JP2009534520A - 星型ポリマー潤滑組成物 - Google Patents
星型ポリマー潤滑組成物 Download PDFInfo
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- JP2009534520A JP2009534520A JP2009507898A JP2009507898A JP2009534520A JP 2009534520 A JP2009534520 A JP 2009534520A JP 2009507898 A JP2009507898 A JP 2009507898A JP 2009507898 A JP2009507898 A JP 2009507898A JP 2009534520 A JP2009534520 A JP 2009534520A
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- 150000002148 esters Chemical class 0.000 claims description 17
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
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- 230000005540 biological transmission Effects 0.000 abstract description 9
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- 239000005069 Extreme pressure additive Substances 0.000 description 6
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
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- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 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
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Abstract
Description
本発明は、星形ポリマーなどのポリマー、過塩基性洗浄剤および分散剤を含有する潤滑組成物に関する。本発明は、潤滑組成物を使用する、機械装置の潤滑方法も提供する。
潤滑組成物中に星形ポリマーを使用することは、知られている。潤滑組成物において知られる星形ポリマーは、以下の従来技術に要約されている。
一実施形態では、本発明は、
(a)放射状形または星形構造を有するポリマー0.001重量%〜15重量%と、
(b)過塩基性洗浄剤と、
(c)分散剤と、
(d)潤滑粘性油と
を含む潤滑組成物を提供する。
(a)放射状形または星形構造を有するポリマー0.001重量%〜15重量%と、
(b)過塩基性洗浄剤と、
(c)分散剤と、
(d)金属ジアルキルジチオホスフェートなどの摩耗防止剤と、
(e)潤滑粘性油と
を含む潤滑組成物を提供する。
(a)放射状形または星形構造を有するポリマー0.001重量%〜15重量%と、
(b)過塩基性洗浄剤0.1重量%〜15重量%と、
(c)分散剤0.1重量%〜25重量%と、
(d)潤滑粘性油45重量%〜99.7重量%と
を含む潤滑組成物を提供する。
(a)放射状形または星形構造を有するポリマー0.001重量%〜15重量%と、
(b)過塩基性洗浄剤と、
(c)分散剤と、
(d)潤滑粘性油と
を含む潤滑組成物を供給することを含む、機械装置の潤滑方法を提供する。
(a)放射状形または星形構造を有するポリマー0.001重量%〜15重量%と、
(b)過塩基性洗浄剤と、
(c)分散剤と、
(d)潤滑粘性油と
を含む潤滑組成物を内燃機関に供給することを含む、内燃機関の潤滑方法を提供する。
本発明は、上記に開示した潤滑組成物および機械装置の潤滑方法を提供する。
潤滑組成物は、過塩基性洗浄剤、またはその混合物を含む。過塩基性洗浄剤には、フェネート(アルキルフェネートおよび硫黄含有フェネートを含めた)、スルホネート、サリキサレート(salixarate)、カルボキシレート(サリチレートなどの)、過塩基性リン酸、アルキルフェノール、過塩基性硫黄カップリングアルキルフェノール化合物、またはサリゲニン洗浄剤が挙げられる。一実施形態では、過塩基性洗浄剤は、サリキサレート、フェネート、スルホネート、またはサリチレートを1つまたは複数含む。一実施形態では、過塩基性洗浄剤はサリチレートである。一実施形態では、過塩基性洗浄剤はスルホネートである。一実施形態では、過塩基性洗浄剤はフェネートである。一実施形態では、過塩基性洗浄剤はサリキサレートである。
過塩基性洗浄剤を調製するために使用される酸性過塩基化剤は、ギ酸、酢酸または硝酸などの液体であり得る。適切な無機酸添加剤には、SO2、二酸化炭素、またはそれらの混合物が挙げられる。異なる実施形態では、酸性過塩基化剤は、二酸化炭素または酢酸である。一実施形態では、酸性過塩基化剤は、二酸化炭素および酢酸の混合物である。
本明細書で使用される場合、「ポリマーは、からなるモノマーを有する(または含有する)」などの用語は、ポリマーが、言及される特定のモノマーから誘導される単位を含むことを意味する。
(a)そのメタクリレートのアルキル基が10〜30個、または10〜20個、または12〜18個、または12〜15個の炭素原子を有するアルキルメタクリレート50重量%〜100重量%(または65重量%〜95重量%)と、
(b)そのメタクリレートのアルキル基が1〜9個、または1〜4個の炭素原子(例えばメチル、ブチル、または2−エチルヘキシル)を有するアルキルメタクリレート0重量%〜40重量%(または5重量%〜30重量%)と、
(c)窒素含有モノマー0重量%〜10重量%(または0重量%〜5重量%)と
を含むモノマー組成物から誘導され得る。
Qは水素またはメチルであり、一実施形態では、Qはメチルであり、
Zは、N−H基またはO(酸素)であり、
各Riiは、独立に、水素または1〜8個、もしくは1〜4個の炭素原子を含有するヒドロカルビル基であり、
各Riは、独立に、水素または1〜2個の炭素原子を含有するヒドロカルビル基であり、一実施形態では、各Riは水素であり、
gは1〜6の整数であり、一実施形態では、gは1〜3である)
により表すことができる(メタ)アクリルアミドまたは窒素含有(メタ)アクリレートモノマーも更に含む。
潤滑組成物は、分散剤を含む。この分散剤は、スクシンイミド分散剤(例えばN−置換長鎖アルケニルスクシンイミド)、Mannich分散剤、エステル含有分散剤、長鎖ヒドロカルビル(脂肪ヒドロカルビルまたはポリイソブチレンなどの)モノカルボン酸アシル化剤とアミンもしくはアンモニアとの縮合生成物、アルキルアミノフェノール分散剤、ヒドロカルビル−アミン分散剤、ポリエーテル分散剤、またはポリエーテルアミン分散剤であり得る。
潤滑組成物は、潤滑粘性油を含む。このような油には、天然油および合成油、水添分解法、水素添加、および水素化精製から誘導される油、未精製油、精製油および再精製油、ならびにこれらの混合物が挙げられる。
組成物は、他性能の添加剤を任意選択で含む。他性能の添加剤は、金属不活性剤、粘度調整剤、摩擦調整剤、摩耗防止剤、腐食防止剤、分散粘度調整剤、極圧添加剤、抗酸化剤、抑泡剤、乳化破壊剤、流動点降下剤、シール膨潤剤およびそれらの混合物の少なくとも1つを含む。通常、完全配合された潤滑油には、これらの性能の添加剤が1つまたは複数含有されよう。
抗酸化剤化合物は公知であり、これには、例えば、硫化オレフィン、アルキル化ジフェニルアミン(通常、ジ−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)、ヒンダードフェノール、モリブデン化合物(モリブデンジチオカルバメートなどの)、またはそれらの混合物が挙げられる。抗酸化剤化合物は、単独または組合せで使用してもよい。抗酸化剤は、潤滑組成物の0重量%〜20重量%、または0.1重量%〜10重量%、または1重量%〜5重量%の範囲内で存在し得る。
潤滑剤組成物は、任意選択で他の摩耗防止剤も少なくとも1つ含む。この摩耗防止剤は、潤滑組成物の0重量%〜15重量%、または0.1重量%〜10重量%または1重量%〜8重量%を含める範囲内で存在し得る。適切な摩耗防止剤の例には、ホスフェートエステル、硫化オレフィンが挙げられ、硫黄含有無灰摩耗防止添加剤は、金属ジヒドロカルビルジチオホスフェート(亜鉛ジアルキルジチオホスフェートまたはモリブデンジアルキルジチオホスフェートなどの)、チオカルバメートエステル、チオカルバメートアミド、チオカルバミン酸エーテル、アルキレンカップリングチオカルバメート、およびビス(S−アルキルジチオカルバミル)ジスルフィドなどのチオカルバメート含有化合物である。
本発明のポリマー(a)以外の粘度調整剤には、スチレン−ブタジエンの水素化コポリマー、エチレン−プロピレンコポリマー、ポリイソブテン、水素化スチレン−イソプレンポリマー、水素化イソプレンポリマー、ポリメタクリレート、ポリアクリレート、ポリアルキルスチレン、アルケニルアリール共役ジエンコポリマー、ポリオレフィン、無水マレイン酸−スチレンコポリマーのエステルが挙げられる。従来のポリ(メタ)アクリレートポリマーは、そのポリマーアーム用に定められるものと実質的に同じモノマーから誘導することができる。しかし、従来のポリ(メタ)アクリレートは、通常、ハロゲン、−O−N=基および−S−C(=S)−基から選択される官能基を含まない。一実施形態では、本発明のポリマーは従来の粘度調整剤と混合される。
油中に溶ける極圧(EP)添加剤には、硫黄含有および塩素硫黄含有EP添加剤、塩素化炭化水素EP添加剤およびリン系EP添加剤が挙げられる。このようなEP添加剤の例には、塩素化ワックス;ジベンジルジスルフィド、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、およびディールスアルダー硫化付加物などの有機スルフィドおよび有機ポリスルフィド;硫化リンとターペンタインまたはメチルオレエートとの反応生成物などのリン硫化炭化水素;ジ炭化水素およびトリ炭化水素ホスファイト、例えば、ジブチルホスファイト、ジヘプチルホスファイト、ジシクロヘキシルホスファイト、ペンチルフェニルホスファイト、ジペンチルフェニルホスファイト、トリデシルホスファイト、ジステアリルホスファイトおよびポリプロピレン置換フェノールホスファイトなどのリンエステル;亜鉛ジオクチルジチオカルバメートなどの金属チオカルバメートおよびヘプチルフェノール二酸バリウム;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を含めたアルキルおよびジアルキルリン酸のアミン塩;ならびにそれらの混合物が挙げられる。
腐食防止剤などの他性能の添加剤には、米国出願US05/038319(2004年10月25日出願、名前が挙げられた発明者としてMcAteeおよびBoyer)のパラグラフ5〜8に記載されているもの、オクチルアミンオクタノエート、ドデセニルコハク酸または無水物およびオレイン酸などの脂肪酸とポリアミンとの縮合生成物が挙げられる。一実施形態では、腐食防止剤は、Synalox(登録商標)腐食防止剤を含める。Synalox(登録商標)腐食防止剤は、通常、プロピレンオキシドのホモポリマーまたはコポリマーである。Synalox(登録商標)腐食防止剤は、Dow Chemical社により刊行されている様式番号118−01453−0702 AMSの製品カタログにより詳細に記載されている。この製品カタログの表題は、「SYNALOX潤滑剤、苛酷な用途向け高性能ポリグリコール」である。
本発明の方法は、種々の機械装置の潤滑に有用である。この機械装置は、少なくとも1つの内燃機関(クランクケース潤滑用)、油圧系統、タービン系統、循環油系統、工業潤滑油系統、ギヤ、ギヤボックス、自動変速機またはマニュアル変速機を含む。
28.3L/hrで流れる窒素注入口、中速機械撹拌機、熱電対および水冷式凝縮器を備えた容器に、C12〜15アルキルメタクリレート80g、メチルメタクリレート20g、TrigonoxTM−21(開始剤)0.55g、2−ドデシルスルファニルチオカルボニルスルファニル−2−メチル−プロピオン酸ドデシルエステル(連鎖移動剤)4.07gおよび油48.2gを装填する。この容器の内容物を窒素ブランケット下で20分間撹拌することにより、十分な混合を確実にする。窒素フローを14.2L/hrに下げ、この混合物が、3時間、90℃に加熱されるように設定する。エチレングリコールジメタクリレート6.05gをその容器に添加し、その混合物を90℃で更に3時間撹拌する。生じた生成物はポリマーの混合物であり、次いでこれを周囲温度に冷却する。生成物の主要部分は、重量平均分子量283300g/molおよび数平均分子量215900g/molを有する特徴がある。このポリマーは、少なくとも9つのポリマーアーム(C12〜15アルキルメタクリレート80重量%、メチルメタクリレート20重量%を含有する)を有すると考えられ、星形ポリマーへの変換率は72%であり、28%は非カップリング線状ポリマー鎖である。
Prep2の調製方法は、反応物の量が以下の通りであることを除き、上記のPrep1と同じである:0.63gの連鎖移動剤、0.11gの開始剤、68.8gのC12〜15アルキルメタクリレート、11.2gのメチルメタクリレート、1.58gのエチレングリコールジメタクリレート。生じたポリマーは、重量平均分子量407600および数平均分子量289900を有する。この星形ポリマーは、少なくとも5つのアームを有すると考えられ、星形ポリマーへの変換率は70%であり、30%は非カップリング線状ポリマー鎖である。
Prep3の調製方法は、反応物の量が以下の通りであることを除き、上記のPrep1と同じである:0.71gの連鎖移動剤、0.14gの開始剤、80gのC12〜15アルキルメタクリレート、20gのメチルメタクリレート、1.59gのエチレングリコールジメタクリレート。生じたポリマーは、重量平均分子量696100、および数平均分子量814600を有する。この星形ポリマーは、少なくとも6つのアームを有すると考えられ、星形ポリマーへの変換率は40%であり、60%は非カップリング線状ポリマー鎖である。
(i)炭化水素置換基、即ち、脂肪族(例:アルキルまたはアルケニル)、脂環式(例:シクロアルキル、シクロアルケニル)置換基と、芳香族置換、脂肪族置換、および脂環式置換芳香族置換基、ならびに環が分子の別の部分を通って完成する環式置換基(例:2個の置換基が一緒になって環を形成する);
(ii)置換炭化水素置換基、即ち、本発明に関しては、置換基の炭化水素の主な性質を変えない非炭化水素基(例: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、ニトロソならびにスルホキシ)を含有する置換基;
(iii)ヘテロ置換基、即ち、炭化水素の主な特性を有する一方、本発明に関しては、それ以外は炭素原子からなる環または鎖中に炭素以外の原子を含有する置換基
が挙げられる。ヘテロ原子には、硫黄、酸素、窒素が挙げられ、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が包含される。全般的に、ヒドロカルビル基中には、各10個の炭素原子に対して、2個以下、好ましくは1個以下の非炭化水素置換基が存在し、通常、ヒドロカルビル基中には、非炭化水素置換基は存在しないであろう。
Claims (33)
- (a)放射状形または星形構造を有するポリマー0.001重量%〜15重量%と、
(b)過塩基性洗浄剤と、
(c)分散剤と、
(d)潤滑粘性油と
を含む潤滑組成物。 - 前記ポリマーが、20重量%以上、または50重量%超、または55重量%以上、または70重量%以上、または95重量%以上のモノビニルモノマーを含有する、請求項1に記載の潤滑組成物。
- 前記ポリマーが、100,000〜1,000,000、または300,000〜1,000,000、または350,000〜1,000,000、または400,000〜800,000の重量平均分子量を有する、請求項1に記載の潤滑組成物。
- 前記ポリマーがコポリマーである、請求項1に記載の潤滑組成物。
- 前記潤滑組成物が線状ポリマー鎖の部分をさらに含む、請求項1に記載の潤滑組成物。
- 前記ポリマーが、ランダム、テーパード、ジブロック、トリブロック、またはマルチブロックの構造を有するアームを含む、請求項1に記載の潤滑組成物。
- 前記ポリマーが、RAFT、ATRP、窒素酸化物媒介、またはアニオン重合法から得られる、請求項1に記載の潤滑組成物。
- 前記ポリマーが、RAFT、ATRP、またはアニオン重合法から得られる、請求項7に記載の潤滑組成物。
- 前記ポリマーが、RAFTまたはATRP重合法から得られる、請求項8に記載の潤滑組成物。
- 前記ポリマーが、RAFT重合法から得られる、請求項9に記載の潤滑組成物。
- 前記ポリマーが、(a)(i)ビニル芳香族モノマー、および(ii)カルボン酸モノマーまたはそれらの誘導体を含むモノマーから誘導されるポリマー、(b)ポリ(メタ)アクリレート、(c)官能化ポリオレフィン、(d)エチレン酢酸ビニルコポリマー、(e)フマレートコポリマー、(f)(i)α−オレフィンおよび(ii)カルボン酸モノマーまたはそれらの誘導体から誘導されるコポリマー、あるいは(g)それらの混合物のうちの少なくとも1つを含む、請求項1に記載の潤滑組成物。
- 前記ポリマーが、ポリメタクリレート、またはその混合物である、請求項11に記載の潤滑組成物。
- 前記ポリメタクリレートが、
(a)そのメタクリレートのアルキル基が10〜20個、または12〜15個の炭素原子を有するアルキルメタクリレート50重量%〜100重量%と、
(b)そのメタクリレートのアルキル基が1〜9個の炭素原子を有するアルキルメタクリレート0重量%〜40重量%と、
(c)窒素含有モノマー0重量%〜10重量%と
を含むモノマー組成物から誘導される、請求項12に記載の潤滑組成物。 - 前記ポリマーが、潤滑組成物の0.01〜12重量%、または0.075〜8重量%で存在する、請求項1に記載の潤滑組成物。
- 前記過塩基性洗浄剤が、フェネート、スルホネート、サリキサレート、サリチレート、カルボキシレート、過塩基性リン酸、またはサリゲニン洗浄剤を1つまたは複数含む、請求項1に記載の潤滑組成物。
- 前記過塩基性洗浄剤が、サリキサレート、フェネート、スルホネート、またはサリチレートを1つまたは複数含む、請求項15に記載の潤滑組成物。
- 前記過塩基性洗浄剤が、潤滑組成物の0.1重量%〜10重量%、または0.1重量%〜8重量%で存在する、請求項1に記載の潤滑組成物。
- 前記分散剤が、スクシンイミド分散剤、Mannich分散剤、エステル含有分散剤、長鎖ヒドロカルビルモノカルボン酸アシル化剤とアミンもしくはアンモニアとの縮合生成物、アルキルアミノフェノール分散剤、ヒドロカルビル−アミン分散剤、ポリエーテル分散剤、またはポリエーテルアミン分散剤を1つまたは複数含む、請求項1に記載の潤滑組成物。
- 前記分散剤がスクシンイミド分散剤を1つまたは複数含む、請求項18に記載の潤滑組成物。
- 前記分散剤が、前記潤滑組成物の0.1重量%〜20重量%、または0.25重量%〜15重量%、または0.5重量%〜10で存在する、請求項1に記載の潤滑組成物。
- 摩耗防止剤をさらに含む、請求項1に記載の潤滑組成物。
- 前記摩耗防止剤が金属ジアルキルジチオホスフェートを含む、請求項21に記載の潤滑組成物。
- 抗酸化剤をさらに含む、請求項1に記載の潤滑組成物。
- 前記抗酸化剤が、硫化オレフィン、アルキル化ジフェニルアミン、ヒンダードフェノール、モリブデン化合物、およびそれらの混合物からなる群から選択される、請求項23に記載の潤滑組成物。
- 前記抗酸化剤がモリブデン化合物である、請求項24に記載の潤滑組成物。
- 前記抗酸化剤がアルキル化ジフェニルアミンである、請求項24に記載の潤滑組成物。
- 前記抗酸化剤がヒンダードフェノールである、請求項24に記載の潤滑組成物。
- 前記潤滑粘性油が、APIのII群、III群もしくはIV群の油またはそれらの混合物である、請求項1に記載の潤滑組成物。
- 前記潤滑粘性油がAPIのIII群の油である、請求項28に記載の潤滑組成物。
- (i)0.5重量%以下の硫黄含量、(ii)0.1重量%以下のリン含量、および(iii)1.5重量%以下の硫酸塩灰分含量を有する、請求項1に記載の潤滑組成物。
- Xが0〜20の整数であり、Yが20〜50の整数であるXW−Yからのを有する、請求項1に記載の潤滑組成物。
- (a)放射状形または星形構造を有するポリマー0.001重量%〜15重量%と、
(b)過塩基性洗浄剤0.1重量%〜15重量%と、
(c)分散剤0.1重量%〜25重量%と、
(e)潤滑粘性油45重量%〜99.7重量%と
を含む潤滑組成物。 - (a)放射状形または星形構造を有するポリマー0.001重量%〜15重量%と、
(b)過塩基性洗浄剤と、
(c)分散剤と、
(d)潤滑粘性油と
を含む潤滑組成物を内燃機関に供給することを含む、内燃機関の潤滑方法。
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Also Published As
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JP5230606B2 (ja) | 2013-07-10 |
US20090298729A1 (en) | 2009-12-03 |
ES2601428T3 (es) | 2017-02-15 |
AU2007243015A1 (en) | 2007-11-08 |
SG10201602831RA (en) | 2016-05-30 |
CN105296067A (zh) | 2016-02-03 |
CA2650337C (en) | 2015-06-16 |
US9006159B2 (en) | 2015-04-14 |
CN101479367A (zh) | 2009-07-08 |
US20120289444A1 (en) | 2012-11-15 |
EP3106506A1 (en) | 2016-12-21 |
EP2021442A1 (en) | 2009-02-11 |
WO2007127661A1 (en) | 2007-11-08 |
EP2021442B1 (en) | 2016-08-17 |
AU2007243015B2 (en) | 2011-07-21 |
CA2650337A1 (en) | 2007-11-08 |
SG10201404267UA (en) | 2014-10-30 |
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