8.5 to 12.5, a boiling point or decomposition point of 120 to 300 ° C, and an HLB of 0.8 to 10.9. Additive.   The fuel oil additive according to any one of claims 1 to 3, wherein the metal content in (A) is 2 ppm or less for each metal, and the halogen content is 10 ppm or less. A fuel oil composition comprising a gasoline satisfying the conditions of (i) to (viii) and 50 to 10,000 ppm of the fuel oil additive according to any one of claims 1 to 4.
(I) 35% by volume or less of all aromatic compounds based on the total amount of unleaded gasoline (ii) 0 to 5% by volume of benzene based on the total amount of unleaded gasoline (iii) 0 to 25% of toluene based on the total amount of unleaded gasoline (iv) Unleaded Aromatic compounds with 8 carbon atoms based on the total amount of gasoline are 0 to 15% by volume (v) 0 to 15% by volume of aromatic compounds with 9 carbon atoms based on the total amount of unleaded gasoline (vi) 10 or more carbon atoms based on the total amount of unleaded gasoline 0 to 15% by volume of aromatic compounds (vii) Sum of aromatic compounds having 9 carbon atoms and aromatic compounds having 10 or more carbon atoms based on the total amount of unleaded gasoline / Toluene based on the total amount of unleaded gasoline and aromatics having 8 carbon atoms Unleaded gasoline when the total number of compounds is 0 to 0.2 (viii) 2 or more alkyl-substituted aromatic compounds based on the total amount of unleaded gasoline is 0, or 2 or more alkyl-substituted aromatic compounds based on the total amount of unleaded gasoline is not 0 Monoalkyl-substituted aromatic / 2 or more alkyl-substituted aromatic compound in an amount criterion 1 or more A fuel oil composition comprising the fuel oil additive according to any one of claims 1 to 4 and a diesel oil having a sulfur content of 0.05% by weight or less.