CN1023408C - Anti-friction compound - Google Patents
Anti-friction compound Download PDFInfo
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- CN1023408C CN1023408C CN 90109013 CN90109013A CN1023408C CN 1023408 C CN1023408 C CN 1023408C CN 90109013 CN90109013 CN 90109013 CN 90109013 A CN90109013 A CN 90109013A CN 1023408 C CN1023408 C CN 1023408C
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- sulphur
- boronation
- acid
- trimethylolpropane
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Abstract
The present invention relates to an anti-friction compound agent which can be directly added into lubricating oil for an internal combustion engine with the content of 3 to 12m%, which comprises 2 to 80 m% of (a) zinc salt with ester with a hydroxy group, which is partially bononized and phosphosulfurized or 10 to 24c of fat amine salt, 2 to 80m % of (b) 3 to 20c of dialkyl molybdenum oxide monophosphate disulfide, 2 to 30m % of (C) 7 to 21c of alkaline alkyl calcium salicylate, and 15 to 80m% of (d) mineral lubricating oil, wherein the ester with a hydroxy group is ester with a hydroxy group part, and the ester is prepared from neopentyl dyadic alcohol, at least one kind of polyols selected from trimethylolpropane, and at least one kind of acid selected from 10 to 24c of fatty acid.
Description
The present invention relates to be used for the anti-friction compound of internal combustion (IC) engine lubricating oil, specifically the present invention relates to contain abrasion resistant extreme-pressure, antioxygen, the anticorrosive multifunction additive of two types, the internal combustion (IC) engine lubricating oil anti-friction compound of the compositions such as mineral lubricating oils of alkaline alkyl sodium salicylate detergent-dispersant additive and a dilution and solvency action.
The lubricating oil that oil engines such as the automobile that obtains on the market are used, the particularly present more widely used few internal combustion (IC) engine lubricating oil of dosage that adds is in the non-optimizing of friction and wear performance Shang ， And.Therefore, people can supply the direct commodity anti-friction compounds (claiming energy-saving agent again) that add of oil engine user oneself for the friction that reduces engine so that fuel economy has developed some in lubricating oil.Many commercially available anti-friction compounds can not improve the antifriction performance of engine oil significantly.
The tetramethylolmethane and the TriMethylolPropane(TMP) partial fatty acid ester zinc salt of known part boronation part sulphur phosphatization, though abrasion resistant extreme-pressure, antioxygen and corrosion resistance are preferably arranged, hydrolysis produces sedimentary shortcoming but have when using separately the relatively poor ， And of antifriction performance and be exposed under the atmospheric condition easily.
Known dialkyl dithiophosphoric acid sulphur molybdenum oxide is used for internal combustion (IC) engine lubricating oil, though have abrasion resistant extreme-pressure, antioxygen and corrosion resistance preferably, its antifriction performance is also desirable not enough.
At present, the technology that the additive of above-mentioned two types compound use ， And and the hydrolysis that overcomes the former are produced sedimentary shortcoming still is new.
The purpose of this invention is to provide a kind of anti-friction compound that internal combustion (IC) engine lubricating oil such as automobile are used, it not only is better than commercially available anti-friction compound and above-mentioned two known multifunction additives on antifriction performance, but also overcomes the shortcoming of above-mentioned additive.Therefore, reduce the friction and wear of engine effectively, reach fuel economy and prolong the engine purpose in work-ing life.
Anti-friction compound of the present invention can directly add in the internal combustion (IC) engine lubricating oil and use by the amount (referring to the quality consumption) of 3～12m% usually.Anti-friction compound of the present invention contains 2～80m%'s (a) composition; (b) composition of 2～80m%; (c) composition of 2～30m%; (d) composition of 15～80m%.Best (a) composition is 10～50m%; (b) composition is 10～50m%; (c) composition is 7～15m%; (d) composition is 30～50m%.
(a) composition is zinc salt or 10～24C fatty amine salt of the hydroxyl ester of part boronation part sulphur phosphatization, and said here hydroxyl ester is the hydroxyl containing portion ester by at least a acid preparation of selecting at least a polyvalent alcohol of selecting in neo-pentyl dibasic alcohol and the TriMethylolPropane(TMP) and the 10～24C lipid acid.(b) composition is that general formula is (I) (R here
1, R
2It is 3～20C alkyl identical or inequality; X, y are the arithmetic numbers that satisfies x+y=4) shown in two (3～20C alkyl) phosphorodithioic acid sulphur molybdenum oxide.
〔（R
1O）（R
2O）P（＝S）S〕
2M
oS
xO
y（Ⅰ）
(C) composition is alkalescence 7～21C alkyl salicylate calcium salt.(d) composition is a mineral lubricating oils.
When speaking of (a) of the present invention composition, part one speech is meant complete normal hydroxyl in the polyvalent alcohol with not enough normal fatty acid esterification, with not enough normal sulphur phosphorization agent sulphur phosphatization with not enough normal boronating agent boronation.
When preparing (a) of the present invention composition, usually by (1) partial esterification, (2) part sulphur phosphatization, carry out with the order that zn cpds or aliphatic amide are carried out to reactant salt and (4) part boronation (3).Simultaneously, also can take method that boronation is moved to before the sulphur phosphatization or carries out before the salt-forming reaction.The above steps reaction all can be carried out in accordance with known methods.In each step, there is no particular limitation usually to make the ratio of hydroxyl reaction.
In the partial esterification reaction, can make hydroxyl and the 10～24C fatty acid response of 20～70mol%, preferably make the hydroxy esterification of 30～50mol%.Can capric acid, undecanoic acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, oleic acid, dodecylic acid, docosoic acid, Lignoceric acid and 10～24C synthetic fatty acid etc. be arranged for 10～24C lipid acid of selecting for use, preferably select lauric acid and oleic acid.
In the part sulfur phosphatization reaction, make the sulphur phosphorization agent with thiophosphoric anhydride, make hydroxyl and the thiophosphoric anhydride reaction of 20～70mol%, preferably make the hydroxyl sulphur phosphatization of 30～50mol%.
In salt-forming reaction, zn cpds can be selected from zinc acetate, zinc oxide and zinc hydroxide etc., preferably selects zinc acetate and zinc oxide.10～24C aliphatic amide has decyl amine, lauryl amine, tetradecy lamine, cetylamine, stearylamine, 20 amine, two amino dodecanes, two tetradecy lamines and 10～24C synthetic fatty amine etc., preferably selects lauryl amine and stearylamine.
In the reaction of part boronation, boronating agent can be selected from boric acid and tri butyl boron acid esters etc., preferably selects boric acid, and consumption is by hydroxyl and the boride reaction of 10～60mol%, and preferably the hydroxyl boronation of 15～50mol% is selected.
(a) of the present invention composition can be selected from the neo-pentyl dibasic alcohol of the neo-pentyl dibasic alcohol of the TriMethylolPropane(TMP) monoleate zinc salt of the neo-pentyl dibasic alcohol monoleate zinc salt of part boronation part sulphur phosphatization, part boronation part sulphur phosphatization, part boronation part sulphur phosphatization and TriMethylolPropane(TMP) alcohol mixture part oleic acid ester 12C fatty amine salt and part boronation part sulphur phosphatization and TriMethylolPropane(TMP) alcohol mixture part laurate zinc salt.
(b) of the present invention composition can be by known method preparation, for example by molybdic oxide, sodium sulphite, sulfuric acid and two (3～20C alkyl) phosphorodithioic acid prepared in reaction in solvent.Wherein, 3～20C alkyl can be selected from sec.-propyl, isobutyl-, normal-butyl, hexyl, heptyl, octyl group, iso-octyl, nonyl, decyl, isodecyl, lauryl, tridecyl, tetradecyl, hexadecyl, octadecyl, octadecylene base, eicosyl etc.(b) composition can be selected from diisooctyl phosphorodithioic acid sulphur molybdenum oxide, two (9-octadecylene base) phosphorodithioic acid sulphur molybdenum oxide and isobutyl-iso-octyl phosphorodithioic acid sulphur molybdenum oxide.
Anti-friction compound of the present invention contains various active element and polarity carboxylic acid ester groups such as boron, sulphur, phosphorus, zinc, molybdenum.Good antifriction consonance effect is arranged between them.
When (a) and (b) the composition consumption was less than 2m%, after anti-friction compound added internal combustion (IC) engine lubricating oil, activeconstituents did not have substantial amount; During greater than 80m%, certainly will cause other composition consumption very few.Therefore, either way can not give full play to the effect of consonance antifriction.
(c) of the present invention composition, in in recombiner, not only plaing and acidic substance and peace and quiet dispersive effect, but also work to suppress (a) composition hydrolytic precipitation, can produce as the T109(Lanzhou Oil Refinery from alkalescence 7～21C alkyl salicylate calcium salt of commodity) and the middle selection of AC agent (production of Ying He Shell Co. Ltd).Preferably select T109, it is that total basicnumber is 10～21C alkyl salicylate calcium salt of 140～200mgKOH/g.
When (c) the composition consumption is lower than 2m%, weak effect; When being higher than 30m%, not only effect can further not improve, but also causes the consumption of other composition to reduce.
(d) of the present invention composition mainly plays dilution and dissolves other composition in recombiner.Though (d) viscosity of composition does not have special qualification, can select the Dormant oils of N15～N68 viscosity grade usually for use.When its consumption was lower than 15m%, dilution and solubility property deficiency when being higher than 80m%, caused the consumption of other composition to reduce, and also are unfavorable.
Anti-friction compound allotment of the present invention is easy, as long as with the extremely dissolving of (a)～(d) of the present invention composition method heated and stirred routinely.
The additive of anti-friction compound of the present invention and other type has good consistency as oxidation inhibitor and rust-preventive agent etc.Therefore, in case of necessity, anti-friction compound of the present invention can also contain other various types of additives.
Anti-friction compound of the present invention has very low frictional coefficient and good stability to hydrolysis.
Enumerate synthetic test example and embodiment below and further specify the present invention.
Synthetic test example A～G
Synthesizing of the neo-pentyl dibasic alcohol monoleate zinc salt of part boronation part sulphur phosphatization (being called for short A)
Neo-pentyl dibasic alcohol 52g(0.5mol), oleic acid 141g(0.5mol) tosic acid (catalyzer) 0.2g, toluene (solvent) 150ml packs into and is with in the 500ml there-necked flask of water trap and stirring, behind stirring, heating, the reflux water-dividing, add thiophosphoric anhydride 22.2g(0.1mol), stir 4h in 100～110 ℃, add zinc acetate 22g(0.1mol), stir, heat, reflux and tell the acetate of generation, add boric acid 6.2g(0.1mol), behind restir, heating, the reflux water-dividing, tell solution layer, decompression steams solvent, obtains brown viscous liquid.
Adopt the preparation method of similar A, the neo-pentyl dibasic alcohol of composite part boronation part sulphur phosphatization and TriMethylolPropane(TMP) alcohol mixture part oleic acid ester 12C fatty amine salt (being called for short B); The TriMethylolPropane(TMP) monoleate zinc salt of part boronation part sulphur phosphatization (being called for short C); The neo-pentyl dibasic alcohol of part boronation part sulphur phosphatization and TriMethylolPropane(TMP) alcohol mixture part laurate zinc salt (being called for short D).
The title and the consumption of the main raw material that synthetic A～D is used, the results of elemental analyses of A～D is listed in the table 1.
Synthesizing of diisooctyl phosphorodithioic acid sulphur molybdenum oxide (being called for short E)
Molybdic oxide 36g(0.25mol), each 50ml of isobutyl alcohol and water (solvent), Na
2S9H
2O 60g(0.25mol), stir, be heated to about 50 ℃, splash into vitriol oil 22.5g(0.23mol), stir 20min after, add diisooctyl phosphorodithioic acid 177g(0.5mol) and 90～120 ℃ sherwood oil 100ml, stir, heat backflow 8h.Tell the petroleum ether solution layer, steam solvent after the washing, obtain paleturquoise liquid.Results of elemental analyses: P3.43%, Mo9.66%.
Except using two (9-octadecylene base) phosphorodithioic acid (0.5mol) and isobutyl-iso-octyl phosphorodithioic acid (0.5mol) replacement diisooctyl phosphorodithioic acid (0.5mol) respectively, all the other adopt the preparation method of similar E, and synthetic two (9-octadecylene base) phosphorodithioic acid sulphur molybdenum oxide (is called for short F; P3.23% Mo4.93%) (is called for short G with isobutyl-iso-octyl phosphorodithioic acid sulphur molybdenum oxide; P5.87%, Mo13.7%).
Embodiment 1～6 and comparative example 1～5
Adopt A～G, T109 and N32 oil petroleum refined by naphthenic (being called for short N32), allocate anti-friction compound of the present invention (embodiment 1～6), its composition is listed in the table 2, in order more also to list comparative example 1～3 in.
The white oil (abbreviation white oil) of QB level automobile engine oil of SAE30 viscosity grade (be called for short QB oil) and N15 viscosity grade as lubricating base oils.The composition of the anti-friction compound of embodiment 1～6 and comparative example 1～3 adds in the lubricating base oils with the amount of 5m% respectively, adds frictional coefficient (μ) after the agent with SRV trier mensuration.Condition determination: load 20N, vibrational frequency 20Hz, amplitude 0.2mm, 50 ℃ of temperature, time 30min, steel ball size 12.7mm.
The anti-friction compound of embodiment 1～6 and the composition of comparative example 1～3 are carried out placing in the atmosphere stability to hydrolysis test of 30d.
The test-results of embodiment 1～6 and comparative example 1～3 is listed in the table 3.For further comparison, the anti-friction compound of two external commodity (comparative example 4 and 5) is added in the lubricating base oils with the amount of 5m% respectively, carry out the mensuration of frictional coefficient (μ).The result lists in the table 3 in the lump.
Find out by table 2 and 3, (a) composition (comparative example 1 and 2) or (b) composition (comparative example 3) when using separately, though also reduced the frictional coefficient of lubricating base oils, desirable not enough.Anti-friction compound of the present invention (embodiment 1～6) is because (a) and (b) two kinds of composition generation consonances effect, thereby reduced the frictional coefficient of lubricating base oils significantly.
(a) composition is exposed in the atmosphere behind moisture absorption 1～2d, produces a large amount of white precipitate (comparative example 2), and (c) composition has the effect (comparative example 1) of inhibition (a) composition hydrolytic precipitation.Anti-friction compound of the present invention (embodiment 1～6) has good storing stability.
In addition, anti-friction compound of the present invention (embodiment 1～6) has better antifriction function than inward (comparative example 4 and 5).
Table 1
A B C D
The neo-pentyl dibasic alcohol, 52 26-26
g（mol） （0.5） （0.25） （0.25）
TriMethylolPropane(TMP) ,-33.5 67 33.5
g（mol） （0.25） （0.5） （0.25）
Oleic acid, 141 169 141-
g（mol） （0.5） （0.6） （0.5）
Lauric acid ,---100
g（mol） （0.5）
Thiophosphoric anhydride, 22.2 22.2 27.5 27.5
g（mol） （0.1） （0.1） （0.12） （0.12）
Zinc acetate, 22-27 27
g（mol） （0.1） （0.12） （0.12）
The 12C aliphatic amide ,-37--
g（mol） （0.2）
Boric acid, 6.2 6.2 12.4 12.4
g（mol） （0.1） （0.1） （0.2） （0.2）
S% 7.28 6.12 3.78 6.46
P% 6.04 3.13 1.89 4.46
Zn% 3.79 - 1.42 4.13
B% 0.23 0.32 0.24 0.63
N% - 1.42 - -
Table 2
Embodiment of the invention comparative example
1 2 3 4 5 6 1 2 3
A 30 20 10 50
B 10
C 40
D 20 50
E 20 30 20 30
F 40 50
G 40
T109 7 15 7 15 7 10 10
N32 43 35 33 35 43 40 40 50 50
(μ of QB oil is 0.155 to table 3; The μ of white oil is 0.167)
Add in the QB oil to add in the agent atmosphere in the agent white oil and place 30d,
5m%, μ 5m%, μ precipitation
This 1 0.035 0.050 nothing
Sending out 2 0.035 0.070 does not have
Bright 3 0.037 0.075 do not have
Real 4 0.040 0.067 do not have
Executing 5 0.040 0.072 does not have
Example 6 0.052 0.075 does not have
Do not have than 1 0.135 0.140
Have in a large number than 2 0.110 0.120 1～2d
White precipitate
Example 3 0.056 0.088 does not have
4 0.118 0.130 -
5 0.116 0.127 -
Claims (1)
1, a kind of anti-friction compound that directly adds internal combustion (IC) engine lubricating oil with the amount of 3～12m%, contain multifunction additive and detergent-dispersant additive and thinning oil, it is characterized in that recombiner of the present invention contains (a) composition of 10～50m%, from the neo-pentyl dibasic alcohol monoleate zinc salt of three hydroxyl firstization of part boronation part sulphur phosphatization, select in the neo-pentyl dibasic alcohol of the neo-pentyl dibasic alcohol of the TriMethylolPropane(TMP) monoleate zinc salt of part boronation part sulphur phosphatization and part boronation part sulphur phosphatization and TriMethylolPropane(TMP) alcohol mixture part oleic acid ester 12c fatty amine salt and part boronation part sulphur phosphatization and the TriMethylolPropane(TMP) alcohol mixture part laurate zinc salt; (b) composition of 10～50m% is selected from diisooctyl phosphorodithioic acid sulphur molybdenum oxide, two (9-octadecylene base) phosphorodithioic acid sulphur molybdenum oxide and isobutyl-iso-octyl phosphorodithioic acid sulphur molybdenum oxide; (c) composition of 7～15m%, alkalescence 10～21c alkyl salicylate calcium salt, its total basicnumber is 140～200mgKOH/g; (d) composition mineral lubricating oils of 30～50m%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90109013 CN1023408C (en) | 1990-11-14 | 1990-11-14 | Anti-friction compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90109013 CN1023408C (en) | 1990-11-14 | 1990-11-14 | Anti-friction compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1061428A CN1061428A (en) | 1992-05-27 |
| CN1023408C true CN1023408C (en) | 1994-01-05 |
Family
ID=4881245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90109013 Expired - Fee Related CN1023408C (en) | 1990-11-14 | 1990-11-14 | Anti-friction compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1023408C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3613530B2 (en) * | 1993-05-27 | 2005-01-26 | 東燃ゼネラル石油株式会社 | Lubricating oil composition |
| US5672572A (en) * | 1993-05-27 | 1997-09-30 | Arai; Katsuya | Lubricating oil composition |
| CN1045213C (en) * | 1996-01-25 | 1999-09-22 | 朱卫民 | Lubricant oil additive |
| US7618467B2 (en) * | 2004-01-29 | 2009-11-17 | Chemtura Corporation | Detergent / anti-oxidant additives for fuels and lubricants |
| CN101173201B (en) * | 2006-10-31 | 2010-05-12 | 中国石油化工股份有限公司 | Method for producing phosphor boronation ashless dispersant |
-
1990
- 1990-11-14 CN CN 90109013 patent/CN1023408C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1061428A (en) | 1992-05-27 |
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