Completely-synthesized CI-4 diesel engine oil composite additive composition as well as preparation and application thereof

Abstract

The invention discloses a total synthesis CI-4 diesel engine oil composite additive composition as well as preparation and application thereof. The total synthesis CI-4 diesel engine oil composite additive composition mainly comprises the following components in parts by weight: 6.5-7.5 parts of a high-base-number calcium salicylate detergent; 19.0 to 22.0 parts of a low base number calcium salicylate clearing agent; 6.5 to 8.0 parts of a high base number sulfurized calcium alkyl phenolate detergent; 6.0 to 7.0 parts of a zinc dialkyl dithiophosphate oxidation and corrosion inhibitor; 40.0 to 45.0 parts of a succinimide type ashless dispersant; 8.0 to 10.0 parts of an amine type antioxidant; 5.0 to 6.0 parts of a phenol type antioxidant; and 1.0 to 2.0 parts of carbamic acid ester. The total-synthesis CI-4 diesel engine oil composition obtained by blending the total-synthesis CI-4 diesel engine oil composite additive composition still has excellent low-temperature startability at the temperature of-30 DEG C or below, and passes a bench test.

Description

Technical Field

[0001] The invention relates to a fully synthetic CI-4 diesel engine oil composite additive composition and the preparation and application thereof. Background Art

[0002] The increasingly stringent environmental regulations have also prompted the continuous innovation of engine technology. For example, when using technologies such as SCR, EGR, and high-pressure common rail, diesel engine oil is required to have excellent soot dispersibility, high-temperature detergency, and oxidation stability. However, the engine is difficult to start under low temperature conditions. Summary of the invention

[0003] The present invention is made in order to make the diesel engine oil meet the API CI-4 diesel engine oil specification and also have excellent low temperature cold starting performance.

[0004] As a first aspect of the present invention, it relates to a composite additive composition for a fully synthetic CI-4 diesel engine oil, which mainly comprises the following components by weight:

[0005] 6.5-7.5 parts of high base calcium salicylate detergent;

[0006] 19.0-22.0 parts of low base value calcium salicylate detergent;

[0007] 6.5-8.0 parts of high base value sulfurized alkyl phenol calcium detergent;

[0008] 6.0-7.0 parts of zinc dialkyl dithiophosphate antioxidant and anticorrosive agent;

[0009] 40.0-45.0 parts of succinimide ashless dispersant;

[0010] 8.0-10.0 parts of amine antioxidant;

[0011] 5.0-6.0 parts of phenolic antioxidant;

[0012] 1.0-2.0 parts of carbamate;

[0013] The high base value calcium salicylate has a base value of 265-295 mgKOH / g;

[0014] The low alkalinity calcium salicylate has an alkalinity of 160-175 mgKOH / g;

[0015] The high base value sulfurized alkyl phenol calcium has a base value of 245-265 mgKOH / g.

[0016] In one or some optional embodiments, the succinimide ashless dispersant is an aromatic amine succinimide, which has the following structural formula:

[0017]

[0018] Wherein, R1 is a straight chain alkane having 2-6 carbon atoms, R2 is H or CH3, PIB is polyisobutylene, and n is a natural number of 2-4.

[0019] In one or some optional embodiments, the high base value sulfurized calcium alkyl phenate detergent is sulfurized calcium alkyl phenate T115B.

[0020] In one or some optional embodiments, the high base value calcium salicylate detergent is calcium salicylate T109B.

[0021] In one or some optional embodiments, the low base value calcium salicylate detergent is calcium salicylate T109.

[0022] In one or some optional embodiments, the dialkyl zinc dithiophosphate is bis-octyl zinc dithiophosphate T203.

[0023] In one or some optional embodiments, the amine antioxidant is a mixture of butyl octyl diphenylamine RHY057 and N-phenyl-α-naphthylamine T531.

[0024] In one or some optional embodiments, the mass ratio of the butyl octyl diphenylamine RHY057 and the N-phenyl-α-naphthylamine T531 is 5:3 to 6:4.

[0025] In one or some optional embodiments, the phenolic antioxidant is hindered phenol ester RHY505.

[0026] In one or some optional embodiments, the carbamate is dibutyl dithiocarbamate.

[0027] As a second aspect of the present invention, it relates to a method for preparing the above-mentioned fully synthetic CI-4 diesel engine oil composite additive composition, the method comprising:

[0028] High alkalinity calcium salicylate detergent, low alkalinity calcium salicylate detergent, high alkalinity sulfurized alkylphenol calcium detergent, dialkyl dithiophosphate zinc antioxidant and corrosion inhibitor, succinimide ashless dispersant, amine antioxidant, phenol antioxidant and carbamate are uniformly mixed according to their weight proportions.

[0029] As a third aspect of the present invention, it relates to the use of the above-mentioned fully synthetic CI-4 diesel engine oil composite additive composition in the preparation of a fully synthetic CI-4 diesel engine oil composition. The preparation method of the fully synthetic CI-4 diesel engine oil composition comprises:

[0030] The fully synthetic CI-4 diesel engine oil composite additive composition according to any one of claims 1 to 10, an OCP viscosity index improver, a PMA pour point depressant and a base oil are uniformly mixed;

[0031] The base oil is API Class IV or V base oil.

[0032] The fully synthetic CI-4 diesel engine oil composite additive composition provided by the present invention is prepared by compounding high-alkalinity calcium salicylate, low-alkalinity calcium salicylate and high-alkalinity sulfurized alkylphenol calcium. The metal detergent system composed of the metal detergent system solves the problem of high-temperature deposits caused by the use of SCR technology in diesel engine oil, and effectively improves the problem of deposit generation such as carbon deposits and paint films on pistons and valve systems. The fully synthetic CI-4 diesel engine oil composite additive composition provided by the present invention adopts a dispersant system constructed by a succinimide-type ashless dispersant, which solves the problem of a large number of soot particle aggregation caused by the EGR technology in diesel engines, and is particularly capable of improving the soot dispersibility of oil products after using API IV and V base oils. The fully synthetic CI-4 diesel engine oil composite additive composition provided by the present invention is prepared by compounding dialkyl dithiophosphate zinc, amine-type and phenol-type antioxidants, and carbamate. The anti-wear-antioxidant system composed of the metal detergent system solves the problem of oxidation durability and wear of oil products after using API IV and V base oils.

[0033] The fully synthetic CI-4 diesel engine oil composite additive composition provided by the present invention improves the low-temperature starting performance of the oil product when it is applied as an additive to API IV and V group base oils. The fully synthetic CI-4 diesel engine oil composition blended therewith passes the engine bench tests such as Mack T-12, Cat.1P, Cummins ISM, etc., and can meet the lubrication requirements of national V and below vehicle engines in severe cold areas (below -30°C). DETAILED DESCRIPTION

[0034] The following is a detailed description of the embodiments of the present invention: The embodiments of the present invention are implemented on the premise of the technical solution of the present invention, and detailed implementation methods and processes are given, but the protection scope of the present invention is not limited to the following embodiments. The process parameters for which specific conditions are not specified in the following embodiments are generally based on conventional conditions.

[0035] The endpoints and any values ​​of the ranges disclosed in the present invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in the present invention.

[0036] It should be noted that the raw materials used in the embodiments of the present invention are all commercially available products.

[0037] It should be noted that the structural formula of the aromatic amine succinimide mentioned in the embodiments of the present invention is as follows:

[0038]

[0039] Wherein, R1 is a straight chain alkane having 2-6 carbon atoms, R2 is H or CH3, PIB is polyisobutylene, and n is a natural number of 2-4.

[0040] Example 1

[0041] 6.5 parts of calcium salicylate T109B, 22.0 parts of calcium salicylate T109, 6.5 parts of calcium sulfide alkylphenol T115B, 6.0 parts of zinc dioctyl dithiophosphate T203, 45.0 parts of aromatic amine succinimide, 5.0 parts of butyl octyl diphenylamine RHY057, 5.0 parts of hindered phenol ester RHY505, 3.0 parts of N-phenyl-α-naphthylamine T531 and 1.0 part of dibutyl dithiocarbamate are mixed uniformly to obtain a fully synthetic CI-4 diesel engine oil composite additive composition.

[0042] Example 2

[0043] 7.0 parts of calcium salicylate T109B, 19.0 parts of calcium salicylate T109, 7.0 parts of calcium sulfide alkylphenol T115B, 6.5 parts of zinc dioctyl dithiophosphate T203, 42.5 parts of aromatic amine succinimide, 6.0 parts of butyl octyl diphenylamine RHY057, 6.0 parts of hindered phenol ester RHY505, 4.0 parts of N-phenyl-α-naphthylamine T531 and 2.0 parts of dibutyl dithiocarbamate are mixed uniformly to obtain a fully synthetic CI-4 diesel engine oil composite additive composition.

[0044] Example 3

[0045] 7.5 parts of calcium salicylate T109B, 22.0 parts of calcium salicylate T109, 8.0 parts of calcium sulfide alkylphenol T115B, 7.0 parts of zinc dioctyl dithiophosphate T203, 40.0 parts of aromatic amine succinimide, 5.4 parts of butyl octyl diphenylamine RHY057, 5.4 parts of hindered phenol ester RHY505, 3.5 parts of N-phenyl-α-naphthylamine T531 and 1.2 parts of dibutyl dithiocarbamate are mixed uniformly to obtain a fully synthetic CI-4 diesel engine oil composite additive composition.

[0046] Test Example 1

[0047] The fully synthetic CI-4 diesel engine oil composite additive composition in Examples 1 to 3 was applied to API IV and V base oils, and the antioxidant, anti-wear, detergency and dispersancy performance tests were performed:

[0048] Take 21.4 parts of the fully synthetic CI-4 diesel engine oil composite additive composition in Examples 1 to 3, mix them evenly with 7.5 parts of OCP viscosity index improver RHY615, 0.4 parts of PMA pour point depressant RHY 806, 12.0 parts of diol adipate, 48.7 parts of PAO 4 base oil and 10.0 parts of PAO 40 base oil, and blend them to obtain fully synthetic CI-4 diesel engine oil compositions I, II and III. The blended fully synthetic CI-4 diesel engine oil compositions were tested. The test results are shown in Table 1.

[0049] Table 1 Oil performance test results

[0050] project Example 1 Example 2 Example 3 Experimental methods Coke board / mg 322.5 341.5 319.2 RH01ZB4111 Heat pipe oxidation / stage 9.0 9.0 9.0 QB / KLHZX-B01 TEOST / mg 34.3 27.8 36.2 SH / T0750 Wear spot diameter / mm 0.54 0.53 0.52 NB / SH / T0189 Copper corrosion / grade 1a 1a 1a GB / T5096

[0051] From the analysis of Table 1, it can be seen that the fully synthetic CI-4 diesel engine oil composite additive composition in Examples 1 to 3 of the present invention has excellent and basically equivalent performance in terms of anti-oxidation, anti-wear, detergency and dispersibility.

[0052] Test Example 2

[0053] The fully synthetic CI-4 diesel engine oil compositions I, II and III obtained by blending the fully synthetic CI-4 diesel engine oil composite additive compositions prepared in Examples 1 to 3 of the present invention in Test Example 1 were tested for their low temperature starting performance. The test results are shown in Table 2.

[0054] Table 2 Cold startability test results of fully synthetic CI-4 diesel engine oil composition

[0055]

[0056]

[0057] As can be seen from Table 2, the fully synthetic CI-4 diesel engine oil compositions I, II and III obtained by blending the fully synthetic CI-4 diesel engine oil composite additive compositions prepared in Examples 1 to 3 of the present invention all have excellent low-temperature starting performance below -30°C, and can meet the lubrication requirements of National V and below vehicle engines in severe cold areas.

[0058] Test Example 3

[0059] Combining the test results of Test Example 1 and Test Example 2, it can be seen that the performance of the fully synthetic CI-4 diesel engine oil composite additive composition prepared in Examples 1 to 3 of the present invention is similar. Therefore, this test example will conduct a bench test on the fully synthetic CI-4 diesel engine oil composition obtained by blending the fully synthetic CI-4 diesel engine oil composite additive composition in Example 2. The test results are shown in Table 3.

[0060] Table 3 Fully synthetic CI-4 diesel engine oil engine bench test results

[0061]

[0062]

[0063] As shown in Table 3, the fully synthetic CI-4 diesel engine oil composition prepared by the fully synthetic CI-4 diesel engine oil composite additive composition provided by the present invention has passed all engine bench tests. Moreover, from the results of Mack T-8E, Cummins ISM and Mack T-12, it not only solves the soot dispersibility problem of fully synthetic diesel engine oil, but also overcomes the problem of reduced performance of anti-wear agents in fully synthetic base oils, greatly improving the anti-wear performance of fully synthetic diesel engine oil. In addition, from the results of Cat. 1K and Cat. 1P, the fully synthetic CI-4 diesel engine oil composition also has excellent high temperature detergency.

[0064] Although the specific embodiments of the present invention have been described in detail, it will be understood by those skilled in the art. According to all the teachings disclosed, various modifications and replacements can be made to those details, and these changes are all within the protection scope of the present invention. The full scope of the present invention is given by the attached claims and any equivalents thereof.

Claims

1. A fully synthetic CI-4 diesel engine oil additive package, characterized in that: The composite additive composition mainly comprises the following components in parts by weight: 6.5-7.5 parts of high base calcium salicylate detergent; 19.0-22.0 parts of low base value calcium salicylate detergent; 6.5-8.0 parts of high base value sulfurized alkyl phenol calcium detergent; 6.0-7.0 parts of zinc dialkyl dithiophosphate antioxidant and anticorrosive agent; 40.0-45.0 parts of succinimide ashless dispersant; 8.0-10.0 parts of amine antioxidant; 5.0-6.0 parts of phenolic antioxidant; 1.0-2.0 parts of carbamate; The high base value calcium salicylate has a base value of 265-295 mgKOH / g; The low alkalinity calcium salicylate has an alkalinity of 160-175 mgKOH / g; The high base value sulfurized alkyl phenol calcium has a base value of 245-265 mgKOH / g.

2. The fully synthetic CI-4 diesel engine oil additive package composition according to claim 1, characterized in that: The succinimide ashless dispersant is an aromatic amine succinimide, which has the following structural formula: Wherein, R1 is a straight chain alkane having 2-6 carbon atoms, R2 is H or CH3, PIB is polyisobutylene, and n is a natural number of 2-4.

3. The fully synthetic CI-4 diesel engine oil additive package composition according to claim 1, characterized in that: The high base value sulfurized calcium alkyl phenate detergent is sulfurized calcium alkyl phenate T115B.

4. The fully synthetic CI-4 diesel engine oil additive package composition according to claim 1, characterized in that: The high base value calcium salicylate detergent is calcium salicylate T109B.

5. The fully synthetic CI-4 diesel engine oil additive package composition according to claim 1, characterized in that: The low base value calcium salicylate detergent is calcium salicylate T109.

6. The fully synthetic CI-4 diesel engine oil additive package composition according to claim 1, characterized in that: The dialkyl zinc dithiophosphate is bis-octyl zinc dithiophosphate T203.

7. The fully synthetic CI-4 diesel engine oil additive package composition according to claim 1, characterized in that: The amine antioxidant is a mixture of butyl octyl diphenylamine RHY057 and N-phenyl-α-naphthylamine T531.

8. The fully synthetic CI-4 diesel engine oil additive package composition according to claim 7, characterized in that: The mass ratio of the butyl octyl diphenylamine RHY057 and the N-phenyl-α-naphthylamine T531 is 5:3 to 6:

4.

9. The fully synthetic CI-4 diesel engine oil additive package composition according to claim 1, characterized in that: The phenolic antioxidant is hindered phenol ester RHY505.

10. The fully synthetic CI-4 diesel engine oil additive package composition according to claim 1, characterized in that: The carbamate is dibutyl dithiocarbamate.

11. A method for preparing the fully synthetic CI-4 diesel engine oil additive package composition according to any one of claims 1 to 10, characterized in that: The method comprises: High alkalinity calcium salicylate detergent, low alkalinity calcium salicylate detergent, high alkalinity sulfurized alkylphenol calcium detergent, dialkyl dithiophosphate zinc antioxidant and corrosion inhibitor, succinimide ashless dispersant, amine antioxidant, phenol antioxidant and carbamate are uniformly mixed according to their weight proportions.

12. Use of the fully synthetic CI-4 diesel engine oil composite additive composition according to any one of claims 1 to 10 in the preparation of a fully synthetic CI-4 diesel engine oil composition, characterized in that: The preparation of the fully synthetic CI-4 diesel engine oil composition comprises: The fully synthetic CI-4 diesel engine oil composite additive composition according to any one of claims 1 to 10, an OCP viscosity index improver, a PMA pour point depressant and a base oil are uniformly mixed; The base oil is API Class IV or V base oil.

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