JP3920363B2 - Dispersant for lubricating oil - Google Patents

Description

【００８４】
成分ａ）は実施例Ａ−５におけるように生成され、そして成分ｂ）は実施例Ｂ−４におけるように生成される。成分ｃ）は亜鉛ジアルキルジチオホスフェートの混合物であり、その５０％はＣ₃及びＣ₆の第二級アルキル基であり、そして５０％はＣ₃、Ｃ₄及びＣ₈の第一級及び第二級アルキル基である。成分ｄ）は、１．３２％の過度塩基スルホン酸カルシウム、０．７％の低塩基スルホン酸カルシウム、及び０．６５％の硫化アルキルフェナートの混合物である。成分ｅ）は、０．８％の第三級ブチル化フェノール性酸化防止剤、０．２％の芳香族アミン酸化防止剤、０．４％の硫化オレフィン酸化抑制剤、及び０．００１％未満のシリコーンタイプの泡抑制剤の混合物である。この成分混合物を生成させる際に使用される商業的物質は、ＨＩＴＥＣ^(R)６１１、１６５６、４７３３、７１６９及び７３０４添加剤（Ｅｔｈｙｌ Ｐｅｔｒｏｌｅｕｍ Ａｄｄｉｔｉｖｅｓ，Ｌｔｄ．；Ｅｔｈｙｌ Ｐｅｔｒｏｌｅｕｍ Ａｄｄｉｔｉｖｅｓ，Ｉｎｃ．）；ＯＬＯＡ ２１６Ｃ 添加剤（Ｃｈｅｖｒｏｎ Ｃｈｅｍｉｃａｌ Ｃｏｍｐａｎｙ）；並びにＮａｕｇａｌｕｂｅ ４３８Ｌ 添加剤（Ｕｎｉｒｏｙａｌ Ｃｈｅｍｉｃａｌ Ｃｏｍｐａｎｙ）を含む。粘度指数向上剤は、ＯＣＰタイプ（Ｐａｒａｔｏｎｅ ８０００；Ｅｘｘｏｎ Ｃｈｅｍｉｃａｌ Ｃｏｍｐａｎｙ）のものである。仕上げされた潤滑剤は、ＡＳＴＭ Ｄ２８９６の手順を使用して１グラムあたり１０ｍｇのＫＯＨの全アルカリ価（ＴＢＮ）、０．１２％の亜鉛含量、０．１１％のリン含量、０．３５％のカルシウム含量及び０．０２％のホウ素含量を有する。
【００８５】
実施例ＩＩ
本発明の１０Ｗ−４０潤滑剤を、以下の成分から生成させる：
【００８６】
【表２】

【００８７】
成分ａ）は実施例Ａ−３７におけるように生成され、そして成分ｂ）は実施例Ｂ−４におけるように生成される。成分ｃ）はＣ₃及びＣ₆の亜鉛ジアルキルジチオホスフェートの混合物である。成分ｄ）は、１．１８％の過度塩基スルホン酸カルシウム、０．８５％の低塩基スルホン酸カルシウム、及び０．３３％の硫化アルキルフェナートの混合物である。成分ｅ）は、１．０％の第三級ブチル化フェノール性酸化防止剤、０．５％の芳香族アミン酸化防止剤、及び０．００１％未満のシリコーンタイプの泡抑制剤の混合物である。
【００８８】
実施例ＩＩＩ
本発明の仕上げされた潤滑剤を、実施例Iにおけるのと同じ成分から、ただし以下の割合を使用して製造する：
【００８９】
【表３】

【００９０】
実施例ＩＶ
本発明の潤滑油組成物を、以下の表中に与えられた割合で実施例IIにおける成分ａ）及びｂ）、成分ｄ）として４００ＴＢＮの過度塩基アルキルベンゼンスルホン酸マグネシウム、並びに実施例Iにおける成分ｃ）及びｅ）を使用して製造する：
【００９１】
【表４】

【００９２】
本発明の組成物の性能を、制御された条件下で酷使に耐えるジーゼルエンジン潤滑剤の性能を測定するＭＷＭ ＫＤ １２Ｅエンジン試験の結果によって例示する。性能は数のスケールに換算して表され、そして数の値が大きければ大きいほど性能はそれだけ良い。２つのこのような試験において、本発明の潤滑剤及び本発明のものではない匹敵する潤滑剤を使用した。両方とも、分散剤に加えて、第一級及び第二級アルキル亜鉛ジアルキルジチオホスフェートの混合物、高塩基及び低塩基スルホン酸カルシウムの混合物、並びにカルシウム硫化アルキルフェナートを実質的に同じ相対的割合で含んでいた。これらの２つの潤滑剤の間の主な差は、本発明のものではない潤滑剤の分散剤がより高い用量レベルの成分ａ）だけから成っていたことである。両方の潤滑剤ともに、１０Ｗ−４０規格グレードに調合され、そして１グラムあたり１０ｍｇのＴＢＮ及び１．４２％の灰分レベルを有していた。本発明の潤滑剤は、本発明のものではない潤滑剤に関する７０．９の評点と比較して８０．６の評点を与えた。
【００９３】
Ｖｏｌｋｓｗａｇｅｎ Ｉｎｔｅｒｃｏｏｌｅｄ（ＰＶ １４３１）Ｔｅｓｔを使用する類似の様式で行われた試験において、実施例IIにおけるようにして生成された本発明の典型的な組成物は、本発明のものではない匹敵する潤滑剤組成物よりも顕著に良いピストン清潔度を与えることが見い出された。両方の場合ともに、ジーゼルエンジンは、０．３％の硫黄含量を有するジーゼル燃料で運転された。
【００９４】
標準的なＯＭ ３６４Ａ 試験において、本発明の１０Ｗ−４０潤滑剤は、優れた分散性及び光沢制御性能、並びに良好な摩耗性能を示した。
【００９５】
本発明によって可能にされた優れたフルオロエラストマーシール性能を、厳格なＶｏｌｋｓｗａｇｅｎ ＰＶ ３３４４試験手順を使用して行われた試験の結果によって例示する。一組の試験においては、ＶＩＴＯＮ ＡＫ６フルオロエラストマー及び実施例IのＳＡＥ １０Ｗ−４０の酷使に耐えるクランクケース潤滑剤を使用した。表Iは、これらの結果を要約する。
【００９６】

同様の組の試験を、同じ試験手順及びフルオロエラストマーを使用して、しかし実施例IIIにおけるようにして生成された組成物を使用して実施した。結果を表II及びIII中に要約する。
【００９７】

これらの試験において本発明の潤滑剤組成物は厳しいＶｏｌｋｓｗａｇｅｎ ＰＶ ３３４４試験手順のすべての要件に合格しそしてそうする際に優れた結果を与えたことが表I、II及びIIIから見られるであろう。類似の優れた結果は、本発明の他の組成物によっても達成された。
【００９８】
本明細書中で使用される時には、“油溶性”という術語は、議論されている生成物が２５℃で少なくとも１重量％の濃度まで１００溶媒中性鉱油中に溶解又は安定に分散され得ることを意味する。
【００９９】
この開示を通じて種々の場所で、特許及び他の刊行物が引用された。すべてのこのような文書の内容は、まるでこの明細書中で完全に述べられたかのように引用によって全部が本明細書中に組み込まれる。
【０１００】
本発明の主なる特徴及び態様は以下の通りである。
【０１０１】
１．ａ）アミノグアニジンを長鎖のアルキル又はアルケニルコハク酸のアシル化剤と１モルの該アシル化剤あたり約０．４〜約１．３モルのアミノグアニジン及び／又はその塩基性塩のモル比で反応させることによって生成された油溶性生成物、並びに
ｂ）（Ｉ）非環式ヒドロカルビルコハク酸のアシル化剤及び（ＩＩ）１分子あたり平均で約３〜約６の窒素原子を有するアルキレンポリアミンを１モルの（ＩＩ）あたり約１．６〜２モルの（Ｉ）のモル比で反応させてスクシンイミドを生成させ、そしてこのようにして生成されたスクシンイミドを同時に又は任意の順序でそして約１５０〜約１８０℃の範囲の温度で（III）分子中に２０未満の炭素原子を有する少なくとも一種のジカルボン酸のアシル化剤、及び（ＩＶ）少なくとも一種のホウ素化合物と共に加熱して、（１）生成物に伴う可能性がある溶媒又は希釈剤の重量を、もしあれば、除いて１グラムの生成物あたり約３３〜約４５ミリグラムのＫＯＨの範囲の全アルカリ価、及び（２）生成物に伴う可能性がある溶媒及び／又は希釈剤の重量を除いて約１．０〜約１．４重量％の範囲のホウ素含量を有する生成物を生成させることによって生成された油溶性生成物を含んで成り、０．７〜１．８重量部のａ）からの窒素ごとに約０．３〜約１．５重量部のｂ）からの窒素が存在するようにａ）及びｂ）が釣り合わせられる油溶性分散剤組成物。
【０１０２】
２．ａ）における該モル比が１モルの該アシル化剤あたり約０．８〜約１．３モルのアミノグアニジン及び／又はその塩基性塩であり、ｂ）の該アルキレンポリアミンが１分子あたり平均で約４〜約５の窒素原子を有し、ｂ）における１モルの（ＩＩ）あたり（Ｉ）の該モル比が１モルの（ＩＩ）あたり約１．８〜２モルであり、そして０．８〜１．７重量部のａ）からの窒素ごとに約０．４〜約１．４重量部のｂ）からの窒素が存在する、上記１記載の組成物。
【０１０３】
３．該成分ａ）が、生成物に伴う溶媒及び／又は希釈剤の重量を、もしあれば、除いてそれが約１重量％までのホウ素含量を有するようにホウ素化される、上記２記載の組成物。
【０１０４】
４．１〜９９重量％の少なくとも一種の粘着性を滑らかにするオイル及び９９〜１重量％の上記１記載の組成物を含んで成る組成物。
【０１０５】
５．１〜９９重量％の少なくとも一種の粘着性を滑らかにするオイル及び９９〜１重量％の上記３記載の組成物を含んで成る組成物。
【０１０６】
６．ａ）アミノグアニジンを長鎖のアルキル又はアルケニルコハク酸のアシル化剤と１モルの該アシル化剤あたり約０．４〜約１．３モルのアミノグアニジン及び／又はその塩基性塩のモル比で反応させることによって生成された油溶性生成物、
ｂ）（Ｉ）非環式ヒドロカルビルコハク酸のアシル化剤及び（ＩＩ）１分子あたり平均で約３〜約６の窒素原子を有するアルキレンポリアミンを１モルの（ＩＩ）あたり約１．６〜２モルの（Ｉ）のモル比で反応させてスクシンイミドを生成させ、そしてこのようにして生成されたスクシンイミドを同時に又は任意の順序でそして約１５０〜約１８０℃の範囲の温度で（III）分子中に２０未満の炭素原子を有する少なくとも一種のジカルボン酸のアシル化剤、及び（ＩＶ）少なくとも一種のホウ素化合物と共に加熱して、（１）生成物に伴う可能性がある溶媒又は希釈剤の重量を、もしあれば、除いて１グラムの生成物あたり約３３〜約４５ミリグラムのＫＯＨの範囲の全アルカリ価、及び（２）生成物に伴う可能性がある溶媒及び／又は希釈剤の重量を除いて約１．０〜約１．４重量％の範囲のホウ素含量を有する生成物を生成させることによって生成された油溶性生成物、
ｃ）少なくとも一種の油溶性金属ジヒドロカルビルジチオホスフェート、
ｄ）少なくとも一種のアルカリ又はアルカリ土類金属含有洗剤、並びに
ｅ）少なくとも一種の酸化抑制剤、少なくとも一種の泡抑制剤、少なくとも一種の錆抑制剤、少なくとも一種の腐食抑制剤、及び少なくとも一種の摩擦抑制剤から選ばれた１以上の抑制剤
を含んで成る添加剤濃厚物であって、該成分ａ）及びｂ）が０．７〜１．８重量部のａ）からの窒素ごとに約０．３〜約１．５重量部のｂ）からの窒素が存在するように釣り合わせられ、そして成分ａ）、ｂ）、ｃ）、ｄ）及びｅ）が、少ない割合の添加剤濃厚物をベースオイル中にブレンドすることが分散剤量の上のように釣り合わせられたａ）＋ｂ）、摩耗抑制量のｃ）、洗剤量のｄ）、及び抑制量の選ばれた各々の該抑制剤を含むオイルブレンドを与えるように添加剤濃厚物中で釣り合わせられる添加剤濃厚物。
【０１０７】
７．該金属ジヒドロカルビルジチオホスフェートが少なくとも一種の亜鉛ジアルキルジチオホスフェート耐摩耗／極端圧力剤である、上記６記載の組成物。
【０１０８】
８．該亜鉛ジアルキルジチオホスフェートのアルキル基が第一級アルキル基及び第二級アルキル基の混合物である、上記７記載の組成物。
【０１０９】
９．該成分ａ）が、生成物に伴う溶媒及び／又は希釈剤の重量を、もしあれば、除いてそれが約１重量％までのホウ素含量を有するようにホウ素化される、上記６記載の組成物。
【０１１０】
１０．該金属ジヒドロカルビルジチオホスフェートが少なくとも一種の亜鉛ジアルキルジチオホスフェート耐摩耗／極端圧力剤である、上記９記載の組成物。１１．該亜鉛ジアルキルジチオホスフェートのアルキル基が第一級アルキル基及び第二級アルキル基の混合物である、上記１０記載の組成物。
【０１１１】
１２．多い量の少なくとも一種の粘着性を滑らかにするオイル、並びに
ａ）アミノグアニジンを長鎖のアルキル又はアルケニルコハク酸のアシル化剤と１モルの該アシル化剤あたり約０．４〜約１．３モルのアミノグアニジン及び／又はその塩基性塩のモル比で反応させることによって生成された、少ない分散剤量の油溶性生成物、
ｂ）（Ｉ）非環式ヒドロカルビルコハク酸のアシル化剤及び（ＩＩ）１分子あたり平均で約３〜約６の窒素原子を有するアルキレンポリアミンを１モルの（ＩＩ）あたり約１．６〜２モルの（Ｉ）のモル比で反応させてスクシンイミドを生成させ、そしてこのようにして生成されたスクシンイミドを同時に又は任意の順序でそして約１５０〜約１８０℃の範囲の温度で（III）分子中に２０未満の炭素原子を有する少なくとも一種のジカルボン酸のアシル化剤、及び（ＩＶ）少なくとも一種のホウ素化合物と共に加熱して、（１）生成物に伴う可能性がある溶媒又は希釈剤の重量を、もしあれば、除いて１グラムの生成物あたり約３３〜約４５ミリグラムのＫＯＨの範囲の全アルカリ価、及び（２）生成物に伴う可能性がある溶媒及び／又は希釈剤の重量を除いて約１．０〜約１．４重量％の範囲のホウ素含量を有する生成物を生成させることによって生成された、少ない分散剤量の油溶性生成物、
ｃ）少ない摩耗抑制量の、少なくとも一種の油溶性金属ジヒドロカルビルジチオホスフェート、
ｄ）少ない洗剤量の、少なくとも一種のアルカリ又はアルカリ土類金属含有洗剤、並びに
ｅ）少なくとも一種の酸化抑制剤、少なくとも一種の泡抑制剤、少なくとも一種の錆抑制剤、少なくとも一種の腐食抑制剤、及び少なくとも一種の摩擦抑制剤から選ばれた、少ない抑制剤量の１以上の抑制剤
を含んで成る潤滑油組成物であって、該潤滑油組成物が０．０４２重量％よりも多いｂ）からの窒素を含まないという条件付きで、該成分ａ）及びｂ）が０．７〜１．８重量部のａ）からの窒素ごとに約０．３〜約１．５重量部のｂ）からの窒素が存在するように釣り合わせられる潤滑油組成物。
【０１１２】
１３．粘度指数向上量の粘度指数向上剤を更に含んで成る、上記１２記載の組成物。
【０１１３】
１４．該金属ジヒドロカルビルジチオホスフェートが少なくとも一種の亜鉛ジアルキルジチオホスフェート耐摩耗／極端圧力剤である、上記１２記載の組成物。
【０１１４】
１５．該亜鉛ジアルキルジチオホスフェートのアルキル基が第一級アルキル基及び第二級アルキル基の混合物である、上記１４記載の組成物。
【０１１５】
１６．該組成物が粘度指数向上量の粘度指数向上剤を更に含んで成り、そして該金属ジヒドロカルビルジチオホスフェートが少なくとも一種の亜鉛ジアルキルジチオホスフェート耐摩耗／極端圧力剤である、上記１２記載の組成物。
【０１１６】
１７．ｅ）が、少ない酸化抑制量の少なくとも一種の酸化抑制剤、少ない泡抑制量の泡抑制剤、及び少ない摩擦抑制量の摩擦抑制剤を含んで成る、上記１２記載の組成物。
【０１１７】
１８．該成分ａ）が、生成物に伴う溶媒及び／又は希釈剤の重量を、もしあれば、除いてそれが約１重量％までのホウ素含量を有するようにホウ素化される、上記１２記載の組成物。
【０１１８】
１９．該組成物が粘度指数向上量の粘度指数向上剤を更に含んで成り、そして該金属ジヒドロカルビルジチオホスフェートが少なくとも一種の亜鉛ジアルキルジチオホスフェート耐摩耗／極端圧力剤である、上記１８記載の組成物。
【０１１９】
２０．該亜鉛ジアルキルジチオホスフェートのアルキル基が第一級アルキル基及び第二級アルキル基の混合物であり、そしてｅ）が、少ない酸化抑制量の少なくとも一種の酸化抑制剤、少ない泡抑制量の泡抑制剤、及び少ない摩擦抑制量の摩擦抑制剤を含んで成る、上記１９記載の組成物。[0001]
The present invention relates to new and highly useful dispersants for use as additives in natural and synthetic lubricating oils. More specifically, the present invention is a novel having reduced reactivity to fluoroelastomers combined with effective dispersibility, especially for engine oils for diesel engine service that withstand spark-ignited passenger car service or abuse. Relates to a dispersant composition.
[0002]
An ongoing problem in lubrication technology is to provide lubricant compositions that meet the demands placed on them by creative equipment manufacturers. One such requirement is that the lubricant satisfies one or more tests for fluoroelastomer degradation under specified laboratory test conditions. The commercial reality is that if a lubricant fails to pass one or more appropriate tests, it is unlikely to be acceptable in the market. Standard test methods for evaluating the fluoroelastomer compatibility of the lubricant composition include the Volkswagen PV 3334 Seal Test and the CCMC Viton Seal Test (CEC L-39-T-87 Oil / Elastomer Compatibility Test).
[0003]
More recently, a new and more stringent fluoroelastomer test procedure has been developed, namely the Volkswagen PV 3344 Seal Test. This test is so severe that various commercially available premium motor oils from various manufacturers have been found to fail this test.
[0004]
Thus, a need has arisen for dispersants that exhibit reduced hostility to fluoroelastomers in at least one of the above standard test procedures. At the same time, it is important that the product has sufficient effectiveness as a dispersant satisfying the various requirements of sludge, varnish and wear control.
[0005]
The present invention appears to meet the above needs in an effective and efficient manner. Because the dispersant compositions of the present invention are hardly hostile to fluoroelastomers and most if not all can achieve acceptable results in one or more of the above test procedures, It seems to meet these requirements. Furthermore, the dispersant of the present invention allows highly effective control of sludge, gloss and wear under various types of engine service.
[0006]
According to the present invention,
a) Aminoguanidine from about 0.4 to about 1.3 moles [and preferably from about 0.8 to about 1.3 moles per long chain alkyl or alkenyl succinic acylating agent and 1 mole of the acylating agent. An oil soluble product produced by reacting at a molar ratio of aminoguanidine and / or its basic salt
b) (I) an acyclic hydrocarbyl succinic acylating agent and (II) an alkylene having an average of about 3 to about 6 nitrogen atoms [and preferably an average of about 4 to about 5 nitrogen atoms] per molecule The polyamine is reacted at a molar ratio of about 1.6-2 [and preferably about 1.8-2] moles of (I) per mole of (II) to produce a succinimide and thus produced Succinimide simultaneously or in any order and at a temperature in the range of about 150 to about 180 ° C. (III) at least one dicarboxylic acid acylating agent having less than 20 carbon atoms in the molecule, and (IV) at least one (1) [excluding the weight of solvent or diluent, if any, as an active ingredient that may accompany the product] A total base number in the range of about 33 to about 45 milligrams of KOH, and (2) [excluding the weight of solvent and / or diluent that may accompany the product again] about 1.0 Oil-soluble product produced by producing a product having a boron content in the range of ~ 1.4 wt%
About 0.3 to about 0.7 to 1.8 parts by weight of nitrogen from a) [and preferably 0.8 to 1.7 parts by weight of nitrogen from a)] An oil-soluble dispersion in which a) and b) are balanced so that there is 1.5 parts by weight of nitrogen from b) [and preferably from about 0.4 to about 1.4 parts by weight of nitrogen from b). An agent composition is provided.
[0007]
Another embodiment of the present invention comprises 1 to 99% by weight of at least one viscosity-viscosity oil and 99 to 1% by weight of the above-balanced ingredients a ) And b).
[0008]
Yet another embodiment is the above components a) and b), c) balanced as above, at least one oil-soluble metal dihydrocarbyl dithiophosphate [preferably one or more zinc dialkyldithiophosphate antiwear / D) at least one alkali or alkaline earth metal-containing detergent [eg, alkali or alkaline earth metal sulfonate, carboxylate, salicylate, or sulfurized alkyl phenate Or two or more combinations of such detergents], and e) an additive comprising one or more inhibitors selected from oxidation inhibitors, foam inhibitors, rust inhibitors, corrosion inhibitors and friction inhibitors. Concentrate, wherein components a), b), c), d) and e) are low in additive concentration Blending thick into base oil [eg at concentrations in the range of 3.2 to 16.1% by weight on an active ingredient basis] balanced above the amount of dispersant a) + b) wear A crankcase lubricant additive [DI] balanced in an additive concentrate to provide an oil blend comprising an inhibitory amount c), a detergent amount d), and an inhibitory amount of each selected inhibitor. Additive concentrates formulated for use as-also known as packs. On an active ingredient basis, a small dispersion of a) + b) in the finished lubricant is typical, provided that the level of nitrogen from b) in the finished lubricant does not exceed 0.042%. Specifically, it is in the range of about 2 to about 5.5% by weight. Similarly, the low wear inhibition amount of c) in the finished lubricating oil is typically in the range of about 0.5 to about 1.25% by weight and the wear inhibitor is in the form of a phosphorus-containing product. At times, a low wear inhibitor amount is typically equivalent to a phosphorus content in the finished lubricating oil in the range of about 0.04 to about 0.12% by weight phosphorus. Similarly, the d) low detergent level in the finished lubricating oil is typically in the range of about 0.5 to about 3.5% by weight, with low oxidation inhibitor in the finished lubricating oil. The amount of oxidation inhibition is typically in the range of about 0.2 to about 3% by weight, and the amount of low foam control in the finished lubricating oil is typically about 0.0002 to about The amount of rust inhibition of the rust inhibitor in the finished lubricating oil, which is in the range of 0.001% by weight, is typically in the range of about 0.01 to about 0.4% by weight and finished. The low corrosion inhibition amount of the corrosion inhibitor in the lubricating oil is typically in the range of about 0.01 to about 0.04 weight percent and the low friction inhibition amount of the friction inhibitor in the finished lubricating oil. Is typically in the range of about 0.02 to about 2 weight percent. In each case, each of the selected components of each component a), b), c) and d), and e) may be a single component, or it may be of two or more specified types of components. A mixture may be used.
[0009]
Further embodiments include a large amount of at least one tack smoothing oil, a small amount of dispersant balanced a) + b), a small amount of friction suppression c), a small amount of detergent. d), and at least one inhibitor of e), for example, if necessary, but preferably with a low oxidation-inhibiting amount of at least one oxidation inhibitor, optionally, but preferably with a low foam-inhibiting amount. Foam suppressant, if necessary, comprising a small amount of friction inhibitor, if necessary, a small amount of rust inhibitor, and optionally, a small amount of corrosion inhibitor A finished lubricating oil composition is provided. The finished lubricating oil composition preferably additionally comprises a small viscosity enhancing amount of at least one viscosity index improver. Accordingly, the present invention provides a lubricant composition comprising an oil that smoothes tack and one or more and preferably all of the following ingredients: a viscosity index improver, a metal (most preferably zinc ) Dialkyl dithiophosphates, alkali or alkaline earth metal detergents (preferably sulfonates, sulfurized phenates and / or salicylates), antioxidants (preferably phenolic, aromatic amines, sulfurized olefins or copper based), and Antifoam (preferably silicone based). Other typical additive components may also be present. For further details, see, for example, US Pat. No. 5,137,980.
[0010]
Yet another embodiment is for imparting dispersibility and minimizing the degradation of fluoroelastomers that come into contact with oil during additive qualification testing or during actual service conditions. Including the use of components a) and b) balanced as above in small amounts in oils that smooth the tack.
[0011]
In each and any of the above-described embodiments, component a) is a boronated component, i.e., the product may accompany the product with a boron compound or other suitable boron source. It is not necessary to heat the solvent and / or diluent, if any, at a sufficiently high temperature to produce a product having a boron content in the range of up to about 1% by weight, if any. Is also preferable.
[0012]
These and other embodiments of the present invention will become more apparent from the following description and the appended claims.
[0013]
Base oil. The base oil used in producing the lubricant composition of the present invention may be a natural or synthetic oil that smoothes the tack, or a suitable blend thereof. Thus, the base oil may be a hydrocarbon oil derived from petroleum (or bituminous sandstone, coal, shale, etc.). Similarly, base oils include natural oils of appropriate viscosity, such as rapeseed oil, as well as synthetic oils, such as hydrogenated polyolefin oils; poly-α-olefins (eg, hydrogenated or unhydrogenated α-olefin oligomers, such as hydrogenated poly-1- Decene); alkyl esters of dicarboxylic acids; complex esters of dicarboxylic acids; polyglycols and alcohols; and the like, or the like. Mixtures of appropriate proportions of mineral, natural and / or synthetic oils can also be used.
[0014]
In most cases, the base oil is preferably a passenger car engine oil, a diesel engine oil that withstands abuse, or a mineral oil derived from petroleum of the appropriate type and viscosity for use in generating drive train lubricants. is there.
[0015]
Ingredient a). For convenience, the term “AG dispersant” refers to about 0.4 to 1.3 moles of amino per aminoguanidine or its basic salt with hydrocarbyl-substituted succinic acid or anhydride and 1 mole succinic acid or anhydride compound. Used to name the product made by reacting at a molar ratio of guanidine or its basic salt. Similarly, the term “boronated AG dispersant” is used in two stages: (I) aminoguanidine or its basic salt hydrocarbyl-substituted succinic acid or anhydride and 1 mole of succinic acid or anhydride. Production made by reacting at a molar ratio of about 0.4 to 1.3 moles of aminoguanidine or its basic salt per compound and (II) boration of the product thus produced Used to name things.
[0016]
In order to produce AG dispersants, appropriately balanced an aliphatic hydrocarbyl substituted succinic acid derivative (acid, anhydride, lower alkyl ester, or acyl halide) and aminoguanidine or its basic salt The mixture is heated, preferably under an inert atmosphere, at a temperature in the range of about 80 to about 200 ° C and preferably in the range of 140 to 200 ° C. Most preferred is a temperature in the range of 160-170 ° C. This reaction can be carried out in the presence or absence of a solvent or reaction diluent. When using an alkenyl succinic acylating agent derived from a polyolefin whose alkenyl substituent is of relatively low molecular weight (eg, GPC number average molecular weight of 1300), the acylation reaction is carried out in the absence of a reaction diluent, It is then preferred to add a diluent, such as mineral oil, to the reaction product after it has been produced. On the other hand, for alkenyl succinic acylating agents in which the alkenyl substituent is derived from a polyolefin of some relatively high molecular weight (eg, GPC number average molecular weight of 2100), the reaction is carried out in a suitable diluent such as process oil or the like. It is desirable to do in. The reaction time is typically in the range of 1 to 4 hours. Suitable inert atmospheres include nitrogen, argon, krypton, neon and the like. As noted above, using products made using about 0.4 to 1.3 moles of aminoguanidine or its basic salt per mole of aliphatic hydrocarbyl substituted succinic acid derivative. Is required according to the present invention.
[0017]
In order to produce a borated AG dispersant, the AG dispersant produced as described above is combined with a suitable boron-containing material to produce a product (diluent that may accompany the product). Or (except for the weight of the solvent) to contain up to about 1% by weight boron. Temperatures in the range of about 80 to about 200 ° C. are generally satisfactory for use in the boronation reaction. Appropriate methods for performing the boration are very well known to those skilled in the art. In this connection, U.S. Pat. Nos. 3,087,936, 3,254,025, 3,322,670, 3,344,069, 4,080,303, 4,426. 305, 4,925,983 and 5,114,602.
[0018]
AG dispersant is 1590cm^-1Characterized by having an infrared peak in the region. In addition, the spectrum is 1690 cm^-1An AG dispersant that does not show this latter peak can also be used. When made at a molar ratio of about 1: 1 or less, 1725 cm^-1The peak appears. 1590cm^-1This peak is almost absent in the example of US Pat. No. 5,080,815. The chemical structure of the products of the present invention is unknown, but based on their infrared spectra, the 1640 cm present in the example of US Pat. No. 5,080,815.^-1They appear to have no significant content of triazole moieties, as indicated by the absence of the IR peak.
[0019]
Producing suitable aliphatic hydrocarbyl substituted succinic acid derivatives (acids, anhydrides, lower alkyl esters, or acyl halides) such as alkenyl succinic anhydrides to be used in the reaction with aminoguanidine or its basic salts Methods for doing this are known. Such acylating agents are described in the literature, for example, U.S. Pat. Nos. 3,215,707, 3,219,666, 3,231,587, 3,254,025, 3,282, 955, 3,361,673, 3,401,118, 3,912,764, 4,110,349, 4,234,435, 4,908,145 5,071,919, 5,080,815 and 5,137,978 have been extensively described and discussed. In fact, this type of suitable acylating agent is produced in large quantities and widely used in the manufacture of dispersants. Preferred acylating agents for use in producing component a) are derived from polyalkenes having a number average molecular weight measured by GPC in the range of 900-5000. Most preferably, they have a number average molecular weight in the range of 1200-2500. Although various 1-olefin homopolymers and copolymers can be used to produce the acylating agent, commercial grade polyisobutene is the preferred material.
[0020]
The synthesis of typical AG and boronated AG dispersants is described in the examples below.
[0021]
【Example】
Example A-1
In a reaction vessel, 1665 g (0.48 mol) of 60% active polyisobutenyl succinic anhydride (PIBSA) (generated from polyisobutylene having a number average molecular weight of about 2060), 76.8 g (0.56 mol) Charge 98.5% aminoguanidine bicarbonate (AGB) and 600 g of 100 neutral base oil. The molar ratio of AGB to PIBSA is 1.2: 1. The mixture is heated at 170 ° C. for 2 hours with stirring under a strong continuous stream of nitrogen. The product is filtered while hot and allowed to cool.
[0022]
Example A-2
Using a chemically equivalent amount of PIBSA prepared using polyisobutylene having a number average molecular weight of about 1290 instead of the relatively high molecular weight PIBSA of Example A-1, Example A-1 Repeat the procedure.
[0023]
Example A-3
The procedure of Example A-1 is repeated except that the AGB: PIBSA molar ratio is 1.1: 1.
[0024]
Example A-4
Example A-3 is repeated except that the PIBSA of Example A-2 is used.
[0025]
Example A-5
The product produced as in Example A-3 was replaced with 2290 g of the 44% active product thus produced with 212.5 g of superborated polyisobute containing about 2.5% boron. Boronate by heating with tenyl succinate amide at 160 ° C. for 2 hours. The resulting product is diluted with 154 g of oil to produce a product containing 0.2% boron.
[0026]
Example A-6
Example A-5 is repeated but using 2000 g of the product produced as in Example A-4 and 185.6 g of superborated ester amide. The boron content of the borated product is 0.2% when diluted with 134 g of oil.
[0027]
Example A-7
The product produced as in Example A-1 (2290 g) was borated by heating with 572.5 g of superborated ester amide and diluted with oil to contain 0.5% boron. Product.
[0028]
Example A-8
Example A-7 is repeated except that 2000 g of the active product produced as in Example A-2 is used in place of the relatively high molecular weight product of Example A-1.
[0029]
Examples A-9 to A-15
The respective AGB: PIBSA molar ratios are 0.4: 1, 0.5: 1, 0.6: 1, 0.7: 1, 0.8: 1, 0.9: 1 and 1: 1. The procedure of Example A-1 is repeated seven times in the same manner except that the ratio of AGB and PIBSA is changed.
[0030]
Examples A-16 to A-22
Examples A-9 to A-15 are repeated, but using the product produced as in Example A-2 instead of the product produced as in Example A-1.
[0031]
Examples A-23 to A-36
Each product produced as in Examples A-9 to A-22 is borated to a boron level of 0.2% using the boration procedure of Example A-5.
[0032]
Example A-37
Example A-1 is repeated except that 1.0 mole of AGB is reacted with 0.8 mole of PIBSA. Boronation to a 0.2% boron level is performed at an appropriate temperature between 145 and 165 ° C. using boric acid. When the boration is complete, water is expelled at about 155 ° C. and 40 mm Hg.
[0033]
Detailed description
Component b). The oil-soluble ash-free dispersant comprises (I) an acyclic hydrocarbyl succinic acylating agent and (II) an average of about 3 to about 6 nitrogen atoms per molecule [and preferably an average of about 4 Succinimide is reacted with an alkylene polyamine having from about 5 nitrogen atoms] at a molar ratio of about 1.6 to 2 [and preferably about 1.8 to 2] moles of (I) per mole of (II). And the succinimide thus produced is formed of (III) at least one dicarboxylic acid having less than 20 carbon atoms in the molecule, simultaneously or in any order and at a temperature in the range of about 150 to about 180 ° C. Per acylate and (IV) heated with at least one boron material, (1) [excluding the weight of solvent and / or diluent that may be associated with the product] per gram of product A total alkali number in the range of 33 to about 45 milligrams of KOH, and (2) [excluding the weight of solvent and / or diluent that may accompany the product again] about 1.0 to about 1.4 weight Obtained by producing a product having a boron content in the range of%.
[0034]
Aliphatic hydrocarbyl-substituted succinic acid derivatives (acids, anhydrides, lower alkyl esters, or acyl halides) used as reactant (I) above, such as alkenyl succinic anhydrides, in forming component a) It is of the same general type used for Thus, for further details, reference should be made to the description given hereinabove. However, it should be understood and appreciated that the acylating agents used in producing components a) and b) need not be identical to one another. For example, the number average molecular weights of the polyolefins used in producing these respective succinic acylating agents may be the same or they may be different from each other, in which case one of the polyolefins The number average molecular weight of may be higher than the other. Similarly, the succinic acylating agent used in producing components a) and b) may both be anhydrides (and preferably anhydrides), but in producing these respective components. Using different types of functionalized succinic acid acylating agents (eg using an anhydride to produce one of the components and a free acid to produce the other) Is possible.
[0035]
Alkylene polyamines having an average of from about 3 to about 6 nitrogen atoms per molecule used as reactant (II) in producing component b) are generally dialkylenetriamines, trialkylenetetramines, It is called tetraalkylenepentamine and pentaalkylenehexamine. The alkylene groups of these materials can each have 2 to 4 or more carbon atoms. Preferred for use are polyethylene polyamines, ie, polyalkylene polyamines in which the alkylene group is an ethylene (ie, dimethylene) group. The alkylene polyamine used in the synthesis of component b) has a specific structure (e.g. the formula:
H₂N-C₂H_Four-NH-C₂H_Four-NH-C₂H_Four-NH-C₂H_Four-NH₂
Substantially pure tetraethylenepentamine), or they may be technical grade materials such as are available in open markets from a number of suppliers. These technical grade products are often referred to as, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine, although they typically contain linear, branched and cyclic species.
[0036]
The dicarboxylic acid acylating agent having less than 20 carbon atoms in the molecule used as reactant (III) in the post-treatment of succinimide is preferably (a) having up to 6 carbon atoms in the molecule. An acyclic dicarboxylic acid having and having a carboxyl group bonded to the adjacent carbon atom, (b) anhydrides of these dicarboxylic acids, (c) acyl halides of these dicarboxylic acids, and (d) one Acyclic mono- and / or dihydrocarbyl esters of these dicarboxylic acids having no more than 7 carbon atoms per hydrocarbyl group. Examples of these acylating agents are maleic acid, maleic anhydride, α-ethylmaleic acid, malic acid, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, succinic acid, succinic anhydride, α Methyl succinic acid, α, α-dimethyl succinic acid, α, β-dimethyl succinic acid, α-ethyl succinic acid, thiomalic acid, tartaric acid, monoalkyl esters of the above-mentioned acids in which the alkyl group has 1 to 7 carbon atoms, Dialkyl esters of the above-mentioned acids in which the alkyl group has 1 to 7 carbon atoms, monoalkenyl esters of the above-mentioned acids in which the alkenyl group has 2 to 7 carbon atoms, each alkenyl group having 2 to 7 carbon atoms Including dialkenyl esters of the above-mentioned acids, acyl chlorides of the above-mentioned acids and the like. The most preferred post-treatment agent for use in the practice of the present invention is maleic anhydride.
[0037]
Reactant (IV) is the same general type of boron-containing material that can be used in boronating component a) according to a preferred embodiment of component a). Similarly, the temperature and other boriding conditions used may be the same or similar to those applicable for use in producing the borated form of component a). Thus, for further details, reference should be made to the applicable discussion herein above. However, it is understood and appreciated that the boronating agent and the boronation conditions used in generating component b) and in generating the boronated form of component a) need not be identical to each other. Should. Thus, for example, the boronating agent can be the same boric acid, boron ester, boron halide, boron oxide, ammonium borate, organoborane, or a superborated ash-free dispersant, or vice versa. The boronating agent used in producing one of the components may be different from that used in boronating the other. Similarly, the time, temperature, and component ratios used in each boronation may be the same or different from one another, and one component may be boronated to a higher level than the other.
[0038]
Suitable procedures for preparing component b) are illustrated in the examples below.
[0039]
In the first stage reaction, polyisobutenyl succinic anhydride (PIBSA) and tetraethylenepentamine (TEPA), produced from polyisobutylene having a GPC number average molecular weight of about 1300, are added at a molar ratio of 165: 1. React at ~ 170 ° C for 4 hours. In the second stage reaction, maleic anhydride (MA) is added to the first stage reaction product in an amount equivalent to 0.35 moles per mole of TEPA used in the first stage and produced. The mixture to be heated is heated at 165-170 ° C. for 1.5 hours, after which the oil is added. In the third stage reaction, boric acid is added to the second stage reaction mixture at a temperature of 150-155 ° C. in an amount corresponding to 4.0 moles per mole of TEPA used initially. The mixture is heated at 150 ° C. for 1 hour and then the water produced in the third stage reaction is removed by applying a 40 mm vacuum for 1 hour. The resulting succinimide is acylated and boronated to have a nitrogen content of 1.74% and a boron content of 1.20%.
[0040]
Example B-2
The procedure of Example B-1 is repeated except that the amount of boric acid is reduced to 3.0 moles per mole of TEPA initially used. The final product diluted to 1.70% nitrogen content with 100 solvent neutral mineral oil contains 0.82% boron.
[0041]
Example B-3
Repeating Example B-1 further reducing the amount of boron to 2.0 moles per mole of TEPA initially used is a concentrate having a boron content of 0.62% (as in Example B-1). To be diluted).
[0042]
Example B-4
Example B-1 is repeated but using 3.25 moles of boric acid per mole of TEPA used initially. The product concentrate (diluted as in Example B-1) contains 0.88% boron.
[0043]
Example B-5
The reaction with boric acid is performed prior to the reaction with maleic anhydride, and the amount of boric acid used corresponds to 3.0 moles per mole of TEPA used in the first stage reaction. Repeat the procedure of Example B-1. The final product (diluted as in Example B-1) contains 0.9% boron.
[0044]
Example B-6
Example 5 is repeated except that maleic anhydride and boric acid are simultaneously reacted with the succinimide produced in the first stage reaction. One such product diluted with 100 solvent neutral mineral oil contained 1.66% nitrogen and 0.87% boron.
[0045]
Example B-7
In the first stage reaction, polyisobutenyl succinic anhydride (PIBSA) and tetraethylenepentamine (TEPA), produced from polyisobutylene having a GPC number average molecular weight of about 1300, are added at a molar ratio of 165: 1. React at ˜170 ° C. for 4 hours and then add mineral oil. In the second stage reaction, maleic anhydride (MA) is added to the first stage reaction product in an amount equivalent to 0.3 moles per mole of TEPA used in the first stage and produced. The mixture to be heated is heated at 165-170 ° C. for 1-1 / 2 hours. In the third stage reaction, boric acid (BA) was added to and formed in the second stage reaction product in an amount equivalent to 3.0 moles per mole of TEPA used in the first stage. The mixture is heated at 150-155 ° C. for 2-1 / 2 hours. The additive concentrate has a nitrogen content of 1.8% and a boron content of 0.9%.
[0046]
Example B-8
The procedure of Example B-7 is repeated except that PIBSA and TEPA are reacted in a molar ratio of 1.7: 1 in the first stage. In the second stage, MA is used in an amount equivalent to a molar ratio of 0.4: 1 to the TEPA used in the first stage. In the third stage, boric acid (3.0 moles per mole of TEPA used in the first stage reaction) is added into the oil slurry. The diluted product has a nitrogen content of 1.95% and a boron content of 0.64%.
[0047]
Example B-9
In the first stage reaction, polyisobutenyl succinic anhydride having a GPC number average molecular weight of about 1200 and TEPA are reacted in a molar ratio of 1.8: 1. In the second stage, maleic anhydride is added to the first stage reaction product in an amount equivalent to 0.35 moles per mole of TEPA used in the first stage, and the resulting mixture is added to 165- Heat at 170 ° C. for 1-1 / 2 hours, after which mineral oil is added. In the third stage reaction, boric acid is added to the second stage reaction product in an amount equivalent to 0.4 moles per mole of TEPA used in the first stage, and the resulting mixture is Heat at ~ 155 ° C for 3 hours. The product has a nitrogen content of 1.85% and a boron content of 0.15%.
[0048]
Detailed description
Component c). Metal hydrocarbyl dithiophosphates are usually produced by reacting phosphorus pentasulfide with one or more alcohols or phenolic compounds or diols to produce hydrocarbyl dithiophosphoric acid, which is then neutralized with one or more metal-containing bases. Is done. When a monohydric alcohol or phenol is used in this reaction, the final product is zinc dihydrocarbyl dithiophosphate. On the other hand, when a suitable diol (eg, 2,4-pentanediol) is used in this reaction, the final product is a zinc salt of a cyclic hydrocarbyl dithiophosphate. See, for example, US Pat. No. 3,089,850. These cyclic derivatives function in essentially the same way as the dihydrocarbyl congeners.
[0049]
Suitable oil-soluble metal dihydrocarbyl dithiophosphates include molybdenum dihydrocarbyl dithiophosphate, nickel dihydrocarbyl dithiophosphate, copper dihydrocarbyl dithiophosphate, cadmium dihydrocarbyl dithiophosphate, cobalt dihydrocarbyl dithiophosphate, and similar materials. Hydrocarbyl groups include both saturated and unsaturated cyclic and acyclic groups such as alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, cycloalkylalkyl, aralkyl and the like. It will be understood that hydrocarbyl groups may contain elements other than carbon and hydrogen, provided that such other elements do not reduce the predominantly hydrocarbon nature of the hydrocarbyl group. Thus, the hydrocarbyl group can be an ether oxygen atom, a thioether sulfur atom, a secondary or tertiary amino nitrogen atom, and / or an inert functional group such as an esterified carboxyl group, a keto group, a thioketo group, and Similar may be included. Preferred materials are oil-soluble zinc dihydrocarbyl dithiophosphates, especially oil-soluble zinc dialkyldithiophosphates, and most particularly oil-soluble zinc dialkyldithiophosphates in which the alkyl group is a mixture of primary and secondary alkyl groups. Such a mixture of primary and secondary alkyl groups produces a mixture of two or more zinc dialkyldithiophosphates that results in a mixture or combination of primary and secondary alkyl groups of the desired type and proportion. Can be generated. Instead, the mixture of primary and secondary alkyl groups converts the phosphorus pentasulfide to a primary that produces a zinc dialkyldithiophosphate product having the desired type and proportion of primary and secondary alkyl groups. And can be produced by reacting with a mixture or combination of secondary alcohols.
[0050]
The dithiophosphoric acid from which the metal salt is formed is about 4 moles of one or more alcohols (cyclic or acyclic) or one or more phenols or one or more alcohols and one or more phenols per mole of phosphorus pentasulfide. It can be prepared by reaction of a mixture (or about 2 moles of one or more diols) and the reaction may be carried out within a temperature range of about 50 to about 200 ° C. The reaction is generally complete in about 1 to 10 hours. Hydrogen sulfide is liberated during the reaction.
[0051]
The alcohol used in producing dithiophosphoric acid by the above method is preferably a primary alcohol or a secondary alcohol. Mixtures of these are also suitable. Primary alcohols are propanol, butanol, isobutyl alcohol, pentanol, 2-ethyl-1-hexanol, isooctyl alcohol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, octadecanol, eicosanol, and the like Including things. Primary alcohols may contain various substituents that do not interfere with the desired reaction, such as halogen atoms, nitro groups, and the like. Among suitable secondary alcohols are 2-butanol, 2-pentanol, 3-pentanol, 2-hexanol, 4-methyl-2-pentanol, 5-methyl-2-hexanol, and the like included. In some cases, mixtures of various alcohols, such as mixtures of 2-propanol and one or more higher molecular weight primary alcohols, especially primary alcohols having from 4 to about 13 carbon atoms in the molecule. It is preferable to use it. Such a mixture will preferably contain at least 10 mole percent 2-propanol and will usually contain from about 20 to about 90 mole percent 2-propanol. In one particular embodiment, the alcohol consists of about 30-50 mol% 2-propanol, about 30-50 mol% isobutyl alcohol and about 10-30 mol% 2-ethyl-1-hexanol.
[0052]
Other suitable mixtures of alcohols are: 2-propanol / butanol; 2-propanol / 2-butanol; 2-propanol / 2-ethyl-1-hexanol; butanol / 2-ethyl-1-hexanol; isobutyl alcohol / 2- Ethyl-1-hexanol; and 2-propanol / tridecanol. Suitable cycloaliphatic alcohols for use in the production of dithiophosphoric acid include cyclopentanol, cyclohexanol, methylcyclohexanol, cyclooctanol, borneol and the like. Preferably, such alcohols are used in combination with one or more primary alkanols such as butanol, isobutyl alcohol or the like.
[0053]
Exemplary phenols that can be used in generating dithiophosphoric acid include phenol, o-cresol, m-cresol, p-cresol, 4-ethylphenol, 2,4-xylenol, and the like. It is desirable to use phenolic compounds in combination with primary alcohols such as propanol, butanol, hexanol, or the like.
[0054]
Other alcohols that can be used include benzyl alcohol, cyclohexanol, and their ring alkylated analogs.
[0055]
When using a mixture of two or more alcohols and / or phenols in the production of dithiophosphoric acid, the products produced usually have a statistical distribution related to the number and proportion of alcohol and / or phenol used. It will be appreciated that it will usually consist of a mixture of three or more different dihydrocarbyl dithiophosphoric acids in form.
[0056]
Exemplary diols that can be used in generating dithiophosphoric acid are 2,4-pentanediol, 2,4-hexanediol, 3,5-heptanediol, 7-methyl-2,4-octanediol, neo Including pentyl glycol, 2-butyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, and the like.
[0057]
Preparation of the zinc salt of dihydrocarbyl dithiophosphoric acid or cyclic hydrocarbyl dithiophosphoric acid involves reacting the acid product with a suitable zinc compound such as zinc oxide, zinc carbonate, zinc hydroxide, zinc alkoxide, or other suitable zinc salt. Usually implemented. Simply mixing and heating such reactants is usually sufficient to allow the reaction to take place, and the resulting product is usually of sufficient purity for use. Typically, these salts are produced in the presence of a diluent such as alcohol, water or light mineral oil. Neutral salts are prepared by reacting 1 equivalent of oxidation or zinc hydroxide with 1 equivalent of acid. Basic zinc salts are prepared by adding an excess (ie, more than 1 equivalent) of oxidized or zinc hydroxide together with 1 equivalent of dihydrocarbyl dithiophosphate or cyclic hydrocarbyl dithiophosphate.
[0058]
In some cases, incorporation of certain components, such as small amounts of zinc acetate or acetic acid, in combination with the zinc reactant will facilitate the reaction and provide an improved product. For example, the use of up to about 5% zinc acetate in combination with the required amount of zinc oxide tends to facilitate the formation of zinc dihydrocarbyl dithiophosphate.
[0059]
Examples of useful zinc salts of dihydrocarbyl dithiophosphoric acid and methods for making such salts are described in prior art, for example, U.S. Pat. Nos. 4,263,150, 4,289,635, 4, Nos. 308,154, 4,322,479, 4,417,990 and 4,466,895.
[0060]
Preferred zinc salts of dialkyldithiophosphates generally contain alkyl groups each having at least 3 carbon atoms, and preferably the alkyl group contains up to 10 carbon atoms, but as noted above, higher molecular weight alkyls Even a radical is quite possible. Some exemplary zinc dialkyl dithiophosphates include zinc diisopropyl dithiophosphate, zinc dibutyl dithiophosphate, zinc diisobutyl dithiophosphate, zinc di-sec. -Including butyl dithiophosphate, zinc dipentyl dithiophosphate, zinc dihexyl dithiophosphate, zinc diheptyl dithiophosphate, zinc dioctyl dithiophosphate, zinc dinonyl dithiophosphate, zinc didecyl dithiophosphate, and higher homologues thereof. A mixture of two or more such zinc compounds, such as isopropyl alcohol and secondary butyl alcohol; isopropyl alcohol, isobutyl alcohol, and 2-ethylhexyl alcohol; isopropyl alcohol, butyl alcohol, and pentyl alcohol; isobutyl alcohol and octyl alcohol; Zinc salts of dithiophosphoric acid produced from mixtures of analogs are often preferred for use.
[0061]
The metal dihydrocarbyl dithiophosphate may be a product post-treated with a compound such as a carboxylic acid or epoxide.
[0062]
Component d). In general, metal-containing detergents that can be used are oil-soluble or oil-dispersible basic salts (or mixtures thereof) of alkali or alkaline earth metals and one or more of the following acidic substances: (1) sulfonic acids (2) carboxylic acids, (3) salicylic acid, (4) alkylphenols, (5) sulfurized alkylphenols, and (6) organophosphoric acids characterized by at least one direct carbon-to-phosphorus bond. Such an organic phosphoric acid is an olefin polymer (for example, a molecular weight of 1000, such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, yellow phosphorus and halogenated sulfur, or chloromonothiophosphoric acid. Produced by the treatment of polyisobutenes). The most commonly used salts of such acids are the sodium, potassium, lithium, calcium, magnesium, strontium and barium salts. These salts may be low base materials or overbased materials or combinations thereof. Preferably, at least a portion of component d) is an overbased metal detergent having a total alkali number (TBN) of at least 200, and more preferably in the range of about 250 to about 500. In this regard, TBN is measured according to ASTM D-2896-88.
[0063]
The term “basic salt” is used to name a metal salt in which the metal is present in a stoichiometrically greater amount than the organic acid group. A common method for producing basic salts is to use a mineral oil solution of acid with at least a stoichiometric excess of a metal neutralizer such as a metal oxide, hydroxide, carbonate, bicarbonate, or sulfide. Heating at a temperature of about 50 ° C. and filtering the resulting product. The use of a “promoter” in the neutralization step to help incorporate a large excess of metal is likewise desirable. Examples of compounds useful as accelerators include phenolic materials such as phenol, naphthol, alkylphenols, thiophenol, sulfurized alkylphenols, and condensation products of formaldehyde with phenolic materials; alcohols such as methanol, 2-propanol, octyl alcohol, 2 -Ethoxyethanol, 2-ethoxy (2-ethoxyethanol), ethylene glycol, stearyl alcohol, and cyclohexyl alcohol; and amines such as aniline, phenylenediamine, phenothiazine, phenyl-β-naphthylamine, and dodecylamine. A particularly effective method for preparing the basic salt is to mix the acid with excess basic alkaline earth metal neutralizer and at least one alcohol promoter, and to increase the mixture at an elevated temperature, for example 60. Consisting of carbonating at ~ 200 ° C.
[0064]
Examples of suitable metal-containing detergents are lithium phenate, sodium phenate, potassium phenate, calcium phenate, magnesium phenate where each aromatic group has one or more aliphatic groups to confer hydrocarbon solubility. , Lithium sulfide phenate, sodium sulfide phenate, potassium sulfide phenate, calcium sulfide phenate, and magnesium sulfide phenate; each sulfonic acid moiety is attached to an aromatic nucleus and the aromatic nucleus now has hydrocarbon solubility. Lithium sulfonate, sodium sulfonate, potassium sulfonate, calcium sulfonate, and magnesium sulfonate, usually containing one or more aliphatic groups to impart; one or more aromatic moieties to impart hydrocarbon solubility Salicyl usually substituted by an aliphatic substituent Lithium, sodium salicylate, potassium salicylate, calcium salicylate, and salicylmagnesium; hydrolyzed phosphosulfurized olefins having 10 to 2,000 carbon atoms, or hydrolyzed phosphorus having 10 to 2,000 carbon atoms Lithium, sodium, potassium, calcium and magnesium salts of sulfurized alcohols and / or aliphatic substituted phenolic compounds; lithium, sodium, potassium, calcium and magnesium of aliphatic carboxylic acids and aliphatic substituted alicyclic carboxylic acids Salts; and other similar oil-soluble organic acid alkali and alkaline earth metal salts of materials such as, but not limited to, basic or overbased salts. Mixtures of basic or overbased salts of two or more different alkali and / or alkaline earth metals can also be used. Similarly, basic or overbased salts of two or more different acids or mixtures of two or more different types of acids (eg, one or more calcium phenates and one or more calcium sulfonates) can also be used.
[0065]
As is well known, overbased metal detergents are generally considered to contain an overbased amount of inorganic base, possibly in the form of a microdispersion or colloidal suspension. Thus, the terms “oil-soluble” and “oil-dispersible” refer to metal detergents in the base oil where there is an inorganic base that is not necessarily completely or truly oil-soluble in the strict sense of the term. Applied to these metal-containing detergents to include as long as they behave in much the same way as if they were completely and totally dissolved in the oil when mixed.
[0066]
Collectively, the various basic or overbased detergents referred to herein above have sometimes been referred to very simply as basic alkali metal or alkaline earth metal-containing organic acid salts.
[0067]
Processes for the preparation of oil-soluble basic and overbased alkali and alkaline earth metal-containing detergents are known and widely reported in the patent literature. For example, U.S. Pat. Nos. 2,451,345, 2,451,346, 2,485,861, 2,501,731, 2,501,732, 2,585,520 No. 2,671,758, No. 2,616,904, No. 2,616,905, No. 2,616,906, No. 2,616,911, No. 2,616,924, 2,616,925, 2,617,049, 2,695,910, 3,178,368, 3,367,867, 3,496,105, third 629, 109, 3,865,737, 3,907,691, 4,100,085, 4,129,589, 4,137,184, 4,148 No. 740, No. 4,212,752, No. 4,617,135, No. , Cf. the disclosure of 647,387 and EP No. 4,880,550.
[0068]
Component e). Inhibitors that can be used in the practice of the present invention include one or more oxidation inhibitors, foam inhibitors, rust inhibitors, corrosion inhibitors, and friction inhibitors.
[0069]
Suitable oxidation inhibitors for use in the compositions of the present invention include hindered phenolic antioxidants, secondary aromatic amine antioxidants, sulfurized phenolic antioxidants, sulfurized. Olefin antioxidants, oil-soluble copper compounds, phosphorus-containing antioxidants, and the like. Mixtures of two or more of each of these types of antioxidants can also be used.
[0070]
Exemplary sterically hindered phenolic antioxidants are ortho-alkylated phenolic compounds such as 2,6-di-tert. -Butylphenol, 4-methyl-2,6-di-tert. -Butylphenol, 2,4,6-tri-tert. -Butylphenol, 2-tert. -Butylphenol, 2,6-diisopropylphenol, 2-methyl-6-tert. -Butylphenol, 2,4-dimethyl-6-tert. -Butylphenol, 4- (N, N-dimethylaminomethyl) -2,6-di-tert. -Butylphenol, 4-ethyl-2,6-di-tert. -Butylphenol, 2-methyl-6-styrylphenol, 2,6-di-styryl-4-nonylphenol, and analogs and homologues thereof. Mixtures of two or more such phenolic compounds are also suitable. Methylene-bridged alkylphenols are also useful, and these may be used alone or instead in combination with each other or with sterically hindered unbridged phenolic compounds. Can do. Exemplary methylene-bridged compounds are 4,4′-methylenebis (6-tert.-butyl-o-cresol), 4,4′-methylenebis (2-tert.-amyl-o-cresol), 2 , 2'-methylenebis (4-methyl-6-tert.-butylphenol), 4,4'-methylenebis (2,6-di-tert.-butylphenol), and similar compounds. Preferred compounds of alkylphenols bridged with methylene are described in US Pat. No. 3,211,652.
[0071]
Amine antioxidants, especially oil-soluble aromatic secondary amines, can also be used. Although aromatic secondary monoamines are preferred, aromatic secondary polyamines are also suitable. Exemplary aromatic secondary monoamines include diphenylamine, ring alkylated diphenylamines containing one or more alkyl ring substituents each having up to about 16 carbon atoms, phenyl-α-naphthylamine, phenyl-β-naphthylamine, about 16 each. Alkyl or aralkyl substituted phenyl-α-naphthylamine containing 1 or 2 alkyl or aralkyl groups having up to 16 carbon atoms, alkyl or aralkyl substituted phenyl containing 1 or 2 alkyl or aralkyl groups each having up to about 16 carbon atoms -Β-naphthylamine, and similar compounds.
[0072]
A preferred type of aromatic amine antioxidant is substituted by alkyl groups (preferably branched alkyl groups) in which one or both rings have 8 to 12 carbon atoms, and more preferably 8 or 9 carbon atoms. Alkylated diphenylamine. One such preferred compound is commercially available as a material understood to be Naugalube 438L, primarily 4,4'-dinonyldiphenylamine, where the nonyl group is branched.
[0073]
Another useful type of oxidation inhibitor for inclusion in the compositions of the present invention is one or more oil-soluble sulfurized phenolic compounds. Oil soluble sulfurized linear α-olefins are also highly satisfactory oxidation inhibitors. Copper compounds when used at low controlled concentrations, all as described in US Pat. No. 4,867,890 are also suitable.
[0074]
Mixtures of different antioxidants can also be used. One suitable mixture is (I) an oil-soluble mixture of at least three different sterically hindered tertiary butylated monohydric phenols in the liquid state at 25 ° C., (II) at least three different An oil-soluble mixture of sterically hindered tertiary butylated methylene bridged polyphenols, and (III) each alkyl group is a branched alkyl group having 8 to 12 carbon atoms, Consisting of a combination of one ring alkylated di (phenyl) amine, wherein the proportion of (I), (II) and (III) on a weight basis is from 3.5 to 1 part by weight of component (III) Within the range of 5.0 parts of component (I) and 0.9 to 1.2 parts of component (II).
[0075]
Suitable suds suppressors are H.264. T. T. et al. By KernerFoam control agent(Noyes Data Corporation, 1976, pages 125-176). Typical suds suppressors include silicones and organic polymers such as acrylate polymers. Mixtures of silicone type antifoams such as liquid dialkyl silicone polymers with various other materials are also effective. Typical of such mixtures are silicones mixed with acrylate polymers, silicones mixed with one or more amines, and silicones mixed with one or more amine carboxylates. Other such mixtures include dimethyl silicone oil and (I) polyhydric alcohol partial fatty acid esters (US Pat. No. 3,235,498), (II) polyhydric alcohol alkoxylated partial fatty acid esters (US No. 3,235,499), (III) polyalkoxylated aliphatic amines (US Pat. No. 3,235,501), and (IV) alkoxylated aliphatic acids (US Pat. No. 3,235,502). ). Also useful are metal salts of styrene-maleic anhydride copolymers (US Pat. No. 3,296,131). The rust inhibitor that can be used may be a single compound or a mixture of a plurality of compounds having the property of inhibiting corrosion of iron metal surfaces. Such materials include oil-soluble monocarboxylic acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, serotic acid, and the like, as well as dimers and trimer acids. Includes oil-soluble polycarboxylic acids such as those made from tall oil fatty acids, oleic acid, linoleic acid or the like. Other suitable corrosion inhibitors include alkenyl succinic acids in which the alkenyl group contains 10 or more carbon atoms, such as tetrapropenyl succinic acid, tetradecenyl succinic acid, hexadecenyl succinic acid, and the like; Long chain α, ω-dicarboxylic acids in the 3000 molecular weight range; as well as other similar materials. This type of product is currently available from a variety of commercial sources, such as dimer and trimer acid. Another useful type of acidic corrosion inhibitor is a half ester of an alkenyl succinic acid having 8 to 24 carbon atoms in the alkenyl group and an alcohol such as polyglycol. The corresponding half amides of such alkenyl succinic acids are also useful. Other suitable corrosion inhibitors include ether amines; acid phosphates; amines; polyethoxylated compounds such as ethoxylated amines, ethoxylated phenols, and ethoxylated alcohols; imidazolines; and the like.
[0076]
Among suitable corrosion inhibitors are thiazole, triazole and thiadiazole. Examples of these are benzotriazole, tolyltriazole, octyltriazole, decyltriazole, dodecyltriazole, 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-5-hydrocarbylthio-1 , 3,4-thiadiazole, 2-mercapto-5-hydrocarbyldithio-1,3,4-thiadiazole, 2,5-bis (hydrocarbylthio) -1,3,4-thiadiazole, and 2,5-bis (hydrocarbyl) Dithio) -1,3,4-thiadiazole. Preferred compounds are 1,3,4-thiadiazole, especially 2-hydrocarbyldithio-5-mercapto-1,3,4-dithiadiazole and 2,5-bis (hydrocarbyldithio) -1,3,4-thiadiazole. There are some of them available as commercial items. Such products are generally synthesized from hydrazine and carbon disulfide by known procedures. For example, U.S. Pat. Nos. 2,749,311, 2,760,933, 2,765,289, 2,850,453, 2,910,439, 3,663,561 3,862,798, 3,840,549 and 4,097,387. Other suitable corrosion inhibitors include ether amines; polyethoxylated compounds such as ethoxylated amines, ethoxylated phenols, and ethoxylated alcohols; imidazolines; and the like.
[0077]
Friction suppressors that can be used are derived from alkyl phosphonates as disclosed in US Pat. No. 4,356,097, ammonia or alkyl monoamines as disclosed in European Patent Publication No. 20037. Materials such as aliphatic hydrocarbyl substituted succinimides, dimer acid esters, oleamides, sulfurized linear olefins, and the like as disclosed in US Pat. No. 4,105,571. Glycerol oleates such as glycerol monooleate, glycerol dioleate and pentaerythritol monooleate are further examples of suitable friction inhibitors that can be used to control friction and improve fuel economy.
[0078]
Other suitable friction modifiers include aliphatic amines or ethoxylated aliphatic amines, aliphatic fatty acid amides, aliphatic carboxylic acids, aliphatic carboxylic acid esters, aliphatic carboxylic acid ester-amides, aliphatic phosphates, aliphatic Including thiophosphonates, aliphatic thiophosphates, etc., where the aliphatic group typically contains more than about 8 carbon atoms to render the compound properly oil soluble.
[0079]
A preferred friction modifier additive combination that may be used in the practice of the present invention is described in European Patent Publication No. 389,237. This combination involves the use of a long chain succinimide derivative and a long chain amide.
[0080]
Still other suitable additives can be included if desired.
[0081]
The practice and advantages of the present invention will become more apparent from the following illustrative examples. It should be understood that these examples do not limit the general aspects of the invention, are not intended to be made, and should not be considered made. In these examples, all percentages are by weight and are active ingredient based.
[0082]
Example I
A 10W-40 finished lubricant of the present invention is formed from the following ingredients:
[0083]
[Table 1]

[0084]
Component a) is produced as in Example A-5 and component b) is produced as in Example B-4. Component c) is a mixture of zinc dialkyldithiophosphates, 50% of which is C_ThreeAnd C₆Secondary alkyl groups and 50% C_Three, C_FourAnd C₈Primary and secondary alkyl groups. Component d) is a mixture of 1.32% overbased calcium sulfonate, 0.7% low base calcium sulfonate, and 0.65% sulfurized alkyl phenate. Component e) is 0.8% tertiary butylated phenolic antioxidant, 0.2% aromatic amine antioxidant, 0.4% sulfurized olefin oxidation inhibitor, and less than 0.001% This is a mixture of silicone type foam control agents. Commercial materials used in producing this component mixture are HITEC^(R)611, 1656, 4733, 7169 and 7304 additives (Ethyl Petroleum Additives, Ltd .; Ethyl Petroleum Additives, Inc.); OLOA 216C Additives (Chevron Chemical Company); The viscosity index improver is of the OCP type (Paratone 8000; Exxon Chemical Company). The finished lubricant was 10 mg KOH per gram total alkalinity (TBN), 0.12% zinc content, 0.11% phosphorus content, 0.35% per gram using the procedure of ASTM D2896. It has a calcium content and a boron content of 0.02%.
[0085]
Example II
The 10W-40 lubricant of the present invention is produced from the following components:
[0086]
[Table 2]

[0087]
Component a) is produced as in Example A-37 and component b) is produced as in Example B-4. Component c) is C_ThreeAnd C₆Of zinc dialkyldithiophosphates. Component d) is a mixture of 1.18% overbased calcium sulfonate, 0.85% low base calcium sulfonate, and 0.33% sulfurized alkyl phenate. Component e) is a mixture of 1.0% tertiary butylated phenolic antioxidant, 0.5% aromatic amine antioxidant, and less than 0.001% silicone type foam inhibitor. .
[0088]
Example III
The finished lubricant of the present invention is made from the same ingredients as in Example I, but using the following proportions:
[0089]
[Table 3]

[0090]
Example IV
The lubricating oil composition of the present invention was prepared in the proportions given in the table below with components a) and b) in Example II, 400 TBN of overbased magnesium alkylbenzene sulfonate as component d) and component c in Example I. ) And e):
[0091]
[Table 4]

[0092]
The performance of the composition of the present invention is illustrated by the results of the MWM KD 12E engine test that measures the performance of diesel engine lubricants that withstand abuse under controlled conditions. Performance is expressed in terms of a number scale, and the larger the number, the better the performance. In two such tests, a lubricant of the present invention and a comparable lubricant not of the present invention were used. Both, in addition to the dispersant, contain a mixture of primary and secondary alkyl zinc dialkyldithiophosphates, a mixture of high and low base calcium sulfonates, and calcium sulfide alkyl phenate in substantially the same relative proportions. Included. The main difference between these two lubricants is that the non-inventive lubricant dispersant consisted only of the higher dose level of component a). Both lubricants were formulated to 10W-40 standard grade and had 10 mg TBN per gram and an ash level of 1.42%. The lubricant of the present invention gave a score of 80.6 compared to a score of 70.9 for lubricants not according to the present invention.
[0093]
In a test conducted in a similar manner using Volkswagen Intercooled (PV 1431) Test, an exemplary composition of the present invention produced as in Example II is a comparable lubricant not of the present invention. It has been found to give piston cleanliness significantly better than the composition. In both cases, the diesel engine was operated with diesel fuel having a sulfur content of 0.3%.
[0094]
In a standard OM 364A test, the 10W-40 lubricant of the present invention showed excellent dispersibility and gloss control performance, as well as good wear performance.
[0095]
The superior fluoroelastomer sealing performance enabled by the present invention is illustrated by the results of tests conducted using the rigorous Volkswagen PV 3344 test procedure. In one set of tests, a crankcase lubricant that withstands the abuse of the VITON AK6 fluoroelastomer and the SAE 10W-40 of Example I was used. Table I summarizes these results.
[0096]

A similar set of tests was performed using the same test procedure and fluoroelastomer, but using the composition produced as in Example III. The results are summarized in Tables II and III.
[0097]

It can be seen from Tables I, II and III that in these tests the lubricant composition of the present invention passed all the requirements of the stringent Volkswagen PV 3344 test procedure and gave excellent results in doing so. . Similar superior results were achieved with other compositions of the present invention.
[0098]
As used herein, the term “oil-soluble” means that the product under discussion can be dissolved or stably dispersed in 100 solvent neutral mineral oil at 25 ° C. to a concentration of at least 1% by weight. Means.
[0099]
At various places throughout this disclosure, patents and other publications have been cited. The contents of all such documents are hereby incorporated by reference in their entirety as if fully set forth in this specification.
[0100]
The main features and aspects of the present invention are as follows.
[0101]
1. a) Aminoguanidine at a molar ratio of long chain alkyl or alkenyl succinic acylating agent to about 0.4 to about 1.3 moles aminoguanidine and / or its basic salt per mole of acylating agent. An oil-soluble product produced by reacting, and
b) (I) an acyclic hydrocarbyl succinic acylating agent and (II) an alkylene polyamine having an average of about 3 to about 6 nitrogen atoms per molecule of about 1.6-2 per mole of (II) Reacting at a molar ratio of (I) to form succinimide, and the succinimide thus produced is simultaneously or in any order and at a temperature in the range of about 150 to about 180 ° C. in (III) molecules Heating with at least one dicarboxylic acid acylating agent having less than 20 carbon atoms and (IV) at least one boron compound, and (1) the weight of solvent or diluent that may be associated with the product Excluding, if any, a total alkali number in the range of about 33 to about 45 milligrams KOH per gram of product, and (2) solvents and / or dilute that may be associated with the product Comprising an oil-soluble product produced by producing a product having a boron content in the range of about 1.0 to about 1.4% by weight, excluding the weight of the agent; An oil-soluble dispersant composition in which a) and b) are balanced such that there is about 0.3 to about 1.5 parts by weight of nitrogen from b) for every part by weight of nitrogen from a).
[0102]
2. The molar ratio in a) is about 0.8 to about 1.3 moles of aminoguanidine and / or a basic salt thereof per mole of the acylating agent, and the alkylene polyamine of b) is an average per molecule. Having from about 4 to about 5 nitrogen atoms, the molar ratio of (I) per mole (II) in b) being about 1.8-2 moles per mole (II); The composition of claim 1 wherein from about 0.4 to about 1.4 parts by weight of nitrogen from b) is present for every 8 to 1.7 parts by weight of nitrogen from a).
[0103]
3. The composition of claim 2, wherein component a) is boronated so that it removes the weight of solvent and / or diluent associated with the product, if any, so that it has a boron content of up to about 1% by weight. object.
[0104]
4. A composition comprising 1 to 99% by weight of at least one tackifying oil and 99 to 1% by weight of the composition of claim 1 above.
[0105]
5. A composition comprising 1 to 99% by weight of at least one tackifying oil and 99 to 1% by weight of the composition of claim 3 above.
[0106]
6). a) Aminoguanidine at a molar ratio of long chain alkyl or alkenyl succinic acylating agent to about 0.4 to about 1.3 moles aminoguanidine and / or its basic salt per mole of acylating agent. An oil-soluble product produced by reacting,
b) (I) an acyclic hydrocarbyl succinic acylating agent and (II) an alkylene polyamine having an average of about 3 to about 6 nitrogen atoms per molecule of about 1.6-2 per mole of (II) Reacting at a molar ratio of (I) to form succinimide, and the succinimide thus produced is simultaneously or in any order and at a temperature in the range of about 150 to about 180 ° C. in (III) molecules Heating with at least one dicarboxylic acid acylating agent having less than 20 carbon atoms and (IV) at least one boron compound, and (1) the weight of solvent or diluent that may be associated with the product Excluding, if any, a total alkali number in the range of about 33 to about 45 milligrams KOH per gram of product, and (2) solvents and / or dilute that may be associated with the product Oil-soluble products produced by generating a product having a boron content in the range of from about 1.0 to about 1.4 wt% with the exception of the weight of the agent,
c) at least one oil-soluble metal dihydrocarbyl dithiophosphate;
d) at least one alkali or alkaline earth metal-containing detergent, and
e) one or more inhibitors selected from at least one oxidation inhibitor, at least one foam inhibitor, at least one rust inhibitor, at least one corrosion inhibitor, and at least one friction inhibitor.
An additive concentrate comprising from about 0.3 to about 1.5 parts by weight of b for each nitrogen from 0.7 to 1.8 parts by weight of a) )) And the components a), b), c), d) and e) can be blended with a small proportion of additive concentrate into the base oil. Additive concentrate to give an oil blend comprising a) + b), an anti-wear amount c), a detergent amount d), and an inhibitor amount of each of the inhibitors selected as balanced above. Additive concentrate that can be balanced in.
[0107]
7). The composition of claim 6 wherein said metal dihydrocarbyl dithiophosphate is at least one zinc dialkyldithiophosphate antiwear / extreme pressure agent.
[0108]
8). The composition according to 7 above, wherein the alkyl group of the zinc dialkyldithiophosphate is a mixture of a primary alkyl group and a secondary alkyl group.
[0109]
9. 7. A composition according to claim 6 wherein component a) is boronated so that it removes the weight of solvent and / or diluent associated with the product, if any, so that it has a boron content of up to about 1% by weight. object.
[0110]
10. The composition of claim 9 wherein the metal dihydrocarbyl dithiophosphate is at least one zinc dialkyldithiophosphate antiwear / extreme pressure agent. 11. 11. The composition according to 10 above, wherein the alkyl group of the zinc dialkyldithiophosphate is a mixture of a primary alkyl group and a secondary alkyl group.
[0111]
12 A large amount of at least one oil that smoothes the tack, and
a) Aminoguanidine at a molar ratio of long chain alkyl or alkenyl succinic acylating agent to about 0.4 to about 1.3 moles aminoguanidine and / or its basic salt per mole of acylating agent. A low dispersant oil-soluble product produced by reacting,
b) (I) an acyclic hydrocarbyl succinic acylating agent and (II) an alkylene polyamine having an average of about 3 to about 6 nitrogen atoms per molecule of about 1.6-2 per mole of (II) Reacting at a molar ratio of (I) to form succinimide, and the succinimide thus produced is simultaneously or in any order and at a temperature in the range of about 150 to about 180 ° C. in (III) molecules Heating with at least one dicarboxylic acid acylating agent having less than 20 carbon atoms and (IV) at least one boron compound, and (1) the weight of solvent or diluent that may be associated with the product Excluding, if any, a total alkali number in the range of about 33 to about 45 milligrams KOH per gram of product, and (2) solvents and / or dilute that may be associated with the product The product produced by generating a less dispersant amount of an oil-soluble product having a boron content in the range of from about 1.0 to about 1.4 wt% with the exception of the weight of the agent,
c) at least one oil-soluble metal dihydrocarbyl dithiophosphate with a low wear-inhibiting amount,
d) a small amount of detergent, at least one alkali or alkaline earth metal-containing detergent, and
e) one or more of a small amount of inhibitor selected from at least one oxidation inhibitor, at least one foam inhibitor, at least one rust inhibitor, at least one corrosion inhibitor, and at least one friction inhibitor. Inhibitor
Wherein the components a) and b) are 0.7, provided that the lubricating oil composition does not contain more than 0.042% by weight of nitrogen from b). A lubricating oil composition that is balanced so that there is about 0.3 to about 1.5 parts by weight of nitrogen from b) for every -1.8 parts by weight of nitrogen from a).
[0112]
13. 13. The composition of claim 12, further comprising a viscosity index improver amount of a viscosity index improver.
[0113]
14 13. The composition of claim 12, wherein the metal dihydrocarbyl dithiophosphate is at least one zinc dialkyldithiophosphate antiwear / extreme pressure agent.
[0114]
15. 15. The composition according to the above 14, wherein the alkyl group of the zinc dialkyldithiophosphate is a mixture of a primary alkyl group and a secondary alkyl group.
[0115]
16. 13. The composition of claim 12, wherein the composition further comprises a viscosity index improver amount of a viscosity index improver and the metal dihydrocarbyl dithiophosphate is at least one zinc dialkyldithiophosphate antiwear / extreme pressure agent.
[0116]
17. 13. The composition of claim 12, wherein e) comprises a low oxidation suppression amount of at least one oxidation inhibitor, a low foam suppression amount of foam suppression agent, and a low friction suppression amount of friction suppression agent.
[0117]
18. 13. A composition according to claim 12, wherein component a) is boronated so that it removes the weight of solvent and / or diluent associated with the product, if any, so that it has a boron content of up to about 1% by weight. object.
[0118]
19. 19. A composition according to claim 18 wherein the composition further comprises a viscosity index improver amount of a viscosity index improver, and the metal dihydrocarbyl dithiophosphate is at least one zinc dialkyldithiophosphate antiwear / extreme pressure agent.
[0119]
20. The alkyl group of the zinc dialkyldithiophosphate is a mixture of a primary alkyl group and a secondary alkyl group, and e) is a low oxidation inhibiting amount of at least one kind of oxidation inhibitor, and a small foam inhibiting amount of a foam inhibiting agent. 20. A composition according to claim 19 comprising a friction inhibitor in a low friction suppression amount.

Claims (4)

a) Aminoguanidine is reacted with a long chain alkyl or alkenyl succinic acylating agent in a molar ratio of 0.4 to 1.3 moles of aminoguanidine and / or its basic salt per mole of the acylating agent. 1) (b) (I) an acylating agent for acyclic hydrocarbyl succinic acid and (II) an alkylene polyamine having an average of 3 to 6 nitrogen atoms per molecule ( Reaction) at a molar ratio of 1.6 to 2 moles of (I) per II) to form succinimide, and the succinimide thus produced can be simultaneously or in any order and at a temperature in the range of 150-180 ° C. Together with (III) at least one dicarboxylic acid acylating agent having less than 20 carbon atoms in the molecule, and (IV) at least one boron compound Upon heating, (1) the weight of solvent or diluent that may accompany the product, excluding any if present, the total alkali number in the range of 33-45 milligrams KOH per gram of product, and ( 2) Oil-soluble production produced by producing a product having a boron content in the range of 1.0 to 1.4% by weight, excluding the weight of solvent and / or diluent that may be associated with the product. A) and b) are fishing so that there is 0.3 to 1.5 parts by weight of nitrogen from b) for every 0.7 to 1.8 parts by weight of nitrogen from a). An oil-soluble dispersant composition to be added to an oil having a lubricant viscosity, characterized by being combined.   A composition comprising 1 to 99% by weight of an oil having at least one lubricant viscosity and 99 to 1% by weight of a dispersant composition according to claim 1. a) Aminoguanidine is reacted with a long chain alkyl or alkenyl succinic acylating agent in a molar ratio of 0.4 to 1.3 moles of aminoguanidine and / or its basic salt per mole of the acylating agent. Oil-soluble product produced by
b) (I) an acyclic hydrocarbyl succinic acylating agent and (II) an alkylene polyamine having an average of 3 to 6 nitrogen atoms per molecule of 1.6 to 2 moles ( Reacting at a molar ratio of I) to form succinimide, and the succinimide thus produced is simultaneously or in any order and at a temperature in the range of 150-180 ° C. (III) less than 20 carbons in the molecule Heating with at least one dicarboxylic acid acylating agent having an atom, and (IV) at least one boron compound, and (1) the weight of solvent or diluent that may accompany the product, if any, Excluding the total alkali number in the range of 33-45 milligrams KOH per gram of product, and (2) the weight of solvents and / or diluents that may be associated with the product. An oil-soluble product produced by producing a product having a boron content in the range of 1.0 to 1.4% by weight, excluding
c) at least one oil-soluble metal dihydrocarbyl dithiophosphate;
d) at least one alkali or alkaline earth metal-containing detergent, and e) at least one oxidation inhibitor, at least one foam inhibitor, at least one rust inhibitor, at least one corrosion inhibitor, and at least one friction. An additive concentrate comprising one or more inhibitors selected from inhibitors,
The components a) and b) are balanced so that from 0.7 to 1.8 parts by weight of nitrogen from a) there is present from 0.3 to 1.5 parts by weight of nitrogen from b); A dispersion in which components a), b), c), d) and e) are balanced to above 2 to 5.5% by weight when a small proportion of additive concentrate is blended into the base oil. Agents a) and b), 0.5 to 1.25% by weight of wear inhibitor c), 0.5 to 3.5% by weight of detergent d), and 0.0002 to 3% by weight of inhibitor e). An additive concentrate to be added to an oil having a lubricant viscosity, characterized in that it is balanced in the additive concentrate to provide an oil blend comprising: An oil having at least one lubricant viscosity; and a) aminoguanidine with a long chain alkyl or alkenyl succinic acylating agent and 0.4 to 1.3 moles of aminoguanidine per mole of said acylating agent and / or Or an oil-soluble product produced by reacting at a molar ratio of its basic salt,
b) (I) an acyclic hydrocarbyl succinic acylating agent and (II) an alkylene polyamine having an average of 3 to 6 nitrogen atoms per molecule of 1.6 to 2 moles ( Reacting at a molar ratio of I) to form succinimide, and the succinimide thus produced is simultaneously or in any order and at a temperature in the range of 150-180 ° C. (III) less than 20 carbons in the molecule Heating with at least one dicarboxylic acid acylating agent having an atom, and (IV) at least one boron compound, and (1) the weight of solvent or diluent that may accompany the product, if any, Excluding the total alkali number in the range of 33-45 milligrams KOH per gram of product, and (2) the weight of solvents and / or diluents that may be associated with the product. An oil-soluble product produced by producing a product having a boron content in the range of 1.0 to 1.4% by weight, excluding
c) 0.5-1.25% by weight of at least one oil-soluble metal dihydrocarbyl dithiophosphate,
d) 0.5-3.5% by weight of at least one alkali or alkaline earth metal-containing detergent, and e) at least one oxidation inhibitor, at least one foam inhibitor, at least one rust inhibitor, at least A lubricating oil composition comprising 0.0002 to 3% by weight of one or more inhibitors selected from one type of corrosion inhibitor and at least one type of friction inhibitor, wherein the lubricating oil composition is 0 Component a) and b) is added for each nitrogen from 0.7 to 1.8 parts by weight of a) , provided that it does not contain more than 0.042% by weight of nitrogen from b). A lubricating oil composition comprising a total of 2 to 5.5% by weight, balanced so that 1.5 parts by weight of nitrogen from b) is present.