CN1351134A - Antioxidizing B-contained disperser - Google Patents
Antioxidizing B-contained disperser Download PDFInfo
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- CN1351134A CN1351134A CN 00129836 CN00129836A CN1351134A CN 1351134 A CN1351134 A CN 1351134A CN 00129836 CN00129836 CN 00129836 CN 00129836 A CN00129836 A CN 00129836A CN 1351134 A CN1351134 A CN 1351134A
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Abstract
An antioxidizing B-contained (0.1-2%) disperser for machine oil of IC engine is prepared from polyene polyamine, methoxyl phenol, aldehyde, alkylene butanedioic acid and boric acid through reaction. Its advantages include high cleaning power and high initial oxidizing temp (greater than 310 deg.C).
Description
The present invention relates to be used for the boron-containing dispersant with antioxygen property of I. C. engine oil.
Along with the raising day by day of environmental protection and energy-conservation requirement, each engine manufacturer constantly dwindles size of engine, increases compression ratio, improves the service temperature of engine.Particularly the apical ring groove temperature of high-power diesel engine will be brought up to 310 ℃ by 270 ℃, and this antioxidant property to I. C. engine oil and oil fuel is had higher requirement.Because dispersion agent special consumption in lubricating oil in oil product is very big, therefore the antioxygen property that improves dispersion agent becomes this area main research work, one of research direction is to introduce different antioxygen functional groups in the structure of dispersion agent, and used antioxygen functional group is based on phenols.US 5182038 has reported a kind of with the amino succimide dispersion agent that generates of nonyl phenol coupling acid amides.US 4636322,4699724,4713189 disclosed link coupled succimide dispersion agents are to be prepared from by the coupling succimide by phenol, dihydroxyphenyl propane, Resorcinol, single nonyl phenol and 2-Naphthol.
CN 96106725 discloses a kind of link coupled succimide dispersion agent, is by a kind of phenol in Resorcinol, pyrocatechol and the p-cresol or its mixture the coupling of succimide dispersion agent to be formed.This additive has good antioxidant property, thermal oxidation stability and dispersiveness.
All there is the low problem of thermooxidizing decomposition temperature in the dispersion agent of above-mentioned patent preparation, and the initial oxidation decomposition temperature of its dispersion agent all is lower than 300 ℃.
The objective of the invention is to overcome the above-mentioned defective of prior art, a kind of antioxidizing B-contained succimide dispersion agent with high initial oxidation decomposition temperature and good detergent-dispersant performance is provided.
Boracic antioxidant dispersant of the present invention is to be made by polyamines polyene, methoxyphenol, aldehyde, alkenyl succinic acid and acid reaction, can prepare according to following two kinds of methods:
First method comprises:
1) add aldehyde in the mixture of methoxyphenol and polyamines polyene, be warming up to 120~200 ℃ of dehydration reactions 1~8 hour, collect amine condensation, wherein phenol: amine: the mol ratio of aldehyde is 1: 0.5~2.5: 2~5;
2) amine condensation and polyolefin-based Succinic Acid (acid anhydride) are mixed according to 1: 0.5~4 mol ratio (mole number of amine condensation calculates with amine wherein), 100~180 ℃ of dehydration reactions 2~10 hours;
3) in step 2) product in add the Fatty Alcohol(C12-C14 and C12-C18) of its weight 1~5% and 0.5~10% boric acid, 100~180 ℃ of reactions 2~10 hours, collect product.
Specifically, first method may further comprise the steps:
1) with methoxyphenol and polyamines polyene according to 1: 0.5~2.5, preferred 1: 1~2 mixed in molar ratio drips 2~5 times of phenol mole numbers under nitrogen protection; preferred 2.5~3.5 times aldehyde; for the ease of mixing, can suitably be warming up to 50~100 ℃, and fully stir 0.5~4 hour; elevated temperature to 120~200 ℃ then; preferred 130~180 ℃, reacted preferred 2~5 hours 1~8 hour; stripping water and unreacted aldehyde promptly obtain amine condensation.
2) with amine condensation and polyolefin-based Succinic Acid (acid anhydride) according to 1: 0.5~4, preferred 1: 1~2 mol ratio (mole number of amine condensation calculates with amine wherein) is mixed, can suitably be heated to 50~100 ℃ and also fully stir 0.5~4 hour so that mix, at 100~180 ℃, preferred 125~145 ℃ of dehydration reactions 2~10 hours, preferred 4~6 hours, obtain intermediate product.
3) in this intermediate product, add 1~5%, preferred 2~3% Fatty Alcohol(C12-C14 and C12-C18) and 0.5~10%, preferred 1~6% boric acid, fully stir and mixed in 0.5~4 hour, at 100~180 ℃, preferred 125~145 ℃ of dehydration reactions 2~10 hours, preferred 4~6 hours, carry out the boronation reaction, promptly obtain boracic antioxidant dispersant of the present invention after filtration.
Second method comprises:
1) add aldehyde in the mixture of methoxyphenol and polyamines polyene, be warming up to 120~200 ℃ of dehydration reactions 1~8 hour, collect amine condensation, wherein phenol: amine: the mol ratio of aldehyde is 1: 0.5~2.5: 2~5;
2) in being the mixture of 1: 0.5~4 (mole number of amine condensation calculates with amine wherein), amine condensation and polyolefin-based Succinic Acid (acid anhydride) mol ratio add the Fatty Alcohol(C12-C14 and C12-C18) of its weight 1~5% and 0.5~10% boric acid, 100~180 ℃ of reactions 2~10 hours, collect product.
Specifically, second method may further comprise the steps:
1) with methoxyphenol and polyamines polyene according to 1: 0.5~2.5, preferred 1: 1~2 mixed in molar ratio drips 2~5 times of phenol mole numbers under nitrogen protection; preferred 2.5~3.5 times aldehyde; for the ease of mixing, can suitably be warming up to 50~100 ℃, and fully stir 0.5~4 hour; elevated temperature to 120~200 ℃ then; preferred 130~180 ℃, reacted preferred 2~5 hours 1~8 hour; stripping water and unreacted aldehyde promptly obtain amine condensation.
2) with amine condensation and polyolefin-based Succinic Acid (acid anhydride) according to 1: 0.5~4, preferred 1: 1~2 mol ratio (mole number of amine condensation calculates with amine wherein) is mixed, can suitably be heated to 50~100 ℃ and also fully stir 0.5~4 hour so that mix, in mixture, add its weight 1~5%, preferred 2~3% Fatty Alcohol(C12-C14 and C12-C18) and 0.5~10%, preferred 1~6% boric acid, fully stir and mixed in 0.5~4 hour, at 100~180 ℃, preferred 125~145 ℃ of dehydrations 2~10 hours, preferred 4~6 hours, carry out the boronation reaction, promptly obtain boracic antioxidant dispersant of the present invention after filtration.
The said polyamines polyene of the present invention is meant to have H
2N[(CH
2)
nNH]
mThe amine of H general formula, wherein n is 2~4, preferred 2~3 integer, m are 1~5, preferred 2~4 integer.As quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines, propylene diamine, two propylene triamines, three propylene tetramines, tetrapropylene five amine, five propylene hexamines etc., preferred triethylene tetramine, tetraethylene pentamine and five ethene hexamines.
The said phenol of the present invention is a kind of or its mixture in p methoxy phenol, hydroxyanisole, the meta-methoxy phenol.
The polyolefin-based C that comes from the said polyolefin-based Succinic Acid of the present invention (acid anhydride)
3~C
4The multipolymer of monoolefine or homopolymer can be polyisobutene, Atactic Polypropelene, ethylene-propylene copolymer.Its number-average molecular weight Mn=850~5000 are preferably 950~2500.
The said Fatty Alcohol(C12-C14 and C12-C18) of the present invention is selected from C
2~C
10Fatty Alcohol(C12-C14 and C12-C18), preferred alcohol, propyl alcohol and propyl carbinol.
The said aldehyde of the present invention can be formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, salicylic aldehyde or phenyl aldehyde, or the polymer of above-mentioned aldehyde or the aqueous solution, preferred formaldehyde, Paraformaldehyde 96 and salicylic aldehyde.The adding mode of aldehyde preferably drips.
Said boric acid preferably is mixed with suspension in 1: 0.5~5 ratio and mineral oil, so that drip.
The boron content of boracic antioxidant dispersant provided by the invention is 0.1~2%, has the following advantages than the existing not detergent-dispersant additive of boracic: 1) have good detergency; 2) the initial oxidation decomposition temperature is greater than 310 ℃.
The invention will be further described below by example.
Example 1
This example is the preparation of amine condensation.
In the there-necked flask of 250ml, add 75g (0.4mol) tetraethylene pentamine (TEPA); 21.4g (0.17mol) p methoxy phenol; under nitrogen protection, rise to 70 ℃; drip 44g (0.53mol) formalin (containing 36% formaldehyde); 0.5 hour add; stir and made the material thorough mixing in 2 hours, rise to 130 ℃ of reactions 3 hours, get amine condensation AN1.
Example 2
This example is the preparation of amine condensation.
Add 75g (0.4mol) tetraethylene pentamine (TEPA) in the 250ml there-necked flask, 32.8g (0.26mol) p methoxy phenol rises to 80 ℃ under nitrogen protection, drips salicylic aldehyde 65g (0.53mol), adds in 0.5 hour.Stir and made the material thorough mixing in 2 hours, rise to 180 ℃ of reactions 3 hours, get amine condensation AN2.
Example 3
This example adopts first method to prepare boron-containing dispersant.
(the soap valency is 58.74mgKOH/g to add the 100g polyisobutenyl succinic anhydride in the 250ml there-necked flask, contain 60%150SN neutral oil, the polyisobutene number-average molecular weight is 1300, Suzhou specialty oil products factory produces) and 17.5g150SN neutral oil (Dalian Petrochemical Industry Company's production), behind the nitrogen replacement, rise to 70 ℃, stir.Add 10g example 1 gained amine condensation AN1, stirred 1 hour, rise to 120 ℃, dehydration reaction is cooled to 80 ℃ after 3 hours, obtain intermediate product XN1, add the 2.4g propyl carbinol, drip the mixture of 2.5g boric acid and 10g 150SN neutral oil, added, and stirred in 1 hour, rise to 140 ℃, dehydration reaction gets product B N1 after 3 hours.
Example 4
This example adopts first method to prepare boron-containing dispersant.
(the soap valency is 42mgKOH/g to add the 100g polyisobutenyl succinic anhydride in the 250ml there-necked flask, contain 60%150SN, the polyisobutene number-average molecular weight is 2300, Suzhou specialty oil products factory produces) and 17.5g150SN neutral oil (Dalian Petrochemical Industry Company's production), behind the nitrogen replacement, rise to 80 ℃, stir.Add 6g example 2 gained amine condensation AN2 again, added in 2 hours, rise to 120 ℃, dehydration reaction was cooled to 80 ℃ in 3 hours, obtained intermediate product XN2, add the 2.4g propyl alcohol, drip the mixture of 2.5g boric acid and 10g150SN neutral oil, added in 1 hour, restir rises to 140 ℃ after 1 hour, dehydration reaction 3 hours gets product B N2 after the filtration.
Example 5
This example adopts second method to prepare boron-containing dispersant.
(the soap valency is 58.74mgKOH/g to add the 100g polyisobutenyl succinic anhydride in the 250ml there-necked flask, contain 60%150SN, the polyisobutene number-average molecular weight is 1300, Suzhou specialty oil products factory produces) and 17.5g150SN neutral oil (Dalian Petrochemical Industry Company's production), behind the nitrogen replacement, rise to 70 ℃, stir.Add 10g amine condensation AN1, stirred 1 hour, behind the adding 2.4g propyl carbinol, drip the mixture of 2.5g boric acid and 10g150SN neutral oil, added in 1 hour, rise to 140 ℃ after stirring, dehydration reaction 3 hours gets product B N3 after the filtration.
Example 6
This example adopts second method to prepare boron-containing dispersant.
(the soap valency is 58.74mgKOH/g to add the 1200g polyisobutenyl succinic anhydride in the 3000ml there-necked flask, contain 60%150SN, the polyisobutene number-average molecular weight is 1300, Suzhou specialty oil products factory produces) and 90g150SN neutral oil (Dalian Petrochemical Industry Company's production), behind the nitrogen replacement, rise to 70 ℃, stir.Add 120g amine condensation AN1, stirred 1 hour, behind the adding 25g propyl carbinol, drip the mixture of 135g boric acid and 120g150SN neutral oil, added in 1 hour, rise to 150 ℃ after stirring, dehydration reaction 6 hours gets product B N4 after the filtration.
Comparative Examples 1
The intermediate product XN1 that obtains with example 4 contrasts
Comparative Examples 2
Contrast with traditional divinyl imines dispersion agent T151.
Example 7
This example is that detergent-dispersant performance can be evaluated.With the gained dispersion agent, the weight ratio by 2.5% joins in the non-dispersant 10W30 SF/CC oil carries out coke test by SH/T0300-92, and it the results are shown in Table 1.
Table 1
Numbering | The sample name | Burnt heavy, mg |
Example 3 | ????BN1 | ????10.7 |
Example 4 | ????BN2 | ????11.5 |
Example 5 | ????BN3 | ????6.1 |
Example 6 | ????BN4 | ????4.1 |
Comparative Examples 1 | ????XN1 | ????12.6 |
Comparative Examples 2 | ????T151 | ????24.7 |
Table 1 is the result show, the heavy dispersion agent less than prior art of Jiao of antioxygen dispersion agent of the present invention has high temperature detergency preferably.
Example 8
This example is the antioxygen property evaluation.Measure the initial oxidation decomposition temperature of each dispersion agent with DSC under oxygen atmosphere, evaluation result sees Table 2.
Table 2
Numbering | The sample name | Temperature of initial decomposition, ℃ |
Example 3 | ????BN1 | ????358 |
Example 4 | ????BN2 | ????318 |
Example 5 | ????BN3 | ????357 |
Example 6 | ????BN4 | ????342 |
Comparative Examples 1 | ????XN1 | ????271 |
Comparative Examples 2 | ????T151 | ????260 |
As can be seen from Table 2, antioxidant dispersant of the present invention has good oxidative stability, and the initial oxidation decomposition temperature is apparently higher than existing dispersion agent.
Claims (17)
1. a boracic antioxidant dispersant is to be made by polyamines polyene, methoxyphenol, aldehyde, alkenyl succinic acid and acid reaction, it is characterized in that may further comprise the steps:
1) add aldehyde in the mixture of methoxyphenol and polyamines polyene, be warming up to 120~200 ℃ of dehydration reactions 1~8 hour, collect amine condensation, wherein phenol: amine: the mol ratio of aldehyde is 1: 0.5~2.5: 2~5;
2) with amine condensation and polyolefin-based Succinic Acid (acid anhydride) according to 1: 0.5~4 mixed in molar ratio, 100~180 ℃ of dehydration reactions 2~10 hours;
3) in step 2) product in add the Fatty Alcohol(C12-C14 and C12-C18) of its weight 1~5% and 0.5~10% boric acid, 100~180 ℃ of reactions 2~10 hours, collect product.
2. dispersion agent according to claim 1 is characterized in that, the mixing mol ratio of methoxyphenol and polyamines polyene is 1: 1~2 in the step 1), and the amount that drips aldehyde is 2.5~3.5 times of phenol mole numbers.
3. dispersion agent according to claim 1 is characterized in that, the temperature of reaction of step 1) is 130~180 ℃, and the reaction times is 2~5 hours.
4. dispersion agent according to claim 1 is characterized in that step 2) in the mol ratio of mixing of amine condensation and polyolefin-based Succinic Acid (acid anhydride) be 1: 1~2.
5. dispersion agent according to claim 1 is characterized in that step 2) temperature of reaction be 125~145 ℃, 4~6 hours reaction times.
6. dispersion agent according to claim 1 is characterized in that, in the step 3) in step 2) product in the Fatty Alcohol(C12-C14 and C12-C18) that adds and the amount of boric acid be respectively 2~3% and 1~6%.
7. dispersion agent according to claim 1 is characterized in that, 125~145 ℃ of the temperature of reaction of step 3), and the reaction times is 4~6 hours.
8. a boracic antioxidant dispersant is to be made by polyamines polyene, methoxyphenol, aldehyde, alkenyl succinic acid and acid reaction, it is characterized in that may further comprise the steps:
1) add aldehyde in the mixture of methoxyphenol and polyamines polyene, be warming up to 120~200 ℃ of dehydration reactions 1~8 hour, collect amine condensation, wherein phenol: amine: the mol ratio of aldehyde is 1: 0.5~2.5: 2~5;
2) in amine condensation and polyolefin-based Succinic Acid (acid anhydride) mol ratio are 1: 0.5~4 mixture, add the Fatty Alcohol(C12-C14 and C12-C18) of its weight 1~5% and 0.5~10% boric acid,, collect product 100~180 ℃ of reactions 2~10 hours.
9. dispersion agent according to claim 8 is characterized in that, the mol ratio of methoxyphenol and polyamines polyene is 1: 1~2 in the step 1), and the amount that drips aldehyde is 2.5~3.5 times of phenol mole numbers.
10. dispersion agent according to claim 8 is characterized in that, the temperature of reaction of step 1) is 130~180 ℃, and the reaction times is 2~5 hours.
11. dispersion agent according to claim 8, it is characterized in that, step 2) amine condensation is 1: 1~2 with the mol ratio of mixing of polyolefin-based Succinic Acid (acid anhydride) in, and the Fatty Alcohol(C12-C14 and C12-C18) that adds in the mixture of amine condensation and polyolefin-based Succinic Acid (acid anhydride) and the amount of boric acid are respectively 2~3% and 1~6%.
12. dispersion agent according to claim 8 is characterized in that step 2) temperature of reaction be 125~145 ℃, the reaction times is 4~6 hours.
13., it is characterized in that said polyamines polyene has following general formula, H according to claim 1 or 8 described dispersion agents
2N[(CH
2)
nNH]
mH, wherein n is 2~4 integer, m is 1~5 integer.
14., it is characterized in that said phenol is a kind of or its mixture in p methoxy phenol, hydroxyanisole, the meta-methoxy phenol according to claim 1 or 8 described dispersion agents.
15., it is characterized in that the polyolefin-based C that comes from the said polyolefin-based Succinic Acid (acid anhydride) according to claim 1 or 8 described dispersion agents
3~C
4The multipolymer of monoolefine or homopolymer, its number-average molecular weight are 850~5000.
16., it is characterized in that said Fatty Alcohol(C12-C14 and C12-C18) is selected from C according to claim 1 or 8 described dispersion agents
2~C
10Fatty Alcohol(C12-C14 and C12-C18).
17., it is characterized in that said aldehyde is selected from formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, salicylic aldehyde and phenyl aldehyde, or the polymer of above-mentioned aldehyde or the aqueous solution according to claim 1 or 8 described dispersion agents.
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CN 00129836 CN1122100C (en) | 2000-10-30 | 2000-10-30 | Antioxidizing B-contained disperser |
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CN 00129836 CN1122100C (en) | 2000-10-30 | 2000-10-30 | Antioxidizing B-contained disperser |
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CN1122100C CN1122100C (en) | 2003-09-24 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100338198C (en) * | 2004-11-30 | 2007-09-19 | 中国石油化工股份有限公司 | Internal combustion engine oil additive composition |
CN115975696A (en) * | 2021-10-14 | 2023-04-18 | 中国石油化工股份有限公司 | Lubricating oil composition for diesel engine and preparation method thereof |
-
2000
- 2000-10-30 CN CN 00129836 patent/CN1122100C/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100338198C (en) * | 2004-11-30 | 2007-09-19 | 中国石油化工股份有限公司 | Internal combustion engine oil additive composition |
CN115975696A (en) * | 2021-10-14 | 2023-04-18 | 中国石油化工股份有限公司 | Lubricating oil composition for diesel engine and preparation method thereof |
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