CN1396949A - 包含泡沫诱导添加剂的致冷润滑组合物 - Google Patents

包含泡沫诱导添加剂的致冷润滑组合物 Download PDF

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CN1396949A
CN1396949A CN01804343A CN01804343A CN1396949A CN 1396949 A CN1396949 A CN 1396949A CN 01804343 A CN01804343 A CN 01804343A CN 01804343 A CN01804343 A CN 01804343A CN 1396949 A CN1396949 A CN 1396949A
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lubricating composition
foam
group
lubricating
additive
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CN1210387C (zh
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S·博伊德
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Lubrizol Corp
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Imperial Chemical Industries Ltd
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Abstract

本发明公开了一种润滑组合物，它具有合成润滑基础油，优选多元醇酯，和聚醚泡沫诱导添加剂。该组合物适用于尤其具有HFC致冷气体的致冷体系。该泡沫诱导添加剂可替代不是对所有致冷体系都适合的已知的含硅泡沫诱导添加剂。

Description

包含泡沫诱导添加剂的致冷润滑组合物
本发明涉及一种润滑组合物及其在致冷体系中的用途。
已知在致冷体系中过度发泡是不理想的。它降低了润滑组合物在发动机线圈冷却和压缩机去热方面的效力。另外，太多的泡沫可造成太多的润滑组合物通过体系泵并进入致冷体系的低压侧。但中等量的发泡可以是有益的，尤其用于抑制致冷体系压缩机内的噪音。1998 ASHRAERefrigeration Handbook的7.20章叙述″润滑液面上的泡沫层减缓了由压缩机的运动部件所产生的噪音″。产生泡沫有其它益处；例如公开于WO/9512649的对蒸气释放速率的控制和公开于US4829786的对增强油返回的促进。
历史上，矿物油用于氯氟碳(CFC)和氢氯氟碳(HCFC)致冷气体的润滑组合物。这些润滑组合物/CFC/HCFC混合物表现出发泡倾向。在其中发泡不是所期望的或过度的某些情况下，发现需要控制泡沫的产生。在其它情况下，如果发泡是有利的，发现需要促进发泡。例如，US 3,792,755公开了一种减缓由操作的密封压缩机装置所产生的噪音的方法，该装置具有一个用于在操作过程中搅动该润滑组合物的工具，所述润滑组合物包含一种为有机硅氧烷的发泡剂。发泡剂帮助产生和保持用于吸收并因此减缓压缩机装置在操作过程中所产生的噪音的泡沫或细泡沫。公开于US 3,792,755的CFC包括三氯乙烯，二氯二氟甲烷(R-12)和一氯二氟甲烷(R-22)。
近年来，立法上已要求从这些传统的致冷气体过渡到具有较低或零臭氧消耗潜力的替代品，如氢氟碳气体(HFC)。致冷气体的这种改变要求改变润滑组合物以远离与这些新HFC气体不相容的矿物油。使用了更极性的、HFC可相容的、合成润滑组合物。适用于这些合成润滑组合物的基础流体的例子是聚亚烷基二醇，多元醇酯，聚乙烯醚和烷基苯。
已经发现，HFC致冷气体和这些合成润滑组合物的混合物与矿物油基润滑组合物和CFC的混合物相比具有明显较低的发泡倾向；例如参见1998年3月的″致冷剂/润滑剂混合物的发泡特征″的第5章，参考号DOE/CE/23810-88a，它报道了由美国能源部支持并为空调和制冷剂技术研究所准备的工作。因此，如果产生泡沫是优点，需要在润滑组合物中产生泡沫或细泡沫。这种泡沫的产生可通过向润滑组合物中加入发泡添加剂而实现。
已知的发泡添加剂是硅基的，例如有机硅氧烷或硅氧烷。WO95/12649公开一种包含合成多元醇酯润滑剂和泡沫密度增加添加剂的润滑组合物，用于具有至少一个压缩机和卤化碳致冷气体，优选HFC的致冷体系。该泡沫密度增加添加剂优选为硅氧烷但也可以是卤化脂族聚合物酯(例如，得自3M的Fluorad FC430)，而且发现能同时增加泡沫密度和控制压缩机的蒸气释放。
EP0590238 A1公开一种用于压缩HFC致冷剂的压缩机，该制冷剂的特征在于存在一种由季戊四醇酯和硅氧烷发泡添加剂组成的润滑组合物，其中在压缩机操作过程中产生油泡沫层以降低发动机噪音。
JP10088173 A2公开用于致冷压缩机以降低噪音的润滑组合物，包含HFC致冷剂，具有至少2酯键的酯油润滑剂，水解稳定剂，抗氧化剂和0.001-0.01wt％的硅氧烷油。
但这些含硅发泡添加剂可能不适合所有的致冷体系，因为它们仅与该润滑组合物的基础油部分相容。这可能导致含硅添加剂在致冷体系的冷部件中的分离。含硅添加剂的这种损失还可能因为添加剂消耗、热交换器表面的结垢和阀堵塞而造成发泡损失。另外，存在于金属表面上的硅氧烷会妨碍这些表面的涂漆。
因此，正在寻求替代的发泡添加剂。
因此，本发明在第一方面提供了一种润滑组合物，包含：
a)合成润滑基础油；和
b)泡沫诱导添加剂，它包含一种具有结构式X-O-(RO)n-Y的聚醚，其中-O-(RO)n-是聚醚主链
R是具有1-10个碳原子的部分或完全卤化烷基基团且其中相邻的R基团可相同或不同
n是1-1000和
X和Y是端基。
部分卤化是指，烷基基团的至少一个氢原子已被替代为卤素原子。优选，烷基基团的每个碳原子中的至少一个氢原子已被替代为卤素原子，更优选烷基基团的所有氢原子已被替代为卤素原子，这样R是完全卤化烷基基团。优选，卤素原子是氟原子。尤其优选的是，氟原子已替代烷基的所有氢原子。
烷基基团R可以是支链或直链的且它可以是饱和或不饱和。R优选具有1-7个碳原子，更优选1-4个碳原子。优选的R的例子包括-CF2-、-CF2CF2-、-CF(CF3)-、-CF(CF3)CF2-、-CF2CF2CF2-和-CF2CF2CF2CF2-。R可选择使得该聚醚是嵌段、无规或接枝共聚物或均聚物。
n优选为1-100，更优选1-50。n对于R基团可相同或不同。
一个优选的实施方案的一个例子是
                 X-O-(R1O)n1-(R2O)n2-Y
其中R1和R2定义如R但R1不同于R2。n1和n2可相同或不同。
聚醚主链具有两个端基X和Y。优选，端基X和Y的至少一个包含至少一个官能化基团。官能化基团的种类包括羟基，酯，乙氧基化羟基，乙氧基化酯，有机和无机的，胺，氰基，和酰胺。该或每个官能化基团可位于端基上以直接键接到聚醚主链上；或它可位于该端基远离聚醚主链的末端；或它可位于端基的主链内。优选，官能化基团位于该端基远离聚醚主链的末端。可存在于该或每个端基内的其它基团包括烷基和卤代烷基，尤其是氟烷基。优选，该端基赋予泡沫诱导添加剂在合成润滑基础油中的溶解性。
具有官能化基团的端基的例子为
-CF2COOCH3，-CF2CH2OH，-CF2CH2O(CH2CH2O)nH和
-CF2CH2OCH2CH(OH)CH2OH
泡沫诱导添加剂优选的分子量为100-10000个原子单位，更优选200-5000个原子单位。它以0.0001-1.0％重量，优选0.0001-0.05％的量存在于润滑组合物中。
选择合成润滑基础油使得该润滑组合物与HFC致冷气体相容。优选，它选自烷基苯，聚乙烯醚，聚亚烷基二醇和酯。优选，该合成润滑基础油是酯；更优选该酯是具有2-6个羟基基团，及优选3-12个碳原子的多元醇，优选脂族烃-基多元醇的衍生物。合适的多元醇包括新戊基二醇，季戊四醇，三羟甲基丙烷，二三羟甲基丙烷和二季戊四醇。该酯衍生自该多元醇与一种或多种具有3-12个碳原子的直链或支链，饱和或不饱和单羧酸和可有可无的一种或多种具有4-54个碳原子的直链或支链，饱和或不饱和聚羧酸的反应。优选，该聚羧酸(如果存在)具有2或3个羧基基团。所有的以上酸可被其可酯化衍生物，例如酸酐替代。
合适的润滑组合物的例子包括EMKARATE RL系列致冷润滑剂，得自Uniqema，Imperial Chemical Industries plc的企业。用于这些润滑组合物的合成润滑基础油衍生自与具有5-10个碳原子的直链和/或支化酸(或其可酯化衍生物)反应的季戊四醇或其低聚物和/或新戊基二醇。
合成润滑基础油在40℃下的粘度为2-500cSt。
润滑组合物在40℃下的粘度为2-500cSt。润滑组合物还可包含其它的发泡添加剂，例如有机硅氧烷或硅氧烷。如果存在，这些其它的发泡添加剂在润滑组合物中的量为0.0001-1.0％重量，优选0.0001-0.1％，更优选0.0001-0.05％。润滑组合物还可包含其它的功能润滑添加剂。合适的添加剂包括抗氧化剂，抗磨添加剂，极压剂，酸清除剂，稳定剂，表面活性剂，粘度指数改进剂，腐蚀抑制剂，金属减活化剂或钝化剂，润滑性改进剂或油质剂和摩擦改性剂。
本发明在第二方面提供了润滑组合物在致冷体系中的用途，其中润滑组合物包含
a)合成润滑基础油；和
b)泡沫诱导添加剂，包含具有结构式X-O-(RO)nY的聚醚，其中-O-(RO)n-是聚醚主链
R是具有1-10个碳原子的部分或完全卤化烷基基团且其中相邻的R基团可相同或不同
n是1-1000和
X和Y是端基。
致冷体系中的致冷剂合适地包含氢氯氟碳(HCFC)，HFC或包含至少一种HFC，HCFC或两者的致冷剂共混物。优选，该致冷剂不含任何氯原子。合适的HFC气体包括R134a(1，1，1，2-四氟乙烷)，R-32(二氟甲烷)，R-125(1，1，1，2，2-五氟乙烷)，R-152a(1，1-二氟乙烷)和R-143a(1，1，1-三氟乙烷)。致冷剂共混物中可以有其它的组分例如优选具有1-6个碳原子的烃，氟化烃和其它的致冷剂，例如碳二氧化物或氨。
本发明通过以下非限定性实施例进一步说明。
实施例1
在室温(24.5℃)下测定200毫升包含EMKARATE RL 22H(来自ICI)和各种含量的泡沫诱导添加剂Fomblin HC-OH(来自Ausimont)(HOCH2CF2O-(CF2CF2O)p-(CF2O)q-CF2CH2OH)的组合物的发泡倾向和泡沫稳定性。该润滑组合物的发泡倾向使用标准试验方法ASTMD-892-97(用于润滑油的发泡特性的标准试验方法)来测定。该试验以将空气鼓泡经过200毫升润滑组合物所产生的泡沫的体积来确定发泡倾向。泡沫稳定性是泡沫消失所需的时间(秒)。
结果示于表1。
实施例2
重复实施例1，只是将R134a鼓泡通过润滑组合物而不是空气。结果示于表2。
实施例3
重复实施例1，只是Fomblin HC-OH被替代为FluorolinkE10(H(OCH2CH2)nOCH2CF2O-(CF2CF2O)p-(CF2O)q-CF2CH2O(CH2CH2O)nH)(来自Ausimont)。结果示于表3。
表1
 Fomblin HC-OH的浓度(ppm)   泡沫倾向(毫升)   泡沫稳定性(秒)
    0     0     0
    20     20     0
    50     380     135
    100     380     219
    250     400     206
    500     370     220
表2
 Fomblin HC-OH的浓度(ppm)   泡沫倾向(毫升)   泡沫稳定性(秒)
    0     0     0
    20     0     0
    50     40     35
    100     30     27
    250     20     10
    500     30     19
表3
Fluorolink E10的浓度(ppm)   泡沫倾向(毫升)   泡沫稳定性(秒)
    0     0     0
    250     390     194
实施例4
在室温(24.5℃)下，通过鼓泡经过空气和R134a，测定200毫升包含各种EMKARATE RL等级(来自ICI)和250ppm泡沫诱导添加剂Fomblin HC-OH的润滑组合物的发泡倾向和泡沫稳定性。结果示于表4。
表4
 EMKARATE RL等级 在空气中的发泡倾向(毫升) 在R134a中的发泡倾向(毫升) 在空气中的泡沫稳定性(秒) 在R134a中的泡沫稳定性(秒)
    32H     480     50     294     58
    15H     230     50     112     21
    7H     50     30     21     12
实施例5
在室温(24.5℃)下测定200毫升包含EMKARATE RL 22H(来自ICI)和各种泡沫诱导添加剂的润滑组合物的发泡倾向和泡沫稳定性。结果示于表5。
表5
    泡沫诱导添加剂 在空气中的发泡倾向(毫升) 在空气中的泡沫稳定性(秒)
Fomblin HC-OH(250ppm)     470     237
Fluorolink E10(250ppm)     390     194
Fluorad FC430(250ppm)(对比)     0     0
FS1265(250ppm)(对比)     360     222
Fomblin Y Lvac(250ppm)(对比)     0     0
PDMS 1(500ppm)(对比)     5     13
PDMS 2(500ppm)(对比)     5     30
FS1265是三氟甲基硅氧烷，来自Dow。
Fomblin Y Lvac是分子量约2400的全氟烷基醚，来自Ausimont。
PDMS 1是粘度50cSt的硅氧烷Fluid SWS-101 50，来自Akrochem。
PDMS 2是粘度350cSt的硅氧烷Fluid SWS-101 350，来自Akrochem。
Fluorad FC430是氟化表面活性剂，来自3M。
结果表明本发明润滑组合物具有优异的发泡倾向和稳定性。
实施例6
重复实施例1，其中使用250ppm Fomblin HC-OH并加入120ppm 50cSt硅氧烷Fluid SWS-101 50(来自Akrochem)。结果示于表6。
表6
    泡沫诱导添加剂 在空气中的发泡倾向(毫升) 在空气中的泡沫稳定性(秒)
Fomblin HC-OH(250ppm)和硅氧烷(120ppm)     350     178
  仅硅氧烷(120ppm)-对比     150     78

Claims (11)

1.一种润滑组合物，包含：
a)合成润滑基础油；和
b)泡沫诱导添加剂，它包含一种具有结构式X-O-(RO)nY的聚醚，其中-O-(RO)n-是聚醚主链
R是具有1-10个碳原子的部分或完全卤化烷基基团且其中相邻的R基团可相同或不同
n是1-1000和
X和Y是端基。
2.根据权利要求1的润滑组合物，其中R是具有1-7个碳原子的完全卤化烷基基团。
3.根据权利要求1或权利要求2的润滑组合物，其中卤素是氟。
4.根据权利要求1-3之任一项的润滑组合物，其中n是1-100。
5.根据权利要求1-4之任一项的润滑组合物，其中端基X和Y的至少一个包含至少一个官能化基团。
6.根据权利要求5的润滑组合物，其中至少一个官能化基团位于该端基远离聚醚主链的末端。
7.根据权利要求5或权利要求6的润滑组合物，其中至少一个官能化基团包括卤代烷基基团。
8.根据权利要求1-7之任一项的润滑组合物，其中泡沫诱导添加剂的存在量为润滑组合物的0.0001-0.1％重量。
9.根据权利要求1-8之任一项的润滑组合物，其中合成润滑基础油选自烷基苯，聚乙烯醚，聚亚烷基二醇和酯。
10.根据权利要求9的润滑组合物，其中合成润滑基础油是一种为多元醇衍生物的酯。
11.润滑组合物在致冷体系中的用途，其中所述润滑组合物包含
a)合成润滑基础油；和
b)泡沫诱导添加剂，它包含一种具有结构式X-O-(RO)nY的聚醚，其中-O-(RO)n-是聚醚主链
R是具有1-10个碳原子的部分或完全卤化烷基基团且其中相邻的R基团可相同或不同
n是1-1000和
X和Y是端基。
CNB018043437A 2000-01-31 2001-01-24 包含泡沫诱导添加剂的致冷润滑组合物 Expired - Lifetime CN1210387C (zh)

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US20030040445A1 (en) 2003-02-27
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