CN1188501C - 功能流体组合物 - Google Patents

功能流体组合物 Download PDF

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CN1188501C
CN1188501C CNB008046794A CN00804679A CN1188501C CN 1188501 C CN1188501 C CN 1188501C CN B008046794 A CNB008046794 A CN B008046794A CN 00804679 A CN00804679 A CN 00804679A CN 1188501 C CN1188501 C CN 1188501C
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fluid
triazole
weight
hbf
tolyl
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CN1343243A (zh
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P·勒维斯克
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Union Carbide Chemicals and Plastics Technology LLC
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Union Carbide Chemicals and Plastics Technology LLC
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Abstract

一种功能流体，包括作为基础油的选自二醇、二醇醚、酯、烃和其混合物的至少一种化合物，和作为多官能添加剂组合物的苯并三唑、其衍生物或其混合物与1，2，4-三唑、其衍生物或其混合物的混合物。该功能流体显示较高的耐腐蚀性和较少的沉积物形成，且特别适合用作制动液。

Description

功能流体组合物
发明领域
本发明涉及可用于很多应用中的功能流体，如制动液、液压液体、发动机冷却剂、传输流体、润滑剂、金属加工流体等，涉及用于这些流体中防止腐蚀、锈蚀和形成沉积物并提供长时间热稳定性的添加剂。
发明背景
当用于诸如制动液的应用中时，功能流体通常在极端条件如高温下暴露于包括铜、锌、铝和黄铜等的金属表面和橡胶部件下，导致诸如腐蚀、氧化和形成沉积物这样的问题。现代汽车和卡车中在较高防护罩温度下，随着防抱死制动系统的出现和对维修访问之间更长间隔的需求已导致需要具有更好的耐腐蚀、沉积物形成和长时间使用后的降解性能的高性能功能流体。
功能流体通常包括含二醇、二醇醚、酯(包括硼酸酯和磷酸酯)、乙氧基化或丙氧基化醇、烃等的基础流体和特别用于提供防止各种金属腐蚀、沉积物形成和降解的添加剂包。很多化合物在本领域中是公知的，如可在包括某些三唑化合物的功能流体中用作抗氧剂、腐蚀抑制剂等。例如，氨基取代的1，2，4-三唑公开于英国专利1,111,680中，在基于酯的润滑剂组合物中作为合适的添加剂。尽管这些氨基取代的三唑显示良好的对某些金属的抗腐蚀性，但表II中的数据显示与铜相关的一些缺陷和沉积物形成。
还认识到苯并三唑和其衍生物，特别是甲苯基三唑的铜腐蚀抑制性能，并且已在制动液中用作腐蚀抑制剂。然而，正如日本特开No.59-157,188中指出的，这些化合物在抑制铜腐蚀中存在缺陷并在制动液中形成沉积物。该日本特开专利提出苯并三唑和其衍生物的缺陷可通过将三唑与一种或多种噻二唑结合来克服。这种结合，尽管对于降低沉积物形成和抑制铜腐蚀有效，但存在的缺点是将含硫的化合物引入制动液中，这种化合物对制动液的长时间热稳定性会有不利影响。
本发明概述
根据本发明，申请人已发现，两种特定类型的三唑化合物的独特组合(当一起使用时)，可提供具有优良的包括优异的耐腐蚀、氧化和沉积物形成的性能平衡并同时保持长时间热稳定性的功能流体。更具体地，本发明涉及功能流体，特别是可用作制动液的那些流体，这些流体含有有效量的苯并三唑，其衍生物如甲苯基三唑或其混合物及1，2，4-三唑、其衍生物或其混合物。由含本发明三唑混合物的功能流体所体现的优异性能平衡可通过用存在的少量三唑化合物来实现。
本发明详述
本发明的功能流体包括基础流体和添加剂包，其中基础流体的组成由功能流体的预定用途确定，添加剂包特别用于提供防止腐蚀、沉积物形成和长时间使用后的降解。可用于本发明功能流体的基础流体是公知的，通常包括预定量的一种或多种选自如下的化合物：二醇，如乙二醇、二甘醇、三甘醇、聚乙二醇、丙二醇以及聚合衍生物和其混合物；二醇醚，如甲基、乙基、丙基、丁基或己基的二、三和四二醇醚，例如乙基二甘醇醚、丁基二甘醇醚、甲氧基三甘醇、乙氧基三甘醇、丁氧基三甘醇、甲氧基四甘醇、丁氧基四甘醇等；酯，包括硼酸酯，例如但不限于三甘醇单甲基醚硼酸酯或四甘醇单甲基醚硼酸酯，和磷酸酯如磷酸三甲苯基酯、磷酸三苯基酯、取代苯酚磷酸酯或烷基磷酸酯等。此外，必要时可使用二醇与二醇醚和/或硼酸酯或磷酸酯的混合物。为用于诸如润滑剂、传输油等中，基础流体可为烃。在制备本发明的功能流体中选取用于任何特定领域的合适基础流体是有经验的配料人员公知的。
向基础流体中加入三唑化合物的独特组合以提供本发明的呈现优异耐腐蚀、氧化和沉积物形成性能并同时提供长时间热稳定性的功能流体，这种三唑化合物的独特组合定义为一种混合物，含有效腐蚀抑制量的(a)苯并三唑、其衍生物和其混合物与(b)1，2，4-三唑和其衍生物和其混合物。
可用于本发明的苯并三唑和其衍生物可用下式表示：
其中R和R′是相同或不同的，并可为氢，含1至8个碳原子的烷基，氨基如-NH、-NHR或-NRR′，酰基如-COR，或芳基如苯或甲苯。苯并三唑和甲苯基三唑或其混合物特别适合用于本发明的功能流体中。
可用于本发明的1，2，4-三唑或其衍生物可用下式表示：
Figure C0080467900062
其中R和R′是相同或不同的，并可为氢，含1至8个碳原子的烷基，氨基如-NH、-NHR或-NRR′，酰基如-COR，或芳基如苯或甲苯。1，2，4-三唑特别适合用于本发明的功能流体中。
(a)和(b)的三唑都应以能足以提供包括有效耐腐蚀、氧化和沉积物形成的最佳性能平衡并同时提供长时间热稳定性的量存在于本发明的功能流体中。各类三唑的用量并不十分重要，并且本领域熟练技术人员公知优化各功能流体应用的量。(a)和(b)的各三唑的浓度可为约0.01％至约0.4％，优选约0.02％至约0.2％(重量)，按功能流体的总重量计。功能流体中存在的(a)和(b)三唑的总合并重量应为约0.05％至约0.5％，优选约0.05％至约0.3％(重量)，按功能流体的总重量计。尽管三唑(a)的存在量与三唑(b)的存在量的比例并不重要，但通常为约1∶4至约4∶1。正如配制功能流体领域的熟练技术人员容易理解的，最终使用的两种三唑的浓度可通过功能流体的组成和最佳性能与经济考虑之间的平衡确定。
在本发明功能流体中可有利地与三唑并用的其它材料包括二唑、噻唑、胺、苯酚、聚合的氢醌，和无机盐如硝酸盐等，所有这些都是本领域公知的用于通过功能贡献如pH控制、耐氧化性等改进流体总体性能的材料。本发明的权利要求将包括这些材料和可由这些材料与本发明的两种三唑的混合物并用所获得的任何协同效果。还注意到，尽管显然不包括噻唑，但本发明功能流体的一个优点是，获得优良的耐腐蚀和沉积物形成性能及热稳定性，同时没有因存在含硫的噻唑化合物而引起的潜在问题。
正如在下面的实施例中说明的，本发明提供改进的耐铜、铜基合金(例如黄铜)和锌腐蚀性，以及这些材料在使用时的改进外观。此外，本发明提供优异的对金属如锌的抗氯腐蚀性，并减少因功能流体暴露于金属如铜及其合金和其它材料如橡胶下而导致的沉积物形成。
实施例
下面的非限制性实施例说明本发明和其某些优选的实施方案。作为实施例中使用的：简称“HBF”是指液压制动液。简称“DOT3”和“DOT4”分别指Department of Transportation类型3和4制动液。SAE腐蚀试验按照汽车工业协会标准(Society of Automotive Engineeringstandard)J 1703(1995年1月)的描述进行。铜线圈(Copper Coil)试验为Union Carbide方法并按如下方式进行：向在样品缸内的95ml制动液中，加入5ml NaCl/水溶液并使该混合物打漩。所得制动液含5％(体积)水和50ppm氯离子。然后将由5m长、直径1mm的铜丝构成的铜线圈加入该流体中并将该样品缸的盖子系紧。然后将包含制动液/水/氯化物混合物和铜线圈的样品试验缸在100℃的烘箱中放置7天。7天结束后取出样品缸，将流体冷却至室温并检测铜线圈。测定铜外观、铜的溶解量和沉积物的量。
由HBF DOT3或HBF DOT4基础流体制备试验的功能流体。HBF Dot3基础流体按流体组合物的总重量计含约80wt％二醇醚如甲基和丁基三甘醇醚和约20％二醇如三甘醇，余量约1％为由硝酸盐、酚抗氧剂和链烷醇胺构成的添加剂包。HBF DOT4基础流体按流体组合物的总重量计含约45wt％甲氧基三甘醇硼酸酯、约45％二醇醚如甲基和丁基三甘醇醚、约10％二醇如二甘醇，余量约1％为由硝酸盐、酚抗氧剂和链烷醇胺构成的添加剂包。将三唑或三唑混合物加入要测试的组合物的基础流体中。测试含本发明三唑混合物的流体组合物，并与含单一三唑的流体组合物对比。SAE腐蚀试验的结果(所有试验都在加入的100ppm氯存在下进行)记载于表1(对于DOT3流体)和表2(对于DOT4流体)中。对于铜、黄铜和锌条重量变化的SAE接受极限最大为±0.4mg/cm2。铜线圈试验的结果记载于表3、4和5中。
表1
流体类型 添加剂 SAE腐蚀试验(100ppm Cl-加入)
铜和黄铜条 锌
HBFDOT3 0.15wt％苯并三唑 有光泽的条：重量变化0.0mg/cm2 变污的条，重量变化-2.0mg/cm2
HBFDOT3 0.15wt％甲苯基三唑 有光泽或轻微变污的条，重量变化-0.02至-0.09mg/cm2 变污的条，重量变化-1.7mg/cm2
HBFDOT3 0.15wt％1，2，4-三唑 轻微变污的条：wt变化+0.01至+0.04mg/cm2 轻微变污的条，重量变化+0.13mg/cm2
HBFDOT3 O.20wt％甲苯基三唑和0.20wt％1，2，4-三唑 有光泽或在条上轻微变污，重量变化-0.05至-0.09mg/cm2 变污的条，重量变化+0.28mg/cm2
HBFDOT3 0.05wt％甲苯基三唑和0.20wt％1，2，4-三唑 有光泽的条，重量变化0至-0.02mg/cm2 轻微变污的条，重量变化+0.07mg/cm2
HBFDOT3 0.05％甲苯基三唑+0.10％1，2，4-三唑 有光泽的条，重量变化-0.03至-0.05mg/cm2 轻微变污的条，重量变化-0.09mg/cm2
HBFDOT3 0.03％甲苯基三唑+0.06％1，2，4-三唑 有光泽的条，重量变化-0.01至-0.05mg/cm2 轻微变污的条，重量变化-0.06mg/cm2
HBFDOT3 0.015％甲苯基三唑+0.03％1，2，4-三唑 有光泽的条，重量变化-0.08至-0.12mg/cm2 轻微变污的条，重量变化-0.11mg/cm2
                                           表2
流体类型 添加剂 SAE腐蚀试验(100ppm Cl-加入)
铜和黄铜条 锌
HBFDOT4 0.2wt％甲苯基三唑 变污或轻微变污的条，重量变化-0.29至-0.38mg/cm2 轻微变污的条，重量变化-0.40mg/cm2
HBFDOT4 0.15wt％1，2，4-三唑 轻微变污的条；wt变化-0.12至-0.14mg/cm2 变污的条，重量变化+0.25mg/cm2
HBFDOT4 0.08wt％甲苯基三唑和0.02wt％1，2，4-三唑 有光泽的条，重量变化-0.02至-0.04mg/cm2 轻微变污，重量变化-0.30mg/cm2
HBFDOT4 0.075wt％甲苯基三唑和0.075wt％1，2，4-三唑 有光泽或变污的条，重量变化-0.12至-0.16mg/cm2 轻微变污的条，重量变化0.0mg/cm2
HBFDOT4 0.10％甲苯基三唑+0.10％1，2，4-三唑 变污至轻微变污的条，wt变化-0.12至-0.19mg/cm2 轻微变污的条，重量变化+0.04mg/cm2
                                        表3
流体类型 添加剂 铜线圈试验
在溶液中的铜(ppm) 铜线圈外观 沉积物(％体积)
HBFDOT3 0.15wt％甲苯基三唑 30至100 无 无(检测到一些颗粒；体积未测量)
HBFDOT3 0.15wt％1，2，4-三唑 0 清洁、良好、较深色、无固体 无
HBFDOT3 0.20wt％甲苯基三唑和0.20wt％1，2，4-三唑 10 在线圈上出现一些涂层 无(检测到一些颗粒；体积未测量)
HBFDOT3 0.05wt％甲苯基三唑和0.20wt％1，2，4-三唑 0 有光泽的线圈 0.1
HBFDOT3 0.05％甲苯基三唑+0.10％1，2，4-三唑 20 有光泽的线圈 低于0.1％
HBFDOT3 0.03％甲苯基三唑+0.06％1，2，4-三唑 20 有光泽的线圈 低于0.1％
HBFDOT3 0.015％甲苯基三唑+0.03％1，2，4-三唑 35 有光泽的线圈 无
                                        表4
流体类型 添加剂 铜线圈试验
在溶液中的铜(ppm) 铜线圈外观 沉积物(％体积)
HBFDOT4 0.2wt％甲苯基三唑 20 树胶状白色涂层 3
HBFDOT4 0.15wt％1，2，4-三唑 10 清洁、良好、较深色、无固体 无
HBFDOT4 0.08wt％甲苯基三唑和0.02wt％1，2，4-三唑 30 在线圈上出现一些固体 无
HBFDOT4 0.075wt％甲苯基三唑和0.075wt％1，2，4-三唑 5 有光泽的铜(淡红色) 0
HBFDOT4 0.10％甲苯基三唑+0.10％1，2，4-三唑 10 一些固体 无
                                         表5
流体类型 添加剂 铜线圈试验
在溶液中的铜(ppm) 铜线圈外观 沉积物(％体积)
HBFDOT3 0.01wt％苯并三唑 300 绿色 2
HBFDOT3 0.11wt％苯并三唑 5 铜(淡红色) 8
HBFDOT3 0.11wt％苯并三唑+0.10wt％甲苯基三唑 0 铜(淡红色) 6
HBFDOT3 0.11wt％苯并三唑+0.10wt％1，2，4-三唑 0 绿色 1
从表1至表5中的数据可以看出，本发明含两种特定类型三唑的混合物的功能流体提供包括耐腐蚀、氧化和沉积物形成性能的优良平衡。

Claims (13)

1.一种功能流体，包括含选自二醇、二醇醚、酯和烃的至少一种化合物的基础流体，掺混(a)一种或多种下式表示的苯并三唑
和(b)一种或多种下式表示的1，2，4-三唑
Figure C008046790002C2
其中(a)和(b)的总合并重量为功能流体的0.05％-0.3％；
其中R和R′是相同或不同的，并为氢、含1至8个碳原子的烷基、氨基、酰基、或芳基。
2.权利要求1的流体，其中(a)为苯并三唑、甲苯基三唑或其混合物和(b)为1，2，4-三唑。
3.权利要求2的流体，其中(a)为苯并三唑和(b)为1，2，4-三唑。
4.权利要求2的流体，其中(a)为甲苯基三唑和(b)为1，2，4-三唑。
5.权利要求1的流体，其中至少一种三唑是被取代的三唑。
6.权利要求5的流体，其中至少一种三唑含有烷基或芳基取代基。
7.权利要求1的流体，还含有一种或多种二唑。
8.权利要求1的流体，还含有一种或多种选自胺、抗氧化剂和无机盐的添加剂。
9.权利要求1的流体，其中基础流体包含硼酸酯、二醇醚、二醇或其混合物。
10.权利要求2的流体，其中(a)和(b)的各三唑的存在量为0.01重量％至0.4重量％，按功能流体的总重量计。
11.权利要求1的流体，其为制动液。
12.权利要求1的流体，其为发动机传输流体。
13.权利要求1的流体，其为发动机冷却流体。
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JP4629232B2 (ja) 2011-02-09
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CA2360632A1 (en) 2000-08-10
ATE307866T1 (de) 2005-11-15
EP1159380B1 (en) 2005-10-26
KR20010112253A (ko) 2001-12-20
BR0009311A (pt) 2001-11-27
US6074992A (en) 2000-06-13
DE60023459T2 (de) 2006-07-13
CN1343243A (zh) 2002-04-03
WO2000046325A1 (en) 2000-08-10
AU2748500A (en) 2000-08-25
JP2002536494A (ja) 2002-10-29
MXPA01007818A (es) 2003-09-10
CA2360632C (en) 2009-04-07
ES2249247T3 (es) 2006-04-01

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