JPH0195194A - Novel oil-soluble, ash-free dispersant - Google Patents

Abstract

PURPOSE:To obtain the title dispersant which has excellent sludge dispersion and oxidation inhibiting capability and is valuable as a lubricant additive or a liq. fuel additive, by adding a reaction product of a particular polyamine with a hydrocarbon-substd. succinic anhydride to a lubricant. CONSTITUTION:A polyamine (a) having an average MW of 170-2000, pref. 300-1100, and having prim. and tert. amino groups in respective amts. of 30% or above and 35% or below based on the total amino groups of the polyamine is obtd. by effecting addn. reaction between a compd. (i) of formula I (wherein n is 1-10) and acrylonitrile (ii) in an amt. of 0.5mol or more to N of component (i), hydrogenating optionally repeating addn. of component (ii) followed by hydrogenation once or more times. A reaction product (A) of component (a) with a hydrocarbon-substd. succinic anhydride (b) is mixed with a lubricant (B) of formula II and/or formula III [wherein R is a 1-30C hydrocarbon residue, a (thio)ether group or a (COOH-contg.) hydrocarbon residue; M is Zn or formula IV; and X is O or S] in a ratio of A to B of 1-50:50-1.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to novel ashless dispersants useful as lubricant additives and liquid fuel oil additives. In particular, the present invention relates to an ashless dispersant that has excellent sludge dispersibility and antioxidant properties, and has the ability to enhance the effects of various additives in lubricants.

[Conventional technology and problems]

Many ashless dispersants for use in hydrocarbon oils and various synthetic oils or fuel oils are already known. Many of these are reactants of high molecular weight carboxylic acids and amines, and known examples of these high molecular weight carboxylic acids include hydrocarbon-substituted succinic acid or succinic anhydride. No. 172,892 discloses a reaction product of hydrocarbon-substituted succinic anhydride and ethylene amine, and U.S. Pat.
8,247 also contains hydrocarbon-substituted succinic anhydride and N
, N-dialkylaminoalkylamine reactants are disclosed as ashless dispersants. The mechanisms of action of these ashless dispersants, for example in lubricating oils for internal combustion engines, are said to be neutralization of produced acids, solubilization of sludge precursors, and dispersion of sludge. For this purpose, large amounts of succinimide dispersants are currently used, but recently the performance requirements for these dispersants have become increasingly strict. In other words, thermal deterioration of engine oil as engines become smaller and more efficient, and EG for exhaust gas regulations.
“Increase in spa and stop starting in urban areas” with R device
Problems include the generation of low-temperature sludge due to operation.

In addition, conventionally known ashless dispersants have one or two primary amino groups in their molecules as raw amines, and therefore the number of hydrocarbon-substituted succinic acids is one or two.
I could only do individual things.

Currently, the performance requirements for this dispersant are extremely diversified, and the balance of polar and non-polar groups in the molecule ranges from those that are extremely polar group-rich to those that are highly non-polar group-rich. requested. However, conventional ashless dispersants can only have one or two non-polar hydrocarbon groups, and can only have a very narrow balance between polar and non-polar groups.

Therefore, the purpose of the present invention is to provide an ashless dispersant that has excellent dispersion performance and antioxidant performance, can freely balance polar groups and non-polar groups, and has a synergistic effect with various other additives. It's about doing.

[Means for solving problems]

In order to solve the above problems, the present inventors conducted extensive research and arrived at the present invention. That is, the present invention provides general formula [I
] 82N(CI-T2CH2NH)nH (where n=1 to 10) To a polyethylene polyamine represented by 82N(CI-T2CH2NH)nH (where n=1 to 10), acrylonitrile (0.5 mol or more relative to N in 13 is added, and then hydrogenated) and/or a polyamine obtained by further adding acrylonitrile to this polyamine and repeating hydrogenation one or more times, the polyamine having an average molecular weight of 170 to 2000, and the reaction of a hydrocarbon-substituted succinic anhydride. This invention relates to an oil-soluble ashless dispersant containing the compound obtained in the following.

The polyamine used here has several to several tens of primary amine groups, and therefore, almost any number of hydrocarbon-substituted succinimide groups can be introduced depending on the purpose. Examples of the compound of formula 1a [I] used in the present invention include ethylenediamine, diethylenetriamine,
triethylenetetramine, tetraethylenepentamine,
Examples include pentaethylene hexamine and higher molecular weight polyethylene polyamines and mixtures thereof.

In the reaction between the compound of general formula N) and acrylonitrile, it is desirable to use 0.5 mol or more of acrylonitrile based on N in general formula [I]. If the amount is less than this, sufficient performance cannot be obtained in the finally produced oil-soluble ashless dispersant.

The reaction temperature is preferably such that the reaction is initially carried out at a low temperature of 50°C or lower for 2 to 10 hours, and then the reaction is carried out at 100°C for 0.5 to 5 hours to complete the reaction.

The nitrile addition reaction product is reduced with hydrogen gas and aminated. In this case it is advisable to use a catalyst. Catalysts for this purpose include, for example, nickel, Raney nickel,
What is commonly called a hydrogenation catalyst such as platinum can be used.

The conditions for the reduction reaction are, for example, when a Raney nickel catalyst is used, the catalyst amount is 0.5 to 3%, the temperature is 120 to 180°C, and the hydrogen pressure is 0 to 100 kg/cn+2. The reduction reaction time varies depending on the hydrogen pressure and temperature, but
For example, under a pressure of 50 to 80 kg/am2, at 150°C
When doing this, it should be done for about 30 minutes. In addition, it is preferable to coexist 5 to 10% of ammonia gas with hydrogen, since an amine with a higher proportion of primary amine can be obtained.

If ammonia gas is not present, the molecular weight distribution will be widened, but the desired product can be obtained if the molecular weight separated by passion separation is used as a raw material for the subsequent reaction. In order to obtain an amine with a higher molecular weight, this reaction of acrylonitrile addition and hydrogen reduction may be further repeated. The polyamine obtained as described above and used in the present invention has an average molecular weight of 170 to 2000, preferably 300. If the molecular weight is smaller than this, sufficient performance will not be obtained, and if it is larger, the viscosity will be too high and practical handling will be difficult. Further, in this polyamine, it is preferable that the primary amino groups account for 30% or more of the total amine groups in the polyamine.

The polyamine obtained as described above is reacted with hydrocarbon-substituted succinic anhydride.

This reaction can be carried out in the presence of an azeotropic dehydrating solvent such as toluene, benzene, xylene, etc. at normal pressure, or under reduced pressure in the case of no solvent, while dehydrating at 80 to 160°C, preferably 100 to 140°C. Note that when the reaction is carried out in the presence of a solvent, it is preferable to elute the solvent under reduced pressure after the reaction is completed.

The reaction time may be appropriately selected, but the higher the reaction temperature, the shorter the reaction time; for example, at a temperature of 120° C. or higher, 2 hours or less is sufficient.

The hydrocarbon-substituted succinic anhydride used in the present invention is not particularly limited, but it is preferably one obtained by reacting a long-chain alpha olefin or polybutene with maleic anhydride, and more preferably has an average molecular weight of 500. ~2
Succinic anhydride having 000 polybutenyl groups is preferred. The molar ratio of the reaction between the polyamine and the hydrocarbon-substituted succinic anhydride is preferably 2.0 moles or less of the hydrocarbon-substituted succinic anhydride to the primary amino groups in the polyamine.

If the amount of hydrocarbon-substituted succinic anhydride is greater than this,
The number of amide bonds increases, resulting in poor mineral oil solubility, dispersion performance, etc. If the amount is less than 0.2 mol, unreacted amine increases, and mineral oil solubility, dispersion performance, etc. also deteriorate.

However, in this case, there is no problem in terms of performance if the unreacted amine is removed by hot melting under reduced pressure.

The present invention relates to a novel ashless dispersant useful as a lubricant additive and a liquid fuel oil additive.6 Lubricants are typically made from a base oil or base material and various additives added depending on the application. The compound of the present invention can be used in combination with these base oils, base materials, and additives as appropriate. In particular, the dispersant of the present invention not only has excellent sludge dispersibility when used in lubricating oil, but also has antioxidant properties and is effective against extreme pressure agents, anti-wear agents, and friction modifiers that are added to lubricating oil. It has the ability to enhance its effect when combined with fire. Such additives that can be used simultaneously include S-based additives, P-based additives, CI-based additives, and M-based additives.
There are o-based additives, Zn-based additives, etc. -For example,
Zinc dithiophosphate, sulfurized olefin, sulfurized phosphoric acid ester, various organic molybdenum compounds, chlorinated paraffin, etc. are mentioned, but particularly preferably -maximum and /mana are general formulas [where R is 1 to 1 carbon atoms] 30 hydrocarbon groups containing or not containing an ether group, thioether group or carboxyl group, which may be different or the same, M is Z
It is an additive represented by (X-〇 or S may be the same or different)].

In addition, these additives and the ashless dispersant of the present invention have a dispersant:additive ratio of 1:50 to 50:1, preferably 1:1.
Preferably, they are used in a ratio of 0 to 10:1.

That is, the ashless dispersant of the present invention is obtained by adding 0.5 mol or more of acrylonitrile to the compound of formula (1) based on N in (1), and then hydrogenating it. and/or a polyamine obtained by further adding acrylonitrile to this polyamine and repeating hydrogenation one or more times, the polyamine having an average molecular weight of 170 to 2000, and the reaction of a hydrocarbon-substituted succinic anhydride. Oil-soluble ashless dispersant (
a) and at least one of the following lubricants (II) or l[) [wherein R contains a C1 to C1° hydrocarbon group, an ether group, a thioether group or a carboxyl group] or non-containing hydrocarbon groups, which may be the same or different, M represents Zn or (X is O or S, and may be the same or different); (a):(b )=1:50~50:1
, preferably in a ratio of 1:10 to 10:1.

In addition, various additives added depending on the purpose include:
Ash-forming detergents, corrosion and oxidation inhibitors, pour point depressants,
Examples include oily agents, coloring agents, anti-coloring agents, antifoaming agents, and the like.

The uses of the lubricant using the dispersant of the present invention are not particularly limited, and specific uses include automobile and truck engines, two-stroke engines, aircraft engines, marine engines, and t! Crankcase lubricants for spark-ignition and compression-ignition internal combustion engines, including diesel engines, as well as lubricants for gas engines, stationary power engines, and turbines, automatic transmission fluids, transaxle lubricants, and gear lubrication. Examples include lubricants, metalworking lubricants, and other lubricating oil and grease compositions.

[Example-1 Triethylenetetramine 292y (
456 g (8 mol) of acrylonitrile was added dropwise to 2 mol) over 2 hours, and then reacted at the same temperature for 5 hours.Next, the temperature was raised to 96°C over 2 hours, and the reaction was continued for 2 hours.Finally, the pressure was reduced. A nitrile composition was obtained. next,
This nitrile composition was heated in an autoclave using a Raney nickel catalyst (3% present), a hydrogen pressure cuff of 5kFI/cn+2,
Ammonia partial pressure 8kg/cm2.30 at 150℃
After reduction for 1 minute, polyamine 7052 was obtained. The analysis value of this polyamine is amine value 1160 ml? KOII/
g, primary amine was approximately 50%, secondary amine and tertiary amine were 30% and 20%, respectively. Further, the average molecular weight was about 350 as determined by gel permeation chromatography.

Production-Far Side-2 350g (about 1 mol) of polyamine produced in Production Example-1
was reacted with 285 g (5 moles) of acrylonitrile, and a polyamine was obtained in the same manner as in Example-1. The analysis value of this polyamine is amine value 1130 mgKO1l
/g, primary amine was about 45%, secondary amine and tertiary amine were 30% and 25%, respectively. The average molecular weight was about 600 as determined by gel permeation chromatography.

Warijun Milk-L Polyamine manufactured in Production Example-1 11.71? (0,0
33 mol) was dissolved in toluene 10011e, and 1.06y (0.1 mol) of polybutenyl succinic anhydride having a polybutenyl group having a molecular weight of 960 was added dropwise over 15 minutes at 80°C in a nitrogen stream. Water produced was separated and removed while raising the temperature and refluxing toluene, and the reaction was allowed to proceed for 2 hours. Finally, under a reduced pressure of 5 x 1 g, the temperature was raised to 140°C and toluene was added to obtain a high viscosity liquid. This high viscosity liquid has a nitrogen content of 3.3% and an infrared absorption spectrum of 1.
It was a polybutenyl succinimide with strong imide bond absorption at 701cz-'.

8.8 g (0,025
mol) and 106 g (0.1 mol) of polybutenyl succinic anhydride having polybutenyl groups with a molecular weight of 960 were carried out.
Polybutenyl succinimide was obtained by reacting in the same manner as A-1. Nitrogen content was 2.3%.

Harmful and 21 Polyamine 12.0I produced in Production Example-2? (0,0
2 mol) and 108 g (0.18 mol) of polybutenyl succinic anhydride having a polybutenyl group having a molecular weight of 960 were reacted in the same manner as in Example-1 to obtain polybutenyl succinimide. Nitrogen content was 2.8%.

The compounds obtained in Examples 1-3 and a conventional ashless dispersant were added to 100 neutral oil. While stirring 100 g of this oil at 25° C. in a 200+e1 beaker, concentrated sulfuric acid was added dropwise from a microbiulet, and the amount of concentrated sulfuric acid added until it started to become cloudy was measured. These results are shown in Table 1.

Table 1 Example-13,320,83 Tour 22.321.08 jl -32,821,96 Comparative product B Succinimide (bis type) Example-5 Polyamine 35y (0, 1 mole)
and 106 g (0.1 mol) of polybutenyl succinic anhydride 'fh having a polybutenyl group having a molecular weight of 960 were reacted in the same manner as in Example-1 to obtain polybutenyl succinimide. The nitrogen content was 7.3%.

Polyamine 17.5y (0,05
mol) and 106 g (0.1 mol) of polybutenyl succinic anhydride having a polybutenyl group with a molecule fi of 960 were reacted in the same manner as in Example-1 to obtain polybutenyl succinimide. The nitrogen content was 4.2%.

Example-7 30.0 g (0.05 g) of polyamine produced in Production Example-2
mol) and 106 g (0.1 mol) of polybutenyl succinic anhydride having a polybutenyl group having a molecular weight of 960 were reacted in the same manner as in Example-1 to obtain polybutenyl succinimide. The nitrogen content was 6.3%.

Support 1''-1 The degree of sludge formation of the monster obtained in each example and the commercial product was compared by an oil deterioration test using the ISO method.

Test method The compounds obtained in each example were dissolved in 200 mZ of 500 N tral oil and stirred vigorously at 165.5° C. for 48 hours in the presence of iron and copper. Next, this oil was dropped onto approximately 1-me filter paper, and the degree of sludge formation was observed. The results are shown in Table 2.

Table 2 Attachment ``Opening 1'' [Example - 11% Trace amount 2], IR amount 3
1 Not at all 5 1 Not at all 6 1 Not at all 7 1 Comparative product A, not at all 1 A small amount B
1 Small amount C1 Quite a lot D 1 Quite a lot 1 discharge 2 11゜ The compounds obtained in each example were combined with a commercially available ashless dispersant and an organic molyfinanization solution, and the friction reduction effect was tested using a repeated vibration friction tester. It was measured. The measurement results are shown in Table 3.

Measurement conditions: Concentration; Example compound 2% Commercially available dispersant 2% No-DTC
Asahi Denka's Cuteto 7゛100)) 1,0% (420 pp+* as Mo) No-DTP (warp)
)) 0.5% (450 ppm as Mo) Temperature; 12
0°C Load: 12.2kgf Frequency: 500rpm Amplitude: 2.5mm Test piece: Material 5UJ-2 Upper 3/4 inch ball, lower flat plate Base oil: 150 nitral oil Example-1+ No -DTP 0. 051
77 -2+ II O,055 not -3+ not
0.04111-5+17 0
．． 043 knots -6+ 77
0.052 knots -3+
No -DTC0,043H-5+ n
O,048 Comparative product A + No -DTP
0.10311 B + Not
O,096 knots
C+n
O,108II A 10Ha -DTCO
, 16211D+ II
0.157 Example-5 alone 0
．． 189No-DTP alone 0.
101No-DTC alone 0.1
58 base oil alone 0.223% starvation 92 Lυ and a commercially available ashless dispersant and ZD were added to the compound obtained in the example.
In combination with TP, the anti-wear effect was measured using a high-speed four-ball tester. The measurement results are shown in Table 4.

Measurement conditions: Concentration; Example compound 2% Commercially available dispersant 2% ZDTP (zinc dithiophosphate 1.1% (Zn
As i o o o ppm)) Temperature: 80℃ Load: 40ky Rotation speed: 1800rpm Base oil: 150 Neutral oil Daiichi-Ichisai-j! Example-1+ZDTP (C, 2nd class) 0.341
ノ -2+ 7ノ
0.36 no 7 -3 ten
Noah 0.3
177 −5+ n O
,34/7 -6+ 11
0.33n -7+ 77
0.42! No -
3 +ZDTP (C, 1st grade) 0.
43 Noah -5+ 17
0.42 Comparative product A + ZDT
P (C, 2nd grade) 0.571JB 10
Horn 0.
49 Noah C-f-tt
O, 531t A +
ZDTP (Ca1 class) 0.68
D + not
O, 74 Example-3 alone 0.9
3ZDTP (C, 2nd grade) alone 0.58
ZDTP (C, 1st grade) alone 0.78 Base oil alone 0.98 [Effects of the invention] The effects of the present invention are that it has excellent dispersion performance and antioxidant performance, and can freely balance the polar groups and non-polar groups. The object of the present invention is to provide an ashless dispersant that can be used as an ashless dispersant and has a synergistic effect with various other additives.

Claims (1)

[Claims] 1. General formula H_2N(CH_2CH_2NH)_nH...[
I] (where n = 1 to 10) to a polyamine obtained by adding 0.5 mole or more of acrylonitrile to the N in [I] and then hydrogenating it, and/or to this polyamine. Furthermore, an oil containing a polyamine obtained by repeating addition of acrylonitrile and hydrogenation one or more times and a compound obtained by reacting a polyamine with an average molecular weight of 170 to 2000 with hydrocarbon-substituted succinic anhydride. Soluble ashless dispersant. 2. The molecular weight of the polyamine is 300 to 1100, and the number of primary amino groups is 30 to 30% of the total amino groups in the polyamine.
% or more, and 35% or less of tertiary amino groups. 3. Hydrocarbon-substituted succinic anhydride has an average molecular weight of 500~
The oil-soluble ashless dispersant according to claim 1 or 2, which is succinic anhydride having 2000 polybutenyl groups. 4. The dispersant is a lubricant with at least one of the following general formulas [II] or [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼...・[III] [Here, R is a hydrocarbon group of C_1 to C_3_0, or a hydrocarbon group containing or not containing an ether group, a thioether group, or a carboxyl group, which may be the same or different, and M is Zn or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (X is O or S, and may be the same or different)] Any one of claims 1 to 3 containing the following The dispersant described in.