JP2002534436A - Triazine derivatives as dispersants for lubricants and fuels - Google Patents

Abstract

  (57) [Summary] Process for preparing triazine derivatives, reaction products of the process, lubricating oil compositions, fuel compositions, and additive concentrates containing such reaction products, as well as additives for dispersants of the reaction products use.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to triazine derivatives, their preparation, lubricating oil compositions, fuel compositions and additive concentrates containing them, and their use as additives for dispersants. According to the present invention, there is provided a method for preparing a triazine derivative, comprising the following steps:
(i) the (a) formula of the compound, then reacted with a polyamine (II) having at least two -NH ₂ groups and / or -NH groups; and

[0002]

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(B) reacting the product of step (a) with a polyalkenyl derivative and / or a chlorinated polyalkenyl derivative of an ethylenically unsaturated carboxyl reactant; or (ii) (a) Reacting the compound of I) with a lipophilic amine, (b) reacting the product of step (a) with a polyamine (II), and (c) reacting the product of step (b) with an ethylenically unsaturated Reacting the carboxyl reactant with a polyalkenyl derivative and / or a chlorinated polyalkenyl derivative; or (iii) (a) reacting the compound of formula (I) with a preformed ethylenically unsaturated carboxyl reactant The polyamine (II) used to react with the reaction product of the alkenyl derivative and the polyamine (II) and (b) optionally forming the product of step (a) to form the preformed reaction product Same or different polyamine (II) or lipophilic amine React step; wherein each R can be the same or different from each other, a chlorine atom, amino or hydroxyl group, or a group selected from the following formulas:

[0004]

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(Where R¹Is an alkyl group; R^TwoIs a hydrogen atom or an alkyl group; R^Three, R ^Four And R^FiveCan be the same or different from each other, and each represents a hydrogen atom or an alkyl group.
Yes; and n is 0 or 1. Or (iv) each R can be the same or different from each other and is an amino or hydroxyl group
Such a compound of formula (I) is converted to an ethylenically unsaturated carboxyl reactant polyalkene.
Step (iii) in the reaction of step (iii) (a) unless step (iii) (b) is carried out in the reaction of step (iii).
Is a chlorine atom, or one R is an amino group and the other is a chlorine atom
For example, the polyamine (I) used to form the aforementioned preformed reaction product
I) is not diethylenetriamine or tetraethylenepentamine.

In the compound of formula (I), each R is preferably a chlorine atom, an amino or hydroxyl group, or a group selected from the following formula:

[0007]

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[0008] The compounds can be prepared by methods known in the art. formula
Particularly preferred examples of the compounds of (I) are melamine, cyanuric chloride and cyanuric acid. Polyamine (II) comprises at least two -NH ₂ groups and / or -NH groups, these groups, having at least one active hydrogen respectively thereon. Examples of polyamines useful in the present invention are those disclosed on page 16, line 21 to page 19, line 53 of EP 0 237 569.

Preferred polyamines are compounds of the general formula: H ₂ N— (CHR ¹ ) _x —CH ₂ — [A—CH ₂ — (CHR ¹ ) _x ] _y —NH ₂ (III) , A is -NH or -0, each R ¹ independently represents a hydrogen atom or a methyl group, x is in the range of 1-3, and if A is -NH, Is in the range of 1 to 10, and A
If is -0-, y ranges from 1 to 200. ). y can be 0. In the above formula (III), A is -NH, and thus x is 1, each R ¹ represents a hydrogen atom, and y ranges from 1 to 8; or, A is -0- Preferably, x is 1 and each R ¹ represents a methyl group, and y is in the range of 1 to 50.

Preferred polyamines are polyethylene and polypropylene polyamines, especially ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetraamine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA) and hexa Ethylene heptamine (HEHA). Particularly preferred are EDA and DETA.

[0011] The ethylenically unsaturated carboxyl reactant has a total of at least 3 carbon atoms, preferably
Preferably a total of 3 to 50, more preferably 3 to 30, even more preferably 4 to 20
, And even more preferably 4 to 10 carbon atoms. The ethylenically unsaturated carboxyl reactant is described in EP 0285609, page 6, line 15
Et al., Line 48 or EP-B-0287569, page 6, lines 11 to 39.
-Β-olefin-based unsaturated carboxyl reactant, for example, acrylic acid (C_Three),
Tacrylic acid (C_Four), Cinnamic acid (C₉), Crotonic acid (C_Four), 2-phenylpropenoic acid (C₉),
Maleic acid (C_Four), Fumaric acid (C_Four), Glutaconic acid (C_Five), Mesaconic acid (C_Five), Itacon
Acid (methylene succinic acid) (C_Five), Citraconic acid (methylmaleic acid) (C_Five), And it
Functional derivatives such as anhydrides (e.g., anhydrous maleic
Inic acid (C_Four), Glutaconic anhydride (C_Five), Itaconic anhydride (C_Five), Citraconic anhydride (C _Five ))), Esters (e.g., methyl acrylate (C_Four)), Amide, imide, salt, halo
Acyl genoides and nitriles. Preferably, the ethylenically unsaturated carboxyl reactant is a monoethylenically unsaturated C_Four -C_TenSelected from dicarboxylic acids and anhydrides, maleic anhydride being the most preferred
No.

[0012] The polyalkenyl derivative of the ethylenically unsaturated carboxyl reactant can be prepared by methods known in the art. For example, if the ethylenically unsaturated carboxyl reactant is maleic anhydride, these polyalkenyl derivatives may be conveniently combined with a polyalkene and a specific amount of a compound such as disclosed in GB-A-949981. It can be prepared by mixing maleic anhydride and passing chlorine through the mixture. Alternatively, this derivative is disclosed in British Patent Publication No. 1483.
As disclosed in Japanese Patent No. 729, it can be prepared by reacting a polyalkene with a specific amount of maleic anhydride by heating at an appropriate temperature. EP 0542380 discloses a process for the preparation of such derivatives, wherein the molar ratio of maleic anhydride to polyalkene is greater than 1: 1 and the temperature range 150-260 ° C. and polyaddition- It involves the reaction of a polyalkene with maleic anhydride in the presence of an inhibiting amount of sulfonic acid. The molar ratio of ethylenically unsaturated carboxyl moiety to polyalkenyl moiety in the resulting derivative is preferably from 1: 1 to 5: 1, more preferably from 1: 1 to 3.
5: 1, especially 1.5: 1 to 1.2: 1. Chlorinated polyalkenyl derivatives can also be prepared by methods known in the art, such as by passing chlorine through the polyalkene.

[0013] The polyalkene used in the preparation of the polyalkene derivative can be, for example, a homopolymer or a copolymer, at least one of which is a C ₂ -C ₁₀ monoolefin. Preferably the polyalkene is a polymer of at least one C ₂ -C ₅ mono-olefins such as ethylene - propylene copolymer. Monoolefin is preferably a C ₃ -C ₄ olefins, in particular propylene or isobutylene, preferred polyalkenes derived therefrom include polyisobutylenes and atactic or isotactic or syndiotactic propylene oligomers. Polyisobutylenes such as those sold by BASF under the trademark "GLISSOPAL" and those sold by the British Petroleum Company under the trademark "ULTRAVIS" (both have high levels of terminal vinylidene unsaturation (about 80-90%). Has), `` HY
VIS "and" NAPVIS "such as" HYVIS 75 "," HYVIS 120 "," NAPVIS 10 ",
"HYVIS 200" and "NAPVIS 120" polyisobutylene are particularly preferred for use in the present invention. These polyalkenes preferably have a number average molecular weight (Mn) ranging from 300 to 7000, more preferably from 500 to 5000, even more preferably from 700 to 3000.

The lipophilic amine used in the present invention may be linear, branched, saturated or unsaturated and includes aromatic amines. Particularly preferred are dodecylamine (C _12), dioctyl amine (C ₁₆₎ and oleylamine (C _18). Instead of "P
RIMENE ”tert-C ₁₈ No. 1 sold as JMT (exclusive distribution right: ROHM HUSS)
Secondary amines can be used.

The reactions (i) (a) and (ii) (b) are preferably carried out at a temperature of 30 to 200 ° C., more preferably 40 to 18 ° C.
It is carried out at 0 ° C, especially at 50-170 ° C. This reaction is performed in the presence of a solvent. Furthermore,
In this reaction, it is preferred to use a molar excess of polyamine (II) over the compound of formula (I), in particular a molar ratio of 2: 1 to 20: 1, more particularly 5: 1 to 16: 1. ,
In particular, it is 9: 1 to 16: 1. Reaction (ii) (a) is preferably carried out in a temperature range of 0 to 10 ° C, more preferably 0 to 5 ° C. This reaction can be carried out in the presence of a solvent and in the presence of a base such as sodium carbonate or sodium bicarbonate. The product of this reaction is subjected to an aqueous wash.

Suitable solvents are hydrocarbon solvents such as higher alkanes, toluene, xylene, mesitylene, such as “SH, available from the Royal Dutch Shell Group of Companies.
ELLSOL® "A solvent; furthermore, synthetic and mineral oils such as" HVI-60 "; ether solvents, such as tetrahydrofuran and 1,4-dioxane; nitriles, such as acetonitrile; 1-pentanol ( There are alcohols, such as amyl alcohol) and 2-methyl-2-propanol (tert-butyl alcohol); and chlorohydrocarbons, such as 1,1,1-trichloroethane. The method can be performed in the absence of a solvent, but, as noted above, this is conveniently performed in the presence of a solvent. Either water or excess alcohol can be removed, for example, using a Gene-Stark trap.

Reactions (i), (b) and (ii) (c) are preferably carried out in a temperature range of 140 to 230 ° C., more preferably 1 to 230 ° C.
Performed at 50-210 ° C. These are more preferably performed in the presence of an inert gas, such as a nitrogen purge. The molar ratio of the products of reactions (i) (a) and (ii) (b) to the polyalkenyl derivative of the ethylenically unsaturated carboxyl reactant is preferably in the range of 1: 1 to 10: 1, more preferably Is 1: 1 to 5: 1, especially 1: 1 to 2.5: 1.

Reaction (iii) (a) is preferably carried out in a temperature range of 120-280 ° C, more preferably 140-240 ° C.
Done in Reaction (iii) (b) is preferably performed at a temperature in the range of 120 to 280 ° C, more preferably 140 to 240 ° C.
Done in Reaction (iv) is preferably carried out in a temperature range from 25 to 280 ° C, more preferably from 100 to 240 ° C. In the process of the present invention, the molar ratio of lipophilic amine: compound of formula (I) is preferably 1
: 1: 1 to 10: 1, more preferably 1: 1 to 5: 1, especially 1: 1 to 2: 1.

Polyalkenyl derivatives of ethylenically unsaturated carboxyl reactants and polyamines (I
The preformed reaction product of I) can be prepared according to a conventional method in the art. Thus, for example, if the ethylenically unsaturated carboxyl reactant is maleic anhydride and the polyamine is an ethylene polyamine, these may be conveniently used, for example, as disclosed in EP-A-0587250. The alkenyl derivatives are reacted with one another in a hydrocarbon solvent having a molar ratio of polyamine of 1: 1 to 4: 1 and a temperature range of 100 to 250 ° C. The binding molar ratio of the polyalkenyl derivative to the amine in the product is preferably in the range of 1: 1 to 3: 1, more preferably
It is 1: 1 to 2.5: 1.

The molar ratio (polyalkenyl derivative of the ethylenically unsaturated carboxyl reactant) :( polyamine) for the reactants of the present invention is preferably in the range of 1: 1 to 4: 1,
More preferably, it is 1: 1 to 3: 1, most preferably 1: 1 to 2.5: 1. The present invention further provides the reaction product of the above method according to the present invention. The reaction products of the present invention can be used as additives in lubricating oils. Therefore,
The invention relates to a large amount (greater than 50% by weight) of lubricant base oil and a small amount (less than 50% by weight) of the reaction product of the invention, preferably 0.1-20% by weight, in particular 0.5-10% by weight (active substance) The present invention provides a lubricating oil composition containing the composition, wherein the weight percent is based on the total weight of the composition.

[0021] Lubricant formulations can be made by adding an additive package to the lubricating oil. If the finished lubricant formulation is for a multigrade, it may contain small amounts of viscosity improvers. The type and amount of additive package used in this formulation depends on the end use, which includes automotive and truck engines, marine and railway diesel engines, gas engines, stationary power engines and turbines. Ignition and compression ignition internal combustion engines can be included. Lubricating oil formulations have been coordinated by the American Society of Automotive Engineers (SAE), the American Petroleum Institute (API), and the American Society for Testing and Materials (ASTM) to a set of performance specifications as classified in the United States. Formulated to match. In addition, the American Automobile Manufacturers Association (AAMA) and the Japan Automobile Manufacturers Association (JAMA) have agreed to the International Lubricant Certification Committee.
Through the Standardization and Approval Committee (ILSAC), jointly announced the minimum performance standards for gasoline-fueled passenger car engine oils.

In Europe, classification of engine oils is based on the technical group of petroleum additive manufacturers (Technical
Committee of Petroleum Additive Manufacturers (ATC) and Association Technique de l'Industries Europeens des Lubr
It has been established by the European Association of Automobile Manufacturers (ACEA) with the advice of ifiants (ATIEL). In addition to these internationally recognized oil classification systems, many, but not all, original equipment manufacturers (OEMs) have developed lubricating oil formulations used in initial (i.e., factory) fillings. Have their own in-house requirements that must be met.

Suitable lubricating base oils are natural, mineral or synthetic lubricating oils. Natural lubricating oils include animal and vegetable oils, for example, castor oil. Mineral oils include lubricating oil fractions derived, for example, from crude, coal or shale oils of the naphthenic or paraffinic type or mixtures thereof, to which specific treatments such as acid clay, solvents or hydrotreating. Will be applied. Synthetic lubricating oils include those known in the art from synthetic polymers of hydrocarbons, such as polyalphaolefins, isomerized slack waxes, modified alkylene oxide polymers and esters. These lubricating oils are preferably crankcase lubricating oil formulations for spark ignition and compression ignition internal combustion engines, but also include hydraulic lubricants, working lubricants, and automatic transmission oils. Preferably, the lubricant base oil component of the composition of the present invention is a mineral oil lubricating oil or, for example, an "HV
A mixture of mineral oils and lubricants, such as those sold by members of the Royal Dutch Shell Group of Companies under the name "I", or by a member of the Royal Dutch Shell Group of Companies under the name "XHVI" (R) It is a synthetic hydrocarbon base oil sold.

[0024] The viscosity of the lubricant base oil composition of the present invention can vary over a wide range, and generally is 3~35mm ² / s at 100 ° C.. The lubricating oil composition of the present invention can contain various other additives known in the art, such as: (a) a viscosity index improver or modifier. The viscosity modifier can be in the solid or concentrated form in a natural or synthetic base material, and by mixing this, the viscosity index
Substantially improve (e.g., ASTM method D2270) (e.g., at least up to 5 units)
Such a substance is usually defined as a polymer. These can all be mixed into the finished lubricant formulation to provide their desired performance characteristics. Examples of such viscosity modifiers are linear or star polymers of dienes such as isoprene or butadiene, or copolymers of such dienes with optionally substituted styrene.
These copolymers are suitably block copolymers and preferably can be hydrogenated to an extent that saturates most of the olefinic unsaturation. Many other types of viscosity modifiers are known in the art, many of which include:
Proceedings of Conference "Viscosity and flow characteristics of multi-grade engine oil (V
iscosity and flow properties of multigrade engine oils) ", Esslingen, Germany, December 1977. In the art, viscosity modifiers are functionalized for incorporation of viscosity adjustment in addition to dispersibility (e.g., dispersant viscosity index improvers based on block copolymers) and / or antioxidant functions, and It is also known to have a pour point of the dispersant mixed with the product which can also cope with cold weather.

(B) Ashless or ash extreme pressure / wear additives, such as those of the metal-containing dithiophosphate or ashless dithiocarbamate type, and mixtures thereof. The actual composition of the individual components will vary depending on the end use, and thus can be based on the type of metal ion and the range of various alcohols, where both the alkyl and aryl moieties are Can fluctuate. Preferred is zinc dithiophosphate (ZDTP)
Or sodium dithiophosphate. (c) Dispersants include succinimide and Mannich bases, borated versions with varying molecular weight and amine species, and esters of varying types and molecular weights. Preferably, an ashless dispersant, such as a polyolefin-substituted succinimide, such as those disclosed in GB-A-2 213 873. (d) For example, “IRGANOX” (registered trademark) L57 (tert-C ₄ -C ₁₂ alkyldiphenylamine
) Or IRGANOX® L135 (2,6-di-tert-butyl-4
-Antioxidants, such as phenol type such as-(2-carboxy (alkyl) ethyl) phenol) (exclusive sales right: CHIBA Specialty Chemical Company) or a soluble copper compound having a copper concentration of 50 to 500 ppm.

(E) Rust inhibitors, for example of the ethylene / propylene block copolymer type. (f) Friction modifiers for fuel economy, which are either metal (eg molybdenum) -containing or metal-free esters and amines, or synergistic mixtures thereof. (g) metal-containing surfactants, such as phenates, sulfonates, salicylates or naphthenates, or mixtures thereof, all of which are neutralized or overbased. And such overbased surfactants are carbonates, hydroxides, or mixtures thereof. The metal is preferably calcium, magnesium or manganese, but alkali metals such as sodium and potassium can also be used. (h) Copper passivating agents, preferably of the alkylated or benzylated triazole type. The reaction products of the present invention can also be used as additives in fuels. Therefore,
The invention further relates to a large amount (greater than 50% by weight) of base fuel and a small amount (less than 50% by weight), preferably 0.001-2% by weight, more preferably 0.001-0.5% by weight and especially 0.002-0.2% by weight.
There is provided a fuel composition comprising% by weight (active substance) of the reaction product of the present invention, wherein% by weight is based on the total weight of the composition.

Suitable base fuels include gasoline and diesel fuel. These base fuels
It may contain a mixture of saturated, olefinic and aromatic hydrocarbons, and may contain, for example, levels of sulfur ranging from 0.001 to 0.1% by weight. These can be derived from straight run gasoline, synthetically produced aromatic hydrocarbon mixtures, thermocatalytically cracked hydrocarbon feedstocks, hydrocracked petroleum fractions or catalytically reformed hydrocarbons. .

The fuel composition of the present invention may contain various other additives known in the art, such as: (a) an anti-knock agent, such as a lead compound, or methylcyclopentadienyl- Other compounds such as manganese tricarbonyl or ortho azidophenyl; (b) antiknock assistants, such as benzoylacetone; (c) antifogging agents (dehazer), such as the commercially available “NALCO” ® EC5462A (exclusive distribution right) : Narco), "TOLAD" (registered trademark) 2683 (exclusive sales right: Baker Petrolite), EXP177, EXP159M, EXP175, EP409 or EP435 (exclusive sales right: RE Specialty Chemical Company), and T9360-K , T9305, T9308, T9311 or T327 (exclusive distribution rights: Baker Petrolite);

(D) Antifoaming agents, for example the commercially available “TEGOPREN” ® 5851, Q25907, MR1027, M
R2068 or MR2057 (Exclusive sales right: Dow Corning), "RHODORSIL" (registered trademark)
(Exclusive sales rights: Rhone-Poulenc) and "WITCO" (registered trademark) SAG TP325 or
SAG327 (exclusive sales right: Witco); (e) ignition improvers (eg, 2-ethylhexyl nitrate, cyclohexyl nitrate, di-tert-
Butyl peroxide, and those disclosed in U.S. Patent Application No. 4208190, column 2, line 27 to column 3, line 21); (f) Rust inhibitors (e.g. from Rhein Chemie, Mannheim, Germany) Those sold as "RC 4801" or polyhydric alcohol esters of succinic acid derivatives, unsubstituted or substituted aliphatic hydrocarbon radicals having from 20 to 500 carbon atoms on at least one of its alpha carbon atoms (E.g., pentaerythritol diester of polyisobutylene-substituted succinic acid); (g) fragrance (h) antiwear agent (i) antioxidant (e.g., 2,6-di-tert Phenolic, such as -butylphenol, or phenylenediamines, such as N, N'-di-sec-butyl-p-phenylenediamine); (j) metal deactivators

(K) Lubricity agent, such as the commercially available EC831, “PARADYNE” ® 6
31 or 655 (exclusive rights: Paramin Inc.), or "VEKTRON" (registered trademark) 6010 (exclusive rights: Shell Additives International, Inc.); (l) a liquid carrier such as polyethers, for example C ₁₂ -C ₁₅ alkyl-substituted propylene glycol (“SAP 949”), “HVI” or “XHVI” ® base oils (commercially available from members of the Royal Dutch / Shell group of companies), C ₂ -C ₆ monomers Polyolefins of origin, for example polyisobutylene having 20 to 175, in particular 35 to 150, carbon atoms, or a viscosity at 100 ° C. of 2 × 10 ⁻⁶ to 2 × 10 ⁻⁵ m ² / s (2 to 20 centistokes) ), Which is a hydrogenated oligomer having 18 to 80 carbon atoms derived from at least one alpha olefin-based monomer having 8 to 18 carbon atoms.

The lubricating oil and fuel composition of the present invention can be prepared by adding the reaction product of the present invention to a lubricant base oil or base fuel. Conveniently, the additive concentrate
It is blended with a lubricant base oil or base fuel. Such concentrates generally contain an inert liquid carrier and one or more additives in concentrated form. The invention therefore also provides an additive concentrate containing an inert liquid carrier and 10 to 80% by weight (active substance) of the reaction product according to the invention, the weight% being based on the total weight of the concentrate. I have to. Examples of inert liquid carriers include hydrocarbons and mixtures of hydrocarbons with alcohols or ethers, such as methanol, ethanol, propanol, 2-butoxyethanol or methyl tert-butyl ether. For example, the liquid carrier may be an aromatic hydrocarbon solvent such as toluene, xylene, mixtures thereof, or a mixture of toluene or xylene and an alcohol. Alternatively, the liquid carrier is a mineral oil base oil or a mixture of mineral oil base oils, such as "HVI 60" base oil sold under the name "HVI" by a member of the Royal Dutch / Shell group of companies. ,
Or "XHVI" (registered trademark) from a member of the Royal Dutch / Shell Group
There is a synthetic hydrocarbon base oil sold under the name.

[0032] Non-limiting examples of suitable additive concentrations in the final formulated lubricating oil composition are as follows:

[Table 1]

The following are non-limiting examples of suitable additive concentrates for formulating lubricating oil compositions:

[Table 2]

The present invention further provides the use of the reaction product of the present invention as an additive for a dispersant.
The invention will now be further described with reference to the following examples. In these examples,
Number average molecular weights ( _Mn ) specified for the polyisobutenyl moiety of polyisobutenyl succinic anhydride (PIBSA) are, for example, WW Yau, JJ Kirkland and DD Bl
y, `` Modern Size Exclusion Liquid C
hromatography), determined by gel chromatography using polystyrene standards, as described in John Wiley and Sons, Inc., New York, 21979.
Examples 1-4 illustrate the steps of reaction (ii).

Example 1 (a) Cyanuric chloride (0.01 mol) in toluene is reacted at 5 ° C. with dodecylamine (0.01 mol), which is a lipophilic amine, in the presence of an aqueous solution of sodium hydrogencarbonate (0.02 mol). did. After washing with an aqueous solution, the mixture was separated to give the desired crude 6-dodecylamino-2,4-dichloro-1,3,5-triazine ("alkylamino cyanuric chloride") in 99% isolated yield. . (b) Then, DETA was reacted with the alkylamino cyanuric chloride of step (a) at a temperature of 60 ° C. (molar ratio 10: 1). The product was isolated by toluene / water partition to give a yield of 82%. (c) The product of step (b) in toluene was added to low molecular weight PIBSA (PIB M _n about 950). The toluene was distilled off and heated at 160 ° C. for 6-7 hours continuously under a nitrogen purge.

Example 2 The procedure described in Example 1 was followed, except that high molecular weight PTBSA (PIB M _n about 2270) was used in step (c). Example 3 Example 1 was followed, except that in step (a) dioctylamine was used as the lipophilic amine. Example 4 Example 2 was followed, except that in step (a) dioctylamine was used as the lipophilic amine.

Examples 5-17 Further compounds were prepared and the characteristics of all of these examples are summarized in Table 1:

[Table 3] Table 1

Example 18 Carbon Black Dispersion Test (CBDT) (British Rail Publication BR 669: 1984) SAE 15W40 Middle East lubrication containing a package of commercially available zinc dialkyldithiophosphate, overbased calcium alkylsalicylate and VI improver Oil samples,
The reaction products of Examples 1 to 4 were modified by mixing to give an oil containing the products at a concentration of 1% by weight of active substance. Thereafter, 3% by weight of carbon black was added to each oil and the (%) increase in kinematic viscosity was determined at 60 ° C. using a Ubbelohde viscometer. Low results indicate good performance. The absolute value obtained depends on the effective surface area of the carbon black used, so that a series of comparisons must be performed on the same carbon black sample. These tests were performed using "Flamruss" (R) carbon black. The test results are shown in Table 2:

[0039]

[Table 4] Table 2 * Comparison to viscosity of dispersant formulation without carbon black

Example 19 Rheology Test This test uses a Haake RV2O Rotary Viscometer and a known concentration of the test dispersant.
(2% by weight of active substance) to the mixture of other compounds, resulting in a fully formulated oil. After that, carbon black was added and the oil content was 4.76% by mass.
And mixed at high temperature (90 ° C.) for a period of time (at least 6 hours). Next, the viscosity properties of the oils containing Examples 5 to 14 were measured and, under the same conditions, the commercial products "SAP 286" and "SAP 2"
30TP "(mono / bis-PIB succinimide, exclusive distribution rights: Shell Additive International).

The base oil formulation used for the Haake rheology test consisted of the following components:

[Table 5]

[0042] The Haake rheology test apparatus is a Haake RV 20 equipped with an RC 20 rheo controller.
Consists of a rheometer and a CV 100 measurement system with a ZA 30 cup and rotor. Samples were prepared by weighing a dispersant sample g (100 / active substance) and weighing 5.75 g with HVI-60-AL base oil followed by a total mass of 50 g with base oil formulation. Carbon black (grade XC72) was activated at 140 ° C. for at least 12 hours before being used for rheological testing. A carbon black amount of 0.25 to 0.30 g was measured, and the completely blended oil was added in an amount calculated by the following formula: M _FFO = M _C × 20 (where M _FFO is the amount of the completely blended oil it is the mass (g), and M _C is the mass of carbon black.). The mixture was made completely homogeneous with oil. After maintaining at 90 ° C. for at least 6 hours, the viscosity properties were measured over the shear rate range for 30 minutes and are shown in FIG. From FIG. 1, it was recognized that Examples 5 to 14 exhibited improved dispersibility compared to “SAP 286” and “SAP 230TP”.

Example 20 Fluoroelastomer Seal Test The reaction product of the present invention was less strong against the fluoroelastomer seal, as shown by the Mercedes-Benz fluoroelastomer seal test.
When the fluoroelastomer seal was applied to the formulation containing Example 5, its tensile strength was reduced to 13.3% and the extent to which it could stretch before breaking was reduced by only 17.6%; Containing "SAP 286" and "SAP 230TP",
The values for a similar formulation at the same dispersant treat rate (13.5 wt%) are also shown in Table 3:

[0044]

[Table 6] Table 3

Example 21 Corrosion Test The reaction product of the present invention exhibited reduced corrosion as shown in the L-10 bench corrosion test without strict control (see API CG-4 test). . Same dispersant treatment rate (13.5
(% By mass) are shown in Table 4. From this, "SAP 286" and "SAP 230TP"
It is clear that the performance improvement of Example 5 was shown as compared to:

[0046]

[Table 7] Table 4

[Brief description of the drawings]

FIG. 1 shows the viscosity properties measured at 90 ° C. for at least 6 hours and then over the shear rate range for 30 minutes.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C10M 133/06 C10M 133/06 133/42 133/42 133/54 133/54 135/10 135/10 159 / 12 159/12 // C10N 30:04 C10N 30:04 (72) Inventor Shaw Robert William UK Kent M10 10 1 Piwi Sittinbourne Gadby Road 89 (72) Inventor Crane Anthony E United Kingdom Chasha Sea H 39 9 HTB Totten Hall ghost field 1F term (reference) 4H104 BC05R BC09R BD07R BE02R BE28R BF01R BG06R DB01C LA02

Claims (19)

[Claims] 1. A method for preparing a triazine derivative, comprising the steps of: (i) (a) converting a compound of the formula_TwoHaving a group and / or -NH group
Reacts with rearamine (II); and(b) converting the product of step (a) to a polyalkenyl ethylenically unsaturated carboxyl reactant;
Reacting with a derivative and / or a chlorinated polyalkenyl derivative; or (ii) reacting (a) a compound of formula (I) with a lipophilic amine, and (b) reacting the product of step (a) with: Po
Reacting with the amine (II) and (c) converting the product of step (b) to an ethylenically unsaturated carboxylic acid.
Derivation of polyalkenyl derivatives and / or chlorinated polyalkenyls of sil reactants
(Iii) reacting the compound of formula (I) with a preformed ethylenically unsaturated carboxyl reaction.
Reacts with the reaction product of the polyalkenyl derivative of the agent with the polyamine (II), and (b)
Using the product of step (a) to form the preformed reaction product
The same or different polyamine (II) as the
Reacting with an oleaginous amine; wherein each R can be the same or different from each other and is a chlorine atom, amino or
A hydroxyl group, or a group selected from the following formula:(Where R¹Is an alkyl group; R^TwoIs a hydrogen atom or an alkyl group; R^Three, R ^Four And R^FiveCan be the same or different from each other, and each represents a hydrogen atom or an alkyl group.
Yes; and n is 0 or 1. Or (iv) each R can be the same or different from each other and is an amino or hydroxyl group
Such a compound of formula (I) is converted to an ethylenically unsaturated carboxyl reactant polyalkene.
Reaction with a polyalkenyl derivative of a polyamine (II) or a polyamine (II), provided that, in the reaction of the step (iii) (a), unless the step (iii) (b) is performed,
R is a chlorine atom, or one R is an amino group and the other is a chlorine atom
If necessary, the polymer used to form the aforementioned preformed reaction product
The amine (II) is not diethylenetriamine or tetraethylenepentamine,
Notation. 2. The method of claim 1, wherein each R is a chlorine atom, an amino or hydroxyl group, or a group selected from the following formula. Embedded image 3. The method according to claim 1, wherein the polyamine is ethylenediamine or diethylenetriamine. 4. The method of claim 1, wherein steps (i) and (a) are performed in a temperature range of 30 to 200 ° C.
4. The method according to 2 or 3. 5. The method according to claim 1, wherein steps (i) and (b) are performed in a temperature range from 140 to 230 ° C. 6. The method of claim 1, wherein step (ii) (a) is performed in a temperature range of 0 to 10 ° C.
4. The method according to 2 or 3. 7. The method of claim 1, wherein step (ii) (b) is performed in a temperature range from 30 to 200 ° C.
The method according to any one of claims 1 to 3. 8. The method according to claim 1, wherein step (ii) (c) is performed in a temperature range of 140 to 230 ° C.
8. The method according to any one of claims 3, 6, and 7. 9. The method according to claim 1, wherein step (iii) (a) is carried out in a temperature range from 120 to 280 ° C. 10. The method according to claim 1, wherein step (iii) (b) is carried out in a temperature range from 120 to 280 ° C. 11. The method according to claim 1, wherein the reaction (iv) is carried out in a temperature range of 25 to 280 ° C.
4. The method according to 2 or 3. 12. The method according to claim 1, wherein the ethylenically unsaturated carboxyl reactant is selected from monoethylenically unsaturated C _4-10 dicarboxylic acids and anhydrides. 13. The process according to claim 1, wherein the polyalkenyl derivative is derived from a polyalkene, which is a polymer of at least one C _2-10 monoolefin. 14. The method according to claim 1, wherein each R is a chlorine atom. 15. The reaction product of the process according to claim 1. 16. A lubricating oil composition comprising a large amount of a lubricant base oil and a small amount of the reaction product according to claim 15. 17. A fuel composition comprising a major amount of base fuel and a minor amount of the reaction product of claim 15. 18. An additive concentrate comprising an inert liquid carrier and from 10 to 80% by weight of the total concentrate of the reaction product according to claim 15. 19. Use of the reaction product according to claim 15 as an additive for a dispersant.