CN116286149A - 一种全合成真空泵油组合物及其应用 - Google Patents
一种全合成真空泵油组合物及其应用 Download PDFInfo
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- CN116286149A CN116286149A CN202111493777.2A CN202111493777A CN116286149A CN 116286149 A CN116286149 A CN 116286149A CN 202111493777 A CN202111493777 A CN 202111493777A CN 116286149 A CN116286149 A CN 116286149A
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Abstract
本发明涉及一种全合成真空泵油组合物及其应用。具体地,所述组合物包括抗氧剂0.5~2.0重量份、防锈剂0.05~1.0重量份、抗破乳剂0~1.0重量份、腐蚀抑制剂0.05~0.2重量份、抗泡剂0.001~0.01重量份、余量为基础油。其中,所述基础油为液态聚乙烯油ETL的一种或多种组合。本发明提供的一种全合成真空泵油组合物不仅具有极佳的氧化安定性、防锈性能和油水分离性能性能,还具有较低的蒸发损失、优异的润滑性能、高低温流动性能和抗泡沫特性,完全满足优等真空泵油的产品要求。
Description
技术领域
本发明属于润滑技术领域,具体地,本发明涉及一种全合成真空泵油组合 物及其应用。
背景技术
真空冶炼、真空镀膜、微电子、高能物理、表面研究、宇航科学等工业发 展和高端科学均与真空技术的发展有着密不可分的联系。真空泵油作为各种机 械真空泵专用润滑油,在真空泵内起到润滑、密封和冷却等作用。尽管机械真 空泵的类型多样,但泵油须具备良好的粘温特性,可适用较宽的工作温度范围; 良好的耐化学药品性、抗腐蚀;卓越的润滑、抗磨损性能;较低的挥发性和油 分离率;不燃性、与高压氧气接触不发生爆炸;良好的热氧化安定性;良好的 密封性、抗水性、抗蒸气性等特性。泵油的质量直接影响真空设备的抽气速率、 背压、返油率和极限压力等。随着真空技术的发展,机械真空泵趋向高效高速、小型化和低噪音的方向发展,对泵油的使用工况提出了更严苛的要求。
机械泵油的主要组分为基础油,可分矿物型和合成型两大类。基于成本考 虑,泵油的调配多采用矿物型基础油。尽管矿物基础油在泵油润滑方面已发挥 其性能的极限,仍不能满足温度变化区间大、以及高负载等特殊工况下的应用 需求。尽管添加剂可一定程度上提高泵油的诸多特性,但改善的幅度有限。因 此,采用性能更优异的合成基础油替代矿物基础油调配用于特殊工况的机械泵 油应运而生。当前,高端的全合成润滑油多是采用合成烃PAO(聚α-烯烃)作 基础油,其可构建满足重多苛刻工况的真空泵油品种。与矿物型泵油相比,PAO 合成型泵油具有更好的粘温特性,能适用更宽的使用温度;同时,其良好的抗乳化性、水解稳定性、以及热氧化稳定性可延长换油周期,降低维护成本。PAO 是α-烯烃(C8、C10和C12)的寡聚物,其原料α-烯烃(C8、C10和C12)由乙 烯齐聚获得(JP 06329562;EP0668105;US 5523507;Kaminsky W.,Angew Makrom Chem,1994,223,101.),但乙烯齐聚难以实现α-烯烃的高选择性制 备,还会副产C4、C6以及高级(>C12)的α-烯烃,导致乙烯利用率低(~40%)、 PAO的制备成本高、价格昂贵,限制了广泛应用。国内高端装备制造业的快速 发展,使得合成润滑油的市场需求与日俱增。中国科学院上海有机所申请的专 利ZL201110126431.9、ZL201210098399.2、WO2012155764、CN201410555078.X、 WO2016058559提供了一类新型高支化聚乙烯油ETL的制备技术,相较于PAO, ETL的乙烯利用率(>95%)大幅提高,同时工艺简单稳定且环保,极具性价比 优势。若基于ETL开发全合成真空泵油,则可解决当前全合成泵油价格昂贵的 问题、实现高端泵油的推广应用。
发明内容
本发明的目的在于提供一种抗氧化性能和防锈性能极佳的全合成真空泵 油组合物。
本发明的第一方面,提供了一种全合成真空泵油组合物,所述组合物包括: 抗氧剂0.5~2.0重量份、防锈剂0.05~1.0重量份、破乳剂0~1.0重量份、腐蚀抑制 剂0.05-0.2重量份、抗泡剂0.001~0.01重量份、余量为基础油(以总重量份为100 计);
其中,所述基础油为液态聚乙烯ETL基础油、市售全合成基础油,或其组 合。
在另一优选例中,所述的组合物包括:抗氧剂0.8~1.6重量份、防锈剂0.2~0.6重量份、破乳剂0.2~0.8重量份、腐蚀抑制剂0.05-0.1重量份、抗泡剂0.002~0.005 重量份、余量为基础油(以总重量份为100计)。
在另一优选例中,所述的组合物包括:抗氧剂0.8~1.4重量份、防锈剂0.3~0.4重量份、破乳剂0.2~0.8重量份、腐蚀抑制剂0.08~0.1重量份、抗泡剂0.002~0.003 重量份、余量为基础油(以总重量份为100计)。
在另一优选例中,所述的液态聚乙烯ETL基础油选自下组:ETL8、ETL10、 ETL20、ETL30、ETL40,或其组合。
在另一优选例中,所述的抗氧剂选自下组:硫磷丁辛伯烷基锌盐、硫磷双 辛伯烷基锌盐、二烷基二硫代磷酸锌盐、二烷基二硫代磷酸胺、辛基丁基二苯 胺、二壬基二苯胺、亚甲基双(二丁基二硫代氨基甲酸酯)衍生物、双十二碳 醇酯、2,6-二叔丁基对甲酚,3,5-二叔丁基-4-羟基苯丙酸异辛基酯,液态高分子 量酚酯型抗氧剂,或其组合。
在另一优选例中,所述的抗氧剂选自下组:二烷基二硫代磷酸胺、亚甲基 双(二丁基二硫代氨基甲酸酯)衍生物、液态高分子量酚酯型抗氧剂、辛基丁 基二苯胺、3,5-二叔丁基-4-羟基苯丙酸异辛基酯、二烷基二硫代磷酸锌盐,或 其组合。
在另一优选例中,所述的防锈剂选自下组:十二烯基丁二酸、烯基丁二酸 单酯及其衍生物、二壬基萘磺酸钙/羧酸钙、中性二壬基萘磺酸钡、4,5-二羟基 -1H-咪唑脂肪酸衍生物、液态烯基琥珀酸半酯,或其组合。
在另一优选例中,所述的防锈剂选自下组:烯基丁二酸单酯及其衍生物、 4,5-二羟基-1H-咪唑脂肪酸衍生物、二壬基萘磺酸钙/羧酸钙,或其组合。
在另一优选例中,所述的市售全合成基础油选自下组:季戊四醇酯、聚α -烯烃PAO、聚异丁烯、烷基萘、己二酸酯、壬二酸酯、癸二酸酯、三羟甲基辛 烷酯、油溶性聚醚OSP,或其组合。
在另一优选例中,所述的市售全合成基础油选自下组:季戊四醇酯、油溶 性聚醚OSP,或其组合。
在另一优选例中,所述的液态聚乙烯ETL基础油在基础油中的质量占比大 于85%,较佳地,大于90%,更佳地,大于95%。
在另一优选例中,所述的液态聚乙烯ETL基础油的数均分子量为400~1000 g/mol。
在另一优选例中,所述的液态聚乙烯ETL基础油在40℃的运动粘度为 40~500mm2/s,在100℃的运动粘度为8~50mm2/s,粘度指数为130~170,倾点 为不高于-35℃,开口闪点不低于230℃。
在另一优选例中,所述的破乳剂选自下组:胺与环氧化合物缩合物、聚醚 类高分子化合物,或其组合。
在另一优选例中,所述的腐蚀抑制剂选自下组:苯三唑衍生物、噻二唑衍 生物、杂环衍生物、甲基苯三唑衍生物,或其组合。
在另一优选例中,所述的抗泡剂选自下组:二甲基硅油、非硅抗泡剂、1 号复合抗泡剂、2号复合抗泡剂,或其组合。
在另一优选例中,所述的抗泡剂选自下组:甲基硅酯聚合物、聚环氧乙烷 -环氧丙烷、1号复合抗泡剂、2号复合抗泡剂,或其组合。
在另一优选例中,所述的组合物用以下方法制备:
(a)将所述的液态聚乙烯ETL基础油和市售全合成基础油按照配比加入调 和釜中,加热搅拌,恒温50~70℃;
(b)将所述添加组分按照配比加入调和釜中,恒温50~70℃条件下继续 搅拌30~150min;过滤,得到所述的真空泵油组合物。
在另一优选例中,在步骤(a)中,搅拌时间为30~120min。
在另一优选例中,在步骤(b)中,搅拌时间为60~150min。
在另一优选例中,所述的组合物用于真空设备中。
本发明的第二方面,提供了一种润滑油,所述的润滑油包括本发明第一方 面所述的真空泵油组合物。
应理解,在本发明范围内中,本发明的上述各技术特征和在下文(如实施例) 中具体描述的各技术特征之间都可以互相组合,从而构成新的或优选的技术方 案。限于篇幅,在此不再一一累述。
附图说明
图1为本发明实施例2与参比油在行车试验中的真空度监测结果。
图2为本发明实施例2与参比油在行车试验中的泵温监测结果。
图3为本发明实施例2与参比油在行车试验前后的对比图。
图4为本发明实施例2与参比油各性能参数对比数据。
具体实施方式
本发明人经过广泛而深入的研究,意外的开发了一种全合成真空泵油组合 物及其应用。所述的全合成真空泵油组合物不仅具有极佳的氧化安定性、防锈 性能和油水分离性能性能,还具有较低的蒸发损失、优异的润滑性能、高低温 流动性能和抗泡沫特性,完全满足优等真空泵油的产品要求。基于以上发现, 发明人完成了本发明。
术语
除非另外定义,否则本文中所用的全部技术与科学术语均具有如本发明所 属领域的普通技术人员通常理解的相同含义。
如本文所用,术语“全合成真空泵油组合物”与“组合物”可互换使用。
如本文所用,术语“包括”、“包含”和“含有”可相互替换,不仅包括 封闭式定义,还包括半封闭、和开放式的定义。换言之,所述术语包括了“由…… 构成”、“基本上由……构成”。
液态聚乙烯ETL基础油
所述液态聚乙烯ETL基础油为中国科学院上海有机化学研究所所属ZL201110126431.9、ZL201210098399.2、WO2012155764、CN201410555078.X、 WO2016058559专利方法制备的一类高支化聚乙烯。该类聚乙烯外观为无色透 明油状物,其数均分子量为400~1000g/mol;分子量分布PDI为1.2~1.8;核磁表 征的支化度branches/1000C为100~180,支化形式为甲基支链30~60%、C4+支链 25~45%、叔丁基支链5~20%。
在一个优选的实施方式中,所述的液态聚乙烯ETL基础油40℃的运动粘度 为40~500mm2/s,100℃的运动粘度为8~50mm2/s,粘度指数为130~170,倾点 为不高于-35℃,开口闪点不低于230℃。
在一个优选的实施方式中,所述的液态聚乙烯ETL基础油在20℃的相对密 度为0.82~0.84g/cm3。
本发明所用牌号ETL基础油的典型理化指标见表1:
表1
全合成真空泵油产品
本发明提供一种全合成真空泵油产品,所述的全合成真空泵油产品包括本 发明所述的全合成真空泵油产品和使用说明书;所述使用说明书记载所述全合 成真空泵油产品的使用方法。
特别地,为了使得到的真空泵油产品具有更好的性能,在本发明中,针对 ETL基础油的性能进行了配方优化,主要包括:优化了抗氧剂和防锈剂的组分和 配比。
为了提高本发明组合物的换油周期,添加了抗氧剂,抗氧剂的组分优选在 0.5~2.0重量份,低于该含量,真空泵油的氧化安定性有所下降;高于该含量, 真空泵油的氧化安定性有所下降。
为了提高本发明组合物的防锈性能,添加了防锈剂,防锈剂的组分优选在 0.05~1.0重量份,低于该含量,真空泵油的防锈性能有所下降;高于该含量, 真空泵油的防锈性能无显著提升,且氧化安定性也有所下降。
本发明的主要优点包括:
(a)本发明提供的真空泵油组合物中液态聚乙烯ETL基础油是基于国内资 源和自主研发技术由乙烯直接高效聚合而来,具有原料来源广泛、合成成本低 廉且工艺简单等优点。
(b)ETL基础油的分子结构和形状大小较为均一,具有内摩擦力低、油膜 强度高、粘度指数高等优异的润滑油特性,可保证机械设备在苛刻条件下长时 间运作,从而提高生产效率。
(c)ETL基础油具有较高的支化度,具有一定的分散性和极高的添加剂配 伍性,应用于油品配方中可降低增溶油的比例,从而实现产品降本的目的。
(d)本发明提供的一种液态聚乙烯真空泵油组合物不仅具有极佳极佳的 氧化安定性、防锈性能和油水分离性能性能,还具有较低的蒸发损失、优异的 润滑性能、高低温流动性能和抗泡沫特性,完全满足优等真空泵油的产品要求。
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说 明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方 法,通常按照常规条件,或按照制造厂商所建议的条件。除非另外说明,否则 百分比和份数按重量计算。
实施例1
抗氧剂为0.3重量份的二烷基二硫代磷酸胺、0.3重量份亚甲基双(二丁基 二硫代氨基甲酸酯)衍生物、0.2重量份的液态高分子量酚酯型抗氧剂,防锈剂 剂为0.3重量份的烯基丁二酸单酯及其衍生物、0.1重量份的4,5-二羟基-1H-咪唑 脂肪酸衍生物,腐蚀抑制剂为0.1重量份的甲基苯三唑衍生物、抗泡剂为0.001 重量份的甲基硅酯聚合物、0.002重量份的聚环氧乙烷-环氧丙烷,基础油为 33.507重量份的ETL8、62.23重量份的ETL40和2.96重量份的季戊四醇酯。本实 施例中液态聚乙烯ETL8和ETL40基础油的基本理化数据参见表1。
将所述基础油ETL8、ETL40和季戊四醇酯按照重量份数加入调和釜中,恒 温70℃加热搅拌;将所述添加组分按照上述配比加入调和釜中,恒温70℃下 继续加热搅拌90min;过滤,即可制得清亮透明的全合成真空泵油,相关性质 的测试数据参见表2。
由表2的数据可知,实施例1所提供的全合成真空泵油具有优异的粘温和低 温性能,兼具良好的抗乳化、抗腐防锈、抗氧化、抗泡以及润滑等特性,各项 关键性能指标远超行业标准SH/T 0528中规范的优等品质量指标。
表2
实施例2
抗氧剂为0.6重量份的辛基丁基二苯胺、0.6重量份3,5-二叔丁基-4-羟基苯丙 酸异辛基酯、0.2重量份的二烷基二硫代磷酸锌盐,防锈剂剂为0.4重量份的二 壬基萘磺酸钙/羧酸钙,腐蚀抑制剂为0.1重量份的甲基苯三唑衍生物、破乳剂 为0.2重量份的胺与环氧化合物缩合物,抗泡剂为0.002重量份的2号复合抗泡剂, 基础油为93.00重量份的ETL10和4.898重量份的油溶性聚醚。本实施例中液态聚 乙烯ETL10基础油的基本理化数据参见表1。
将所述基础油ETL10和油溶性聚醚按照重量份数加入调和釜中,恒温70℃ 加热搅拌;将所述添加组分按照上述配比加入调和釜中,恒温50℃下继续加 热搅拌90min;过滤,即可制得清亮透明的全合成真空泵油,以爱德华原装泵 油作为参比油,其相关性质的对比测试数据参见表3。
表3
对比表3中的数据可知,实施例2所提供的全合成真空泵油,具有更优的粘 温和低温性能、抗乳化、抗腐防锈、抗氧化、抗泡以及润滑等综合性能。将实 施例2所得的真空泵油与爱德华原装泵油进行应用对比实验,其真空度和泵温 监测结果分别如图1和图2所示。经5000h行车试验后,爱德华原装泵油出现了 明显的浑浊现象,如图3所示,而实施例2所提供的真空泵油则保持澄清、维持 较好的粘温、抗腐、润滑特性以及抗氧化性能,如图4,且具有较低水平的酸 值和水分(表4),预示其更长的换油周期。
表4
本发明实施例对以特定分子量和支化度的液态聚乙烯ETL基础油制备的全 合成真空泵油进行润滑油的综合评定,各项理化指标均可达使用要。采用液态 聚乙烯ETL基础油调配的真空泵油能满足优等真空泵油的使用要求,可用于极 端工况下成套大型真空装置,如微电子真空、真空镀膜、真空脱气、真空冶炼、 精密科学仪器等机械真空泵的润滑。
在本发明提及的所有文献都在本申请中引用作为参考,就如同每一篇文献 被单独引用作为参考那样。此外应理解,在阅读了本发明的上述讲授内容之后, 本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申 请所附权利要求书所限定的范围。
Claims (10)
1.一种全合成真空泵油组合物,其特征在于,所述组合物包括:抗氧剂0.5~2.0重量份、防锈剂0.05~1.0重量份、破乳剂0~1.0重量份、腐蚀抑制剂0.05-0.2重量份、抗泡剂0.001~0.01重量份、余量为基础油(以总重量份为100计);
其中,所述基础油为液态聚乙烯ETL基础油、市售全合成基础油,或其组合。
2.如权利要求1所述的组合物,其特征在于,所述的抗氧剂选自下组:硫磷丁辛伯烷基锌盐、硫磷双辛伯烷基锌盐、二烷基二硫代磷酸锌盐、二烷基二硫代磷酸胺、辛基丁基二苯胺、二壬基二苯胺、亚甲基双(二丁基二硫代氨基甲酸酯)衍生物、双十二碳醇酯、2,6-二叔丁基对甲酚,3,5-二叔丁基-4-羟基苯丙酸异辛基酯,液态高分子量酚酯型抗氧剂,或其组合。
3.如权利要求1所述的组合物,其特征在于,所述的防锈剂选自下组:十二烯基丁二酸、烯基丁二酸单酯及其衍生物、二壬基萘磺酸钙/羧酸钙、中性二壬基萘磺酸钡、4,5-二羟基-1H-咪唑脂肪酸衍生物、液态烯基琥珀酸半酯,或其组合。
4.如权利要求1所述的组合物,其特征在于,所述的市售全合成基础油选自下组:季戊四醇酯、聚α-烯烃PAO、聚异丁烯、烷基萘、己二酸酯、壬二酸酯、癸二酸酯、三羟甲基辛烷酯、油溶性聚醚OSP,或其组合。
5.如权利要求1所述的组合物,其特征在于,所述的液态聚乙烯ETL基础油的数均分子量为400~1000g/mol。
6.如权利要求1所述的组合物,其特征在于,所述的液态聚乙烯ETL基础油在40℃的运动粘度为40~500mm2/s,在100℃的运动粘度为8~50mm2/s,粘度指数为130~170,倾点为不高于-35℃,开口闪点不低于230℃。
7.如权利要求1所述的组合物,其特征在于,所述的破乳剂选自下组:胺与环氧化合物缩合物、聚醚类高分子化合物,或其组合。
8.如权利要求1所述的组合物,其特征在于,所述的腐蚀抑制剂选自下组:苯三唑衍生物、噻二唑衍生物、杂环衍生物、甲基苯三唑衍生物,或其组合。
9.如权利要求1所述的组合物,其特征在于,所述的抗泡剂选自下组:二甲基硅油、非硅抗泡剂、1号复合抗泡剂、2号复合抗泡剂,或其组合。
10.一种润滑油,其特征在于,所述的润滑油包括权利要求1所述的真空泵油组合物。
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