JP2004510018A - How to operate an internal combustion engine - Google Patents

Abstract

A method of operating a camless internal combustion engine, comprising: (A) operating the engine using a normally liquid or gaseous fuel composition; and (B) A) lubricating the engine using a low phosphorus or phosphorus-free lubricating oil composition, wherein the low phosphorus or phosphorus-free lubricating oil composition optionally comprises a metal and phosphorus A pressure additive, with the proviso that the amount of phosphorus contributed by the extreme pressure additive to the low phosphorus or phosphorus free lubricating oil composition does not exceed about 0.08% by weight.

Description

１実施形態では、この置換基は、高メチルビニリデン含量、すなわち、少なくとも約７０％メチルビニリデン含量、１実施形態では、少なくとも約８０％のメチルビニリデン含量を有するポリイソブテンからに誘導した基である。適当な高メチルビニリデンポリイソブテンには、三フッ化ホウ素触媒を使用して調製されたものが挙げられる。このようなポリイソブテン（ここで、そのメチルビニリデン異性体は、高い割合の全オレフィン組成を含有する）の調製は、米国特許第４，１５２，４９９号および第４，６０５，８０８号で記述されており、各開示内容は、本明細書中で参考として援用されている。
【００７９】
１実施形態では、このカルボン酸アシル化剤は、炭化水素置換コハク酸またはその無水物である。この置換コハク酸またはその無水物は、炭化水素ベースの置換基およびコハク酸基からなり、ここで、この置換基は、ポリアルケンから誘導され、この酸またはその無水物は、置換基の各当量重量に対して、その構造内に、平均して、少なくとも約０．９個のコハク酸基、１実施形態では、約０．９個〜約２．５個のコハク酸基が存在することにより、特徴づけられる。このポリアルケンは、一般に、少なくとも約７００の（Ｍｎ）、１実施形態では、約７００〜約２０００の（Ｍｎ）、１実施形態では、約９００〜約１８００の（Ｍｎ）を有する。その重量平均分子量（Ｍｗ）と（Ｍｎ）との間の比（すなわち、Ｍｗ／Ｍｎ）は、約１〜約１０、または約１．５〜約５の範囲であり得る。１実施形態では、このポリアルケンは、約２．５〜約５のＭｗ／Ｍｎ値を有する。本発明の目的上、置換基の当量重量数は、この置換コハク酸中に存在する置換基の全重量を、置換基が誘導されるポリアルケンのＭｎ値で割ることにより得られる商に相当する数値であると考えられる。それゆえ、置換コハク酸が、置換基の全重量４０，０００、およびその置換基が誘導されるポリアルケンのＭｎ値２０００により特徴づけられるなら、この置換コハク酸アシル化剤は、置換基の全当量重量２０（４０，０００／２０００＝２０）により特徴づけられる。
【００８０】
１実施形態では、このカルボン酸アシル化剤は、置換コハク酸またはその無水物であり、この置換コハク酸またはその無水物は、置換基およびコハク酸基からなり、ここで、この置換基はポリブテンから誘導され、このポリブテンでは、ブテンから誘導される全単位の少なくとも約５０％は、イソブチレンから誘導される。このポリブテンは、約１５００〜約２０００のＭｎ値、および約３〜約４のＭｗ／Ｍｎ値により、特徴づけられる。これらの酸またはその無水物は、その構造内に、この置換基の各当量重量に対し、平均して、約１．５個〜約２．５個のコハク酸基が存在することにより、特徴づけられる。
【００８１】
１実施形態では、このカルボン酸は、少なくとも１種の置換コハク酸またはその無水物であり、この置換コハク酸またはその無水物は、置換基およびコハク酸基からなり、ここで、この置換基はポリブテンから誘導され、このポリブテンでは、ブテンから誘導される全単位の少なくとも約５０％は、イソブチレンから誘導される。このポリブテンは、約８００〜約１２００のＭｎ値、および約２〜約３のＭｗ／Ｍｎ値を有する。これらの酸またはその無水物は、その構造内に、この置換基の各当量重量に対し、平均して、約０．９個〜約１．２個のコハク酸基が存在することにより、特徴づけられる。
【００８２】
このアミノ化合物は、その構造内に、少なくとも１個のＮＨ＜基が存在することにより特徴づけられ、モノアミンまたはポリアミンであり得る。２種またはそれ以上のアミノ化合物の混合物は、１種またはそれ以上のアシル化試薬との反応に使用できる。１実施形態では、このアミノ化合物は、少なくとも１個の第一級アミノ基（すなわち、−ＮＨ_２）を含有し、さらに好ましくは、このアミンは、ポリアミンであり、特に、少なくとも２個の−ＮＨ−基を含有するポリアミンであり、そのいずれかまたは両方は、第一級アミンまたは第二級アミンである。このアミンは、脂肪族アミン、環状脂肪族アミン、芳香族アミンまたは複素環アミンであり得る。
【００８３】
有用なアミンのうちには、ポリアルキレンポリアミンを含めたアルキレンポリアミンがある。このアルキレンポリアミンには、次式に一致するものが挙げられる：
【００８４】
【化３】

ここで、ｎは１〜約１０である；各Ｒは、別個に、水素原子、ヒドロカルビル基またはヒドロキシ置換ヒドロカルビル基またはアミン置換ヒドロカルビル基（これらは、約３０個までの原子を有する）であり、または異なる窒素原子上の２個のＲ基は、共に結合して、Ｕ基を形成できるが、但し、少なくとも１個のＲ基は水素原子であり、Ｕは、約２個〜１０個の炭素原子を有するアルキレン基である。好ましくは、Ｕは、エチレンまたはプロピレンであり得る。各Ｒが、水素またはアミノ置換ヒドロカルビル基であるアルキレンポリアミンは、エチレンポリアミンおよびエチレンポリアミン混合物と共に、有用である。通常、ｎは、約２〜約７の平均値を有する。このようなアルキレンポリアミンには、メチレンポリアミン、エチレンポリアミン、プロピレンポリアミン、ブチレンポリアミン、ペンチレンポリアミン、ヘキシレンポリアミン、ヘプチレンポリアミンなどが挙げられる。このようなアミンのより高級な同族体、および関連したアミノアルキル置換ピペラジンもまた、挙げられる。
【００８５】
有用なアルキレンポリアミンには、エチレンジアミン、トリエチレンテトラミン、プロピレンジアミン、トリメチレンジアミン、ヘキサメチレンジアミン、デカメチレンジアミン、オクタメチレンジアミン、ジ（ヘプタメチレン）トリアミン、トリプロピレンテトラミン、テトラエチレンペンタミン、トリメチレンジアミン、ペンタエチレンヘキサミン、ジ（トリメチレン）トリアミン、Ｎ−（２−アミノエチル）ピペラジン、１，４−ビス（２−アミノエチル）ピペラジンなどが挙げられる。２種またはそれ以上の上記アルキレンアミンの縮合により得られるより高級な同族体は、上記ポリアミンのいずれかの２種以上の混合物と同様に、有用である。
【００８６】
エチレンポリアミン（例えば、上で述べたもの）は、価格および有効性のために、特に有用である。このようなポリアミンは、「Ｄｉａｍｉｎｅｓ　ａｎｄ　Ｈｉｇｈｅｒ　Ａｍｉｎｅｓ」の表題で、Ｔｈｅ　Ｅｎｃｙｃｌｏｐｅｄｉａ　ｏｆ　Ｃｈｅｍｉｃａｌ　Ｔｅｃｈｎｏｌｏｇｙ（第２版、ＫｉｒｋおよびＯｔｈｍｅｒ、７巻、２７〜３９ページ、Ｉｎｔｅｒｓｃｉｅｎｃｅ　Ｐｕｂｌｉｓｈｅｒｓ、Ｄｉｖｉｓｉｏｎ　ｏｆ　Ｊｏｈｎ　Ｗｉｌｅｙ　ａｎｄ　Ｓｏｎｓ、１９６５）に詳細に記述され、これらの内容は、有用なポリアミンの開示について、本明細書中で参考として援用されている。このような化合物は、アルキレンクロライドとアンモニアとの反応により、またはエチレンイミンと開環試薬（例えば、アンモニアなど）との反応により、最も都合よく調製される。これらの反応により、アルキレンポリアミンの１種の錯体混合物（これには、ピペラジンのような環状の縮合生成物が含まれる）が生成する。
【００８７】
他の有用なタイプのポリアミン混合物には、上記ポリアミン混合物のストリッピングにより得られるものがある。この場合には、低分子量ポリアミンおよび揮発性の不純物は、アルキレンポリアミン混合物から除去され、しばしば「ポリアミンボトムス」と呼ばれる残留物が残る。一般に、アルキレンポリアミンボトムスは、約２００℃以下で沸騰する物質を、２重量％より少ない量、通常は１重量％より少ない量で有するものとして、特徴づけられ得る。エチレンポリアミンボトムス（これは、容易に入手可能であり、極めて有用であることが分かっている）の場合には、このボトムスは、全体で約２重量％より少ない量のジエチレントリアミン（ＤＥＴＡ）またはトリエチレンテトラミン（ＴＥＴＡ）を含有する。Ｄｏｗ　Ｃｈｅｍｉｃａｌ　Ｃｏｍｐａｎｙ（Ｆｒｅｅｐｏｒｔ、Ｔｅｘａｓ）から得られるこのようなエチレンポリアミンボトムスの典型的な試料（これは、「Ｅ−１００」と呼ばれている）は、１５．６℃で１．０１６８の比重、３３．１５重量％の窒素割合、および４０℃で１２１センチストークスの粘度を示した。このような試料のガスクロマトグラフィー分析から、これが、約０．９３％の「ライトエンド」（ほとんどは、ＤＥＴＡである）、０．７２％のＴＥＴＡ、２１．７４％のテトラエチレンペンタミン、および７６．６１％およびそれ以上のペンタエチレンヘキサミンを含有することが示された（重量基準）。これらのアルキレンポリアミンボトムスには、環状の縮合生成物（例えば、ピペラジン）、およびジエチレントリアミンやトリエチレンテトラミンなどのより高級な同族体が挙げられる。
【００８８】
これらのアルキレンポリアミンボトムスは、単独で、このアシル化剤と反応でき（この場合、このアミノ反応物は、本質的に、アルキレンポリアミンボトムスからなる）、またはそれらは、他のアミンおよびポリアミンと共に使用でき、またはアルコールまたはそれらの混合物と共に使用できる。後者の場合には、少なくとも１種のアミノ反応物は、アルキレンポリアミンボトムスを含有する。
【００８９】
他のポリアミンは、例えば、米国特許第３，２１９，６６６号および第４，２３４，４３５号に記述され、これらの特許の内容は、上記アシル化剤と反応して有用なアシル化窒素含有化合物を形成できるアミンの開示について、本明細書中で参考として援用されている。
【００９０】
１実施形態では、このアミンはヒドロキシアミンであり得る。典型的には、このヒドロキシアミンは、第一級、第二級または第三級のアルカノールアミンまたはそれらの混合物である。このようなアミンは、次式により表わされ得る：
【００９１】
【化４】

ここで、各Ｒは、別個に、１個〜約８個の炭素原子を有するヒドロカルビル基、または２個〜約８個の炭素原子、好ましくは、１個〜約４個の炭素原子を有するヒドロキシヒドロカルビル基であり、そしてＲ’は、約２個〜約１８個の炭素原子、好ましくは、２個〜約４個の炭素原子を有する二価ヒドロカルビル基である。このような式の−Ｒ’−ＯＨ基は、ヒドロキシヒドロカルビル基を表わす。Ｒ’は、非環式基、脂環族基または芳香族基であり得る。典型的には、Ｒ’は、非環式の直鎖または分枝鎖アルキレン基（例えば、エチレン基、１，２−プロピレン基、１，２−ブチレン基、１，２−オクタデシレン基など）である。同じ分子内に２個のＲ基が存在する場合、それらは、直接の炭素−炭素結合により、またはヘテロ原子（例えば、酸素または窒素）を介して結合し、五員環構造、六員環構造、七員環構造または八員環構造を形成できる。このような複素環アミンの例には、Ｎ−（ヒドロキシル低級アルキル）−モルホリン、−チオモルホリン、−ピペリジン、−オキサゾリジン、−チアゾリジンなどが挙げられる。しかしながら、典型的には、各Ｒ’は、別個に、メチル基、エチル基、プロピル基、ブチル基、ペンチル基またはヘキシル基である。
【００９２】
これらのアルカノールアミンの例には、モノ−、ジ−およびトリエタノールアミン、ジエチルエタノールアミン、エチルエタノールアミン、ブチルジエタノールアミンなどが挙げられる。
【００９３】
このヒドロキシアミンはまた、エーテル−Ｎ−（ヒドロキシヒドロカルビル）アミンであり得る。これらは、上記ヒドロキシアミンのヒドロキシポリ（ヒドロカルビルオキシ）類似物（これらの類似物には、ヒドロキシル置換されたオキシアルキレン類似物も挙げられる）である。このようなＮ−（ヒドロキシヒドロカルビル）アミンは、エポキシドと上記アミンとの反応により、都合よく調製され、そして次式により表わされる：
【００９４】
【化５】

ここで、ｘは、約２〜約１５の数であり、そしてＲおよびＲ’は、上で記述のものと同じである。Ｒはまた、ヒドロキシポリ（ヒドロカルビルオキシ）基であり得る。
【００９５】
このアシル化窒素含有化合物には、アミン塩、アミド、イミド、アミジン、アミジン酸、アミジン酸塩およびイミダゾリンだけでなく、それらの混合物が挙げられる。このアシル化剤およびアミノ化合物から、このアシル化窒素含有化合物を調製するためには、１種またはそれ以上のアシル化剤および１種またはそれ以上のアミノ化合物は、必要に応じて、実質的に不活性で通常液状の有機液体溶媒／希釈剤の存在下にて、約８０℃から、これらの反応物またはカルボン酸誘導体のいずれかの分解点までの温度であるが、通常、約１００℃から約３００℃までの範囲の温度（但し、３００℃は、この分解点を越えない）で、加熱される。約１２５℃〜約２５０℃の温度が、通常、使用される。このアシル化剤およびアミノ化合物は、このアシル化剤１当量あたり、約１／２当量から約２モルまでのアミノ化合物を提供するのに充分な量で、反応される。
【００９６】
多くの特許は、有用なアシル化窒素含有化合物を記述しており、これには、米国特許第３，１７２，８９２号；第３，２１９，６６６号；第３，２７２，７４６号；第３，３１０，４９２号；第３，３４１，５４２号；第３，４４４，１７０号；第３，４５５，８３１号；第３，４５５，８３２号；第３，５７６，７４３号；第３，６３０，９０４号；第３，６３２，５１１号；第３，８０４，７６３号；および第４，２３４，４３５号が含まれる。この種類の典型的なアシル化窒素含有化合物には、ポリ（イソブテン）置換無水コハク酸アシル化剤（例えば、無水物、酸、エステルなどであり、ここで、このポリ（イソブテン）置換基は、約５０個と約４００個の間の炭素原子を有する）と、エチレンポリアミンの混合物（これは、エチレンポリアミン１個あたり約３個〜約７個のアミノ窒素原子、および約１個〜約６個のエチレン単位を有し、アンモニアと塩化エチレンとの縮合により製造される）とを反応させることにより製造したものがある。上述の米国特許の内容は、アシル化アミノ化合物およびそれらの調製方法の開示について、本明細書中で参考として援用されている。
【００９７】
このクラスに属する他の形のアシル化窒素化合物には、カルボン酸アシル化剤とポリアミンとを反応させることより製造したものがあり、ここで、このポリアミンは、ヒドロキシ物質をアミンで縮合することにより製造した生成物である。これらの化合物は、米国特許第５，０５３，１５２号に記述され、その内容は、このような化合物の開示について、本明細書中で参考として援用されている。
【００９８】
このクラスに属する他の形のアシル化窒素化合物には、上記アルキレンアミンと、上記置換コハク酸またはその無水物、および２個〜約２２個の炭素原子を有する脂肪族モノカルボン酸とを反応させることにより製造したものがある。これらのタイプのアシル化窒素化合物では、コハク酸とモノカルボン酸とのモル比は、約１：０．１〜約１：１の範囲である。このモノカルボン酸の典型には、ギ酸、酢酸、ドデカン酸、ブタン酸、オレイン酸、ステアリン酸、ステアリン酸異性体の市販混合物（これは、イソステアリン酸として知られている）、トール油酸などがある。このような物質は、米国特許第３，２１６，９３６号および第３，２５０，７１５号にさらに詳しく記述されており、この点について、これらの開示は、本明細書中で参考として援用されている。
【００９９】
本発明の組成物を製造する際に有用なさらに他の種類のアシル化窒素化合物には、約１２個〜３０個の炭素原子を有する脂肪モノカルボン酸および上記アルキレンアミン（典型的には、２個〜８個のアミノ基を含有するエチレンポリアミン、プロピレンポリアミンまたはトリメチレンポリアミンおよびそれらの混合物）との反応生成物がある。この脂肪モノカルボン酸は、一般に、１２個〜３０個の炭素原子を含有する直鎖および分枝鎖の脂肪カルボン酸の混合物である。広く用いられるタイプのアシル化窒素化合物は、上記アルキレンポリアミンと、５〜約３０モル％の直鎖脂肪酸および約７０〜約９５モル％の分枝鎖脂肪酸を有する脂肪酸混合物とを反応させることにより、製造される。この市販混合物には、イソステアリン酸として市場で広く知られているものがある。これらの混合物は、米国特許第２，８１２，３４２号および第３，２６０，６７１号に記述のように、不飽和脂肪酸の二量化に由来する副生成物として、製造される。
【０１００】
この分枝鎖脂肪酸には、また、その分枝が、事実上、アルキルではないもの（例えば、フェニルステアリン酸およびシクロヘキシルステアリン酸およびクロロステアリン酸に存在するもの）が挙げられる。分枝鎖脂肪カルボン酸／アルキレンポリアミン生成物は、当該技術分野で広く記述されている。例えば、米国特許第３，１１０，６７３号；第３，２５１，８５３号；第３，３２６，８０１号；第３，３３７，４５９号；第３，４０５，０６４号；第３，４２９，６７４号；第３，４６８，６３９号；第３，８５７，７９１号を参照のこと。これらの特許の内容は、潤滑油調合物に用いる脂肪酸／ポリアミン縮合物の開示について、本明細書中で参考として援用されている。
【０１０１】
１実施形態では、本発明の低リンまたは無リン潤滑油組成物は、約１０ｐｐｍ以下、１実施形態では、約７ｐｐｍ以下、１実施形態では、約５ｐｐｍ以下の塩素レベルにより、特徴付けられる。こうするには、このアシル化窒素含有化合物は、塩素を含ませないか、またはこの潤滑油組成物にこのような化合物を添加すると上記の塩素レベルを有する潤滑油組成物が形成されるような低塩素レベルを含有させる必要がある。１実施形態では、このアシル化窒素含有化合物は、約５０ｐｐｍ以下、１実施形態では、約２５ｐｐｍ以下、１実施形態では、約１０ｐｐｍ以下の塩素含量を有する。１実施形態では、このアシル化窒素含有化合物は、塩素を含まない。
【０１０２】
このアシル化窒素含有化合物は、典型的には、約１重量％〜約２５重量％の範囲、１実施形態では、約５重量％〜約１５重量％の範囲の濃度で、この低リンまたは無リン潤滑油組成物中で使用される。これらの化合物は、この潤滑油組成物に直接添加できる。１実施形態では、しかしながら、それらは、実質的に不活性で通常液状の有機希釈剤（例えば、鉱油、ナフサ、ベンゼン、トルエンまたはキシレン）で希釈されて、添加剤濃縮物を形成する。これらの濃縮物は、通常、約１重量％〜約９９重量％、１実施形態では、約１０重量％〜約９０重量％の希釈剤を含有する。
【０１０３】
上で述べたように、この低リンまたは無リン潤滑油組成物が非消耗潤滑油であるとき、必要に応じて、少量の１種またはそれ以上のＥＰ添加剤（これは、金属およびリンから構成される）を含有し得るが、但し、この添加剤により低リンまたは無リン潤滑油組成物に寄与するリンの量は、その低リンまたは無リン潤滑油組成物の約０．０８重量％を超えない。１実施形態では、このリン含量は、約０．０７重量％を超えず、１実施形態では、約０．０６重量％を超えず、１実施形態では、約０．０５重量％を超えず、１実施形態では、約０．０４重量％を超えず、１実施形態では、約０．０３５重量％を超えず、１実施形態では、約０．０３重量％を超えず、１実施形態では、約０．０２５重量％を超えず、１実施形態では、約０．０２重量％を超えず、１実施形態では、約０．０１５重量％を超えず、そして１実施形態では、リン含量は約０．０１重量％を超えない。これらのＥＰ添加剤を製造する際に有用なリン含有酸は、次式により表わされ得る：
【０１０４】
【化６】

ここで、式（Ａ）では、Ｘ^１、Ｘ^２、Ｘ^３およびＸ^４は、別個に、酸素またはイオウであり、ａおよびｂは、別個に、０または１であり、Ｒ^１、Ｒ^２およびＲ^３は、別個に、ヒドロカルビル基であり、そしてＲ^３は、水素であり得る。例証的な例には、以下が挙げられる：ホスフィノジチオ酸ジヒドロカルビル、ホスホノトリチオ酸Ｓ−ヒドロカルビルヒドロカルビル、ホスフィノジチオ酸Ｏ−ヒドロカルビルヒドロカルビル、ホスホロテトラチオ酸Ｓ，Ｓ−ジヒドロカルビル、ホスホロトリチオ酸Ｏ，Ｓ−ジヒドロカルビル、ホスホロジチオ酸Ｏ，Ｏ−ジヒドロカルビルなど。
【０１０５】
有用なリン含有酸は、リンおよびイオウ含有酸である。これらには、以下のような酸が挙げられる：この酸では、式（Ａ）において、Ｘ^３またはＸ^４の少なくとも１個はイオウ、１実施形態では、Ｘ^３およびＸ^４の両方はイオウであり、Ｘ^１またはＸ^２の少なくとも１個は酸素またはイオウ、１実施形態では、Ｘ^１およびＸ^２の両方は酸素であり、そしてａおよびｂは、それぞれ、１である。これらの酸の混合物は、本発明に従って、使用され得る。
【０１０６】
式（Ａ）では、Ｒ^１およびＲ^２は、独立して、好ましくは、アセチレン性不飽和を含有しないヒドロカルビル基であり、通常、エチレン性不飽和も含有しないヒドロカルビル基であり、このヒドロカルビル基は、１実施形態では、約１個〜約５０個の炭素原子、１実施形態では、約１個〜約３０個の炭素原子、１実施形態では、約３個〜約１８個の炭素原子、１実施形態では、約３個〜約８個の炭素原子を有する。各Ｒ^１およびＲ^２は、互いに同じであり得るが、それらは、異なっていてもよく、その一方または両方は、混合物であり得る。Ｒ^１基およびＲ^２基の例には、イソプロピル、ｎ−ブチル、イソブチル、アミル、４−メチル−２−ペンチル、イソオクチル、デシル、ドデシル、テトラデシル、２−ペンテニル、ドデセニル、フェニル、ナフチル、アルキルフェニル、アルキルナフチル、フェニルアルキル、ナフチルアルキル、アルキルフェニルアルキル、アルキルナフチルアルキル、およびそれらの混合物が挙げられる。有用な混合物の特定の例には、例えば、イソプロピル／ｎ−ブチル；イソプロピル／第二級ブチル；イソプロピル／４−メチル−２−ペンチル；イソプロピル／２−エチル−１−ヘキシル；イソプロピル／イソオクチル；イソプロピル／デシル；イソプロピル／ドデシル；およびイソプロピル／トリデシルが挙げられる。
【０１０７】
式（Ａ）では、Ｒ^３は、水素、または１個〜約１２個の炭素原子、１実施形態では、１個〜約４個の炭素原子を有するヒドロカルビル基（例えば、アルキル）であり得る。
【０１０８】
このリン含有酸の金属塩の調製は、その金属または金属酸化物と反応させることにより、行われ得る。この反応を起こすには、これらの２種の反応物を単に混合し加熱するだけで十分であり、得られた生成物は、本発明の目的上、十分に純粋である。典型的には、この塩の形成は、希釈剤（例えば、アルコール、水または希釈油）の存在下にて、実行される。中性塩は、１当量の金属酸化物または水酸化物を１当量の酸と反応させることにより、調製される。塩基性金属塩は、過剰の（１当量より多い）金属酸化物または水酸化物を１当量のホスホロジチオ酸に添加することにより、調製される。
【０１０９】
式（Ａ）で表わされる有用なリン含有酸の金属塩には、第ＩＡ族金属、第ＩＩＡ族金属または第ＩＩＢ族金属、アルミニウム、鉛、スズ、鉄、モリブデン、マンガン、コバルト、ニッケルまたはビスマスを含有する塩が挙げられる。亜鉛は、有用な金属である。これらの塩は、中性塩または塩基性塩であり得る。リン含有酸の有用な金属塩、およびこのような塩の調製方法の例は、先行文献（例えば、米国特許第４，２６３，１５０号；第４，２８９，６３５号；第４，３０８，１５４号；第４，３２２，４７９号；第４，４１７，９９０号；および第４，４６６，８９５号）に見出され、これらの特許の開示内容は、本明細書中で参考として援用されている。これらの塩には、ホスホロジチオ酸の第ＩＩ族金属塩（例えば、ジシクロヘキシルホスホロジチオ酸亜鉛、ジオクチルホスホロジチオ酸亜鉛、ジ（ヘプチルフェニル）ホスホロジチオ酸バリウム、ジノニルホスホロジチオ酸カドミウム、および五硫化リンとイソプロピルアルコールおよびｎ−ヘキシルアルコールの等モル混合物との反応により生成されるホスホロジチオ酸の亜鉛塩）が挙げられる。
【０１１０】
１実施形態では、この低リンまたは無リン潤滑油組成物は、前述のＥＰ添加剤が存在しないことにより、特徴付けられる。
【０１１１】
前述の低リンまたは無リン潤滑油組成物を使用する利点は、これらの潤滑油組成物が従来の潤滑油よりも環境上の観点から簡単に捨て得ることである。これは、これらの潤滑油組成物中のリンおよび金属を含有するＥＰ剤が低レベルであるか、または存在しないことによる。他方、従来の潤滑油組成物は、典型的には、比較的に高い濃度のこのようなＥＰ剤を含有する。
【０１１２】
この低リンまたは無リン潤滑油組成物は、アシル化窒素含有化合物（これは、上で言及した）に加えて、１種またはそれ以上の無灰分型の清浄剤または分散剤を含有し得る。無灰分の清浄剤および分散剤は、その組成に依存して、この分散剤が、燃焼するとすぐに不揮発性物質（例えば、酸化ホウ素または五酸化リン）を生じ得るという事実にもかかわらず、そう呼ばれている；しかしながら、それは、通常、金属を含有せず、従って、燃焼すると、金属を含有する灰を生じることはない。多くのタイプが、当該技術分野で公知であり、それらのいくつかは、本発明の潤滑剤組成物での使用に適している。これらには、以下が挙げられる：
（１）少なくとも約３４個の炭素原子（１実施形態では、少なくとも約５４個の炭素原子）を含有するカルボン酸（またはそれらの誘導体）と、アミンおよびフェノールのような有機ヒドロキシ化合物、ならびに／または塩基性無機物質との反応生成物。これらの「カルボン酸分散剤」の例は、多くの米国特許（米国特許第３，２１９，６６６号；同第４，２３４，４３５号；および同第４，９３８，８８１号を含む）に記述されている。
【０１１３】
（２）比較的高分子量の脂肪族または脂環族ハロゲン化物と、アミン（好ましくはオキシアルキレンポリアミン）との反応生成物。これらは、「アミン分散剤」として特徴づけられ得、それらの例は、例えば、以下の米国特許に記述されている：米国特許第３，２７５，５５４号；同第３，４３８，７５７号；同第３，４５４，５５５号；および同第３，５６５，８０４号。
【０１１４】
（３）アルキルフェノール（ここで、このアルキル基は、少なくとも約３０個の炭素原子を含有する）と、アルデヒド（特に、ホルムアルデヒド）およびアミン（特に、ポリアルキレンポリアミン）との反応生成物。これは、「マンニッヒ分散剤」として特徴づけられ得る。以下の米国特許に記述の物質は、例示である：米国特許第３，６４９，２２９号；同第３，６９７，５７４号；同第３，７２５，２７７号；同第３，７２５，４８０号；同第３，７２６，８８２号；および同第３，９８０，５６９号。
【０１１５】
（４）アミンまたはマンニッヒ分散剤を、以下のような試薬で後処理することにより得られる生成物；尿素、チオ尿素、二硫化炭素、アルデヒド、ケトン、カルボン酸、炭化水素置換の無水コハク酸、ニトリル、エポキシド、ホウ素含有化合物、リン含有化合物またはその類似物。この種の例示の物質は、以下の米国特許に記述されている：米国特許第３，６３９，２４２号；同第３，６４９，２２９号；同第３，６４９，６５９号；同第３，６５８，８３６号；同第３，６９７，５７４号；同第３，７０２，７５７号；同第３，７０３，５３６号；同第３，７０４，３０８号；および同第３，７０８，４２２号。
【０１１６】
（５）油溶性モノマー（例えば、メタクリル酸デシル、ビニルデシルエーテル、および高分子量オレフィン）と、極性置換基を含有するモノマー（例えば、アクリル酸アミノアルキルまたはアクリルアミドおよびポリ（オキシエチレン）置換アクリレート）とのインターポリマー。これらは、「重合体分散剤」として特徴づけられ得、それらの例は、以下の米国特許で開示されている：米国特許第３，３２９，６５８号；同第３，４４９，２５０号；同第３，５１９，５６５号；同第３，６６６，７３０号；同第３，６８７，８４９号；および同第３，７０２，３００号。
【０１１７】
上記の特許は、無灰分散剤の開示に関して、本明細書中で参考として援用されている。
【０１１８】
この低リンまたは無リン潤滑油組成物は、非消耗潤滑油として使用するとき、灰分生成型の１種またはそれ以上の清浄剤または分散剤を含有し得る。それゆえ、この実施形態では、この低リンまたは無リン潤滑油組成物は、低灰分潤滑油組成物である。この灰分生成清浄剤は、アルカリ金属またはアルカリ土類金属と、スルホン酸、カルボン酸、または少なくとも１個の直接の炭素−リン結合により特徴づけられる有機リン含有酸（例えば、オレフィン重合体（例えば、１０００の分子量を有するポリイソブテン）をリン化剤（例えば、三塩化リン、七硫化リン、五硫化リン、三塩化リンおよびイオウ、白リンおよびハロゲン化イオウ、またはホスホロチオ酸クロライド）で処理することにより調製されるもの）との油溶性の中性塩および塩基性塩により例示される。このような酸の最もよく用いられる塩は、ナトリウム塩、カリウム塩、リチウム塩、カルシウム塩、マグネシウム塩、ストロンチウム塩およびバリウム塩である。この低灰分潤滑油組成物中の灰分生成清浄剤または分散剤の濃度は、ＡＳＴＭ　Ｄ８７４−９６の試験手順により測定したとき、約２重量％まで、１実施形態では、約１．５重量％まで、１実施形態では、約１重量％まで、１実施形態では、約０．６重量％までの灰分含量を提供するのに充分な範囲であり得る。
【０１１９】
この低リンまたは無リン潤滑油組成物はまた、当該技術分野で公知の他の潤滑剤添加剤を含有し得る。これらには、例えば、腐食防止剤、酸化防止剤、粘度調節剤、流動点降下剤、摩擦調節剤、流動性調節剤、消泡剤などが挙げられる。
【０１２０】
流動点降下剤は、オイルベース組成物の低温特性を改良するのに使用される。例えば、Ｃ．Ｖ．ＳｍａｌｈｅｅｒおよびＲ．Ｋｅｎｎｅｄｙ　Ｓｍｉｔｈの「Ｌｕｂｒｉｃａｎｔ　Ａｄｄｉｔｉｖｅｓ」（Ｌｅｚｉｕｓ　Ｈｉｌｅｓ　Ｃｏ．発行元、Ｃｌｅｖｅｌａｎｄ、Ｏｈｉｏ、１９６７年）の８ページを参照のこと。有用な流動点降下剤の例には、ポリメタクリレート；ポリアクリレート；ポリアクリルアミド；ハロパラフィンワックスと芳香族化合物との縮合生成物；ビニルカルボキシレート重合体；フマル酸ジアルキル、脂肪酸のビニルエステルおよびアルキルビニルエーテルの三元共重合体がある。流動点降下剤は、米国特許第２，３８７，５０１号；同第２，０１５，７４８号；同第２，６５５，４７９号；同第１，８１５，０２２号；同第２，１９１，４９８号；同第２，６６６，７４６号；同第２，７２１，８７７号；同第２，７２１，８７８号；および同第３，２５０，７１５号に記述され、その内容は、その関連した開示について、本明細書中で参考として援用されている。
【０１２１】
消泡剤は、安定した泡の形成を低減させるかまたは防止するために、用いられる。典型的な消泡剤には、シリコーンまたは有機重合体が挙げられる。他の消泡組成物は、Ｈｅｎｒｙ　Ｔ．Ｋｅｒｎｅｒによる「Ｆｏａｍ　Ｃｏｎｔｒｏｌ　Ａｇｅｎｔｓ」（Ｎｏｙｅｓ　Ｄａｔａ　Ｃｏｒｐｏｒａｔｉｏｎ，１９７６年）の１２５〜１６２頁に記述されている。
【０１２２】
前述の各添加剤は、使用される場合、この潤滑剤に所望の特性を与えるのに機能的に効果的な量で、使用される。それゆえ、例えば、添加剤が腐食防止剤なら、この腐食防止剤の機能的に効果的な量は、その潤滑剤に所望の腐食防止特性を与えるのに十分な量である。一般に、これらの各添加剤の濃度は、使用される場合、この低リンまたは無リン潤滑油組成物の全重量を基準にして、約０．００１重量％〜約２０重量％の範囲、１実施形態では、約０．０１重量％〜約１０重量％の範囲である。
【０１２３】
これらの添加剤は、この低リンまたは無リン潤滑油組成物に直接添加され得る。しかしながら、１実施形態では、これらは、実質的に不活性で通常液状の有機希釈剤（例えば、鉱油、ナフサ、ベンゼン、トルエンまたはキシレン）で希釈されて、添加剤濃縮物を形成する。これらの濃縮物は、通常、このような希釈剤の約１重量％〜約９９重量％、１実施形態では、約１０重量％〜約９０重量％を含有する。１実施形態では、この希釈剤は、無イオウ組成物である。
【０１２４】
（実施例１および２）
使用され得る低リンまたは無リン潤滑油組成物の例を、以下で開示する（ただし、以下の表では、この組成物の成分（消泡剤を除く）に対して提示した全ての数値は、重量％である）。
【０１２５】
【表１】

本発明は、その好ましい実施形態に関連して説明しているものの、それらの種々の変更は、本明細書を読めば、当業者に明らかなことが理解されるべきである。従って、本明細書中で開示の発明は、添付の請求の範囲内の変更を含むべく意図されていることが理解されるべきである。
【図面の簡単な説明】
添付の図面では、同じ部分および機構は、同じ参照番号を有する。
【図１】
図１は、本発明の方法の１実施形態に従って有用なカムレス内燃機関エンジンの概略図であり、このエンジンは、排気ガス後処理装置を備えている。
【図２】
図２は、本発明の方法の別の実施形態に従って有用なカムレス内燃機関エンジンの概略図であり、このエンジンは、排気ガス後処理装置を備えている。
【図３】
図３は、本発明の方法の別の実施形態に従って有用なカムレス内燃機関エンジンの概略図である。[0001]
This application is a continuation-in-part of U.S. Ser. No. 09 / 664,834, filed on Sep. 19, 2000. The disclosure of this prior application is incorporated herein by reference in its entirety.
[0002]
(Technical field)
The invention relates to a method for operating an internal combustion engine. More particularly, the present invention relates to a method of operating a camless internal combustion engine, comprising lubricating the engine using a low phosphorus or phosphorus free lubricating oil composition. In one embodiment, the invention also relates to a method of operating a camless engine that increases the time interval required for the next oil change.
[0003]
(Background of the Invention)
A problem with conventional internal combustion engines equipped with exhaust gas aftertreatment devices (eg, catalytic converters, particulate traps, catalytic traps, etc.) is that the lubricating oil for such engines is not only in the crankcase, but also in high wear areas. (Eg, a valve mechanism). Because these oils are used in high wear areas, they usually contain extreme pressure (EP) agents, and they typically contain metal and phosphorus to be effective. During operation of the engine, these EP agents decompose and the resulting decomposition products eventually enter this after-treatment unit, often causing damage to the unit. Accordingly, the problem is to provide an engine and a lubricant system for the engine that reduces or avoids damage to the exhaust gas aftertreatment device while fully considering the need for anti-wear protection of the engine.
[0004]
Another problem associated with conventional internal combustion engine engines is that blow-by exhaust gas generated in the crankcase of the engine typically contacts this valve mechanism. Blow-by exhaust gas has been found to be a major factor affecting the wear of the valve mechanism. It is therefore an object to provide an engine which avoids wear of the valve mechanism and a lubricant system for the engine.
[0005]
Another problem with conventional internal combustion engines is that the time interval required between oil changes is less than that required for other service items (eg, air filter changes, coolant changes, brake changes, etc.). It is typically short. Oil change is regarded as one of the most troublesome and sometimes the most expensive maintenance phases for car owners. Traditionally, oil change intervals have been extended by improving the quality of base stocks and additives. For example, since the 1920s, the extension has been more than about 15 times, but despite this progress, the time interval required for the next oil change continues to be longer than that required for other maintenance items. Lagging behind. The problem, therefore, is to improve the lubrication techniques for these engines so that the time interval between subsequent oil changes can be lengthened to coincide with other maintenance intervals.
[0006]
The present invention provides a solution for each of these problems. In the present invention, a lubricating oil composition is used in this engine that is characterized by low or no metal and phosphorus containing EP agents, and consequently the exhaust gas after-treatment device Protected from harmful exposure of the reagents to degradation products. Also, since the engine used in the method of the present invention is a camless engine, there are no camshafts or accessories that can be damaged by blow-by exhaust. According to one embodiment of the present invention, the interval between oil changes required for these engines is increased due to the fact that used engine oil is continuously or periodically removed from the engine and replaced with new oil. Become.
[0007]
Camless internal combustion engines are known. Examples are U.S. Patent Nos. 5,255,641; 5,311,711; 5,367,990; 5,373,817; 5,377,631; No. 5,404,844; No. 5,419,301; No. 5,456,221; No. 5,456,222; No. 5,562,070; No. 5,572. 5,615,646; 5,619,965; 5,694,893; 5,709,178; 5,758,625; Nos. 5,970,956; and 6,024,060.
[0008]
U.S. Pat. No. 4,392,463 discloses a diesel engine having a first lubricating system and a second lubricating system, the first lubricating system containing a normal engine oil and an excess of that engine. Parts that are subject to wear-used to lubricate valve mechanisms, including camshafts, valve lifters, rocker arms, valve stems, etc., and the second lubrication system uses diesel fuel to produce the remainder of the engine. -Lubricates the crankshaft and its associated components, pistons, connecting rods, etc. Diesel fuel used to lubricate crankshafts and the like absorbs contaminants and contaminants contained therein by being exposed to crankcase blow-by exhaust gas, and transfers these contaminants to the fuel system. Recirculating, they are burned and exhausted. With constant lubrication with fresh lubricant, wear on these particular parts is reduced. The reference indicates that this diesel fuel / lubricant is continuously exchanged and circulated through the fuel system, thus eliminating the need for frequent lubricant changes. Since the engine oil and the first lubrication system are not exposed to the crankcase blow-by exhaust gas, their service life is extended and therefore the number of required oil changes is reduced.
[0009]
(Summary of the Invention)
The present invention relates to a method of operating a camless internal combustion engine, comprising the following steps:
(A) operating the engine using a fuel composition, usually liquid or gaseous;
(B) a step of lubricating the engine using a low-phosphorus or non-phosphorus-free lubricating oil composition, wherein the low-phosphorus or non-phosphorus-free lubricating oil composition is composed of a metal and phosphorus, if necessary. Wherein the amount of phosphorus contributed by the extreme pressure additive to the low phosphorus or phosphorus free lubricating oil composition is based on the amount of the low phosphorus or phosphorus free lubricating oil composition. No more than about 0.08% by weight.
[0010]
In one embodiment, the method of the present invention further comprises the following additional steps:
(C) removing a portion of the low phosphorus or phosphorus free lubricating oil composition from the engine, wherein the removed portion of the low phosphorus or phosphorus free lubricating oil composition is blended with (i) a fuel composition And consumed with the fuel composition as the engine is operated, or (ii) blended with and removed from the engine with the exhaust gas from the engine; and
(D) adding an additional amount of the low phosphorus or phosphorus free lubricating oil composition to the engine to replenish the removed portion of the low phosphorus or phosphorus free lubricating oil composition.
[0011]
(Description of a preferred embodiment)
The term "camless" internal combustion engine is used herein to refer to any internal combustion engine that does not use a camshaft to control the timing and lifting of the intake and exhaust valves of the engine.
[0012]
The term "low phosphorus" does not exceed about 0.08% by weight, in one embodiment not more than about 0.07% by weight, in one embodiment not more than about 0.06% by weight, In embodiments, not more than about 0.05% by weight, in one embodiment not more than about 0.04% by weight, in one embodiment not more than about 0.035% by weight, in one embodiment, not more than about 0.035% by weight. Not more than 0.03% by weight, in one embodiment not more than about 0.025% by weight, in one embodiment not more than about 0.02% by weight, in one embodiment about 0.015% by weight In one embodiment, a material having a phosphorus content not exceeding about 0.01% by weight.
[0013]
The term "low ash" refers to up to about 2% by weight, in one embodiment up to about 1.5% by weight, in one embodiment up to about 1% by weight, when tested according to the procedures of ASTM D874-96. In one embodiment, a material that provides a metal-containing ash content of up to about 0.6% by weight.
[0014]
The term "ashless" refers to materials that do not produce metal-containing ash when tested according to the procedures of ASTM D874-96. The ashless lubricating oil compositions of the present invention also rely on the fact that, depending on their components, they can produce non-volatile, non-metal-containing materials, such as boron oxide, phosphorus pentoxide or silicon oxide, when burned. Regardless, it is so called.
[0015]
The term "exhaust gas aftertreatment device" is used herein to refer to any device used in the exhaust gas system of an internal combustion engine to reduce pollutants in the exhaust gas. . These include catalytic converters, particulate traps, catalytic traps, and the like.
[0016]
The term "consumable lubricating oil" is used herein to refer to either (i) consumed in mixture with the fuel composition used in the method of the invention, or (ii) operating the method of the invention. Used to refer to the lubricating oil composition that may be either removed from the engine as it is mixed with the exhaust gases generated during the process.
[0017]
The term "non-consumable lubricating oil" is used herein to refer to a lubricating oil composition that is not a consumable lubricating oil.
[0018]
The term "hydrocarbyl" refers, within the context of the present invention, to a group having a carbon atom directly attached to the remainder of the molecule and having a hydrocarbon or predominantly hydrocarbon character. Such groups include:
(1) pure hydrocarbon groups; that is, aliphatic groups (eg, alkyl or alkenyl), alicyclic groups (eg, cycloalkyl or cycloalkenyl), aromatic groups, aliphatically substituted aromatic groups, and aliphatic groups. Cyclic-substituted aromatic groups, aromatic-substituted aliphatic groups and aromatic-substituted alicyclic groups, and cyclic groups, wherein the ring is completed by another part of the molecule (Ie, any two indicated substituents may together form an alicyclic group). Such groups are known to those skilled in the art. Examples include methyl, ethyl, octyl, decyl, octadecyl, cyclohexyl, phenyl and the like.
[0019]
(2) substituted hydrocarbon groups; that is, groups containing non-hydrocarbon substituents that do not alter the predominantly hydrocarbon character of the group. Suitable substituents are known to those skilled in the art. Examples include hydroxy, nitro, cyano, alkoxy, acyl, and the like.
[0020]
(3) Hetero group; that is, a group mainly having hydrocarbon properties, including atoms other than carbon in a chain or a ring, and others composed of carbon atoms. Suitable heteroatoms will be apparent to those skilled in the art and include, for example, nitrogen, oxygen, and sulfur.
[0021]
Generally, there will be no more than about 3 substituents or heteroatoms, preferably no more than 1 substituent or heteroatom, for every 10 carbon atoms in the hydrocarbyl group.
[0022]
Terms such as "alkyl-based", "aryl-based", and the like, have similar meanings as those described above for alkyl groups, aryl groups, and the like.
[0023]
The term "hydrocarbon-based" has the same meaning and may be used interchangeably with the term "hydrocarbyl" when referring to a molecular group having a carbon atom directly attached to the remainder of the molecule.
[0024]
As used herein, the term "lower", in connection with terms such as hydrocarbyl, alkyl, alkenyl, alkoxy, etc., refers to such groups containing up to a total of 7 carbon atoms. It is intended to be described.
[0025]
The term “oil-soluble” refers to a substance that dissolves in mineral oil at 25 ° C. to at least about 1 gram per liter.
[0026]
First, the method of the present invention will be described with reference to the drawings. Engines 10 (FIG. 1), 10A (FIG. 2) and 10B (FIG. 3) may be spark ignition or compression ignition internal combustion engines. These engines have a camless valve mechanism and are lubricated with a low phosphorus or phosphorus free lubricating oil composition.
[0027]
Referring to FIG. 1, the engine 10 includes a plurality of cylinders C. ₁ ~ C _n Consists of The number n of cylinders can range from 1 to about 12, and in one embodiment, from about 4 to about 8. In one embodiment, n is 4, in one embodiment n is 5, in one embodiment n is 6, and in one embodiment n is 8. Each cylinder includes a piston 12. These pistons are connected to a crankshaft 14. Each cylinder also has an intake valve 16, an exhaust valve 18, and an injector 20. Alternatively, the fuel injector 20 may be located in an intake system (eg, an intake manifold). The intake valve 16 and the exhaust valve 18 can be electro-hydraulic started in response to a control signal sent from an electronic control unit (not shown). The injector 20 is electrically startable in response to a control signal sent from the electronic control unit. This electronic control device issues a control signal responsive to the rotational position of the crankshaft 14. Cylinder C ₁ ~ C _n Are shown with one intake valve 16 and one exhaust valve 18, but each cylinder has between two and about six valves (e.g., two intake valves and one exhaust valve). It should be understood that two exhaust valves and one intake valve; two intake valves and two exhaust valves, etc.) may be used.
[0028]
The engine 10 has a fuel device 22, which includes a fuel tank, a fuel pump, a fuel injector 20, a fuel filter, and the like. The fuel device 22 is provided to advance fuel to these cylinders. Generally, an intake system, indicated by a directional arrow 24, is provided to advance air into these cylinders. Generally, an exhaust gas system indicated by directional arrows 26 is provided to remove exhaust gas from these cylinders. As a part of the exhaust gas system 26, an exhaust gas post-processing device 28 (for example, a catalytic converter, a particulate trap, a catalyst trap, etc.) and an exhaust muffler 30 are provided. The engine 10 includes a pump (not shown) that circulates lubricating oil throughout the engine and an oil sump 32.
[0029]
The low phosphorus or phosphorus free lubricating oil composition used in engine 10 may be a consumable lubricating oil composition or a non-consumable lubricating oil composition. The engine 10 operates in a normal sequence, with air entering the cylinder through an intake valve 16 and fuel entering through a fuel injector 20. The resulting mixture of air and fuel burns in these cylinders. Exhaust gas is removed from these cylinders through the exhaust valve 18 and from there through the exhaust gas aftertreatment device 28 and the exhaust muffler 30. During operation of the engine 10, the low phosphorus or phosphorus free lubricating oil composition circulates through the engine in a conventional manner to lubricate the desired engine components.
[0030]
In the embodiment illustrated in FIG. 2, the engine 10A includes an engine 10A except that the engine 10A includes a make-up oil reservoir 34 and a pump or metering device 36, which advances fresh oil from the make-up oil reservoir 34 to the engine 10A. 1 is the same as the engine 10 shown in FIG. Engine 10A is adapted to use a consumable lubricating oil composition as the low phosphorus or non-phosphorous lubricating oil composition.
[0031]
During operation of engine 10A, a portion of the low phosphorus or phosphorus free lubricating oil composition used in this engine is pumped from oil sump 32 to fuel system 22, as indicated by directional arrow 33. Where it is blended with this fuel. The introduction of this oil into the fuel can be performed by a fuel tank, fuel return pipe, fuel injector, intake manifold, positive crankcase ventilation (PCV) device, exhaust gas recirculation (EGR) system, or intake valve guide. And / or may occur at one or more of the exhaust valve guides. Alternatively, the oil may be mixed with air in the intake system 24 of the engine 10A.
[0032]
The resulting blend of fuel and oil is about 0.01% to about 5% by weight, in one embodiment about 0.05% to about 3% by weight, in one embodiment about 0.1% to about 3% by weight. %, In one embodiment, about 0.1% to about 1%, in one embodiment, about 0.1% to about 0.7%, in one embodiment, From about 0.1% to about 0.5% by weight, in one embodiment from about 0.2% to about 0.3% by weight oil, with the balance being fuel.
[0033]
Alternatively, as indicated by the dashed line 38 in FIG. 2, a portion of the low phosphorus or phosphorus free lubricating oil composition removed from the oil sump 32 may be advanced to the exhaust gas system 26 where it is It is mixed with the exhaust gas from the engine on the upstream side from the exhaust gas after-treatment device 28. The introduction of this oil into the exhaust gas can occur at any point in the exhaust gas system 26 upstream of (ie before entering) the exhaust gas aftertreatment device 28. The sequence of removing used oil from engine 10A and replacing it with fresh oil may be performed continuously or intermittently during operation of engine 10A.
[0034]
In the embodiment illustrated in FIG. 3, the engine 10B is the same as the engine 10A illustrated in FIG. 2, except that the engine 10B does not have the exhaust gas aftertreatment device 28. Engine 10B may be a compression ignition engine. Engine 10B uses a consumable lubricating oil composition as the low phosphorus or non-phosphorous lubricating oil composition. Engine 10B uses the exhaust gas when a portion of the low phosphorus or phosphorus free lubricating oil composition removed from oil sump 32 is advanced to exhaust system 26, as indicated by dashed line 38 in FIG. It operates in the same manner as engine 10A, except that it can be blended with exhaust gas at any point in the system.
[0035]
(Camless engine)
The camless engine that can be operated according to the method of the present invention can be any internal combustion engine that uses a camless valve mechanism. These include compression ignition engines and spark ignition engines (including four cycle spark ignition engines). These camless engines are characterized by the lack of a camshaft that controls the timing and lifting of their intake and exhaust valves. The intake and exhaust valves of the camless engine used in the method of the present invention may be electric, hydraulic or electro-hydraulic started. Each valve can change its lift schedule for different engine operating conditions.
[0036]
Nos. 5,255,641; 5,367,990; 5,373,817; 5,377,631 include camless engines that can be operated in accordance with the method of the present invention. 5,404,844; 5,419,301; 5,456,221; 5,456,222; 5,562,070; and 5th. No. 5,572,961, which use the engine valve assembly disclosed in U.S. Pat. No. 5,572,961, the contents of which are incorporated herein by reference for their disclosure. In summary, US Pat. No. 5,255,641 discloses a variable engine valve control system, wherein each of the reciprocating intake and / or exhaust valves is hydraulically controlled, and It includes a piston, which is exposed to fluid pressure acting on surfaces at both ends of the piston. The space at one end of the piston is connected to a high-pressure fluid source, while the space at the other end is connected to a high-pressure fluid source and a low-pressure fluid source, and by the action of a control mechanism (for example, an electromagnetic valve), Disconnected from each. These control mechanisms may include a rotary hydraulic distributor coupled to each solenoid valve, which allows each solenoid valve to continuously control the operation of multiple engine valves. Controlling the variable duration and timing of the electrical pulses ensures that an equal amount of air is delivered to all engine cylinders with the above variable valve control system, which system uses electrical pulses to control each individual actuator. Of the engine individually, this change ensures that all actuators control the engine intake valve (or exhaust valve) in the same manner ensuring equal valve stroke in all cylinders. Nature.
[0037]
U.S. Pat. Nos. 5,367,990 and 5,404,844 disclose a variable engine valve control system wherein each of the reciprocating engine valves has a hydraulically controlled or electrically operated valve. The lift schedule can be controlled and varied for various engine operating conditions. During partial load operation of this engine, before the top dead center position of the piston, during its exhaust stroke, the intake valve opens and the exhaust valve closes, so that the intake port exhausts exhaust gas. This, in turn, returns to that cylinder during this intake stroke, eliminating the need for an external exhaust gas recirculation system and improving fuel evaporation to the intake. Furthermore, during part load, the intake valve closes before the end of its intake stroke, and this intake air is heated by a heat exchanger before it enters this cylinder, thus compromising compression ratio and ignition characteristics. No air restriction is required.
[0038]
U.S. Pat. No. 5,373,817 discloses an electro-hydraulic engine valve control system in a four cylinder per cylinder engine, wherein an intake valve and / or an exhaust valve in each cylinder. Are hydraulically controlled by another set of solenoid valves. Each engine valve includes a piston, which is exposed to fluid pressure acting on the surfaces at both ends, the volume at one end being connected to a source of high pressure fluid, while the volume at the other end is high pressure. It is selectively connected to a fluid source and a low-pressure fluid source, and is disconnected from each other by the action of the solenoid valve. Each pair of corresponding valves may be hydraulically connected together and moved in unison, or one may be moved relative to the other by a valve deactivator (including one valve that has completely failed). , Movement may be reduced. This differential travel between pairs of valves accounts for various engine operating conditions and manufacturing tolerances. Controlling the variable duration and timing electrical pulses in conjunction with activation of the valve deactivator ensures that an equal volume of air is delivered to all engine cylinders having the variable valve control system.
[0039]
U.S. Pat. No. 5,377,631 discloses the operation of a four-stroke engine in a skip-cycle manner, in which each intake and exhaust valve for each cylinder is individually activated or virtually instantaneously activated. Providing an engine with a valve controller so that it can stall and provide a skip cycle pattern, which varies as a function of load. Each of these valves allows the purpose of moving the stroke away from each piston of a deactivated cylinder to change from compression to exhaust or intake to expansion, as the case may be, for a short time as one skip cycle Thus, all of the engine cylinders are reliably ignited to prevent cooling of the cylinders and promote exhaust. By closing the intake and exhaust valves in a particular order during the skip cycle operation, and by controlling the intake valve closing timing during the load period during the skip cycle period, unthrottle ( By continuing the unthrottled operation, an unthrottled operation is also provided. Further, starting or deactivating the fuel injector and spark plug individually enhances this skip cycle unthrottle operation.
[0040]
U.S. Pat. No. 5,419,301 discloses a variable camless engine valve control system wherein each of its reciprocating intake and / or exhaust valves is hydraulically controlled. Each valve includes a piston, which is exposed to fluid pressure acting on the surfaces at both ends of the piston, with a volume at one end connected to a source of high pressure fluid, while a volume at the other end. , Connected to a high pressure fluid source and a low pressure fluid source, and disconnected from each other by the action of a control mechanism (eg, a computer controlled solenoid valve). An optimal intake and residual gas volume in each engine cylinder having the variable valve control system is ensured by controlling electrical pulses having variable duration and timing. The timing and duration of this pulse are determined by values in the computer's permanent storage (which correspond to information obtained from the sensors) and correction values (which correspond to feedback from other sensors). Calculated).
[0041]
U.S. Patent Nos. 5,456,221 and 5,456,222 disclose engine valve assemblies in an electro-hydraulic camless valve mechanism that cooperate with a hydraulic system having a low pressure branch and a high pressure branch. Then, each valve is selectively opened and closed. Each valve is fixed to a valve piston in a piston chamber. The volume below the piston is connected to the high pressure branch, and the volume above the piston is selectively connected to the high pressure branch and the low pressure brine to open and close the engine valve. U.S. Patent No. 5,456,221 discloses the use of a rotary valve to open and close the valve, and U.S. Patent No. 5,456,222 discloses the use of a spool valve. are doing.
[0042]
U.S. Pat. No. 5,562,070 discloses an engine valve assembly in an electro-hydraulic camless valve mechanism that cooperates with a hydraulic system having a low pressure branch and a high pressure branch to selectively control each valve. Open and close. Each valve is fixed to a valve piston in a piston chamber. The volume below the piston is connected to the high pressure branch and the volume above the piston is selectively connected to this high pressure branch or low pressure brine via a rotary valve to open and close the engine valve. The motor causes the rotation of this rotary valve. The rotary valve includes an interior hollow, which is operably and selectively connected to a window in the valve sleeve to allow high and low pressure fluid flow through the valve.
[0043]
U.S. Pat. No. 5,572,961 discloses an electro-hydraulic engine valve control system in a multi-valve engine, wherein a plurality of intake (or exhaust) valves in each cylinder are controlled by a set of hydraulic valves. , Hydraulically controlled. Each engine valve includes a valve piston, which is exposed to fluid pressure acting on the surfaces at both ends, with a volume at one end connected to a source of high pressure fluid, while a volume at the other end is It is selectively connected to a high pressure fluid source and a low pressure fluid source, and is disconnected from each other by the action of the hydraulic valve. The corresponding groups of engine valves are hydraulically connected together and can move together. Balancing springs operably engage each valve piston to balance the movement of these engine valves during their opening and closing, thereby causing manufacturing tolerances and other factors.
[0044]
Camless engines that can be used include those that use the outward opening valve system disclosed in U.S. Patent Nos. 5,615,646; 5,694,893; and 5,709,178. And the contents of which are incorporated herein by reference for their disclosure of such valve systems. In summary, U.S. Patent No. 5,615,646 discloses an outward opening valve system for an engine, the engine having a hollow piston in fluid communication with a gas passage via an opening. Is mentioned. The engine also has a piston bore, which is open to the hollow piston cylinder. A portion of the opening includes an outwardly facing valve seat, which is located adjacent to the gas passage. An outward valve member with a valve face is located substantially within this gas passage. The valve member is in a closed position (where the valve face rests against the valve seat and closes its opening) and in an open position (in which position the valve face separates from the valve seat). Can be moved between them. To reciprocate in this piston bore, an augmentation piston is located, which has one end in gas contact within its hollow piston cylinder. A coupling chain interconnects the augmentation piston to the outwardly facing valve member such that the valve member is kept closed by utilizing the combustion pressure within the hollow piston cylinder.
[0045]
U.S. Pat. No. 5,694,893 discloses an outward opening valve system which includes an engine, which has a fluid cavity in fluid communication with an accumulator chamber by a travel passage, a hollow piston, which has Include a fluid communication with the gas passage via an opening) and an augmented bore, which opens into the hollow piston cylinder. The opening includes an outwardly facing valve seat adjacent the gas passage. The outgoing valve member with the valve face is in a closed position (in this position, the valve face rests against the valve seat and closes its opening) and in an open position (in this position, the valve face is (Away from the valve seat). A compression spring is used to bias the outward valve member toward its open position. An augmentation piston is located in the augment bore and one end is exposed to fluid pressure in the hollow piston cylinder. A coupling chain interconnects the augmentation piston and the outward valve member. An accumulator plunger is located in the accumulator chamber and is movable between a release position and a storage position, but is biased toward the release position by a compression spring. A control valve member is located in the travel passage, which includes a first position (where the accumulator chamber is open to the fluid cavity) and a second position (where the accumulator is located). The chamber is closed to the fluid cavity).
[0046]
U.S. Pat. No. 5,709,178 discloses an outward opening valve system for an engine that includes an actuator body (which rocks a guide bore), a fluid cavity (which is filled with hydraulic fluid). And open to the valve plunger bore), an augmented plunger bore and a resupply passage. A check valve located in the resupply passage is operable to prevent backflow of hydraulic fluid from entering the fluid cavity. An outgoing valve member with a valve face is positioned to reciprocate in this guide bore. The augment plunger is slidably located in the augment plunger bore. A valve plunger is slidably located in the augmented plunger bore. The over-center cam mechanism includes a cam (which is attached to the actuator and is rotatable around a pivot pin), a push rod (one end is in contact with the cam, and the other end is (In contact with the valve member), and finally the pivot pin is mounted on the valve plunger. Attached to the actuator body is a solenoid, which includes a control rod. The computer can contact and control this solenoid.
[0047]
A camless engine using the method for determining the rotational position of a crankshaft disclosed in US Pat. No. 5,311,771 may be used. The contents of this patent are incorporated herein by reference for their disclosure of such methods. In summary, the method includes monitoring the rotation of the crankshaft and generating a crankshaft pulse train in response. A clock signal having a predetermined frequency is generated. The clock signal and the crankshaft pulse train are received. Each pulse of the crankshaft pulse train is sampled and, in response, the duration of each sampled pulse is determined. A representative signal is generated during the determined pulse period. The method further includes receiving the determined pulse duration signal and, in response, determining a predicted value of a period during which the next pulse will occur. A signal representative of the predicted value is generated, and the predicted value signal is received. An intermediate position signal is generated based on the predicted value. This intermediate position signal represents a predetermined angular rotation of the crankshaft.
[0048]
U.S. Patent No. 5,619,965 is incorporated herein by reference for its disclosure of a camless engine that can operate in either a positive output mode or a compression release engine braking mode. In summary, this patent discloses a camless internal combustion engine having an electronically or computer controlled electro-hydraulic actuator for selectively opening its engine cylinder valve. The hydraulic fluid pressure applicable to this hydraulic actuator is automatically adjusted from a relatively low pressure during the positive output mode to a relatively high pressure during the compression release engine braking mode. The stroke length of these engine cylinder valves can be automatically adjusted for various engine operating conditions using a feedback loop, which includes a sensor that detects the opening of each engine cylinder valve, The stroke length should be controlled in this way. The shape of the valve opening and closing trajectory as a function of engine crank angle can be varied.
[0049]
U.S. Pat. No. 5,758,625 is incorporated herein by reference for its disclosure of a method of tuning an internal combustion engine without a cam position sensor. In summary, this patent discloses a method for generating a phase signal exceeding 720 degrees for an internal combustion engine, the engine including a multi-point electronic injection system, which operates continuously. During the start-up phase, only part of the cylinders can be ignited and the angular position at which the first ignition occurs is detected.
[0050]
U.S. Pat. No. 5,970,956 is incorporated herein by reference for its disclosure of a control module for an internal combustion engine (which controls camless hydraulically driven intake and exhaust valves) and a hydraulically driven fuel injector. It has been incorporated as a reference. In summary, the module includes a valve assembly for controlling an intake valve, a valve assembly for controlling an exhaust valve, and a valve assembly for controlling a fuel injector. These valve assemblies preferably each include a pair of solenoid activated two-way spool valves. These solenoids are activated by digital pulses sent by the electronics assembly in the module. The solenoid actuated spool valve controls the flow of hydraulic fluid to and from its fuel injectors and intake and exhaust valves. The hydraulic fluid opens and closes the intake and exhaust valves. The hydraulic fluid also activates the fuel injector to discharge fuel into the combustion chamber of the engine. The electronic assembly of each module can be connected to a main microprocessor that sends instructions to each assembly. Each electronic assembly processes this command, signals and historical data from the hydraulic activator to ensure the desired operation of the fuel injector and intake and exhaust valves.
[0051]
U.S. Patent No. 6,024,060 is incorporated herein by reference for its disclosure of a valve operating mechanism for an internal combustion engine. In summary, this patent discloses a reciprocating valve actuation control system, which includes: a poppet valve, which is movable between a first position and a second position. A source of pressurized hydraulic fluid; a hydraulic actuator, which includes an actuator piston coupled to the poppet valve, and responsive to a flow of pressurized hydraulic fluid to the hydraulic actuator; Reciprocating to and from a second position; an electrically actuated valve, which controls the flow of pressurized hydraulic fluid to the actuator; and an engine computer, which relocates the electrically actuated valve. Generate electrical pulses to control. The electrically actuated valve includes a three-way rotary latch magnetic motor, which activates a rotary valve portion, which has a housing, a rotor, and a stator, which has a hydraulic pressure for the rotor. Hydraulic fluid pressure is received and supplied and the hydraulic fluid pressure is alternately directed to a valve cylinder to open the valve or return to the engine oil sump to close the valve. . In one embodiment, the hydraulic actuator includes a self-contained cartridge assembly that includes an actuator piston, which includes a damper that dampens movement of the actuator piston, to limit the stroke of the actuator. Ensures soft seating of this actuator and avoids overshoot during the engine valve opening stroke and the engine valve return stroke. These electro-hydraulic valves are electrically controlled by the engine computer, which generates electrical signals that are conveyed to the electro-hydraulic valves. The engine computer senses normal engine variables and uses the information sent to the engine computer by the sensors to optimize the performance of the valve actuation control system according to pre-established guidelines. The engine computer controls all aspects of engine performance, works with all of the peripheral sensors, and calculates fuel parameters, ignition timing, and engine valve timing based on a prior mapping of the engine. In this way, the engine can be controlled to provide maximum fuel economy, minimum emissions, maximum engine torque, or a compromise between these parameters.
[0052]
(Usually liquid fuel or normal gaseous fuel)
The normally liquid or normally gaseous fuel can be a hydrocarbonaceous petroleum distillate fuel (eg, automotive gasoline as defined in ASTM Specification D439 and diesel fuel as defined in ASTM Specification D396). Normally liquid hydrocarbon fuels containing substances such as alcohols, ethers, organic nitrogen compounds, etc. (eg, methanol, ethanol, diethyl ether, methyl ethyl ether, nitromethane) can also be plant or mineral sources (eg, corn, Liquid fuels derived from alfalfa, shale and coal) are within the scope of the present invention. Examples of such mixtures include a mixture of gasoline and ethanol, and a mixture of diesel fuel and ether.
[0053]
In one embodiment, the fuel is gasoline, a mixture of hydrocarbons having an ASTM distillation range from about 60 ° C at 10% distillation point to about 205 ° C at 90% distillation point. In one embodiment, the gasoline fuel composition is a lead-free fuel composition. In one embodiment, the gasoline is a chlorine-free or low-chlorine gasoline characterized by a chlorine content of about 10 ppm or less. In one embodiment, the gasoline comprises no more than about 300 ppm, in one embodiment no more than about 150 ppm, one embodiment no more than about 100 ppm, one embodiment no more than about 50 ppm, one embodiment no more than about 25 ppm, In embodiments, a low sulfur fuel characterized by a sulfur content of about 10 ppm or less.
[0054]
Useful diesel fuel can be any diesel fuel. These diesel fuels typically have a 90% point distillation temperature ranging from about 300C to about 390C, and in one embodiment about 330C to about 350C. Viscosity for these fuels typically ranges from about 1.3 to about 24 centistokes at 40C. These diesel fuels can be classified as grade numbers 1-D, 2-D or 4-D as specified in ASTM D975. These diesel fuels can contain alcohols and esters. In one embodiment, the diesel fuel has a sulfur content of up to about 0.05% by weight as measured by the test method specified in ASTM D2622-87 (low sulfur diesel fuel).
[0055]
These fuel compositions may contain one or more additives known to those skilled in the art to enhance the performance of the fuel. These include sediment inhibitors or regulators, cetane improvers, antioxidants (e.g., 2,6-di-tert-butyl-4-methylphenol), corrosion inhibitors (e.g., alkylated succinic acid). And their anhydrides), bacteriostats, rubberization inhibitors, metal deactivators, demulsifiers, upper cylinder lubricants, deicers, ashless dispersants and the like.
[0056]
These fuel additives may be added directly to the fuel, or may be diluted with a normally liquid diluent (eg, naphtha, benzene, toluene or xylene) prior to addition to the fuel, to provide an additive concentrate. Can be formed. These concentrates typically contain from about 10% to about 90% by weight of diluent.
[0057]
The fuel can be a gaseous fuel (eg, natural gas). This fuel may be stored as a liquid and used in its gaseous form. Examples include propane and dimethyl ether.
[0058]
(Low phosphorus lubricating oil composition or non-phosphorous lubricating oil composition)
The low phosphorus or phosphorus free lubricating oil composition may be a consumable lubricating oil composition or a non-consumable lubricating oil composition.
[0059]
The consumable lubricating oil composition may, in one embodiment, be comprised of components that add only C, H, O or N to the lubricating oil composition. In one embodiment, Si may be present. Any other elements that may be present are present as impurities and are therefore of relatively low concentration. The concentration of each of these impurities (prior to using the oil in the engine) is typically less than about 500 ppm, in one embodiment less than about 250 ppm, in one embodiment less than about 100 ppm, one embodiment Less than about 50 ppm, in one embodiment less than about 25 ppm, and in one embodiment less than about 10 ppm. The lubricating oil composition is characterized by the absence of an EP additive composed of metal (eg, zinc) and phosphorus. In one embodiment, the lubricating oil composition is characterized by the absence of ash-forming detergents or dispersants. In one embodiment, the lubricating oil composition has about 250 ppm or less, in one embodiment about 200 ppm or less, and in one embodiment about 5 to about 10 ppm, as measured by inductively coupled radio frequency plasma (ICP) or X-ray techniques. In the range of 250 ppm, in one embodiment, about 5 to about 200 ppm, in one embodiment, about 5 to about 150 ppm, in one embodiment, about 5 to about 100 ppm, in one embodiment, about 5 to about 100 ppm. In one embodiment, it is characterized by a sulfur content in the range of about 5 to about 25 ppm, and in one embodiment about 5 to about 15 ppm. In one embodiment, the lubricating oil composition is free of sulfur.
[0060]
Except that the non-consumable lubricating oil composition may contain a small amount of one or more EP additives, which are composed of metal (eg, zinc) and phosphorus, And the phosphorus content provided by such EP additives in the lubricating oil composition is less than about 0.08% by weight. The non-consumable lubricating oil composition may also contain one or more ash-forming detergents or dispersants, provided that the total amount of metal-containing ash in the lubricating oil composition is ASTM D874- Not more than about 1.5% by weight, in one embodiment not more than about 1.2% by weight, in one embodiment not more than about 1.0% by weight, as measured by the test method of 96. In embodiments, it does not exceed about 0.8% by weight.
[0061]
The low phosphorus or phosphorus free lubricating oil composition is comprised of one or more base oils commonly present in major amounts (ie, greater than about 50% by weight). Generally, the base oil is present in an amount greater than about 60%, or greater than about 70%, or greater than about 80% by weight of the lubricating oil composition.
[0062]
The low phosphorus or phosphorus free lubricating oil composition has a viscosity at 100 ° C. of up to about 16.3 cSt, in one embodiment a viscosity of about 5 to about 16.3 cSt at 100 ° C., and in one embodiment at about 100 ° C. It may have a viscosity of 6 to about 13 cSt. In one embodiment, the lubricating oil composition comprises 0W, 0W-20, 0W-30, 0W-40, 0W-50, 0W-60, 5W, 5W-20, 5W-30, 5W-40, 5W- It has a SAE viscosity rating of 50, 5W-60, 10W, 10W-20, 10W-30, 10W-40 or 10W-50.
[0063]
The low phosphorus or phosphorus free lubricating oil composition has a viscosity of up to about 4 centipoise, in one embodiment, up to about 3.7 centipoise, and in one embodiment, about 2 to about 3 centipoise, as measured by the method of ASTM D4683. It may have a high temperature / high shear viscosity of about 4 centipoise, in one embodiment, about 2.2 to about 3.7 centipoise, and in one embodiment, about 2.7 to about 3.5 centipoise.
[0064]
The base oil used in the low phosphorus or phosphorus free lubricating oil composition can be a natural oil, a synthetic oil, or a mixture thereof. Useful natural oils include animal and vegetable oils (e.g., castor oil, lard oil) as well as liquid petroleum oils and paraffin, naphthene or mixed paraffin-naphthene types and are solvent treated. Mineral lubricating oils or acid-treated mineral lubricating oils may be mentioned. Oils of lubricating viscosity derived from coal or shale are also useful. Synthetic lubricating oils include, for example, hydrocarbon oils and halo-substituted hydrocarbon oils, such as polymerized olefins and interpolymerized olefins such as polybutylene, polypropylene, propylene-isobutylene copolymer, and the like; 1-hexene), poly (1-octene), poly (1-decene), and the like, and mixtures thereof; alkylbenzenes (eg, dodecylbenzene, tetradecylbenzene, dinonylbenzene, di (2-ethylhexyl) benzene, and the like); Polyphenyl (eg, biphenyl, terphenyl, alkylated polyphenyl, etc.); alkylated diphenyl ethers and derivatives thereof, analogs and homologs thereof, and the like.
[0065]
Alkylene oxide polymers and interpolymers and their derivatives, in which the terminal hydroxyl groups have been modified by esterification, etherification, etc., constitute known types of synthetic lubricating oils that can be used. These include oils prepared by the polymerization of ethylene oxide or propylene oxide, alkyl ethers and aryl ethers of these polyoxyalkylene polymers (e.g., methyl polyisopropylene glycol ether having an average molecular weight of about 1000, about 500 to 1000 Diphenyl ethers of polyethylene glycol having a molecular weight of about 1,000 to about 1500, and diethyl ether of polypropylene glycol having a molecular weight of about 1000 to 1500, or mono- and polycarboxylic acid esters thereof (for example, acetate esters of tetraethylene glycol, mixed C _3-8 Fatty acid ester or C _Thirteen Oxo acid diester).
[0066]
Other suitable types of synthetic lubricating oils that can be used include dicarboxylic acids such as phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid Linoleic acid dimer, malonic acid, alkylmalonic acid, alkenylmalonic acid, etc.) and various alcohols (eg, butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol) And esters with Specific examples of these esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, Examples include dieicosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, and complex esters formed by the reaction of 1 mol of sebacic acid with 2 mol of tetraethylene glycol and 2 mol of 2-ethylhexanoic acid.
[0067]
Esters useful as synthetic oils include C ₅ ~ C ₁₂ Also included are esters produced from monocarboxylic acids and polyols and polyol ethers (eg, neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.).
[0068]
The oil may be a poly-α-olefin (PAO). Typically, the PAO is derived from a monomer having about 4 to about 30 carbon atoms, or about 4 to about 20 carbon atoms, or about 6 to about 16 carbon atoms. . Examples of useful PAOs include those derived from octene, decene, mixtures thereof, and the like. These PAOs may have a viscosity at 100 ° C. of about 2 to about 15 cSt, or about 3 to about 12 cSt, or about 4 to about 8 cSt. Examples of useful PAOs include 4 cSt poly-α-olefin at 100 ° C., 6 cSt poly-α-olefin at 100 ° C., and mixtures thereof. Mixtures of mineral oil and one or more of the above poly-α-olefins may be used.
[0069]
Unrefined, refined and rerefined oils, which are either natural or synthetic oils of the type disclosed above, and a mixture of two or more of any of these oils Can be used inside. Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from a retort operation, a petroleum oil obtained directly from a first-stage distillation, or an ester oil obtained directly from an esterification step and used without further treatment is an unrefined oil. Refined oils are similar to the unrefined oils except they have been further processed in one or more purification steps to improve one or more properties. Many such purification methods are well known to those skilled in the art. This method includes, for example, solvent extraction, secondary distillation, acid or base extraction, filtration, osmosis, and the like. Rerefined oils are obtained by applying processes that are similar to those used to obtain refined oils that have already been used. Such rerefined oils are also known as reclaimed or reprocessed oils and are often further processed by processes directed to remove spent additives and oil breakdown products. You.
[0070]
In one embodiment, the low phosphorus or phosphorus free lubricating oil composition further comprises an acylated nitrogen-containing compound having a substituent of at least about 10 aliphatic carbon atoms. These compounds typically function as ashless dispersants in lubricating oil compositions.
[0071]
Numerous acylated nitrogen-containing compounds having a substituent of at least about 10 aliphatic carbon atoms and prepared by reacting a carboxylic acylating agent with an amino compound are known to those skilled in the art. In such compositions, the acylating agent is attached to the amino compound via an imide, amide, amidine or salt bond. The substituents of at least about 10 aliphatic carbon atoms can be either on the moiety derived from the carboxylic acylating agent of the molecule or on the moiety derived from the amino compound of the molecule. In one embodiment, it is on the acylating moiety. The acylating agent converts from formic acid and its acylated derivatives to an acylating agent having a high molecular weight aliphatic substituent of up to about 5,000, up to 10,000 or up to 20,000 carbon atoms, Can change. The amino compound is characterized by the presence of at least one HN <group in its structure.
[0072]
In one embodiment, the acylating agent is a mono- or polycarboxylic acid (or reactive equivalent thereof), such as a substituted succinic or propionic acid, and the amino compound is a polyamine or polyamine mixture, Most typically, it is an ethylene polyamine mixture. The amine can also be a hydroxyalkyl-substituted polyamine. The aliphatic substituents of such acylating agents typically have, on average, at least about 30 or at least about 50 and up to about 400 carbon atoms.
[0073]
Exemplary hydrocarbon-based groups containing at least 10 carbon atoms include n-decyl, n-dodecyl, tetrapropylene, n-octadecyl, oleyl, chlorooctadecyl, triicontanyl, and the like. Generally, the hydrocarbon-based substituent is a homo- or interpolymer (e.g., copolymer, terpolymer) of mono- and di-olefins having 2 to 10 carbon atoms, e.g., ethylene. , Propylene, 1-butene, isobutene, butadiene, isoprene, 1-hexene, 1-octene and the like. Typically, these olefins are 1-monoolefins. The substituents can also be derived from halogenated (eg, chlorinated or brominated) analogs of such homopolymers or interpolymers. However, the substituents may be replaced by other feedstocks, such as monomeric high molecular weight alkenes (eg, 1-tetracontent), and their chlorinated and hydrochlorinated analogs, aliphatic petroleum fractions ( In particular, paraffin waxes and their decomposed and chlorinated and hydrochlorinated analogues), white oils, synthetic alkenes (for example those produced by the Ziegler-Natta process (for example poly (ethylene) grease)), And other materials known to those skilled in the art. Any unsaturation in this substituent may be reduced or eliminated by hydrogenation according to methods known to those skilled in the art.
[0074]
The hydrocarbon-based substituents are substantially saturated, i.e., they do not contain more than one carbon-carbon unsaturated bond for each 10 carbon-carbon single bonds present . Usually, they do not contain more than one non-aromatic carbon-carbon unsaturated bond for each 50 carbon-carbon bonds present.
[0075]
The hydrocarbon-based substituents are also substantially aliphatic in nature, i.e., they have less than 6 carbon atoms for each 10 carbon atoms of the substituent. Does not contain more than one aromatic moiety (cycloalkyl, cycloalkenyl or aromatic) group. However, typically, the substituents will not contain more than one such non-aliphatic group for each 50 carbon atoms, and in many cases, they will replace such non-aliphatic groups. Does not contain at all. That is, typical substituents are purely aliphatic. Typically, these pure aliphatic substituents are alkyl or alkenyl groups.
[0076]
Particular examples of substantially saturated hydrocarbon-based substituents containing on average more than about 30 carbon atoms include:
A mixture of poly (ethylene / propylene) groups having about 35 to about 70 carbon atoms;
A mixture of oxidatively or mechanically degraded poly (ethylene / propylene) groups having about 35 to about 70 carbon atoms;
A mixture of poly (propylene / 1-hexene) groups having about 80 to about 150 carbon atoms;
On average, a mixture of poly (isobutene) groups having about 50 to about 200 carbon atoms.
[0077]
Useful raw materials for this substituent include a butene content of about 35 to about 75% by weight and about 30 to about 60% by weight in the presence of a Lewis acid catalyst (e.g., aluminum trichloride or boron trifluoride). C with isobutene content ₄ There are poly (isobutenes) obtained by polymerization of purified streams. These polybutenes contain predominantly (more than 80% of the total repeating units) isobutene repeating units of the following configuration:
[0078]
Embedded image

In one embodiment, the substituent is a group derived from polyisobutene having a high methylvinylidene content, ie, at least about 70% methylvinylidene content, and in one embodiment, at least about 80% methylvinylidene content. Suitable high methylvinylidene polyisobutenes include those prepared using a boron trifluoride catalyst. The preparation of such polyisobutenes, where the methylvinylidene isomer contains a high proportion of the total olefin composition, is described in US Pat. Nos. 4,152,499 and 4,605,808. And the contents of each disclosure are incorporated herein by reference.
[0079]
In one embodiment, the carboxylic acylating agent is a hydrocarbon-substituted succinic acid or anhydride. The substituted succinic acid or anhydride comprises a hydrocarbon-based substituent and a succinic acid group, wherein the substituent is derived from a polyalkene, and the acid or anhydride is an equivalent weight of each substituent. In contrast, on average, at least about 0.9 succinic groups, and in one embodiment about 0.9 to about 2.5 succinic groups, are present in the structure, Characterized. The polyalkene generally has a (Mn) of at least about 700, in one embodiment from about 700 to about 2000 (Mn), and in one embodiment about 900 to about 1800 (Mn). The ratio between the weight average molecular weights (Mw) and (Mn) (i.e., Mw / Mn) can range from about 1 to about 10, or from about 1.5 to about 5. In one embodiment, the polyalkene has a Mw / Mn value from about 2.5 to about 5. For the purposes of the present invention, the equivalent weight number of the substituent is a numerical value corresponding to the quotient obtained by dividing the total weight of the substituent present in the substituted succinic acid by the Mn value of the polyalkene from which the substituent is derived. It is considered to be. Therefore, if a substituted succinic acid is characterized by a total weight of the substituent of 40,000 and a Mn value of the polyalkene from which the substituent is derived of 2000, then the substituted succinic acylating agent will have a total equivalent weight of the substituent. It is characterized by a weight of 20 (40,000 / 2000 = 20).
[0080]
In one embodiment, the carboxylic acylating agent is a substituted succinic acid or anhydride, wherein the substituted succinic acid or anhydride comprises a substituent and a succinic acid group, wherein the substituent is a polybutene In this polybutene, at least about 50% of the total units derived from butene are derived from isobutylene. The polybutene is characterized by a Mn value of about 1500 to about 2000, and a Mw / Mn value of about 3 to about 4. These acids or anhydrides are characterized by the average presence of about 1.5 to about 2.5 succinic groups in the structure for each equivalent weight of the substituent. Attached.
[0081]
In one embodiment, the carboxylic acid is at least one substituted succinic acid or anhydride, wherein the substituted succinic acid or anhydride comprises a substituent and a succinic acid group, wherein the substituent is It is derived from polybutene, in which at least about 50% of the total units derived from butene are derived from isobutylene. The polybutene has a Mn value of about 800 to about 1200, and a Mw / Mn value of about 2 to about 3. These acids or anhydrides are characterized by the presence of, on average, from about 0.9 to about 1.2 succinic groups for each equivalent weight of the substituent in the structure. Attached.
[0082]
The amino compound is characterized by the presence of at least one NH <group in its structure and can be a monoamine or a polyamine. Mixtures of two or more amino compounds can be used for reaction with one or more acylating reagents. In one embodiment, the amino compound has at least one primary amino group (ie, -NH ₂ More preferably, the amine is a polyamine, especially a polyamine containing at least two -NH- groups, either or both of which are primary or secondary amines It is. The amine can be an aliphatic, cycloaliphatic, aromatic or heterocyclic amine.
[0083]
Among the useful amines are the alkylene polyamines, including the polyalkylene polyamines. The alkylene polyamine includes those according to the formula:
[0084]
Embedded image

Wherein n is 1 to about 10; each R is independently a hydrogen atom, a hydrocarbyl group or a hydroxy-substituted hydrocarbyl group or an amine-substituted hydrocarbyl group, which have up to about 30 atoms; Or two R groups on different nitrogen atoms can be linked together to form a U group, provided that at least one R group is a hydrogen atom and U has about 2-10 carbon atoms. It is an alkylene group having an atom. Preferably, U can be ethylene or propylene. Alkylene polyamines where each R is hydrogen or an amino-substituted hydrocarbyl group are useful with ethylene polyamines and ethylene polyamine mixtures. Typically, n has an average value of about 2 to about 7. Such alkylene polyamines include methylene polyamine, ethylene polyamine, propylene polyamine, butylene polyamine, pentylene polyamine, hexylene polyamine, heptylene polyamine and the like. Higher homologs of such amines, and related aminoalkyl-substituted piperazines, are also mentioned.
[0085]
Useful alkylene polyamines include ethylenediamine, triethylenetetramine, propylenediamine, trimethylenediamine, hexamethylenediamine, decamethylenediamine, octamethylenediamine, di (heptamethylene) triamine, tripropylenetetramine, tetraethylenepentamine, trimethylene Diamine, pentaethylenehexamine, di (trimethylene) triamine, N- (2-aminoethyl) piperazine, 1,4-bis (2-aminoethyl) piperazine and the like can be mentioned. Higher homologues obtained by the condensation of two or more of the above alkyleneamines are useful, as are mixtures of any two or more of the above polyamines.
[0086]
Ethylene polyamines, such as those mentioned above, are particularly useful for their price and effectiveness. Such polyamines are described in The Encyclopedia of Chemical Technology (2nd ed., Kirk and Othmer, Vol. 7, pages 27-39, Interscience Publishing, D.J. Which are incorporated herein by reference for their disclosure of useful polyamines. Such compounds are most conveniently prepared by the reaction of an alkylene chloride with ammonia, or the reaction of ethyleneimine with a ring-opening reagent such as ammonia. These reactions produce one complex mixture of alkylene polyamines, including cyclic condensation products such as piperazine.
[0087]
Other useful types of polyamine mixtures include those obtained by stripping the above polyamine mixtures. In this case, low molecular weight polyamines and volatile impurities are removed from the alkylene polyamine mixture, leaving a residue often referred to as "polyamine bottoms". In general, the alkylene polyamine bottoms can be characterized as having less than 2% by weight, usually less than 1% by weight, of substances that boil below about 200 ° C. In the case of ethylene polyamine bottoms, which are readily available and have been found to be very useful, the bottoms may contain less than about 2% by weight of diethylene triamine (DETA) or triethylene in total. Contains tetramine (TETA). A typical sample of such ethylene polyamine bottoms from the Dow Chemical Company (Freeport, Texas), which is called "E-100", has a specific gravity of 1.0168 at 15.6C, It exhibited a nitrogen content of 33.15% by weight and a viscosity of 121 centistokes at 40 ° C. From gas chromatographic analysis of such a sample, it was found that about 0.93% "light end" (mostly DETA), 0.72% TETA, 21.74% tetraethylenepentamine, and It was shown to contain 76.61% and more pentaethylenehexamine (by weight). These alkylene polyamine bottoms include cyclic condensation products (eg, piperazine) and higher homologs such as diethylenetriamine and triethylenetetramine.
[0088]
These alkylene polyamine bottoms can react alone with the acylating agent (where the amino reactant consists essentially of the alkylene polyamine bottoms), or they can be used with other amines and polyamines. Or with alcohols or mixtures thereof. In the latter case, at least one amino reactant contains alkylene polyamine bottoms.
[0089]
Other polyamines are described, for example, in U.S. Pat. Nos. 3,219,666 and 4,234,435, the contents of which are incorporated by reference. The disclosure of amines capable of forming is incorporated herein by reference.
[0090]
In one embodiment, the amine can be a hydroxyamine. Typically, the hydroxyamine is a primary, secondary or tertiary alkanolamine or a mixture thereof. Such an amine may be represented by the formula:
[0091]
Embedded image

Wherein each R is independently a hydrocarbyl group having 1 to about 8 carbon atoms, or a hydroxycarbyl group having 2 to about 8 carbon atoms, preferably 1 to about 4 carbon atoms. A hydrocarbyl group, and R 'is a divalent hydrocarbyl group having about 2 to about 18 carbon atoms, preferably 2 to about 4 carbon atoms. The -R'-OH group in such a formula represents a hydroxyhydrocarbyl group. R ′ can be an acyclic, alicyclic or aromatic group. Typically, R 'is an acyclic, linear or branched alkylene group (eg, an ethylene group, a 1,2-propylene group, a 1,2-butylene group, a 1,2-octadecylene group, etc.). is there. When two R groups are present in the same molecule, they are linked by a direct carbon-carbon bond or through a heteroatom (eg, oxygen or nitrogen) to form a five-membered, six-membered, , A seven-membered ring structure or an eight-membered ring structure. Examples of such heterocyclic amines include N- (hydroxyl lower alkyl) -morpholine, -thiomorpholine, -piperidine, -oxazolidine, -thiazolidine and the like. However, typically, each R 'is independently a methyl, ethyl, propyl, butyl, pentyl or hexyl group.
[0092]
Examples of these alkanolamines include mono-, di- and triethanolamine, diethylethanolamine, ethylethanolamine, butyldiethanolamine, and the like.
[0093]
The hydroxyamine can also be an ether-N- (hydroxyhydrocarbyl) amine. These are the hydroxypoly (hydrocarbyloxy) analogs of the above-described hydroxyamines, which also include hydroxyl-substituted oxyalkylene analogs. Such N- (hydroxyhydrocarbyl) amines are conveniently prepared by the reaction of an epoxide with the amine, and are represented by the following formula:
[0094]
Embedded image

Where x is a number from about 2 to about 15 and R and R 'are the same as described above. R can also be a hydroxypoly (hydrocarbyloxy) group.
[0095]
The acylated nitrogen-containing compounds include amine salts, amides, imides, amidines, amidic acids, amidates and imidazolines, as well as mixtures thereof. To prepare the acylated nitrogen-containing compound from the acylating agent and the amino compound, the one or more acylating agents and the one or more amino compounds are, if necessary, substantially Temperatures from about 80 ° C. to the decomposition point of any of these reactants or carboxylic acid derivatives in the presence of an inert, usually liquid organic liquid solvent / diluent, but usually from about 100 ° C. Heating is performed at temperatures up to about 300 ° C., where 300 ° C. does not exceed this decomposition point. Temperatures from about 125C to about 250C are typically used. The acylating agent and the amino compound are reacted in an amount sufficient to provide from about 1/2 equivalent to about 2 moles of the amino compound per equivalent of the acylating agent.
[0096]
Many patents describe useful acylated nitrogen-containing compounds, including U.S. Patent Nos. 3,172,892; 3,219,666; 3,272,746; No. 3,341,542; No. 3,444,170; No. 3,455,831; No. 3,455,832; No. 3,576,743; No. 3,630. No. 3,632,511; 3,804,763; and 4,234,435. Typical acylated nitrogen-containing compounds of this type include poly (isobutene) -substituted succinic anhydride acylating agents (eg, anhydrides, acids, esters, etc.), wherein the poly (isobutene) substituent is A mixture of ethylene polyamines (having between about 50 and about 400 carbon atoms), which comprises from about 3 to about 7 amino nitrogen atoms per ethylene polyamine, and from about 1 to about 6 Which is produced by the condensation of ammonia and ethylene chloride). The contents of the aforementioned U.S. patents are incorporated herein by reference for their disclosure of acylated amino compounds and methods for their preparation.
[0097]
Other forms of acylated nitrogen compounds belonging to this class include those prepared by reacting a carboxylic acylating agent with a polyamine, wherein the polyamine is obtained by condensing a hydroxy material with an amine. It is a manufactured product. These compounds are described in US Pat. No. 5,053,152, the contents of which are incorporated herein by reference for their disclosure.
[0098]
Other forms of acylated nitrogen compounds belonging to this class include reacting the alkylene amines with the substituted succinic acids or anhydrides and aliphatic monocarboxylic acids having 2 to about 22 carbon atoms. There are products manufactured by this. For these types of acylated nitrogen compounds, the molar ratio of succinic acid to monocarboxylic acid ranges from about 1: 0.1 to about 1: 1. Typical of these monocarboxylic acids are formic acid, acetic acid, dodecanoic acid, butanoic acid, oleic acid, stearic acid, commercially available mixtures of stearic acid isomers (known as isostearic acid), tall oil acids and the like. is there. Such materials are described in further detail in U.S. Pat. Nos. 3,216,936 and 3,250,715, the disclosures of which are hereby incorporated by reference. I have.
[0099]
Still other types of acylated nitrogen compounds useful in making the compositions of the present invention include fatty monocarboxylic acids having about 12 to 30 carbon atoms and the above alkylene amines (typically 2 Reaction products with ethylene polyamines, propylene polyamines or trimethylene polyamines containing from 1 to 8 amino groups and mixtures thereof. The fatty monocarboxylic acid is generally a mixture of straight and branched chain fatty carboxylic acids containing from 12 to 30 carbon atoms. A widely used type of acylated nitrogen compound is the reaction of the above alkylene polyamines with a fatty acid mixture having from about 5 to about 30 mole% of linear fatty acids and from about 70 to about 95 mole% of branched chain fatty acids, Manufactured. Some of these commercial mixtures are widely known on the market as isostearic acid. These mixtures are produced as by-products from the dimerization of unsaturated fatty acids, as described in U.S. Pat. Nos. 2,812,342 and 3,260,671.
[0100]
The branched chain fatty acids also include those whose branches are not substantially alkyl (eg, those present in phenylstearic acid and cyclohexylstearic acid, and chlorostearic acid). Branched fatty carboxylic acid / alkylene polyamine products have been widely described in the art. For example, US Pat. Nos. 3,110,673; 3,251,853; 3,326,801; 3,337,459; 3,405,064; 3,429,674. No. 3,468,639; 3,857,791. The contents of these patents are incorporated herein by reference for their disclosure of fatty acid / polyamine condensates for use in lubricating oil formulations.
[0101]
In one embodiment, the low phosphorus or phosphorus free lubricating oil compositions of the present invention are characterized by a chlorine level of about 10 ppm or less, in one embodiment about 7 ppm or less, and in one embodiment about 5 ppm or less. To do so, the acylated nitrogen-containing compound is free of chlorine or such that the addition of such a compound to the lubricating oil composition results in the formation of a lubricating oil composition having the aforementioned chlorine levels. It must contain low chlorine levels. In one embodiment, the acylated nitrogen-containing compound has a chlorine content of about 50 ppm or less, in one embodiment about 25 ppm or less, and in one embodiment about 10 ppm or less. In one embodiment, the acylated nitrogen-containing compound does not contain chlorine.
[0102]
The acylated nitrogen-containing compound is typically present at a concentration ranging from about 1% to about 25% by weight, and in one embodiment from about 5% to about 15% by weight, at a concentration ranging from about 5% to about 15% by weight. Used in phosphorus lubricating oil compositions. These compounds can be added directly to the lubricating oil composition. In one embodiment, however, they are diluted with a substantially inert, normally liquid organic diluent (eg, mineral oil, naphtha, benzene, toluene or xylene) to form an additive concentrate. These concentrates typically contain from about 1% to about 99% by weight, and in one embodiment about 10% to about 90% by weight of diluent.
[0103]
As noted above, when the low phosphorus or phosphorus free lubricating oil composition is a non-consumable lubricating oil, if desired, small amounts of one or more EP additives (which may be derived from metals and phosphorus) Wherein the amount of phosphorus that contributes to the low phosphorus or phosphorus free lubricating oil composition by the additive is about 0.08% by weight of the low phosphorus or phosphorus free lubricating oil composition. Not exceed. In one embodiment, the phosphorus content does not exceed about 0.07% by weight, in one embodiment does not exceed about 0.06% by weight, in one embodiment does not exceed about 0.05% by weight, In one embodiment, not more than about 0.04% by weight, in one embodiment not more than about 0.035% by weight, in one embodiment not more than about 0.03% by weight, in one embodiment, Not more than about 0.025% by weight, in one embodiment not more than about 0.02% by weight, in one embodiment not more than about 0.015% by weight, and in one embodiment, the phosphorus content is about Does not exceed 0.01% by weight. Phosphorus acids useful in making these EP additives can be represented by the following formula:
[0104]
Embedded image

Here, in equation (A), X ¹ , X ² , X ³ And X ⁴ Is independently oxygen or sulfur; a and b are independently 0 or 1; ¹ , R ² And R ³ Is, independently, a hydrocarbyl group; ³ Can be hydrogen. Illustrative examples include: dihydrocarbyl phosphinodithioate, S-hydrocarbyl phosphonotrithioate, O-hydrocarbyl phosphinodithioate, S, S-dihydrocarbophosphorotetrathioate, O, S-dihydrocarbyl phosphorotrithioate. And phosphorodithioic acid O, O-dihydrocarbyl.
[0105]
Useful phosphorus containing acids are phosphorus and sulfur containing acids. These include acids such as the following: In formula (A), X ³ Or X ⁴ At least one is sulfur, in one embodiment X ³ And X ⁴ Are both sulfur and X ¹ Or X ² At least one is oxygen or sulfur, in one embodiment X ¹ And X ² Are oxygen and a and b are each 1. Mixtures of these acids can be used according to the invention.
[0106]
In the formula (A), R ¹ And R ² Is independently preferably a hydrocarbyl group containing no acetylenic unsaturation, usually a hydrocarbyl group containing no ethylenic unsaturation, wherein in one embodiment the hydrocarbyl group is from about 1 to about 1 50 carbon atoms, in one embodiment, about 1 to about 30 carbon atoms, in one embodiment, about 3 to about 18 carbon atoms, in one embodiment, about 3 to about 8 Has carbon atoms. Each R ¹ And R ² Can be the same as each other, but they can be different, and one or both can be a mixture. R ¹ Group and R ² Examples of groups include isopropyl, n-butyl, isobutyl, amyl, 4-methyl-2-pentyl, isooctyl, decyl, dodecyl, tetradecyl, 2-pentenyl, dodecenyl, phenyl, naphthyl, alkylphenyl, alkylnaphthyl, phenylalkyl , Naphthylalkyl, alkylphenylalkyl, alkylnaphthylalkyl, and mixtures thereof. Specific examples of useful mixtures include, for example, isopropyl / n-butyl; isopropyl / secondary butyl; isopropyl / 4-methyl-2-pentyl; isopropyl / 2-ethyl-1-hexyl; isopropyl / isooctyl; / Decyl; isopropyl / dodecyl; and isopropyl / tridecyl.
[0107]
In the formula (A), R ³ Can be hydrogen or a hydrocarbyl group having 1 to about 12 carbon atoms, in one embodiment, 1 to about 4 carbon atoms (eg, alkyl).
[0108]
The preparation of the metal salt of the phosphorus acid can be performed by reacting the metal or metal oxide. It is sufficient to simply mix and heat these two reactants to cause this reaction, and the resulting product is sufficiently pure for the purposes of the present invention. Typically, the salt formation is performed in the presence of a diluent (eg, alcohol, water or diluent oil). Neutral salts are prepared by reacting one equivalent of a metal oxide or hydroxide with one equivalent of an acid. Basic metal salts are prepared by adding an excess (more than one equivalent) of a metal oxide or hydroxide to one equivalent of phosphorodithioic acid.
[0109]
Useful metal salts of phosphorus-containing acids of the formula (A) include Group IA metals, Group IIA metals or Group IIB metals, aluminum, lead, tin, iron, molybdenum, manganese, cobalt, nickel or bismuth. And salts containing. Zinc is a useful metal. These salts can be neutral or basic salts. Examples of useful metal salts of phosphorus-containing acids and methods of preparing such salts are described in the prior art (eg, US Pat. Nos. 4,263,150; 4,289,635; 4,308,154). Nos. 4,322,479; 4,417,990; and 4,466,895), the disclosures of which are incorporated herein by reference. I have. These salts include Group II metal salts of phosphorodithioic acids such as zinc dicyclohexyl phosphorodithioate, zinc dioctyl phosphorodithioate, barium di (heptylphenyl) phosphorodithioate, cadmium dinonyl phosphorodithioate, and A zinc salt of phosphorodithioic acid formed by the reaction of phosphorus sulfide with an equimolar mixture of isopropyl alcohol and n-hexyl alcohol).
[0110]
In one embodiment, the low phosphorus or phosphorus free lubricating oil composition is characterized by the absence of the aforementioned EP additives.
[0111]
An advantage of using the aforementioned low phosphorus or phosphorus free lubricating oil compositions is that these lubricating oil compositions can be more easily discarded from an environmental standpoint than conventional lubricating oils. This is due to the low or absence of phosphorus and metal containing EP agents in these lubricating oil compositions. On the other hand, conventional lubricating oil compositions typically contain relatively high concentrations of such EP agents.
[0112]
The low phosphorus or phosphorus free lubricating oil composition may contain one or more ashless detergents or dispersants in addition to the acylated nitrogen-containing compound (as mentioned above). Ashless detergents and dispersants depend on their composition, despite the fact that this dispersant can produce non-volatile substances (eg, boron oxide or phosphorus pentoxide) upon combustion. It is, however, usually free of metals and, therefore, does not produce ash containing metals when combusted. Many types are known in the art, some of which are suitable for use in the lubricant compositions of the present invention. These include:
(1) carboxylic acids (or derivatives thereof) containing at least about 34 carbon atoms (in one embodiment, at least about 54 carbon atoms), and organic hydroxy compounds such as amines and phenols, and / or Reaction products with basic inorganic substances. Examples of these "carboxylic dispersants" are described in a number of U.S. Patents, including U.S. Patent Nos. 3,219,666; 4,234,435; and 4,938,881. Have been.
[0113]
(2) Reaction products of relatively high molecular weight aliphatic or alicyclic halides with amines (preferably oxyalkylene polyamines). These may be characterized as "amine dispersants", examples of which are described, for example, in the following U.S. Patents: U.S. Pat. Nos. 3,275,554; 3,438,757; No. 3,454,555; and No. 3,565,804.
[0114]
(3) Reaction products of alkylphenols (where the alkyl group contains at least about 30 carbon atoms) with aldehydes (especially formaldehyde) and amines (especially polyalkylenepolyamines). This can be characterized as a "Mannich dispersant". The materials described in the following U.S. Patents are exemplary: U.S. Pat. Nos. 3,649,229; 3,697,574; 3,725,277; 3,725,480. No. 3,726,882; and No. 3,980,569.
[0115]
(4) a product obtained by post-treating an amine or Mannich dispersant with the following reagents: urea, thiourea, carbon disulfide, aldehyde, ketone, carboxylic acid, hydrocarbon-substituted succinic anhydride, Nitriles, epoxides, boron-containing compounds, phosphorus-containing compounds or analogs thereof. Exemplary materials of this type are described in the following U.S. Patents: U.S. Patents 3,639,242; 3,649,229; 3,649,659; Nos. 3,658,836; 3,697,574; 3,702,757; 3,703,536; 3,704,308; and 3,708,422. .
[0116]
(5) oil-soluble monomers (eg, decyl methacrylate, vinyl decyl ether, and high molecular weight olefins) and monomers containing polar substituents (eg, aminoalkyl acrylate or acrylamide and poly (oxyethylene) substituted acrylates) Interpolymer. These may be characterized as "polymer dispersants", examples of which are disclosed in the following U.S. Patents: U.S. Pat. Nos. 3,329,658; 3,449,250; Nos. 3,519,565; 3,666,730; 3,687,849; and 3,702,300.
[0117]
The above patents are incorporated herein by reference for their disclosure of ashless dispersants.
[0118]
The low phosphorus or phosphorus free lubricating oil composition, when used as a non-consumable lubricating oil, may contain one or more ash-forming detergents or dispersants. Thus, in this embodiment, the low phosphorus or phosphorus free lubricating oil composition is a low ash lubricating oil composition. The ash-forming detergent comprises an alkali metal or alkaline earth metal and a sulfonic acid, a carboxylic acid, or an organic phosphorus-containing acid characterized by at least one direct carbon-phosphorus bond (eg, an olefin polymer (eg, Prepared by treating a polyisobutene having a molecular weight of 1000) with a phosphating agent (eg, phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and sulfur halide, or phosphorothioic acid chloride). And oil-soluble neutral and basic salts. The most commonly used salts of such acids are sodium, potassium, lithium, calcium, magnesium, strontium and barium salts. The concentration of the ash producing detergent or dispersant in the low ash lubricating oil composition can be up to about 2% by weight, in one embodiment up to about 1.5% by weight, as measured by the test procedure of ASTM D874-96. In one embodiment, the range may be sufficient to provide an ash content of up to about 1% by weight, and in one embodiment up to about 0.6% by weight.
[0119]
The low phosphorus or phosphorus free lubricating oil composition may also contain other lubricant additives known in the art. These include, for example, corrosion inhibitors, antioxidants, viscosity modifiers, pour point depressants, friction modifiers, flow modifiers, defoamers and the like.
[0120]
Pour point depressants are used to improve the low temperature properties of oil-based compositions. For example, C.I. V. Smallheer and R.A. See page 8 of Kennedy Smith's "Lubricant Additives" (published by Lezius Hills Co., Cleveland, Ohio, 1967). Examples of useful pour point depressants include polymethacrylates; polyacrylates; polyacrylamides; condensation products of haloparaffin waxes with aromatic compounds; vinyl carboxylate polymers; dialkyl fumarate, vinyl esters of fatty acids and alkyl vinyl ethers Is a terpolymer. Pour point depressants are disclosed in U.S. Pat. Nos. 2,387,501; 2,015,748; 2,655,479; 1,815,022; 2,191,498. Nos. 2,666,746; 2,721,877; 2,721,878; and 3,250,715, the contents of which are incorporated herein by reference. Is incorporated herein by reference.
[0121]
Antifoams are used to reduce or prevent the formation of stable foam. Typical defoamers include silicone or organic polymers. Other antifoam compositions are described in Henry T.W. Kerner, "Foam Control Agents" (Noyes Data Corporation, 1976), pages 125-162.
[0122]
Each of the foregoing additives, when used, is used in an amount that is functionally effective to impart the desired properties to the lubricant. Thus, for example, if the additive is a corrosion inhibitor, a functionally effective amount of the corrosion inhibitor is an amount sufficient to impart the desired corrosion inhibiting properties to the lubricant. Generally, the concentration of each of these additives, when used, ranges from about 0.001% to about 20% by weight, based on the total weight of the low phosphorus or phosphorus free lubricating oil composition. In the form, it ranges from about 0.01% to about 10% by weight.
[0123]
These additives may be added directly to the low phosphorus or phosphorus free lubricating oil composition. However, in one embodiment, they are diluted with a substantially inert, normally liquid organic diluent (eg, mineral oil, naphtha, benzene, toluene, or xylene) to form an additive concentrate. These concentrates typically contain from about 1% to about 99%, in one embodiment about 10% to about 90%, by weight of such diluent. In one embodiment, the diluent is a sulfur-free composition.
[0124]
(Examples 1 and 2)
Examples of low phosphorus or phosphorus free lubricating oil compositions that may be used are disclosed below (provided in the following table that all values provided for the components of this composition (excluding antifoams) Wt%).
[0125]
[Table 1]

While the invention has been described in connection with preferred embodiments thereof, it should be understood that various modifications thereof will become apparent to those skilled in the art upon reading the present specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover modifications within the scope of the appended claims.
[Brief description of the drawings]
In the accompanying drawings, the same parts and features have the same reference numerals.
FIG.
FIG. 1 is a schematic diagram of a camless internal combustion engine useful in accordance with one embodiment of the method of the present invention, the engine including an exhaust gas aftertreatment device.
FIG. 2
FIG. 2 is a schematic diagram of a camless internal combustion engine useful in accordance with another embodiment of the method of the present invention, the engine including an exhaust gas aftertreatment device.
FIG. 3
FIG. 3 is a schematic diagram of a camless internal combustion engine useful in accordance with another embodiment of the method of the present invention.

Claims (13)

A method of operating a camless internal combustion engine, comprising:
(A) operating the engine using a normally liquid or gaseous fuel composition; and (B) lubricating the engine using a low phosphorus or phosphorus free lubricating oil composition. The low phosphorus or phosphorus-free lubricating oil composition optionally contains an extreme pressure additive composed of metal and phosphorus, provided that the low phosphorus or phosphorus-free lubricating oil composition contains the extreme pressure additive. Wherein the amount of phosphorus contributing to the oil composition does not exceed about 0.08% by weight, based on the weight of the low phosphorus or phosphorus free lubricating oil composition,
A method comprising: 2. The method of claim 1, wherein said method further comprises the following additional steps:
(C) removing a portion of the low phosphorus or phosphorus free lubricating oil composition from the engine, wherein the removed portion of the low phosphorus or phosphorus free lubricating oil composition comprises (i) the fuel composition Being blended with the fuel composition and operating with the engine and consumed with the fuel composition, or (ii) blended with the exhaust gas from the engine and removed from the engine with the exhaust gas; and (D) adding an additional amount of the low phosphorus or phosphorus free lubricating oil composition to the engine to replenish the removed portion of the low phosphorus or phosphorus free lubricating oil composition. The method of claim 1, wherein the engine comprises a camless valve mechanism. The method according to claim 1, wherein the intake and exhaust valves used with the engine are electro-started, hydraulic-started or electro-hydraulic-started. The method of claim 1, wherein the intake and exhaust valves used with the engine are capable of changing their lift schedule for various engine operating conditions. A blend of the fuel composition formed in step (C) with the low phosphorus or phosphorus free lubricating oil composition comprising from about 0.01% to about 5% by weight of the low phosphorus or phosphorus free lubricating oil; 3. The method of claim 2, wherein the method is comprised of a composition. In the step (C), the removed portion of the low-phosphorus or non-phosphorus-free lubricating oil composition includes a fuel tank, a fuel return pipe, a fuel injector, an intake manifold, a blow-by gas reducing device, and an exhaust gas recirculation of the engine. 3. The method of claim 2, wherein in a system or air intake system, the removal portion is introduced into the fuel composition or the removal portion is blended with exhaust gas upstream from an exhaust gas aftertreatment device. The method of claim 1, wherein the low phosphorus or phosphorus free lubricating oil composition is comprised of components that add only C, H, O or N, and optionally, Si to the composition. The method of claim 1, wherein the low phosphorus or phosphorus free lubricating oil composition is comprised of an acylated nitrogen-containing compound having a substituent of at least about 10 aliphatic carbon atoms. 20. The method of claim 19, wherein the acylated nitrogen-containing compound is a polyisobutene-substituted succinimide containing at least about 50 aliphatic carbon atoms in the polyisobutene group. The method of claim 1, wherein the extreme pressure additive is a compound represented by the formula:

Wherein, in formula (A), X ¹ , X ² , X ³ and X ⁴ are independently O or S, a and b are independently 0 or 1, and R ¹ , R ² and R ³ are independently hydrocarbyl groups, and R ³ can be hydrogen, provided that the amount of phosphorus that contributes to the first lubricating oil composition by the salt is equal to the amount of the first lubricating oil Does not exceed about 0.04% by weight, based on the weight of the composition. The low phosphorus or phosphorus free lubricating oil composition comprises at least one ashless detergent or dispersant, corrosion inhibitor, antioxidant, viscosity modifier, pour point depressant, friction modifier, flow modifier or The method of claim 1, comprising a defoamer. The method of claim 1, wherein the low phosphorus or phosphorus free lubricating oil composition has a sulfur content of less than about 250 ppm.