CN106147959A - 一种润滑剂组合物及其制备方法和应用 - Google Patents
一种润滑剂组合物及其制备方法和应用 Download PDFInfo
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- CN106147959A CN106147959A CN201510189203.4A CN201510189203A CN106147959A CN 106147959 A CN106147959 A CN 106147959A CN 201510189203 A CN201510189203 A CN 201510189203A CN 106147959 A CN106147959 A CN 106147959A
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- rubber
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- lubricant compositions
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- oil
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/02—Natural products
- C10M159/10—Rubber
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/02—Petroleum fractions
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及润滑剂领域,具体提供了一种润滑剂组合物及其制备方法和应用。所述润滑剂组合物含有基础油和分散在所述基础油中的通过辐照交联方法制备的具有交联结构的橡胶粒子,所述基础油为连续相,所述橡胶粒子为分散相。本发明提供的润滑剂组合物能够随着温度的变化有效地调节粘度,与含有通过化学交联的橡胶粒子的润滑剂组合物相比,其在低温下粘度更低,而在高温下粘度更高,并且其粘度指数较大,能够满足温度达到200℃以上场合的使用要求。此外,本发明提供的润滑剂组合物还具有优异的抗磨减摩性能。
Description
技术领域
本发明涉及一种润滑剂组合物、所述润滑剂组合物的制备方法、由该方法制备得到的润滑剂组合物以及所述润滑剂组合物作为润滑油或润滑脂的应用。
背景技术
纳米材料是指由尺寸小于100纳米的超细微粒组成的固体材料。由于它具有尺寸效应、量子效应、表面效应和界面效应,从而具有传统材料所不具备的性能。随着纳米材料的兴起和制备方法的日益成熟,人们发现纳米材料具有极好的摩擦性能。采用纳米粒子作为润滑油添加剂可使润滑油既具有流体润滑的优点,又具有固体润滑的优点,它不仅可以在摩擦表面形成一层易剪切的薄膜,而且可以对摩擦表面进行一定程度的填充和修复,起到良好的润滑作用。
现有技术中已经有大量关于无机纳米粒子在润滑油领域中的应用的报道。例如,CN1150958A公开了一种低密度耐高温耐磨自润滑纳米微粒填充增强高分子复合材料,其由热塑性耐高温聚合物和纳米微粒组成,所述纳米微粒包括纳米氮化硅、纳米碳化硅和纳米二氧化硅,该产品具有优良的自润滑性能。CN1301319C公开了一种含有纳米二氧化硅微粒的润滑油组合物,该润滑油组合物是一种性能优良的润滑油极压、抗磨组合物,该技术方案采用以基础油和纳米二氧化硅以及添加分散助剂与增效剂的方式实现了纳米二氧化硅微粒的分散。CN1180079A和CN1354056A分别公开了经脂肪酸修饰金属氧化物或氢氧化物的纳米微粉以及经含硫代磷有机化合物修饰的金属铜纳米颗粒在润滑油领域的应用。CN1827753A公开了一种含氟稀土纳米润滑油添加剂及其制备方法,该添加剂包括基础油以及含氮有机物表面包覆的氟化稀土纳米粒子。CN101058760A公开了一种纳米陶瓷润滑油及其制备方法,其含有常规润滑油的成分,并且在常规润滑油基础上添加了改性纳米陶瓷颗粒,其属于机械运行用润滑油介质的制备领域,特别适用于汽车行业所使用的润滑油及其制备方法。在该发明中,通过预分散方法成功制得稳定分散的纳米陶瓷颗粒的浓缩液,进而制备出纳米陶瓷颗粒重量百分含量为0.00001%-5%的纳米陶瓷机油。CN101235337B公开了一种适用于汽车内燃机或动力传动设备的滑动部分或滑动构件以显著降低摩擦系数的润滑剂组合物,该润滑剂组合物含有润滑油用基础油、含氧有机化合物、金刚石纳米颗粒和金刚石纳米颗粒用分散剂。CN101555430A公开了一种润滑油组合物,其含有基础油料和纳米碳球,所述纳米碳球表面接枝有烷基,使其分散于基础油料中,所述纳米碳球为中空结构或填充有金属、金属合金、金属氧化物、金属碳化物、金属硫化物、金属氮化物或金属硼化物。
此外,除了无机纳米粒子之外,也有一些关于有机微粒凝胶在润滑剂领域中的应用的报道。例如,莱茵化学莱茵瑙有限公司申请的专利CN1856527A、CN1840622A和CN1861673A公开了一种在不可交联的有机介质中的微粒凝胶以及交联的微粒凝胶用于改性非可交联的有机介质的温度依赖性能的用途。然而,这几篇专利申请无一例外地指出,所述微粒凝胶均是采用化学交联的方式(例如,通过与多官能化合物共聚交联或者通过过氧化物交联)制备得到的微粒凝胶,而不是用高能辐射交联的微粒凝胶。上述专利申请认为高能辐射交联的微粒凝胶实际上不能以工业规模制备,放射性钴源的高能辐射的使用伴有严重的安全问题,并且将辐射交联的微粒凝胶用于塑料基质中时,在基质和分散相之间可以发生撕裂效应,从而损害了含有该微粒凝胶的塑料的机械性能、溶胀性能、应力腐蚀开裂性能等。然而,莱茵化学莱茵瑙有限公司申请的专利CN1856527A、CN1840622A和CN1861673A中公开的润滑剂组合物的粘温性能较差,该润滑剂组合物的粘度随着温度的降低会急剧增大,而随着温度的升高会急剧减小,但是在低温下粘度过大或者在高温下粘度过小均不利用润滑剂组合物的应用,这将在很大程度上限制了该润滑剂组合物的应用。因此,亟需开发一种具有较好的粘温性能的润滑剂组合物。
发明内容
本发明的目的是为了克服现有的润滑剂组合物粘温性能较差的缺陷,而提供一种具有优良粘温性能的润滑油组合物、一种润滑剂组合物的制备方法、由该方法制备得到的润滑剂组合物以及所述润滑剂组合物作为润滑油或润滑脂的应用。
本发明的发明人经过深入研究后发现,莱茵化学莱茵瑙有限公司申请的上述几篇专利CN1856527A、CN1840622A和CN1861673A公开的润滑剂组合物中的分散相为采用多官能化合物或过氧化物通过化学交联方式得到的微粒凝胶,虽然含有该凝胶微粒的润滑剂组合物能够在一定程度上降低有机介质的摩擦系数,但是这些润滑剂组合物的粘度受温度的影响较大,温度太高(粘度太小)或太低(粘度太大)均会限制该润滑剂组合物的使用,适用温度范围较窄。而通过辐照交联方法制备的具有交联结构的橡胶粒子与通过采用多官能化合物或过氧化物进行化学交联制备的具有交联结构的橡胶粒子具有完全不同的微观结构。当润滑剂组合物中的分散相为通过辐照交联方法制备的具有交联结构的橡胶粒子时,对应的润滑剂组合物具有良好的粘温性能,能够非常好地随着温度的变化而调节粘度,降低低温粘度并提高高温粘度,因此,可以在很大程度上弥补由于温度的变化对粘度造成的影响。此外,高能辐射实际上是非常清洁、安全和高效的能源,目前已被很多发达国家广泛地用于医疗卫生、食品加工、工业生产等领域,反而是采用化学交联方法(过氧化物)存在一些不可忽视的问题,如生产效率不高、过氧化物残留以及可能引起的环境污染等,这些都会限制其应用。基于此,完成了本发明。
具体地,本发明提供了一种润滑剂组合物,其中,所述润滑剂组合物含有基础油和分散在所述基础油中的通过辐照交联方法制备的具有交联结构的橡胶粒子,所述基础油为连续相,所述橡胶粒子为分散相。
本发明还提供了一种润滑剂组合物的制备方法,该方法包括将基础油和通过辐照交联方法制备的具有交联结构的待分散橡胶粒子进行混合并分散。
本发明还提供了由上述方法制备得到的润滑剂组合物。
此外,本发明还提供了所述润滑剂组合物作为润滑油或润滑脂的应用。
本发明提供的润滑剂组合物能够随着温度的变化有效地调节粘度,与含有通过化学交联的橡胶粒子的润滑剂组合物相比,其在低温下粘度更低,而在高温下粘度更高,并且其粘度指数较大,能够满足温度达到200℃以上场合的使用要求,因此,显著拓宽了该润滑剂组合物的使用温度范围。
本发明提供的润滑剂组合物可用于调配发动机油、齿轮油、液压油等其他高温工业油,能够用于润滑油、润滑脂等领域,尤其是应用于对粘温性能要求较高的领域如发动机油,适用于调节粘温性能较差的以双环芳烃、多环芳烃以及非烃类基础油为主要组分的润滑组合物的粘温性能,可以根据不同工作场所的需求,轻松调节出具有不同粘温性能的润滑剂。此外,本发明提供的润滑剂组合物还具有优异的抗磨减摩性能。
由于辐照交联使橡胶粒子所具有的特殊结构,本发明提供的润滑剂组合物的耐老化性能优异,不易变色,因此这种润滑剂组合物可以作为性能优异的润滑油或润滑脂使用,特别是应用于对润滑油体系或润滑脂体系的粘温性能、老化性能和摩擦性能要求较高的领域。
本发明的其他特征和优点将在随后的具体实施方式部分予以详细说明。
具体实施方式
以下对本发明的具体实施方式进行详细说明。应当理解的是,此处所描述的具体实施方式仅用于说明和解释本发明,并不用于限制本发明。
本发明提供的润滑剂组合物含有基础油和分散在所述基础油中的通过辐照交联方法制备的具有交联结构的橡胶粒子,所述基础油为连续相,所述橡胶粒子为分散相。其中,所述橡胶粒子在基础油中呈稳定分散状态。
本发明对所述润滑剂组合物中基础油和橡胶粒子的含量没有特别地限定,但为了使得两者起到更好的协同配合作用,并进而使得到的润滑剂组合物具有更好的粘温性能,优选地,相对于100重量份的所述基础油,所述橡胶粒子的含量为0.001-200重量份,更优选为0.1-100重量份,特别优选为0.5-50重量份。
根据本发明提供的润滑剂组合物,优选地,所述橡胶粒子的平均粒径为20-2000nm,更优选为50-1000nm,特别优选70-500nm。当将所述橡胶粒子的平均粒径控制在上述范围内时,能够更有效地调节润滑剂组合物的粘度,具有更好的低温泵送和流动性能,有利于机械设备的冷启动,而在高温下也有利于形成较厚的油膜,降低表面摩擦,即,可适应更宽的使用温度范围。
根据本发明提供的润滑剂组合物,优选地,所述橡胶粒子的凝胶含量为60重量%以上,更优选为75重量%以上,特别优选为80重量%以上。当将所述橡胶粒子的凝胶含量控制在上述范围内时,能够随着温度的变化更有效地调节润滑剂组合物的粘度,可适应更宽的使用温度范围。在本发明中,所述凝胶含量是本领域用于表征橡胶交联程度的一种常用参数,其按照CN1402752A中公开的方法测得。
本发明对所述橡胶粒子的种类没有特别地限定,例如,可以选自天然橡胶、丁苯橡胶、羧基丁苯橡胶、丁腈橡胶、羧基丁腈橡胶、聚丁二烯橡胶、硅橡胶、氯丁橡胶、丙烯酸酯橡胶、丁苯吡橡胶、异戊橡胶、丁基橡胶、聚硫橡胶、丙烯酸酯-丁二烯橡胶、聚氨酯橡胶、氟橡胶和乙烯-乙烯乙酸酯橡胶中的至少一种,优选选自丁苯橡胶、羧基丁苯橡胶、丁腈橡胶、羧基丁腈橡胶、丙烯酸酯类橡胶和乙烯-乙烯乙酸酯橡胶中的至少一种。
此外,本发明提供的橡胶粒子优选具有均相结构。在本发明中,所述“均相结构”是指在现有显微技术下观察,橡胶粒子内没有发现分层、分相等不均相的现象。
根据本发明提供的润滑剂组合物,所述辐照交联所用的高能射线源具体可以选自钴源、紫外、高能电子加速器中的至少一种,优选地,所述高能射线源的波长小于0.1μm,例如为钴源。此外,一般情况下,辐照的剂量应使得橡胶胶乳辐照交联后的橡胶粒子的凝胶含量达到60重量%以上,优选达到75重量%以上,更优选达到80重量%以上。具体地,辐照的剂量可以为0.1-30Mrad,优选为0.5-20Mrad。
本发明对所述基础油的种类没有特别地限制,可以为矿物基础油,也可以为合成基础油,还可以为以上两种基础油的混合物。
所述矿物基础油根据我国基础油分类标准QSHR 001-95进行划分包括:低粘度指数矿物基础油(粘度指数VI≤40)、中粘度指数矿物基础油(40<粘度指数VI≤90)、高粘度指数矿物基础油(90<粘度指数VI≤120)、很高粘度指数矿物基础油(120<粘度指数VI≤140)和超高粘度指数矿物基础油(粘度指数VI>140)五类基础油。而根据GB/T1995-1998国家标准“石油产品粘度指数计算法”所定义,粘度指数(VI)表示油品粘度随温度变化这个特征的一个约定量值。对于运动粘度相近的油品,粘度指数越高,表示油品粘度随温度变化越小。具体地,所述矿物基础油主要包括烷烃、环烷烃、芳烃、环烷芳烃与含氧、含氮、含硫有机化合物以及胶质、沥青质等非烃化合物,其中几乎没有烯烃。所述矿物基础油可以是由原油中高沸点、高相对分子质量的烃类和非烃类的混合物经过常压蒸馏/减压蒸馏、溶剂精制、脱蜡、脱沥青等工艺制得。从矿物基础油馏分来看,其烃类碳数分布一般为C20-C40,沸点范围约为300-550℃,相对分子质量为250-1000或更高。
所述合成基础油则通常是采用有机合成方法制备的、具有稳定化学结构和特殊性能的润滑油。所述合成基础油选自合成烃、烷基芳烃、合成酯、聚醚、卤代烃、聚硅氧烷和含氟油中的至少一种。上述每一种类的合成基础油可以为单一纯物质或由同系物组成的混合物。其中,所述合成烃选自乙烯低聚物、丙烯低聚物、聚丁烯、聚异丁烯、聚α-烯烃(PAO)、聚内烯烃以及上述合成烃的卤代产物中的至少一种。其中,所述聚α-烯烃不包括乙烯低聚物、丙烯低聚物和聚1-丁烯。所述烷基芳烃选自烷基苯、烷基萘以及含有杂原子(氧、硫、卤素等)的烷基芳烃中的至少一种。所述合成酯选自单酯、双酯、多元醇酯、聚合物酯、碳酸酯、磷酸酯、柠檬酸酯、硅酸酯以及烯烃-丙烯酸酯类共聚物中的至少一种。所述聚醚选自脂肪族聚醚、聚苯醚、聚多硫醚和全氟烃基聚醚中的至少一种。所述聚硅氧烷选自二聚硅氧烷、三聚硅氧烷、四聚硅氧烷、八聚硅氧烷和环聚四硅氧烷中的至少一种。
此外,本发明提供的润滑剂组合物还可以含有常用的添加剂。所述添加剂的种类包括但不限于:防老剂、抗磨剂、防滑剂、抗氧剂、抗泡剂、防锈剂、清净剂、分散剂、颜料、极压组合物、摩擦保护组合物、清净剂、偶联剂等中的至少一种。所述添加剂的用量可以为本领域的常规选择,对此本领域技术人员均能知悉,在此不作赘述。
本发明提供的润滑剂组合物的制备方法包括将基础油和通过辐照交联方法制备的具有交联结构的待分散橡胶粒子进行混合并分散。
本发明对所述基础油和待分散橡胶粒子的用量没有特别地限定,但为了使得两者起到更好的协同配合作用,并进而使得到的润滑剂组合物具有更好的粘温性能,优选地,相对于100重量份的所述基础油,所述待分散橡胶粒子的用量为0.001-200重量份,更优选为0.1-100重量份,特别优选为0.5-50重量份。
根据本发明提供的润滑剂组合物的制备方法,优选地,所述待分散橡胶粒子为由平均粒径为20-2000nm、更优选为50-1000nm、特别优选为70-500nm的橡胶粒子团聚而形成的橡胶粒子团。当将所述待分散橡胶粒子分散在基础油中之后,团聚的橡胶粒子能够得以很好地分散,从而以20-2000nm、优选以50-1000nm、更优选以70-500nm的平均粒径分布在基础油中。此外,所述待分散橡胶粒子的平均粒径优选为20-2000nm,更优选为50-1000nm,特别优选为70-500nm。
根据本发明提供的润滑剂组合物的制备方法,优选地,所述待分散橡胶粒子的凝胶含量为60重量%以上,更优选为75重量%以上,特别优选为80重量%以上。当将所述待分散橡胶粒子的凝胶含量控制在上述范围内时,能够随着温度的变化更有效地调节润滑剂组合物的粘度,可适应更宽的使用范温度围。
所述待分散橡胶粒子优选为均相结构。在本发明中,所述“均相结构”是指在现有显微技术下观察,待分散橡胶粒子内没有发现分层、分相等不均相的现象。
本发明提供的橡胶粒子是由橡胶乳液通过辐照交联制备并通过喷雾干燥法干燥得到。在所述待分散橡胶粒子的制备过程中,辐照交联所用的高能射线源具体可以选自钴源、紫外、高能电子加速器中的至少一种,优选地,所述高能射线源的波长小于0.1μm,例如为钴源。此外,一般情况下,辐照的剂量应使得橡胶胶乳辐照交联后的橡胶粒子的凝胶含量达到60重量%以上,优选达到75重量%以上,更优选达到80重量%以上。具体地,辐照的剂量可以为0.1-30Mrad,优选为0.5-20Mrad。
所述待分散橡胶粒子可以通过商购得到,也可以按照本领域技术公知的各种方法制备得到。例如,所述待分散橡胶粒子可以为按照本发明的申请人于2000年9月18日递交的国际专利申请WO01/40356(优先权日1999年12月3日)以及本发明的申请人于2001年6月15日递交的国际专利申请WO01/98395(优先权日2000年6月15日)所制备的全硫化粉末橡胶。此外,所述全硫化粉末橡胶的实例包括但不限于:全硫化粉末天然橡胶﹑全硫化粉末丁苯橡胶﹑全硫化粉末羧基丁苯橡胶、全硫化粉末丁腈橡胶、全硫化粉末羧基丁腈橡胶、全硫化粉末聚丁二烯橡胶、全硫化粉末硅橡胶、全硫化粉末氯丁橡胶、全硫化粉末丙烯酸酯橡胶、全硫化粉末丁苯吡橡胶、全硫化粉末异戊橡胶、全硫化粉末丁基橡胶、全硫化粉末聚硫橡胶、全硫化粉末丙烯酸酯-丁二烯橡胶、全硫化粉末聚氨酯橡胶、全硫化粉末氟橡胶、全硫化粉末乙烯-乙烯乙酸酯橡胶等中的至少一种,优选为全硫化粉末丁苯橡胶、全硫化粉末羧基丁苯橡胶、全硫化粉末丁腈橡胶、全硫化粉末羧基丁腈橡胶、全硫化粉末丙烯酸酯类橡胶、全硫化粉末乙烯-乙烯乙酸酯橡胶中的至少一种。所述全硫化粉末橡胶的凝胶含量优选为60重量%以上,更优选为75重量%以上,特别优选为80重量%以上。所述全硫化粉末橡胶的平均粒径优选为20-2000nm,更优选为50-1000nm,特别优选为70-500nm。此外,所述全硫化粉末橡胶中的每一个微粒都是均相的,即在现有显微技术的观察下微粒内没有发现分层、分相等不均相的现象。
此外,在所述待分散橡胶粒子的辐照交联制备过程中,可以不使用交联助剂,也可以使用交联助剂。所述交联助剂可以选自单官能团交联助剂、二官能团交联助剂、三官能团交联助剂、四官能团交联助剂和五官能团以上交联助剂中的任意一种。所述单官能团交联助剂的实例包括但不限于:(甲基)丙烯酸辛酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸缩水甘油酯中的至少一种;所述二官能团交联助剂的实例包括但不限于:1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、二乙烯基苯中的至少一种;所述三官能团交联助剂的实例包括但不限于:三羟甲基丙烷三(甲基)丙烯酸酯和/或季戊四醇三(甲基)丙烯酸酯;所述四官能团交联助剂的实例包括但不限于:季戊四醇四(甲基)丙烯酸酯和/或乙氧化季戊四醇四(甲基)丙烯酸酯;所述五官能团以上交联助剂的实例包括但不限于:二季戊四醇五(甲基)丙烯酸酯。在本文中,所述(甲基)丙烯酸酯是指丙烯酸酯或甲基丙烯酸酯。这些交联助剂可以以任意方式组合使用,只要它们在辐照下有助于交联即可。此外,所述交联助剂的加入量一般为胶乳中干胶重量的0.1-10重量%,优选为0.5-9重量%,更优选为0.7-7重量%。
此外,本发明提供的润滑剂组合物的制备方法还可以包括将添加剂与基础油和待分散橡胶粒子一同进行混合并分散。
所述基础油和添加剂的种类已经在上文中有所描述,在此不作赘述。
本发明对所述混合和再分散的方式没有特别地限定,只要能够使得所述待分散橡胶粒子有效分散在基础油中、从而得到以基础油作为连续相并且以橡胶粒子为分散相的润滑剂组合物即可。根据本发明的一种优选实施方式,所述混合并分散的方式包括:
(1)将所述待分散橡胶粒子加入所述基础油中并通过机械搅拌混合,使得所述待分散橡胶粒子分散或悬浮于所述基础油中,得到初步分散的组合物;
(2)将所述初步分散的组合物进行再分散,直至分散后的橡胶粒子的平均粒径达到20-2000nm的范围内、优选达到50-1000nm的范围内、更优选达到70-500nm的范围内。通过这种优选的混合并分散的方式能够使得橡胶粒子以原始粒径分散在基础油中,得到的润滑剂组合物的粘温性能更佳。
根据本发明的另一种优选实施方式,所述润滑剂组合物的制备方法还包括步骤(3),将步骤(2)得到的产物在不低于80℃的温度下、优选在不低于100℃的温度下放置至少1小时,优选放置至少2小时,更优选放置至少4小时,最优选放置4-10小时之后将得到的产物进行二次再分散,这样能够使得交联的橡胶粒子和基础油充分浸润并溶胀,并且橡胶粒子以更小的粒径分散在基础油中,从而获得粘温性能更好的润滑剂组合物。此外,步骤(3)中,将步骤(2)的产物在不低于80℃的温度下放置至少1小时期间,可以配合连续或间歇搅拌,以使搅拌物料受热更均匀。
步骤(1)中所述的机械搅拌混合可以在现有的各种机械混合设备中进行,例如,可以在高速搅拌机、捏合机等机械混合设备中进行。本发明对所述机械搅拌混合的条件也没有特别地限制,只要在使通过辐照交联方法制备的具有交联结构的待分散橡胶粒子和基础油的性能没有任何变化的前提下,使通过辐照交联方法制备的具有交联结构的待分散橡胶粒子分散或悬浮于基础油中即可,对此本领域技术人员均能知悉,在此不作赘述。
根据本发明提供的润滑剂组合物的制备方法,步骤(2)中所述的再分散以及步骤(3)中所述的二次再分散可以各自独立地在均化器、玻珠研磨机、三辊研磨机、单螺杆挤出机、多螺杆挤出机、捏合机、溶解器和超声波分散器中的至少一种混合设备中进行,优选在均化器、三辊研磨机和超声波分散器中进行,这三种优选的混合设备具有加工产量高、混合效果好、后续清洁比较简单的优点。最优选地,步骤(2)的再分散和步骤(3)中的二次再分散在均化器中进行。在分散过程中,根据不同的分散质量要求,需要将样品循环冷却,再反复通过混合设备进行多次分散,直至分散在基础油中的橡胶粒子的平均粒径达到20-2000nm范围内,优选达到50-1000nm范围内,更优选达到70-500nm范围内。此外,本发明对所述再分散和二次再分散的条件没有特别地限定,只要使得基础油和橡胶粒子在分散过程中性能不发生破坏,并使得橡胶粒子的粒径达到20-2000nm、优选达到50-1000nm、更优选达到70-500nm即可,对此本领域技术人员均能知悉,在此不作赘述。
此外,步骤(3)中所述的放置优选在现有的各种密闭加热设备中进行,具体可以在高温烘箱、真空高温烘箱、加热釜或类似密闭加热容器中进行,这样可以提高热处理效率,节约能源,同时也可以减少基础油和橡胶粒子与空气(氧气)的接触,降低热氧化程度,使产品性能保持稳定。
本发明还提供了由上述方法制备得到的润滑剂组合物。
此外,本发明还提供了所述润滑剂组合物作为润滑油或润滑脂的应用。通常来说,所述润滑油是指以橡胶粒子的含量小于10重量%的润滑剂组合物。而润滑脂是指橡胶粒子的含量为10重量%以上的润滑剂组合物。
以下将通过实施例对本发明进行详细描述。
(一)实施例及对比例中所用的原料如下:
矿物基础油,中国石化生产,牌号为Ib150,40℃时的粘度为32.6mm2/s,粘度指数为90。
合成基础油,中国石化生产,牌号为PAO40,聚α-烯烃,40℃时的粘度为40.0mm2/s,粘度指数为110。
待分散丁苯橡胶粒子,中国石化生产,牌号为VP101,平均粒径为100nm,凝胶含量为90重量%,在显微镜下观察,该待分散丁苯橡胶粒子内没有发现分层、分相现象,其由丁苯橡胶乳液采用钴源进行辐照交联方法制备并通过喷雾干燥方法得到。
过氧化物交联丁苯橡胶粒子按照专利CN1840622A公开的方法进行制备并采用喷雾干燥方法得到,橡胶乳液是丁苯橡胶乳液(与制备待分散丁苯橡胶粒子VP101所采用的橡胶乳液的组成相同),采用的交联剂为过氧化二异丙苯(DCP),最终获得的过氧化物交联丁苯橡胶粒子的平均粒径为100nm,凝胶含量均为90重量%。
待分散丙烯酸酯橡胶粒子,中国石化生产,牌号为VP301,平均粒径为100nm,凝胶含量为90重量%,在显微镜下观察,该待分散丙烯酸酯橡胶粒子内没有发现分层、分相现象,其由丙烯酸酯橡胶乳液采用钴源进行辐照交联方法制备并通过喷雾干燥法干燥得到。
过氧化物交联丙烯酸酯橡胶粒子按照专利CN1840622A公开的方法进行制备并采用喷雾干燥方法得到,橡胶乳液是丙烯酸酯橡胶乳液(与制备待分散丙烯酸酯橡胶粒子VP301所采用的橡胶乳液的组成相同),采用的交联剂为过氧化二异丙苯(DCP),最终获得的过氧化物交联丙烯酸酯橡胶粒子的平均粒径均为100nm,凝胶含量均为90重量%。
待分散丁腈橡胶粒子,中国石化生产,牌号为VP401,平均粒径为100nm,凝胶含量为90重量%,在显微镜下观察,该待分散丁腈橡胶粒子内没有发现分层、分相现象,其丁腈橡胶乳液采用钴源进行辐照交联方法制备并通过喷雾干燥方法得到。
过氧化物交联丁腈橡胶粒子按照专利CN1840622A公开的方法进行制备并采用喷雾干燥方法得到,橡胶乳液是丁腈橡胶乳液(与制备待分散丁腈橡胶粒子VP401所采用的橡胶乳液的组成相同),采用的交联剂为过氧化二异丙苯(DCP),最终获得的过氧化物交联丁腈橡胶粒子的平均粒径均为100nm,凝胶含量均为90重量%。
待分散乙烯-醋酸乙烯酯橡胶粒子,中国石化生产,牌号为VP801,由平均粒径为500nm的乙烯-醋酸乙烯酯橡胶粒子团聚而成,凝胶含量为90重量%,在显微镜下观察,该待分散乙烯-醋酸乙烯酯橡胶粒子内没有发现分层、分相现象,其由乙烯-醋酸乙烯橡胶乳液采用钴源进行辐照交联方法制备并通过喷雾干燥方法干燥得到。
过氧化物交联乙烯-醋酸乙烯酯橡胶粒子按照专利CN1840622A公开的方法进行制备并采用喷雾干燥方法得到,橡胶乳液是乙烯-醋酸乙烯橡乳液液(与制备待分散乙烯-醋酸乙烯酯橡胶粒子VP801所采用的橡胶乳液的组成相同),采用的交联剂为过氧化二异丙苯(DCP),最终获得的过氧化物交联乙烯-醋酸乙烯酯橡胶粒子的平均粒径为500nm,凝胶含量均为90重量%。
(二)实施例和对比例中的实验数据用以下仪器设备及测定方法测定:
(1)运动粘度:按照GB/T265-1998“石油产品运动粘度测定法和动力粘度计算法”标准提供的方法,采用标准玻璃毛细管法测定,分别测试40℃、100℃下的运动粘度;
(2)粘度指数(VI):按照GB/T1995-1998“石油产品粘度指数计算法”测定,包括A法、B法,当VI<100时,粘度指数采用A法计算得到:
具体地,VI=[(L-H)]/[(L-U)]×100
其中,L是与试样在100℃时的运动粘度相同,粘度指数为0的油品在40℃时的运动粘度,mm2/s;H是与试样在100℃时的运动粘度相同,粘度指数为100的油品在40℃时的运动粘度,mm2/s;U是试样在40℃时的运动粘度,mm2/s。
当VI≥100时,粘度指数采用B法计算得到:
具体地,VI={[(anti logN-1)/0.00715]}+100
其中,N=(logH-logU)/logY,U是试样在40℃时的运动粘度,mm2/s;Y是试样在100℃时的运动粘度,mm2/s;H是与试样100℃时的运动粘度相同,粘度指数为100的油品在40℃时的运动粘度,mm2/s;anti logN是指logN的反函数。
(3)变色指数(IC):按照HG/T3862-2006“塑料黄色指数试验方法”采用TCP2系列全自动测色色差计测试按照以下公式计算润滑剂组合物的黄色指数(YI):
YI=100(1.28X-1.06Z)/Y,其中X、Y、Z分别为标准C光源下测得的三刺激值。定义润滑剂组合物的变色指数(IC)为
IC=YI150/YI25
其中YI150是润滑剂在高温试验后(150℃保持4小时)的黄色指数,YI25是润滑剂在常温下(25℃)的黄色指数,IC值可以直观反映润滑剂组合物的耐高温和耐老化性能。
(4)动力粘度:采用NDJ-5S型数字旋转粘度计分别测试40℃和100℃下的润滑剂组合物的动力粘度,其中,采用油浴控温加热。
(5)分油量:按照SH/T 0324-92“润滑脂钢网分油测定法(静态法)”标准方法测试,具体地,将样品放置于100目铜网上,在100℃烘箱中静置24小时再取出测量分油量。
(6)摩擦系数:在电子拉力试验机上测试润滑剂组合物的界面摩擦性能,载荷为0.2kg,比较铝-钢(无润滑)和铝-钢(有润滑)的静摩擦系数μs和动摩擦系数μk,其中,无润滑表示铝-钢材料表面上未涂覆任何润滑剂组合物,有润滑表示铝-钢表面上已经涂覆了相应的润滑剂组合物。
实施例1
该实施例用于说明本发明提供的润滑剂组合物及其制备方法。
将100重量份矿物基础油Ib150和0.5重量份待分散丁苯橡胶粒子VP101混合并机械搅拌均匀,然后在高压均质机中均化循环四次,均质压力为100MPa,每循环一次都通过水浴冷却将物料的温度控制在不超过70℃,得到混合物料,其运动粘度和粘度指数见表1。
将上述混合物料在150℃高温烘箱中保持至少4小时,再通过高压均质机第二次均化循环四次,均化压力为100MPa,得到润滑剂组合物,其运动粘度和粘度指数以及高温试验前后的颜色变化分别见表1和表2。
对比例1
该对比例用于说明参比的润滑剂组合物及其制备方法。
按照实施例1的方法制备混合物料和润滑剂组合物,不同的是,将待分散丁苯橡胶粒子VP101用相同重量份的过氧化物交联丁苯橡胶粒子替代,得到参比混合物料和参比润滑剂组合物。其中,参比混合物料的运动粘度和粘度指数见表1。参比润滑剂组合物的运动粘度和粘度指数以及高温试验前后的颜色变化分别见表1和表2。
实施例2
该实施例用于说明本发明提供的润滑剂组合物及其制备方法。
将100重量份矿物基础油Ib150和1重量份待分散丁苯橡胶粒子VP101混合并机械搅拌均匀,然后在高压均质机中均化循环六次,均化压力为100MPa,每循环一次都通过水浴冷却将物料的温度控制在不超过70℃,得到混合物料,其运动粘度和粘度指数见表1。
将上述混合物料在150℃高温烘箱中保持至少4小时,再通过高压均质机第二次均化循环六次,均化压力为100MPa,得到润滑剂组合物,其运动粘度和粘度指数以及高温试验前后的颜色变化分别见表1和表2。
对比例2
该对比例用于说明参比的润滑剂组合物及其制备方法。
按照实施例2的方法制备混合物料和润滑剂组合物,不同的是,将待分散丁苯橡胶粒子VP101用相同重量份的过氧化物交联丁苯橡胶粒子替代,得到参比混合物料和参比润滑剂组合物。其中,参比混合物料的运动粘度和粘度指数见表1。参比润滑剂组合物的运动粘度和粘度指数以及高温试验前后的颜色变化分别见表1和表2。
实施例3
该实施例用于说明本发明提供的润滑剂组合物及其制备方法。
将100重量份矿物基础油Ib150和3重量份待分散丁苯橡胶粒子VP101混合并机械搅拌均匀,然后按照实施例2的方法进行高压均质,得到混合物料,其运动粘度和粘度指数见表1。
将上述混合物料在150℃高温烘箱中保持至少4小时,再通过高压均质机第二次均化循环六次,均化压力为100MPa,得到润滑剂组合物,其运动粘度和粘度指数以及高温试验前后的颜色变化分别见表1和表2。
对比例3
该对比例用于说明参比的润滑剂组合物及其制备方法。
按照实施例3的方法制备混合物料和润滑剂组合物,不同的是,将待分散丁苯橡胶粒子VP101用相同重量份的过氧化物交联丁苯橡胶粒子替代,得到参比混合物料和参比润滑剂组合物。其中,参比混合物料的运动粘度和粘度指数见表1。参比润滑剂组合物的运动粘度和粘度指数以及高温试验前后的颜色变化分别见表1和表2。
实施例4
该实施例用于说明本发明提供的润滑剂组合物及其制备方法。
将100重量份矿物基础油Ib150和5重量份待分散丁苯橡胶粒子VP101混合并机械搅拌均匀,然后在高压均质机中均化循环十次,均化压力为100MPa,每循环一次都通过水浴冷却将物料的温度控制在不超过70℃,得到混合物料,其运动粘度和粘度指数见表1。
将上述混合物料在150℃高温烘箱中保持至少4小时,再通过高压均质机第二次均化循环十次,均化压力为100MPa,得到润滑剂组合物,其运动粘度和粘度指数以及高温试验前后的颜色变化分别见表1和表2。
实施例5
该实施例用于说明本发明提供的润滑剂组合物及其制备方法。
将100重量份矿物基础油Ib150和0.5重量份待分散丙烯酸酯橡胶粒子VP301混合并机械搅拌均匀,然后在高压均质机中均化循环四次,均化压力为100MPa,每循环一次都通过水浴冷却将物料的温度控制在不超过70℃,得到混合物料,其运动粘度和粘度指数见表1。
将上述混合物料在150℃高温烘箱中保持4小时,再通过高压均质机第二次均化循环四次,均化压力为100MPa,得到润滑剂组合物,其运动粘度和粘度指数以及高温试验前后的颜色变化分别见表1和表2。
对比例4
该对比例用于说明参比的润滑剂组合物及其制备方法。
按照实施例5的方法制备混合物料和润滑剂组合物,不同的是,将待分散丙烯酸酯橡胶粒子VP301用相同重量份的过氧化物交联丙烯酸酯橡胶粒子替代,得到参比混合物料和参比润滑剂组合物。其中,参比混合物料的运动粘度和粘度指数见表1。参比润滑剂组合物的运动粘度和粘度指数以及高温试验前后的颜色变化分别见表1和表2。
实施例6
该实施例用于说明本发明提供的润滑剂组合物及其制备方法。
将100重量份矿物基础油Ib150和0.5重量份待分散丁腈橡胶粒子VP401混合并机械搅拌均匀,然后在高压均质机中均化循环四次,均质压力为100MPa,每循环一次都通过水浴冷却将物料的温度控制在不超过70℃,得到混合物料,其运动粘度和粘度指数见表1。
将上述混合物料在150℃高温烘箱中保持4小时,再通过高压均质机第二次均化循环四次,均化压力为100MPa,得到润滑剂组合物,其运动粘度和粘度指数以及高温试验前后的颜色变化分别见表1和表2。
对比例5
该对比例用于说明参比的润滑剂组合物及其制备方法。
按照实施例6的方法制备混合物料和润滑剂组合物,不同的是,将待分散丁腈橡胶粒子VP401用相同重量份的过氧化物交联丁腈橡胶粒子替代,得到参比混合物料和参比润滑剂组合物。其中,参比混合物料的运动粘度和粘度指数见表1。参比润滑剂组合物的运动粘度和粘度指数以及高温试验前后的颜色变化分别见表1和表2。
实施例7
该实施例用于说明本发明提供的润滑剂组合物及其制备方法。
将100重量份矿物基础油Ib150和0.5重量份待分散乙烯-醋酸乙烯酯橡胶粒子VP801混合并机械搅拌均匀,然后在高压均质机中均化循环四次,均化压力为100MPa,每循环一次都通过水浴冷却将物料的温度控制在不超过70℃,得到混合物料,其运动粘度和粘度指数见表1。
将上述混合物料在150℃高温烘箱中保持4小时,再通过高压均质机第二次均化循环四次,均化压力为100MPa,得到润滑剂组合物,其运动粘度和粘度指数以及高温试验前后的颜色变化分别见表1和表2。
对比例6
该对比例用于说明参比的润滑剂组合物及其制备方法。
按照实施例7的方法制备混合物料和润滑剂组合物,不同的是,将待分散乙烯-醋酸乙烯酯橡胶粒子VP801用相同重量份的过氧化物交联乙烯-醋酸乙烯酯橡胶粒子VP801替代,得到参比混合物料和参比润滑剂组合物。其中,参比混合物料的运动粘度和粘度指数见表1。参比润滑剂组合物的运动粘度和粘度指数以及高温试验前后的颜色变化分别见表1和表2。
表1 润滑剂组合物的运动粘度和粘度指数
表2 高温处理前后润滑剂组合物的外观变化
实施例 | 常温黄色指数YI25 | 高温黄色指数YI150 | 变色指数IC |
实施例1 | 5.1 | 37.2 | 7.3 |
对比例1 | 5.0 | 44.0 | 8.8 |
实施例2 | 7.0 | 50.5 | 7.2 |
对比例2 | 7.2 | 68.6 | 9.5 |
实施例3 | 7.4 | 44.7 | 6.0 |
对比例3 | 7.5 | 66.4 | 8.8 |
实施例4 | 7.2 | 46.9 | 6.5 |
实施例5 | 5.0 | 37.2 | 7.4 |
对比例4 | 5.5 | 46.9 | 8.5 |
实施例6 | 6.2 | 45.0 | 7.3 |
对比例5 | 7.0 | 66.9 | 9.6 |
实施例7 | 5.0 | 35.2 | 7.0 |
对比例6 | 5.1 | 40.0 | 7.8 |
从表1的结果可以看出,与含有通过过氧化物交联得到的橡胶粒子的润滑剂组合物相比,含有通过辐照交联方法得到的具有交联结构的橡胶粒子的润滑剂组合物在低温时(40℃)粘度更低,而在高温时(100℃)粘度更高,并且其粘度指数较大,因此,本发明提供的润滑剂组合物具有更好的粘温性能,并且具有更好的低温泵送和流动性能,有利于机械设备的冷启动,而在高温下也有利于形成较厚的油膜,降低表面摩擦,提高润滑效果,同时可适应更宽的温度使用范围,并且能够减小摩擦,节能效果更佳。
此外,从表2的结果可以看出,本发明的润滑剂组合物的耐老化性能优异,不易变色。
实施例8
该实施例用于说明本发明提供的润滑剂组合物及其制备方法。
将100重量份矿物基础油Ib150和10重量份待分散丁苯橡胶粒子VP101混合并机械搅拌均匀,然后在三辊研磨机中均化循环五次,均化时辊转速为280转/分钟,得到润滑剂组合物,其动力粘度、分油量及润滑性能见表3和表4。
实施例9
该实施例用于说明本发明提供的润滑剂组合物及其制备方法。
将100重量份矿物基础油Ib150和30重量份待分散丁苯橡胶粒子VP101混合并机械搅拌均匀,然后在三辊研磨机中均化循环五次,均化时辊转速为200转/分钟,得到润滑剂组合物,其动力粘度、分油量及润滑性能见表3和表4。
实施例10
该实施例用于说明本发明提供的润滑剂组合物及其制备方法。
将100重量份矿物基础油Ib150和50重量份待分散丁苯橡胶粒子VP101混合并机械搅拌均匀,然后在三辊研磨机中均化循环五次,均化时辊转速为200转/分钟,得到润滑剂组合物,其动力粘度、分油量及润滑性能见表3和表4。
实施例11
该实施例用于说明本发明提供的润滑剂组合物及其制备方法。
将100重量份矿物基础油Ib150和100重量份待分散丁苯橡胶粒子VP101混合并机械搅拌均匀,然后在高压均质机中均化循环五次,均化时辊转速为100转/分钟,得到润滑剂组合物,其动力粘度、分油量及润滑性能见表3和表4。
实施例12
该实施例用于说明本发明提供的润滑剂组合物及其制备方法。
将100重量份合成基础油PAO40和10重量份待分散丁苯橡胶粒子VP101混合并机械搅拌均匀,然后在高压均质机中均化循环五次,均化时辊转速为200转/分钟,得到润滑剂组合物,其动力粘度、分油量及润滑性能见表3和表4。
实施例13
该实施例用于说明本发明提供的润滑剂组合物及其制备方法。
将100重量份合成基础油PAO40和50重量份待分散丁苯橡胶粒子VP101混合并机械搅拌均匀,然后在高压均质机中均化循环五次,均化时辊转速为100转/分钟,得到润滑剂组合物,其动力粘度、分油量及润滑性能见表3和表4。
实施例14
该实施例用于说明本发明提供的润滑剂组合物及其制备方法。
将100重量份合成基础油PAO40和100重量份待分散丁苯橡胶粒子VP101混合并机械搅拌均匀,然后在高压均质机中均化循环五次,均化时辊转速为100转/分钟,得到润滑剂组合物,其动力粘度、分油量及润滑性能见表3和表4。
表3 润滑剂组合物的动力粘度和分油量
实施例 | 动力粘度(40℃),mPa.s | 动力粘度(100℃),mPa.s | 分油量,% |
实施例8 | 345 | 880 | >20 |
实施例9 | 1480 | 13340 | 5.0 |
实施例10 | 5920 | 80200 | 4.8 |
实施例11 | 25500 | - | 0 |
实施例12 | 860 | 2800 | >10 |
实施例13 | 6950 | 95600 | 5.2 |
实施例14 | 35600 | - | 0.5 |
表3中,“-”表示超出测试量程(105mPa.s)
表4 润滑剂组合物的润滑性能
从表3的结果可以看出,含有通过辐照交联方法得到的具有交联结构的橡胶粒子的润滑剂组合物在低温时(40℃)粘度更低,而在高温时(100℃)粘度更高,因此,本发明提供的润滑剂组合物具有更好的粘温性能,应用温度范围宽。
此外,从表4的结果可以看出,本发明提供的润滑剂组合物的抗磨减摩性能非常优异。
以上详细描述了本发明的优选实施方式,但是,本发明并不限于上述实施方式中的具体细节,在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,这些简单变型均属于本发明的保护范围。
另外需要说明的是,在上述具体实施方式中所描述的各个具体技术特征,在不矛盾的情况下,可以通过任何合适的方式进行组合。为了避免不必要的重复,本发明对各种可能的组合方式不再另行说明。
此外,本发明的各种不同的实施方式之间也可以进行任意组合,只要其不违背本发明的思想,其同样应当视为本发明所公开的内容。
Claims (19)
1.一种润滑剂组合物,其特征在于,所述润滑剂组合物含有基础油和分散在所述基础油中的通过辐照交联方法制备的具有交联结构的橡胶粒子,所述基础油为连续相,所述橡胶粒子为分散相。
2.根据权利要求1所述的润滑剂组合物,其中,相对于100重量份的所述基础油,所述橡胶粒子的含量为0.001-200重量份,优选为0.1-100重量份,更优选为0.5-50重量份。
3.根据权利要求1或2所述的润滑剂组合物,其中,所述橡胶粒子的平均粒径为20-2000nm,优选为50-1000nm,更优选为70-500nm。
4.根据权利要求1或2所述的润滑剂组合物,其中,所述橡胶粒子的凝胶含量为60重量%以上,优选为75重量%以上,更优选为80重量%以上。
5.根据权利要求1或2所述的润滑剂组合物,其中,所述橡胶粒子具有均相结构。
6.根据权利要求1或2所述的润滑剂组合物,其中,所述橡胶粒子选自天然橡胶、丁苯橡胶、羧基丁苯橡胶、丁腈橡胶、羧基丁腈橡胶、聚丁二烯橡胶、硅橡胶、氯丁橡胶、丙烯酸酯橡胶、丁苯吡橡胶、异戊橡胶、丁基橡胶、聚硫橡胶、丙烯酸酯-丁二烯橡胶、聚氨酯橡胶、氟橡胶和乙烯-乙酸乙烯酯橡胶中的至少一种,优选选自丁苯橡胶、羧基丁苯橡胶、丁腈橡胶、羧基丁腈橡胶、丙烯酸酯类橡胶和乙烯-乙酸乙烯酯橡胶中的至少一种。
7.根据权利要求1或2所述的润滑剂组合物,其中,所述基础油为矿物基础油和/或合成基础油;
优选地,所述矿物基础油选自粘度指数VI≤40的低粘度指数矿物基础油、40<粘度指数VI≤90的中粘度指数矿物基础油、90<粘度指数VI≤120的高粘度指数矿物基础油、120<粘度指数VI≤140的很高粘度指数矿物基础油、粘度指数VI>140的超高粘度指数矿物基础油中的至少一种;
优选地,所述合成基础油选自合成烃、烷基芳烃、合成酯、聚醚、卤代烃、聚硅氧烷和含氟油中的至少一种;优选地,所述合成烃选自乙烯低聚物、丙烯低聚物、聚丁烯、聚异丁烯、聚α-烯烃、聚内烯烃以及上述合成烃的卤代产物中的至少一种;优选地,所述烷基芳烃选自烷基苯、烷基萘以及含有杂原子的烷基芳烃中的至少一种;优选地,所述合成酯选自单酯、双酯、多元醇酯、聚合物酯、碳酸酯、磷酸酯、柠檬酸酯、硅酸酯以及烯烃-丙烯酸酯类共聚物中的至少一种;优选地,所述聚醚选自脂肪族聚醚、聚苯醚、聚多硫醚和全氟烃基聚醚中的至少一种;优选地,所述聚硅氧烷选自二聚硅氧烷、三聚硅氧烷、四聚硅氧烷、八聚硅氧烷和环聚四硅氧烷中的至少一种。
8.一种润滑剂组合物的制备方法,该方法包括将基础油和通过辐照交联方法制备的具有交联结构的待分散橡胶粒子进行混合并分散。
9.根据权利要求8所述的方法,其中,所述混合并分散的方式包括:
(1)将所述待分散橡胶粒子加入所述基础油中并通过机械搅拌混合,使得所述待分散橡胶粒子分散或悬浮于所述基础油中,得到初步分散的组合物;
(2)将所述初步分散的组合物进行再分散,直至分散后的橡胶粒子的平均粒径达到20-2000nm的范围内、优选达到50-1000nm的范围内、更优选达到70-500nm的范围内。
10.根据权利要求9所述的方法,其中,该方法还包括步骤(3),将步骤(2)得到的产物在不低于80℃的温度下,优选在不低于100℃的温度下放置至少1小时,优选放置至少2小时,更优选放置至少4小时,之后将得到的产物进行二次再分散。
11.根据权利要求10所述的方法,其中,步骤(2)所述的再分散和步骤(3)所述的二次再分散各自独立地在均化器、玻珠研磨机、三辊研磨机、单螺杆挤出机、多螺杆挤出机、捏合机、溶解器和超声波分散器中的至少一种混合设备中进行,优选在均化器、三辊研磨机和超声波分散器中的至少一种混合设备中进行,更优选在均化器中进行;优选地,步骤(3)所述的放置在密闭加热设备中进行。
12.根据权利要求8所述的方法,其中,相对于100重量份的所述基础油,所述待分散橡胶粒子的用量为0.001-200重量份,优选为0.1-100重量份,更优选为0.5-50重量份。
13.根据权利要求8-12中任意一项所述的方法,其中,所述待分散橡胶粒子为由平均粒径为20-2000nm、优选为50-1000nm、更优选为70-500nm的橡胶粒子团聚而形成的橡胶粒子团。
14.根据权利要求8-12中任意一项所述的方法,其中,所述待分散橡胶粒子的凝胶含量为60重量%以上,优选为75重量%以上,更优选为80重量%以上。
15.根据权利要求8-12中任意一项所述的方法,其中,所述待分散橡胶粒子具有均相结构。
16.根据权利要求8-12中任意一项所述的方法,其中,所述待分散橡胶粒子选自天然橡胶、丁苯橡胶、羧基丁苯橡胶、丁腈橡胶、羧基丁腈橡胶、聚丁二烯橡胶、硅橡胶、氯丁橡胶、丙烯酸酯橡胶、丁苯吡橡胶、异戊橡胶、丁基橡胶、聚硫橡胶、丙烯酸酯-丁二烯橡胶、聚氨酯橡胶、氟橡胶和乙烯-乙酸乙烯酯橡胶中的至少一种,优选选自丁苯橡胶、羧基丁苯橡胶、丁腈橡胶、羧基丁腈橡胶、丙烯酸酯类橡胶和乙烯-乙酸乙烯酯橡胶中的至少一种。
17.根据权利要求8-12中任意一项所述的方法,其中,所述基础油为矿物基础油和/或合成基础油;
优选地,所述矿物基础油选自粘度指数VI≤40的低粘度指数矿物基础油、40<粘度指数VI≤90的中粘度指数矿物基础油、90<粘度指数VI≤120的高粘度指数矿物基础油、120<粘度指数VI≤140的很高粘度指数矿物基础油、粘度指数VI>140的超高粘度指数矿物基础油中的至少一种;
优选地,所述合成基础油选自合成烃、烷基芳烃、合成酯、聚醚、卤代烃、聚硅氧烷和含氟油中的至少一种;优选地,所述合成烃选自乙烯低聚物、丙烯低聚物、聚丁烯、聚异丁烯、聚α-烯烃、聚内烯烃以及以上合成烃的卤代产物中的至少一种;优选地,所述烷基芳烃选自烷基苯、烷基萘以及含有杂原子的烷基芳烃中的至少一种;优选地,所述合成酯选自单酯、双酯、多元醇酯、聚合物酯、碳酸酯、磷酸酯、柠檬酸酯、硅酸酯以及烯烃-丙烯酸酯类共聚物中的至少一种;优选地,所述聚醚选自脂肪族聚醚、聚苯醚、聚多硫醚和全氟烃基聚醚中的至少一种;优选地,所述聚硅氧烷选自二聚硅氧烷、三聚硅氧烷、四聚硅氧烷、八聚硅氧烷和环聚四硅氧烷中的至少一种。
18.由权利要求8-17中任意一项所述的方法制备得到的润滑剂组合物。
19.权利要求1-7和18中任意一项所述的润滑剂组合物作为润滑油或润滑脂的应用。
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RU2684910C2 (ru) | 2019-04-16 |
JP6509158B2 (ja) | 2019-05-08 |
RU2016115186A3 (zh) | 2018-10-01 |
SG10201603101YA (en) | 2016-11-29 |
CA2927584A1 (en) | 2016-10-20 |
US9944883B2 (en) | 2018-04-17 |
MY194005A (en) | 2022-11-07 |
CA2927584C (en) | 2021-02-16 |
RU2016115186A (ru) | 2017-10-24 |
CN106147959B (zh) | 2019-08-20 |
EP3091065A1 (en) | 2016-11-09 |
JP2016204660A (ja) | 2016-12-08 |
BR102016008723A2 (pt) | 2016-10-25 |
US20160304803A1 (en) | 2016-10-20 |
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EP3091065B1 (en) | 2022-04-20 |
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