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CN106471105B - 抗腐蚀润滑剂 - Google Patents

抗腐蚀润滑剂 Download PDF

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CN106471105B
CN106471105B CN201480077013.7A CN201480077013A CN106471105B CN 106471105 B CN106471105 B CN 106471105B CN 201480077013 A CN201480077013 A CN 201480077013A CN 106471105 B CN106471105 B CN 106471105B
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propylene oxide
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CN106471105A (zh
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M·R·格里夫斯
J·马
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Abstract

一种以下润滑剂适用作用于压缩机的润滑剂:其含有醇引发的环氧丙烷均聚物、除所述醇引发的环氧丙烷均聚物以外的油溶性聚二醇以及二壬基萘磺酸钙盐,其中所述润滑剂的特征进一步在于含有以总体润滑剂重量计少于10重量%的多元醇酯。

Description

抗腐蚀润滑剂
技术领域
本发明涉及含有聚二醇基础油、单独的油溶性聚二醇以及二壬基萘磺酸钙盐的润滑剂。
背景技术
现代旋转螺旋空气压缩机(RSAC)润滑剂一般包含作为主要基础油的合成聚二醇(PAG)和较低浓度的多元醇酯共基础油。PAG组分一般是醇引发的环氧丙烷均聚物。PAG往往会导致一些弹性组分(如丙烯腈丁二烯橡胶(NBR))收缩。弹性体(如NBR)常常在压缩机设备中用作如密封垫。不期望润滑剂使弹性密封垫在与所述润滑剂接触时收缩,因为这可能导致润滑剂泄漏。相比而言,可期望润滑剂使弹性密封垫稍微膨胀以防止润滑剂泄漏。多元醇酯共基础油用以促进弹性化合物膨胀,借此抵消PAG的收缩效应。多元醇酯共基础油还充当铁腐蚀抑制剂辅助剂。铁腐蚀抑制剂典型地包括于RSAC润滑剂中,并且多元醇酯共基础油促进铁腐蚀抑制剂添加剂的抗腐蚀性能。
PAG/多元醇酯润滑剂典型地在大多数RSAC环境中提供非凡的流体使用寿命。举例来说,PAG/多元醇酯润滑剂的流体改变间隔时间为约8000小时,然而常规的矿物油RSAC润滑剂的流体改变间隔时间为约2000小时。
当RSAC在含有酸性气体(如二氧化硫)的氛围中操作时,PAG/多元醇酯润滑剂会出现问题。水和酸性气体可从所述氛围进入到润滑剂中,并且导致多元醇酯水解,从而导致流体使用寿命缩短。在高酸环境中,PAG/多元醇酯润滑剂的寿命可能少于2000小时。
本领域中PAG类RSAC润滑剂的另一难题是腐蚀抑制剂典型地为含钡添加剂。钡组分不适用于环境,因此需要替代的添加剂。
期望找到基于PAG基础油的RSAC润滑剂,其不需要多元醇酯共基础油或含钡腐蚀抑制剂,仍具有与多元醇酯制剂相当或比其更佳的抗腐蚀性。
发明内容
本发明提供一种PAG类RSAC润滑剂,其不需要多元醇酯共基础油或含钡腐蚀抑制剂,仍具有与多元醇酯制剂相当或比其更佳的抗腐蚀性。本发明的润滑剂使用醇引发的环氧丙烷均聚物作为基础油和除所述醇引发的环氧丙烷均聚物以外的油溶性PAG作为共基础油。本发明的润滑剂进一步包括二壬基萘磺酸钙盐作为铁腐蚀抑制剂。
本发明是发现以下的结果:在无所述含钡抑制剂的情况下,油溶性PAG可类似于多元醇酯使弹性体膨胀,并且当二壬基萘磺酸钙盐包括于本发明的润滑剂中时,可充当铁腐蚀抑制剂,其结果与所述含钡抑制剂一样好。出人意料地,所述油溶性PAG和二壬基萘磺酸钙盐具有协同效应,导致抗腐蚀性提高。
在第一方面中,本发明是一种润滑剂,其包含醇引发的环氧丙烷均聚物、除所述醇引发的环氧丙烷均聚物以外的油溶性聚二醇以及二壬基萘磺酸钙盐,其中所述润滑剂的特征进一步在于含有以总体润滑剂重量计少于10重量%的多元醇酯。
在第二方面中,本发明是一种用于润滑压缩机的方法,所述方法包含以下步骤:将所述第一方面的润滑剂添加到所述压缩机中。
本发明的润滑剂适用于润滑机械设备如旋转螺旋空气压缩机的本发明方法。
具体实施方式
“和/或”意谓“和或替代地”。除非另外陈述,否则所有范围包括端点。
除非日期利用呈带有连字符的两位数形式的测试方法编号来指示,否则测试方法是指从此文件的优先权日起最近的测试方法。参考测试方法含有参考测试协会和测试方法编号。通过以下缩写中的一个参考测试方法组织:ASTM是指ASTM国际性组织(原名是美国测试与材料协会(American Society for Testing and Materials));EN是指欧洲标准(EuropeanNorm);DIN是指德国标准化学会(Deutsches Institut für Normung);并且ISO是指国际标准化组织(International Organization for Standards)。
本发明的润滑剂包含醇引发的环氧丙烷均聚物。式I呈现醇引发的环氧丙烷均聚物的通式:
R1[O(CH2CH(CH3)O)mR2]n I
其中R1对应于醇引发剂(除羟基或已与环氧丙烷反应的基团以外的残余组分)的主链;R2选自由氢和含有1到18个碳原子的烷基、芳基和烷基芳基组成的基团;m对应于聚合到醇引发剂的羟基上的环氧丙烷分子的平均数目,并且一般是10或更高并且同时是40或更小,优选的是15或更小;并且n是从醇引发剂主链延伸的聚环氧丙烷链的数目,并且等于聚合期间与环氧丙烷反应的在醇引发剂上的羟基数目。n的值一般是1、2或3,其取决于引发剂是否分别为单醇、二醇或三醇。引发剂宜为单醇(n等于1),并且优选地醇引发剂是丁醇,其意味着R1是四碳烷基。
醇引发的环氧丙烷均聚物在100℃下动态粘度宜为5厘沲(cSt)或更大,优选的是6cSt或更大,并且可为7cSt或更大并且甚至为8cSt或更大。同时,醇引发的环氧丙烷均聚物在100摄氏度(℃)下动态粘度宜为15cSt或更小。根据ASTM D445测定动态粘度。
醇引发的环氧丙烷均聚物以总体润滑剂重量计宜以超过50重量%(wt%)、更优选地60wt%或更多、再更优选地70wt%或更多、甚至更优选地75wt%或更多的浓度存在,并且可以80wt%或更多、85wt%或更多、甚至90wt%或更多的浓度存在。同时,醇引发的环氧丙烷均聚物以总体润滑剂重量计典型地以98wt%或更少、更加典型地95wt%或更少的浓度存在,并且可为90wt%或更少、85wt%或更少并且甚至75wt%或更少。特别地,醇引发的环氧丙烷均聚物可为两种或更多种醇引发的环氧丙烷均聚物的掺合物,在此情况下wt%醇引发的环氧丙烷均聚物对应于所有醇引发的环氧丙烷均聚物的组合重量。
本发明进一步包含除醇引发的环氧丙烷均聚物以外的油溶性聚二醇(OSP)。OSP宜选自由醇引发的环氧丁烷均聚物和醇引发的环氧丁烷与环氧丙烷共聚物组成的群组。优选地,OSP是一种或超过一种的醇引发的环氧丁烷与环氧丙烷共聚物。共聚物可为无规共聚物或嵌段共聚物。当是嵌段共聚物时,环氧丁烷和环氧丙烷可以以下任一次序进行聚合:形成从醇引发剂延伸出的PO/BO或BO/PO嵌段共聚物,其中“PO”是指开环(聚合)环氧丙烷组分,并且“BO”是指在聚合之后剩余的开环(聚合)环氧丁烷组分。OSP宜为醇引发的PO/BO无规共聚物。BO的量以PO和BO的总重量计宜为40重量%(wt%)或更多、优选地50wt%或更多,并且可为60wt%或更多、65wt%或更多并且甚至70wt%或更多,并且同时典型地为80wt%或更少,并且可为70wt%或更少。OSP以PO和BO的总重量计宜为50wt%PO和50wt%BO(亦即PO和BO以50/50重量比共聚合)。
OSP宜由醇引发剂制备,所述醇引发剂具有8个或更多个碳原子、优选地10个或更多个碳原子、再更优选地12个或更多个碳原子、更优选地14个或更多个碳原子,并且可为16个或更多个碳原子并且甚至18个或更多个碳原子,同时典型地具有20个或更少碳原子。同时,引发剂宜为直链的,并且更优选地为伯醇。一种用于制备OSP的尤其合乎需要的醇引发剂是十二烷醇。
用于OSP的醇引发剂可为单醇、二醇或三醇。优选地,醇引发剂是单醇。
OSP可利用氢(H)封端,形成末端醇(羟基)键,或可利用除氢以外的基团,优选的是碳原子进行封端,形成如选自醚和酯的那些键。未端键位于OSP中与醇引发剂相对的末端。
OSP在40℃下的动态粘度一般是15cSt或更高、优选地18cSt或更高、更优选地32cSt或更高,并且可为68cSt或更高、80cSt或更高、100cSt或更高、150cSt或更高并且甚至220cSt或更高,同时一般是250cSt或更低。根据ASTM D445测定动态粘度。
OSP的平均分子量一般是500克/摩尔(g/mol)或更大、优选地750g/mol或更大,并且可为1000g/mol或更大、1250g/mol或更大、1500g/mol或更大、1900g/mol或更大、或2400g/mol或更大,并且同时一般是3600g/mol或更小、优选地2400g/mol或更小并且更优选地1900g/mol或更小并且甚至更优选地1400g/mol或更小并且最优选地少于1400g/mol。根据凝胶渗透色谱法(gel permeation chromatography)测定平均分子量。除非另有指示,否则“分子量”是指数目平均分子量(Mn)。
当OSP的平均分子量是1400g/mol时,其往往既不使丙烯腈丁二烯橡胶(NBR)膨胀也不使丙烯腈丁二烯橡胶(NBR)收缩,并且当所述OSP的平均分子量小于1400g/mol时,其往往会使NBR膨胀。平均分子量大于1400g/mol的OSP可使NBR橡胶收缩。合乎需要的是润滑剂不会使由NBR橡胶制成的密封垫收缩,并且最合乎需要的是使所述密封垫当与润滑剂接触时稍微膨胀,因此防止密封垫封口周围发生润滑剂泄漏。
OSP的浓度以总体润滑剂重量计一般是2wt%或更多、优选地5wt%或更多,并且可为10wt%或更多、15wt%或更多并且甚至20wt%或更多,同时是典型地30wt%或更少,并且一般25wt%或更少或甚至20wt%或更少。
本发明是发现以下的结果:典型的润滑剂制剂中的部分或全部多元醇酯可用OSP替换以获得更加稳定的润滑剂。为此,多元醇酯的浓度以总体润滑剂重量计少于10wt%,并且是优选地5wt%或更少并且甚至更优选地3wt%或更少。润滑剂可不含多元醇酯。多元醇酯包括烷酸酯,如具有3-8个羟基的受阻多元醇的烷酸酯。
本发明进一步包含二壬基萘磺酸钙盐作为腐蚀抑制剂。当腐蚀抑制剂是二壬基萘磺酸钙盐时,润滑剂制剂表现出惊人的协同效应。与具有不同腐蚀抑制剂(如二壬基萘磺酸钡盐)的类似制剂相比,具有二壬基萘磺酸钙盐的本发明润滑剂制剂更加易于通过根据ASTM D665-12的腐蚀测试。
二壬基萘磺酸钙盐的浓度以总体润滑剂重量计宜以0.1wt%或更多、优选地0.2wt%或更多、再更优选地0.25wt%或更多、又更优选地0.5wt%或更多,并且可为0.75wt%或更多、1wt%或更多并且甚至1.5wt%或更多,同时是典型地5wt%或更少、优选地3wt%或更少,并且可为2wt%或更少并且甚至1wt%或更少的浓度存在。
本发明的益处是其并不需要含钡材料,如钡类腐蚀抑制剂。实际上,本发明的润滑剂可含有相对于总体润滑剂重量以wt%为单位少于0.1wt%、优选地0.05wt%或更少、再更优选地0.01wt%或更少的含钡材料,并且可不含有含钡材料。
本发明的润滑剂适用于润滑机械装置,尤其是压缩机并且更具体来说是旋转螺旋空气压缩机。本发明的润滑剂可作为润滑剂根据压缩机的说明书添加到压缩机中。本发明在不需要使用多元醇酯或含钡材料的情况下符合旋转螺旋空气压缩机润滑剂的需要。
实例
用于实例(Ex)和比较实例(Comp Ex)的材料在表1和表2中列出。UCON是联合碳化物公司(Union Carbide Corporation)的商标。SYNALOX是陶氏化学公司(The DowChemicalCompany)的商标。SYNATIVE是科宁知识产权管理股份有限公司(Cognis IPManagementGmbH)的商标。IRGANOX是巴斯夫股份公司(BASF SE Company)。VANLUBE是R.T.VanderbiltMinerals,LLC的商标。SULLUBE是美国寿力公司(Sullair Corporation)的商标。Na-Sul是King Industries,Inc的商标。
表1
表2
在500毫升(mL)玻璃杯子中通过添加制剂的每一种组分以获得400公克混合物来制备制剂。在50℃下搅拌混合物60分钟,直至透明并且均相为止,并且接着使其冷却到约23℃。所有掺合物在20-25℃下储存一周之后为透明并且稳定的。
根据ASTM D665-12腐蚀测试A和B来评价Ex和Comp Ex制剂的腐蚀抑制性。ASTMD665A是使用去离子水的腐蚀测试。ASTM D665B是使用合成海水的腐蚀测试,并且与ASTMD665A相比更加难以通过。ASTM D665-12方法建议进行测试持续四(4)或24小时。在一些情况下,Ex和/或Comp Ex实际上测试了48小时。制剂通过(P)或没有通过(F)腐蚀测试。
比较实例A-D:钡盐腐蚀抑制剂制剂
表3列举使用钡盐腐蚀抑制剂的比较实例制剂以及关于ASTM D665A测试持续24小时后的腐蚀测试结果。数值为400g制剂的每一种组分的wt%。腐蚀测试结果为通过(P)或没有通过(F)。
表3
组分 比较实例A 比较实例B 比较实例C 比较实例D
UCON润滑剂LB-165 66.08 75.98 66.98 57.98
UCON润滑剂LB-285 0 8.4 7.4 6.4
UCON OSP-32 0 10 20 30
Vanlube 961 5 5 5 5
甲苯基三唑 0.12 0.12 0.12 0.12
Synative ES 2931 28.3 0 0 0
Na-Sul 611 0.5 0.5 0.5 0.5
24小时腐蚀结果-ASTM D665A P F F F
比较实例A是含有PO均聚物、多元醇酯和钡腐蚀抑制剂的典型压缩机润滑剂。用醇引发的无规PO/BO共聚物(UCON OSP-32)以范围介于10-30wt%的多个取代水平替换多元醇酯(Synative ES 2931)使得制剂没有通过ASTM D665A腐蚀测试。
实例1-9:钙盐腐蚀抑制剂制剂
表4列举使用钙盐腐蚀抑制剂的实例制剂以及关于ASTM D665A测试持续24小时后的腐蚀测试结果。
表5列举使用钙盐腐蚀抑制剂但在无OSP组分(UCON OSP-32)情况下的比较制剂。
数值为400g制剂的每一种组分的wt%。腐蚀测试结果为通过(P)或没有通过(F)。
结果展示制剂与OSP和钙盐腐蚀抑制剂组合通过ASTM D665A腐蚀测试,但是具有钙盐而非OSP的样品没有通过ASTM D665A腐蚀测试。此等结果揭示了钙盐腐蚀抑制剂与OSP之间在制剂中有利于通过腐蚀测试的协同效应。
表4
表5
组分 比较实例E 比较实例F 比较实例G
SYNALOX PB-200 94.63 94.38 93.88
UCON OSP-32 0 0 0
VANLUBE 961 5 5 5
甲苯基三唑 0.12 0.12 0.12
Na-Sul Ca-1089 0.25 0.5 1
24小时腐蚀结果-ASTM D665A F F F
实例10-12和比较实例H-J:ASTM D665B测试
表6列举用于实例10-12和比较实例H-J的制剂以及关于ASTM D665B测试超过4小时、24小时和48小时的测试结果。所有制剂都包括钙盐腐蚀抑制剂。实例包括OSP,然而比较实例不包括OSP。每种制剂都包括IRGANOX L57。
结果揭示了当OSP存在时所达到的抗腐蚀性程度较大,此外证实了钙盐与OSP之间存在有利于腐蚀抑制的协同效应。
数值为400g制剂的每一种组分的wt%。腐蚀测试结果为通过(P)或没有通过(F)。
表6
实例13-15和比较实例K:OSP浓度改变和参考物
表7列举用于实例13-15和比较实例K的制剂以及关于ASTM D665B测试超过4小时、24小时和48小时的测试结果。所有制剂都包括钙盐腐蚀抑制剂。实例包括不同浓度的OSP以测定浓度对性能是否有影响。
比较实例K是以商标SULLUBE 32出售的市售压缩机润滑剂,并且其衍生自PAG(PO均聚物)、多元醇酯和二壬基萘磺酸钡盐。
数值为400g制剂的每一种组分的wt%。腐蚀测试结果为通过(P)或没有通过(F)。
表7
结果揭示当钙盐腐蚀抑制剂是以1wt%的制剂重量时,在此等制剂中浓度范围在5-20wt%的OSP并不显著影响腐蚀抑制性。结果还揭示本发明制剂表现以及包含多元醇酯和钡腐蚀抑制剂的市售制剂表现。
实例16:不同的钙腐蚀抑制剂
除了使用1wt%的Na-Sul Ca-50而非Na-Sul 611,并且UCON LB-165的浓度降低了0.5%到66.48%以外,重复比较实例C。Na-Sul Ca-50是二壬基萘磺酸钙盐,但是不含任何羧酸盐部分。所得制剂(实例16)通过了ASTM D665A腐蚀测试。此结果指示二壬基萘磺酸钙盐类型对于本发明的腐蚀抑制特征很可能不是至关重要的。
弹性体膨胀测试
测试数种不同分子量的醇引发的环氧丙烷与环氧丁烷共聚物OSP使腈丁二烯橡胶(等级类型72NBR 902)膨胀的能力。测试使用DIN ISO 1817测试方法完成,其中弹性体在100℃的温度下完全浸没于OSP中持续1000小时时段。报导弹性体的体积增加程度。OSP是以商标名UCON从陶氏化学公司购得的那些OSP。测试结果展示于表8中。
表8
OSP的平均分子量(g/mol) NBR的体积改变百分比
UCON OSP-18 500 19
UCON OSP-32 760 16
UCON OSP-68 1400 0
UCON OSP-150 1900 -7
UCON OSP-220 2300 -9
测试结果揭示当此特定OSP的分子量低于1400g/mol时,其使NBR膨胀,当其分子量是1400g/mol时,其既不使NBR膨胀也不使NBR收缩,并且当OSP的分子量是1900g/mol时,其使NBR收缩。测试结果适用于此特定OSP,其是具有50/50重量比的PO与BO的醇(十二烷醇)引发的PO/BO无规共聚物。不同的OSP有可能具有不同的结果。

Claims (10)

1.一种润滑剂,其包含醇引发的环氧丙烷均聚物、除所述醇引发的环氧丙烷均聚物以外的油溶性聚二醇、以及以总体润滑剂重量计至少0.25重量%的二壬基萘磺酸钙盐,其中所述除所述醇引发的环氧丙烷均聚物以外的油溶性聚二醇选自醇引发的环氧丁烷均聚物、醇引发的环氧丁烷与环氧丙烷共聚物及其组合,并且以总体润滑剂重量计为2重量%至30重量%,其中所述润滑剂的特征进一步在于a)含有以总体润滑剂重量计少于10重量%的多元醇酯和b)所述醇引发的环氧丙烷均聚物的浓度以总体润滑剂重量计大于50重量%。
2.根据权利要求1所述的润滑剂,其中所述润滑剂的特征进一步在于所述醇引发的环氧丙烷均聚物是丁醇引发的环氧丙烷均聚物。
3.根据任一前述权利要求所述的润滑剂,其中所述润滑剂的特征进一步在于除所述醇引发的环氧丙烷均聚物以外的所述油溶性聚二醇是醇引发的环氧丙烷与环氧丁烷无规共聚物。
4.根据权利要求1或2所述的润滑剂,其中所述润滑剂的特征进一步在于除所述醇引发的环氧丙烷均聚物以外的所述油溶性聚二醇的数目平均分子量小于1400克/摩尔。
5.根据权利要求1或2所述的润滑剂,其中所述润滑剂的特征进一步在于所述醇引发的环氧丙烷均聚物的浓度以总体润滑剂重量计大于60重量%。
6.根据权利要求1或2所述的润滑剂,其中所述润滑剂的特征进一步在于所述二壬基萘磺酸钙盐的浓度以总体润滑剂重量计在0.25与1重量%范围内。
7.根据权利要求1或2所述的润滑剂,其中所述润滑剂的特征进一步在于不含有含钡材料。
8.根据权利要求1或2所述的润滑剂,其中所述醇引发的环氧丙烷均聚物是丁醇引发的环氧丙烷均聚物,并且除所述醇引发的环氧丙烷均聚物以外的所述油溶性聚二醇是十二烷醇引发的环氧丙烷与环氧丁烷无规共聚物,其中所述环氧丙烷与环氧丁烷以50/50重量比进行共聚合。
9.一种用于润滑压缩机的方法,所述方法包含将根据任一前述权利要求所述的润滑剂添加到所述压缩机中的步骤。
10.根据权利要求9所述的方法,其中所述压缩机是旋转螺旋空气压缩机。
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