CN1010692B - 在冷却润滑剂存在下机械加工铝和铝合金的方法以及冷却润滑剂浓缩物 - Google Patents

在冷却润滑剂存在下机械加工铝和铝合金的方法以及冷却润滑剂浓缩物

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Publication number
CN1010692B
CN1010692B CN87103469A CN87103469A CN1010692B CN 1010692 B CN1010692 B CN 1010692B CN 87103469 A CN87103469 A CN 87103469A CN 87103469 A CN87103469 A CN 87103469A CN 1010692 B CN1010692 B CN 1010692B
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China
Prior art keywords
cooling lubricant
carbon atom
lubricant
weight
compound
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CN87103469A
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CN87103469A (zh
Inventor
埃利那·桑德伯格
罗尔夫·斯科尔德
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Berol Nobel Suisse SA
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Berol Nobel Suisse SA
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Publication of CN87103469A publication Critical patent/CN87103469A/zh
Publication of CN1010692B publication Critical patent/CN1010692B/zh
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Abstract

在水基冷却润滑剂存在下机械加工铝或铝合金，该冷却润滑剂具有稳定的溶液形态，其中作为润滑剂和防腐剂含有(a)具有7-14个碳原子的疏水基的羧基化合物及(b)分子量低于300的烷基烷醇叔胺的混合物。羧基化合物和烷基烷醇叔胺的用量选择，要使烷醇胺和羧基化合物之间的碱/酸当量比低于1.0。其浓缩物用水稀释后即可用作冷却润滑剂。

Description

本发明涉及在水基冷却润滑剂存在下机械加工铝和铝合金的方法以及用水稀释后可用作为冷却润滑剂的浓缩物。本发明技术特别适用于冷轧。
一般来说，煤油基冷却润滑剂适用于铝的冷轧，但其应用还存在许多不利因素，如烃的排放量大，火灾危险性大且冷却效果有限。冷却效果差又对生产能力产生不利影响。
因此已提出用含特定添加剂的水基乳液代替煤油基冷却润滑剂，其中的添加剂可降低（特别是在高压下）金属表面和加工工具之间的腐蚀和/或摩擦。特别是USP4，243，537和欧洲专利申请115，926提出了这种水基润滑体系，其中包括烷醇胺，羧酸和聚氧化烃的混合物作为润滑剂和防腐剂。USP3，374，171也公开了用于金属加工如用于机械加工铁的类似润滑剂组合物。
尽管水基冷却润滑体系具有尽人皆知的优点，但还不能广泛用于轧制铝和铝合金，因为其中的润滑剂和防腐剂含量低，致使水锈蚀金属表面且对加工工具的润滑和/或防腐效果差。引起金属铝表面的水锈（即所谓的百锈）的主要原因是冷却润滑剂中添加的有关成分对铝的防腐效果差。尽管增加润滑剂和防腐剂的含量无疑会改善润滑和防腐效果，但在后续的热处理过程中又会有不希望出现的锈蚀问题，这是因为所用冷却润滑剂各成分的残余物已进行了转化，并会烧蚀金属表面。
轧制加工中难于解决的另一问题是在轧制金属表面上会出现轧痕和其它机械损伤，因为金属会从正在轧制的金属坯段上撒裂下来并焊接在轧辊上。在进一步轧制过程中这种不规则轧辊构型会损伤铝表面。
现已发现可对铝或铝合金进行有效的冷轧或热轧加工，其中可得到令人满意的润滑和防腐效果，且在后续的热处理中金属表面不会出现不希望有的锈蚀。本发明中这一效果是这样达到的，即在稳定溶液形态的水基冷却润滑剂存在下于至少20～70℃进行机械加工，润滑剂中含（a）通式为R1COOH的羧基化合物，其中R1为具有7～14个碳原子的疏水基团和（b）分子量低于300的烷基烷醇叔胺，胺和羧基化合物之间的碱/酸当量比小于1.0。所谓的“稳定溶液”在本发明中是指在可预见的一段时间即至少1个月内不会分成两相或多相的溶液。
为获得上述优点，首要的是碱/酸当量比小于1.0，优选为0.5～0.9。EP-A-115，926和USP3，374，171公开的仅是当量比大大高于1.0的实施方案。在USP3，374，171中，水溶性烷醇胺，诸如三乙醇胺在金属加工流体中用作防腐剂，羧酸可溶于其中并形成相应的盐。除作为防腐剂外，烷醇胺还于机械零件上形成残余物。这意味着烷醇胺的摩尔用量须比羧酸更大。本发明中，为了避免形成退火残余物，铝表面上的所有残余物都必须降到最低限度。这是使用其用量使碱/酸当量比小于1.0的烷基烷醇叔胺来达到的。本发明的这一当量比一般可形成pH小于8.5的冷却润滑剂。在空气中，铝表面受到氧化，且这一表面在pH约为8.5～9时一般有一等电位点。本发明方法在等电位点的酸侧，最好在pH为6～8时进行。
胺化合物的选择也是至关重要的。本发明的烷基叔胺既有助于形成溶液，又有利于获得防腐性能，同时还不会形成退火残余物。当将USP4，243，537公开的组合物用于铝轧制试验时，所得铝薄板呈现出机械损伤且其退火残余物量不合要求，板面颜色变暗。已发现这些结果至少是部分取决于三乙醇胺的使用。
实际试验表明，冷却润滑剂以稳态溶液而不是乳液存在，这对轧制特性来说是非常重要的。可推测的是，本发明稳态溶液的动力学特性会得到 提高，致使金属表面迅速形成检验且覆盖良好的羧基和烷基醇叔胺保护层，从而阻碍了局部沉淀以及在后续热处理过程中会引起锈蚀的过量残余物的形成。另一重要优点是可避免轧制表面上出现机械损伤。
本发明冷却润滑剂的再一重要优点是易于进行过滤以除去加工过程中形成的杂质。因此本发明冷却润滑剂可重复使用，同时又不会有任何明显的污染，金属催化氧化降解或微生物降解等危险。
本发明的冷却润滑剂除含有羧基化合物（a）和烷基烷醇叔胺（b）而外，还可含有（c）水溶性有机增溶剂，以改善冷却润滑剂的稳定性。增溶剂（c）优选的是包含分子量低于400并具有最高为6个碳原子的疏水基团的极性非离子化合物。为提高润滑效果，冷却润滑剂还可含有（d）极性且主要为疏水性的非离子化合物。
作为羧基化合物中疏水基团R1，尽管也可为支化不饱和脂肪基，但优选的是衍生自直链饱和脂肪化合物，特别优选的是含8～11个碳原子的烷基。适宜羧酸的具体例子为壬酸，癸酸，月桂酸，椰子脂酸及其混合物。
疏水基团R1还可含杂原子如氧，硫和氮，这些杂原子包含在醚、硫醚、酯、羟基、羧基和酰胺基等官能团中。这类羧基化合物的具体例子为：
Figure 87103469_IMG1
其中R8为具有1～4个碳原子的烷基或氢，R7为烃基，优选为脂肪烃基， R7和R8的选择应使R1的定义得到满足。
烷基烷醇叔胺（b）中含至少一个带羟基的取代基，因而为水溶性的或可形成胶粒。优选烷基烷醇叔胺为R2R3R4N，其中R2为具有1～4个碳原子的羟烷基或（A）nH，式中A为具有2～4个碳原子的亚烷氧基，n为1～3的整数，R3为具有1～6个碳原子的烷基，R4代表定义同R2和R3的基团。适宜烷基烷醇叔胺的具体例子为二乙醇乙基胺，二乙醇丙基胺，二乙醇丁基胺，二乙醇戊基胺，二乙醇己基胺和相应的二丙醇胺，乙醇二乙基胺，乙醇二丙基胺，乙醇二丁基胺和相应的丙醇胺。上述化合物也可用环氧乙烷，环氧丙烷或环氧丁烷进行烷氧基化。
一般来说，羧基化合物和烷醇胺的用量应使碱/酸当量比达到0.5～0.9，这通常可形成pH约为6～8的冷却润滑剂。已发现烷醇胺化合物相对于羧基化合物的用量不足时可提高润滑效果。因此，如果希望获得良好的润滑效果，建议选择烷醇胺和羧基化合物之间的碱/酸当量比为0.5至高达0.8。
增溶剂（c）为带有极性基如羟基和醚基的低分子量水溶性化合物，其分子量最好低于250，具体例子为乙二醇如单或双丁基乙二醇，单或双丙基乙二醇，单或双乙基乙二醇或二乙二醇，三乙二醇的相应单或双化合物的醚类以及戊醇，丁醇，丙醇和异丙醇等醇类，优选的是单或二乙二醇的单醚类。
主要有利于提高冷却润滑剂润滑效果的非离子化合物（d）的性质必须主要是疏水性的，即其HLB值小于10，最好小于9，并且最好为基本上不溶于水的非离子化合物。
适宜的化合物（d）为R5（B）mOR6，其中R5为具有8～24个碳原子的烃基或酰基，B为具有2～4个碳原子的氧亚烷基，R6为氢，具有1～4个碳原子的烷基或酰基，m为0～4的整数。
非离子化合物（d）既可为芳烃又可为脂肪烃，但优选用脂肪烃化合物， 最适宜的具体例子为羟基化合物，如辛醇，癸醇，十二（烷）醇，十四（烷）醇，十六（烷）醇，具有9～17个碳原子的羰基合成醇，壬基酚，辛基酚和十二烷基酚以及上述醇中每摩尔羟基化合物含1～4摩尔环氧乙烷的乙氧基化合物。这些羟基化合物可用通式表示为R5（B）mOH，其中R5，B和m同上述定义。
非离子化合物的其它具体例子为用H（B）mOR6烷氧基化或酯化的脂肪酸，其中B，R6和m同上述定义。这类化合物的具体例子为
C11H21COOC2H4OH;
C11H23COOCH3;
C9H19CO（OC2H4）O2CH3。
优选酯化合物为R5OR6，其中R5为具有8～24个碳原子的酰基，R6为具有1～4个碳原子的烷基。
除了上述成分而外，本发明水基冷却润滑剂还可含有常用的添加剂如杀菌剂，防沫剂，粘度调节剂，香料以及可增加润滑和防腐效果的其它添加剂。提高润滑效果的其它添加剂的具体例子为基于环氧乙烷和更高级环氧烷烃的聚合物。这些环氧烷烃既可任意偶联又可嵌段偶联。
在根据本发明制备冷却润滑剂的过程中，最好是首先制得适当含下列成分的浓缩物。
成分    含量，%（重量）
羧基化合物    15～75，优选为20～45
烷基烷醇叔胺    3～60，优选为10～45
非离子化合物    0～30，优选为2～30
增溶剂    0～87，优选为10～68
杀菌剂，香料，粘度调节剂等    0～30，优选为0～15
水    0～82，优选为0～58
浓缩物用水稀释后即可制得备用的冷却润滑剂。适宜的组成如下。
成分    含量，%（重量）
羧基化合物    0.5～25，优选为2～15
烷基烷醇叔胺    0.1～20，优选为    1～15
增溶剂    0.0～33，优选为1～18
非离子化合物    0.0～10，优选为0.2～10
常用添加剂如杀菌剂，香料，
粘度调节剂    0～5，优选为0.1～2
水    25～99.4，优选为40～95.7
备用溶液中水含量优选为70～95%（重量）。
本发明用下述实例作进一步说明。
实例
AA3004级退火铝薄板在单支座上用直径为159mm的轧辊于下述任何一种冷却润滑剂存在下进行冷轧。轧制过程中，薄板厚度从1.05mm减薄到0.63mm。必须的轧制力由将挤压力传给轧辊的液压系统的压力加以确定。轧制后用肉眼以0至1级标准对表面机械损伤进行评价，0表示表面合乎标准，即表面有肉眼可见的机械损伤。将轧制后的铝薄板清扫干净并抹上足够的冷却润滑剂，之后将其在空气中于5小时内加热到360℃。加热后的外观用肉眼以0至4级标准一方面对变黑程度，另一方面对锈蚀表面比例进行评价。
标准，级    暗色程度    锈蚀表面，%
0    完好，无暗色    0
1    可辩识出暗色    1～5
2    出现轻微暗色    6～15
3    出现明显暗色    16～50
4    出现强烈暗色    51～100
在可接受的退火残余物下对暗色程度和锈蚀表面进行总评。0～1级表示极佳，2～3级表示非常合乎标准，4～5级表示正好合乎标准，6～8级表示低于标准。所谓“正好合乎标准”（合格）意指从退火残余物观点来看，铝薄板恰好合乎商品规格。
为了确定冷却润滑剂对铁的腐蚀作用，将测试用的“铸铁船”放在用特定量冷却润滑剂浸渍过的滤纸上达24小时。再将1500平方厘米面积上有126个交点的栅格置于滤纸上，并测试每一栅格交点出现的腐蚀度。然后用锈蚀的交点数与交点总数之比来表示的铁的腐蚀情况。
白锈的确定方法是，用冷却润滑剂在铝薄板上涂层，然后将薄板重叠并在-20℃下冷却1小时，之后在室温空气中将其暴露2小时。再将薄板于10小时内加热到80℃。并用评价铁锈蚀的方式对白锈进行评价。
用基本上无水的浓缩物制得本发明的下列润滑剂，并将其用于本实例中的冷轧操作。所有冷却润滑剂在20℃下均呈稳定的溶液形态。
冷却润滑剂1
成分    含量，%（重量）
月桂酸    3.2
C4H9N（C2H4OH）21.5
C14H29O（C2H4O）2H 0.7
丁基二乙二醇    9.0
水    其余
碱/酸当量比    0.58
冷却润滑剂2
成分    含量，%（重量）
壬酸    6.0
C4H9N（C2H4OH）23.5
C12-14H25-29O（C2H4O）2H 1.5
丁基二乙二醇    3.6
水    其余
碱/酸当量比    0.57
冷却润滑剂3
成分    含量，%（重量）
月桂酸    6.0
C4H9N（C2H4OH）23.4
C12-14H25-29O（C2H4O）2H 1.5
丁基二乙二醇    4.4
水    其余
碱/酸当量比    0.70
冷却润滑剂4
成分    含量，%（重量）
月桂酸    6.0
C4H9N（C2H4OH）23.9
C12-14H25-29O（C2H4O）2H 1.5
丁基二乙二醇    2.7
水    其余
碱/酸当量比    0.81
冷却润滑剂5
成分    含量，%（重量）
月桂酸    8.0
C4H9N（C2H4OH）24.5
C12-14H25-29O（C2H4O）2H 1.3
丁基二乙二醇    6.7
水    其余
碱/酸当量比    0.70
冷却润滑剂6
成分    含量，%（重量）
月桂酸    6.7
C4H9N（C2H4OH）23.8
C12-14H25-29OH 1.7
丁基二乙二醇    7.8
水    其余
碱/酸当量比    0.70
冷却润滑剂7
成分    含量，%（重量）
月桂酸    6.7
C4H9N（C2H4OH）23.7
C11H23COOCH31.7
丁基二乙二醇    8.0
水    其余
碱/酸当量比    0.69
冷却润滑剂8
成分    含量，%（重量）
C11H23COOH（支化） 6.0
C4H9N（C2H4OH）23.0
C12H25O（C2H4O）2H 1.0
丁基二乙二醇    5.9
水    其余
碱/酸当量比    0.62
冷却润滑剂9
成分    含量，%（重量）
月桂酸    6.0
C4H9N（C2H4OH）23.4
C14H29O（C2H4O）2H 1.0
丁基二乙二醇    3.8
水    其余
碱/酸当量比    0.70
冷却润滑剂10
成分    含量，%（重量）
月桂酸    6.7
二亚乙基乙醇胺+EO（环氧乙烷）    3.8
C12-14H25-29OH 1.4
丁基二乙二醇    8.2
水    其余
碱/酸当量比    0.70
冷却润滑剂11
成分    含量，%（重量）
月桂酸    4.0
丁基二乙醇胺    2.7
月桂酸甲酯    1.0
丁基二乙二醇    4.8
水    其余
碱/酸当量比    0.84
冷却润滑剂12
成分    含量，%（重量）
月桂酸    6.9
丁基二乙醇胺    3.9
C12-14H25-29OH 1.4
戊基二乙二醇    7.9
水    其余
碱/酸当量比    0.70
冷却润滑剂13
成分    含量，%（重量）
月桂酸    8.56
C4H9N（C2H4OH）26.44
水    其余
碱/酸当量比    0.93
冷却润滑剂14
成分    含量，%（重量）
月桂酸    12.0
C4H9N（C2H4OH）28.0
水    其余
碱/酸当量比    0.83
冷却润滑剂15
成分    含量，%（重量）
月桂酸    8.51
C4H9N（C2H4OH）26.34
C12-14H25-29OH 0.14
水    其余
碱/酸当量比    0.93
冷却润滑剂16
成分    含量，%（重量）
壬酸    8.62
C4H9N（C2H4OH）26.38
水    其余
碱/酸当量比    0.72
冷却润滑剂17
成分    含量，%（重量）
壬酸    7.4
C12-14H25-29OH 0.9
2，2-二甲基氨基甲基丙醇    3.6
丁基二乙二醇    5.0
水    其余
碱/酸当量比    0.67
冷却润滑剂18
成分    含量，%（重量）
月桂酸    6.2
2，2-二甲基氨基甲基丙醇    2.5
丁基二乙二醇    7.1
C12-14H25-29OH 1.2
水    其余
碱/酸当量比    0.69
冷却润滑剂19
成分    含量，%（重量）
月桂酸    8.21
C4H9N（C2H4OH）25.12
丁基二乙二醇    6.67
水    其余
碱/酸当量比    0.77
冷却润滑剂20
成分    含量，%（重量）
月桂酸    5.69
C4H9N（C2H4OH）23.55
丁基二乙二醇    4.63
C12-14H25-29OH 1.13
水    其余
碱/酸当量比    0.78
冷却润滑剂21
成分    含量，%（重量）
癸酸    11.26
2，2-二甲基氨基甲基丙醇    5.36
水    其余
碱/酸当量比    0.70
为了对比，制成下列冷却润滑剂。在20～70℃范围内，它们均呈乳液状态。冷却润滑剂A，B及C按照USP4243537方法制备，而D和E则按照EP-A-115926方法制备。
冷却润滑剂A
成分    含量，%（重量）
油酸    2
三乙醇胺    1
聚（亚烷基）二醇（UCON5HB100）10
水    其余
碱/酸当量比    0.95
冷却润滑剂B
成分    含量，%（重量）
油酸    2
三乙醇胺    1
聚（亚烷基）二醇（UCON5HB100）10
Figure 87103469_IMG2
3
水    其余
碱/酸当量比    0.95
冷却润滑剂C
成分    含量，%（重量）
油酸    2.0
三乙醇胺    1.6
聚（亚烷基）二醇（UCON5HB100）10
水    其余
碱/酸当量比    1.5
冷却润滑剂D
成分    含量，%（重量）
月桂酸    1.5
三乙醇胺    1.5
聚（亚烷基）二醇（Pluronic    17R2）    10
Figure 87103469_IMG3
1.0
水    其余
碱/酸当量比    1.9
冷却润滑剂E
成分    含量，%（重量）
油酸    1.0
三乙醇胺    0.8
聚（亚烷基）二醇（Pluronic    17R2）    5.0
水    其余
碱/酸当量比    1.5
冷却    加压    退火    铁    白锈    机械
润滑剂    kN    残余物    腐蚀    %    外观
A    13.3    5    5    20    1
B    13.5    8    4    6    1
C    14.0    8    0.1    12    1
D    16.5    5    0    0    1
E    14.5    5    4    30    1
1    14.7    1    1    0    0
2    14.3    2    0    0    0
3    14.3    3    0    0    0
4    14.4    2    0    0    0
5    13.2    3    0    0    0
6    13.4    3    0    0    0
7    13.5    2    0    0    0
8    14.0    3    0    0    0
9    13.4    2    0    0    0
10    13.5    3    0    1
11    12.5    2    0    5    0
12    13.0    3    0    4    0
13    13.5    3    0    0    0
14    13.5    3    0    0    0
15    13.2    3    0    0    0
-续-
冷却    加压    退火    铁    白锈    机械
润滑剂    kN    残余物    腐蚀    %    外观
16    13.5    2    0    0    0
17    14.5    1    0    0    0
18    14.5    1    0    0    0
19    13.1    3    0    0    0
20    13.5    2    0    0    0
21    13.0    3    0    0    0
从这一试验结果清楚看出，与现有已知技术相比，用本发明提出的冷却润滑剂轧制的铝表面具有较好的机械外观。铁腐蚀和白锈均很轻微，一般说远低于用参比组分制成的冷却润滑剂。此外，采用本发明的冷却润滑剂时其退火残余物很少，在各种情况下均远低于对比试验。

Claims (7)

1、在含有润滑剂和防腐剂的水基冷却润滑剂存在之下机械加工铝或铝合金的方法，其特点是，该冷却润滑剂至少在20-70℃温度范围内在金属加工时呈稳态溶液，并且作为润滑剂和防腐剂含有(a)通过为R1GOOH的羧基化合物，其中R1为具有7-14个碳原子的疏水基团和(b)分子量低于300的烷基烷醇叔胺，而且烷醇胺和羧基化合物之间的碱/酸当量比小于1.0，所用胺(b)的通式为R2R3R4N，其中R3为具有1-4个碳原子的羟烷基，或为具有通式为(A)nH的基团，其中A为具有2-4个碳原子的亚烷氧基，n为1至3的整数，R3为具有1-6个碳原子的烷基，而R4的定义同于R2或者R3，冷却润滑剂中所含羧基化合物(a)的含量为0.5-25%(重量)，而所含烷基烷醇叔胺(b)的含量为0.1-20%(重量)。
2、根据权利要求1所述的方法，其特点是，用来进行金属加工的冷却润滑剂尚含有（c）分子量低于400并具有最多为6个碳原子的疏水基的水溶性有机增溶剂。
3、根据权利要求2所述的方法，其特点是，用来进行金属加工的冷却润滑剂尚含有（d）极性的且主要为疏水性的非离子化合物。
4、根据权利要求3所述的方法，其特点是，化合物（d）的通式为R5（B）mOR6，其中R5为具有8-24碳原子的烃基或酰基，B为具有2-4个碳原子的亚氧烷基，而R6为氢，具有1-4个碳原子的烷基或酰基，m为0至4的整数。
5、根据权利要求1所述的方法，其特点是，羧基化合物（a）的疏水基团R1为具有8-11个碳原子的脂肪烃基。
6、根据权利要求1和5中任何一项所述的方法，其特点是烷基烷醇叔胺和羧基化合物之间的碱/酸当量之比为0.5至0.9。
7、根据权利要求2，3和4中任何一项所述的方法，其特点是，冷却润滑剂中所含增溶剂（c）的含量为最多33%（重量），而所含非离子化合物（d）的含量为最多10%（重量）。
CN87103469A 1986-05-13 1987-05-13 在冷却润滑剂存在下机械加工铝和铝合金的方法以及冷却润滑剂浓缩物 Expired CN1010692B (zh)

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