TWI490331B - 包含經中和之脂肪酸的金屬加工潤滑油 - Google Patents

包含經中和之脂肪酸的金屬加工潤滑油 Download PDF

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TWI490331B
TWI490331B TW096115881A TW96115881A TWI490331B TW I490331 B TWI490331 B TW I490331B TW 096115881 A TW096115881 A TW 096115881A TW 96115881 A TW96115881 A TW 96115881A TW I490331 B TWI490331 B TW I490331B
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acid
mwf
fatty acid
aqueous
neutralized
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TW200745325A (en
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Patrick E Brutto
Bonnie A Pyzowski
Charles E Coburn
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Angus Chemical
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Description

包含經中和之脂肪酸的金屬加工潤滑油 發明領域
本發明是關於金屬加工潤滑油。一方面,本發明是關於水性金屬加工潤滑油(MWF),而另一方面,本發明是關於能抑制鋁和其他金屬的生銹的水性MWF。再另一方面,本發明是關於包含經中和的脂肪酸的水性MWF,而又另一方面,本發明是關於各種使用該MWF的方法。
發明背景
水性金屬加工潤滑油是眾所週知的,並且因為其優於非水性金屬加工潤滑油的經濟、環保和安全優點而被廣泛使用。水性MWF具有非常低的可燃性,並且隨著以石油為主的產物的不斷增加的成本,它們優於非水性MWF的經濟性的優點繼續增加。此外,水性MWF不具有明顯的以石油為主的液體具有的用途和處理的環境負擔(至少對相同的程度來說)。可是,在這些安全、經濟和環保優點之外,水性MWF必須也顯示其他性質,例如,不使工件生銹以及在儲存和使用的時候的穩定性。
水性MWF包含大部分的水,代表性地是超過95wt%,通常是超過97wt%。在典型的金屬加工條件下,特別是如果該MWF具有一典型的很多水性MWF具有的相對高的pH,例如高於9,水會腐蝕某些鐵和非鐵工件,尤其是鋁。可是,某些材料可被併入該水性MWF而阻止工件的生銹,材料例如矽酸鈉和磷酸酯,但是這些材料常常具有它們自身的缺陷。例如,矽酸鹽會阻塞常常被用於該MWF迴圈的超濾膜,並且磷酸酯容易受到相對迅速的細菌降解作用。
因此,在一加工操作之中和之後,金屬加工工業在確定減少或消除一金屬工件(尤其是在一像鋁的非鐵金屬工件)的生銹的添加劑和水性MWF配方上有一持續的關注。此外,企業(尤其是對於小型和中型的加工車間)在對鐵和非鐵金屬都有效的這些添加劑和配方中具有一持續的關注,因為它允許這些加工車間避免購買並且保存多樣的水性MWF的必要。
發明概要
在一具體例中,本發明是一用於一水性MWF的經中和的脂肪酸添加劑,該添加劑包含經一胺、烷醇胺和一苛性鹼中的至少一個中和的一C12-20 脂肪酸。在另一具體例中,本發明是一包含該經中和的脂肪酸添加劑的水性濃縮物。在又另一具體例中,本發明是一水性MWF,該水性MWF具有至少約是7的pH並且包含以該水性MWF的重量計的至少約0.1wt%的一經一胺、烷醇胺和一苛性鹼中的至少一個中和的C12-20 脂肪酸。
當被用於本文時,”經中和的脂肪酸添加劑”、”脂肪酸添加劑”和類似術語是指一包含本質上唯一的該經中和的脂肪酸的一本質上地非水性溶液。只要經中和的脂肪酸被製備,它的形式是與該水性MWF的剩餘物分離。在這種形式中,該添加劑可被包裝、被儲存及/或被賣給批發商及/或最終消費者。
“濃縮物”、”母料”和類似術語是指用水、油及/或另一該水性MWF的功能性組分部分被稀釋的該經中和的脂肪酸。”部分被稀釋”是指該濃縮物在它被準備用於一水性MWF的用途之前需要進一步的稀釋,一般是用水稀釋。典型地,該濃縮物包含至少約1wt%、典型地至少約5wt%和偶爾多於或等於10wt%的該經中和的脂肪酸。該濃縮物典型地含有少於95wt%、更典型地是少於約75wt%以及又更典型地是少於約50wt%的水。該濃縮物可直接由該添加劑被製備,例如,用水稀釋該添加劑並且選擇性地加入其他該MWF的組分,或者該濃縮物可從頭被製造,例如,該經中和的脂肪酸可在原處透過分別加入該脂肪酸和中和劑而被製造。像該添加劑一樣,該濃縮物可被包裝、被儲存及/或被賣給批發商及/或最終消費者。
“水性MWF”和類似術語是指,該MWF包含全部其組分以及準備供使用。在這種形式中,該水性MWF被完全稀釋,也就是在它準備使用之前,它不需要用水或任何其他組分的任何進一步的稀釋,並且它典型地包含大於或等於95wt%的水。像該濃縮物一樣,它可透過其前驅物(也就是,典型地具有在約10至20之間或更多的一稀釋因數的濃縮物)的稀釋被製備或直接從該等單獨組分而被製備。在這種第二種製備方法中,該經中和的脂肪酸可被直接加入,也就是隨著該先前被製備的經中和的脂肪酸添加劑,或它可在原處被製備,也就是該脂肪酸和中和劑以其合適的量被分開加入。
“中和劑”和類似術語是指與該MWF的該等其他組分相容的任何胺、烷醇胺或苛性鹼,並且能中和該MWF的脂肪酸組分而保留該經中和的脂肪酸的本質溶解度。”本質溶解度”是指其效力是作為該水性MWF的一生銹抑制組分的情況下,該經中和的脂肪酸的任何沉澱是可忽略的。
在另一具體例中,本發明是一種用於用機器製造或加工一金屬工件的方法,該方法包含使用一水性MWF而用機器加工的工件,該水性MWF具有一至少約是7的pH並且包含一該水性MWF的重量計的至少約0.1wt%的一由一胺、烷醇胺和一苛性鹼中的至少一個中和的C12-20 脂肪酸。本發明的水性MWF以相同的方式作為已知的水性MWF而被使用。
圖式簡單說明
第1圖顯示了在表Ex.2B中報導的該等Al 2024鋁合金試料的圖像。
第2圖顯示了在表Ex.2C中報導的該等Al 6061鋁合金試料的圖像。
第3圖顯示了在表Ex.2D中報導的該等Al 7075鋁合金試料的圖像。
第4圖顯示了在表Ex.2E中報導的該等Al 380鋁合金試料的圖像。
第5A圖和第5B圖顯示了在表Ex.3中報導的該等鋁合金試料的圖像。
第6圖是在暴露至具有和不具有一生銹抑制劑的各種水性MWF之後一鋁合金和鍍鋅鋼試料的圖像。
第7圖顯示了在表Ex.6中報導的該等鋁合金試料的圖像。
較佳實施例之詳細說明
任何C12-20 脂肪酸(i)作為一組分且與該水性MWF的其他組分相容,(ii)能被一胺、烷醇胺或苛性鹼中和,以及(iii)減少或消除一鋁工件的生銹而該工件是使用該水性MWF而被機器製造,這樣的C12-20 脂肪酸可被用於本發明的實踐中。典型地,該水性MWF的脂肪酸組分具有通式CH3 -(CH2 )n -COOH
其中n是至少約是10的一整數,較佳地至少約是12,更佳地至少約是14,以及較佳地不超過約18,更佳地不超過約16。該脂肪酸可包含一個或多個不飽和位點,及/或一個或多個取代基,其就該脂肪酸與該MWF的該等其他組分的相容性,如果有的話,或會使該工件明顯生銹的,不會干擾至任何相當大的程度。這樣的取代基包括芳香基、羥基、磺酸酯基、鹵素基和醚基。該脂肪酸的結構可是直鏈、分枝的或環狀的,並且因為分枝脂肪酸比線型脂肪酸具有較小的形成泡沫的趨勢,分枝脂肪酸是本發明的該等較佳的脂肪酸。具有一全部碳含量是大於或等於18的經中和的、飽和的、直鏈脂肪酸是比被用於本發明實踐中的其他經中和的脂肪酸差,因為大量的這種脂肪酸顯然地被要求達到像由該等其他脂肪酸提供的生銹抑制的相同位準,全部其他是相等的。
可被用於本發明實踐的代表的脂肪酸包括月桂酸、肉豆蔻酸、棕櫚酸、2-己基癸酸、硬脂酸、油酸、亞麻油酸、蘇子油酸、花生油酸、蓖麻油酸、2-環己烯-1-辛酸、5-羧基-4-己基辛酸、大風子酸、異硬脂酸(混合物異構物)、順-11-二十烯酸、植烷酸、降植烷酸、4,8,12-三甲基十三酸和松油脂肪酸。該等脂肪酸可被單獨使用或者彼此是兩個或多個被組合使用。可購買的C12-20 脂肪酸通常是混合物,並且這些混合物可含有具有少於12個碳原子及/或多於20個碳原子的脂肪酸的量。這些混合物可被用於本發明的實踐中,並且在該混合物中非C12-20 脂肪酸的量較佳地是小於一不合理的量,例如小於脂肪酸的全部量的約10wt%。
該中和胺可具有任何種類並且具有任何分子量,並且能被單獨使用或與一個或多個其他胺組合使用,及/或與一個或多個烷醇胺及/或輻射劑組合使用。這些胺包含一級胺、二級胺和三級胺。它們是脂肪族(較佳地是一級或三級烷基)、脂環族或芳香族結構,並且具有一個或多個取代基,其就該胺與該MWF的該等其他組分的相容性,如果有的話,或會使該工件明顯生銹的,不會干擾至任何相當大的程度。這樣的取代基包括醚基。代表性的胺包括氨(為達到本發明的目的被看作一胺),甲胺、二甲胺和三甲胺,乙胺、二乙胺和三乙胺,正丙胺、二正丙胺和三正丙胺,異丙胺,正丁胺、異丁胺、二級丁胺和三級丁胺,環己胺,二環己胺,苄胺,α-苯乙胺、β-苯乙胺,乙二胺,四亞甲二胺,六亞甲二胺,氫氧化四(C1-3 烷基)銨(例如,氫氧化四甲銨、氫氧化三甲基乙銨等等),苯胺,甲基苯胺,鄰-、間-和對-胺,鄰-、間-和對-甲氧苯胺,鄰-、間-和對-氯苯胺以及聯苯胺。
具有特別關注和用途的是該等烷醇胺,特別是該等具有一較低分子量的烷醇胺。像胺一樣,該烷醇胺可被單獨使用或與一個或多個其他烷醇胺組合使用,及/或與一個或多個胺及/或苛性鹼組合使用。該烷醇胺也可具有一個或多個取代基,其就該烷醇胺與該MWF的該等其他組分的相容性,如果有的話,或會使該工件明顯生銹的,不會干擾至任何相當大的程度。代表性的烷醇胺包括單-、二-和三乙醇胺,單-、二-和三異丙醇胺,二甘醇胺,正丁基乙醇胺,2-胺基-2-甲基-1-丙醇(AMP),以及2-胺基-2-乙基-1,3-丙二醇。
如本文所使用的,”苛性鹼”包括任何類似於氫氧化鈉的化合物,並且當它與該脂肪酸組合而形成一脂肪酸鹽時,該脂肪酸鹽在該水性MWF中是本質上可溶的。該苛性鹼可具有任何種類,並且可被單獨使用或者與一個或多個其他苛性鹼組合使用,及/或與一個或多個胺及/或烷醇胺組合使用。代表性的苛性鹼包括氫氧化鈉、氫氧化鋰、氫氧化鉀、苛性酒精(例如,C2 H5 ONa)、碳酸鹽、磷酸鹽等等。氫氧化鉀是一較佳的苛性鹼。
該脂肪酸和胺、烷醇胺及/或苛性鹼是以該脂肪酸被有效地中和的這樣的量被使用。儘管使用一稍低或稍高的比例本發明的一些優勢可被得到,中和基團與羧基的莫爾比例典型地是約1:1。一過量的中和劑可被使用,但是它不具有任何較大的優勢的作用。
在本發明的一具體例中,該經中和的脂肪酸是與MWF分開被製備,並且繼而被包裝以及作為一添加劑被出售,該添加劑是用於各種濃縮物及/或水性MWF配方的製備。在這個具體例中,該脂肪酸和中和劑以任何方便的方式被混合,典型地是在週圍條件下使用攪拌。在其他具體例中,在被包裝及/或使用之前,該經中和的脂肪酸可用水被稀釋及/或與該濃縮物及/或水性MWF的其他組分摻合。
在另一具體例中,作為製備該水性MWF的方法的一部分,該經中和的脂肪酸在加入該MWF的水性介質之前或在原處被製備。不管其製備的方法,在該水性MWF中經中和的脂肪酸的量典型地至少約是0.1wt%、較佳地約是0.4wt%以及更佳地約是0.07wt%的該水性MWF。在該水性MWF中經中和的脂肪酸的最大量可廣泛地改變並且通常是一經濟性的功能。典型地,該最大量不會超過約1wt%的該水性MWF,較佳地它不會超過約0.7wt%以及更佳地它不會超過約0.5wt%。
本發明的該水性MWF僅僅包含水和一經中和的脂肪酸,但是典型地還包含多個其他組分。這些其他組分可包括,但不限制在烴及/或合成油、各種無機鹽、表面活性劑、除生物劑、潤滑劑、染料、消泡劑、乳化劑等等。這些其他組分以已知的量和組合被使用,以及該水性MWF典型地包含至少約大於或等於95wt%的水,水是自來水或去離子水。被用於本發明實踐中的該等經中和的脂肪酸與該水性MWF配方的其他組分匹配而使所欲的性能達到最大。
本發明的該水性MWF既適合用於含鐵金屬(例如,鐵、鋼和鍍鋅鋼),又適合用於不含鐵的金屬(例如,鋁和鋁合金)。該等金屬工件以已知和傳統的方式被機器製造,並且本發明的該水性MWF是以已知和傳統的方式被使用。
在該等下面的實施例中,除非另外指出,所有部分和百分比是按重量計算的
特別具體例 實施例1
2-胺基-2-甲基-1-丙醇(AMP)的松油脂肪酸鹽被用於一生銹測試中。為進行這個測試,溶於去離子水的33.5g 1%的一水性溶液被加入300g溶解在芝加哥伊利諾自來水中的0.27%的松油脂肪酸。所產生的0.34%的松油脂肪酸-AMP鹽溶液被放入玻璃罐中,並且鋁合金Al 2024、Al 380(一鑄鋁)、Al 6061和Al 7075(都是飛機級別的鋁)的試料被半浸入該等溶液中。使用由氫氧化鉀被調節到pH為9.5的平原自來水和去離子水製備對照組。該等罐在空氣中被密封並且被放入40℃的烘箱內。試料被移動並且在24小時、1週和5週之後檢查生銹。在氣相中的生銹在相對於該等對照組系統的一些情況中被減少。對於除Al 380的全部合金,生銹在液相中被本質地消除;Al 380發生了較輕的生銹但是這遠小於該等對照組所受到的生銹。
實施例2
在表Ex.2A中報導的該等鹽溶液是在芝加哥自來水中被製備的,並且用中和劑為准被調節到一9.0的pH。在這個實施例中,僅僅經中和的松油代表本發明。
使用在實施例1中描述的該協議的具有該等上面鹽溶液的生銹測試的結果被顯示在下面的表Ex.2B-E中。儘管生銹的程度(例如,深度、中度、輕度、非常輕度和無)是客觀的,該等測試試料的圖像在第1圖至第4圖中被提供。在一特別的工件上的一被報導的生銹程度的可接受性對於該工件的使用者而言,是主觀的。為達到這些實施例的目的,可接受的生銹是輕度的、非常輕度的或無。
實施例3
為了測量鏈長度對作為生銹抑制劑的脂肪酸烷醇胺的效力的作用,從新癸酸(見上面的實施例2,一10-碳的支鏈的單羧酸)至二十二酸(一22-碳的直鏈的單羧酸)的鹽被評估。在自來水中用2-胺基-2-甲基-1-丙醇中和至pH 9.5的0.3%的酸(或在新癸酸的情況下是0.4%)的該等結果被報導在下面的表Ex.3中和圖5A-B中。
這些資料證實了鏈長度對性能具有一影響(很可能某種程度上由於該鹽的溶解度/分散性)。硬脂酸鹽和二十二酸鹽在水中比在其他中分散較少,並且這可影響為使該金屬表面潤濕的可利用的鹽的量。更多的硬脂酸很可能被要求在這個特殊的實驗中達到可接受的結果。該新癸酸鹽的效率的缺乏是無法解釋的,但是於C12-20 酸鹽比較,它可與其在水中較高的溶解度有關。
實施例4
為了證實分枝脂肪酸鹽(與直鏈脂肪酸鹽相反)的降低的形成泡沫的趨勢,使用芝加哥自來水(20份水對1份濃縮物)製備一大體的合成的水性MWF。該合成的MWF配方包含該等下列組分:
該被稀釋的基液被分為四等份,並且向三份中加入在下面的表Ex.4中鑒定的0.1wt%的該等酸的鹽。恰好50毫升(ml)被稀釋的液體被放入100ml的帶塞刻度量筒中。該等量筒繼而被振盪一分鐘,並且估計初始泡沫體積(時間等於0 min)以及接下來然後在被選定的時間估計初始泡沫體積。在表Ex.4中的資料顯示在包含有一分枝脂肪酸鹽的液體中的初始泡沫的塌陷比在包含有一直鏈脂肪酸鹽的液體中要更快。
實施例5
在pH經調控的水中選擇的鋁合金和鍍鋅鋼試料的生銹對照組使用並且不使用0.1wt%的AMP松油脂肪酸來測試。第6圖顯示當這個鹽被加入到芝加哥中自來水中(用KOH調節pH到9.5)時,在全部試料的液相接觸區域內生銹被完全消除。因為這個鹽是不揮發的,在氣相區域內生銹沒有被消除。
實施例6
使用用於Al 2024、380、6061和7075鋁合金試料的上面的實施例5的程序,測試各種經苛性鹼中和的脂肪酸和經一胺中和的脂肪酸。該等結果被報導在下面的表Ex.6和第7圖中。
表Ex.6的資料和第7圖顯示本發明的經苛性鹼中和和經胺中和的松油脂肪酸在一水性MWF中是有效的鋁生銹抑制劑。該資料也顯示經苛性鹼中和的異硬脂酸是一有效的鋁生銹抑制劑,但是新癸酸(不是本發明的一脂肪酸)不比其經烷醇胺中和的對應物在抑制鋁生銹上是更有效的。
儘管本發明已經被更詳細描述,這個細節是為了說明的目的。正如在下面的該等申請專利範圍中描述的,因為上面所描述的沒有脫離本發明的精神和範圍,對本發明可進行很多變化和修改。被確定為與上面一樣的所有美國專利和允許的專利申請案在本文被併入為參考資料。
第1圖顯示了在表Ex.2B中報導的該等Al 2024鋁合金試料的圖像。
第2圖顯示了在表Ex.2C中報導的該等Al 6061鋁合金試料的圖像。
第3圖顯示了在表Ex.2D中報導的該等Al 7075鋁合金試料的圖像。
第4圖顯示了在表Ex.2E中報導的該等Al 380鋁合金試料的圖像。
第5A圖和第5B圖顯示了在表Ex.3中報導的該等鋁合金試料的圖像。
第6圖是在暴露至具有和不具有一生銹抑制劑的各種水性MWF之後一鋁合金和鍍鋅鋼試料的圖像。
第7圖顯示了在表Ex.6中報導的該等鋁合金試料的圖像。

Claims (8)

  1. 一種用於機器製造一非鐵之金屬工件的方法,該方法包含:提供一水性金屬加工潤滑油(MWF),以該MWF之重量計,其基本上由(i)水,(ii)自0.1至1wt%之經一胺或烷醇胺之至少一者中和的一C12-20 脂肪酸,以及可擇地,(iii)烴油、合成油、表面活性劑、除生物劑、潤滑劑、染料、消泡劑及乳化劑之一或多者所組成,以及;將一非鐵金屬工件與該水性MWF接觸,其中該MWF具有介於7及10之間的pH;其中該脂肪酸是月桂酸、肉豆蔻酸、棕櫚酸、硬脂酸、2-己基癸酸、油酸、亞麻油酸、蘇子油酸、花生油酸、蓖麻油酸、2-環己烯-1-辛酸、5-羧基-4-己基辛酸、大風子酸、異硬脂酸、植烷酸、降植烷酸、4,8,12-三甲基十三酸和松油脂肪酸中的至少一個;且其中該胺是氨,甲胺、二甲胺和三甲胺,乙胺、二乙胺和三乙胺,正丙胺、二正丙胺和三正丙胺,異丙胺,正丁胺、異丁胺、二級丁胺和三級丁胺,環己胺,二環己胺,苄胺,α-苯乙胺、β-苯乙胺,乙二胺,四亞甲二胺,氫氧化四甲銨,六亞甲二胺,苯胺,甲基苯胺,鄰-、間-和對-胺,鄰-、間-和對-甲氧苯胺,鄰-、間-和對-氯苯胺以及聯苯胺中的至少一個。
  2. 如申請專利範圍第1項之方法,其中該工件是鋁。
  3. 如申請專利範圍第1項之方法,其中該脂肪酸是分枝的。
  4. 如申請專利範圍第1項之方法,其中該烷醇胺是單-、二-和三乙醇胺,單-、二-和三異丙醇胺,二甘醇胺,正丁基乙醇胺,2-胺基-2-甲基-1-丙醇和2-胺基-2-乙基-1,3-丙二醇中的至少一個。
  5. 如申請專利範圍第1項之方法,該水性MWF具有一在8至9.5之間的pH。
  6. 如申請專利範圍第1項之方法,其中該MWF抑制於金屬加工操作中經該潤滑油接觸之該非鐵金屬工件的生銹。
  7. 如申請專利範圍第1項之方法,其中,以該MWF之重量計,該水性金屬加工潤滑油(MWF)是由(i)水,(ii)自0.1至1wt%之經一胺或烷醇胺之至少一者中和的一C12-20 脂肪酸,以及可擇地,(iii)烴油、合成油、表面活性劑、除生物劑、潤滑劑、染料、消泡劑及乳化劑之一或多者所組成。
  8. 如申請專利範圍第1項之方法,其中,以該MWF之重量計,該水性金屬加工潤滑油(MWF)是由(i)水,(ii)自0.1至1wt%之經一胺或烷醇胺之至少一者中和的一C12-20 脂肪酸,以及可擇地,(iii)胺二羧酸鹽、相反地可溶的脂肪酯、三乙醇胺以及雙環唑啶除生物劑之一或多者所組成。
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