JP5372376B2 - 添加剤の調製方法およびその使用 - Google Patents
添加剤の調製方法およびその使用 Download PDFInfo
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- JP5372376B2 JP5372376B2 JP2007545635A JP2007545635A JP5372376B2 JP 5372376 B2 JP5372376 B2 JP 5372376B2 JP 2007545635 A JP2007545635 A JP 2007545635A JP 2007545635 A JP2007545635 A JP 2007545635A JP 5372376 B2 JP5372376 B2 JP 5372376B2
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- polymer
- acylating agent
- acylated
- medium
- additive
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- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
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- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
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- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
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- C10M129/92—Carboxylic acids
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- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
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- C10M133/56—Amides; Imides
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Description
本発明は、腐食低減、分散性または清浄性の少なくとも1つの特性を有する添加剤を調製する方法に関する。本発明は、さらに、液体燃料または潤滑粘性のあるオイルにおけるこの添加剤の使用に関する。
市販のディーゼル燃料は、燃料の燃焼中にエンジン内で固形物および粘性物質の堆積を引き起こし得る不純物を含有する。ディーゼル燃料は、一般に、高濃度を高分子量物質を含有するので、このようなエンジン堆積物の問題は、ガソリン燃料よりもディーゼル燃料において、非常に重要である。このような物質が熱分解すると、エンジンにおいて、不溶性物質が形成され、これらは、操作効率を低下させ得、最終的には、エンジンの燃料噴射器および他の重要な作用要素の腐食または閉塞を引き起こし得る。これらの問題を克服するために、清浄剤/分散剤(例えば、ポリイソブチレンスクシンイミド)は、堆積物の形成を減らすために広く使用されているのに対して、加水分解されたポリイソブチレンコハク酸は、腐食を減らすために使用される。
本発明は、添加剤を調製する方法を提供し、該方法は、以下の工程を包含する:
(1)2個〜8個の炭素原子を含有するオレフィンから誘導された重合体とアシル化剤とを反応させて、アシル化重合体を形成する工程;および
(2)工程(1)のアシル化重合体を、実質的にイオウを含まない媒体にて、
a.アンモニアまたはアミンと反応させて、スクシンイミド生成物を形成する工程;または
b.水と反応させて、加水分解生成物を形成する工程であって、
ここで、該アシル化剤と工程(1)の重合体とのモル比は、0.3:1〜1.6:1である、
方法。
(a)実質的にイオウを含まない媒体;および
(b)アシル化基と2個〜8個の炭素原子を含有するオレフィンから誘導された重合体とを含有する添加剤であって、
ここで、該添加剤は、0.3:1〜1.6:1のアシル化基と重合体とのモル比を有する。
(a)実質的にイオウを含まない媒体;
(b)アシル化剤と2個〜8個の炭素原子を含有するオレフィンから誘導された重合体とを含有する添加剤;および
(c)液体燃料または潤滑粘性のあるオイルであって、
ここで、該添加剤は、0.3:1〜1.6:1のアシル化剤と重合体とのモル比を有する。
本発明は、添加剤を調製する方法を提供し、該方法は、以下の工程を包含する:
(1)2個〜8個の炭素原子を含有するオレフィンから誘導された重合体とアシル化剤とを反応させて、アシル化重合体を形成する工程;および
(2)工程(1)のアシル化重合体を、実質的にイオウを含まない媒体にて、
(1)アンモニアまたはアミンと反応させて、スクシンイミド生成物を形成する工程;または
(2)水と反応させて、加水分解生成物を形成する工程であって、
ここで、該アシル化剤と工程(1)の重合体とのモル比は、0.3:1〜1.6:1である。
この方法は、2個〜8個の炭素原子、別の実施態様では、3個〜6個の炭素原子を含有するオレフィンから誘導された重合体を反応させる工程を包含する。適当なオレフィンの例には、プロピレン、イソブチレン、ペンテンまたはヘキサンが挙げられる。1実施態様では、この重合体は、イソブチレンから誘導され、ポリイソブチレンを形成する。
本発明のアシル化剤は、1種またはそれ以上の酸官能性基(例えば、カルボン酸またはその無水物)を有する化合物であり得る。アシル化剤の例には、α,β−不飽和モノ−またはポリカルボン酸、それらの無水物、エステルまたは誘導体が挙げられる。アシル化剤の例には、(メタ)アクリル酸、(メタ)アクリル酸メチル、マレイン酸またはその無水物、フマル酸、イタコン酸またはその無水物、あるいはそれらの混合物が挙げられる。
このアミンは、一般に、当該技術分野で周知であり、一般に、少なくとも1個の反応性N−H結合(窒素結合または水素結合)を有する。このアミンは、必要に応じて、他の官能基(例えば、ヒドロキシル)でさらに置換されている。このアミンには、モノアミン、ポリアミン、またはそれらの混合物が挙げられる。1実施態様では、このアミンは、1個またはそれ以上の第一級または第二級アミノ基を含有する。
本発明の実質的にイオウを含まない媒体(本明細書中では、「媒体」と呼ぶ)はまた、溶媒または希釈剤として、記述され得る。この媒体は、脂肪族、芳香族、またはそれらの混合物であり得る。この媒体は、炭化水素、非炭化水素(例えば、アルコールまたはカルボン酸エステル)、またはそれらの混合物であり得る。この媒体は、単一の溶媒または希釈剤、あるいは2種またはそれ以上の溶媒または希釈剤の混合物であり得る。本発明の1実施態様では、この媒体は、芳香族炭化水素、他の実施態様では、脂肪族および芳香族炭化水素の混合物、脂肪族および芳香族炭化水素の混合物であって、その脂肪族炭化水素が50重量%またはそれ以上であるもの、および脂肪族炭化水素である。
本発明は、さらに、以下を含有する組成物を提供する:
(a)実質的にイオウを含まない媒体;および
(b)アシル化基と2個〜8個の炭素原子を含有するオレフィンから誘導された重合体とを含有する添加剤であって、
ここで、該添加剤は、0.3:1〜1.6:1、0.8:1〜1.45:1、または1:1〜1.4:1のアシル化基と重合体とのモル比を有する。本発明の実施態様では、この組成物の添加剤は、本願全体にわたって記述されているように、アシル化重合体と、アンモニア、アミンまたは水との反応生成物であり得る。
本発明の燃料組成物は、必要に応じて、液体燃料を含有し、そして内燃機関に燃料供給する際に有用である。この液体燃料は、通常、周囲条件で液体である。この液体燃料は、炭化水素燃料、非炭化水素燃料、またはそれらの混合物であり得る。この炭化水素燃料は、石油留出物であり得、これには、ASTM仕様D4814で規定されるガソリンまたはASTM仕様D975で規定されるディーゼル燃料が挙げられる。本発明の1実施態様では、この液体燃料は、ガソリンであり、他の実施態様では、この液体燃料は、有鉛ガソリンまたは無鉛ガソリンである。本発明の別の実施態様では、この液体燃料は、ディーゼル燃料である。この炭化水素燃料は、気液プロセスにより調製された炭化水素であり得、これらには、例えば、フィッシャー−トロプシュプロセスのようなプロセスにより調製された炭化水素が挙げられる。この非炭化水素燃料は、酸素含有炭化水素(これは、しばしば、含酸素物(oxygenate)と呼ばれている)であり得、これらには、アルコール、エーテル、ケトン、カルボン酸のエステル、ニトロアルカン、またはそれらの混合物が挙げられる。この非炭化水素燃料には、例えば、メタノール、エタノール、メチルt−ブチルエーテル、メチルエチルケトン、植物および動物の由来のエステル交換油および/または脂肪(例えば、菜種メチルエステルおよび大豆メチルエステル)、ならびにニトロメタンが挙げられ得る。炭化水素燃料と燃料と混合物には、例えば、ガソリンとメタノールおよび/またはエタノール、ディーゼル燃料とエタノール、およびディーゼル燃料とエステル交換植物油(例えば、菜種メチルエステル)が挙げられ得る。本発明の1実施態様では、この液体燃料は、炭化水素燃料、非炭化水素燃料、またはそれらの混合物中の水の乳濁液である。本発明のいくつかの実施態様では、この液体燃料は、重量基準で、5000ppmまたはそれ未満、1000ppmまたはそれ未満、300ppmまたはそれ未満、200ppmまたはそれ未満、30ppmまたはそれ未満、または10ppmまたはそれ未満であるイオウ含量を有し得る。
この潤滑油組成物には、潤滑粘性のある天然油または合成油、水素化分解、水素化、ハイドロフィニッシングから誘導されたオイル、および未精製油、精製油および再精製油、およびそれらの混合物が挙げられる。
本発明の方法は、必要に応じて、さらに、少なくとも1種の他の性能添加剤を含有する組成物を包含する。これらの他の性能添加剤には、金属不活性化剤、清浄剤、分散剤、粘度調整剤、摩擦調整剤、分散剤粘度調整剤、極圧剤、耐摩耗剤、酸化防止剤、腐食防止剤、発泡防止剤、解乳化剤、流動点降下剤、シール膨潤剤、およびそれらの混合物が挙げられる。
(d)実質的にイオウを含まない媒体;
(e)アシル化剤と2個〜8個の炭素原子を含有するオレフィンから誘導された重合体とを含有する添加剤;および
(f)液体燃料または潤滑粘性のあるオイルであって、
ここで、該添加剤は、0.3:1〜1.6:1、0.8:1〜1.45:1、または1:1〜1.4:1のアシル化剤と重合体とのモル比を有する。本発明の1実施態様では、この組成物の添加剤は、本明細書全体で記述されているように、アシル化重合体と、アンモニア、アミンまたは水との反応生成物であり得る。
1実施態様では、本発明は、液体燃料または内燃機関に有用である。別の実施態様では、本発明は、内燃機関を潤滑させるための潤滑粘性のあるオイルに有用である。
Glissopal 1000(数平均分子量 約1000および>70%のビニリデン含量、1当量)18.18Kgを、100℃で、密封容器に充填し、そして撹拌する。この容器を167℃まで加熱し、そして真空を適用する。次いで、この容器を、175℃まで加熱しつつ、窒素雰囲気(1barg)で加圧する。一旦、175℃で安定化すると、ジャケット付き注射器ポンプ(ISCOポンプ)を経由して、追跡したラインと共に(with traced lines)、無水マレイン酸を加える。次いで、この容器を、無水マレイン酸添加の初期充填から4時間にわたって、220℃まで加熱する。追加無水マレイン酸65mlを加え、続いて、50分間にわたって、22ml/分の速度で、無水マレイン酸の連続給送を行う。さらに3時間10分後、この容器を添加の最後まで225℃まで加熱しつつ、37分間にわたって、追加無水マレイン酸818mlを充填する。次いで、その反応物を、225℃で、さらに10時間保持する。この反応の全体にわたって加えられたMAAの全量は、2.32kg、1.3当量である。最終生成物は、100℃で570cSt(mm/s)の動粘度、および127mgKOH/gのTANを有する。
この方法は、生成物に1.2:1の無水マレイン酸とポリイソブチレンとの比を与えるように無水マレイン酸の量を減らすこと以外は、調製実施例1と同じである。
Glisopal(登録商標)1000に代えて、ポリイソブチレンTPC(登録商標)555およびTPC(登録商標)575を使用すること以外は、調製実施例1と同じである。TPC(登録商標)555は、550の数平均分子量を有し、そしてTPC(登録商標)575は、750の数平均分子量を有する。
密封容器に、100℃で、消泡剤1リットルと共に、Glissopal(登録商標)1000(37,000Kg)を充填する。この容器を、真空下にて、167℃まで加熱し、次いで、窒素で100kPaまで加圧した後、175℃まで加熱する。この容器を4時間にわたって220℃まで加熱しつつ、70分間にわたって、無水マレイン酸1883Kgを加える。この容器に無水マレイン酸6240Kgを充填し、そして4時間反応させる。真空ストリッピングにより、未反応無水マレイン酸を除去する。最終生成物は、152の全酸価、および2.24:1の無水マレイン酸とGlissopal(登録商標)1000との比を有する。
容器にて、調製実施例1の生成物1366gをPilot(登録商標)900(134g)に撹拌して、混合物を形成する。次いで、この混合物を、真空下にて、セライトパッドで濾過する。次いで、この混合物を110℃まで加熱し、そして窒素下にて、300rpmで撹拌する。30分間にわたって、テトラエチレンペンタミン(TEPA)36.1gを滴下した後、この容器を175℃まで加熱し、そして4時間保持する。次いで、この容器を冷却して、100℃で482mm/s(cSt)の動粘度;72のTBNおよび3.66重量%の窒素含量を有する生成物が得られた。最終生成物は、73重量%のポリイソブチレンスクシンイミドおよび27重量%のPilot(登録商標)900、ならびに1.8:1の窒素とカルボニルとの比を有する。
調製実施例2の生成物の容器に、さらに、Pilot(登録商標)900(122.4g)(これは、Petrochem Carlessから市販されている)を充填する。この容器に、パドル攪拌機、ドッグレッグアダプタおよび機械攪拌機ょを備え付け、次いで、入口を不活性ガス(窒素)で密封する。この容器の内容物を110℃まで温め、そして500rpmで撹拌する。次いで、この容器に、78分間にわたって、テトラエチレンペンタミン(TEPA)114.9gを滴下する。滴下漏斗に、Pilot(登録商標)900(10g)を充填し、この反応物に加えて、残留しているいずれかのTEPAを洗う。この容器にガラスウールを被覆し、そして温度を175℃まで上げる。一旦、175℃になると、この反応物を4時間保持する。生成物を分析すると、1.79:1の窒素とカルボニルとの比が明らかとなる。最終生成物は、15重量%のPilot(登録商標)900および85重量%のポリイソブチレンスクシンイミドを有する。
調製実施例1から得たポリイソブチレン無水コハク酸340g、およびPilot(登録商標)900(60g)を容器に充填し、そして1時間ブレンドする。この容器の内容物を400rpmで撹拌し、そして90℃まで加熱する。次いで、この容器に窒素を充填して、不活性雰囲気にした後、10分間にわたって水5.9gを充填し、そして2時間撹拌する。形成された生成物は、163mg/KOHの全酸価および100℃で500mm/s(cSt)の動粘度を有する。形成された生成物は、85重量%の加水分解生成物および15重量%のPilot(登録商標)900を含有する。カルボニルと水との比は、0.5:1である。
Pilot(登録商標)900をSN330基油で置き換えたこと以外は、実施例1と類似のプロセスで、参考例1を調製する。スクシンイミド最終生成物は、60重量%で存在しており、SN330は、40重量%で存在している。
調製比較例1の生成物35560Kgを使用し、SN330基油を加え、さらに、容器に入れて窒素でパージして、参考例2を調製する。この容器を110℃まで加熱し、この添加の始めから終わりまで、温度を110℃から120℃まで変えつつ、3時間にわたって、テトラエチレンペンタミン(TEPA)3777Kgを加える。次いで、この容器を、4時間にわたって、150℃まで加熱し、さらに、窒素で1時間パージする。次いで、この容器を175℃まで加熱し、そして4時間保持する。冷却した後、最終生成物は、2.24:1の窒素とカルボニルとの比、100℃で495mm/s(cSt)の動粘度および79のTBNを有する。存在しているSN330基油の量は、60重量%のスクシンイミドおよび40重量%のSN330を有する最終生成物を提供するのに十分である。
参考例3は、SN330をPilot(登録商標)900で置き換えたこと以外は、参考例2と同じである。
CEC試験方法CEC F−23−A−01および国際標準方法ISO 4010に従って、XUD9試験を実行する。一般に、低い流れ閉塞値および高い残留流れ値を有する試料について、良好な結果が得られる。各試料についてこの試験で使用された添加剤の量もまた、表1で示す。得られた結果は、以下であった:
(表1)
ASTM Method D665−03、Procedure A(蒸留水)およびProcedure B(Synthetic Sea Water)に従って、参考例3Aの60ppmの処理速度を使用して、この腐食試験を実行する。参考例3Aについて、Procedure AおよびProcedure Bで得られた結果は、腐食が起こらなかったことを示している。
Claims (10)
- 添加剤を調製する方法であって、該方法は、以下の工程を包含する:
(1)2個〜8個の炭素原子を含有するオレフィンから誘導された重合体とアシル化剤とを反応させて、アシル化重合体を形成する工程であって、該アシル化剤は、α,β−不飽和モノ−またはポリカルボン酸、それらの無水物、エステルまたは誘導体である、工程;および
(2)工程(1)のアシル化重合体を、重量基準で、25ppm未満のイオウ含量を有する媒体にて、アンモニアまたはアミンと反応させて、スクシンイミド生成物を形成する工程であって、
ここで、該アシル化剤と工程(1)の重合体とのモル比は、1:1〜1.4:1であり、そして、
アミン窒素基とアシル化重合体カルボニル基との比は、1.3〜2.7:1である、
方法。 - 工程(1)の前記アシル化重合体が、一置換アシル化重合体として、60重量%またはそれ以上を含有する、請求項1に記載の方法。
- 工程(1)の前記重合体が、20モル%未満の未反応重合体を含有する、請求項1に記載の方法。
- 前記重合体が、450〜2500の数平均分子量を有する、請求項1に記載の方法。
- 前記オレフィンが、3個〜6個の炭素原子を含有する、請求項1に記載の方法。
- 前記重合体が、重合体分子の60%以上で、ビニリデン基を含有する、請求項1に記載の方法。
- 前記アミンが、1個またはそれ以上の第一級または第二級アミノ基を含有する、請求項1に記載の方法。
- 前記媒体が、105℃またはそれより高い引火点を有する、請求項1に記載の方法。
- 以下を含有する、組成物:
(a)重量基準で、25ppm未満のイオウ含量を有する媒体;および
(b)アシル化基とアミン基と2個〜8個の炭素原子を含有するオレフィンから誘導された重合体とを含有する添加剤であって、
ここで、該アシル化剤は、α,β−不飽和モノ−またはポリカルボン酸、それらの無水物、エステルまたは誘導体であり、
該添加剤は、1:1〜1.4:1のアシル化基と重合体とのモル比を有し、そして、
アミン窒素基とアシル化重合体カルボニル基との比は、1.3〜2.7:1である、
組成物。 - 液体燃料または潤滑組成物に、清浄性、分散性、腐食防止または腐食低減の少なくとも1つを与える方法であって、該方法は、以下を含有する組成物で潤滑または燃料供給する工程を包含する:
(a)重量基準で、25ppm未満のイオウ含量を有する媒体;
(b)アシル化剤とアミン基と2個〜8個の炭素原子を含有するオレフィンから誘導された重合体とを含有する添加剤であって、ここで、該アシル化剤は、α,β−不飽和モノ−またはポリカルボン酸、それらの無水物、エステルまたは誘導体である、添加剤;および
(c)液体燃料または潤滑粘性のあるオイル、
ここで、該添加剤は、1:1〜1.4:1のアシル化剤と重合体とのモル比を有し、そして、
アミン窒素基とアシル化重合体カルボニル基との比は、1.3〜2.7:1である、
方法。
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- 2005-12-08 WO PCT/US2005/044475 patent/WO2006063161A2/en active Application Filing
- 2005-12-08 SG SG2013011457A patent/SG188788A1/en unknown
- 2005-12-08 JP JP2007545635A patent/JP5372376B2/ja not_active Expired - Fee Related
- 2005-12-08 CN CN2005800421940A patent/CN101072798B/zh active Active
- 2005-12-08 US US11/719,458 patent/US9481841B2/en active Active
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Also Published As
Publication number | Publication date |
---|---|
WO2006063161A2 (en) | 2006-06-15 |
SG188788A1 (en) | 2013-04-30 |
JP2008523222A (ja) | 2008-07-03 |
JP2012229446A (ja) | 2012-11-22 |
EP1819739B1 (en) | 2019-07-24 |
KR20070093082A (ko) | 2007-09-17 |
SG158085A1 (en) | 2010-01-29 |
CN101072798B (zh) | 2013-10-16 |
US9481841B2 (en) | 2016-11-01 |
CA2589358A1 (en) | 2006-06-15 |
CA2589358C (en) | 2015-01-27 |
WO2006063161A3 (en) | 2007-02-22 |
KR101225874B1 (ko) | 2013-01-24 |
EP1819739A2 (en) | 2007-08-22 |
CN101072798A (zh) | 2007-11-14 |
US20090149358A1 (en) | 2009-06-11 |
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