CN114058422B - Mannich ashless dispersant and preparation method thereof - Google Patents

Mannich ashless dispersant and preparation method thereof Download PDF

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CN114058422B
CN114058422B CN202010770877.4A CN202010770877A CN114058422B CN 114058422 B CN114058422 B CN 114058422B CN 202010770877 A CN202010770877 A CN 202010770877A CN 114058422 B CN114058422 B CN 114058422B
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ashless dispersant
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amine
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CN114058422A (en
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刘智峰
黄卿
张荷
周旭光
薛卫国
汤仲平
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Petrochina Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/12—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/14—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds a condensation reaction being involved
    • C10M149/22—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers

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Abstract

The invention relates to a preparation method of a Mannich ashless dispersant, which comprises the following steps: (1) firstly, adding polyethylene polyamine and base oil into a reactor, uniformly stirring, and then adding hydrocarbyl substituted succinic anhydride into the reactor for continuous reaction; finally, dewatering and cooling to obtain a universal single-hanging ashless dispersant A; (2) adding the ashless dispersant A into a reactor, adding a post-treatment agent containing carboxyl groups and phenol groups, stirring, continuing to react, removing water, and cooling to obtain a post-treatment ashless dispersant B; (3) and adding the post-treatment ashless dispersant B into a reactor, adding an aldehyde compound, an amine compound and a polyether amine compound into the reactor at one time, stirring, continuing to react, and then removing water and cooling to obtain a Mannich ashless dispersant C. The invention also relates to a Mannich ashless dispersant.

Description

Mannich ashless dispersant and preparation method thereof
Technical Field
The invention belongs to the field of lubricating oil additives, and relates to a Mannich ashless dispersant and a preparation method thereof.
Background
With the development of the automobile industry in the 40-50 th of the 20 th century, the number of automobiles is increased sharply, urban traffic jam is caused, and air pollution is serious. In order to reduce air pollution, a positive pressure intake and exhaust (PCV) system is commonly used, which easily causes the decomposition products (peroxides, hydroperoxides and free radicals) of fuel oil to leak into the crankcase, so as to initiate the oxidation of lubricating oil, and finally deposit on the surface of the piston, thereby reducing the lubricating effect. Various non-polymeric succinimide ashless dispersants have been developed in the united states in the early 60 th of the last century, so that the problem of low-temperature oil sludge dispersion is solved, and the non-polymeric succinimide ashless dispersant is the most widely used ashless dispersant so far. However, in the 80 s, due to traffic congestion, the operating conditions of automobile engines become worse, the engines stop and start, the engine oil in the crankcase often does not reach the most efficient operating temperature, fuel hydrocarbons and water cannot be discharged from the lubricating oil, deposits including films, carbon deposits, sludge and soot are gradually formed, wherein the most notable is soot which is formed by hydrocarbon fragments without some hydrogen atoms, possibly generated by incomplete combustion of the fuel and the lubricating oil entering the combustion chamber from the crankcase through piston rings, and the charged particles are easy to agglomerate, which not only promotes the combination of carbon and sludge to generate a large amount of deposits, but also causes the problems of increased viscosity of the lubricating oil, serious wear of valve systems, poor oxidation resistance, poor detergency, easy hardening of materials and the like. The prior common ashless dispersants have failed to meet the requirements for solving the soot dispersion problem, and the development of the ashless dispersants is seen structurally: the low molecular weight, single-hanging and double-hanging are converted into multi-functionalization and high molecular weight, such as boronation, phosphorization, esterification, Mannich benzylamination and the like, and the purposes of increasing the product functions and improving the product performance are achieved by introducing functional groups or improving the structure of partial fragments of the product on the basis of the original product. At present, succinimide dispersants are generally adopted at home and abroad, which are poor in dispersion and adsorption on sediments such as soot and the like, and are easy to oxidize at high temperature.
U.S. Pat. Nos. 3,3649659, 3558743, 3539633, 3704308, 3724277 and the like disclose Mannich condensation products synthesized from alkylated nitrophenols, aldehydes, polyamines and aminopyridines, which have good dispersancy and antioxidancy properties as lubricating oil additives. US patent US20080318813 discloses a dispersant reaction product having antioxidant ability obtained by reacting a hindered phenol antioxidant methyl 3- ((3, 5-di-t-butyl) -4-hydroxyphenyl) propionate with a dispersant containing succinimide series or mannich series, which can exert the function of an antioxidant while retaining at least two structural domains, one being a polar domain capable of associating with sludge and an oil-soluble hydrocarbon domain, but the graft ratio is not high, the number of reaction sites is large, and the product composition is complicated.
Chinese patent CN1098345C discloses an oxidation-resistant succinimide ashless dispersant, which is prepared by the following method: (1) in the presence of 2, 6-di-tert-butylphenol, phenol containing alpha H, polyene polyamine and formaldehyde are mixed to carry out Mannich reaction, and a product is separated to prepare an intermediate product, namely condensed amine; (2) and carrying out amination reaction on alkenyl succinic anhydride and the condensed amine to obtain a final product. The dispersant has good high-temperature antioxidant performance because the polyene polyamine is coupled while the antioxidant group is introduced, but the process easily causes the end capping of the polyamine terminal amine by the phenol, so that the grafting rate is reduced, and the free polyene polyamine finally generates precipitate to influence the product quality.
Chinese patent CN107235856A provides an amine compound, an ashless dispersant and a preparation method thereof, and finally obtains a novel ashless dispersant containing phenolic hydroxyl, ester and amide, which has good dispersibility and partial anti-oxidation function, but the preparation process is complicated, organic solvent and catalyst are required to be used, and in addition, as the added materials are more in variety, side reaction is easy to occur between active functional groups of the novel ashless dispersant, and the structure is complex and uncontrollable.
U.S. Pat. No. 4, 8455568, 2 discloses a post-treated polymeric dispersant which is obtained by first reacting PIBSA with an aromatic amine and a polyetheramine to give a dispersant and then post-treating with a cyclic carbonate, a linear monocarbonate, a linear polycarbonate, an aromatic polycarboxylic acid, an aromatic polycarboxylic anhydride or an aromatic polycarboxylic ester. The method is characterized in that two kinds of amine are simply mixed and then react with PIBSA, and the grafting rate of aromatic amine and polyether amine is limited due to the limited number of reaction sites of the PIBSA.
Disclosure of Invention
Aiming at the defects of poor low-temperature oil sludge and soot dispersibility, easy oxidation at high temperature and the like of the existing ashless dispersant, the invention aims to provide the Mannich ashless dispersant and the preparation method thereof. .
Therefore, the invention provides a preparation method of a Mannich ashless dispersant, which comprises the following steps:
(1) firstly, adding polyethylene polyamine and base oil into a reactor, heating to 85-110 ℃, uniformly stirring, adding alkyl substituted succinic anhydride into the reactor, and reacting for 2-5 hours at 115-125 ℃; finally, heating to 150-160 ℃, removing water for 5-8 hours, cooling to obtain the universal single-hanging ashless dispersant A,
wherein it is preferred that the molar ratio of the hydrocarbyl-substituted succinic anhydride to the polyethylene polyamine is 1: 0.95 to 1.35, wherein the base oil accounts for 35 to 75 percent by weight of the ashless dispersant A, and is further preferably 40 to 55 percent by weight;
(2) adding the ashless dispersant A into a reactor, heating to 120-130 ℃, adding a post-treatment agent containing carboxyl groups (-COOH groups) and phenol groups, stirring for 0.5 hour, heating to 150-165 ℃, continuously reacting for 3-6 hours, removing water for 4-8 hours, cooling to obtain a post-treatment ashless dispersant B,
among them, it is preferable that the molar ratio of the ashless dispersant a to the post-treatment agent is 1: 0.86 to 1.1;
(3) adding the post-treatment ashless dispersant B into a reactor, heating to 75-85 ℃, adding an aldehyde compound, an amine compound and a polyether amine compound into the reactor at one time, stirring for 0.5-1 hour, gradually heating to 115-125 ℃ at the speed of 5-10 ℃/h, then heating to 150-165 ℃, removing water for 6-8 hours, cooling to obtain a Mannich ashless dispersant C,
among them, it is preferable that the molar ratio of the ashless dispersant B to the aldehyde compound is 1: 1.0-1.5, wherein the molar ratio of the ashless dispersant B to the amine compound is 1: 0.6-1.0, wherein the molar ratio of the ashless dispersant B to the polyether amine compound is 1: 0.8 to 1.5.
In the method for preparing the Mannich ashless dispersant, the hydrocarbyl-substituted succinic anhydride is oil-soluble, and the hydrocarbyl substituent of the oil-soluble hydrocarbyl-substituted succinic anhydride is formed by at least one of polypropylene, polyethylene, polystyrene, polyisobutylene, an ethylene-propylene copolymer and poly alpha olefin.
In the method for preparing the mannich ashless dispersant, preferably, the polyethylene polyamine compound contains at least one primary amine, and the polyethylene polyamine comprises at least one of diethylenetriamine, triethylene tetramine, tetraethylene pentamine, pentaethylenehexamine, hexaethyleneheptamine and heavy mixed amine.
The method for producing a Mannich ashless dispersant according to the present invention, wherein the post-treatment agent preferably comprises at least one of p-hydroxybenzoic acid, m-hydroxybenzoic acid, o-hydroxybenzoic acid, p-hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid, 2- (4-hydroxybenzoyl) benzoic acid, 2-methyl-3-hydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid, 2- (4-hydroxyphenyl) propionic acid, 3-hydroxyphenylglycolic acid, 2- (p-hydroxyphenylazo) benzoic acid, 4-amino-3-hydroxybenzoic acid, and 2-amino-5-hydroxybenzoic acid.
In the method for producing the mannich ashless dispersant according to the present invention, it is preferable that the aldehyde compound includes at least one of paraformaldehyde and an aqueous formaldehyde solution.
In the method for preparing the Mannich ashless dispersant, the amine compound is preferably aromatic amine or heterocyclic amine.
In the method of preparing the Mannich ashless dispersant according to the present invention, it is preferable that the aromatic amine includes at least one of m-phenylenediamine, o-phenylenediamine, 2, 6-diaminotoluene, aniline, p-toluidine, benzhydrylamine, triphenylmethylamine, 3-tert-butylaniline, 4-octylaniline, 2, 4-dimethylaniline, 4 '-diaminodiphenylamine, 3-benzyloxyaniline, 3' -diaminobenzidine, 3, 5-di-tert-butylaniline, 4-amino-N, N-dimethylaniline, 4-aminodiphenylamine, 4 '-diaminodiphenylmethane, 3,4' -diaminodiphenyl ether, 4-nitrodiphenylamine.
In the method of preparing the Mannich ashless dispersant according to the present invention, preferably, the heterocyclic amine includes at least one of 2- (4-aminophenyl) -5-aminobenzimidazole, diaminoquinoline, 2-amino-8-hydroxyquinoline, 7-amino-4-methyl-2-quinolinone, 5-amino-2, 3-dihydroisoindol-1-one, and 2, 2-diphenylethylamine.
In the method for preparing the Mannich ashless dispersant, the polyether amine compound preferably comprises at least one of polyether monoamine, polyether polyamine, polyether amino alcohol and polyether amino mercaptan.
In the method of producing the mannich ashless dispersant according to the present invention, it is preferable that the base oil includes at least one of a mineral base oil, a synthetic base oil, and a vegetable oil.
Therefore, the invention also provides a Mannich ashless dispersant prepared by the preparation method of the Mannich ashless dispersant, and the structural formula of the Mannich ashless dispersant is shown as follows:
Figure BDA0002616557500000051
wherein n is an integer of 0-8; x is-H, -CH 3 、-O-CH 3 、-NH 2 (ii) a Y is-CH 2 -、-CH 2 CH 2 -、-CH(CH 3 ) -, -CH (OH) -; r is a substituent formed by at least one of polypropylene, polyethylene, polystyrene, polyisobutylene, ethylene-propylene copolymer and poly alpha olefin; r 1 Is a substituent formed by an amine compound; r 2 Is a substituent formed by polyether amine compounds.
The preparation method of the Mannich ashless dispersant specifically comprises the following steps:
(1) firstly, adding polyethylene polyamine and base oil into a reactor with a stirring and temperature control system, heating to 85-110 ℃, uniformly stirring, then continuously adding alkyl substituted succinic anhydride into the reactor, and reacting for 2-5 hours at 115-125 ℃; and finally, heating to 150-160 ℃, introducing a large amount of inert gas for stripping and dewatering for 5-8 hours, and cooling to obtain the universal single-hanging ashless dispersant A.
In the step (1), the molar ratio of the hydrocarbyl-substituted succinic anhydride to the polyethylene polyamine is 1: (0.95-1.35), wherein the base oil accounts for 35-75% (preferably 40-55%) of the whole ashless dispersant A;
(2) adding the ashless dispersant A into a reactor with a stirring and temperature control system, heating to 120-130 ℃, adding an after-treatment agent containing-COOH groups and phenol groups, stirring for 0.5 hour, heating to 150-165 ℃, continuing to react for 3-6 hours, introducing a large amount of inert gas for stripping for 4-8 hours, and cooling to obtain an after-treatment ashless dispersant B;
in the step (2), the molar ratio of the ashless dispersant A to the post-treatment agent is 1: (0.86-1.1);
(3) adding the post-treatment ashless dispersant B into a reactor with a stirring and temperature control system, heating to 75-85 ℃, adding an aldehyde compound, an amine compound and a polyether amine compound into the reactor at one time, stirring for 1 hour, gradually heating to 115-125 ℃ at the speed of 10 ℃/h, reacting for two hours, quickly heating to 150-165 ℃, introducing a large amount of inert gas for stripping for 6-8 hours, and cooling to obtain a Mannich ashless dispersant C;
in the step (3), the molar ratio of the ashless dispersant B to the aldehyde compound is 1: (1.0-1.5), wherein the molar ratio of the ashless dispersant B to the amine compound is 1: (0.6-1.0), wherein the molar ratio of the ashless dispersant B to the polyether amine compound is 1: (0.8 to 1.5).
According to the preparation method, the Mannich ashless dispersant has the following structural formula:
Figure BDA0002616557500000071
wherein n is an integer of 0-8; x is H, -CH 3 、-O-CH 3 、-NH 2 (ii) a Y is-CH 2 -、-CH 2 CH 2 -、-CH(CH 3 ) -, -CH (OH) -; r is a substituent formed by at least one of polypropylene, polyethylene, polystyrene, polyisobutylene, ethylene-propylene copolymer and poly alpha olefin; r 1 Is a substituent formed by the amine compound; r 2 Is a substituent formed by the polyether amine compound.
The invention has the following beneficial effects:
the preparation method of the Mannich ashless dispersant provided by the invention comprises the steps of firstly introducing a phenolic group into a structure of a general ashless dispersant, and then grafting an aromatic amine group and a polyether amine group onto phenol by utilizing a Mannich reaction. Structurally, the introduction of the phenolic group provides double reaction sites for the subsequent amine grafting, and greatly improves the grafting rate. On one hand, the phenolic group has excellent oxidation resistance at low temperature, the aromatic amine group has more advantages at high temperature, the phenolic group and the aromatic amine group are introduced into the ashless dispersant at the same time to play a role in antioxidation synergistic effect, and the prepared ashless dispersant has excellent oxidation resistance; on the other hand, the introduction of the polyether amine compound and the aromatic amine group with high-temperature cleaning performance increases the adsorption and suspension capacity of the polar group of the ashless dispersant, is more favorable for adsorbing larger particles such as soot in lubricating oil, avoids the over-quick increase of the viscosity of the oil, and prolongs the service life of the oil.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
All ranges disclosed herein are inclusive of the endpoints and independently combinable. The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values.
The preparation method of the Mannich ashless dispersant provided by the invention comprises the following steps:
(1) firstly, adding polyethylene polyamine and base oil into a reactor, heating to 85-110 ℃, uniformly stirring, adding alkyl substituted succinic anhydride into the reactor, and reacting for 2-5 hours at 115-125 ℃; finally, heating to 150-160 ℃, removing water for 5-8 hours, and cooling to obtain the universal single-hanging ashless dispersant A;
(2) adding the ashless dispersant A into a reactor, heating to 120-130 ℃, adding an after-treatment agent containing carboxyl groups (-COOH groups) and phenol groups, stirring for 0.5 hour, heating to 150-165 ℃, continuing to react for 3-6 hours, removing water for 4-8 hours, and cooling to obtain an after-treatment ashless dispersant B;
(3) adding the post-treatment ashless dispersant B into a reactor, heating to 75-85 ℃, adding an aldehyde compound, an amine compound and a polyether amine compound into the reactor at one time, stirring for 0.5-1 hour, gradually heating to 115-125 ℃ at the speed of 5-10 ℃/h, then heating to 150-165 ℃, removing water for 6-8 hours, and cooling to obtain the Mannich ashless dispersant C.
In some embodiments, the molar ratio of the hydrocarbyl-substituted succinic anhydride to the polyethylene polyamine is 1: 0.95 to 1.35, wherein the base oil accounts for 35 to 75 percent by weight of the ashless dispersant A, and is further preferably 40 to 55 percent by weight;
in some embodiments, the molar ratio of the ashless dispersant a to the post-treatment agent is 1: 0.86 to 1.1.
In some embodiments, the molar ratio of the ashless dispersant B to the aldehyde compound is 1: 1.0-1.5, wherein the molar ratio of the ashless dispersant B to the amine compound is 1: 0.6-1.0, wherein the molar ratio of the ashless dispersant B to the polyether amine compound is 1: 0.8 to 1.5.
In some embodiments, the hydrocarbyl-substituted succinic anhydride is oil-soluble, and the hydrocarbyl substituent in the oil-soluble hydrocarbyl-substituted succinic anhydride is formed from at least one of polypropylene, polyethylene, polystyrene, polyisobutylene, an ethylene-propylene copolymer, a poly (alpha-olefin).
In some embodiments, the polyethylene polyamine compound contains at least one primary amine, and the polyethylene polyamine comprises at least one of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, and remixed amine.
In some embodiments, the post-treatment agent comprises at least one of p-hydroxybenzoic acid, m-hydroxybenzoic acid, o-hydroxybenzoic acid, p-hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid, 2- (4-hydroxybenzoyl) benzoic acid, 2-methyl-3-hydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid, 2- (4-hydroxyphenyl) propionic acid, 3-hydroxyphenylglycolic acid, 2- (p-hydroxyphenylazo) benzoic acid, 4-amino-3-hydroxybenzoic acid, 2-amino-5-hydroxybenzoic acid.
In some embodiments, the aldehyde compound comprises at least one of paraformaldehyde and an aqueous formaldehyde solution.
In some embodiments, the amine-based compound is an aromatic amine or a heterocyclic amine.
In some embodiments, the aromatic amine comprises at least one of meta-phenylene diamine, ortho-phenylene diamine, 2, 6-diaminotoluene, aniline, para-toluidine, benzhydrylamine, triphenylmethylamine, 3-tert-butylaniline, 4-octylaniline, 2, 4-dimethylaniline, 4 '-diaminodiphenylamine, 3-benzyloxyaniline, 3' -diaminobenzidine, 3, 5-di-tert-butylaniline, 4-amino-N, N-dimethylaniline, 4-aminodiphenylamine, 4 '-diaminodiphenylmethane, 3,4' -diaminodiphenyl ether, 4-nitrodiphenylamine.
In some embodiments, the heterocyclic amine includes at least one of 2- (4-aminophenyl) -5-aminobenzimidazole, diaminoquinoline, 2-amino-8-hydroxyquinoline, 7-amino-4-methyl-2-quinolinone, 5-amino-2, 3-dihydroisoindol-1-one, 2-diphenylethylamine.
In some embodiments, the polyetheramine-based compound includes at least one of a polyether monoamine, a polyether polyamine, a polyether aminoalcohol, a polyether aminothiol.
In some embodiments, the base oil comprises at least one of a mineral base oil, a synthetic base oil, and a vegetable oil.
The Mannich ashless dispersant provided by the invention is prepared by the preparation method of the Mannich ashless dispersant, and the structural formula of the Mannich ashless dispersant is shown as follows:
Figure BDA0002616557500000101
wherein n is an integer of 0-8; x is-H, -CH 3 、-O-CH 3 、-NH 2 (ii) a Y is-CH 2 -、-CH 2 CH 2 -、-CH(CH 3 ) -, -CH (OH) -; r is a substituent formed by at least one of polypropylene, polyethylene, polystyrene, polyisobutylene, ethylene-propylene copolymer and poly alpha olefin; r 1 Is a substituent formed by an amine compound; r 2 Is a substituent formed by polyether amine compounds.
Comparative example 1
123g of tetraethylenepentamine and 1000g of base oil Youbase6 are added into a 5L four-neck flask with a stirring and thermometer, the temperature is raised to 85 ℃, after uniform stirring and mixing, 1500g of polyisobutylene succinic anhydride PIBSA-2300 (oil soluble) is slowly and continuously added into the four-neck flask within 2 hours, the temperature is raised to 120 ℃, the reaction is carried out for 4 hours, then the temperature is raised to 155 ℃, nitrogen gas is stripped to remove water for 8 hours, and the universal single-hanging ashless dispersant A1 is obtained after cooling.
Example 1
200g of the general ashless dispersant A1 described in comparative example (1) was added into a 500ml four-necked flask equipped with a stirring and temperature control system, the temperature was raised to 125 ℃ and 6.9g of p-hydroxybenzoic acid as a post-treatment agent was added, after stirring for 0.5 hour, the temperature was raised to 165 ℃ and the reaction was continued for 5 hours, then a large amount of inert gas was introduced to strip off water for 5 hours, obtaining post-treatment ashless dispersant B1;
cooling the post-treated ashless dispersant B1 to 80 ℃, then adding 9g of paraformaldehyde, 9.2g of 4-aminodiphenylamine and 30g of polyetheramine M-600 at one time, stirring for 1 hour, gradually raising the temperature to 125 ℃ at the speed of 10 ℃/h, reacting for two hours, quickly raising the temperature to 155 ℃, introducing a large amount of inert gas to strip water for 6.5 hours, and cooling to obtain the Mannich ashless dispersant C1.
Example 2
200g of the general ashless dispersant A1 described in comparative example (1) was added into a 500ml four-necked flask equipped with a stirring and temperature control system, the temperature was raised to 120 ℃ and 5.5g of p-hydroxybenzoic acid as a post-treating agent was added, after stirring for 0.5 hour, the temperature was raised to 160 ℃ and the reaction was continued for 5.5 hours, then a large amount of inert gas was introduced to strip the mixture for 5.5 hours, yielding a post-treated ashless dispersant B2;
cooling the post-treated ashless dispersant B2 to 85 ℃, then adding 7.2g of paraformaldehyde, 7.4g of 4-aminodiphenylamine and 9.2g of polyetheramine D-230 at one time, stirring for 1 hour, gradually raising the temperature to 122 ℃ at the speed of 10 ℃/h, reacting for two hours, rapidly raising the temperature to 158 ℃, introducing a large amount of inert gas for stripping for 6.5 hours, and cooling to obtain the Mannich ashless dispersant C2.
Example 3
200g of the universal ashless dispersant A1 described in comparative example (1) was added into a 500ml four-necked flask equipped with a stirring and temperature control system, the temperature was raised to 123 ℃, 6.9g of p-hydroxybenzoic acid as a post-treatment agent was added, after stirring for 0.5 hour, the temperature was raised to 157 ℃, after continuing to react for 5 hours, a large amount of inert gas was introduced to strip for 6 hours, and a post-treatment ashless dispersant B3 was obtained; cooling the post-treated ashless dispersant B3 to 85 ℃, then adding 9g of paraformaldehyde, 5.6g of 4-aminodiphenylamine and 28g of polyetheramine D-400 at one time, stirring for 1 hour, gradually raising the temperature to 125 ℃ at the speed of 10 ℃/h, reacting for two hours, quickly raising the temperature to 160 ℃, introducing a large amount of inert gas for stripping for 6.5 hours, and cooling to obtain the Mannich ashless dispersant C3.
Example 4
200g of the general ashless dispersant A1 described in comparative example (1) was added into a 500ml four-necked flask equipped with a stirring and temperature control system, the temperature was raised to 120 ℃ and 6.8g of p-hydroxyphenylacetic acid as a post-treatment agent was added, after stirring for 0.5 hour, the temperature was raised to 150 ℃ and the reaction was continued for 5 hours, then a large amount of inert gas was introduced to strip the mixture for 6 hours, yielding post-treatment ashless dispersant B4; cooling the post-treated ashless dispersant B4 to 85 ℃, then adding 11.7g of paraformaldehyde, 3.4g of p-toluidine and 35.1g of polyether amine ED-600 at a time, stirring for 1 hour, gradually raising the temperature to 125 ℃ at the speed of 10 ℃/h, reacting for two hours, rapidly raising the temperature to 160 ℃, introducing a large amount of inert gas for stripping for 6.5 hours, and cooling to obtain the Mannich ashless dispersant C4.
Example 5
200g of the universal ashless dispersant A1 described in comparative example (1) was added into a 500ml four-necked flask equipped with a stirring and temperature control system, the temperature was raised to 125 ℃ and 7.6g of p-hydroxyphenylacetic acid as a post-treatment agent was added, after stirring for 0.5 hour, the temperature was raised to 155 ℃ and the reaction was continued for 6 hours, then a large amount of inert gas was introduced to strip the mixture for 5.5 hours, yielding a post-treatment ashless dispersant B5; cooling the post-treatment ashless dispersant B5 to 85 ℃, then adding 13.5g of paraformaldehyde, 3.7g of aniline and 54g of polyether amine ED-900 at one time, stirring for 1 hour, gradually heating to 125 ℃ at the speed of 10 ℃/h, reacting for two hours, quickly heating to 160 ℃, introducing a large amount of inert gas for stripping for 7 hours, and cooling to obtain the Mannich ashless dispersant C5.
Comparative example 2
151g of heavy mixed amine and 1500g of base oil Youbase6 are added into a 5000L four-neck flask with a stirring and thermometer, the temperature is raised to 90 ℃, after uniform stirring and mixing, 1500g of polyisobutylene maleic anhydride (PIBSA-2300) is slowly and continuously added into the four-neck flask within 2 hours, the temperature is raised to 125 ℃, the reaction is carried out for 4 hours, then the temperature is raised to 160 ℃, nitrogen gas is stripped for 8 hours, and the universal single-hanging ashless dispersant A2 is obtained after cooling.
Example 6
200g of the general ashless dispersant A2 described in comparative example (2) was added into a 500ml four-necked flask equipped with a stirring and temperature control system, the temperature was raised to 130 ℃ and 7.6g of p-hydroxyphenylpropionic acid as a post-treatment agent was added, after stirring for 0.5 hour, the temperature was raised to 165 ℃ and the reaction was continued for 6 hours, then a large amount of inert gas was introduced to strip the mixture for 5.5 hours, yielding a post-treatment ashless dispersant B6; cooling the post-treated ashless dispersant B6 to 85 ℃, then adding 13.5g of paraformaldehyde, 4.75g of 4-aminodiphenylamine and 54.2g of polyether amine ED-900 at one time, stirring for 1 hour, gradually raising the temperature to 125 ℃ at the speed of 10 ℃/h, reacting for two hours, rapidly raising the temperature to 160 ℃, introducing a large amount of inert gas for stripping for 7 hours, and cooling to obtain the Mannich ashless dispersant C6.
Example 7
200g of the general ashless dispersant A2 described in comparative example (2) was added into a 500ml four-necked flask equipped with a stirring and temperature control system, the temperature was raised to 130 ℃ and 8.3g of p-hydroxyphenylpropionic acid as a post-treatment agent was added, after stirring for 0.5 hour, the temperature was raised to 165 ℃ and the reaction was continued for 6 hours, then a large amount of inert gas was introduced to strip the mixture for 5.5 hours, yielding a post-treatment ashless dispersant B7; cooling the post-treated ashless dispersant B7 to 85 ℃, then adding 11.7g of paraformaldehyde, 4.76g of 4-amino-N, N-dimethylaniline and 9.62g of polyetheramine EDR-148 in one step, stirring for 1 hour, gradually heating to 125 ℃ at the speed of 10 ℃/h, reacting for two hours, quickly heating to 160 ℃, introducing a large amount of inert gas for stripping for 7 hours, and cooling to obtain the Mannich ashless dispersant C7.
Example 8
200g of the universal ashless dispersant A2 described in comparative example (2) is added into a 500ml four-neck flask with a stirring and temperature control system, the temperature is raised to 130 ℃, 8.4g of the post-treatment agent 3-hydroxyphenylglycolic acid is added, after stirring for 0.5 hour, the temperature is raised to 155 ℃, after reaction is continued for 5 hours, a large amount of inert gas is introduced for stripping for 6 hours, and the post-treatment ashless dispersant B8 is obtained; cooling the post-treated ashless dispersant B8 to 85 ℃, then adding 9.9g of paraformaldehyde, 8.4g of 3-benzyloxy aniline and 8.8g of polyether amine EDR-176 at one time, stirring for 1 hour, gradually heating to 125 ℃ at the speed of 10 ℃/h, reacting for two hours, rapidly heating to 160 ℃, introducing a large amount of inert gas for stripping for 6 hours, and cooling to obtain the Mannich ashless dispersant C8.
Example 9
The antioxidant ashless dispersants obtained in comparative examples 1 to 2 and examples 1 to 8 were evaluated for their performance:
(1) evaluation of Low temperature sludge dispersibility
0.5g of antioxidant ashless dispersant, 5g of base oil and 4.5g of oil sludge are mixed, heated and stirred for 1.5 hours at the constant temperature of 150 ℃ in a 50ml beaker, a drop of the test oil is dropped on filter paper while the test oil is hot, and the filter paper is placed in an oven for 2 hours at the constant temperature of 80 ℃ to measure the ratio of a diffusion ring to an oil ring, so that spot test data are obtained. The high speck dispersion value indicates the better low temperature sludge dispersancy.
(2) Evaluation of Oxidation resistance
Adding 6.3 percent of antioxidant ashless dispersant into HVI150 base oil, and carrying out antioxidant performance evaluation according to SH/T0193-; according to SH/T0719 high-Pressure Differential Scanning Calorimetry (PDSC) high-temperature oxidation resistance evaluation. The longer the RPVOT time, the higher the PDSC onset temperature, indicating the better the dispersant's resistance to high temperature oxidation.
(3) Soot dispersancy
4.5 percent of antioxidant ashless dispersant is prepared into CI-4 diesel engine oil, bench test evaluation of soot dispersion performance is carried out by using a CA 6DL2-35 heavy-load diesel engine, the relative viscosity increase value of the oil product after the engine operates for 120 hours is analyzed, and the smaller the viscosity increase is, the better the soot dispersion of the dispersant is.
(4) High temperature detergency
A test oil of 300ml was prepared by adding 3% of an antioxidant ashless dispersant to HVI150 base oil. The parameters of the coke-forming plate tester are set as follows: the plate temperature was 310 ℃ and the oil temperature was 100 ℃ and the formation of paint films was examined after 2 hours of continuous oil splashing. The method is that the internal combustion engine oil containing additive is splashed to the surface of high-temperature metal to form a paint film, so that the paint forming amount of a crankcase when a piston works is simulated, and the high-temperature cleaning performance of the oil is inspected by measuring the weight of coke on a metal plate.
The above evaluation results are shown in Table 1.
TABLE 1
Figure BDA0002616557500000151
Figure BDA0002616557500000161
As can be seen from the data in Table 1, comparative examples 1 and 2 are similar to the preparation process of the commercial T161, and the data in Table 1 also shows that the performance indexes of the three are equivalent; the low-temperature oil sludge dispersibility, high-temperature oxidation resistance, soot dispersibility and high-temperature detergency of the examples 1 to 8 are all superior to those of the commercial ashless dispersant T161.
In summary, in the preparation method of the mannich ashless dispersant provided by the invention, firstly, a phenolic group is introduced to the structure of the general ashless dispersant, and then an aromatic amine group and a polyether amine group are grafted to phenol by utilizing mannich reaction. Structurally, the introduction of the phenolic group provides double reaction sites for the subsequent amine grafting, and greatly improves the grafting rate. On one hand, the phenolic group has excellent oxidation resistance at low temperature, the aromatic amine group has more advantages at high temperature, the phenolic group and the aromatic amine group are introduced into the ashless dispersant at the same time to play a role in antioxidation synergistic effect, and the prepared ashless dispersant has excellent oxidation resistance; on the other hand, the introduction of the polyether amine compound and the aromatic amine group with high-temperature cleaning performance increases the adsorption and suspension capacity of the polar group of the ashless dispersant, is more favorable for adsorbing larger particles such as soot in lubricating oil, avoids the over-quick increase of the viscosity of the oil, and prolongs the service life of the oil.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.

Claims (15)

1. A preparation method of a Mannich ashless dispersant is characterized by comprising the following steps:
(1) firstly, adding polyethylene polyamine and base oil into a reactor, heating to 85-110 ℃, uniformly stirring, adding alkyl substituted succinic anhydride into the reactor, reacting for 2-5 hours at 115-125 ℃, finally heating to 150-160 ℃, removing water for 5-8 hours, and cooling to obtain a universal single-hanging ashless dispersant A;
(2) adding the ashless dispersant A into a reactor, heating to 120-130 ℃, adding an after-treatment agent containing carboxyl groups and phenol groups, stirring for 0.5-1 hour, heating to 150-165 ℃, continuing to react for 3-6 hours, removing water for 4-8 hours, and cooling to obtain an after-treatment ashless dispersant B;
(3) adding the post-treatment ashless dispersant B into a reactor, heating to 75-85 ℃, adding an aldehyde compound, an amine compound and a polyether amine compound into the reactor at one time, stirring for 0.5-1 hour, gradually heating to 115-125 ℃ at the speed of 5-10 ℃/h, then heating to 150-165 ℃, removing water for 6-8 hours, and cooling to obtain the Mannich ashless dispersant C.
2. A method of making a mannich ashless dispersant as claimed in claim 1, wherein in step (1), the molar ratio of said hydrocarbyl-substituted succinic anhydride to said polyethylene polyamine is 1: 0.95-1.35, wherein the base oil accounts for 35-75% of the ashless dispersant A by weight.
3. The method of producing a Mannich ashless dispersant according to claim 2, wherein the base oil is contained in the ashless dispersant A in an amount of 40 to 55% by weight.
4. The method of producing a mannich ashless dispersant as claimed in claim 1, wherein in step (2), the molar ratio of the ashless dispersant a to the post-treatment agent is 1: 0.86 to 1.1.
5. The method of producing a mannich ashless dispersant according to claim 1, characterized in that in step (3), the molar ratio of the ashless dispersant B to the aldehyde compound is 1: 1.0-1.5, wherein the molar ratio of the ashless dispersant B to the amine compound is 1: 0.6-1.0, wherein the molar ratio of the ashless dispersant B to the polyether amine compound is 1: 0.8 to 1.5.
6. The method of claim 1 wherein the hydrocarbyl-substituted succinic anhydride is oil-soluble and the hydrocarbyl substituent of the oil-soluble hydrocarbyl-substituted succinic anhydride is formed from at least one of polypropylene, polyethylene, polystyrene, polyisobutylene, an ethylene-propylene copolymer, and a polyolefin.
7. The method of claim 1, wherein the polyethylene polyamine compound comprises at least one primary amine, and the polyethylene polyamine comprises at least one of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and hexaethyleneheptamine.
8. The method of preparing a mannich ashless dispersant according to claim 1, characterized in that the post-treatment agent comprises at least one of p-hydroxybenzoic acid, m-hydroxybenzoic acid, o-hydroxybenzoic acid, p-hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid, 2- (4-hydroxybenzoyl) benzoic acid, 2-methyl-3-hydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid, 2- (4-hydroxyphenyl) propionic acid, 3-hydroxyphenylglycolic acid, 2- (p-hydroxyphenylazo) benzoic acid, 4-amino-3-hydroxybenzoic acid, 2-amino-5-hydroxybenzoic acid.
9. The method of preparing a mannich ashless dispersant according to claim 1, characterized in that the aldehyde compound includes at least one of paraformaldehyde and an aqueous formaldehyde solution.
10. The method of preparing a mannich ashless dispersant according to claim 1, characterized in that said amine compound is an aromatic amine or a heterocyclic amine.
11. The method of preparing a Mannich ashless dispersant according to claim 10, the aromatic amine includes at least one of m-phenylenediamine, o-phenylenediamine, 2, 6-diaminotoluene, aniline, p-toluidine, benzhydrylamine, triphenylmethylamine, 3-tert-butylaniline, 4-octylaniline, 2, 4-dimethylaniline, 4 '-diaminodiphenylamine, 3-benzyloxyaniline, 3' -diaminobenzidine, 3, 5-di-tert-butylaniline, 4-amino-N, N-dimethylaniline, 4-aminodiphenylamine, 4 '-diaminodiphenylmethane, 3,4' -diaminodiphenyl ether, 4-nitrodiphenylamine.
12. The method of claim 10 wherein said heterocyclic amine comprises at least one of 2- (4-aminophenyl) -5-aminobenzimidazole, diaminoquinoline, 2-amino-8-hydroxyquinoline, 7-amino-4-methyl-2-quinolinone, 5-amino-2, 3-dihydroisoindol-1-one, and 2, 2-diphenylethylamine.
13. The method of claim 1, wherein the polyetheramine compound comprises at least one member selected from the group consisting of a polyether monoamine, a polyether polyamine, a polyether aminoalcohol, and a polyether aminothiol.
14. The method of making a Mannich ashless dispersant according to claim 1, wherein said base oil comprises at least one of a mineral base oil, a synthetic base oil, and a vegetable oil.
15. A mannich ashless dispersant obtained by the method for producing the mannich ashless dispersant of any one of claims 1 to 14, characterized in that the structural formula of the mannich ashless dispersant is as follows:
(I)
Figure DEST_PATH_FDA0003609251990000031
wherein n is an integer of 0-8; x is-H, -CH 3 、-O-CH 3 、-NH 2 (ii) a Y is-CH 2 -、-CH 2 CH 2 -、-CH(CH 3 ) -, -CH (OH) -; r is a substituent formed by at least one of polypropylene, polyethylene, polystyrene, polyisobutylene, ethylene-propylene copolymer and poly alpha olefin; r 1 Is a substituent formed by an amine compound; r 2 Is a substituent formed by polyether amine compounds.
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