Low ash high base number environmentally friendly diesel engine oil antioxidant composition and use thereof

Abstract

The present application relates to diesel engine oil additive technical field, specifically relates to a kind of low ash high base value's environmental protection diesel engine oil additive composition and its application.The present application provides a kind of diesel engine oil additive composition, including mass ratio (2~8) :1:1 of dialkyldiphenylamine, phenolic ester compound and sulfenyl compound;The structural formula of dialkyldiphenylamine is wherein, R1 And R2 Same or different C1~C8 Alkyl;The molecular weight of the phenolic ester compound is 200~400.The present application is by optimizing antioxidant composition, not only significantly improve the antioxidation performance, more important is that can in the case where ash of oil product is not increased, significantly improve oil product initial total base number, significantly enhance the service life of oil product.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of diesel engine oil additive technology, in particular to a low-ash high-alkalinity environmentally friendly diesel engine oil antioxidant composition and application thereof. BACKGROUND

[0002] In recent years, in order to solve the increasingly prominent problem of air pollution, the vehicle pollutant emission standard has been upgraded for many times, especially more stringent requirements for particulate matter and nitrogen oxide emissions, and the aftertreatment technology of diesel engine has also been continuously developed. At present, with the innovation of engine technology and the gradual implementation of national six emission regulations, OEM manufacturers have upgraded their filling oils and after-sales oils, and require low-ash diesel engine oils with long oil change period.

[0003] At present, national six commercial vehicle engine oils all require API CJ-4 / CK-4 / FA-4 or ACEA E6 / E8 / E9 / E11 specification diesel engine oils with ash content not greater than 1.0% (mass fraction) to protect the vehicle aftertreatment device. The ash mainly comes from the detergent component providing alkalinity in the oil, and the limit value of ash and the increase of alkalinity are mutually restricted. Therefore, how to meet the low-ash limit value requirement of environmentally friendly oil while effectively improving the initial alkalinity and antioxidant performance of the product, and thus enhancing the durability of the oil and bringing a longer oil change period for commercial vehicles, has become a difficult problem to be solved.

[0004] In the prior art, CN 102690714 A discloses a railway high-speed diesel engine lubricating oil composition, but it only optimizes the antioxidant performance of the lubricating oil, and does not involve the contradiction between ash content and alkalinity, so it can be seen that there is still room for improvement in the current lubricating oil. SUMMARY

[0005] Diesel engines often need to be used under high load and high temperature conditions, and the oil will continuously produce acidic substances with oxidation. The initial alkalinity provided by the oil neutralizes these acidic substances, reducing the risk of acid corrosion of the engine. After the alkalinity decreases to a certain extent, the oil reaches the recommended oil change period, i.e. it needs to be replaced. The alkalinity of diesel engine oil in the prior art is mainly provided by functional additives containing calcium, magnesium, zinc, molybdenum, boron, etc. Excessive addition of the above functional additives can increase the alkalinity of the product, but at the same time, it will also bring too high sulfate ash, which may block the vehicle's aftertreatment device, adversely affect the environment through vehicle emissions, and make it difficult for diesel engine oil to meet the high standard of environmental quality requirements.

[0006] The application unexpectedly discovers that, by compounding a specific phenolic ester antioxidant with a sulfenide antioxidant and an amine antioxidant, the alkalinity can be effectively contributed without generating sulfate ash, and the antioxidant performance of the oil product can be improved.

[0007] Specifically, the technical solutions of the application are as follows:

[0008] The application provides an additive composition of diesel engine oil, which comprises dialkyldiphenylamine, a phenolic ester compound and a sulfenide compound in a mass ratio of (2-8):1:1. wherein R1 and R2 are the same or different C1-C8 alkyl;

[0009] The molecular weight of the phenolic ester compound is 200-400.

[0010] The application finds that, by compounding the phenolic ester compound with the above molecular weight with a sulfenide antioxidant and an amine antioxidant and applying the compound to diesel engine oil, the alkalinity can be significantly improved without increasing the ash content of the oil product, and the antioxidant performance of the oil product can be improved, thereby solving the problem that the service life of lubricating oil and environmental protection cannot be considered simultaneously.

[0011] In the application, the phenolic ester compound is a liquid high-molecular phenolic ester antioxidant; preferably, the phenolic ester compound is 3,5-di-tert-butyl-4-hydroxyphenyl propionate and / or 2,6-di-tert-butyl-4-hydroxyphenyl propionate, and the effect is better.

[0012] In the application, different phenolic ester antioxidants can be applied to the additive composition according to the needs of those skilled in the art, including but not limited to the following product models: T512 (Beijing Xingpu Fine Chemical Technology Development Company), RF1135 (Xinxiang Ruifeng New Material Co., Ltd.) and the like.

[0013] Preferably, the molecular weight of the sulfenide compound is 500-1000.

[0014] Preferably, the sulfenide compound is thio-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], and the structural formula is as follows:

[0015] In the application, different sulfenide antioxidants can be applied to the additive composition according to the needs of those skilled in the art, including but not limited to the following product models: T535 (Beijing Xingpu Fine Chemical Technology Development Company), RF1035 (Xinxiang Ruifeng New Material Co., Ltd.), Irganox 1035 (BASF) and the like.

[0016] Preferably, the molecular weight of the dialkyldiphenylamine is 300-500, and / or the base value of the dialkyldiphenylamine is 150-200 mgKOH / g.

[0017] Preferably, the dialkyldiphenylamine is butyloctyl diphenylamine.

[0018] In the present application, the skilled person in the art can apply different butyloctyl diphenylamine type antioxidants to the additive composition as needed, including but not limited to the following trade models: T534 (Beijing Xingpu Fine Chemical Technology Development Co., Ltd.), RF5057 (Xinxiang Ruifeng New Material Co., Ltd.), L57 (BASF), etc.

[0019] The present application also provides a diesel engine oil containing the antioxidant composition described above.

[0020] Preferably, the amount of the antioxidant composition is 0.2-2.0 wt% based on the total mass of the diesel engine oil; more preferably, the amount of the antioxidant composition is 0.4-1.0 wt%.

[0021] Preferably, the base oil in the diesel engine oil is HVI Group II base oil.

[0022] Preferably, the kinematic viscosity of the base oil at 100°C is 4.0-11.0 mm 2 / s.

[0023] The present application finds that the antioxidant composition can synergistically further improve the comprehensive performance of the oil product when compounded with the HVI Group II base oil with the above kinematic viscosity.

[0024] In the present application, the specifications of the diesel engine oil meet API CJ-4, CK-4, FA-4, ACEA, E6, E8, E9 or E11.

[0025] Based on the above technical solutions, the present application has the following beneficial effects:

[0026] The present application optimizes the antioxidant composition, not only significantly improves the antioxidant performance, but more importantly, significantly improves the initial total base number of the oil product without increasing the ash content of the oil product, and significantly enhances the service life of the oil product. DETAILED DESCRIPTION

[0027] In order to make the objectives, technical solutions and advantages of the present application clearer, the technical solutions in the present application will be clearly and completely described below. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application.

[0028] Unless otherwise specified, the various raw materials used in the examples are commercially available conventional raw materials, and the technical means used is the conventional means well known to those skilled in the art.

[0029] Unless otherwise specified, the following "%" is the mass percentage.

[0030] The base oil of the diesel engine oil described in the following examples and comparative examples is HVI II+6, and the kinematic viscosity at 100°C is 5.96 mm 2 / s.

[0031] Examples 1-3 and Comparative Examples 1-2

[0032] The formula of the additive composition of the diesel engine oil provided by the examples and comparative examples is shown in Table 1.

[0033] Table 1 Lubricating oil composition examples

[0034]

[0035]

[0036] Performance verification of engine oil of experimental examples

[0037] 1. In order to further verify the performance of the diesel engine oil of the examples and comparative examples, the antioxidant performance, base number and sulfated ash content of the engine oil are verified respectively.

[0038] The physicochemical data of each example meet the API CK-4 specification requirements, and the test results of oxidation induction period PDSC, base number and sulfated ash content are shown in Table 2.

[0039] Table 2 Laboratory formulation analysis of engine oil

[0040] Elemental content Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 PDSC (190°C), min 132 140 144 149 120 122 Base number, mgKOH / g 9.05 9.43 9.78 10.10 8.93 8.81 Sulfate ash, % 0.91 0.90 0.91 0.91 0.90 0.91

[0041] As can be seen from Table 2, the oxidation induction period of Examples 1-4 is significantly longer than that of Comparative Examples 1-2, and the base number is also significantly increased compared with Comparative Examples 1-2, indicating that the antioxidant performance of the engine oil of Examples 1-4 is significantly improved, and the base number level reaches the industry leading level. In the case of increasing the antioxidant performance and the total base number level, the sulfated ash of Examples 1-4 is basically unchanged, indicating that the addition of the additive composition of the present application to the oil product does not have a negative impact on the environmental performance of the product.

[0042] 2. In order to further verify the performance of the diesel engine oil of the examples and comparative examples, the base number change during the use of the engine oil was verified by engine bench test.

[0043] The physical and chemical data of the examples meet the API CK-4 specification requirements, and the total base number test results of different oil products in the bench test are shown in Table 3.

[0044] Table 3 Analysis of base number decay of laboratory formulation of lubricating oil

[0045]

[0046]

[0047] From the bench test performance, the total base number decay of Example 1 is significantly better than that of Comparative Examples 1-2. It indicates that the oil product has excellent base number retention capability. The lubricating oils of Examples 1-3 and Example 4 have comparable base number retention capability.

[0048] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the present application, but not to limit it; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that: it can still modify the technical solutions recorded in the foregoing examples, or make equivalent replacement for part of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A diesel engine oil containing an antioxidant composition, characterized in that, The antioxidant composition comprises dialkyl diphenylamine, phenolic esters, and thiophenols in a mass ratio of (2-8):1:1; wherein the dialkyl diphenylamine is butyloctyl diphenylamine. The phenolic ester compounds are 3,5-di-tert-butyl-4-hydroxyphenylpropionate and / or 2,6-di-tert-butyl-4-hydroxyphenylpropionate; The thiophenolic compound is .

2. The diesel engine oil according to claim 1, characterized in that, The antioxidant composition is present in the diesel engine oil at a mass percentage of 0.2–2.0 wt%.

3. The diesel engine oil according to claim 1 or 2, characterized in that, The base oil in the diesel engine oil is a Group HVIII base oil.

4. The diesel engine oil according to claim 3, characterized in that, The base oil has a kinematic viscosity of 4.0–11.0 mm at 100°C. 2 / s.

Images