CN1098345C - Antioxidative succinimide dustless dispersing agent - Google Patents
Antioxidative succinimide dustless dispersing agent Download PDFInfo
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- CN1098345C CN1098345C CN99103269A CN99103269A CN1098345C CN 1098345 C CN1098345 C CN 1098345C CN 99103269 A CN99103269 A CN 99103269A CN 99103269 A CN99103269 A CN 99103269A CN 1098345 C CN1098345 C CN 1098345C
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- phenol
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Abstract
The present invention relates to an ashless dispersant with antioxidative succinimide, which is prepared according to the following method: alpha H-phenol, polyene polyamine and formaldehyde are mixed for a Mannich reaction under the condition that 2, 6-ditertiary butyl phenol exists, and condensed amine as an intermediate product is prepared after reaction products are separated; an aminating reaction is carried out between the condensed amine and alkenyl butanedioic anhydride, and a final product is obtained. The polyene polyamine in the dispersant is coupled when oxidation resistant groups are introduced, which increases the content of nitrogen, achieves favorable resistance to high temperature oxidation, improves the dispersibility and ensures favorable oil solubility. Therefore, the present invention can be used for internal combustion engine oil or fuel oil.
Description
The present invention relates to a kind of oil dope, exactly is a kind of Ashless butyl diimide dispersant with antioxidant property that is used for I. C. engine oil or oil fuel.
The succimide dispersion agent just begins a large amount of uses the sixties, be still most widely used at present and a kind of dispersion agent consumption maximum, its preparation method is: polyisobutene and the maleic anhydride by molecular weight 1000-3000 reacts earlier, generate the polyisobutenyl maleic anhydride, and then with the reaction of the polyamines polyene of different ratios, make single, double and poly isobutenyl succimide.
Because the operating temperature range of engine is very wide, under the operational condition of stopping in the winter time to stop out, the temperature of automobile crane case is low, and fuel hydrocarbon and moisture (moisture content) are difficult for discharging from lubricating oil, cause engine oil to produce a large amount of greasy filth, influence the normal operation of engine; In summer, driving causes service temperature to raise continuously, and oxidation easily takes place I. C. engine oil, and viscosity is increased rapidly, and carbon deposit and paint film increase on the piston.For this reason, require I. C. engine oil that good low temperature greasy filth dispersiveness should be arranged, require to have the excellent high-temperature resistance of oxidation again.
US 4973412 discloses a kind of multi-functional lubricating oil additive; its preparation method is: earlier with the partially acylated succimide of organic dibasic acid coupling; use the unsaturated fatty acids acid treatment again, react promptly with nitroso-group Ursol D more at last with antioxidant property.This additive improved the antioxidant property of succimide, but its preparation technology's more complicated.
US 4636322,4699724,4713189 discloses link coupled succimide dispersion agent; be to pass through Mannich reaction coupling succimide, be prepared from oxyacetic acid acidylate part polyamines polyene again by phenol, dihydroxyphenyl propane, Resorcinol, single nonyl phenol or 2-Naphthol.This additive has improved dispersed and to the adaptability of rubber seal, but does not mention and improve the oxidation stability problem.
The purpose of this invention is to provide and a kind ofly different with the prior art structure can improve the low temperature dispersity energy, can strengthen the succimide type ashless dispersant of antioxidant property again.
Contain following group on the antioxidative succinimide dustless dispersing agent structure provided by the invention: the allyl butyrate diacyl, phenol link coupled polyamines polyene base, link to each other with the polyamines polyene base 2,6-di-t-butyl phenolic group.This dispersion agent prepares as follows:
(1) 2, under the existence of 6-di-tert-butylphenol, phenol, polyamines polyene and the formaldehyde that will contain α H mix
Close, carry out Mannich reaction, separated product makes the intermediates amine condensation;
(2) enetutanedioic acid anhydride and above-mentioned amine condensation are carried out amination reaction, obtain the finished product.
Specifically, dispersion agent provided by the invention can prepare as follows:
(1) under nitrogen protection; with 2; 6-di-tert-butylphenol, the phenol that contains α H, polyamines polyene and formaldehyde mix; under agitation slowly heat up, in room temperature～150 ℃, preferred 60～120 ℃ of reactions 1～10 hour down; preferred 2～8 hours; underpressure distillation removes water and unreacted matters, obtains the polyamines polyene that link coupled contains antioxidant group, i.e. amine condensation.
Wherein, the phenol that contains α H can be selected from one of phenol, p-cresol, Resorcinol, dihydroxyphenyl propane or 2-Naphthol, it also can be two or more mixture wherein, containing the phenol of α H and the mol ratio of polyamines polyene is 1: 1～4, contains the phenol and 2 of α H, and the mol ratio of 6-di-tert-butylphenol is 1: 0.2～3, preferred 1: 0.5～2, these two kinds of phenol can add reactor simultaneously with formaldehyde and polyamines polyene, also can add later on, and the temperature of adding is advisable not surpass 70 ℃.
The general formula of said polyamines polyene is H
2N (CH
2CH
2NH)
nH, n is 1～6 integer in the formula, as quadrol (EDA), diethylenetriamine (DETA), triethylene tetramine (TETA), tetraethylene pentamine (TEPA), five ethene hexamines (DEHA) etc.
Said formaldehyde can be the Paraformaldehyde 96 that can be decomposed into formaldehyde after being heated; Also can be formalin, preferably concentration be the formaldehyde saturated aqueous solution of 36 heavy %.If Paraformaldehyde 96 then can mix simultaneously with other reactant; If formalin after then preferably earlier other reactant being mixed, progressively splashes into formalin again.The consumption of formaldehyde should be suitably excessive, preferably contains the phenol and 2 of α H, has 1～2 times of summation of the H of reactive behavior in the 6-di-tert-butylphenol.
In the structure of the amine condensation that this step makes, the phenol that contains α H can link to each other with 1～4 polyamines polyene according to its contained quantity with H of reactive behavior, can be connected on the primary amino, also can be connected on the secondary amino group.For example, phenol not only has two ortho position H, also has a contraposition H also can participate in reaction, and therefore three H with reactive behavior are arranged.2, in the contraposition of 6-di-tert-butylphenol, can link to each other with a polyamines polyene, can be connected in equally on the primary amino, also can be connected on the secondary amino group.The phenol and 2 that contains α H, the relative content of 6-di-tert-butylphenol in product structure decided on feed ratio.
(2) in the presence of thinning oil and nitrogen, amine condensation that step (1) is made and enetutanedioic acid anhydride be at 60～160 ℃, preferred 80～140 ℃ of reactions 1～8 hour, preferred 2～6 hours, decompression removed the water that reaction generates, filter, the finished product ashless dispersant.Wherein the add-on of enetutanedioic acid anhydride is 0.6～3 times of polyamines polyene mole number in the step (1), preferred 0.7～2.5 times.In addition, carry out, can under nitrogen protection, earlier enetutanedioic acid anhydride be dissolved in the thinning oil, be heated to 60～90 ℃, slowly add amine condensation again and react for the ease of reacting balance.
Thiazolinyl in the said enetutanedioic acid anhydride is C
2～C
10Olefin copolymer or homopolymer, polyisobutene preferably.The number-average molecular weight of thiazolinyl can be 500～5000, and is preferred 900～2500, and molecular weight distribution is generally 1.5～4.5, preferred 1.5～3.5.
When generating end product, enetutanedioic acid anhydride can be connected on the primary amino, forms imide; Also can be connected on two secondary amino groups after the open loop, form acid amides.Enetutanedioic acid anhydride is to carry out alkylation reaction with long-chain olefin polymkeric substance and maleic anhydride to make, and can make by oneself, also can buy from market.
Ashless dispersant provided by the invention with the polyamines polyene coupling, has improved nitrogen content when introducing antioxidant group, therefore not only had the good high-temperature antioxygen property, has also improved dispersing property, and can guarantee good oil soluble.
The invention will be further described below by embodiment.
Embodiment 1～8 is the preparation of amine condensation intermediate.
Embodiment 1
In the there-necked flask of the 250ml that has mechanical stirring, temperature-control heat couple and thermometer, add 56.8g (0.3mol) tetraethylene pentamine and 16.5g Paraformaldehyde 96; under nitrogen protection; be heated to 90 ℃, keep 1h, be cooled to 65 ℃ and add 20.6g (0.1mol) 2; 6-di-tert-butylphenol and 9.4g (0.1mol) phenol; keep 0.5h, slowly be heated to 120 ℃, keep 3h; underpressure distillation removes water and unreacted matters, the amine condensation intermediate A that makes.
Embodiment 2
In the there-necked flask of the 250ml that has mechanical stirring, temperature-control heat couple and thermometer; add 56.8g (0.3mol) tetraethylene pentamine; 9.4g (0.1mol) phenol; 20.6g (0.1mol) 2,6-di-tert-butylphenol and 15g Paraformaldehyde 96 are under nitrogen protection; slowly be heated to 90 ℃; keep continuing to be heated to 110 ℃ of maintenance 2h behind the 2h, underpressure distillation removes water and unreacted matters, the amine condensation intermediate B that makes.
Embodiment 3
In the there-necked flask of the 250ml that has mechanical stirring, temperature-control heat couple and thermometer; add 38.0g (0.2mol) tetraethylene pentamine and 12.0g Paraformaldehyde 96, under nitrogen protection, be heated to 65 ℃; kept 1 hour; add 10.3g (0.05mol) 2,6-di-tert-butylphenol (0.1mol) and 9.4g (0.1mol) phenol keep 1h; slowly be heated to 120 ℃; keep 1h, underpressure distillation removes water and unreacted matters, the amine condensation intermediate C that makes.
Embodiment 4
In the there-necked flask of the 250ml that has mechanical stirring, temperature-control heat couple and thermometer; add 56.8g (0.3mol) tetraethylene pentamine; 9.4g (0.1mol) phenol; 41.2g (0.2mol) 2, the 6-di-tert-butylphenol and and the 19g Paraformaldehyde 96, under nitrogen protection; slowly be heated to 90 ℃; keep continuing to be heated to 110 ℃ of maintenance 2h behind the 2h, underpressure distillation removes water and unreacted matters, the amine condensation intermediate D that makes.
Embodiment 5
In the there-necked flask of the 250ml that has mechanical stirring, temperature-control heat couple and thermometer; add 73g (0.5mol) triethylene tetramine, 9.4g (0.1mol) phenol, 61.8g (0.3mol) 2; the 6-di-tert-butylphenol; under nitrogen protection, add 42ml formaldehyde solution gradually, then; be heated to 100 ℃; behind the backflow 4h, underpressure distillation removes water and unreacted matters, the amine condensation intermediate E that makes.
Embodiment 6
In the there-necked flask of the 250ml that has mechanical stirring, temperature-control heat couple and thermometer; add 75.7g (0.4mol) tetraethylene pentamine; 9.4g (0.1mol) phenol; 30.9g (0.15mol) 2,6-di-tert-butylphenol and 15g Paraformaldehyde 96 are under nitrogen protection; slowly be heated to 90 ℃; keep continuing to be heated to 110 ℃ of maintenance 2h behind the 2h, underpressure distillation removes water and unreacted matters, the amine condensation intermediate F that makes.
Embodiment 7
In the there-necked flask of the 250ml that has mechanical stirring, temperature-control heat couple and thermometer; add 38.2g (0.2mol) tetraethylene pentamine; 10.9g (0.1mol) p-cresol; 20.6g (0.1mol) 2, the 6-di-tert-butylphenol is under nitrogen protection; splash into the 32ml formalin gradually; slowly be heated to 100 ℃, underpressure distillation removes water and unreacted matters behind the backflow 4h, the amine condensation intermediate G that makes.
Embodiment 8
In the there-necked flask of the 250ml that has mechanical stirring, temperature-control heat couple and thermometer; add 79.5 (0.42mol) g tetraethylene pentamine; 22.2g (0.1mol) dihydroxyphenyl propane, 30.2g (0.15mol) 2,6-di-tert-butylphenol; under nitrogen protection; splash into the 32ml formalin gradually, slowly be heated to 100 ℃, backflow 2h; underpressure distillation removes water and unreacted matters, the amine condensation intermediate H that makes.
Embodiment 9～16 is the preparation of antioxidative succinimide dustless dispersing agent.
Embodiment 9
In the there-necked flask of the 250ml that has mechanical stirring, temperature-control heat couple and thermometer; add 50g enetutanedioic acid anhydride (molecular weight of polyisobutene is 2300) and 50g150SN thinning oil; be heated to 85 ℃ under the nitrogen protection; add the amine condensation intermediate A 5.1g among the embodiment 1; keep 1h, heat up 140 ℃, keep 2h; vacuum hydro-extraction 1h, after filtration ashless dispersant finally.
Embodiment 10
The amination condition replaces amine condensation A with embodiment 9 with the amine condensation B among the embodiment 2, and making the mol ratio of alkene acid anhydride and amine condensation (being equivalent to tetraethylene pentamine) is 1.5: 1, makes ashless dispersant, and its assessment of performance sees Table 1.
Embodiment 11
The amination condition is with embodiment 9, and the amine condensation C replacement amine condensation A with identical mole number among the embodiment 3 makes ashless dispersant, and assessment of performance sees Table 1.
Embodiment 12
The amination condition is with embodiment 9, and with the amine condensation D replacement amine condensation A of identical mole number among the embodiment 4, employing polyisobutene molecular weight is 900 alkene acid anhydride, makes ashless dispersant, and assessment of performance sees Table 1.
Embodiment 13
The amination condition is with embodiment 9, and the amine condensation E replacement amine condensation A with identical mole number among the embodiment 5 makes ashless dispersant, and its assessment of performance sees Table 1.
Embodiment 14
The amination condition is with embodiment 9, and the amine condensation F replacement amine condensation A with identical mole number among the embodiment 6 makes ashless dispersant, and its assessment of performance sees Table 1.
Embodiment 15
The amination condition is with embodiment 9, and with the amine condensation G replacement amine condensation A of identical mole number among the embodiment 7, employing polyisobutene molecular weight is 1300 alkene acid anhydride, makes ashless dispersant, and assessment of performance sees Table 1.
Embodiment 16
The amination condition replaces amine condensation A with embodiment 9 with the amine condensation F among the embodiment 8, and making the mol ratio of alkene acid anhydride and amine condensation (being equivalent to tetraethylene pentamine) is 0.78: 1, makes ashless dispersant, and its assessment of performance sees Table 1.
Comparative Examples 1
This Comparative Examples is common single preparation of hanging ashless dispersant.
According to the reaction conditions of embodiment 9, change 5.1 gram amine condensations into 3.2 gram tetraethylene pentamine, make common single ashless dispersant of hanging, its assessment of performance sees Table 1.
Comparative Examples 2
This Comparative Examples is the preparation that common double is hung ashless dispersant.
According to the reaction conditions of embodiment 9, change 5.1 gram amine condensations into 1.7 gram tetraethylene pentamine, make common double and hang ashless dispersant.Its assessment of performance sees Table 1.
Embodiment 17
Present embodiment is the dispersing property evaluation.
Adopt adverse current viscosity growth method, make the soot stand-in with carbon black, be distributed in the 150SN base oil that contains 0.5% dispersion agent, the carbon black consumption is 1%, measures the viscosity rate of increase, the good dispersity that rate of increase is little.Test result sees Table 1.
Embodiment 18
Present embodiment is the antioxygen property evaluation.
Adopt PDSC pressure difference scanning calorimeter instrument to measure the oxidation induction period of additive, the big more explanation antioxygen property of this value is good more.Test condition is: U.S. DuPont2100 instrument, O
2Under the atmosphere, pressure 5kg/cm
2, 220 ℃ of constant temperature, sample size 2mg.Test result sees Table 1.
As can be seen from Table 1, antioxidative succinimide dustless dispersing agent provided by the invention is compared with common single the extension with two ashless dispersants of hanging, and has not only had antioxygen property, has also improved dispersing property.
Table 1
| Additive | The viscosity rate of increase, % | Oxidation induction period, min |
| Embodiment 9 | 13.6 | 10.8 |
| Embodiment 10 | 16.7 | 6.4 |
| Embodiment 11 | 15.4 | 9.8 |
| Embodiment 12 | 11.8 | 24.8 |
| Embodiment 13 | 20.0 | 8.2 |
| Embodiment 14 | 14.4 | 15.5 |
| Embodiment 15 | 13.8 | 25.2 |
| Embodiment 16 | 14.6 | 18.9 |
| Comparative Examples 1 | 27.6 | 0 |
| Comparative Examples 2 | 69.3 | 0 |
Claims (9)
1. an antioxidative succinimide dustless dispersing agent contains following group: allyl butyrate diacyl, phenol link coupled polyamines polyene base on the structure, link to each other with the polyamines polyene base 2,6-di-t-butyl phenolic group is characterized in that it prepares as follows: (1) is 2, under the existence of 6-di-tert-butylphenol, phenol, polyamines polyene and the formaldehyde that will contain α H mix, carry out Mannich reaction, temperature of reaction is room temperature～150 ℃, and the reaction times is 1～10 hour, separated product makes the intermediates amine condensation; (2) enetutanedioic acid anhydride and above-mentioned amine condensation are carried out amination reaction, temperature of reaction is 60～160 ℃, and the reaction times is 1～8 hour, gets the finished product.
2. according to the said dispersion agent of claim 1, it is characterized in that the phenol that contains α H is selected from phenol, p-cresol, Resorcinol, one of dihydroxyphenyl propane or 2-Naphthol, or two or more mixture wherein.
3. according to claim 1 or 2 said dispersion agents, it is characterized in that containing the phenol of α H and the mol ratio of polyamines polyene is 1: 1～4, contains the phenol and 2 of α H, the mol ratio of 6-di-tert-butylphenol is 1: 0.2～3.
4. according to the said dispersion agent of claim 1, it is characterized in that formaldehyde is selected from Paraformaldehyde 96 or formalin, the consumption of formaldehyde is the phenol and 2 that contains α H, has 1～2 times of summation of the H of reactive behavior in the 6-di-tert-butylphenol.
5. according to the said dispersion agent of claim 1, it is characterized in that said polyamines polyene is selected from the compound with following general formula: H
2N (CH
2CH
2NH)
nH, n is 1～6 integer in the formula.
6. according to the said dispersion agent of claim 1, it is characterized in that the add-on of the middle enetutanedioic acid anhydride of step (2) is 0.6～3 times of the middle polyamines polyene mole number of step (1).
7. according to the said dispersion agent of claim 1, it is characterized in that the thiazolinyl in the enetutanedioic acid anhydride is C
2～C
10Olefin copolymer or homopolymer, its number-average molecular weight is 500～5000, molecular weight distribution is 1.5～4.5.
8. according to claim 1 or 7 said dispersion agents, it is characterized in that the thiazolinyl in the enetutanedioic acid anhydride is a polyisobutene, number-average molecular weight is 900～2500, and molecular weight distribution is 1.5～3.5.
9. according to the said dispersion agent of claim 1, it is characterized in that the temperature of reaction of step (1) is 60～120 ℃, the reaction times is 2～8 hours, and the temperature of reaction of step (2) is 80～140 ℃, and the reaction times is 2～6 hours.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99103269A CN1098345C (en) | 1999-03-30 | 1999-03-30 | Antioxidative succinimide dustless dispersing agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99103269A CN1098345C (en) | 1999-03-30 | 1999-03-30 | Antioxidative succinimide dustless dispersing agent |
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| CN1268554A CN1268554A (en) | 2000-10-04 |
| CN1098345C true CN1098345C (en) | 2003-01-08 |
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|---|---|---|---|
| CN99103269A Expired - Fee Related CN1098345C (en) | 1999-03-30 | 1999-03-30 | Antioxidative succinimide dustless dispersing agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20080040968A1 (en) * | 2006-08-17 | 2008-02-21 | Malfer Dennis J | Fuel additive compounds and method of making the compounds |
| CN103374454B (en) * | 2012-04-26 | 2015-10-28 | 中国石油化工股份有限公司 | Gas engine oil compositions and manufacture method thereof |
| CN114507301B (en) * | 2020-10-28 | 2023-12-12 | 中国石油化工股份有限公司 | Method and system for producing polyisobutene succinimide ashless dispersant |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4636322A (en) * | 1985-11-04 | 1987-01-13 | Texaco Inc. | Lubricating oil dispersant and viton seal additives |
| US4699724A (en) * | 1986-08-20 | 1987-10-13 | Texaco Inc. | Post-coupled mono-succinimide lubricating oil dispersant and viton seal additives |
| US4713189A (en) * | 1986-08-20 | 1987-12-15 | Texaco, Inc. | Precoupled mono-succinimide lubricating oil dispersants and viton seal additives |
| US4973412A (en) * | 1990-05-07 | 1990-11-27 | Texaco Inc. | Multifunctional lubricant additive with Viton seal capability |
-
1999
- 1999-03-30 CN CN99103269A patent/CN1098345C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4636322A (en) * | 1985-11-04 | 1987-01-13 | Texaco Inc. | Lubricating oil dispersant and viton seal additives |
| US4699724A (en) * | 1986-08-20 | 1987-10-13 | Texaco Inc. | Post-coupled mono-succinimide lubricating oil dispersant and viton seal additives |
| US4713189A (en) * | 1986-08-20 | 1987-12-15 | Texaco, Inc. | Precoupled mono-succinimide lubricating oil dispersants and viton seal additives |
| US4973412A (en) * | 1990-05-07 | 1990-11-27 | Texaco Inc. | Multifunctional lubricant additive with Viton seal capability |
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