JP2022044771A - 潤滑組成物のための脂肪族四面体ボレート化合物 - Google Patents
潤滑組成物のための脂肪族四面体ボレート化合物 Download PDFInfo
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- JP2022044771A JP2022044771A JP2022010936A JP2022010936A JP2022044771A JP 2022044771 A JP2022044771 A JP 2022044771A JP 2022010936 A JP2022010936 A JP 2022010936A JP 2022010936 A JP2022010936 A JP 2022010936A JP 2022044771 A JP2022044771 A JP 2022044771A
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 description 1
- IOYXJNDDBALLFR-UHFFFAOYSA-N tridecane-1,2-diol Chemical compound CCCCCCCCCCCC(O)CO IOYXJNDDBALLFR-UHFFFAOYSA-N 0.000 description 1
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical class CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- DXRFOGXSSDRZFP-UHFFFAOYSA-N tripentyl 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound CCCCCOC(=O)CC(O)(C(=O)OCCCCC)CC(=O)OCCCCC DXRFOGXSSDRZFP-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical class CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- BUMVVNKGNPPUME-UHFFFAOYSA-N undecane-1,2-diol Chemical compound CCCCCCCCCC(O)CO BUMVVNKGNPPUME-UHFFFAOYSA-N 0.000 description 1
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 1
- 229940072690 valium Drugs 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000010698 whale oil Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- USEBTXRETYRZKO-UHFFFAOYSA-L zinc;n,n-dioctylcarbamodithioate Chemical compound [Zn+2].CCCCCCCCN(C([S-])=S)CCCCCCCC.CCCCCCCCN(C([S-])=S)CCCCCCCC USEBTXRETYRZKO-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
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- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
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- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/04—Hydroxy compounds
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- C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
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- C10M137/04—Phosphate esters
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- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
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- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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- C10M2203/1025—Aliphatic fractions used as base material
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Abstract
Description
本発明の例示的な実施形態は、潤滑組成物において有用な、特に潤滑剤において改善された溶解度および摩擦性能を有する摩擦調整剤として有用な、潤滑剤添加剤および特にイオン性ボレート化合物に関する。
例示的な実施形態の一態様によると、潤滑組成物のための添加剤は、カチオンと、ホウ素原子を含む四面体ホウ酸アニオンとを含むイオン性四面体ボレート化合物を含み、このホウ素原子は、脂肪族ジヒドロキシル化合物から誘導された少なくとも1つの二座ジオキソ配位子を有する。
例示的な実施形態の態様は、潤滑組成物のための添加剤、添加剤を形成する方法、および添加剤の使用に関する。
A.イオン性ボレート化合物
R3およびR4は、独立して、水素(R3とR4の両方が通常水素でないことを条件とする)もしくは1~48個の炭素原子の脂肪族ヒドロカルビル基であるか、または一緒になって、複素環式環(1~32個の炭素原子の1つもしくは複数のヒドロカルビル基で置換されていてよい)であってよい置換もしくは非置換の5もしくは6員の脂肪族環を形成し、
mは、0または1であり、
Xは、水素、1~24個の炭素原子のヒドロカルビル基、-OR5、-NHR5、=O、およびこれらの混合物から選択され、
R5は、1~24個の炭素原子のヒドロカルビル基であり、
Mは、カチオンを表し、
nは、整数、すなわち、少なくとも1であり、最大7、または最大4であることができる)
で示される一般的構造で表すことができる。
(i)炭化水素置換基、すなわち、脂肪族(例えば、アルキルまたはアルケニル)、脂環式(例えば、シクロアルキル、シクロアルケニル)置換基、および芳香族置換されている脂肪族または脂環式置換基、ならびに環が分子の別の部分を介して完成する環式置換基(例えば、2つの置換基が一緒になって環を形成する);
(ii)置換されている炭化水素置換基、すなわち、本発明との関連で非炭化水素基を含有する置換基は、置換基の主に炭化水素の性質を変化させない(例えば、ハロ(特にクロロおよびフルオロ)、ヒドロキシ、アルコキシ、メルカプト、アルキルメルカプト、ニトロ、ニトロソ、およびスルホキシ);
(iii)ヘテロ置換基、すなわち、主に炭化水素の性状を有する一方で、その他は炭素原子で構成される環または鎖内に炭素以外を含有し得る置換基。
ル、第二級オクチル、2-エチルヘキシル、n-ノニル、第二級ノニル、ウンデシル、第二級ウンデシル、ドデシル、第二級ドデシル、トリデシル、第二級トリデシル、テトラデシル、第二級テトラデシル、ヘキサデシル、第二級ヘキサデシル、ステアリル、イコシル、ドコシル、テトラコシル、2-ブチルオクチル、2-ブチルデシル、2-ヘキシルオクチル、2-ヘキシルデシル(hexydecyl)、2-オクチルデシル、2-ヘキシルドデシル
(hexydodecyl)、2-オクチルドデシル、2-デシルテトラデシル、2-ドデシルヘキ
サデシル、2-ヘキシルデシルオクチルデシル、2-テトラデシルオクチルデシル(tetradecyloctyldecy)、モノメチル分枝イソステアリルなどが挙げられる。
ル、エチルフェニル、プロピルフェニル、ブチルフェニル、ペンチルフェニル、ヘキシルフェニル、ヘプチルフェニル、オクチルフェニル、ノニルフェニル、デシルフェニル、ウンデシルフェニル、ドデシルフェニルベンジルフェニル、スチレン化フェニル、p-クミルフェニル、α-ナフチル、β-ナフチル基、およびこれらの混合物が挙げられる。本発明の目的のため、イオン性四面体ボレート化合物のホウ素原子に連結した酸素原子のうちの1個または複数に直接結合している芳香族基を含む化合物は除外される。
X’およびm’は、Xおよびmに対してそれぞれ記載されている通りであってよい)
で示される構造で表すことができる。
のいずれか2つは、単一炭素鎖の2つの末端であってもよく、この場合、このアミンは環式構造の一部である。一実施形態では、アンモニウムカチオンは、非置換のアンモニウムカチオン(NH4 +)である。別の実施形態では、R11はHであり、R12、R13、R14のうちの1つまたは複数はヒドロカルビル基である。
塩である化合物(またはカチオンがこのような分子量を有する場合)は、高いTBNを有する潤滑組成物を提供するのに特に有用である。
[B]- n-pqMn+([A]q-)p
(式中、[A]-は、第2のアニオンを表し、q≧1、p≧1、かつn-pq≧1である)
のものであってよい。
B.潤滑粘度油
(硫黄含有量>0.03重量%、および/または<90重量%の飽和分、粘度指数80~120);グループII(硫黄含有量≦0.03重量%、および≧90重量%の飽和分、粘度指数80~120);グループIII(硫黄含有量≦0.03重量%、および≧90重量%の飽和分、粘度指数≧120);グループIV(すべてのポリアルファオレフィン(PAO));およびグループV(グループI、II、III、またはIVに含まれない他すべて)。例示的な潤滑粘度油は、APIグループI、グループII、グループIII、グループIV、グループVの油、またはこれらの混合物を含む。一部の実施形態では、潤滑粘度油は、APIグループI、グループII、グループIII、もしくはグループIVの油、またはこれらの混合物である。一部の実施形態では、潤滑粘度油は、APIグループI、グループII、もしくはグループIIIの油、またはこれらの混合物である。一実施形態では、潤滑粘度油は、APIグループII、グループIII鉱油、グループIV合成油、またはこれらの混合物であってよい。一部の実施形態では、潤滑組成物の少なくとも5重量%、または少なくとも10重量%、または少なくとも20重量%、または少なくとも40重量%は、ポリアルファオレフィン(グループIV)である。
組成物を形成する方法
素または2~30個の炭素または2~20個の炭素を有する分枝または非分枝の化合物を含み得る。脂肪族1,2ビシナルジオールは、モノアルキルグリコール、モノアルキルグリセロール、またはモノアシルグリセロールを含み得る。
で表すことができる。
とも1である場合、適切な構造は、グリコール酸、HO-CH2-CO2Hに基づく、すなわち、Xが-CH2-基である構造である。Xが-CH2CH2-である対応する酸は乳酸であり、これも有用であり得る。このような材料は、対応するエステルおよびアミドを形成し得る。aまたはbのうちの少なくとも1つが1より大きい酸の例として、リンゴ酸(a=2、b=1)、酒石酸(a=2、b=2)、およびクエン酸(a=3、b=1)が挙げられる。aが2またはこれよりも大きい材料はイミド形態でも存在し得る。エステルアミド、エステルイミド、アミドイミド、ジエステル、ジアミド、ジエステルアミド、エステルジアミド、およびジイミドなどの混合した材料を用いることもできるが、ただし、カルボキシル基の数が適切に大きい(および誘導体が2つの反応性ヒドロキシル基を保持する)ことを条件とする。一実施形態では、脂肪族ジヒドロキシル化合物は、イミド、ジエステル、ジアミド、ジイミド、エステル-アミド、エステル-イミド、またはイミド-アミドを含んでよい。一実施形態では、脂肪族ジヒドロキシル化合物は、イミド、ジエステル、ジアミド、またはエステル-アミドを含む。
として示されている。
溶液が所望の特性のうちの1つまたは複数を示すことを可能にする程度まで組成物が機能することが意図される油(例えば、鉱油、合成油)中で、組成物が可溶性であることを意味することを意図する。同様に、このような「溶液」は、厳密な物理的または化学的意味で真の溶液である必要はない。代わりに、これらの溶液は、実用目的のため、本発明の文脈内で交換可能であるように真の溶液の特性に十分に近い特性を本発明の目的で示すマイクロエマルジョンまたはコロイド状分散液であってよい。
、クエン酸ジペンチルエチルを有するクエン酸トリペンチル、ホウ素化クエン酸トリエチル、クエン酸トリブチル、1,2-プロパンジオール(1,2-propandiol)とエステル交換したクエン酸トリエチル、クエン酸トリエチルO-アセチル、トリエチルシトレートオクタデシルスクシネート、またはこれらの混合物が挙げられる。他の適切なクエン酸エステルとして、クエン酸2-エチルヘキシル、クエン酸ドデシル、またはこれらの混合物が挙げられる。適切なクエン酸エステルのより詳細な記載はWO2005/087904および米国特許第5,338,470号に開示されている。
いこともある。一例では、形成されるイミドは、オレイルタルトリミドである。
。ホウ酸エステルおよび酸の例は、一般的な形態B(OR)3(式中、各Rは、独立して、Hおよび1~48個の炭素原子のヒドロカルビル基から選択される)のものである。例として、ホウ酸、三価ホウ素化ヒドロキシルエステル、例えば、ホウ素化グリセロールモノオレエート(GMO)、ホウ素化グリセロールジオレエート(GDO)、ホウ素化グリセロールトリオレエート(GTO)、ホウ素化グリセロールモノココエート(GMC)、ホウ素化モノタロエート(GMT)、ホウ素化グリセロールモノ-ソルビテート(GMS)、ペンダントヒドロキシル基を有するホウ素化ポリオールエステル、例えば、ホウ素化ペンタエリトリトールジ-C8エステル、トリ-ヒドロキシルオルトボレート、ホウ素化分散剤、例えば、ホウ素化スクシンイミド、ホウ素化清浄剤、およびこれらの組合せが挙げられる。
C.他の性能添加剤
清浄剤
れたような1種または複数種の油溶性アルキルトルエンスルホネート化合物の金属塩であってよい。
酸化防止剤
。例示的なアルキル化ジフェニルアミンとして、ジノニルジフェニルアミン、ノニルジフェニルアミン、オクチルジフェニルアミン、ジオクチルジフェニルアミン、ジデシルジフェニルアミン、デシルジフェニルアミン、およびこれらの混合物が挙げられる。例示的なアルキル化ジアリールアミンとして、オクチル、ジオクチル、ノニル、ジノニル、デシルおよびジデシルフェニルナフチルアミンが挙げられる。
分散剤
よい。
摩耗防止剤
油溶性チタン化合物
極圧(EP)剤
ルジスルフィド、ビス-(クロロベンジル)ジスルフィド、ジブチルテトラスルフィド、オレイン酸の硫化メチルエステル、硫化アルキルフェノール、硫化ジペンテン、硫化テルペン、および硫化ディールスアルダー付加体;ホスホ硫化炭化水素、例えば、リン硫化物とテレビンまたはオレイン酸メチルとの反応生成物;リンエステル、例えば、ジヒドロカーボンおよびトリヒドロカーボンホスファイト、例えば、亜リン酸ジブチル、亜リン酸ジヘプチル、亜リン酸ジシクロヘキシル、亜リン酸ペンチルフェニル;亜リン酸ジペンチルフェニル、亜リン酸トリデシル、亜リン酸ジステアリルおよびポリプロピレン置換亜リン酸フェノール;金属チオカルバメート、例えば、ジオクチルジチオカルバミン酸亜鉛およびバリウムヘプチルフェノール二酸;例えば、ジアルキルジチオリン酸とプロピレンオキシドとの反応生成物のアミン塩、およびこれに続くさらなるP2O5との反応物を含めた、アルキルおよびジアルキルリン酸のアミン塩または誘導体;ならびにこれらの混合物が挙げられる。一部の有用な極圧剤は、米国特許第3,197,405号に記載されている。
消泡剤
粘度調整剤
腐食防止剤および金属不活性化剤
流動点降下剤
摩擦調整剤
牛脂アルキルアミン、およびダイズ油アルキルアミン;ジアルキル(またはアルケニル)アミン、例えば、N-テトラデシルメチルアミン、N-ペンタデシルメチルアミン、N-ヘキサデシルメチルアミン、N-ステアリルメチルアミン、N-オレイルメチルアミン、N-ドコシルメチルアミン、N-牛脂アルキルメチルアミン、N-硬化牛脂アルキルメチルアミン、N-ダイズ油アルキルメチルアミン、ジテトラデシルアミン、ジペンタデシルアミン、ジヘキサデシルアミン、ジステアリルアミン、ジオレイルアミン、ジココイルアミン、ビス(2-ヘキシルデシル)アミン、ビス(2-オクチルドデシル)アミン、ビス(2-デシルテトラデシル)アミン、牛脂ジアルキルアミン、硬化牛脂ジアルキルアミン、およびダイズ油ジアルキルアミン;ならびにトリアルキル(トリアルケニル)アミン、例えば、テトラデシルジメチルアミン、ヘキサデシルジメチルアミン、オクタデシルジメチルアミン、牛脂アルキルジメチルアミン、硬化牛脂アルキルジメチルアミン、ダイズ油アルキルジメチルアミン、ジオレイルメチルアミン、トリテトラデシルアミン、トリステアリルアミン、およびトリオレイルアミンが挙げられる。適切な第二級アミンは、14~18個の炭素原子を有する2つのアルキル(またはアルケニル)基を有する。
リブデン化合物であり、上記と同じように、モリブデン酸アンモニウム、モリブデン酸ナトリウム、酸化モリブデンおよびこれらの混合物を含む。1つの適切なモリブデン供給源は、三酸化モリブデン(MoO3)を含む。
抗乳化剤
シール膨張剤
Oil(商標)(FN3200)が挙げられる。
い。リン含有量は0.2重量%もしくはそれ未満、または0.12重量%もしくはそれ未満、または0.1重量%もしくはそれ未満、または0.085重量%もしくはそれ未満、または0.08重量%もしくはそれ未満、またはさらに0.06重量%もしくはそれ未満、0.055重量%もしくはそれ未満、または0.05重量%もしくはそれ未満であってよい。一実施形態では、リン含有量は、100ppm~1000ppm、または200ppm~600ppmであってよい。全硫酸化灰分含有量は、2重量%もしくはそれ未満、または1.5重量%もしくはそれ未満、または1.1重量%もしくはそれ未満、または1重量%もしくはそれ未満、または0.8重量%もしくはそれ未満、または0.5重量%もしくはそれ未満、または0.4重量%もしくはそれ未満であってよい。一実施形態では、硫酸化灰分含有量は、0.05重量%~0.9重量%、または0.1重量%~0.2重量%または0.45重量%までであってよい。一実施形態では、潤滑組成物はエンジンオイルであってよく、この場合、この潤滑組成物は、(i)0.5重量%もしくはそれ未満の硫黄含有量、(ii)0.1重量%もしくはそれ未満のリン含有量、(iii)1.5重量%もしくはそれ未満の硫酸化灰分含有量、またはこれらの組合せのうちの少なくとも1つを有することで特徴付けることができる。
N-オレイルタルトリミド/トリス(2-エチルヘキシル)ボレート/ポリイソブチレンスクシンイミドベースのイオン性四面体ボレート化合物:イオン性四面体ボレート化合物を含む混合物を、N-オレイルタルトリミド(44.6g)、トリス(2-エチルヘキシル)ボレート32.6g)、および100 TBNの直接アルキル化ポリイソブチレンスクシンイミド(PIBSA)分散剤(14%希釈油を含有する)(22.8g)をブレンドして、タルトリミド:ボレート:PIBSAのモル比2:1:1を得ることにより形成する。PIBSA分散剤は、1000Mnの高ビニリデンポリイソブチレンおよびN:CO(m)比1.79およびTBN 100を有するコハク酸無水物から作製する。大気圧下、反応は80℃で2時間行う。生成物はさらに精製せずに単離する。
N-オレイルタルトリミド/トリス(2-エチルヘキシル)ボレート/ポリイソブチレンスクシンイミドベースのイオン性四面体ボレート化合物:イオン性四面体ボレート化合物含有混合物を実施例1の通りであるが、N-オレイルタルトリミド(21.9g)は、60%OTおよび40%鉱油の混合物として供給し、PIBSA分散剤を2000Mnの高ビニリデンポリイソブチレンならびにN:CO(m)比1.79およびTBN 13を有するコハク酸無水物から作製して、形成する。
N-オレイルタルトリミド/トリス(2-エチルヘキシル)ボレート/過塩基性カルシウムスルホネート清浄剤ベースのイオン性四面体ボレート化合物:イオン性四面体ボレート化合物を含む混合物を、60%OTと40%鉱油との混合物として供給されるN-オレイルタルトリミド(70.8g)、トリス(2-エチルヘキシル)ボレート(21.7g)、および400 TBNのカルシウムスルホネート清浄剤(7.5g)をブレンドして、タルトリミド:ボレート:清浄剤のモル比2:1:1を得ることによって形成する。反
応は80℃で2時間行う。生成物はさらに精製せずに単離する。
N-オレイルタルトリミド/トリス(2-エチルヘキシル)ボレート/過塩基性カルシウムスルホネート清浄剤ベースのイオン性四面体ボレート化合物:イオン性四面体ボレート化合物を含む混合物を、反応を100℃で2時間行うこと、および生じた混合物を減圧下に配置して、アルコール(2-エチルヘキサノール)を共沸蒸留することを除いて、実施例2の通り形成する。生成物はさらに精製せずに単離する。
N-オレイルタルトリミド/トリス(2-エチルヘキシル)ボレート/中性のカルシウムスルホネート清浄剤ベースのイオン性四面体ボレート化合物:イオン性四面体ボレート化合物を含む混合物を、85 TBNのカルシウムスルホネート清浄剤(28.0g)を使用することを除いて、実施例2の通り形成する。
N-オレイルタルトリミド/トリス(2-エチルヘキシル)ボレート/フェノール系酸化防止剤ベースのイオン性四面体ボレート化合物:イオン性四面体ボレート化合物を含む混合物を、2,6-ジ-(secブチル),4-(2-エチルヘキシルアミノメチルフェノール(21.6g)を塩基として使用することを除いて、実施例2の通り形成する。
N-オレイルタルトリミド/トリス(2-エチルヘキシル)ボレート/過塩基性カルシウムスルホネート清浄剤ベースのイオン性四面体ボレート化合物:イオン性四面体ボレート化合物を含む混合物を、(11.6g)の400 TBNのカルシウムスルホネート清浄剤を用いて、タルトリミド:ボレート:清浄剤のモル比1:1:1を得ることを除いて、実施例2に記載されている通り形成する。
N-オレイルタルトリミド/トリス(2-エチルヘキシル)ボレート/過塩基性カルシウムスルホネート清浄剤ベースのイオン性四面体ボレート化合物:イオン性四面体ボレート化合物を含む混合物を、(11.6g)の400のTBNのカルシウムスルホネート清浄剤を用いて、タルトリミド:ボレート:清浄剤のモル比1:1:1を得ることを除いて、実施例3に記載されている通り形成する。
溶媒プロセス手順1による四面体ホウ素化N-オレイルタルトリミド(四面体の複合体を形成するための、ホウ酸の存在下でのin situでのタルトリミドの形成):187.6gの酒石酸(1.25mol、2.0当量)および19.3gのホウ酸(0.31mol、0.5当量)を110gのペンタノール中で撹拌し、還流加熱する。334.4gのオレイルアミン(1.25mol、2.0当量)を添加漏斗を介して添加する。生じた反応物を140℃で5時間保持する。次いで、溶媒を、真空蒸留を介して除去して、さらに精製せずに最終生成物を得る。11B NMR (160 MHz, CDCl3) ppm: 9.60 (br).
元素分析:0.6%B、3.2%N。
溶媒プロセス手順1による四面体ホウ素化N-オレイルタルトリミド:250gの酒石酸(0.93mol、2.0当量)および28.9gのホウ酸(0.47mol、1.0当量)を153gのブタノール中で撹拌し、加熱還流する。140.3gのオレイルアミン(0.93mol、2.0当量)を添加漏斗を介して添加する。一部の溶媒を除去しな
がら、生じた反応物を140~145℃に加熱し、5時間保持する。次いで、溶媒を、真空蒸留を介して除去して、さらに精製せずに最終生成物を得る。11B NMR (160 MHz, CDCl3) ppm: 9.48 (br).元素分析:1.3%B、3.2%N。
溶媒プロセス手順2による四面体ホウ素化N-オレイルタルトリミド(四面体の複合体を形成するための、ホウ酸を後で添加する、in situでのタルトリミドの形成):1201gの酒石酸(8.0mol、2.0当量)を850gのペンタノール中で撹拌し、加熱還流する。2140gのオレイルアミン(8.0mol、2.0当量)を1時間にわたり添加する。反応物を140℃で5時間保持し、次いで110℃に冷却する。123.6gのホウ酸(2.0mol、0.5当量)を一度に添加する。次いで、反応混合物を140℃に加熱し、2時間保持する。次いで、溶媒を、真空蒸留を介して除去して、さらに精製せずに最終生成物を得る。11B NMR (160 MHz, CDCl3) ppm: 10.39 (br), 7.32 (br), 6.21 (br).元素分析:0.6%B、3.3%N。
グリセロールモノオレエート(GMO)、ホウ酸およびアミンから調製される四面体ボレート:254gのGMO(0.5mol、2.0当量)および15.5gのホウ酸(0.25mol、1.0当量)を撹拌しながら165℃に加熱する。反応物をこの温度で3時間保持する。次いで、46.4gのトリ-n-ブチルアミン(0.25mol、1.0当量)を一度に添加する。生じた反応混合物を165℃でさらに3時間保持して、さらに精製せずに所望の生成物を得る。11B NMR (160 MHz, CDCl3) ppm: 11.39 (br).
グリセロールモノオレエート(GMO)、ホウ酸および400 TBNのCa清浄剤から調製される四面体ボレート:257gのGMO(0.5mol、2.0当量)および15.7gのホウ酸(0.25mol、1.0当量)を撹拌しながら165℃に加熱する。反応物をこの温度で4時間保持する。35.5gの400 TBNのCa清浄剤を添加して、反応を165℃でさらに3時間保持する。粗生成物を濾過して、所望の生成物を得る。11B NMR (160 MHz, CDCl3) ppm: 9.98 (br), 6.75 (br).
グリセロールモノオレエート(GMO)、ホウ酸および100 TBNのポリイソブチレンスクシンイミド(PIBSA)分散剤から調製される四面体ボレート:508gのGMO(1.0mol、2.0当量)、241.3gの三面体ホウ酸エステル(0.5mol、1.0当量)、および280.5gの100 TBNのポリイソブチレンスクシンイミド(PIBSA)分散剤(0.5mol、1.0当量)を80℃で2時間混合して、さらに精製せずに所望の生成物を得る。11B NMR (160 MHz, CDCl3) ppm: 22.73 (br), 17.58 (br), 10.08 (br).
1,2-オクタンジオール、ホウ酸およびアミンから調製される四面体ボレート:146gの1,2-オクタンジオール(1.0mol、2.0当量)および30.9gのホウ酸(0.5mol、1.0当量)を撹拌しながら165℃に加熱する。反応物をこの温度で2時間保持し、次いで140℃に冷却する。64.6gの2-エチルヘキシルアミン(0.5mol、1.0当量)を添加漏斗を介して添加する。生じた混合物を140℃で3時間撹拌して、さらに精製せずに所望の生成物を得る。11B NMR (160 MHz) ppm: 11.71 (br)
製することができる。
比較用潤滑剤実施例CLE4:全Caスルホネート過塩基性清浄剤を含む乗用車エンジンオイル中のOTを含む潤滑組成物。
少の試験結果を表2に示す。
れる。それらへの、現在予想されていないまたは予期しない様々な代替形態、修正形態、変化形態または改善形態が、今後、当業者により作製され得るが、これらも以下の特許請求の範囲により包含されることが意図される。
(項1)
潤滑組成物のための添加剤であって、
カチオンと、ホウ素原子を含む四面体ホウ酸アニオンとを含む、イオン性四面体ボレート化合物を含み、前記ホウ酸アニオンが三価ホウ素化合物と脂肪族ジヒドロキシル化合物の反応から形成される少なくとも1つの二座ジオキソ配位子を有し、
前記ホウ酸アニオンが二座芳香族ジオキソ配位子を実質的に含まない、添加剤。
(項2)
前記三価ホウ素化合物が、ホウ酸、ホウ酸エステル、およびこれらの組合せからなる群から選択される、上記項1に記載の添加剤。
(項3)
前記脂肪族ジヒドロキシル化合物が、1,2ビシナルジオール、ヒドロキシカルボン酸の脂肪族誘導体、ジおよびポリカルボン酸の脂肪族誘導体ならびにこれらのブレンドからなる群から選択される、上記項1または2に記載の添加剤。
(項4)
前記ヒドロキシカルボン酸が、式:
[式中、
a=2、b=1であるか、または
aおよびbの両方とも2に等しいか、または
a=3、b=1であり、
Xは、脂肪族もしくは脂環式の基、または炭素鎖内に酸素原子を含有する脂肪族もしくは脂環式の基、または前述の種類の置換されている基であり、前記基が最大6個の炭素原子を含有し、a+b個の利用可能な結合点を有し、
各Yは、独立して、-O-、もしくは>NR 1 であるか、または2つのYが一緒になって、2つのカルボニル基の間に形成されるイミド構造R-N<の窒素を表し、
各RおよびR 1 は、独立して、水素またはヒドロカルビル基であるが、ただし、少なくとも1つのRまたはR 1 基がヒドロカルビル基であることを条件とし、各R 2 は、独立して、水素、ヒドロカルビル基またはアシル基であり、さらに、少なくとも1つの-OR 2 基が、-C(O)-Y-R基のうちの少なくとも1つに対してαまたはβである、X内の炭素原子上に位置することを条件とする]
で表される、上記項1から3のいずれか一項に記載の添加剤。
(項5)
前記ヒドロキシカルボン酸が、酒石酸またはクエン酸である上記項4に記載の添加剤。
(項6)
前記脂肪族ジヒドロキシル化合物が、酒石酸(tartartic acid)のイミド誘導体であ
る、上記項1から5のいずれか一項に記載の添加剤。
(項7)
前記1,2ビシナルジオールが、モノアルキルグリコール、モノアルキルグリセロール、モノアシルグリセロール、およびこれらのブレンドからなる群から選択される、上記項1から3のいずれか一項に記載の添加剤。
(項8)
前記1,2ビシナルジオールが、グリセロールモノオレエートである、上記項7に記載の添加剤。
(項9)
前記イオン性四面体ボレート化合物が、式:
[式中、R 1 およびR 2 は、独立して、1~48個の炭素原子のヒドロカルビル基から選択されるか、または一緒になって、置換もしくは非置換の5もしくは6員の環を形成し、R 3 およびR 4 は、独立して、1~48個の炭素原子の脂肪族ヒドロカルビル基であるか、または一緒になって、複素環式環(1~32個の炭素原子の1つもしくは複数のヒドロカルビル基で置換されていてよい)であってよい置換もしくは非置換の5もしくは6員の脂肪族環を形成し、
mは、0または1であり、
Xは、水素、1~24個の炭素原子のヒドロカルビル基、-OR 5 、-NHR 5 、=O、およびこれらの混合物から選択され、ここで、R 5 は、1~24個の炭素原子のヒドロカルビル基であり、
Mは、前記カチオンを表し、
nは少なくとも1である]
で表される、上記項1から8のいずれか一項に記載の添加剤。
(項10)
前記置換の5員または6員の環が、脂肪族ヒドロカルビル基、少なくとも1個のヘテロ原子を含む脂肪族ヒドロカルビル基、およびこれらの組合せから選択される少なくとも1つの置換基で置換されている、上記項9に記載の添加剤。
(項11)
mが、0である、上記項9および10のいずれか一項に記載の添加剤。
(項12)
R 1 およびR 2 が、一緒になって、置換または非置換の5または6員の環を形成し、前記置換または非置換の5または6員の環が、0~2個のヘテロ原子を含む、上記項9から11のいずれか一項に記載の添加剤。
(項13)
R 1 およびR 2 で形成される前記置換の5員または6員の環が、脂肪族ヒドロカルビル基、少なくとも1個のヘテロ原子を含む脂肪族ヒドロカルビル基、およびこれらの組合せから選択される少なくとも1つの置換基で置換されている、上記項12に記載の添加剤。
(項14)
前記カチオンが、金属カチオン、アンモニウムイオン、ホスホニウムイオン、灰分を含まない有機カチオン、およびこれらの混合物からなる群から選択される、上記項1から13のいずれか一項に記載の添加剤。
(項15)
前記灰分を含まない有機カチオンが、アンモニウムカチオンおよびホスホニウムカチオンから選択される、上記項14に記載の添加剤。
(項16)
前記四面体ボレート化合物が、アンモニウム塩、第四級アンモニウム塩、およびこれらの混合物から選択される、上記項13から14のいずれか一項に記載の添加剤。
(項17)
Mが、アルカリ金属カチオン、アルカリ土類金属カチオン、遷移金属カチオン、およびこれらの組合せから選択される金属カチオンである、上記項9に記載の添加剤。
(項18)
前記カチオンMが、前記組成物に少なくとも5(または少なくとも10、または少なくとも15、または少なくとも25)の全塩基価(TBN)を提供する、上記項1から17のいずれか一項に記載の添加剤。
(項19)
前記カチオンMが、ポリイソブチレンスクシンイミドから誘導される、上記項1から18のいずれか一項に記載の添加剤。
(項20)
前記ポリイソブチレンスクシンイミドが誘導される元となるポリイソブチレンが、350~5000、または750~2500の範囲の数平均分子量を有する、19に記載の添加剤。
(項21)
前記カチオンMが、アルカリ金属清浄剤またはアルカリ土類金属清浄剤から誘導される、上記項1から18のいずれか一項に記載の添加剤。
(項22)
前記カチオンMが、過塩基性のアルカリ金属清浄剤またはアルカリ土類金属清浄剤から誘導される、上記項21に記載の添加剤。
(項23)
三価ボレート化合物をさらに含む、上記項1から22のいずれか一項に記載の添加剤。
(項24)
前記三価ボレート化合物中のホウ素と前記四面体ボレート化合物中のホウ素との重量比が、少なくとも80:20(または少なくとも90:10、または少なくとも95:5)である、上記項23に記載の添加剤。
(項25)
添加剤濃縮物を形成するための量の油をさらに含む、上記項1に記載の添加剤。
(項26)
潤滑組成物のための添加剤を形成する方法であって、
液体溶媒媒体中で脂肪族ジヒドロキシル化合物を、三価ボレート化合物、および、必要に応じて、塩基性構成成分と反応させて、カチオンと、ホウ素原子を含む四面体ホウ酸アニオンとを含むイオン性四面体ボレート化合物を形成することを含み、前記ホウ酸アニオンが、前記三価ホウ素化合物と前記脂肪族ジヒドロキシル化合物との反応から形成される少なくとも1つの二座ジオキソ配位子を有し、
前記溶媒媒体が、アルコール溶媒、エーテル溶媒、エステル溶媒、ケトン溶媒、およびこれらのブレンドからなる群から選択され、
前記脂肪族ジヒドロキシル化合物と三価ボレート化合物との前記反応から生じた水が、前記液体溶媒媒体の一部分と共に共沸蒸留される、方法。
(項27)
前記液体溶媒媒体が、アルコール溶媒を含む、上記項26に記載の方法。
(項28)
添加剤濃縮物であって、上記項1に記載の添加剤と、前記濃縮物を形成するために十分な量の潤滑油を含む、添加剤濃縮物。
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CA3031619A1 (en) | 2018-01-25 |
EP3487968B1 (en) | 2020-10-21 |
JP2019521235A (ja) | 2019-07-25 |
JP7126487B2 (ja) | 2022-08-26 |
WO2018017911A1 (en) | 2018-01-25 |
WO2018017913A1 (en) | 2018-01-25 |
US20190264123A1 (en) | 2019-08-29 |
JP7402683B2 (ja) | 2023-12-21 |
CN109715767B (zh) | 2022-01-21 |
US20190292483A1 (en) | 2019-09-26 |
JP2019521237A (ja) | 2019-07-25 |
CN109906265B (zh) | 2023-06-27 |
JP2023171616A (ja) | 2023-12-01 |
US11459520B2 (en) | 2022-10-04 |
CA3031625A1 (en) | 2018-01-25 |
EP3487967A1 (en) | 2019-05-29 |
US10774283B2 (en) | 2020-09-15 |
CN109715767A (zh) | 2019-05-03 |
EP3487967B1 (en) | 2021-04-07 |
EP3487968A1 (en) | 2019-05-29 |
CN109906265A (zh) | 2019-06-18 |
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