CN1130918A - 基础流体 - Google Patents

基础流体 Download PDF

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Publication number
CN1130918A
CN1130918A CN94193371A CN94193371A CN1130918A CN 1130918 A CN1130918 A CN 1130918A CN 94193371 A CN94193371 A CN 94193371A CN 94193371 A CN94193371 A CN 94193371A CN 1130918 A CN1130918 A CN 1130918A
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Prior art keywords
acid
alcohol
base fluids
acid number
fluids
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CN94193371A
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CN1046757C (zh
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N·A·库班
H·L·里菲
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Uniqema BV
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Uniqema BV
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Abstract

一种用作水力流体或金属加工流体的基础流体含有羟值低于15、酸值低于10的由聚合脂肪酸和烷氧基化一元醇生成的酯化产物，所述烷氧基化一元醇选自(a)用2-25摩尔C2-C5烯化氧烷氧基化的直链或支链的饱和C1-C24一元醇和(b)用被2-25摩尔C2-C5烯化氧烷氧基化的C1-C4脂族一元醇醚化的烷氧基聚(亚烷基)二醇，该醇组分也任选地含有(c)直链或支链C1-C24脂族一元醇。粗酯的酸值较好是通过将其与C5-C22脂族一元羧酸，优选C6-C12支链脂族一元羧酸的缩水甘油酯反应而降低。

Description

基础流体
本发明涉及含有有效量的特定酯化产物的水力流本或金属加工流体的基础流体。
在本说明书及所附的权利要求书中所谓“水力流体”是指用于水力机械，如制动设备、吸振器、汽车的自动变速***、控制设备和相似操作的水力设备的流体。这些水力流体也可以是水和油的乳化液形式。
在本说明书及所附的权利要求书中所谓“金属加工流体”是指尤其用于(但不限于)金属的机械加工操作，如车削、铣削、钻孔、研磨、冲压、深拉等操作的流体。这类金属加工流体也可以是水和油的乳化液的形式。
水力流体的基础流体应该满足许多要求，如润滑性好、与其它工业上易得的水力流体的相容性好、对(合成)橡胶的溶胀作用很小、对金属无腐蚀、沸点或闪点高、冰点尽可能地低、对环境安全(最好是可生物降解的)，并且无论是蒸汽或液体对人体健康均应无害。很显然，如此多的要求(有时甚至是相互矛盾的)是很难满足的。
过去已提出过以聚(亚烷基)二醇为基础的水力流体的基础流体，但是这种流体是吸湿性的，由于从环境中吸收水，导致闪点降低。
美国专利说明书US-A-2,755,251(Atlas粉体公司)也提出用C3-C10脂族二元醇、C4-C8单烷基乙二醇醚和二聚亚油酸和20-35摩尔的氧化丙烯的反应产物作为基础流体配制水力流体。但是这些产物仍然是吸湿性的。
德国专利申请DE-A-2,426,925(Institut Francais duPétrole)提出，将10-40％(重量)由二聚或三聚酸与含有15-99％(摩尔)由2-50摩尔C2-C3氧化烯与C1-C25的脂族一元醇缩合得到的单羟基醚和85-1％(摩尔)C1-C25脂族一元醇的混合物生成的酯加入到溶剂精制的石蜡烃润滑油中。据说这种复合酯可以改善润滑油的粘滞性，因此将其加入到润滑油中就能制备出通用的马达油。
此外，这种金属加工流体也披露于美国专利说明书US-A-4,172,802(Cincinnati Milacron公司)中，该专利描述了含有水和由二聚或三聚C8-C26不饱和脂肪酸和带两个仲醇端基的聚氧化烯二醇所形成的羧酸基封端的二酯，或所述二酯的碱金属盐或有机铵盐的金属加工流体组合物。
现已发现，聚合的不饱和C12-C24脂肪酸与烷氧基化一元醇，任选地与饱和一元醇的混合物的酯化产物是一种优异的水力流体或金属加工流体的基础流体，可以直接用于或以有效量用于常规水力流体或金属加工流体中，它也可以呈油和水乳化液的形式。
因此，本发明涉及一种含有酸值低于10，羟值低于15的酯化产物的水力流体或金属加工流体的基础流体，它是由下列成分经酯化反应后得到的：
(a)选自二聚酸、三聚酸、氢化二聚酸、氢化三聚酸及其混合物的聚合的不饱和C12-C24脂肪酸，和
(b)选自下列的烷氧基化一元醇：
(1)用2-25摩尔C2-C5烯化氧烷氧基化的、具有1-24个碳原子的，直链或支链的饱和一元醇，和
(2)烷氧基聚(亚烷基)二醇，其中两个端羟基中的一个羟基用被2-25摩尔C2-C3烯化氧烷氧基化的C1-C4脂族一元醇醚化，和任选的
(C)含1-24个碳原子的直链或支链的饱和一元醇。
酯化产物的酸值最好按英国专利说明书GB-A-1,227,748所述方法，通过将酯化产物与缩水甘油酯反应而降低到所要求的值。聚合的不饱和C12-C24脂肪酸可选自二聚酸(如Pripol 1013、1017或1022(商品名)，购自Unichema Chemie BV，Gouda，荷兰)、三聚酸、氢化二聚酸(如Pripol 1009或1025(商品名)，购自Unichema Chemie BV，Gouda，荷兰)、氢三聚酸及其混合物。如果需要，二聚酸和三聚酸在它们氢化前或氢化后可以进行蒸馏。最好是用三聚酸(如Pripol 1040(商品名)，购自Unichema Chemie BV，Gouda，荷兰)。
烷氧基化的一元醇可选自：
(1)用2-25摩尔，优选6-12摩尔C2-C5的烯化氧，如氧化乙烯、氧化丙烯、氧化丁烯和这些烯化氧的混合物烷氧基化的含有1-24个碳原子的直链或支链的饱和一元醇。它们的分子量优选为200-2000，更优选为300-1000。该一元醇例如可以是甲醇、异丙醇、辛醇、癸醇、异辛醇等。也可以用这些醇类的混合物，例如Synpro醇(商品名，购自英国ICI PLC的饱和的合成伯醇混合物，它是由线型α-烯烃羰基化得到的)和Synpro/91(商品名，购自英国ICI PLC的饱和的合成伯醇混合物)。
(2)烷氧基聚(亚烷基)二醇，其中两个端羟基中的一个羟基用含有2-25摩尔，优选6-12摩尔C2-C5烯化氧，如氧化乙烯、氧化丙烯、氧化丁烯和这些烯化氧的混合物的C1-C4脂族一元醇如甲醇或丁醇“封住”或醚化。该二醇的平均分子量优选为200-2000，更优选为300-1000。
酯化反应中的醇组分可以任选地使用组分(b)和第二组分(c)的混合物，第二组分(c)是含有1-24个，优选1-14个碳原子的直链或支链的饱和一元醇。这种醇的例子有甲醇、丁醇、异丙醇、异辛醇、月桂醇以及这些醇的混合物。
酯化产物的酸值最大为10，优选最大为5，最优选小于1，而羟值最大为15，优选最大为10。粗酯化产物的酸值最好按英国专利说明书GB-A-1,237,748(Unilever-Emery N.V)所述方法，通过将酯化产物与含有5-22个碳原子的脂族一元羧酸的缩水甘油酯反应而调整到所要求的10以下的值。适用的缩水甘油酯例如有Cardura E10(商品名；高度支化的C10-异构体的合成饱和一元羧酸混合物的缩水甘油酯，购自Sell树脂公司，荷兰)。如果酯化产物是通过酯交换法制得，通常就不需要用缩水甘油酯处理。
当用于常规的水力流体中时，酯化产物的用量为总水力流体的10-95％(重量)，优选为20-75％(重量)。用量的确定取决于很多因素，其中包括所要求的水力流体的粘度。
水力流体也可含有各种功能添加剂，例如金属钝化剂如苯并***、缓蚀剂如苯基α-萘胺、抗氧剂如酚类抗氧剂，改进高压性能的添加剂，抗磨添加剂如二烷基硫代磷酸锌，增稠剂或基础剂，消泡剂如硅氧烷聚合物，乳化剂，去垢剂或分散剂，倾点下降剂如聚甲基丙烯酸酯，粘度指数改进剂如聚甲基丙烯酸酯或乙烯基吡咯烷酮/甲基丙烯酸酯共聚物，着色剂以及这些功能添加剂任何一种或几种的混合物。
当用作常规金属加工流体中的基础流体时，最终酯的用量为总金属加工流体浓缩物的5-95％(重量)，优选20-70％(重量)。金属加工流体浓缩物通常是用水稀释后转变成水和油的乳液，该乳液最好含有1-10％(重量)的浓缩物。
金属加工流体的基础流体也可含有各种功能添加剂，例如金属钝化剂如苯并***、缓蚀剂如苯基α-萘胺、抗氧剂如酚类抗氧剂，生物杀伤剂、消泡剂如硅氧烷聚合物，乳化剂，去垢剂或分散剂，防霉剂，杀菌剂，着色剂以及这些功能添加剂任何一种或几种的混合物。
本发明将通过下列实施例进一步说明。
                    实施例I
在一个装备有温度计、水冷凝器、机械搅拌器、惰性气体入口管和异丙醇入口管，并与机械泵和2.5升装有异丙醇的烧瓶相连的4升五颈反应器中加入1500克(2.60摩尔)二聚酸和1.5克(0.011摩尔)作为催化剂的氧化锡(II)。
在恒定的氮气流下将该二聚酸和催化剂加热到230℃。当温度达到180℃时，开始加入异丙醇。将反应生成的水和未反应的异丙醇蒸馏出来。大约4小时后，酸值达到100mgKOH/克，停止加异丙醇。将反应温度冷却至100℃以下，在该反应混合物中加入1562克(2.84摩尔)Breox甲氧基聚乙二醇-550(商品名；一种购自BP化学公司(英国)的甲氧基聚乙二醇，平均分子量为525-575，密度1.1克/厘米3：凝固点20℃；100℃时的粘度为7.5毫米2/秒)。该反应混合物再在恒定氮气流下加热到250℃，蒸出反应生成的水。当酸值降至低于15毫克KOH/克时，反应再在250℃和减压(约1000帕)下进行4小时。粗产物为酸值5毫克KOH/克的棕色液体。冷却到100℃后，往反应混合物中加入100克Cardura E-10(见前文)，随后加热到250℃下保持1小时。过量的Cardura E-10在250℃和1000帕下蒸出。得到的反应产物是羟值为8、酸值小于1和粘度指数为188的棕色液体。
                  实施例II
在一个装备有温度计、水冷凝器、机械搅拌器、惰性气体入口管和异丙醇入口管，并与机械泵和装有异丙醇的2.5升烧瓶相连的4升五颈反应器中加入1426克(2.47摩尔)二聚酸和863.5克(2.47摩尔)Breox甲氧基聚乙二醇350(商品名：一种购自BP化学公司(英国)的甲氧基聚乙二醇；平均分子量为335-365；密度1.09克/厘米3：凝固点5℃，100C时的粘度为4.1毫米2/秒)。反应混合物在恒定的氮气流下加热到250℃，反应生成的水通过蒸馏除去。约3小时后，酸值达到60毫克KOH/克，几乎不再有反应水蒸出。
让混合物冷却到230℃后，将2.6克(0.019摩尔)的催化剂氧化锡(II)加到反应混合物中，并开始加入异丙醇。反应在230℃和恒定的异丙醇加入速率和恒定的氮气流下进行，将反应生成的水和未反应的异丙醇蒸出。8小时后，酸值达到5毫克KOH/克。停止反应，得到的粗产物是棕色的液体。在用实施例I所述的Cardura E-10处理后，产物的羟值为、酸值小于1，粘度指数为176。
由实施例II得到的产物在摩擦力计中用固定的钢球压入旋转的钢环中的方法测试。将球压入环中的负荷和环的旋转速度是可变的。球/环的接触处是全部浸入被试产物中。用这个仪器可以测出各种不同润滑油模式的转变。用此可以区别三种不同的润滑油模式：
区域I：特征是无磨耗和低摩擦系数。
区域II：边界区。负荷通过润滑油膜和金属表面共同传递。有限
        的磨耗，起初是高摩擦系数，随后变为低摩擦系数。
区域III：干摩擦。金属表面之间没有润滑油，磨耗量高和高摩擦
         系数。
实施例II的产物，在环速0.5米/秒和2.0米/秒下，以三羟甲基丙烷三油酸酯(TMPTO)作参照物进行测试。试验结果总括如下：
   速度米/秒  实施例II产物  实施例II产物+5％(重量)水    TMPTO
 I至II转变(牛顿)     0.5     525      575     475
 II至III转变(牛顿)     0.5     1150      1450     1050
 I至III转变(牛顿)     2.0     275      125     225
在所试的条件下，实施例II产物的润滑性比TMPTO的润滑性要好。高速情况下，从区域I至区域III的转变在低得多的负荷下出现。
                 实施例III
在装备有机械搅拌器、温度计、水冷凝器和惰性气体入口管的2升四颈反应器中加入816.1克(2.33摩尔)甲氧基聚乙二醇350(与实施例II所用的产品相同)和683.9克(0.78摩尔)三聚酸。将反应混合物蒸馏。当酸值降至低于15毫克KOH/克后，反应再在250℃和减压(约1000帕)下进行4小时。
粗产物是酸值为5毫克KOH/克的棕色粘性油。用50克实施例I所述的Cardura E-10处理后，羟值为14，酸值小于1，粘度指数为195。
实施例IV
在装备有机械搅拌器、温度计、水冷凝器和惰性气体入口管的2升四颈反应器中加入1020.4克(1.64摩尔)Synperonic 91/12(商品名：一种购自ICIPLC(英国)的由含有12个氧化乙烯基的C8/C10线型α-烯烃羰基化后生成的乙氧基化全饱和合成伯醇；倾点为26℃，粘度30厘泊，密度1.013克/厘米3)和479.6克(0.55摩尔)三聚酸。反应混合物在恒定的氮气流下加热至250℃，蒸出反应生成的水。在酸值降至小于15毫克KOH/克后，反应再在250℃和减压(约1000帕)下进行4小时。
粗产物是酸值为5毫克KOH/克的棕色粘性油。用50克实施例I所述的Cardura E-10处理后，羟值为12，酸值小于1，粘度指数为210。
                     实施例V
在装备有机械搅拌器、温度计、水冷凝器和惰性气体入口管的2升四颈反应器中加入412.7克(1.18摩尔)甲氧基聚乙二醇350(与实施例II所用的产品相同)、1087.3克(1.18摩尔)三聚酸三甲酯和27.0克30％(重量/重量)在甲醇中的甲醇钠(0.15摩尔活性物)。
反应混合物在恒定的氮气流下加热到150℃，蒸出甲醇。当羟值降至低于10毫克KOH/克后，反应再在150℃和减压(约1000帕)下进行4小时。
产物是羟值为2、酸值小于1和粘度指数为173的棕色粘性油。

Claims (14)

1.一种含有酸值低于10，羟值低于15的酯化产物的水力流体或金属加工流体的基础流体，它是由下列成分经酯化反应后得到的：
(a)选自二聚酸、三聚酸、氢化二聚酸、氢化三聚酸及其混合物的聚合的不饱和C12-C24脂肪酸，和
(b)选自下列的烷氧基化一元醇：
(1)用2-25摩尔C2-C5烯化氧烷氧基化的、具有1-24个碳原子的，直链或支链的饱和一元醇，和
(2)烷氧基聚(亚烷基)二醇，其中两个端羟基中的一个羟基用被2-25摩尔C2-C5烯化氧烷氧基化的C1-C4脂族一元醇醚化，和任选的
(C)含1-24个碳原子的直链或支链的饱和一元醇。
该酯化反应要进行到酯的酸值低于10，羟值低于15为止。
2.按照权利要求1的方法，其中(a)是三聚酸。
3.按照权利要求1的方法，其中(b)含有6-12摩尔的C2-C5烯化氧
4.按照权利要求1的基础流体，其中(b)的平均分子量为200-2000。
5.按照权利要求1的基础流体，其中(b)的平均分子量为300-1000。
6.按照权利要求1的方法，其中(c)含有1-14个碳原子。
7.按照权利要求1的方法，其中酯化产物的酸值最高为5，羟值最高为10。
8.按照权利要求1的方法，其中酯化产物的酸值低于1。
9.按照权利要求1的方法，其中酯化产物的酸值通过使它与一种含有5-22个碳原子的脂族羧酸的缩水甘油酯反应而降低。
10.一种水力流体，其特征在于它含有10-95％(重量)的按照权利要求1-9的基础流体。
11.一种水力流体，其特征在于它含有20-75％(重量)的按照权利要求1-9的基础流体。
12.一种金属加工流体，其特征在于它含有5-95％(重量)的按照权利要求1-9的基础流体。
13.一种金属加工流体，其特征在于它含有20-70％(重量)的按照权利要求1-9的基础流体。
14.一种金属加工水和油的乳液，其特征在于它含有有效量的按照权利要求1-9的基础流体。
CN94193371A 1993-09-14 1994-09-08 水力流体 Expired - Fee Related CN1046757C (zh)

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CN109439383A (zh) * 2018-10-31 2019-03-08 广州米奇化工有限公司 自乳化酯及其制备方法
CN109439382A (zh) * 2018-11-09 2019-03-08 深圳春雨润滑科技有限公司 一种聚合酯油及其制备方法

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CN109439382A (zh) * 2018-11-09 2019-03-08 深圳春雨润滑科技有限公司 一种聚合酯油及其制备方法

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DE69416145T2 (de) 1999-06-02
DE69416145D1 (de) 1999-03-04
AU7780594A (en) 1995-04-03
JPH09502754A (ja) 1997-03-18
CN1232077A (zh) 1999-10-20
WO1995007961A1 (en) 1995-03-23
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CN1046757C (zh) 1999-11-24
ES2127414T3 (es) 1999-04-16

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