CN1673322A - Prepn of nitrogen sulfate phosphate type phosphorus-containing agent - Google Patents
Prepn of nitrogen sulfate phosphate type phosphorus-containing agent Download PDFInfo
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- CN1673322A CN1673322A CN 200410029723 CN200410029723A CN1673322A CN 1673322 A CN1673322 A CN 1673322A CN 200410029723 CN200410029723 CN 200410029723 CN 200410029723 A CN200410029723 A CN 200410029723A CN 1673322 A CN1673322 A CN 1673322A
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Abstract
The present invention relates to the preparation process lubricant oil additive, and is especially the preparation process of new S-P-N type phosphorus containing agent. The S-P-N type phosphorus containing agent is prepared with thiophosphoric acid, cyclic ether compound, sulfur phosphide, polysulfide and fatty amine in certain proportion as material and through synthesis in the presence of formaldehyde as promoter. The technological process is simple and feasible, and the synthetic product has excellent extreme pressure wear resistance, excellent hydrolysis safety, high emulsification resistance, high heat stability and high anticorrosion, and is one kind of excellent ash-free multifunctional additive for gear oil and hydraulic oil.
Description
One, technical field
The present invention relates to a kind of preparation process lubricant oil additive, especially the preparation method of high-sulfur type S-P-N type phosphorus containing agent belongs to the lubricating oil additive field.
Two, background technology
Phosphor-included additive has good extreme pressure anti-wear, thereby is widely used in comprising in the various lubricating oil of gear oil always.The upgrading of gear oil in recent years proposes new requirement to anti-wear agent, promotes the development of gear oil simultaneously again along with the development of phosphorus containing agent.In existing phosphorus containing agent, because the activity of phosphorus containing agent and the restriction of thermostability, thereby can not satisfy the requirement of modern transmission system.
CN1037781, CN1123316 have proposed structure
The preparation method of (wherein X is primary amine, secondary amine); CN1033811 has introduced
Preparation and performance thereof; US4493780 has mainly illustrated
The preparation of (M is molybdenum or antimony); Compound structure mentioned among US5573696, the US5681798 is
Be multiple ester amine salt of sulphur phosphoric acid or the multiple ester metal ammonium salt of sulphur phosphoric acid; " lubricating oil ", 2002, vol.17, No.4 are reported in people such as loyalty has introduced the multiple ester amine salt of sulphur phosphoric acid in article preparation and performance evaluation situation thereof.By various documents and the practice as can be known, S-P-N type phosphorus containing agent is a comparatively comprehensively phosphor-included additive of a kind of performance, not only have good extreme pressure anti-wear, also have excellent hydrolysis stability, demulsification performance, thermostability and erosion resistance, can be widely used in gear oil and the hydraulic efficiency oil.
Three, summary of the invention
The objective of the invention is to provide a kind of method of the S-P-N of preparation type phosphorus containing agent, thereby provide a kind of good novel extreme pressure anti-wear additives for lubricating oil.
The preparation method of S-P-N type phosphorus containing agent of the present invention is as follows: the there-necked flask that at first will have electronic stirring, condensation water trap, thermometer installs, sulphur phosphoric acid, cyclic ether compounds, sulfur phosphorus compound or the polysulfide and the industrial naptha that add metering, be warming up to 50-130 ℃ of reaction 4-15h, be cooled to below 25 ℃, add the aliphatic amide of metering and add quantitative solvent, be warming up to 20-70 ℃ of formaldehyde that adds metering, react 6-10h down at 70-130 ℃.Air distillation removes and desolvates, and room temperature is filtered, and promptly gets product.
The invention provides a kind of preparation method of S-P-N type phosphorus containing agent, this preparation method characteristic is that certain proportion scale is arranged between each feed composition: sulphur phosphoric acid is in 100 parts (m), the add-on of cyclic ether compounds is that 90-200 part (m), sulfur phosphorus compound or polysulfide are that 20-80 part (m), aliphatic amide are that 40-60 part (m), formaldehyde are 40-60 part (m), solvent 300-700 part (m), reactions steps is in two steps: the first step is an esterification, temperature of reaction can be controlled in 50-130 ℃, reaction times 4-15h; Second step was amination reaction, temperature of reaction 70-130 ℃, and reaction dehydration 6-10h; Reaction solvent can be 70-120 ℃ a gasoline, also can be 90-120 ℃ sherwood oil, also can be normal heptane, benzene, toluene.Sulphur phosphoric acid can be dialkyl dithiophosphoric acid, and alkyl is C
1-C
18Similar and different straight or branched alkyl, C preferably
2-C
12The straight or branched alkyl; Cyclic ether compounds can be C
2-C
5Triatomic ring or pentacyclic cyclic ether compounds, can be oxyethane, propylene oxide, furans; Sulfur phosphorus compound or polysulfide can be thiophosphoric anhydride, Vanadium Pentoxide in FLAKES, and the purity of thiophosphoric anhydride and Vanadium Pentoxide in FLAKES is not less than 95%; Aliphatic amide can be the straight chain primary amine, also can be the side chain primary amine, alkyl size C
4-C
18(straight or branched), preferably C
8-C
14The primary amine of straight or branched; Formaldehyde is 36% formalin or Paraformaldehyde 96.
Products therefrom final structure of the present invention is
The difference of compound described in it and other patent documentation is that its structure has novelty, the multiple ester structure of its sulphur phosphoric acid different from the past, and the most outstanding is that its structure is the multiple ester of temephos acid, has therefore improved the sulphur phosphorus content and the performance thereof of product.
The S-P-N type phosphorus containing agent of the present invention's preparation has good extreme pressure anti-wear, the P in its tetra-ball machine test
DValue is compared very outstanding up to 3087.0N with similar extreme pressure anti-wear additives; Has higher sulphur content simultaneously, therefore it is comprehensive to have improved the extreme pressure property of product and abrasion resistance and this product performance greatly, also have characteristics such as good thermally-stabilised stability, low corrosion, except being applied to also to can be applicable in the hydraulic efficiency oil in the high-grade gear oil.This product synthesis technique is simple, has the certain economic potentiality.
Four, specific implementation method
The present invention is further described below by example, and spirit of the present invention and protection domain are listed in claims.
Embodiment 1, in the 500ml there-necked flask that automatic stirrer and condensation water trap are housed, the dibutyl phosphorodithioic acid (self-control), 44.0g cyclic ethers, 31.0g thiophosphoric anhydride and the 400ml industrial naptha that add 242.0g, be warming up to 90-110 ℃ of reaction 10h, be cooled to below 35 ℃, the amino dodecane that adds 92.5g is warming up to 30-70 ℃ of formaldehyde solution that adds 20.7g, reacts dehydration 6-10h down at 70-90 ℃.Air distillation removes and desolvates, and room temperature is filtered, and promptly gets product (A).Sulphur content 24.70%, phosphorus content 9.33%, 166 ℃ of nitrogen content 2.4%, flash-points.
Embodiment 2, according to embodiment 1 operation, add diisooctyl phosphorodithioic acid (self-control), 63.4.0g cyclic ethers, 31.0g Vanadium Pentoxide in FLAKES and the 400ml industrial naptha of 354.0g, uncle's dodecyl primary amine of 92.5g, the Paraformaldehyde 96 of 20.7g.React product (B).Sulphur content 19.92%, phosphorus content 7.86%, 172 ℃ of nitrogen content 1.56%, flash-points.
Embodiment 3, according to embodiment 1 operation, add di-n-butyl phosphorodithioic acid (self-control), 145.0g cyclic ethers, 155.0g thiophosphoric anhydride and the 500ml industrial naptha of 885.0g, uncle's amino dodecane of 277.0g, the formaldehyde of 45.0g, react product (C).Sulphur content 18.92%, phosphorus content 8.46%, 174 ℃ of nitrogen content 1.84%, flash-points.
Embodiment 4, with product A, B, C respectively with 1% dose-modulated in the 85w/90 base oil, as follows:
The comparative result of the single agent assessment of data of table 1 and similar additive
This type phosphorous has good extreme pressure anti-wear as can be seen from the table.
Embodiment 5, respectively product A, composite other functional additives of C are modulated to its performance of evaluation in the GL-5 gear oil respectively, and the result is as follows:
The simulating bench result of table 2 product application in the GL-5 gear oil
The stand result of table 3 product application in the GL-5 gear oil
Result from table finds out that A, C agent have good extreme pressure anti-wear, are fit to be applied in the gear oil.
Claims (8)
1. the preparation method of the phosphorous extreme pressure anti-wear additives of S-P-N type, it is characterized in that: sulphur phosphoric acid, cyclic ether compounds, sulfur phosphorus compound or polysulfide and the industrial naptha of metering are added in the reaction flask, be warming up to 50-130 ℃ of reaction 4-15h, be cooled to below 25 ℃, add the aliphatic amide of metering and add quantitative solvent, be warming up to 20-70 ℃ of formaldehyde that adds metering, react 6-10h down at 70-130 ℃, air distillation removes and desolvates, and room temperature is filtered, and promptly gets product.
2. the preparation method of the phosphorous extreme pressure anti-wear additives of S-P-N type according to claim 1, it is characterized in that: certain proportion scale is arranged between each feed composition: sulphur phosphoric acid is in 100 parts (m), the add-on of cyclic ether compounds is that 90-200 part (m), sulfur phosphorus compound or polysulfide are that 20-80 part (m), aliphatic amide are that 40-60 part (m), formaldehyde are 40-60 part (m), solvent 300-700 part (m).
3. the preparation method of the phosphorous extreme pressure anti-wear additives of S-P-N type according to claim 1 is characterized in that: sulphur phosphoric acid uses dialkyl dithiophosphoric acid, and alkyl is C
1-C
18Similar and different straight or branched, C preferably
2-C
12The straight or branched alkyl.
4. the preparation method of the phosphorous extreme pressure anti-wear additives of S-P-N type according to claim 1 is characterized in that: cyclic ether compounds uses C
2-C
5Triatomic ring or pentacyclic cyclic ether compounds.
5. the preparation method of the phosphorous extreme pressure anti-wear additives of S-P-N type according to claim 1 is characterized in that: sulfur phosphorus compound or polysulfide use thiophosphoric anhydride or Vanadium Pentoxide in FLAKES, and the purity of thiophosphoric anhydride and Vanadium Pentoxide in FLAKES is not less than 95%.
6. the preparation method of the phosphorous extreme pressure anti-wear additives of S-P-N type according to claim 1 is characterized in that: aliphatic amide uses C
4-C
18Primary amine, C preferably
8-C
14The primary amine of straight or branched, alkyl are straight or branched.
7. the preparation method of the phosphorous extreme pressure anti-wear additives of S-P-N type according to claim 1 is characterized in that: formaldehyde uses 36～40% formalin or Paraformaldehyde 96.
8. the preparation method of the phosphorous extreme pressure anti-wear additives of S-P-N type according to claim 1 is characterized in that: solvent uses the organic solvent of boiling range within 70-130 ℃ of scope, preferably uses gasoline, sherwood oil, benzene, toluene, normal heptane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100297230A CN100355871C (en) | 2004-03-24 | 2004-03-24 | Prepn of nitrogen sulfate phosphate type phosphorus-containing agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100297230A CN100355871C (en) | 2004-03-24 | 2004-03-24 | Prepn of nitrogen sulfate phosphate type phosphorus-containing agent |
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| Publication Number | Publication Date |
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| CN1673322A true CN1673322A (en) | 2005-09-28 |
| CN100355871C CN100355871C (en) | 2007-12-19 |
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| CNB2004100297230A Expired - Fee Related CN100355871C (en) | 2004-03-24 | 2004-03-24 | Prepn of nitrogen sulfate phosphate type phosphorus-containing agent |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102839036A (en) * | 2011-06-23 | 2012-12-26 | 中国石油化工股份有限公司 | Water base extreme pressure wear resistance multifunctional additive and preparation method thereof, and water base lubricating liquid composition |
| CN107312031A (en) * | 2017-06-22 | 2017-11-03 | 新乡市瑞丰新材料股份有限公司 | A kind of preparation method of di-isooctyl dithio zinc phosphate salt |
| CN111454291A (en) * | 2020-05-12 | 2020-07-28 | 新乡市瑞丰新材料股份有限公司 | Preparation method of sulfur-phosphorus-nitrogen type extreme pressure antiwear agent |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5573696A (en) * | 1995-03-31 | 1996-11-12 | Ethyl Corporation | Oil-soluble phosphorus- and nitrogen-containing additives |
| CN1037781C (en) * | 1995-06-22 | 1998-03-18 | 中国石油化工总公司 | Anti-wear additive and preparation method thereof |
-
2004
- 2004-03-24 CN CNB2004100297230A patent/CN100355871C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102839036A (en) * | 2011-06-23 | 2012-12-26 | 中国石油化工股份有限公司 | Water base extreme pressure wear resistance multifunctional additive and preparation method thereof, and water base lubricating liquid composition |
| CN102839036B (en) * | 2011-06-23 | 2014-08-20 | 中国石油化工股份有限公司 | Water base extreme pressure wear resistance multifunctional additive and preparation method thereof, and water base lubricating liquid composition |
| CN107312031A (en) * | 2017-06-22 | 2017-11-03 | 新乡市瑞丰新材料股份有限公司 | A kind of preparation method of di-isooctyl dithio zinc phosphate salt |
| CN111454291A (en) * | 2020-05-12 | 2020-07-28 | 新乡市瑞丰新材料股份有限公司 | Preparation method of sulfur-phosphorus-nitrogen type extreme pressure antiwear agent |
| CN111454291B (en) * | 2020-05-12 | 2023-03-14 | 新乡市瑞丰新材料股份有限公司 | Preparation method of sulfur-phosphorus-nitrogen type extreme pressure antiwear agent |
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| CN100355871C (en) | 2007-12-19 |
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