CN102839036B - Water base extreme pressure wear resistance multifunctional additive and preparation method thereof, and water base lubricating liquid composition - Google Patents
Water base extreme pressure wear resistance multifunctional additive and preparation method thereof, and water base lubricating liquid composition Download PDFInfo
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- CN102839036B CN102839036B CN201110170271.8A CN201110170271A CN102839036B CN 102839036 B CN102839036 B CN 102839036B CN 201110170271 A CN201110170271 A CN 201110170271A CN 102839036 B CN102839036 B CN 102839036B
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Abstract
The present invention provides a water base sulfur-phosphorous type extreme pressure wear resistance multifunctional additive and a preparation method thereof, and a water base lubricating liquid composition containing the additive. The additive is prepared by the following steps: (1) carrying out a reaction of fatty acid amide containing at least a hydroxyl group and P2S5 for 1-8 h at a temperature of 80-120 DEG C to generate sulfuric phosphoric acid; and (2) carrying out a reaction of the sulfuric phosphoric acid generated in the step (1) and alcohol amine for 1-6 h at a temperature of 50-90 DEG C to prepare the finished product. The water base sulfur-phosphorous type extreme pressure wear resistance multifunctional additive has characteristics of excellent extreme pressure wear resistance, good corrosion resistance, good rust resistance, and good solubility in a water base lubricating liquid.
Description
Technical field
The present invention relates to a kind of extreme-pressure anti-wear multifunction additive, relate in particular to a kind of water base sulphur phosphorus type extreme-pressure anti-wear multifunction additive.
Background technology
Over nearly 20 years, water-based lubricating liquid is owing to having good economy, cooling and security, and is conducive to energy-conservation and environmental protection, has been widely used in difficult combustion water-base hydraulic fluid and metal processing treatment liquid, thereby constantly developed.Water-based lubricating liquid wear preventive additive is the important factor that water-based lubricating liquid quality improves, and therefore water-based lubricating liquid is one of research emphasis of this area with the research of wear preventive additive.Traditional water-based lubricating liquid wear preventive additive used is all generally oil-soluble, with tensio-active agent, it is distributed in water again, these oil-soluble wear preventive additives are generally divided into oiliness improver and extreme pressure agent, the former mainly works under underload, be generally long carbochain ester and carboxylic acid, they are adsorbed in metallic surface and form what is called " oil film ", be conducive to the slip between metallic contact face and play antifriction function, but " oil film " break and lose efficacy under high loading; The latter is worked under high loading, conventionally contains sulphur, phosphorus, boron isoreactivity element, forms iron sulphide, iron phosphate membrane and working in metallic surface.Another kind of new water base anti-wear agent is synthesizing water-solubility anti-wear agent, it overcome oil soluble anti-wear agent unstable in water, be subject to water quality impact, disperse feature uneven, that be difficult to each position of effectively lubricating metal.The group that plays water-soluble effect in aqueous modified anti-wear additive is generally polyglycol chain, carboxyl, ammonium ion etc., contains long carbochain simultaneously and plays " oiliness improver " effect, then introduce suitable active element and just have oiliness improver and extreme pressure agent dual-use function.The several functions of synthesizing water-solubility anti-wear agent makes the water-based lubricating liquid composition of formation comparatively simple, and available tap water preparation is not only stable, energy-conservation, is also beneficial to the performance of anti-wear agent abrasion resistance.
The article " oilness of malonate derivative " that is published in " Hunan University's journal " in October, 1996 has disclosed the technical scheme that ZDTP is modified as to thiophosphatephosphorothioate monocarboxylic acid derivative, author introduces propanedioic acid group in thiophosphoric acid ester molecular structure, thereby synthesize novel aqueous modified anti-wear additive, there is the water-soluble lubricant additive of extreme pressure agent and oiliness improver double effects through the anti-wear agent of modification simultaneously.In patent CN00134326, synthesized a kind of water-soluble oleic acid diethanolamine molybdenum, this agent has good extreme pressure, wear-resistant, antifriction performance.
Summary of the invention
The object of the present invention is to provide a kind of water base extreme-pressure anti-wear multifunction additive and preparation method thereof, this additive has excellent extreme pressure and antiwear behavior, has good anticorrosive, rustless property simultaneously, has good solubility energy in water-based lubricating liquid.
The present invention also provides a kind of water based lubrication fluid composition.
A kind of water base extreme-pressure anti-wear multifunction additive, its preparation method comprises the following steps:
(1) fatty acid amide and the P of a hydroxyl will at least be contained
2s
5between 80 DEG C～120 DEG C, react 1h～8h and generate sulphur phosphoric acid;
(2) sulphur phosphoric acid step (1) being generated reacts 1h～6h with hydramine at 50 DEG C～90 DEG C and prepares.
The condensation product that N-acylation reaction occurs for lipid acid and hydramine at the fatty acid amide described in step (1); described lipid acid contains the saturated or undersaturated alkyl between C10～C20; the preferably alkyl between C12～C18; the most preferably unsaturated alkyl between C12～C18; described hydramine is selected from the primary amine and/or the secondary amine that at least contain a hydroxyl; preferably contain primary amine and/or the secondary amine of 1-5 hydroxyl; most preferred ethanol amine and/or diethanolamine, described fatty acid amide and described P
2s
5mol ratio between 1: 1 and 8: 1, preferably, between 2: 1 and 4: 1, temperature of reaction is preferably between 90 DEG C～110 DEG C, the reaction times is preferably between 2h～6h.
Be selected from one or more in primary amine, secondary amine and the tertiary amine that contains at least one hydroxyl at hydramine step (2) Suo Shu, preferably contain one or more in primary amine, secondary amine and the tertiary amine of 1-5 hydroxyl, one or more in most preferred ethanol amine, diethanolamine and trolamine, the mol ratio of described sulphur phosphoric acid and described hydramine is between 0.25: 1 and 4: 1, preferably between 0.5: 1 and 2: 1, preferably 60 DEG C～80 DEG C of temperature of reaction, preferred 1h～4h of reaction times.
In the water base extreme-pressure anti-wear multifunction additive of the present invention the massfraction of sulphur content between 5%～10%, the massfraction of phosphorus content between 2%～8%, the massfraction of nitrogen content is between 3%～10%.
A method of preparing above-mentioned water base extreme-pressure anti-wear multifunction additive, comprising:
(1) fatty acid amide and the P of a hydroxyl will at least be contained
2s
5between 80 DEG C～120 DEG C, react 1h～8h and generate sulphur phosphoric acid;
(2) sulphur phosphoric acid step (1) being generated reacts 1h～6h with hydramine at 50 DEG C～90 DEG C, collects product.
The present invention also provides a kind of water based lubrication fluid composition, in said composition, contain above-mentioned water base extreme-pressure anti-wear multifunction additive and water based lubrication basal liquid, described water base extreme-pressure anti-wear multifunction additive accounts for 0.1%～5% of composition total mass, preferably between 0.2%～2%.Described water based lubrication basal liquid is water and/or ethylene glycol.In this lubricating fluid composition, can also contain the slip additive of other kind, as one or more in oxidation inhibitor, dispersion agent and rust-preventive agent.
Water base extreme-pressure anti-wear multifunction additive of the present invention has excellent extreme pressure, wear-resistant and anticorrosive, rustless property, has good solubility energy in water-based lubricating liquid.
Water based lubrication fluid composition of the present invention has excellent extreme pressure and antiwear behavior and anticorrosive, rustless property.
Embodiment
Except special declaration, various content all represents with massfraction in the present invention.
In additive of the present invention, the mensuration of sulphur, phosphorus content adopts ASTM D5185 method, and the mensuration of nitrogen content adopts SH/T 0224 method, and the mensuration of carbon content adopts SH/T 0656 method.
Example 1
Being equipped with in the there-necked flask of electric stirring, return line, thermometer, 0.4mol oleic acid diethanolamine and 0.1mol thiophosphoric anhydride are heated to 90 DEG C, and reaction 6h, adds 0.2mol trolamine after being then down to normal temperature, be heated to 70 DEG C of reaction 1.5h, thereby make product A.The sulphur content of product A is 6.21%, phosphorus content is 5.98%, nitrogen content is 5.13%, carbon content is 68.14%.
Additive of the present invention comprises the reaction product of various structures, has listed the example equation formula of main reaction in example 1 below:
Step (1):
In formula, selected fatty acid amide is oleic acid diethanolamine, i.e. the condensation product of oleic acid and diethanolamine.
Step (2):
Example 2
Being equipped with in the there-necked flask of electric stirring, return line, thermometer, 0.4mo l laurostearic acid diethanolamine and 0.1mol thiophosphoric anhydride are heated to 110 DEG C, and reaction 6h, adds 0.2mol trolamine after being then down to normal temperature, be heated to 80 DEG C of reaction 1.5h, thereby make product B.The sulphur content of product B is 8.30%, phosphorus content is 3.41%, nitrogen content is 6.11%, carbon content is 55.89%.
Example 3
Being equipped with in the there-necked flask of electric stirring, return line, thermometer, 0.4mol lauroleic acid diethanolamine and 0.1mol thiophosphoric anhydride are heated to 100 DEG C, and reaction 4h, adds 0.2mol trolamine after being then down to normal temperature, be heated to 60 DEG C of reaction 1.5h, thereby make products C.The sulphur content of products C is 7.97%, phosphorus content is 4.0%, nitrogen content is 5.66%, carbon content is 54.50%.
Example 4
Respectively product A, product B, products C and common water base anti-wear agent dimeracid, oleic acid, triethanolamine oleate being added to blending in water-ethylene glycol lubrication base liquid is water based lubrication fluid composition, called after embodiment 1～4 and comparative example 1～3 respectively, these additives account for the massfraction of composition total mass in table 1, evaluate respectively solubility property and the abrasion resistance of these additives in water based lubrication basal liquid, result is same in table 1.
Water base anti-wear agent dimeracid and oleic acid all derive from Mudanjiang detergents and cosmetic factory, and triethanolamine oleate derives from Shanghai Gaoqiao petrochemical corporation (complex).
Mass ratio in water-ethylene glycol lubrication base liquid between water and ethylene glycol is 1: 1.
Endurance check adopts tetra-ball machine test GB/T3142 method, and test conditions is 1200r/min, 294N, 30min; Liquid-phase corrosion test adopts GB/T11143 method; Copper strip test adopts GB/T 5096 methods, and test conditions is 50 DEG C, 3h.
Table 1
As can be seen from Table 1, the water base extreme-pressure anti-wear multifunction additive of the present invention has good extreme pressure and antiwear behavior, and has good resistance to corrosion and antirust ability concurrently, has good solubility energy in water-based lubricating liquid.
Claims (15)
1. a water base extreme-pressure anti-wear multifunction additive, its preparation method comprises the following steps:
(1) fatty acid amide and the P of a hydroxyl will at least be contained
2s
5between 80 DEG C～120 DEG C, react 1h～8h and generate sulphur phosphoric acid;
Described fatty acid amide is the condensation product that N-acylation reaction occurs for lipid acid and hydramine, and wherein said lipid acid contains the saturated or undersaturated alkyl between C10～C20, and described hydramine is selected from the primary amine and/or the secondary amine that at least contain a hydroxyl;
Described fatty acid amide and described P
2s
5mol ratio between 1: 1 and 8: 1;
(2) sulphur phosphoric acid step (1) being generated reacts 1h～6h with hydramine at 50 DEG C～90 DEG C, collects product; Described in step (2), hydramine is selected from one or more in primary amine, secondary amine and the tertiary amine that contains at least one hydroxyl;
Described in step (2), the mol ratio of sulphur phosphoric acid and described hydramine is between 0.25: 1 and 4: 1.
2. according to additive claimed in claim 1, it is characterized in that, wherein said lipid acid contains the alkyl between C12～C18, and described hydramine is selected from the primary amine and/or the secondary amine that contain 1-5 hydroxyl.
3. according to additive claimed in claim 1, it is characterized in that, wherein said lipid acid contains the unsaturated alkyl between C12～C18, and described hydramine is selected from thanomin and/or diethanolamine.
4. according to additive claimed in claim 1, it is characterized in that fatty acid amide and described P described in step (1)
2s
5mol ratio between 2: 1 and 4: 1.
5. according to additive claimed in claim 1, it is characterized in that, in step (1), temperature of reaction is between 90 DEG C～110 DEG C.
6. according to additive claimed in claim 1, it is characterized in that, in step (1), the reaction times is between 2h-6h.
7. according to additive claimed in claim 1, it is characterized in that, described in step (2), hydramine is selected from one or more in primary amine, secondary amine and the tertiary amine that contains 1-5 hydroxyl.
8. according to additive claimed in claim 1, it is characterized in that, described in step (2), hydramine is selected from one or more in thanomin, diethanolamine and trolamine.
9. according to additive claimed in claim 1, it is characterized in that the mol ratio of sulphur phosphoric acid described in step (2) and described hydramine is between 0.5: 1 and 2: 1.
10. according to additive claimed in claim 1, it is characterized in that in step (2) that temperature of reaction is between 60 DEG C～80 DEG C.
11. according to additive claimed in claim 1, it is characterized in that preferred 1h～4h of reaction times in step (2).
12. according to additive claimed in claim 1, the massfraction that it is characterized in that sulphur content in described additive between 5%～10%, the massfraction of phosphorus content between 2%～8%, the massfraction of nitrogen content is between 3%～10%.
The preparation method of 13. 1 kinds of water base extreme-pressure anti-wear multifunction additives, comprising:
(1) fatty acid amide and the P of a hydroxyl will at least be contained
2s
5between 80 DEG C～120 DEG C, react 1h～8h and generate sulphur phosphoric acid;
Described fatty acid amide is the condensation product that N-acylation reaction occurs for lipid acid and hydramine, and wherein said lipid acid contains the saturated or undersaturated alkyl between C10～C20, and described hydramine is selected from the primary amine and/or the secondary amine that at least contain a hydroxyl;
Described fatty acid amide and described P
2s
5mol ratio between 1: 1 and 8: 1;
(2) sulphur phosphoric acid step (1) being generated reacts 1h～6h with hydramine at 50 DEG C～90 DEG C, collects product; Described in step (2), hydramine is selected from one or more in primary amine, secondary amine and the tertiary amine that contains at least one hydroxyl;
Described in step (2), the mol ratio of sulphur phosphoric acid and described hydramine is between 0.25: 1 and 4: 1.
14. 1 kinds of water based lubrication fluid compositions, contain water base extreme-pressure anti-wear multifunction additive and the water based lubrication basal liquid of one of claim 1-12 in said composition, described water base extreme-pressure anti-wear multifunction additive accounts for 0.1%～5% of composition total mass.
15. according to the water based lubrication fluid composition described in claim 14, it is characterized in that described water based lubrication basal liquid is water and/or ethylene glycol.
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| CN201110170271.8A CN102839036B (en) | 2011-06-23 | 2011-06-23 | Water base extreme pressure wear resistance multifunctional additive and preparation method thereof, and water base lubricating liquid composition |
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| CN201110170271.8A CN102839036B (en) | 2011-06-23 | 2011-06-23 | Water base extreme pressure wear resistance multifunctional additive and preparation method thereof, and water base lubricating liquid composition |
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| CN102839036B true CN102839036B (en) | 2014-08-20 |
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| CN110343562A (en) * | 2019-07-09 | 2019-10-18 | 广州市君禾实业有限公司 | A kind of water base extraordinary fatty amine highly-efficient lubricant |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1139151A (en) * | 1994-06-22 | 1997-01-01 | 唐山工程技术学院 | Prepn of efficient antirusting water-base cutting fluid |
| CN1673322A (en) * | 2004-03-24 | 2005-09-28 | 中国石油天然气股份有限公司 | Prepn of nitrogen sulfate phosphate type phosphorus-containing agent |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6638898B2 (en) * | 2001-01-08 | 2003-10-28 | Indian Oil Corporation Limited | Process of preparing multi-functional amino di(alkylcyclohexyl) phosphordithioate additive for lubricant composition from saturated cashew nut shell liquid |
-
2011
- 2011-06-23 CN CN201110170271.8A patent/CN102839036B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1139151A (en) * | 1994-06-22 | 1997-01-01 | 唐山工程技术学院 | Prepn of efficient antirusting water-base cutting fluid |
| CN1673322A (en) * | 2004-03-24 | 2005-09-28 | 中国石油天然气股份有限公司 | Prepn of nitrogen sulfate phosphate type phosphorus-containing agent |
Non-Patent Citations (2)
| Title |
|---|
| "水溶性抗磨添加剂的研究";易伦等;《润滑与密封》;19940815;第6-10、34页 * |
| 易伦等."水溶性抗磨添加剂的研究".《润滑与密封》.1994,第6-10、34页. |
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