JP3938422B2 - Fuel oil additive - Google Patents

Description

（式中、Ｒ³は炭化水素基を表わし、Ｒ⁴はアルキレン基を表わし、ｍ¹は１以上の数を表わす。Ｒ³は好ましくは分子量５００〜５,０００程度のオレフィンオリゴマー基、より好ましくはポリイソブテニル基を表わし、Ｒ⁴は好ましくはエチレン基又はプロピレン基を表わし、ｍ¹は好ましくは１〜１０程度の数を表わす。）で表わされるコハク酸モノイミド；
下記の一般式（４）
【化７】

（式中、Ｒ⁵及びＲ⁶は炭化水素基を表わし、Ｒ⁷はアルキレン基を表わし、ｍ²は０又は１以上の数を表わす。Ｒ⁵及びＲ⁶は好ましくは分子量５００〜５,０００程度のオレフィンオリゴマー基、より好ましくはポリイソブテニル基を表わし、Ｒ７は好ましくはエチレン基又はプロピレン基を表わし、ｍ²は好ましくは０又は１〜１０程度の数を表わす。）で表わされるコハク酸ジイミド；
下記の一般式（５）
【化８】

（式中、Ｒ⁸及びＲ⁹は炭化水素基を表わし、ＡＯ¹はオキシアルキレン基を表わし、ｎ¹は１以上の数を表わす。Ｒ⁸は好ましくは分子量５００〜５,０００程度のオレフィンオリゴマー基、より好ましくはポリイソブテニル基を表わし、Ｒ⁹は炭素数１〜１８程度のアルキル基又はアルケニル基を表わし、ｎ¹は好ましくは１〜１０程度の数を表わす。）で表わされるコハク酸イミドアルキレンオキサイド付加物のエステル化物、又はこれらのホウ素化変性物等が挙げられる。
【００２２】
ベンジルアミン類としては例えば、下記の一般式（６）
【化９】

（式中、Ｒ¹⁰は炭化水素基を表わし、Ｒ¹¹はアルキレン基を表わし、ｒは１〜４の数を表わし、ｍ³は１以上の数を表わす。Ｒ¹⁰は好ましくは分子量５００〜５,０００程度のオレフィンオリゴマー基、より好ましくはポリイソブテニル基を表わし、Ｒ¹¹は好ましくはエチレン基又はプロピレン基を表わし、ｍ³は好ましくは１〜１０程度の数を表わす。）等が挙げられる。
【００２３】
オキシアルキレン基を有するアミン類としては、下記の一般式（７）
【化１０】

（式中、Ｒ¹²は炭化水素基を表わし、ＡＯ²はオキシアルキレン基を表わし、ｍ⁴及びｎ²は１以上の数を表わす。Ｒ¹²は好ましくはアルキル基、アルケニル基又はアリール基を表わし、ＡＯ²は好ましくはオキシプロピレン基又はオキシブチレン基を表わし、ｎ²は好ましくは５〜５０の数を表わし、ｍ⁴は好ましくは１〜３の数を表わす。）で表わされる化合物；
下記の一般式（８）
【化１１】

（式中、Ｒ¹³は炭化水素基を表わし、Ｒ¹⁴はアルキレン基を表わし、ＡＯ³はオキシアルキレン基を表わし、ｎ³及びｍ⁵は１以上の数を表わす。Ｒ¹³は好ましくはアリール基を表わし、Ｒ¹⁴は好ましくはエチレン基又はプロピレン基を表わし、ＡＯ³は好ましくはオキシプロピレン基又はオキシブチレン基を表わし、ｎ³は好ましくは５〜５０の数を表わし、ｍ⁵は好ましくは１〜３の数を表わす。）で表わされる化合物；
下記の一般式（９）
【化１２】

（式中、Ｒ¹⁵は炭化水素基を表わし、ＡＯ⁴はオキシアルキレン基を表わし、ｎ⁴及びｑは１以上の数を表わす。Ｒ¹⁵は好ましくは炭素数１〜１２のアルキル基又はアルケニル基を表わし、ＡＯ⁴は好ましくはオキシプロピレン基又はオキシブチレン基を表わし、ｎ⁴は好ましくは５〜５０の数を表わし、ｑは好ましくは１〜３の数を表わす。）で表わされる化合物等が挙げられる。
【００２４】
ポリアルキレンポリアミン誘導体としては例えば、下記の一般式（１０）
【化１３】

（式中、Ｒ¹⁶は炭化水素基を表わし、Ｒ¹⁷はアルキレン基を表わし、ｍ⁶は１以上の数を表わす。Ｒ¹⁶は好ましくは分子量５００〜５,０００程度のオレフィンオリゴマー基、より好ましくはポリイソブテニル基を表わし、Ｒ¹⁷は好ましくはエチレン基又はプロピレン基を表わし、ｍ⁶は好ましくは１〜３の数を表わす。）で表わされる化合物；
下記の一般式（１１）
【化１４】

（式中、Ｒ¹⁸、Ｒ¹⁹及びＲ²¹は炭化水素基を表わし、Ｒ²⁰はアルキレン基を表わし、ＡＯ⁵はオキシアルキレン基を表わし、ｍ⁷及びｎ⁵は１以上の数を表わす。Ｒ¹⁸、Ｒ¹⁹及びＲ²¹は好ましくは炭素数６〜２４のアルキル基又はアルケニル基を表わし、Ｒ²⁰は好ましくはエチレン基又はプロピレン基を表わし、ＡＯ⁵は好ましくは炭素数２〜４のアルキレン基を表わし、ｍ⁷は好ましくは１〜３の数を表わし、ｎ⁵は好ましくは５〜５０の数を表わす。）で表わされる化合物等が挙げられる。
【００２５】
上記の塩基性窒素原子を含有する化合物の添加量は特に限定されないが、好ましくは燃料油に対して１〜５,０００ｐｐｍ、より好ましくは１〜３,０００ｐｐｍ、更に好ましくは１０〜１,０００ｐｐｍ程度である。
【００２６】
同様に、本発明の燃料油添加剤は、下記の一般式（２）で表わされる化合物と併用すると、更に優れたデポジット除去性能を発揮する。一般式（２）において、Ｒ¹は炭化水素基を表わす。炭化水素基としては例えば、アルキル基、アルケニル基、アリール基、シクロアルキル基、シクロアルケニル基等が挙げられる。
【００２７】
アルキル基としては例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、２級ブチル、ターシャリブチル、ペンチル、イソペンチル、２級ペンチル、ネオペンチル、ターシャリペンチル、ヘキシル、２級ヘキシル、ヘプチル、２級ヘプチル、オクチル、２−エチルヘキシル、２級オクチル、ノニル、２級ノニル、デシル、２級デシル、ウンデシル、２級ウンデシル、ドデシル、２級ドデシル、トリデシル、イソトリデシル、２級トリデシル、テトラデシル、２級テトラデシル、ヘキサデシル、２級ヘキサデシル、ステアリル、イコシル、ドコシル、テトラコシル、トリアコンチル、２−ブチルオクチル、２−ブチルデシル、２−ヘキシルオクチル、２−ヘキシルデシル、２−オクチルデシル、２−ヘキシルドデシル、２−オクチルドデシル、２−デシルテトラデシル、２−ドデシルヘキサデシル、２−ヘキサデシルオクタデシル、２−テトラデシルオクタデシル、モノメチル分枝−イソステアリル等が挙げられる。
【００２８】
アルケニル基としては例えば、ビニル、アリル、プロペニル、ブテニル、イソブテニル、ペンテニル、イソペンテニル、ヘキセニル、ヘプテニル、オクテニル、ノネニル、デセニル、ウンデセニル、ドデセニル、テトラデセニル、オレイル等が挙げられる。
【００２９】
アリール基としては例えば、フェニル、トルイル、キシリル、クメニル、メシチル、ベンジル、フェネチル、スチリル、シンナミル、ベンズヒドリル、トリチル、エチルフェニル、プロピルフェニル、ブチルフェニル、ペンチルフェニル、ヘキシルフェニル、ヘプチルフェニル、オクチルフェニル、ノニルフェニル、デシルフェニル、ウンデシルフェニル、ドデシルフェニル、フェニルフェニル、ベンジルフェニル、スチレン化フェニル、ｐ−クミルフェニル、α−ナフチル、β−ナフチル基等が挙げられる。
【００３０】
シクロアルキル基、シクロアルケニル基としては例えば、シクロペンチル、シクロヘキシル、シクロヘプチル、メチルシクロペンチル、メチルシクロヘキシル、メチルシクロヘプチル、シクロペンテニル、シクロヘキセニル、シクロヘプテニル、メチルシクロペンテニル、メチルシクロヘキセニル、メチルシクロヘプテニル基等が挙げられる。
中でも、Ｒ¹はアルキル基、アルケニル基又はアリール基が好ましい。
【００３１】
又、Ｒ²は、炭化水素基であるが、好ましくは炭素数２〜４のアルキレン基であり、より好ましくはプロピレン基又はブチレン基である。Ｒ²が２種以上の炭化水素基である場合は１種はプロピレン基又はブチレン基であることが好ましい。一般式（２）中の(Ｒ²−Ｏ)_pの部分は、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド、エピクロルヒドリン等のアルキレンオキサイド等を付加重合することにより得ることができる。又、上記の方法により(Ｒ²−Ｏ)_pの部分を形成させる場合は、付加させるアルキレンオキサイド等によりＲ²が決定される。付加させるアルキレンオキサイド等の重合形態は特に限定されず、１種類の単独重合、２種類以上のランダム共重合、ブロック共重合又はランダム／ブロック共重合等であってよい。重合度ｐは１以上の数であり、好ましくは１〜１００、より好ましくは１〜３０、更に好ましくは２〜１５である。
【００３２】
一般式（２）で表わされる化合物の製造方法は特に限定されず通常の公知の方法によればよい。通常は、Ｒ¹―ＯＨで表わされるアルコール又はフェノールにアルキレンオキサイドをアルカリ触媒下で付加重合させることにより得ることができる。
【００３３】
上記一般式（２）で表わされる化合物の添加量は特に限定されないが、好ましくは燃料油に対して１〜５,０００ｐｐｍ、より好ましくは１〜３,０００ｐｐｍ、更に好ましくは１０〜１,０００ｐｐｍ程度である。
【００３４】
又、上記の燃料油添加剤又は燃料油添加剤組成物は、潤滑油留分（キャリアオイル）又は有機溶媒に溶解又は分散させて添加されてもよい。キャリアオイルとしては、通常潤滑油基油として使用される鉱油又は合成油が好ましく使用される。鉱油は、天然の原油から分離されるものであり、これを適当に蒸留、精製等を行って製造される。合成油は、化学的に合成された潤滑油であって、例えばポリ−α−オレフィン、ポリイソブチレン（ポリブテン）、ジエステル、ポリオールエステル、リン酸エステル、ケイ酸エステル、ポリアルキレングリコール、ポリフェニルエーテル、シリコーン、フッ素化化合物、アルキルベンゼン等が挙げられる。これらの中でも、ポリ−α−オレフィン、ポリイソブチレン（ポリブテン）、ジエステル、ポリオールエステル等が挙げられる。キャリアオイルとしては、１００℃における動粘度が３〜３５ｃＳｔ程度の粘度を有するものが好ましい。
【００３５】
有機溶媒としては例えば、ケロシン、ベンゼン、トルエン、キシレン、エチルベンゼン、クロロベンゼン、ニトロベンゼン、トリメチルベンゼン、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン、デカン、ウンデカン、ドデカン、シクロヘキサン、シクロペンタン、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルエーテル、ジエチルエーテル、メチルイソブチルカルビトール等が挙げられる。
【００３６】
本発明の燃料油添加剤又は燃料油添加剤組成物は、他の成分と共に燃料油に添加されてもよい。他の成分としては例えば、テトラエチル鉛、テトラメチル鉛、ビスシクロペンタンジフェニル鉄等のアンチノック剤；メチルターシャリブチルエーテル、メチルターシャリアミルエーテル等のオクタン価向上剤；硝酸ヘプチル、硝酸オクチル、硝酸シクロヘキシル等のセタン価向上剤；トリブチルホスファイト、トリメチルホスファイト、トリクレジルホスフェート、トリシクロヘキシルホスフェート、クレジルジフェニルホスフェート、トリメチルホスフェート、メチルフェニルホスフェート、２−エチルヘキシルボロネート、ブチルジイソブチルボロネート等の表面着火防止剤；トリクレジルホスフェート、トリメチルホスフェート、トリス（クロロエチル）ホスフェート、ポリブテン、ポリプロピレン等の堆積物改良剤；Ｎ，Ｎ’−ジイソプロピル−ｐ−フェニレンジアミン、Ｎ，Ｎ’−ジオクチル−ｐ−フェニレンジアミン、２，６−ジターシャリブチルフェノール、２，６−ジターシャリブチル−４−メチルフェノール、２，４−ジメチル−６−ターシャリブチルフェノール等の酸化防止剤；エチレンジアミン、Ｎ，Ｎ’−ジサリチリデン−１，２−ジアミノプロパン、Ｎ，Ｎ’−ジサリチリデン−２−シクロヘキサンジアミン、Ｎ，Ｎ’−ジサリチリデンエチレンジアミン、Ｎ，Ｎ’−ビス（ジメチルサリチリデン）エチレンジアミン、Ｎ，Ｎ’−ビス（ジメチルサリチリデン）エチレンテトラミン、サリチルアルドキシム等の金属不活性化剤；リン酸アミド、アミノアルカン類、アルキルアミンリン酸エステル等の清浄剤；氷結防止剤、腐食防止剤、微生物殺菌剤、帯電防止剤、潤滑性付与剤、流動性向上剤、染料等を適宜添加することができる。
【００３７】
本発明の燃料油添加剤又は燃料油添加剤組成物が添加される燃料油基油は例えば、ガソリン、ジェット燃料、軽油、灯油、重油等が挙げられるが、ガソリン又は軽油に添加されるのが好ましい。特に自動車用ガソリン燃料や自動車用ディーゼル燃料（軽油）へ添加した場合に優れたクリーン・アップ性能を発揮する。
【００３８】
【実施例】
以下、実施例により本発明を更に具体的に説明する。尚、以下の実施例中、部及び％は特に記載がない限り重量基準である。
試験に使用した各成分は以下のとおり。尚、ＥＯはオキシエチレン基、ＰＯはオキシプロピレン基、ＢＯはオキシブチレン基の略である。又、オキシアルキレン鎖の重合形態はＡ−３を除いて全てブロック共重合である。
【００３９】
＜（Ａ）成分＞
（Ａ−１）
ＨＯ−(ＥＯ)₂(ＰＯ)₁₀(ＥＯ)₂−Ｈ
（Ａ−２）
ＨＯ−(ＥＯ)₁(ＢＯ)₆(ＥＯ)₁−Ｈ
（Ａ−３）
ＨＯ−(ＥＯ)₂(ＡＯ)₈(ＥＯ)₂−Ｈ
（ＡＯはＥＯ、ＰＯ及びＢＯのランダム共重合により形成されたオキシアルキレン基、平均分子量は約１,２００）
【００４０】
（Ａ−４）
【化１５】

【００４１】
（Ａ−５）
【化１６】

【００４２】
（Ａ−６）
【化１７】

（ジグリセリンＰＯ１モルＥＯ１モル付加物）
【００４３】
（Ａ−７）
【化１８】

【００４４】
（Ａ−８）
【化１９】

【００４５】
＜（Ｂ）成分＞
（Ｂ−１）
【化２０】

（Ｒ＝ポリイソブテニル基。化合物の平均分子量１,５００。）
【００４６】
（Ｂ−２）
【化２１】

（Ｒ＝ポリイソブテニル基。化合物の平均分子量２,５００。）
（Ｂ−３）
Ｒ−ＮＨ−ＣＨ₂ＣＨ₂−ＮＨ₂ （Ｒ＝ポリイソブテニル基）
【００４７】
（Ｂ−４）
【化２２】

【００４８】
（Ｂ−５）
【化２３】

（ｎ＝１〜２）
【００４９】
＜（Ｃ）成分＞
（Ｃ−１）
ＨＯ−(ＰＯ)₁₀−Ｈ
（Ｃ−２）
ＲＯ−(ＰＯ)₁₃−Ｈ （Ｒ＝ノニルフェニル基）
（Ｃ−３）
ＲＯ−(ＢＯ)₁₇−Ｈ （Ｒ＝ノニルフェニル基）
【００５０】
上記の試料を用いて以下の試験を行った。
（実施例１）
２５ミリリットル入りのステンレスのシャーレに鉱油を１ｇ入れた。２００℃の恒温槽に放置して鉱油を固化させ、デポジットとした。その後、上記シャーレを、本発明及び比較の各成分を添加したレギュラーガソリンにシャーレごと入れ、室温で放置し、８０時間後のデポジットの減少量を測定した。
【００５１】
【表１】

【００５２】
【発明の効果】
本発明は、新規な燃料油添加剤を提供したことにある。本発明によれば、スラッジやデポジットを分散させ清浄に保ち、燃料の燃焼と共に速やかに分解し燃焼させる機能に優れるばかりでなく、既に沈着したデポジットやラッカーを除去する性能に優れる。これは、構造の末端にオキシエチレン基を有するポリエーテルポリオールからなる本発明の燃料油添加剤特有の効果である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a fuel oil additive.
[0002]
[Prior art]
Currently, the situation surrounding automobiles is becoming stricter, such as fuel efficiency regulations and exhaust gas regulations. This is due to environmental issues such as global warming, air pollution, and acid rain, and the protection of resources from concerns about the limited exhaustion of petroleum energy.
For example, cleanliness has been required for an intake valve and an intake port of an internal combustion engine, but in recent years, in addition to this, reduction of the deposit in the combustion chamber has been required. The background is that high performance internal combustion engines are becoming more sensitive to deposits. When an internal combustion engine is operated, deposits and sludge derived from lubricating oil, fuel, additives contained therein, and the like are generated. Deposits generated in the exhalation valve and the exhalation port cause a decrease in the output of the internal combustion engine, a deterioration in the drivability of a vehicle equipped with an internal combustion engine such as an automobile, and an increase in exhaust gas. In addition, deposits such as sludge and deposits in the combustion chamber cause knocking, leading to deterioration in operability, fuel consumption, and exhaust gas.
[0003]
As described above, when sludge or deposit is generated in the fuel system or combustion chamber of the internal combustion engine, the function of the internal combustion engine is deteriorated and the exhaust gas is also adversely affected. In order to solve these problems, fuel oil additives have been developed. For example, Japanese Patent Laid-Open No. 3-229797 proposes a fuel oil additive excellent in cleanliness using an amino ether compound obtained by aminopropylating an alkylene oxide adduct such as nonylphenol. Japanese Patent Application Laid-Open No. 8-12983 also discloses a gasoline composition using an amino ether compound. Japanese Patent Laid-Open No. 5-117671 discloses a gasoline additive composition containing mono- or bissuccinimide and a polyoxyalkylene glycol having a molecular weight of 500 to 5,000 or an ether thereof.
[0004]
[Problems to be solved by the invention]
However, the fuel oil additive disclosed in the above prior art was excellent in dispersibility and cleanliness such as sludge and deposit, but there was a problem in the performance of removing deposits already deposited in the combustion chamber. there were. Conventional fuel oil additives have been required to disperse sludge and deposits and keep them clean (keep clean performance), and to have an excellent function of quickly decomposing and burning along with fuel combustion. The ability to remove deposits and lacquers already deposited (clean up performance) is also being demanded.
Accordingly, an object of the present invention is to provide a fuel oil additive and a fuel oil additive composition excellent in performance for removing deposits and lacquers that have already been deposited.
[0005]
[Means for Solving the Problems]
That is, the present invention provides the following general formula (1)
[Chemical 3]
R- {O- (R'-O) m - (CH 2 CH 2 O) n -H} k (1)
[Wherein, R represents a polyol residue represented by R— (OH) _k , R ′ represents one type of hydrocarbon group (excluding ethylene group) or two or more types of hydrocarbon groups, Represents a number of 2 or more, and m and n represent a number of 1 or more. ]
The fuel oil additive which consists of polyether polyol represented by these.
Moreover, this invention is a fuel oil additive composition containing the compound which contains the polyether polyol represented by General formula (1) as (A) component, and a basic nitrogen atom as (B) component. In addition, the present invention provides the polyether polyol represented by the general formula (1) as the component (A) and the following general formula (2) as the component (C).
[Formula 4]
R ¹ O— (R ² —O) _p —H (2)
(In the formula, R ¹ represents a hydrogen atom or a hydrocarbon group, R ² represents a hydrocarbon group, and p represents a number of 1 or more.)
The fuel oil additive composition containing the compound represented by these. Moreover, this invention is a fuel oil composition which contains said fuel oil additive or fuel oil additive composition in a fuel oil base oil.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
In the general formula (1), R is a residue of a k-valent polyol represented by R— (OH) _k . Examples of the polyol include divalent to octavalent alcohols and divalent phenols.
[0007]
Examples of the dihydric alcohol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,2-butanediol, neopentyl glycol, 1,6-hexanediol, 1,2-octanediol, sorbite, and hydrogenated bisphenol. A, hydrogenated bisphenol and the like. Examples of the divalent phenol include catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, and the like.
[0008]
Examples of the trihydric alcohol include glycerin, trioxyisobutane, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2, 3,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol 2,4-dimethyl-2,3,4-pentanetriol, pentamethylglycerin, pentaglycerin, 1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylolethane, trimethylolpropane, etc. Can be mentioned.
[0009]
Examples of the tetrahydric alcohol include pentaerythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, 1,3, 4,5-hexanetetrol, diglycerin, sorbitan, N, N, N ′, N′-tetrakis (2-hydroxybutyl) ethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine , N, N, N ′, N′-tetrakis (hydroxyethyl) ethylenediamine and the like.
[0010]
Examples of pentahydric alcohols include adonitol, arabitol, xylitol, trigreserin and the like. Examples of the hexavalent alcohol include dipentaerythritol, sorbitol, mannitol, idiitol, inositol, dulcitol, talose, allose, and the like. Examples of the octahydric alcohol include sucrose. Examples of other trihydric or higher alcohols include polyglycerin.
[0011]
Among these polyols, ethylene glycol, propylene glycol, 1,4-butanediol, 1,2-butanediol, neopentyl glycol, 1,6-hexanediol, , 2-octanediol, sorbite, bisphenol A, (poly) glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitan, N, N, N ′, N′-tetrakis (2-hydroxybutyl) ethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N ′, N′-tetrakis (hydroxyethyl) ethylenediamine, dipentaerythritol, sorbitol and the like.
[0012]
R ′ represents a hydrocarbon group, which may be one type or two or more types of hydrocarbon groups, but when R ′ is one type of hydrocarbon group, it must not be an ethylene group. R ′ is preferably an alkylene group having 2 to 4 carbon atoms, more preferably a propylene group or a butylene group. When R ′ is two or more types of hydrocarbon groups, one type is preferably a propylene group or a butylene group.
[0013]
The part of (R′—O) _{m in} the general formula (1) can be formed by addition polymerization of alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide or styrene oxide. In addition, when the portion of (R′—O) _m is two or more kinds of oxyalkylene groups or oxystyrene groups, the polymerization form such as oxide to be copolymerized is not particularly limited, and random copolymer, block copolymer or random / Block copolymerization may be used. The degree of polymerization m is a number of 1 or more, preferably 1 to 50, more preferably 1 to 30, and still more preferably 2 to 15.
[0014]
Further, if the degree of polymerization of the oxyethylene group in the (R′-O) _m portion is too large, the solubility in the fuel oil may decrease, so that the oxyethylene group in the (R′-O) _m portion may decrease. The proportion is preferably 60 mol% or less, more preferably 50 mol% or less, and most preferably 40 mol% or less.
[0015]
Moreover, the added mole number n of the oxyethylene group located at the terminal of the general formula (1) represents a number of 1 or more, preferably 1 to 10, more preferably 1 to 5.
[0016]
The method for producing the polyether polyol represented by the general formula (1) is not particularly limited and may be a known method. Usually, an intermediate is obtained by subjecting a polyol represented by R— (OH) _k to addition polymerization of an alkylene oxide or the like under an alkali catalyst.
R- {O- (R'-O) _m- H} _k
Can be obtained by adding ethylene oxide under the same conditions.
[0017]
The molecular weight of the polyether polyol represented by the general formula (1) is not particularly limited. However, if the molecular weight is too large, the polyether polyol represented by the general formula (1) itself may become sludge. On the other hand, in order to increase the permeability to the deposit, it is preferable to suppress the molecular weight to some extent. The molecular weight of the polyether polyol represented by the general formula (1) is preferably 150 to 5,000, more preferably 150 to 2,000, and most preferably 200 to 1,500.
[0018]
The addition amount of the fuel oil additive represented by the general formula (1) is not particularly limited, but is preferably 1 to 5,000 ppm, more preferably 1 to 3,000 ppm, still more preferably 10 to 1 with respect to the fuel oil. About 1,000 ppm.
[0019]
Compared with the conventionally proposed nonylphenol propylene oxide adduct, higher alcohol propylene oxide adduct, polypropylene glycol, etc., the fuel oil additive represented by the general formula (1) removes deposits already deposited in the combustion chamber. Excellent performance. Such an effect is an effect peculiar to the fuel oil additive of the present invention comprising a polyether polyol having an oxyethylene group at the end of the structure.
[0020]
In addition, when the fuel oil additive of the present invention is used in combination with the following compound containing basic nitrogen, it exhibits further excellent deposit removal performance. As the compound containing a basic nitrogen atom, succinimide compounds, benzylamines, amines having an oxyalkylene group, polyalkylenepolyamine derivatives and the like which are usually used as ashless dispersants for lubricating oils are preferable.
[0021]
Examples of succinimide compounds include the following general formula (3)
[Chemical 6]

(Wherein R ³ represents a hydrocarbon group, R ⁴ represents an alkylene group, and m ¹ represents a number of 1 or more. R ³ is preferably an olefin oligomer group having a molecular weight of about 500 to 5,000, more preferably Represents a polyisobutenyl group, R ⁴ preferably represents an ethylene group or a propylene group, and m ¹ preferably represents a number of about 1 to 10).
The following general formula (4)
[Chemical 7]

(Wherein R ⁵ and R ⁶ represent a hydrocarbon group, R ⁷ represents an alkylene group, m ² represents 0 or a number of 1 or more, and R ⁵ and R ⁶ preferably have a molecular weight of 500 to 5,000. the degree of olefin oligomers group, more preferably represents a polyisobutenyl group, R7 preferably represents an ethylene group or a propylene group, succinate diimide represented by) represents the number of m ² is preferably about 0 or 1 to 10.;
The following general formula (5)
[Chemical 8]

(Wherein R ⁸ and R ⁹ represent a hydrocarbon group, AO ¹ represents an oxyalkylene group, and n ¹ represents a number of 1 or more. R ⁸ is preferably an olefin oligomer having a molecular weight of about 500 to 5,000. A polyisobutenyl group, more preferably a polyisobutenyl group, R ⁹ represents an alkyl group or alkenyl group having about 1 to 18 carbon atoms, and n ¹ preferably represents a number of about 1 to 10). Examples include esterified products of oxide adducts, and boronated modified products thereof.
[0022]
Examples of benzylamines include the following general formula (6)
[Chemical 9]

(In the formula, R ¹⁰ represents a hydrocarbon group, R ¹¹ represents an alkylene group, r represents a number of 1 to 4, and m ³ represents a number of 1 or more. R ¹⁰ preferably has a molecular weight of 500 to 5). An olefin oligomer group of about 1,000, more preferably a polyisobutenyl group, R ¹¹ preferably represents an ethylene group or a propylene group, and m ³ preferably represents a number of about 1 to 10.
[0023]
As amines having an oxyalkylene group, the following general formula (7)
[Chemical Formula 10]

(In the formula, R ¹² represents a hydrocarbon group, AO ² represents an oxyalkylene group, m ⁴ and n ² represent a number of 1 or more. R ¹² preferably represents an alkyl group, an alkenyl group or an aryl group. , AO ² preferably represents an oxypropylene group or an oxybutylene group, n ² preferably represents a number of 5 to 50, and m ⁴ preferably represents a number of 1 to 3);
The following general formula (8)
Embedded image

(In the formula, R ¹³ represents a hydrocarbon group, R ¹⁴ represents an alkylene group, AO ³ represents an oxyalkylene group, and n ³ and m ⁵ represent a number of 1 or more. R ¹³ is preferably an aryl group. R ¹⁴ preferably represents an ethylene group or a propylene group, AO ³ preferably represents an oxypropylene group or an oxybutylene group, n ³ preferably represents a number of 5 to 50, and m ⁵ preferably represents 1 Represents a number of ~ 3);
The following general formula (9)
Embedded image

(In the formula, R ¹⁵ represents a hydrocarbon group, AO ⁴ represents an oxyalkylene group, n ⁴ and q represent a number of 1 or more. R ¹⁵ is preferably an alkyl or alkenyl group having 1 to 12 carbon atoms. AO ⁴ preferably represents an oxypropylene group or an oxybutylene group, n ⁴ preferably represents a number of 5 to 50, and q preferably represents a number of 1 to 3). Can be mentioned.
[0024]
Examples of the polyalkylene polyamine derivative include the following general formula (10)
Embedded image

(Wherein R ¹⁶ represents a hydrocarbon group, R ¹⁷ represents an alkylene group, m ⁶ represents a number of 1 or more. R ¹⁶ is preferably an olefin oligomer group having a molecular weight of about 500 to 5,000, more preferably Represents a polyisobutenyl group, R ¹⁷ preferably represents an ethylene group or a propylene group, and m ⁶ preferably represents a number of 1 to 3);
The following general formula (11)
Embedded image

(Wherein R ¹⁸ , R ¹⁹ and R ²¹ represent a hydrocarbon group, R ²⁰ represents an alkylene group, AO ⁵ represents an oxyalkylene group, and m ⁷ and n ⁵ represent a number of 1 or more. R ¹⁸ , R ¹⁹ and R ²¹ preferably represent an alkyl or alkenyl group having 6 to 24 carbon atoms, R ²⁰ preferably represents an ethylene group or a propylene group, and AO ⁵ preferably represents an alkylene group having 2 to 4 carbon atoms. the stands, m ⁷ preferably represents a number of 1 to 3, n ⁵ is preferably include compounds represented by the representative.) the number of 5-50.
[0025]
The amount of the compound containing the basic nitrogen atom is not particularly limited, but is preferably 1 to 5,000 ppm, more preferably 1 to 3,000 ppm, and still more preferably about 10 to 1,000 ppm with respect to the fuel oil. It is.
[0026]
Similarly, when the fuel oil additive of the present invention is used in combination with a compound represented by the following general formula (2), it exhibits further excellent deposit removal performance. In the general formula (2), R ¹ represents a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, and a cycloalkenyl group.
[0027]
Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, isopentyl, secondary pentyl, neopentyl, tertiary pentyl, hexyl, secondary hexyl, heptyl, secondary Heptyl, octyl, 2-ethylhexyl, secondary octyl, nonyl, secondary nonyl, decyl, secondary decyl, undecyl, secondary undecyl, dodecyl, secondary dodecyl, tridecyl, isotridecyl, secondary tridecyl, tetradecyl, secondary tetradecyl, Hexadecyl, secondary hexadecyl, stearyl, icosyl, docosyl, tetracosyl, triacontyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldecyl, 2 Octyldodecyl, 2-decyltetradecyl, 2-dodecyl-hexadecyl, 2-hexadecyl octadecyl, 2-tetradecyl-octadecyl, monomethyl branched - include isostearyl.
[0028]
Examples of the alkenyl group include vinyl, allyl, propenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleyl and the like.
[0029]
Examples of the aryl group include phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonyl Examples include phenyl, decylphenyl, undecylphenyl, dodecylphenyl, phenylphenyl, benzylphenyl, styrenated phenyl, p-cumylphenyl, α-naphthyl, β-naphthyl group and the like.
[0030]
Examples of the cycloalkyl group and cycloalkenyl group include cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl, methylcycloheptenyl group, and the like. Is mentioned.
Among these, R ¹ is preferably an alkyl group, an alkenyl group, or an aryl group.
[0031]
R ² is a hydrocarbon group, preferably an alkylene group having 2 to 4 carbon atoms, and more preferably a propylene group or a butylene group. When R ² is two or more hydrocarbon groups, one is preferably a propylene group or a butylene group. The (R ² —O) _p moiety in the general formula (2) can be obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, and the like. When the (R ² —O) _p moiety is formed by the above method, R ² is determined by the alkylene oxide to be added. The polymerization form of alkylene oxide or the like to be added is not particularly limited, and may be one type of homopolymerization, two or more types of random copolymerization, block copolymerization, random / block copolymerization, or the like. The polymerization degree p is a number of 1 or more, preferably 1 to 100, more preferably 1 to 30, and still more preferably 2 to 15.
[0032]
The manufacturing method of the compound represented by General formula (2) is not specifically limited, What is necessary is just to follow a normal well-known method. Usually, it can be obtained by addition polymerization of an alkylene oxide to an alcohol or phenol represented by R ¹ —OH in the presence of an alkali catalyst.
[0033]
The amount of the compound represented by the general formula (2) is not particularly limited, but is preferably 1 to 5,000 ppm, more preferably 1 to 3,000 ppm, and still more preferably about 10 to 1,000 ppm with respect to the fuel oil. It is.
[0034]
The fuel oil additive or fuel oil additive composition may be added by dissolving or dispersing in a lubricating oil fraction (carrier oil) or an organic solvent. As the carrier oil, a mineral oil or a synthetic oil usually used as a lubricating base oil is preferably used. Mineral oil is separated from natural crude oil, and is produced by appropriately distilling and refining it. Synthetic oils are chemically synthesized lubricating oils such as poly-α-olefins, polyisobutylene (polybutene), diesters, polyol esters, phosphate esters, silicate esters, polyalkylene glycols, polyphenyl ethers, Silicone, a fluorinated compound, alkylbenzene, etc. are mentioned. Among these, poly-α-olefin, polyisobutylene (polybutene), diester, polyol ester, and the like can be given. The carrier oil preferably has a kinematic viscosity at 100 ° C. of about 3 to 35 cSt.
[0035]
Examples of the organic solvent include kerosene, benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitrobenzene, trimethylbenzene, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, cyclopentane, dimethylformamide, dimethylacetamide, Examples include dimethyl ether, diethyl ether, and methyl isobutyl carbitol.
[0036]
The fuel oil additive or fuel oil additive composition of the present invention may be added to the fuel oil together with other components. Examples of other components include anti-knock agents such as tetraethyl lead, tetramethyl lead, and biscyclopentane diphenyl iron; octane number improvers such as methyl tertiary butyl ether and methyl tertiary shear ether; heptyl nitrate, octyl nitrate, cyclohexyl nitrate, etc. Cetane number improver: Prevents surface ignition of tributyl phosphate, trimethyl phosphite, tricresyl phosphate, tricyclohexyl phosphate, cresyl diphenyl phosphate, trimethyl phosphate, methyl phenyl phosphate, 2-ethylhexyl boronate, butyl diisobutyl boronate, etc. Agents; deposit modifiers such as tricresyl phosphate, trimethyl phosphate, tris (chloroethyl) phosphate, polybutene, polypropylene, etc .; N, N′-di Sopropyl-p-phenylenediamine, N, N′-dioctyl-p-phenylenediamine, 2,6-ditertiarybutylphenol, 2,6-ditertiarybutyl-4-methylphenol, 2,4-dimethyl-6-tertiary Antioxidants such as butylphenol; ethylenediamine, N, N′-disalicylidene-1,2-diaminopropane, N, N′-disalicylidene-2-cyclohexanediamine, N, N′-disalicylideneethylenediamine, N, N ′ -Metal deactivators such as bis (dimethylsalicylidene) ethylenediamine, N, N'-bis (dimethylsalicylidene) ethylenetetramine, salicylaldoxime; phosphate amides, aminoalkanes, alkylamine phosphates, etc. Anti-freezing agent, corrosion inhibitor, microbial disinfectant, antistatic agent Lubricity imparting agent, fluidity improver may be added a dye or the like as appropriate.
[0037]
The fuel oil base oil to which the fuel oil additive or fuel oil additive composition of the present invention is added includes, for example, gasoline, jet fuel, light oil, kerosene, heavy oil, etc., but is added to gasoline or light oil. preferable. In particular, when it is added to automobile gasoline fuel or automobile diesel fuel (light oil), it exhibits excellent cleanup performance.
[0038]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. In the following examples, parts and% are based on weight unless otherwise specified.
Each component used in the test is as follows. EO is an abbreviation for oxyethylene group, PO is an oxypropylene group, and BO is an oxybutylene group. Moreover, the polymerization form of the oxyalkylene chain is all block copolymer except A-3.
[0039]
<(A) component>
(A-1)
HO- (EO) ₂ (PO) ₁₀ (EO) ₂ -H
(A-2)
HO- (EO) ₁ (BO) ₆ (EO) ₁ -H
(A-3)
HO- (EO) ₂ (AO) ₈ (EO) _2- H
(AO is an oxyalkylene group formed by random copolymerization of EO, PO and BO, and the average molecular weight is about 1,200)
[0040]
(A-4)
Embedded image

[0041]
(A-5)
Embedded image

[0042]
(A-6)
Embedded image

(Diglycerin PO1 mol EO1 mol adduct)
[0043]
(A-7)
Embedded image

[0044]
(A-8)
Embedded image

[0045]
<(B) component>
(B-1)
Embedded image

(R = polyisobutenyl group. Average molecular weight of the compound is 1,500.)
[0046]
(B-2)
Embedded image

(R = polyisobutenyl group. Average molecular weight of the compound is 2500)
(B-3)
R—NH—CH ₂ CH ₂ —NH ₂ (R = polyisobutenyl group)
[0047]
(B-4)
Embedded image

[0048]
(B-5)
Embedded image

(N = 1-2)
[0049]
<(C) component>
(C-1)
HO- (PO) _10- H
(C-2)
RO- (PO) _13- H (R = nonylphenyl group)
(C-3)
RO- (BO) ₁₇ -H (R = nonylphenyl group)
[0050]
The following tests were performed using the above samples.
Example 1
1 g of mineral oil was put into a stainless steel petri dish containing 25 ml. The mineral oil was solidified by leaving it in a constant temperature bath at 200 ° C. to make a deposit. Thereafter, the petri dish was placed in a regular gasoline to which the present invention and comparative components were added together with the petri dish and allowed to stand at room temperature, and the amount of deposit reduction after 80 hours was measured.
[0051]
[Table 1]

[0052]
【The invention's effect】
The present invention provides a novel fuel oil additive. According to the present invention, not only the sludge and deposit are dispersed and kept clean, but also excellent in the function of quickly decomposing and burning with the combustion of fuel, it is excellent in the performance of removing deposited and lacquer that has already been deposited. This is an effect peculiar to the fuel oil additive of the present invention comprising a polyether polyol having an oxyethylene group at the end of the structure.

Claims (6)

The following general formula (1)

[Wherein, R represents a polyol residue represented by R— (OH) _k , R ′ represents one type of hydrocarbon group (excluding ethylene group) or two or more types of hydrocarbon groups, Represents a number of 2 or more, and m and n represent a number of 1 or more. ]
A fuel oil additive comprising a polyether polyol represented by: The fuel oil additive according to claim 1, wherein R 'is an alkylene group having 2 to 4 carbon atoms. The fuel oil additive according to claim 1 or 2, wherein the polyether polyol represented by the general formula (1) has a molecular weight of 150 to 5,000. A fuel oil additive composition comprising a polyether polyol represented by the general formula (1) as the component (A) and a compound containing a basic nitrogen atom as the component (B). As the component (A), the polyether polyol represented by the general formula (1) and the following general formula (2) as the component (C)

(In the formula, R ¹ represents a hydrogen atom or a hydrocarbon group, R ² represents a hydrocarbon group, and p represents a number of 1 or more.)
The fuel oil additive composition containing the compound represented by these. A fuel oil composition comprising the fuel oil base oil containing the fuel oil additive or fuel oil additive composition according to any one of claims 1 to 5.