CN113388434B - Extreme pressure antiwear agent composition, extreme pressure antiwear agent and space lubricant - Google Patents
Extreme pressure antiwear agent composition, extreme pressure antiwear agent and space lubricant Download PDFInfo
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- 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
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- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
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Abstract
本发明提供一种极压抗磨剂组合物、极压抗磨剂以及应用该极压抗磨剂的空间润滑剂,其中该极压抗磨剂组合物包括环烷酸盐和稀释剂,其中稀释剂为多烷基环戊烷,多烷基环戊烷的通式如式I所示;其中,R1为C5~C24的正构或异构烷基,n为2~4的正整数;环烷酸盐通过环烷酸与金属盐反应制得,环烷酸的平均相对分子质量为170~300。本发明提供的极压抗磨剂在空间润滑剂基础油多烷基环戊烷中具有优良的溶解性和低温稳定性,具有优异的低挥发特性,可满足空间润滑剂的低挥发要求,具有良好的空间润滑应用前景。 The present invention provides an extreme pressure antiwear agent composition, an extreme pressure antiwear agent and a space lubricant using the extreme pressure antiwear agent, wherein the extreme pressure antiwear agent composition comprises a naphthenate and a diluent, wherein The diluent is polyalkylcyclopentane, and the general formula of polyalkylcyclopentane is shown in formula I; wherein, R 1 is a normal or isomeric alkyl group of C 5 to C 24 , and n is a group of 2 to 4 Positive integer; naphthenic acid salt is prepared by reacting naphthenic acid and metal salt, and the average relative molecular mass of naphthenic acid is 170-300. The extreme pressure antiwear agent provided by the invention has excellent solubility and low temperature stability in the space lubricant base oil polyalkylcyclopentane, has excellent low volatility characteristics, can meet the low volatility requirements of space lubricants, and has Good prospects for space lubrication applications.
Description
技术领域technical field
本发明涉及润滑剂领域,具体涉及一种极压抗磨剂组合物及其制备方法。The invention relates to the field of lubricants, in particular to an extreme pressure antiwear agent composition and a preparation method thereof.
背景技术Background technique
空间润滑剂主要用于空间装置运动部件的润滑,由于处于高真空度的太空环境下,需要具有优良的低挥发特性和润滑性能,保证润滑部件的长期稳定运行。多烷基环戊烷具有极低的挥发性和饱和蒸气压,良好的黏温性能和润滑性能,是一种理想的空间润滑剂基础油。环烷酸铅的挥发性小于磷酸酯型极压抗磨剂,同时在长期边界润滑条件下具有良好的极压抗磨性能,可用作空间润滑剂的极压抗磨剂,但要求具有优良的溶解性、低温稳定性和低挥发特性。Space lubricants are mainly used for the lubrication of moving parts of space devices. Due to the high vacuum space environment, they need to have excellent low volatility characteristics and lubricating properties to ensure long-term stable operation of lubricated parts. Polyalkylcyclopentane has extremely low volatility and saturated vapor pressure, good viscosity-temperature properties and lubricating properties, and is an ideal base oil for space lubricants. The volatility of lead naphthenate is less than that of phosphate ester type extreme pressure antiwear agent, and it has good extreme pressure antiwear performance under long-term boundary lubrication conditions. It can be used as extreme pressure antiwear agent for space lubricants, but it requires excellent good solubility, low temperature stability and low volatility.
环烷酸铅的合成方法已公开,主要包括复分解法、直接反应法、微波原位合成法等。复分解法制备环烷酸铅是用氢氧化钠溶液将环烷酸皂化,加入醋酸铅溶液进行复分解反应,加入溶剂油后处理得到环烷酸铅。1991年第4期《精细化工》发表的《直接法合成环烷酸铅的研究》披露了在羧酸及其衍生物催化下,环烷酸与氧化铅直接反应,以200#溶剂汽油为稀释剂制得环烷酸铅添加剂。2011年8月《化学物理学报》发表的《环烷酸铅和烷基水杨酸铅的微波原位合成及其摩擦学性能》披露了采用微波原位合成法合成环烷酸铅液体石蜡溶液。The synthesis method of lead naphthenate has been disclosed, mainly including metathesis method, direct reaction method, microwave in-situ synthesis method, etc. The preparation of lead naphthenate by metathesis method is to saponify naphthenic acid with sodium hydroxide solution, add lead acetate solution to carry out metathesis reaction, add solvent oil and then process to obtain lead naphthenate. The "Research on Direct Synthesis of Lead Naphthenate" published in the fourth issue of "Fine Chemical Industry" in 1991 disclosed that under the catalysis of carboxylic acid and its derivatives, naphthenic acid and lead oxide were directly reacted, and 200# solvent gasoline was used as the dilution. Preparation of lead naphthenate additives. In August 2011, "Microwave in-situ synthesis of lead naphthenate and lead alkyl salicylate and their tribological properties" published in "Acta Chemical Physics" disclosed the synthesis of lead naphthenate liquid paraffin solution by microwave in-situ synthesis. .
然而,目前用于常规润滑油脂的环烷酸铅由于对环烷酸原料未加选择,在多烷基环戊烷中的溶解性不佳,低温易析出,环烷酸未精制,且以矿物油、溶剂汽油为稀释剂,易挥发,无法达到空间润滑剂的要求。However, due to the lack of selection of naphthenic acid raw materials, lead naphthenate currently used in conventional lubricating greases has poor solubility in polyalkylcyclopentane, is easy to separate out at low temperature, and is not refined in naphthenic acid. Oil and solvent gasoline are diluents, which are volatile and cannot meet the requirements of space lubricants.
需注意的是,前述背景技术部分公开的信息仅用于加强对本发明的背景理解,因此它可以包括不构成对本领域普通技术人员已知的现有技术的信息。It should be noted that the information disclosed in the preceding Background section is only for enhancement of understanding of the background of the invention and therefore it may contain information that does not form the prior art that is already known to a person of ordinary skill in the art.
发明内容SUMMARY OF THE INVENTION
本发明的一个主要目的在于克服上述现有技术的至少一种缺陷,提供一种极压抗磨剂组合物,以及包含该极压抗磨剂组合物的极压抗磨剂和应用该极压抗磨剂的空间润滑剂,以解决现有极压抗磨剂在以多烷基环戊烷为基础油的空间润滑剂中溶解性差、稳定性低,难以满足空间润滑剂低挥发要求的问题。A main purpose of the present invention is to overcome at least one of the above-mentioned defects of the prior art, to provide an extreme pressure anti-wear agent composition, an extreme pressure anti-wear agent comprising the extreme pressure anti-wear agent composition, and application of the extreme pressure anti-wear agent composition The space lubricant of the antiwear agent is used to solve the problems of poor solubility and low stability of the existing extreme pressure antiwear agent in the space lubricant based on polyalkylcyclopentane, and it is difficult to meet the low volatility requirements of the space lubricant .
为了实现上述目的,本发明采用如下技术方案:In order to achieve the above object, the present invention adopts the following technical solutions:
本发明的第一个方面提供一种极压抗磨剂组合物,包括环烷酸盐和稀释剂,其中,稀释剂为多烷基环戊烷,多烷基环戊烷的通式如式I所示:A first aspect of the present invention provides an extreme pressure antiwear agent composition comprising naphthenate and a diluent, wherein the diluent is polyalkylcyclopentane, and the general formula of polyalkylcyclopentane is as follows: I show:
其中,R1为C5~C24的正构或异构烷基,n为2~4的正整数;wherein, R 1 is a normal or isomeric alkyl group of C 5 -C 24 , and n is a positive integer of 2-4;
环烷酸盐通过环烷酸与金属盐反应制得,环烷酸的平均相对分子质量为170~300。The naphthenic acid salt is prepared by reacting naphthenic acid with a metal salt, and the average relative molecular mass of the naphthenic acid is 170-300.
根据本发明的一个实施方式,环烷酸盐与稀释剂的比例为100:(10~100)。According to one embodiment of the present invention, the ratio of naphthenate to diluent is 100:(10-100).
根据本发明的一个实施方式,所述环烷酸为在真空度1torr~3torr下,经减压蒸馏后馏出温度为130℃~145℃馏分段的环烷酸。According to an embodiment of the present invention, the naphthenic acid is a segmented naphthenic acid with a distillation temperature of 130° C. to 145° C. after vacuum distillation under a vacuum degree of 1 torr to 3 torr.
根据本发明的一个实施方式,环烷酸为脱除中性油的精制环烷酸。According to one embodiment of the present invention, the naphthenic acid is a neutral oil-removed refined naphthenic acid.
根据本发明的一个实施方式,环烷酸为馏出温度为130℃~145℃馏分段的环烷酸。According to one embodiment of the present invention, the naphthenic acid is a fractionated naphthenic acid with a distillation temperature of 130°C to 145°C.
根据本发明的一个实施方式,R1为C10~C24的正构或异构烷基,n为2~3。According to one embodiment of the present invention, R 1 is a C 10 -C 24 n- or iso-alkyl group, and n is 2-3.
根据本发明的一个实施方式,环烷酸盐为环烷酸铅。According to one embodiment of the present invention, the naphthenate is lead naphthenate.
根据本发明的一个实施方式,极压抗磨剂组合物中金属含量为20wt%~40wt%。According to an embodiment of the present invention, the metal content in the extreme pressure antiwear agent composition is 20wt% to 40wt%.
本发明的第二个方面提供一种极压抗磨剂,包含上述极压抗磨剂组合物。A second aspect of the present invention provides an extreme pressure antiwear agent comprising the above extreme pressure antiwear agent composition.
本发明的第三个方面提供一种空间润滑剂,包括基础油和上述极压抗磨剂,其中所述基础油为所述多烷基环戊烷。A third aspect of the present invention provides a space lubricant, comprising a base oil and the above extreme pressure antiwear agent, wherein the base oil is the polyalkylcyclopentane.
根据本发明的一个实施方式,基础油与极压抗磨剂的质量比为100:(1~15)。According to an embodiment of the present invention, the mass ratio of the base oil to the extreme pressure antiwear agent is 100:(1-15).
由上述技术方案可知,本发明的有益效果在于:As can be seen from the above technical solutions, the beneficial effects of the present invention are:
本发明提出的极压抗磨剂组合物,通过选用特定分子量范围的环烷酸作为原料,并对其进行精制处理,使所得环烷酸盐在多烷基环戊烷稀释剂中具有良好的溶解性,同时具有优异的低温稳定性和低挥发性;此外,通过采用多烷基环戊烷作为稀释剂,替代原有的矿物油或溶剂汽油等,可进一步降低极压抗磨剂的挥发性。所制得的极压抗磨剂适用于空间润滑剂,具有良好的工业应用前景。The extreme pressure anti-wear agent composition proposed by the present invention, by selecting naphthenic acid with a specific molecular weight range as a raw material, and subjecting it to refining treatment, so that the obtained naphthenate salt has good properties in the polyalkylcyclopentane diluent. Solubility, excellent low temperature stability and low volatility; in addition, by using polyalkylcyclopentane as a diluent to replace the original mineral oil or solvent gasoline, etc., the volatilization of extreme pressure antiwear agents can be further reduced sex. The prepared extreme pressure antiwear agent is suitable for space lubricants and has good industrial application prospects.
具体实施方式Detailed ways
以下内容提供了不同的实施例或范例,以令本领域技术人员参照说明书文字能够据以实施。当然,这些仅仅是范例,而非意图限制本发明。在本发明中所披露的范围的端点和任何值都不限于该精确的范围或值,这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说,各个范围的端点值之间、各个范围的端点值和单独的点值之间,以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围,这些数值范围应当被视为在本文中具体公开。The following contents provide different embodiments or examples, so that those skilled in the art can implement according to the description text. Of course, these are merely examples and are not intended to limit the invention. The endpoints of ranges and any values disclosed herein are not limited to the precise ranges or values, which are to be understood to encompass values proximate to those ranges or values. For ranges of values, the endpoints of each range, the endpoints of each range and the individual point values, and the individual point values can be combined with each other to yield one or more new ranges of values that Ranges should be considered as specifically disclosed herein.
本发明的第一个方面提供一种极压抗磨剂组合物,包括环烷酸盐和稀释剂,其中,稀释剂为多烷基环戊烷,多烷基环戊烷的通式如式I所示:A first aspect of the present invention provides an extreme pressure antiwear agent composition comprising naphthenate and a diluent, wherein the diluent is polyalkylcyclopentane, and the general formula of polyalkylcyclopentane is as follows: I show:
其中,R1为C5~C24的正构或异构烷基,n为2~4的正整数;wherein, R 1 is a normal or isomeric alkyl group of C 5 -C 24 , and n is a positive integer of 2-4;
环烷酸盐通过环烷酸与金属盐反应制得,环烷酸的平均相对分子质量为170~300。其中,所述“平均相对分子质量”是采用SH/T 0583方法测定的。The naphthenic acid salt is prepared by reacting naphthenic acid with a metal salt, and the average relative molecular mass of the naphthenic acid is 170-300. Wherein, the "average relative molecular mass" is measured by SH/T 0583 method.
本领域技术人员可知,环烷酸又称石油酸,是原油加工过程中分离得到的复杂羧酸混合物,包括环戊基、环己基羧酸等,分子量一般为120至700,其主体部分是有9~20碳原子的环烷基有机羧酸。本发明的发明人发现,通过对环烷酸减压蒸馏切割特定馏分段,经过精制后所得的特定分子量范围的环烷酸所获得的环烷酸盐用作极压抗磨剂,在多烷基环戊烷中具有优良的溶解性和低温稳定性。具体地,本发明选用的环烷酸的平均相对分子质量为170~300,优选为180~280,例如,180,220,250,280等。其中,环烷酸包含至少一个五元环或六元环,其上连接有直链或支链烷基,并包含羧基。可选地,例如,该环烷酸包括但不限于含五元环和/或六元环的单环和多环有机羧酸的混合物,较简单的结构有甲基环戊烷、甲基环己酸等。Those skilled in the art know that naphthenic acid, also known as petroleum acid, is a complex mixture of carboxylic acids separated during crude oil processing, including cyclopentyl, cyclohexyl carboxylic acid, etc. The molecular weight is generally 120 to 700, and its main part is Cycloalkyl organic carboxylic acids of 9 to 20 carbon atoms. The inventors of the present invention have found that the naphthenate salt obtained by cutting a specific fraction of naphthenic acid under reduced pressure distillation and refining the naphthenic acid with a specific molecular weight range is used as an extreme pressure antiwear agent. It has excellent solubility and low temperature stability in cyclopentane. Specifically, the average relative molecular mass of the selected naphthenic acid in the present invention is 170-300, preferably 180-280, for example, 180, 220, 250, 280 and the like. Wherein, the naphthenic acid contains at least one five-membered ring or six-membered ring, on which is connected a straight-chain or branched-chain alkyl group, and contains a carboxyl group. Optionally, for example, the naphthenic acid includes, but is not limited to, a mixture of monocyclic and polycyclic organic carboxylic acids containing five-membered and/or six-membered rings, the simpler structures are methylcyclopentane, methyl ring Caproic acid etc.
在一些实施例中,前述的特定馏分段的环烷酸为在真空度1torr~3torr下,经减压蒸馏后馏出温度为130℃~145℃馏分段的环烷酸,例如130℃、132℃、135℃、141℃、145℃等。In some embodiments, the above-mentioned naphthenic acid of the specific distillation section is the naphthenic acid of the distillation section with a distillation temperature of 130 ° C to 145 ° C under vacuum degree of 1 torr to 3 torr, such as 130 ° C, 132 ° C, and 132 ° C after vacuum distillation. °C, 135 °C, 141 °C, 145 °C, etc.
此外,根据本发明,多烷基环戊烷具有极低的挥发性和饱和蒸气压,良好的黏温性能和润滑性能,是一种理想的空间润滑剂基础油。环烷酸盐,尤其是环烷酸铅,其挥发性小,但作为极压抗磨剂仍需要求具有优良的溶解性、低温稳定性和低挥发特性。本发明的发明人发现,通过以多烷基环戊烷作为稀释剂,替代原有的矿物油或溶剂汽油等,可以降低极压抗磨剂的挥发性,并进一步与以多烷基环戊烷作为基础油的空间润滑剂具有良好的相容性。In addition, according to the present invention, polyalkylcyclopentane has extremely low volatility and saturated vapor pressure, good viscosity-temperature properties and lubricating properties, and is an ideal space lubricant base oil. Naphthenates, especially lead naphthenates, have low volatility, but they still need to have excellent solubility, low temperature stability and low volatility as extreme pressure antiwear agents. The inventors of the present invention have found that by using polyalkylcyclopentane as a diluent to replace the original mineral oil or solvent gasoline, etc., the volatility of extreme pressure antiwear agent can be reduced, and it can be further combined with polyalkylcyclopentane. Alkane as a base oil space lubricant has good compatibility.
在一些实施例中,还包括对前述的环烷酸进行精制处理,以脱除中性油,得到精制环烷酸。环烷酸中常混有中性油,中性油对所述极压抗磨剂低挥发性存在不利影响,须脱除方可用于合成环烷酸盐。对所述环烷酸脱除中性油,可用碱性溶液将环烷酸中和至碱性,采用石油醚反复萃取中性油,然后用强酸酸化碱液,经过洗涤、干燥、过滤、蒸馏等一系列操作,得到脱除中性油的精制环烷酸。通过对环烷酸进行精制,可大大降低抗磨剂组合物的挥发性,同时避免后续不必要的副反应发生,有利于提高所得极压抗磨剂组合物的性能。In some embodiments, it also includes refining the aforementioned naphthenic acid to remove neutral oil to obtain refined naphthenic acid. Neutral oil is often mixed with naphthenic acid, and the neutral oil has an adverse effect on the low volatility of the extreme pressure antiwear agent, and must be removed before it can be used to synthesize naphthenate. To remove the neutral oil from the naphthenic acid, the naphthenic acid can be neutralized to alkaline with an alkaline solution, the neutral oil is repeatedly extracted with petroleum ether, and then the lye is acidified with a strong acid, washed, dried, filtered and distilled. After a series of operations, the purified naphthenic acid from which neutral oil has been removed is obtained. By refining the naphthenic acid, the volatility of the antiwear agent composition can be greatly reduced, and at the same time, subsequent unnecessary side reactions can be avoided, which is beneficial to improve the performance of the obtained extreme pressure antiwear agent composition.
在一些实施例中,环烷酸盐与稀释剂的比例为100:(10~100),例如,100:20,100:35,100:50,100:55,100:60等。环烷酸盐的浓度过高黏度会很大,使用不便,也可能会出现析出现象,不宜稳定储存,优选地,前述比例为100:(20~60)。前述的金属盐一般可以为醋酸盐等,环烷酸盐优选为环烷酸铅。在一些实施例中,极压抗磨剂组合物中金属含量为20wt%~40wt%,优选为25wt%~35wt%,例如25wt%,28wt%,30wt%,32wt%等。以醋酸铅为例,具体的极压抗磨剂组合物的制备过程主要如下:In some embodiments, the ratio of naphthenate to diluent is 100:(10-100), eg, 100:20, 100:35, 100:50, 100:55, 100:60, and the like. If the concentration of naphthenate is too high, the viscosity will be very large, which is inconvenient to use, and may also cause precipitation, which is not suitable for stable storage. Preferably, the aforementioned ratio is 100:(20-60). The aforementioned metal salt can generally be acetate or the like, and the naphthenate is preferably lead naphthenate. In some embodiments, the metal content in the extreme pressure antiwear agent composition is 20wt%-40wt%, preferably 25wt%-35wt%, such as 25wt%, 28wt%, 30wt%, 32wt%, etc. Taking lead acetate as an example, the preparation process of the specific extreme pressure antiwear agent composition is mainly as follows:
采用质量分数为10%~20%的氢氧化钠溶液将前述特定分子量的精制环烷酸完全皂化,反应温度为80℃~100℃,反应时间1h~3h,加入甲苯等有机溶剂使其充分溶解。在搅拌、有机溶剂回流条件下,加入质量分数为15%~20%的醋酸铅溶液反应生成环烷酸铅,反应时间1h~3h,醋酸铅略过量。反应结束后体系静置后弃去水层,热水洗涤有机层3次~6次。脱水后加入前述的多烷基环戊烷作为稀释剂,减压蒸馏即得到本发明的极压抗磨剂组合物,其呈现褐色粘稠液体。The above-mentioned purified naphthenic acid with a specific molecular weight is completely saponified by using sodium hydroxide solution with a mass fraction of 10% to 20%. The reaction temperature is 80 ° C ~ 100 ° C, the reaction time is 1 h ~ 3 h, and organic solvents such as toluene are added to make it fully dissolved. . Under the conditions of stirring and refluxing the organic solvent, lead acetate solution with a mass fraction of 15% to 20% is added to react to generate lead naphthenate. The reaction time is 1h to 3h, and the lead acetate is slightly excessive. After the reaction, the system was allowed to stand, the aqueous layer was discarded, and the organic layer was washed 3-6 times with hot water. After dehydration, the aforementioned polyalkylcyclopentane is added as a diluent, and the extreme pressure antiwear agent composition of the present invention is obtained by distillation under reduced pressure, which is a brown viscous liquid.
本发明还提供一种极压抗磨剂,包括前述的极压抗磨剂组合物。根据实际需要,还可向其中添加其他助剂,本发明不限于此。The present invention also provides an extreme pressure antiwear agent, comprising the aforementioned extreme pressure antiwear agent composition. According to actual needs, other auxiliary agents may also be added thereto, and the present invention is not limited thereto.
根据本发明,多烷基环戊烷具有很低的挥发性。通过前述处理后的环烷酸盐,可以与稀释剂多烷基环戊烷具有很好的相容性。可选地,前述R1为C10~C24的正构或异构烷基,n为2~3,也即多烷基环戊烷为含2个或3个正构或异构C10~C24烷基链的多烷基环戊烷。需要说明的是,本发明的多烷基环戊烷的制备方法可采用本领域常规方法制备获得或市售购得,本发明不限于此。According to the present invention, polyalkylcyclopentanes have very low volatility. The naphthenate after the aforementioned treatment can have good compatibility with the diluent polyalkylcyclopentane. Optionally, the aforementioned R 1 is a normal or isomeric alkyl group of C 10 to C 24 , and n is 2 to 3, that is, the polyalkylcyclopentane contains 2 or 3 normal or isomeric C 10 ~ C24 alkyl chain polyalkylcyclopentane. It should be noted that, the preparation method of the polyalkylcyclopentane of the present invention can be prepared by conventional methods in the art or commercially available, and the present invention is not limited thereto.
本发明还提供一种空间润滑剂,包括上述的极压抗磨剂以及基础油,其中该基础油为多烷基环戊烷。在一些实施例中,基础油与极压抗磨剂的质量比为100:(1~15),优选100:(3~10)。通过选用特定分子量的环烷酸原料,并对其进行精制处理,所得的环烷酸盐可以采用低挥发性的多烷基环戊烷作为稀释剂,使所得极压抗磨剂在空间润滑剂基础油多烷基环戊烷中具有优良的溶解性和低温稳定性,具有良好的低挥发特性,满足空间润滑剂的低挥发要求。The present invention also provides a space lubricant, comprising the above-mentioned extreme pressure antiwear agent and a base oil, wherein the base oil is polyalkylcyclopentane. In some embodiments, the mass ratio of the base oil to the extreme pressure antiwear agent is 100:(1-15), preferably 100:(3-10). By selecting the raw material of naphthenic acid with specific molecular weight and refining it, the obtained naphthenate can use low-volatility polyalkylcyclopentane as a diluent, so that the obtained extreme pressure antiwear agent can be used in space lubricants. The base oil polyalkylcyclopentane has excellent solubility and low temperature stability, and has good low volatility characteristics, meeting the low volatility requirements of space lubricants.
下面将通过实施例来进一步说明本发明,但是本发明并不因此而受到任何限制。The present invention will be further illustrated by the following examples, but the present invention is not limited thereby.
制备例1Preparation Example 1
本制备例用于说明以下实施例所用多烷基环戊烷的制备方法。This preparation example is used to illustrate the preparation method of polyalkylcyclopentane used in the following examples.
将正癸醇、固体氢氧化钾和双环戊二烯混合后加入装有搅拌器、分液漏斗、冷凝管、分水器、温度计的烧瓶中加热反应,当分水器不再有水生成时,停止反应,反应产物水洗、干燥、过滤后,得到多正癸基环戊二烯。将多正癸基环戊二烯与正庚烷配成稀释度10%的溶液,200g此溶液加入3.6g非晶态镍催化剂混合后放入高压反应釜,通入氢气直至氢压达到5MPa,在良好搅拌下加热至155℃,反应20h,反应产物冷却后过滤,得到多正癸基环戊烷。After mixing n-decanol, solid potassium hydroxide and dicyclopentadiene, add it into a flask equipped with a stirrer, a separatory funnel, a condenser, a water separator, and a thermometer for heating reaction. When the water separator no longer has water to generate, The reaction was stopped, and the reaction product was washed with water, dried and filtered to obtain poly-n-decylcyclopentadiene. Poly-n-decylcyclopentadiene and n-heptane are made into a solution with a dilution of 10%, 200g of this solution is added with 3.6g of amorphous nickel catalyst and mixed, put into an autoclave, and the hydrogen is fed until the hydrogen pressure reaches 5MPa, The mixture was heated to 155°C under good stirring, and reacted for 20 h. The reaction product was cooled and filtered to obtain poly-n-decylcyclopentane.
实施例1Example 1
以平均相对分子质量为203的环烷酸(对环烷酸减压蒸馏,真空度3torr,得到馏出温度为130℃~135℃馏分段)作为原料,脱除其中的中性油。之后加入质量分数为10%的氢氧化钠溶液完全皂化,皂化温度为85℃,皂化时间1h,随后加入甲苯使其充分溶解,搅拌、甲苯回流条件下加入质量分数为15%的醋酸铅溶液反应2h生成环烷酸铅。反应结束后弃去水层,80℃热水洗涤有机层4次,脱水后加入制备例1的多烷基环戊烷为稀释剂,稀释剂与环烷酸铅的质量比为20:100,减压蒸馏得到极压抗磨剂。Taking naphthenic acid with an average relative molecular mass of 203 (decompression distillation of naphthenic acid, vacuum degree of 3 torr, to obtain a distillation segment with a distillation temperature of 130 ° C ~ 135 ° C) as a raw material, the neutral oil therein is removed. Then add 10% sodium hydroxide solution for complete saponification, saponification temperature is 85 ℃, saponification time is 1h, then toluene is added to make it fully dissolved, and 15% lead acetate solution is added under the conditions of stirring and toluene reflux to react for 2h Generate lead naphthenate. After the reaction, the water layer was discarded, and the organic layer was washed with hot water at 80° C. 4 times. After dehydration, the polyalkylcyclopentane of Preparation Example 1 was added as a diluent, and the mass ratio of the diluent to lead naphthenate was 20:100. The extreme pressure antiwear agent is obtained by distillation under reduced pressure.
实施例2Example 2
以平均相对分子质量为203的环烷酸(对环烷酸减压蒸馏,真空度3torr,得到馏出温度为130℃~135℃馏分段)作为原料,脱除其中的中性油。之后加入质量分数为20%的氢氧化钠溶液完全皂化,皂化温度为90℃,皂化时间1.5h,随后加入甲苯使其充分溶解,搅拌、甲苯回流条件下加入质量分数为15%的醋酸铅溶液反应3h生成环烷酸铅。反应结束后弃去水层,80℃热水洗涤有机层6次,脱水后加入制备例1的多烷基环戊烷为稀释剂,稀释剂与环烷酸铅的质量比为50:100,减压蒸馏得到极压抗磨剂。Taking naphthenic acid with an average relative molecular mass of 203 (decompression distillation of naphthenic acid, vacuum degree of 3 torr, to obtain a distillation segment with a distillation temperature of 130 ° C ~ 135 ° C) as a raw material, the neutral oil therein is removed. Then add 20% sodium hydroxide solution for complete saponification, the saponification temperature is 90℃, the saponification time is 1.5h, then toluene is added to make it fully dissolved, and 15% lead acetate solution is added under the conditions of stirring and toluene reflux to react 3h generate lead naphthenate. After the reaction, the water layer was discarded, and the organic layer was washed with hot water at 80°C for 6 times. After dehydration, the polyalkylcyclopentane of Preparation Example 1 was added as a diluent, and the mass ratio of the diluent to lead naphthenate was 50:100. The extreme pressure antiwear agent is obtained by distillation under reduced pressure.
实施例3Example 3
以平均相对分子质量为262的环烷酸(对环烷酸减压蒸馏,真空度3torr,得到馏出温度为135℃~145℃馏分段)作为原料,采用冷冻过滤法对其进行精制处理,脱除其中的脂肪酸和中性油。之后加入质量分数为20%的氢氧化钠溶液完全皂化,皂化温度为90℃,皂化时间1.5h,随后加入甲苯使其充分溶解,搅拌、甲苯回流条件下加入质量分数为15%的醋酸铅溶液反应3h生成环烷酸铅。反应结束后弃去水层,80℃热水洗涤有机层6次,脱水后加入制备例1的多烷基环戊烷为稀释剂,稀释剂与环烷酸铅的质量比为50:100,减压蒸馏得到极压抗磨剂。Taking naphthenic acid with an average relative molecular mass of 262 (decompression distillation of naphthenic acid, vacuum degree of 3 torr, obtaining distillation temperature of 135 ℃~145 ℃ distillation section) as raw material, it is purified by freezing filtration method, Remove fatty acids and neutral oils from it. Then add 20% sodium hydroxide solution for complete saponification, the saponification temperature is 90℃, the saponification time is 1.5h, then toluene is added to make it fully dissolved, and 15% lead acetate solution is added under the conditions of stirring and toluene reflux to react 3h generate lead naphthenate. After the reaction, the water layer was discarded, and the organic layer was washed with hot water at 80°C for 6 times. After dehydration, the polyalkylcyclopentane of Preparation Example 1 was added as a diluent, and the mass ratio of the diluent to lead naphthenate was 50:100. The extreme pressure antiwear agent is obtained by distillation under reduced pressure.
对比例1Comparative Example 1
采用实施例3的方法制备极压抗磨剂,不同的是,以平均相对分子质量为346的环烷酸(对环烷酸减压蒸馏,真空度3torr,得到馏出温度为150℃~155℃馏分段)作为原料。The method of Example 3 was used to prepare the extreme pressure antiwear agent. The difference was that with naphthenic acid with an average relative molecular mass of 346 (p-naphthenic acid was distilled under reduced pressure, and the vacuum degree was 3 torr, the distillation temperature was 150° C. to 155° C.) °C fractionation) as the raw material.
对比例2Comparative Example 2
采用实施例3的方法制备极压抗磨剂,不同的是,稀释剂为150SN中性油,稀释剂比例不变。The method of Example 3 was used to prepare the extreme pressure antiwear agent, except that the diluent was 150SN neutral oil, and the proportion of the diluent was unchanged.
测试例1Test Example 1
对实施例1~3和对比例1和2的极压抗磨剂进行测试,测试方法和结果见表1。The extreme pressure antiwear agents of Examples 1 to 3 and Comparative Examples 1 and 2 were tested, and the test methods and results are shown in Table 1.
表1Table 1
从上表1可以看出,本发明的极压抗磨剂在多烷基环戊烷基础油中表现出了优异的性能,相比于非特定分子量的环烷酸原料或采用中性油作为稀释剂的极压抗磨剂,其都具有更好的溶解性、低温稳定性和低挥发性,适用于空间润滑剂。As can be seen from Table 1 above, the extreme pressure antiwear agent of the present invention exhibits excellent performance in polyalkylcyclopentane base oil, compared with the raw material of naphthenic acid of non-specific molecular weight or the use of neutral oil as Diluent extreme pressure antiwear agents, all of which have better solubility, low temperature stability and low volatility, suitable for space lubricants.
本领域技术人员应当注意的是,本发明所描述的实施方式仅仅是示范性的,可在本发明的范围内作出各种其他替换、改变和改进。因而,本发明不限于上述实施方式,而仅由权利要求限定。It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary, and various other substitutions, changes and improvements may be made within the scope of the present invention. Therefore, the present invention is not limited to the above-described embodiments, but only by the claims.
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