JP6117248B2 - 粘度調整剤としての、オレフィン−エステルコポリマーのポリオレフィンとの混合物 - Google Patents
粘度調整剤としての、オレフィン−エステルコポリマーのポリオレフィンとの混合物 Download PDFInfo
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- JP6117248B2 JP6117248B2 JP2014557762A JP2014557762A JP6117248B2 JP 6117248 B2 JP6117248 B2 JP 6117248B2 JP 2014557762 A JP2014557762 A JP 2014557762A JP 2014557762 A JP2014557762 A JP 2014557762A JP 6117248 B2 JP6117248 B2 JP 6117248B2
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- 150000002978 peroxides Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
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- 239000008117 stearic acid Substances 0.000 description 1
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- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical class [H]S* 0.000 description 1
- LVBXEMGDVWVTGY-UHFFFAOYSA-N trans-2-octenal Natural products CCCCCC=CC=O LVBXEMGDVWVTGY-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-N trans-cinnamic acid Chemical compound OC(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
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- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical group CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
- C10M157/04—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential at least one of them being a nitrogen-containing compound
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
- C10M143/06—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing butene
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- C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
- C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/022—Ethene
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- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/024—Propene
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- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
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- C10M2205/024—Propene
- C10M2205/0245—Propene used as base material
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M2205/0265—Butene used as base material
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- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
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- C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
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- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
- C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
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- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
- C10M2219/106—Thiadiazoles
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- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/043—Ammonium or amine salts thereof
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
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- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/42—Phosphor free or low phosphor content compositions
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/43—Sulfur free or low sulfur content compositions
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Description
機械デバイスでの潤滑剤の主な役割は、有害な摩擦を生じ、疲労寿命を短くし、摩耗を速めてしまうような金属の直接的な接触を防ぐことである。流体の粘度が下がるにつれて、移動する部品の分離に必要な膜厚が小さくなる。中程度から高度の負荷(典型的には0.3〜3.0GPa)がかかるとき、膜による保護機構は、弾性流体(EHD)潤滑と呼ばれる。EHD膜厚は、流体にポリマー材料または粘度調整剤を加えることによって改良することができる。しかし、このような添加剤により、表面(例えば、ギア)間の動力分配の効率が比較的低くなってしまうことがある。一方、流体粘度を下げることによって良好な効率を与え、高いVIを与え、低い操作温度または低い静止摩擦を与えるのに特定の潤滑剤添加剤が効果的であるが、不十分なEHD膜厚を与えることがある。動力分配効率およびEHD膜厚の良好な組み合わせを与える潤滑剤を有することが望ましい。
本発明は、例えば、以下を提供する。
(項目1)
潤滑剤組成物であって、
(a)100℃での動粘度が約15mm 2 /s未満の潤滑粘度の油と、
(b)(i)少なくとも約6個の炭素原子を含むα−オレフィンモノマーおよび(ii)エチレン性不飽和カルボン酸またはその誘導体から誘導される単位を含む骨格を有し、(i)α−オレフィンモノマーと(ii)カルボン酸または誘導体モノマーのモル比が約1:3〜約3:1であり、場合により、窒素官能基を含む、エステル化されたコポリマーと、
(c)少なくとも3個の炭素原子を含むオレフィンモノマー単位を含み、このような単位の少なくとも50重量%が、6個より少ない炭素原子を含み、このモノマー単位の5重量%未満がエチレンモノマー単位であり、100℃での動粘度が少なくとも約1000mm 2 /sであるポリマーとを含み;
ポリマー(b)および(c)は、重量比(b):(c)が約1:10〜約10:1、または約1:1〜約10:1、または約6:4〜約9:1になるように存在し、ポリマー(b)と(c)の合計量が、該潤滑剤組成物の約3〜約60重量%である、潤滑剤組成物。
(項目2)
前記潤滑粘度の油が、合成ポリオレフィン炭化水素油を含む、項目1に記載の潤滑剤組成物。
(項目3)
前記コポリマー(b)の骨格は、さらに、ビニル芳香族モノマーの単位を含む、項目1または項目2に記載の潤滑剤組成物。
(項目4)
前記コポリマー(b)は、8〜16個の炭素原子を含むα−オレフィンのエステル化されたコポリマーと、無水マレイン酸とを、約1:2〜約1.5:1のモル比で含む、項目1〜3のいずれか1項に記載の潤滑剤組成物。
(項目5)
前記コポリマー(b)のエステル官能基は、アルコールの混合物から誘導される、項目1〜4のいずれか1項に記載の潤滑剤組成物。
(項目6)
前記アルコールの混合物は、β位またはもっと離れた位置で分岐している一級アルコールと、直鎖一級アルコールとを含む、項目5に記載の潤滑剤組成物。
(項目7)
前記アルコールの混合物は、(i)約50〜約95モル%の8〜10個の炭素原子を含む1種類以上のアルコールおよび約5〜約50モル%の12〜18個の炭素原子を含む1種類以上のアルコールの混合物と、さらに、(ii)約0.01〜約5モル%の5個以下の炭素原子を含むアルコールとを含む、項目5または項目6に記載の潤滑剤組成物。
(項目8)
前記アルコールの混合物は、(i)約70〜約95モル%の8〜10個の炭素原子を含む1種類以上のアルコールおよび約5〜約30モル%の12〜18個の炭素原子を含む1種類以上のアルコールの混合物と、さらに、(ii)約0.01〜約5モル%の5個以下の炭素原子を含むアルコールとを含む、項目5または項目6に記載の潤滑剤組成物。
(項目9)
前記コポリマー(b)は、前記コポリマーとアミンとの反応から誘導される窒素官能基を含む、項目1〜8のいずれか1項に記載の潤滑剤組成物。
(項目10)
前記アミンが、モルホリン、イミダゾリノン、アミノアミド、β−アラニンアルキルエステル、脂肪族アミン、芳香族アミン、脂肪族ポリアミン、芳香族ポリアミンおよびこれらの混合物からなる群から選択される、項目9に記載の潤滑剤組成物。
(項目11)
前記アミンが、脂肪族モノアミンまたは脂肪族ポリアミンを含む、項目9に記載の潤滑剤。
(項目12)
前記アミンが、N,N−ジメチルアミノプロピルアミン、1−(2−アミノエチル)イミダゾリン−2−オン、4−(3−アミノプロピル)モルホリンまたは1−(3−アミノプロピル)イミダゾールを含む、項目9に記載の潤滑剤。
(項目13)
前記アミンが、4−アミノジフェニルアミンのカップリングした生成物を含む、項目9に記載の潤滑剤組成物。
(項目14)
(b)のポリマーが、約0.01〜約1.5重量%の窒素(または0.05〜0.75、または0.05〜0.5、または0.075〜0.25重量%の窒素)を含む、項目1〜13のいずれか1項に記載の潤滑剤。
(項目15)
前記エチレン性不飽和カルボン酸モノマーから誘導される単位のカルボン酸官能基の約0.1〜約25%が、窒素含有化合物でアミノ化されたもの、アミド化されたもの、イミド化されたもののうち、少なくとも1つである、項目1〜14のいずれか1項に記載の潤滑剤。
(項目16)
(b)のポリマーは、重量平均分子量が約5,000から約30,000まで、または約25,000までである、項目1〜15のいずれか1項に記載の潤滑剤。
(項目17)
(b)のポリマーの量が約2〜約50重量%である、項目1〜16のいずれか1項に記載の潤滑剤。
(項目18)
(c)のポリマーがポリイソブチレンを含む、項目1〜17のいずれか1項に記載の潤滑剤。
(項目19)
(c)のポリマーは、数平均分子量が約1000〜約3000である、項目1〜18のいずれか1項に記載の潤滑剤。
(項目20)
(c)のポリマーの量が約1〜約20重量%である、項目1〜19のいずれか1項に記載の潤滑剤。
(項目21)
ポリマー(b)とポリマー(c)の合計量は、前記潤滑組成物の約10〜約55重量%(または約20〜50、または約10〜25、または約25〜50、または約25〜40重量%)である、項目1〜20のいずれか1項に記載の潤滑剤。
(項目22)
清浄剤、分散剤、酸化防止剤、さらなる粘度向上剤、耐摩耗剤、けば立ち防止剤、極圧剤、腐食抑制剤、泡抑制剤、流動点降下剤、または摩擦調整剤のうち、少なくとも1つをさらに含む、項目1〜21のいずれか1項に記載の潤滑剤。
(項目23)
0.01〜1重量%の硫黄と、0.005〜0.1重量%のリンとを含む、項目1〜22のいずれか1項に記載の潤滑剤。
(項目24)
潤滑組成物を調製するためのプロセスであって、このプロセスが、
(A)
(1)(i)少なくとも約6個の炭素原子を含むα−オレフィンおよび(ii)エチレン性不飽和カルボン酸またはその誘導体を反応させてコポリマーを作製し、(i)α−オレフィンモノマーと(ii)カルボン酸または誘導体モノマーのモル比が約1:3〜約3:1であり;
(2)工程(1)の該コポリマーをエステル化し、エステル化されたコポリマーを作製し;
(3)場合により、工程(2)の該コポリマーと窒素含有化合物とを、少なくとも約0.01重量%の窒素を含むエステル化されたコポリマーを与える量で反応させることを含む、エステル化されたコポリマーを作製することと;
(B)(A)から得た該エステル化されたコポリマーと、(i)100℃での動粘度が約15mm 2 /s未満の潤滑粘度の油、および(ii)少なくとも3個の炭素原子を含むオレフィンモノマー単位を含み、このような単位の少なくとも50重量%が、6個より少ない炭素原子を含み、このモノマー単位の5重量%未満がエチレンモノマー単位であり、100℃での動粘度が少なくとも約1000mm 2 /sであるポリマーとを混合することとを含み、
(A)および(B)(ii)のポリマーが、(A):(B)(ii)が約1:10〜約10:1の重量比になるように存在し、ポリマー(A)と(B)(ii)の合計量が、潤滑剤組成物の約3〜約60重量%である、プロセス。
(項目25)
潤滑組成物を調製するためのプロセスであって、このプロセスが、
(A)
(1)(i)少なくとも約6個の炭素原子を含むα−オレフィンおよび(ii)エチレン性不飽和カルボン酸のエステルを反応させてコポリマーを作製し、(i)α−オレフィンモノマーと(ii)不飽和カルボン酸のエステルのモル比が約1:3〜約3:1であり;
(2)場合により、工程(1)の該コポリマーと窒素含有化合物とを、少なくとも約0.01重量%の窒素を含むエステル化されたコポリマーを与える量で反応させることを含む、エステル化されたコポリマーを作製することと;
(B)(A)から得たエステル化されたコポリマーと、(i)100℃での動粘度が約15mm 2 /s未満である潤滑粘度の油および(ii)少なくとも3個の炭素原子を含むオレフィンモノマー単位を含み、このような単位の少なくとも50重量%が、6個より少ない炭素原子を含み、このモノマー単位の5重量%未満がエチレンモノマー単位であり、100℃での動粘度が少なくとも約1000mm 2 /sであるポリマーとを混合することとを含み、
(A)および(B)(ii)のポリマーが、(A):(B)(ii)が約1:10〜約10:1の重量比になるように存在し、ポリマー(A)と(B)(ii)の合計量が、該潤滑剤組成物の約3〜約60重量%である、プロセス。
(項目26)
項目24または項目25に記載のプロセスによって調製された潤滑剤組成物。
(項目27)
項目1〜23または項目26のいずれか1項に記載の潤滑剤を機械デバイスに供給することを含む、機械デバイスを潤滑する方法。
(項目28)
前記機械デバイスがハイポイドギアを備えている、項目27に記載の方法。
(項目29)
前記機械デバイスが、車両の動力伝達システムの構成要素を備えている、項目27または項目28に記載の方法。
(項目30)
自動車の動力伝達システムを潤滑するための項目1〜23または項目26のいずれか1項に記載の潤滑組成物の使用。
(項目31)
潤滑剤組成物であって、
(a)100℃での動粘度が約15mm 2 /s未満の潤滑粘度の油と、
(b)(i)少なくとも約6個の炭素原子を含むα−オレフィンモノマーおよび(ii)エチレン性不飽和カルボン酸またはその誘導体から誘導される単位を含む骨格を有し、(i)α−オレフィンモノマーと(ii)カルボン酸または誘導体モノマーのモル比が約1:3〜約3:1であり、場合により、窒素官能基を含む、エステル化されたコポリマーと、
(c)少なくとも3個の炭素原子を含むオレフィンモノマー単位を含み、このような単位の少なくとも50重量%が、6個より少ない炭素原子を含み、このモノマー単位の5重量%未満がエチレンモノマー単位であり、100℃での動粘度が少なくとも約250mm 2 /sまたは約500mm 2 /sまたは約800mm 2 /sまたは約1000mm 2 /sであるポリマーとを含み;
ポリマー(b)および(c)は、重量比(b):(c)が約1:10〜約10:1、または約1:1〜約10:1、または約6:4〜約9:1になるように存在し、ポリマー(b)と(c)の合計量が、潤滑剤組成物の約3〜約60重量%である、潤滑剤組成物。
ベースオイルのカテゴリー 硫黄(%) 飽和度(%) 粘度指数
グループI >0.03および/または<90 80〜120
グループII ≦0.03 かつ ≧90 80〜120
グループIII ≦0.03 かつ ≧90 >120
グループIV すべてのポリα−オレフィン(PAO)
グループV グループI、II、IIIまたはIVに含まれないその他すべて
グループI、IIおよびIIIは、鉱物油のベース原料である。潤滑粘度の油は、天然油または合成油、およびこれらの混合物を含んでいてもよい。鉱物油と合成油の混合物(例えば、ポリα−オレフィン油および/またはポリエステル油)を使用してもよい。
式中、独立してそれぞれの変項、
R1は、水素またはC1〜5アルキル基(典型的には水素)であってもよく;
R2は、水素またはC1〜5アルキル基(典型的には水素)であってもよく;
Uは、脂肪族、脂環式または芳香族基であってもよいが、但し、Uが脂肪族である場合、脂肪族基は、1〜5個、または1〜2個の炭素原子を含む直鎖または分枝鎖のアルキレン基であってもよく;
wは、0〜9、または0〜3、または0〜1(典型的には0)であってもよい。
当業者は、式(2)および(3)の化合物がさらに環化し、1つ以上のヘテロ環基が存在し得るアクリジン誘導体、例えば、
を形成し得ることを理解するだろう。
およびそのさまざまな異性体が挙げられ、式中、R3およびR4は、独立して、アルキル基またはアルコキシ基、例えば、メチル、メトキシ、またはエトキシである。ある場合には、R4およびR3は、両方とも−OCH3であり、この物質は、Fast Blue RR[CAS番号6268−05−9]として知られている。接続しているアミド基の向きは、−NR−C(O)−に対して逆であってもよい。別の場合に、R4は、−OCH3であり、R3は、−CH3であり、この物質は、Fast Violet B[99−21−8]として知られている。R3およびR4が両方ともエトキシである場合、この物質は、Fast Blue BB[120−00−3]である。米国特許第5,744,429号は、他の保護されているアミン化合物、特に、アミノアルキルフェノチアジンを開示する。また、N−芳香族置換酸アミド化合物(例えば、米国特許出願公開2003/0030033A1号に開示されるもの)を使用してもよい。適切なアミンとしては、アミン窒素が芳香族炭素環化合物の置換基であるもの、すなわち、窒素が、芳香族環の中でsp2混成状態になっていないものが挙げられる。
の一般的な構造の化合物から誘導されてもよく、式中、X=−OHまたは−NH2であり;Hy”は、水素、またはヒドロカルビル基(典型的にはアルキル、またはC1〜4アルキル、またはC2アルキル)であり;Hyは、ヒドロカルビレン基(典型的には、アルキレン、またはC1〜4アルキレン、またはC2アルキレン)であり;Qは、>NH、>NR、>CH2、>CHR、>CR2、または−O−(典型的には、>NH、または>NR)であり、Rは、C1〜4アルキルである。
式中、Hyは、ヒドロカルビレン基(典型的には、アルキレン、またはC1〜4アルキレン、またはC2アルキレン)であり;Hy’は、ヒドロカルビル基(典型的には、アルキル、またはC1−4アルキル、またはメチル)であり;R’は、1〜30個、または6〜20個の炭素原子を含むアルキル基である。適切なアセトアミドの例としては、N−(2−アミノ−エチル)−アセトアミドおよびN−(2−アミノ−プロピル)−アセトアミドが挙げられる。適切なエステルの例としては、β−アラニンオクチルエステル、β−アラニンデシルエステル、β−アラニン2−エチルヘキシルエステル、β−アラニンドデシルエステル、β−アラニンテトラデシルエステルおよびβ−アラニンヘキサデシルエステルが挙げられる。
式中、
R1は、1〜5個、または1〜3個、または2個の炭素原子を含むアルキレン基であってもよく;
R2は、1〜16個、または2〜8個、または4個の炭素原子を含むヒドロカルビル基であってもよく;
Yは、−O−または>NR3であってもよく(典型的には、Yは、−O−であってもよく);
R3は、水素またはR2であってもよい。
本発明の方法および潤滑組成物は、冷蔵用潤滑剤、グリース、ギア油、車軸油、ドライブシャフト油、トラクション油、マニュアルトランスミッション油、オートマチックトランスミッション油、金属作業液、油圧用油、または内燃機関油に適しているだろう。上のものには、動力伝達経路用潤滑剤が含まれる。動力伝達経路用潤滑剤として使用するのに適した潤滑剤であるためには、典型的には、SAE J306仕様によって定義されるような粘度特性を有し、粘度調整剤の選択は、典型的には、CEC L−45−A−99による評価にしたがってグレード内にある流体によって決定される。
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で置換された芳香族置換基、脂肪族で置換された芳香族置換基および脂環系で置換された芳香族置換基、および分子の別の部分を合わせて全体で環が完成する環状置換基(例えば、2個の置換基が合わさって環を形成する);
置換された炭化水素置換基、すなわち、本発明の内容では、置換基の主な炭化水素としての性質を変えない(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)非炭化水素基を含む置換基;
ヘテロ置換基、すなわち、主に炭化水素の特徴を有するが、本発明の内容では、それ以外は炭素原子で構成される環または鎖に炭素以外を含む置換基であり、ピリジル、フリル、チエニルおよびイミダゾリルのような置換基を包含する。ヘテロ原子としては、硫黄、酸素および窒素が挙げられる。一般的に、2個以下、または1個以下の非炭化水素置換基が、ヒドロカルビル基の10個の炭素原子ごとに存在しているか、または、ヒドロカルビル基中に非炭化水素置換基が存在しなくてもよい。
(調製例1:1−ドデセンおよび無水マレイン酸コポリマー)
コポリマー骨格の調製(Cpp):3リットルフラスコ内で、60重量%のトルエン溶媒存在下、1モルの無水マレイン酸とYモル(以下に記載する)の1−ドデセンを反応させることによって、コポリマーを調製する。このフラスコに、フランジ蓋とクリップ、PTFEスターラー押さえ、ロッドおよびオーバーヘッドスターラー、熱電対、窒素注入口および水冷凝縮器を取り付ける。このフラスコに窒素を0.028m3/hr(または1SCFH)で流す。別の枝付き500mLフラスコに、0.05モルのtert−ブチルペルオキシ−2−エチルヘキサノエート開始剤(Trigonox(登録商標)21Sとして知られるAkzo Nobel製の市販の開始剤)、場合により、n−ドデシルメルカプタン(連鎖移動剤、CTA)およびさらなるトルエンを入れる。窒素ラインを枝に取り付け、窒素を0.085m3/hr(または0.3SCFH)で30分間加える。上の3Lフラスコを105℃まで加熱する。Masterflex(商標)ポンプ(流速を0.8mL/minに設定)を介し、5時間かけてTrigonox 21S開始剤/トルエン混合物を500mLフラスコから3Lフラスコに圧送する。3Lフラスコの内容物を1時間攪拌した後、95℃まで冷却する。3Lフラスコの内容物を一晩攪拌する。典型的には、透明無色のゲルが得られる。それぞれの試薬の量を以下の表に示す。
脚注:
アルコールのモル数は、組み込まれた無水マレイン酸1モルあたりである。
直鎖アルコールは、Alfol(登録商標)810として市販のC8〜10混合物である。
B1は、2−ヘキシルデカノールである。
B2は、2−エチルヘキサノールである。
B3は、2−オクチルドデカノールである。
Esc21*は、本発明と同じポリマー骨格を有するが、直鎖エステル基のみを含む比較例のエステル化されたコポリマーである。
脚注:
アミン1は、1−(2−アミノ−エチル)−イミダゾリジン−2−オンである。
アミン2は、4−(3−アミノプロピル)モルホリンである。
アミン3は、3−(ジメチルアミノ)−1−プロピルアミンである。
アミン4は、N−フェニル−p−フェニレンジアミンである。
アミン5は、N−(3−アミノプロピル)−2−ピロリジノンである。
アミン6は、アミノエチルアセトアミドである。
アミン7は、β−アラニンメチルエステルである。
アミン8は、1−(3−アミノプロピル)イミダゾールである。
a.90モル%の直鎖アルコールおよび10モル%の長鎖分岐アルコールでエステル化された無水マレイン酸および1−ドデセンのコポリマーを、さらに、ジエチルトリアミンから誘導されるイミダゾリジノンと反応させ、窒素量を0.15%にしたもの。このコポリマーは、5%未満の油、典型的には、約1%の油を含み、この量は、上の量で別個に数えられない。
動粘度は、ASTM D445による。粘度指数は、ASTM D2270による。
Brookfield粘度は、ASTM D2983による。
(a)100℃での動粘度が15mm2/s未満の潤滑粘度の油と、
(b)(i)少なくとも6個の炭素原子を含むα−オレフィンモノマーおよび(ii)エチレン性不飽和カルボン酸またはその誘導体から誘導される単位を含む骨格を有し、(i)α−オレフィンモノマーと(ii)カルボン酸または誘導体モノマーのモル比が1:3〜3:1であり、場合により、窒素官能基を含む、エステル化されたコポリマーと、
(c)少なくとも3個の炭素原子を含むオレフィンモノマー単位を含み、このような単位の少なくとも50重量%が、6個より少ない炭素原子を含み、このモノマー単位の5重量%未満がエチレンモノマー単位であり、100℃での動粘度が少なくとも1000mm2/sであるポリマーとを含み;
ポリマー(b)および(c)は、重量比(b):(c)が1:10〜10:1、または1:1〜10:1、または6:4〜9:1になるように存在し、ポリマー(b)と(c)の合計量が、潤滑剤組成物の3〜60重量%である、潤滑剤組成物。
(A)
(1)(i)少なくとも約6個の炭素原子を含むα−オレフィンおよび(ii)エチレン性不飽和カルボン酸またはその誘導体を反応させてコポリマーを作製し、(i)α−オレフィンモノマーと(ii)カルボン酸または誘導体モノマーのモル比が1:3〜3:1であり;
(2)工程(1)のコポリマーをエステル化し、エステル化されたコポリマーを作製し;
(3)場合により、工程(2)のコポリマーと窒素含有化合物とを、少なくとも0.01重量%の窒素を含むエステル化されたコポリマーを与える量で反応させることを含む、エステル化されたコポリマーを作製することと;
(B)(A)から得たエステル化されたコポリマーと、(i)100℃での動粘度が約15mm2/s未満の潤滑粘度の油、および(ii)少なくとも3個の炭素原子を含むオレフィンモノマー単位を含み、このような単位の少なくとも50重量%が、6個より少ない炭素原子を含み、このモノマー単位の5重量%未満がエチレンモノマー単位であり、100℃での動粘度が少なくとも1000mm2/sであるポリマーとを混合することとを含み、
(A)および(B)(ii)のポリマーが、(A):(B)(ii)が1:10〜10:1の重量比になるように存在し、ポリマー(A)と(B)(ii)の合計量が、潤滑剤組成物の3〜60重量%である、プロセス。
(A)
(1)(i)少なくとも約6個の炭素原子を含むα−オレフィンおよび(ii)エチレン性不飽和カルボン酸のエステルを反応させてコポリマーを作製し、(i)α−オレフィンモノマーと(ii)不飽和カルボン酸のエステルのモル比が1:3〜3:1であり;
(2)場合により、工程(1)のコポリマーと窒素含有化合物とを、少なくとも0.01重量%の窒素を含むエステル化されたコポリマーを与える量で反応させることを含む、エステル化されたコポリマーを作製することと;
(B)(A)から得たエステル化されたコポリマーと、(i)100℃での動粘度が15mm2/s未満である潤滑粘度の油および(ii)少なくとも3個の炭素原子を含むオレフィンモノマー単位を含み、このような単位の少なくとも50重量%が、6個より少ない炭素原子を含み、このモノマー単位の5重量%未満がエチレンモノマー単位であり、100℃での動粘度が少なくとも約mm2/sであるポリマーとを混合することとを含み、
(A)および(B)(ii)のポリマーが、(A):(B)(ii)が1:10〜10:1の重量比になるように存在し、ポリマー(A)と(B)(ii)の合計量が、潤滑剤組成物の3〜60重量%である、プロセス。
(a)100℃での動粘度が約15mm2/s未満の潤滑粘度の油と、
(b)(i)少なくとも約6個の炭素原子を含むα−オレフィンモノマーおよび(ii)エチレン性不飽和カルボン酸またはその誘導体から誘導される単位を含む骨格を有し、(i)α−オレフィンモノマーと(ii)カルボン酸または誘導体モノマーのモル比が約1:3〜約3:1であり、場合により、窒素官能基を含む、エステル化されたコポリマーと、
(c)少なくとも3個の炭素原子を含むオレフィンモノマー単位を含み、このような単位の少なくとも50重量%が、6個より少ない炭素原子を含み、このモノマー単位の5重量%未満がエチレンモノマー単位であり、100℃での動粘度が少なくとも約250mm2/sまたは約500mm2/sまたは約800mm2/sまたは約1000mm2/sであるポリマーとを含み;
ポリマー(b)および(c)は、重量比(b):(c)が約1:10〜約10:1、または約1:1〜約10:1、または約6:4〜約9:1になるように存在し、ポリマー(b)と(c)の合計量が、潤滑剤組成物の約3〜約60重量%であり、
上の実施形態2〜30が、それぞれ、前記潤滑剤に基づいていてもよい、潤滑剤組成物。
Claims (25)
- 潤滑剤組成物であって、
(a)100℃での動粘度が15mm2/s未満の潤滑粘度の油5〜98.2重量%と、
(b)(i)少なくとも6個の炭素原子を含むα−オレフィンモノマーおよび(ii)エチレン性不飽和カルボン酸またはその誘導体から誘導される単位を含む骨格を有し、(i)α−オレフィンモノマーと(ii)カルボン酸または誘導体モノマーのモル比が1:3〜3:1であり、さらにアミンとコポリマーとの反応から誘導される窒素官能基を含む、エステル化されたコポリマーであって、0.01〜1.5重量%の窒素を含む、コポリマー1.5〜54重量%と、
(c)少なくとも3個の炭素原子を含むオレフィンモノマー単位を含み、このような単位の少なくとも50重量%が、6個より少ない炭素原子を含み、このモノマー単位の5重量%未満がエチレンモノマー単位であり、100℃での動粘度が少なくとも1000mm2/sであるポリマー0.3〜30重量%とを含み;
ポリマー(b)および(c)は、重量比(b):(c)が1:10〜10:1になるように存在し、ポリマー(b)と(c)の合計量が、該潤滑剤組成物の3〜60重量%である、潤滑剤組成物。 - 前記ポリマー(b)および(c)は、重量比(b):(c)が1:1〜10:1になるように存在する、請求項1に記載の潤滑剤組成物。
- 前記ポリマー(b)および(c)は、重量比(b):(c)が6:4〜9:1になるように存在する、請求項1に記載の潤滑剤組成物。
- 前記コポリマー(b)の骨格は、さらに、ビニル芳香族モノマーの単位を含む、請求項1〜3のいずれか1項に記載の潤滑剤組成物。
- 前記コポリマー(b)は、8〜16個の炭素原子を含むα−オレフィンのエステル化されたコポリマーと、無水マレイン酸とを、1:2〜1.5:1のモル比で含む、請求項1〜4のいずれか1項に記載の潤滑剤組成物。
- 前記コポリマー(b)のエステル官能基は、アルコールの混合物から誘導され、前記混合物は、β位またはもっと離れた位置で分岐している一級アルコールと、直鎖一級アルコールとを含む、請求項1〜5のいずれか1項に記載の潤滑剤組成物。
- 前記アミンが、モルホリン、イミダゾリノン、アミノアミド、β−アラニンアルキルエステル、脂肪族アミン、芳香族アミン、脂肪族ポリアミン、芳香族ポリアミンおよびこれらの混合物からなる群から選択される、請求項1〜6のいずれか1項に記載の潤滑剤組成物。
- (b)のポリマーが、0.05〜0.75重量%の窒素を含み、(b)のポリマーは、重量平均分子量が5,000から30,000までである、請求項1〜7のいずれか1項に記載の潤滑剤組成物。
- (b)のポリマーが、0.05〜0.5重量%の窒素を含む、請求項1〜7のいずれか1項に記載の潤滑剤組成物。
- (b)のポリマーが、0.075〜0.25重量%の窒素を含む、請求項1〜7のいずれか1項に記載の潤滑剤組成物。
- (b)のポリマーは、重量平均分子量が5,000から25,000までである、請求項1〜10のいずれか1項に記載の潤滑剤組成物。
- (b)のポリマーの量が2〜50重量%である、請求項1〜11のいずれか1項に記載の潤滑剤組成物。
- (c)のポリマーがポリイソブチレンを含む、請求項1〜12のいずれか1項に記載の潤滑剤組成物。
- (c)のポリマーは、数平均分子量が1000〜3000であり、(c)のポリマーの量が1〜20重量%である、請求項1〜13のいずれか1項に記載の潤滑剤組成物。
- 潤滑剤組成物を調製するためのプロセスであって、このプロセスが、
(A)
(1)(i)少なくとも6個の炭素原子を含むα−オレフィンおよび(ii)エチレン性不飽和カルボン酸またはその誘導体を反応させてコポリマーを作製し、(i)α−オレフィンモノマーと(ii)カルボン酸または誘導体モノマーのモル比が1:3〜3:1であり;
(2)工程(1)の該コポリマーをエステル化し、エステル化されたコポリマーを作製し;
(3)工程(2)の該コポリマーとアミンとを、0.01〜1.5重量%の窒素を含むエステル化されたコポリマーを与える量で反応させることを含む、エステル化されたコポリマーを作製することと;
(B)(A)から得た該エステル化されたコポリマー1.5〜54重量%と、(i)100℃での動粘度が15mm2/s未満の潤滑粘度の油5〜98.2重量%、および(ii)少なくとも3個の炭素原子を含むオレフィンモノマー単位を含み、このような単位の少なくとも50重量%が、6個より少ない炭素原子を含み、このモノマー単位の5重量%未満がエチレンモノマー単位であり、100℃での動粘度が少なくとも1000mm2/sであるポリマー0.3〜30重量%とを混合することとを含み、
(A)および(B)(ii)のポリマーが、(A):(B)(ii)が1:10〜10:1の重量比になるように存在し、ポリマー(A)と(B)(ii)の合計量が、潤滑剤組成物の3〜60重量%である、プロセス。 - 潤滑剤組成物を調製するためのプロセスであって、このプロセスが、
(A)
(1)(i)少なくとも6個の炭素原子を含むα−オレフィンおよび(ii)エチレン性不飽和カルボン酸のエステルを反応させてコポリマーを作製し、(i)α−オレフィンモノマーと(ii)不飽和カルボン酸のエステルのモル比が1:3〜3:1であり;
(2)工程(1)の該コポリマーとアミンとを、0.01〜1.5重量%の窒素を含むエステル化されたコポリマーを与える量で反応させることを含む、エステル化されたコポリマーを作製することと;
(B)(A)から得たエステル化されたコポリマー1.5〜54重量%と、(i)100℃での動粘度が15mm2/s未満である潤滑粘度の油5〜98.2重量%および(ii)少なくとも3個の炭素原子を含むオレフィンモノマー単位を含み、このような単位の少なくとも50重量%が、6個より少ない炭素原子を含み、このモノマー単位の5重量%未満がエチレンモノマー単位であり、100℃での動粘度が少なくとも1000mm2/sであるポリマー0.3〜30重量%とを混合することとを含み、
(A)および(B)(ii)のポリマーが、(A):(B)(ii)が1:10〜10:1の重量比になるように存在し、ポリマー(A)と(B)(ii)の合計量が、該潤滑剤組成物の3〜60重量%である、プロセス。 - 請求項1〜14のいずれか1項に記載の潤滑剤組成物を機械デバイスに供給することを含む、機械デバイスを潤滑する方法。
- 前記機械デバイスが、車両の動力伝達システムの構成要素を備えている、請求項17に記載の方法。
- 自動車の動力伝達システムを潤滑するための請求項1〜14のいずれか1項に記載の潤滑剤組成物の使用。
- 潤滑剤組成物であって、
(a)100℃での動粘度が15mm2/s未満の潤滑粘度の油5〜98.2重量%と、
(b)(i)少なくとも6個の炭素原子を含むα−オレフィンモノマーおよび(ii)エチレン性不飽和カルボン酸またはその誘導体から誘導される単位を含む骨格を有し、(i)α−オレフィンモノマーと(ii)カルボン酸または誘導体モノマーのモル比が1:3〜3:1であり、さらにアミンとコポリマーとの反応から誘導される窒素官能基を含む、エステル化されたコポリマーであって、0.01〜1.5重量%の窒素を含む、コポリマー1.5〜54重量%と、
(c)少なくとも3個の炭素原子を含むオレフィンモノマー単位を含み、このような単位の少なくとも50重量%が、6個より少ない炭素原子を含み、このモノマー単位の5重量%未満がエチレンモノマー単位であり、100℃での動粘度が少なくとも250mm2/sであるポリマー0.3〜30重量%とを含み;
ポリマー(b)および(c)は、重量比(b):(c)が1:10〜10:1になるように存在し、ポリマー(b)と(c)の合計量が、該潤滑剤組成物の3〜60重量%である、潤滑剤組成物。 - ポリマー(c)が少なくとも500mm 2 /sの100℃での動粘度を有する、請求項20に記載の潤滑剤組成物。
- ポリマー(c)が少なくとも800mm 2 /sの100℃での動粘度を有する、請求項20に記載の潤滑剤組成物。
- ポリマー(c)が少なくとも1000mm 2 /sの100℃での動粘度を有する、請求項20に記載の潤滑剤組成物。
- ポリマー(b)および(c)は、重量比(b):(c)が1:1〜10:1になるように存在する、請求項20〜23のいずれか1項に記載の潤滑剤組成物。
- ポリマー(b)および(c)は、重量比(b):(c)が6:4〜9:1になるように存在する、請求項20〜23のいずれか1項に記載の潤滑剤組成物。
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