CN107011973B - 一种锂-复合钙基润滑脂及其制备方法 - Google Patents
一种锂-复合钙基润滑脂及其制备方法 Download PDFInfo
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Abstract
本发明提供一种锂复合钙基润滑脂的制备方法,包括:(1)在部分基础油中加入部分氢氧化钙水溶液,搅拌均匀;(2)加热升温至20℃~60℃时,加入小分子酸,进行反应;(3)继续升温至75~100℃,加入一元长链有机酸;(4)待一元长链有机酸完全溶解,加入剩余氢氧化钙和单水氢氧化锂的混合碱液进行皂化反应;(5)加热升温至180~250℃进行高温炼制,冷却,加入余量基础油,加入必要的添加剂,循环剪切均化、脱气、过滤后得成品。本发明提供的锂复合钙基润滑脂的制备方法,可以实现任意调配氢氧化钙和氢氧化锂的质量比,同时避免了小分子酸挥发、皂化反应不完全等问题。所得润滑脂产品具有更高的滴点、更好的机械安定性、抗水淋性,综合性能更稳定。
Description
技术领域
本发明属于润滑脂及其制备方法。
背景技术
复合钙基润滑脂是最早合成和使用的高温润滑脂,具有原料来源广泛、价格便宜、性能优良等特点,但在贮存和高温使用条件下存在表层硬化的问题。在复合钙基润滑脂中引入锂皂,制备锂-复合钙基润滑脂,可有效解决复合钙基润滑脂的硬化问题,同时改善复合钙基润滑脂的机械安定性。
CN 104449983A提出了一种锂复合钙基润滑脂的制备方法,其制备工艺中先加入12-羟基硬脂酸与氢氧化锂进行反应制得锂皂,再加入小分子酸、氢氧化钙与余量的12-羟基硬脂酸反应制得复合钙皂,经升温、冷却得到锂-复合钙基润滑脂。该制备工艺存在的问题为小分子酸挥发现象严重、皂化反应不能完全进行且所得润滑脂产品各项性能不稳定、综合性能较差。
发明内容
本发明的目的是克服现有技术存在的缺陷,提供一种锂-复合钙基润滑脂的制备方法。本发明制备方法解决了现有技术存在的各种问题,并且实现了任意调配润滑脂中氢氧化钙和氢氧化锂的质量比,所得润滑脂产品的各项性能均优于现有技术提供的润滑脂。
本发明提供的锂-复合钙基润滑脂的制备方法,包括:
(1)在部分基础油中加入部分氢氧化钙水溶液,搅拌均匀;
(2)加热升温至20℃~60℃时,加入小分子酸,进行反应;
(3)继续升温至75~100℃,加入一元长链有机酸;
(4)待一元长链有机酸完全溶解,加入剩余氢氧化钙和单水氢氧化锂的混合碱液进行皂化反应;
(5)加热升温至180~250℃进行高温炼制,冷却,加入余量基础油,加入必要的添加剂,循环剪切均化、脱气、过滤后得成品。
具体地说,步骤(1)中,所加入的基础油最好占全部基础油的1/2~2/3,所述的氢氧化钙占全部氢氧化钙的1/2~5/6。
氢氧化钙水溶液中水量是氢氧化钙重量的2~6倍,优选3~4倍。
步骤(2)中,所述小分子酸可以是分子量小于180的小分子有机酸或无机酸,例如甲酸、乙酸、丙酸、乙二酸、苯甲酸、对苯二甲酸、辛酸、磷酸、硼酸等,优选乙酸、硼酸、对苯二甲酸。
所述的小分子酸(有机酸或无机酸的酸根总和)与步骤(1)中所述氢氧化钙的理论摩尔比为2:1,氢氧化钙可以少量过量。
为了避免小分子酸的剧烈挥发,优选在30~60℃时加入小分子酸,反应时间为20min~90min。
步骤(3)中所述的一元长链有机酸可以是C12~C24的一元有机酸,优选12-羟基硬脂酸和硬脂酸中至少一种。所述一元长链有机酸与步骤(2)中所述小分子酸(有机酸或无机酸的酸根总和)的摩尔比为1:0.1~1:5,优选1:2~1:5。
步骤(4)中,混合碱液中水量是单水氢氧化锂和氢氧化钙总重量的2~15倍,优选6~10倍。单水氢氧化锂总重量与步骤(4)和步骤(1)中氢氧化钙总重量的比可选任意值,优选1:0.04~1:5。
为了便于反应快速进行,优选在80~110℃,最好是在85~100℃时加入混合碱液,进行皂化反应。皂化时间为20min~150min,优选30min~90min。
步骤(5)中恒温炼制温度为180~240℃,优选190~220℃,恒温时间为5min~30min。冷却到180~200℃加入剩余基础油,在110℃以下加入必要的添加剂。
本发明制备的润滑脂中,以润滑脂重量为基准,包括以下组分:
(1)基础油,含量65-95%,优选70-90%,更优选75-84%;
(2)锂-复合钙稠化剂,含量5-35%,优选9-30%,更优选12-25%;
(3)必要的添加剂,含量0~15%,优选0.5~5%。
其中锂-复合钙稠化剂由一元长链有机酸锂皂、一元长链有机酸钙皂和小分子酸钙盐组成。锂皂和复合钙皂的质量比可以是任意值,优选1:0.1~1:9,其中复合钙皂包括一元长链有机酸钙皂和小分子酸钙盐。
本发明提供的锂-复合钙基润滑脂的制备方法,将氢氧化钙分两步加入,可以确保氢氧化钙分别与小分子酸和一元长链有机酸充分反应,避免了因小分子酸挥发带来的操作困难、反应不完全以及反应原料浪费等问题,同时缩短了高温反应时间。所得润滑脂产品的各项性能均优于现有技术提供的润滑脂。更重要的是,本发明提供的制备方法可以实现任意调配润滑脂中氢氧化钙和单水氢氧化锂的质量比。
具体实施方式
以下的实施例将对本发明作进一步的说明,但并不因此限制本发明。
以下实施例中所述锂皂的质量是指一元长链有机酸锂皂的质量,所述复合钙皂的质量是指一元长链有机酸钙皂和小分子酸钙盐的总质量。
实施例1:
制备20kg润滑脂,稠化剂量12%,复合钙皂与锂皂质量比为1:9,氢氧化钙和单水氢氧化锂质量比为1:4.8。
原料组分:12-羟基硬脂酸(1.27kg);乙酸(0.11kg,含量≥99%);单水氢氧化锂(0.41kg);氢氧化钙(0.09kg);基础油大庆400(17.6kg,100℃运动粘度9.7mm2/s)。
在皂化反应釜中加入11kg矿物基础油大庆400以及用3倍水量溶解的0.06kg氢氧化钙水溶液,混合搅拌均匀,加热升温至38℃,加入0.11kg乙酸,反应30min后,升温至87℃,加入1.27kg12-羟基硬脂酸,待12-羟基硬脂酸完全溶解,加入用8倍水量溶解的0.03kg氢氧化钙和0.41kg单水氢氧化锂的混合碱液,在90℃条件下反应60min,然后升温至210℃恒温20min。加入剩余的6.6kg基础油大庆400进行冷却,待温度降至110℃,循环过滤、均化、脱气得到成品。产品性能如表1所示。
实施例2:
制备20kg润滑脂,稠化剂量20%,复合钙皂与锂皂质量比为3:7,氢氧化钙和单水氢氧化锂质量比为1:1.08。
原料组分:12-羟基硬脂酸(2.67kg);对苯二甲酸(0.54kg);单水氢氧化锂(0.39kg);氢氧化钙(0.36kg);大庆400(16kg,100℃运动粘度9.7mm2/s)。
按照实施例1的方法制备锂复合钙基润滑脂,所不同的是制备中使用的一种原料发生改动,所用的乙酸改为对苯二甲酸,稠化剂含量由12%改为20%,稠化剂中复合钙皂和锂皂的质量比由1:9改为3:7;并且制备工艺条件发生改动,氢氧化钙与小分子酸反应时间由30min改为60min。产品性能如表1所示。
实施例3:
制备20kg润滑脂,稠化剂量30%,复合钙皂与锂皂质量比为5:5,氢氧化钙和单水氢氧化锂质量比为1:0.46。
原料组分:硬脂酸(4.16kg);硼酸(1.34kg,含量≥99%);单水氢氧化锂(0.44kg);氢氧化钙(0.95kg);大庆400(14kg,100℃运动粘度9.7mm2/s)。
按照实施例1的方法制备锂复合钙基润滑脂,所不同的是制备中使用的两种原料发生改动,使用的12-羟基硬脂酸改为硬脂酸,使用的乙酸改为硼酸,稠化剂含量由12%改为30%,稠化剂中复合钙皂和锂皂的质量比由1:9改为5:5。
实施例4:
制备20kg润滑脂,稠化剂量23%,复合钙皂和锂皂的质量比为6:4,氢氧化钙和单水氢氧化锂质量比为1:0.36。
原料组分:12-羟基硬脂酸(1.17kg);乙二酸(0.63kg,含量≥99.6%);单水氢氧化锂(0.23kg);氢氧化钙(0.64kg);大庆400(15.4kg,100℃运动粘度9.7mm2/s)。
按照实施例1的方法制备锂复合钙基润滑脂,所不同的是制备中使用的一种反应原料发生改动,使用的乙酸改为乙二酸,稠化剂含量由12%改为23%,稠化剂中复合钙皂和锂皂的质量比由1:9改为6:4;并且制备工艺条件发生改动,最高炼制温度由210℃改为230℃,恒温炼制时间由20min改为10min。产品性能如表1所示。
实施例5:
制备20kg润滑脂,稠化剂量28%,复合钙皂和锂皂的质量比为9:1,氢氧化钙和单水氢氧化锂质量比为1:0.04。
原料组分:12-羟基硬脂酸(2.67kg);磷酸(2.12kg,含量≥98%);单水氢氧化锂(0.07kg);氢氧化钙(1.71kg);PAO6(14.4kg,100℃粘度为6mm2/s)。
按照实施例1的方法制备锂复合钙基润滑脂,所不同的是制备中使用的两种原料发生改动,使用的乙酸改为磷酸,基础油由大庆400改为合成油PAO6,稠化剂含量由12%改为28%,稠化剂中复合钙皂和锂皂的质量比由1:9改为9:1;并且制备工艺条件发生改动,先加入占基础油总重1/2的基础油,剩余基础油作为急冷油加入。产品性能如表1所示。
实施例6:
制备20kg润滑脂,稠化剂量25%,复合钙皂和锂皂的质量比为8:2,氢氧化钙和单水氢氧化锂质量比为1:0.11。
原料组分:12-羟基硬脂酸(2.63kg);丙酸(1.65kg,含量≥99.5%);单水氢氧化锂(0.15kg);氢氧化钙(1.34kg);150BS(15kg,100℃运动粘度31mm2/s)。
按照实施例1的方法制备锂复合钙基润滑脂,所不同的是制备过程中使用的两种反应原料发生改动,使用的乙酸改为丙酸,基础油由大庆400改为150BS,稠化剂含量由12%改为25%,稠化剂中复合钙皂和锂皂的质量比由1:9改为8:2;并且制备工艺条件发生改动,混合碱液皂化反应温度由90℃改为80℃,反应时间由60min改为90min。产品性能如表1所示。
实施例7:
制备20kg润滑脂,稠化剂量25%,复合钙皂和锂皂的质量比为7:3,氢氧化钙和单水氢氧化锂质量比为1:0.24。
原料组分:12-羟基硬脂酸(2.63kg);甲酸(1.44kg,含量>85%);单水氢氧化锂(0.28kg);氢氧化钙(1.17kg);500SN(15kg,100℃运动粘度11mm2/s)。
添加剂:T321(0.3kg);T704(0.1kg);V81(0.3kg);T202(0.4kg)。
按照实施例1的方法制备锂复合钙基润滑脂,所不同的是使用的两种原料发生改动,使用的乙酸改为甲酸,基础油由大庆400改为500SN,稠化剂含量由12%改为25%,稠化剂中复合钙皂和锂皂的质量比由1:9改为7:3。上述制备的润滑脂温度冷却到110℃后,分批加入添加剂并搅拌均匀,循环过滤、均化、脱气得到成品。产品性能如表1所示。
对比例1
对比例1中所述锂皂的质量是指12-羟基硬脂酸锂的质量,所述复合钙皂的质量是指12-羟基硬脂酸钙和小分子酸钙盐的总质量。
按照CN 104449983A公开的方法制备锂复合钙基润滑脂,所用原料与实施例1相同。
制备20kg润滑脂,稠化剂量25%,复合钙皂和锂皂的质量比为8:2,氢氧化钙和单水氢氧化锂质量比为1:0.11。
原料组分:12-羟基硬脂酸(2.63kg);乙酸(1.65kg,含量>99%);单水氢氧化锂(0.15kg);氢氧化钙(1.34kg);大庆400(100℃运动粘度9.7mm2/s,15kg)。
将10kg基础油加入反应釜中,加入2.63kg 12-羟基硬脂酸,加热到90℃,待12-羟基硬脂酸充分溶解后加入用8倍水量溶解的氢氧化锂,95℃恒温反应40min;反应完毕后加入1.34kg氢氧化钙,搅拌均匀后保持温度在110℃缓慢滴加1.65kg乙酸,滴加完毕后115℃反应60min,然后升温至210℃恒温30min。加入剩余的5kg基础油大庆400,待温度降至110℃,循环过滤、均化、脱气得到成品。产品性能如表1所示。
对比例2
制备20kg锂基润滑脂,稠化剂量8%,原料中不含癸二酸、小分子酸、氢氧化钙,其它原料与实施例1相同。
原料组分:12-羟基硬脂酸(1.56kg);单水氢氧化锂(0.23kg);大庆400(100℃运动粘度9.7mm2/s,18.4kg)。
在皂化反应釜中加入11kg矿物基础油大庆400、1.56kg12-羟基硬脂酸,待12-羟基硬脂酸完全溶解,加入用8倍碱量的水溶解的0.23kg单水氢氧化锂,在90℃条件下反应60min,然后升温至200℃恒温30min。加入剩余的7.4kg基础油;待温度降至110℃,循环过滤、均化、脱气得到成品。产品性能如表1所示。
对比例3
制备20kg复合钙基润滑脂,稠化剂量26%,原料中不含癸二酸、单水氢氧化锂,其它原料与实施例1相同。
原料组分:12-羟基硬脂酸(2.19kg);乙酸(2.18kg,浓度≥99.5%);氢氧化钙(1.75kg);大庆400(100℃运动粘度9.7mm2/s,14.8kg)。
在皂化反应釜中加入8.8kg矿物基础油大庆400以及用4倍水量溶解的1.75kg氢氧化钙,混合搅拌均匀,加热升温至30℃,加入2.18kg乙酸,反应30min,加热升温至87℃,加入2.19kg12-羟基硬脂酸,在90℃条件下反应90min,然后升温至200℃恒温30min。加入剩余的6kg基础油;待温度降至110℃,循环过滤、均化、脱气得到成品。产品性能如表1所示。
表1:各润滑脂样品性能数据
表1(续)
Claims (10)
1.一种锂-复合钙基润滑脂的制备方法,包括以下步骤:
(1)在部分基础油中加入部分氢氧化钙水溶液,搅拌均匀;
(2)加热升温至20℃~60℃时,加入小分子酸,进行反应;
(3)继续升温至75~100℃,加入一元长链有机酸;
(4)待一元长链有机酸完全溶解,加入剩余氢氧化钙和单水氢氧化锂的混合碱液进行皂化反应;
(5)加热升温至180~250℃进行高温炼制,冷却,加入余量基础油,加入必要的添加剂,循环剪切均化、脱气、过滤后得成品。
2.按照权利要求1所述的制备方法,其中,步骤(1)中,所加入的基础油占全部基础油的1/2~2/3,所述的氢氧化钙占全部氢氧化钙的1/2~5/6。
3.按照权利要求1所述的制备方法,其中,所述小分子酸是分子量小于180的小分子有机酸或无机酸。
4.按照权利要求1所述的制备方法,其中,所述小分子酸选自甲酸、乙酸、丙酸、乙二酸、苯甲酸、对苯二甲酸、辛酸、磷酸、硼酸中至少一种。
5.按照权利要求1所述的制备方法,其中,步骤(3)中所述的一元长链有机酸是C12~C24的一元有机酸。
6.按照权利要求1所述的制备方法,其中,所述一元长链有机酸是12-羟基硬脂酸和硬脂酸中至少一种。
7.按照权利要求1所述的制备方法,其中,所述一元长链有机酸与步骤(2)中所述小分子酸的摩尔比为1:0.1~1:5。
8.按照权利要求1所述的制备方法,其中,步骤(4)中单水氢氧化锂总重量与步骤(4)和步骤(1)中氢氧化钙总重量的比为1:0.04~1:5。
9.权利要求1-8之一所述方法制备的润滑脂,以润滑脂重量为基准,包括以下组分:
(1)基础油,含量65-95%;
(2)锂-复合钙稠化剂,含量5-35%;
(3)必要的添加剂,含量0~15%;
其中锂-复合钙稠化剂由一元长链有机酸锂皂、一元长链有机酸钙皂和小分子酸钙盐组成。
10.按照权利要求9所述的润滑脂,其中,锂皂和复合钙皂的质量比为1:0.1~1:9。
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