CN102850396A - Amido boron phosphate and preparation method of amido boron phosphate - Google Patents
Amido boron phosphate and preparation method of amido boron phosphate Download PDFInfo
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- CN102850396A CN102850396A CN2012103704549A CN201210370454A CN102850396A CN 102850396 A CN102850396 A CN 102850396A CN 2012103704549 A CN2012103704549 A CN 2012103704549A CN 201210370454 A CN201210370454 A CN 201210370454A CN 102850396 A CN102850396 A CN 102850396A
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- acid ester
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Abstract
The invention relates to amido boron phosphate, which comprises the following ingredients: organic amine, dibutyl phosphite, formaldehyde and bononizing agents according to a ratio being 1:(2-3):(2-3):1. A preparation method of the amido boron phosphate comprises the following steps that a, the dibutyl phosphite and the formaldehyde are added into a reaction kettle, then, the organic amine is completely dripped into the reaction kettle under a stirring condition, the temperature in the reaction kettle is controlled to be smaller than or equal to 30 DEG C, and the stirring is continuously carried out for 1 to 2 hours when the temperature in the kettle is not raised; b, the bononizing agents are added into the reaction kettle, a water distribution device is started, temperature is raised to 110 to 130 DEG C through heating, the backflow reaction is carried out for 3 to 5 hours, the reaction is completed when the liquid surface of water in the water distribution device is not increased, cooling is carried out to the room temperature, and a target product is obtained. The synthetized amido boron phosphate belongs to a B-N-P type multifunctional Y lubricating oil additive, when the amido boron phosphate is added into water-base metal processing liquid, the anti-corrosion performance and the anti-rust performance of the processing liquid can be improved, and the lubricating performance of the water-base metal processing liquid can also be improved.
Description
Technical field
The present invention relates to a kind of water soluble anti-rust agent and preparation method thereof, relate in particular to a kind of amido boron phosphoric acid ester and preparation method thereof.
Background technology
Lubricated and antirust is the key property of metal working fluid, also is the hot issue of various countries scientific worker research.In recent years, along with the enhancing of people's environmental consciousness and constantly raising up of oil price, usage quantity complete synthesis and semi-synthetic lubricating oil is more and more, and the range of application of water-base cutting fluid is also more and more wider aspect metal processing, and is therefore lubricated more outstanding with antirust problem.Oilness and the rust-preventing characteristic of complete synthesis in order to solve, semi-synthetic lubricating oil and water-based metal working fluid, scientific research person both domestic and external drops into a large amount of energy aspect the exploitation rust-preventive agent.
Owing to being subjected to the impact of healthy and environmental protection problem, nitrite, sulfonate and alkenyl succinic acid class rust-preventive agent are restricted in use, from 20 century 70s, the emphasis of various countries' development work mainly concentrates on the exploitation aspect of multi-functional rust-preventive agent, as the people such as Horodysky of Mobil company in US4522734, mention 1,2-epoxy hexadecyl boric acid ester, it is by 1, after the 2-epoxy n-Hexadecane hydrolysis again with the product of acid reaction, this boric acid ester has good antifriction quality, but such boric acid ester does not contain other active element except B, function is relatively single, and its typical structural formula is (1); In order to improve the abrasion resistance of boric acid ester, the more effective characteristic such as heat-resisting, wear-resisting, antibacterial of utilizing boron, the people such as Horodysky of Mobil company have synthesized again a kind of boric acid ester of phosphate ester-containing ammonia salt structure in its patent US4557844 after US4522734, this boric acid ester is except having anti-wear and wear-resistant performance, also have the multiple efficacies such as antioxygen and inhibition corrosion of copper alloy, almost can be used in any lubricating oil, its typical structural formula is (2); The people such as Schwind of Lubrizol company have also introduced a kind of sulphur-phosphorus-boron type boric acid ester, this boric acid ester in US228818
Because also having active element S and P except having antifriction, resistance to abrasion, also have fabulous extreme pressure property, can extensively be used as the slip additive of oil base or water-based metal working fluid, its typical structural formula is (3); The domestic people such as Yao Junbing in 1994 utilize the chemically reactive of boron to synthesize a kind of N-S-B type additive, and the antifriction antiwear of this additive is also fine, and its structural formula is (4); Even to this day, containing the N boric acid ester is most study
One of organic boride, because the N atom can form various coordinate bonds with the B atom of electron deficiency with lone electron pair, thereby the resistant to hydrolysis ability of boric acid ester is strengthened, the amido boric acid ester of in US4743386, reporting such as the people such as John P.Doner of Mobil company, it is to synthesize first alkaline substance by phenol, aldehyde, amine by Mannich reaction, and then carrying out esterification with boric acid and the product that obtains, its structural formula is (5).
The above-mentioned various B additive that contains is except formula (5), B atom in other each molecule all is combined on the molecule with the structure of B-O key, this structure is less stable in the environment that water exists, particularly the B-O key very easily ruptures and is hydrolyzed under heating condition, can't realize the design requirements of product performance.Patent US4743386 utilizes Mannich reaction to form the B-N bond structure in molecule, this B-N key resistant to hydrolysis energy force rate B-O key is strong, its product can be used in complete synthesis, semi-synthetic and the water-based metal working fluid as low friction compound, but it is functional not strong only to contain two kinds of active elements of N and B in this products molecule, can't satisfy the lubricated and antirust requirement of water-based metal working fluid.Therefore, develop a kind of resistant to hydrolysis ability strong, the multi-functional boron-containing compound that has again lubricated, antirust, extreme pressure, the effect such as antibacterial is very important.
Summary of the invention:
The object of the invention is to overcome the deficiency of above-mentioned various organic boric acid esters of the prior art, a kind of amido boron phosphoric acid ester is provided, in this amido boron phosphoric acid ester molecule the B-N bond structure is arranged not only, also contain N, P and B isoreactivity element, have fabulous antifriction, antioxygen, antirust and oilness, the resistant to hydrolysis ability is strong, adds oilness and the rust-preventing characteristic that can improve working fluid in the water-based metal working fluid, extreme pressure property and the work-ing life that also can improve working fluid simultaneously.It is a kind of good multifunctional water-soluble additive.
Another object of the present invention is to provide the preparation method of this amido boron phosphoric acid ester.
For achieving the above object, the present invention is achieved in that
A kind of amido boron phosphoric acid ester, wherein each component is calculated in molar ratio as:
Organic amine: dibutyl phosphite: formaldehyde: boronating agent=1: 2～3: 2～3: 1.
Described organic amine is quadrol or diethylenetriamine.
Described boronating agent is boric acid.
A kind of preparation method of amido boron phosphoric acid ester, carry out in two steps:
A. according to the mol ratio of raw material: organic amine: dibutyl phosphite: formaldehyde: boronating agent=1: 2～3: 2～3: 1, dibutyl phosphite and formaldehyde are added in the reactor, then under agitation all be added drop-wise to organic amine in the reactor, 1～2h is treated to continue when temperature in the kettle no longer rises to stir in control reactor temperature≤30 ℃;
B. the boronating agent of formula ratio is added in the reactor of step a, open division box, heat to 110～130 ℃ of back flow reaction 3～5h, reaction finished when the liquid level for the treatment of water in the water trap no longer increased, and was cooled to room temperature, obtained target product.
Reaction principle of the present invention:
At first dibutyl phosphite and formaldehyde and organic amine be lower than≤30 ℃ condition under, Mannich reaction occurs, and N and P are attached in the molecule; Then Mannich reaction products is carried out condensation reaction with boronating agent again B is introduced in the molecular structure, obtains amido boron phosphoric acid ester, and typical chemical equation is as follows:
Compared with prior art, the invention has the beneficial effects as follows: the B-N key in the molecular structure is stronger than B-O key resistant to hydrolysis ability; Contain N, two kinds of active elements of P are better than oilness and the extreme pressure property of additive formula (5), table 1 is stability to hydrolysis and the oilness detected result of product of the present invention and several existing boric acid esters.
The Performance Ratio of table 1 amido boron phosphoric acid ester and other boric acid ester
Annotate: stability to hydrolysis is measured with uncovered observation: namely get dry 25ml glass cylinder, each adds the paraffin oil solution that 10ml contains 1.0% boric acid ester, under identical experiment condition, observe liquid and begin to become the time (become muddy expression and be hydrolyzed into the boric acid that is insoluble to paraffin oil) of muddiness, and judge the hydrolysis rate of boric acid ester with this time; Oilness is measured with four ball methods: undertaken by GB3142-82.
The test result of table 1 shows, its stability to hydrolysis of amido boron phosphoric acid ester of the present invention and structural formula (5) are suitable, but high more a lot of than unazotized common boric acid ester and the boric acid ester that contains the hindered phenol group, and three iso-octyl boric acid ester ammonium salts significantly better than outer coordinate bond, simultaneously, four ball methods tests shows, the antifriction of product of the present invention, resistance to abrasion and oilness have clear improvement and improve than nitrogen-containing borate with than common boric acid ester.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
With dibutyl phosphite (38.8g, 0.2mol) and 36% formaldehyde (16.7g, 0.2mol) add in the reactor, under agitation with quadrol (6.1g, 0.1mol) be added drop-wise to gradually in the reactor, 1.5h is treated to continue when temperature in the kettle no longer rises to stir in control reactor temperature≤30 ℃; And then in the reactor that boric acid (6.1g, 0.1mol) adding is above-mentioned, open division box, heat to 110 ℃ of back flow reaction 4h, reaction finished when the liquid level for the treatment of water in the water trap no longer increased, and was cooled to room temperature, obtain target product, chemical equation is as follows:
Embodiment 2
With dibutyl phosphite (58.2g, 0.3mol) and 36% formaldehyde (25.0g, 0.3mol) add in the reactor, under agitation with diethylenetriamine (10.3g, 0.1mol) be added drop-wise to gradually in the reactor, 2h is treated to continue when temperature in the kettle no longer rises to stir in control reactor temperature≤30 ℃; And then in the reactor that boric acid (6.1g, 0.1mol) adding is above-mentioned, open division box, heat to 130 ℃ of back flow reaction 5h, reaction finished when the liquid level for the treatment of water in the water trap no longer increased, and was cooled to room temperature, obtain target product, typical chemical equation is as follows:
Organic synthesis is the chemical reaction process of a complexity, its boronation reaction can obtain the amido boron phosphoric acid ester material of monobasic and two kinds of structures of binary with regard to embodiment 2, what of each amount are mainly determined by proportioning raw materials (being mol ratio) and the processing condition of reacting, and mask work is very difficult.The amido boron phosphoric acid ester that the present invention synthesizes also is the mixture of a kind of monobasic and binary boride, but take the monobasic boride as main, the technical indicator of product is as follows:
Outward appearance: salmon liquid; PH:5～6;
Working substance content: 〉=70%; Total phosphorous (in P): 10%～12%.
Above-mentioned amido boron phosphoric acid ester product confirms to have at the 1401cm-1 place stretching vibration absorption peak of B-N key through Infrared spectroscopy, the charateristic avsorption band of B-O key is arranged at the 1374cm-1 place, and the boron skeleton vibration performance absorption peak at 660cm-1 place.Explanation by the reaction of Mannich and boronation after the B element be that structure with the B-N key is combined in the molecule, the resistant to hydrolysis ability strengthens.
The Performance Detection of amido boron phosphoric acid ester
1, measures the non-corrosibility of amido boron phosphoric acid ester with weight-loss method
Take the 45# steel disc as test materials, measure the Corrosion Protection of amido boron phosphoric acid ester under the different concns, detected result sees Table 2.
The non-corrosibility test-results of table 2 amido boron phosphoric acid ester
Annotate: experiment condition is: 3cm * 5cm 45# steel disc, static immersing 10 days.
By the testing data in the table 2 as can be known, amido boron phosphoric acid ester has preferably corrosion mitigating effect to the 45# steel disc, corrosion inhibition rate is 98.5% when concentration reaches 4%, continue to increase the concentration of amido boron phosphoric acid ester, corrosion inhibition rate changes very little, illustrates to have formed the uniform adsorption film of one deck on the test piece surface when concentration is 4%.
2, the rust-preventing characteristic of cast iron monolithic experimental test amido boron phosphoric acid ester
Test is undertaken by GB/T6144-85, measures the rust-preventing characteristic of amido boron phosphoric acid ester under the different concns, and detected result sees Table 3.
The rust-preventing characteristic test-results of table 3 amido boron phosphoric acid ester
Amido boron phosphoric acid ester has preferably rust-preventing characteristic to cast iron as can be seen from Table 3, when content reaches 5% monolithic can reach 5 days stainless, can satisfy the antirust requirement of water-base metal complete processing fully.
3, test the oilness of amido boron phosphoric acid ester with four-ball tester
Test is undertaken by GB3142-82 " load carrying capacity of lubricant assay method (four ball methods) ", and test(ing) liquid is 5% water-based metal working fluid, measures the oilness of amido boron phosphoric acid ester under the different dosages, and detected result sees Table 4.
The lubricity test result of table 4 amido boron phosphoric acid ester
As can be seen from Table 4, add amido boron phosphoric acid ester after, under the same concentrations water-based metal working fluid last non seizure load P
BValue increases, P when content reaches 6%
BValue reaches more than the 500N, can satisfy the complete processing requirement of most metals material.The amido boron phosphoric acid ester that the present invention synthesizes is a kind of B-N-P type multifunctional additive for lubricating oil, add it to not only can improve working fluid in the water-based metal working fluid preservative property and rust-preventing characteristic, can also increase the oilness of water-based metal working fluid, be a kind of good boracic type lubricating oil additive.
Claims (4)
1. amido boron phosphoric acid ester is characterized in that the component of this amido boron phosphoric acid ester has: organic amine, dibutyl phosphite, formaldehyde and boronating agent, and wherein each component is calculated in molar ratio as:
Organic amine: dibutyl phosphite: formaldehyde: boronating agent=1: 2～3: 2～3: 1.
2. a kind of amido boron phosphoric acid ester according to claim 1 is characterized in that described organic amine is quadrol or diethylenetriamine.
3. a kind of amido boron phosphoric acid ester according to claim 1 is characterized in that described boronating agent is boric acid.
4. the preparation method of a kind of amido boron phosphoric acid ester claimed in claim 1 is characterized in that the method carries out in two steps:
A. according to the mol ratio of each component: organic amine: dibutyl phosphite: formaldehyde: boronating agent=1: 2～3: 2～3: 1, dibutyl phosphite and formaldehyde are added in the reactor, then under agitation all be added drop-wise to organic amine in the reactor, 1～2h is treated to continue when temperature in the kettle no longer rises to stir in control reactor temperature≤30 ℃;
B. the boronating agent of formula ratio is added in the reactor of step a, open division box, heat to 110～130 ℃ of back flow reaction 3～5h, reaction finished when the liquid level for the treatment of water in the water trap no longer increased, and was cooled to room temperature, obtained target product.
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| CN201210370454.9A CN102850396B (en) | 2012-09-27 | 2012-09-27 | A kind of amido boron phosphonate ester and preparation method thereof |
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| CN201210370454.9A CN102850396B (en) | 2012-09-27 | 2012-09-27 | A kind of amido boron phosphonate ester and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104818101A (en) * | 2015-03-19 | 2015-08-05 | 柳州市永益机械制造有限公司 | Preparation method for wire electrical discharge machining working fluid |
| CN104818102A (en) * | 2015-03-19 | 2015-08-05 | 柳州市永益机械制造有限公司 | Wire electrical discharge machining working fluid |
| CN115820329A (en) * | 2022-12-30 | 2023-03-21 | 太原理工大学 | Lubricating oil with layered boron phosphate amine compound as additive and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4743386A (en) * | 1983-01-10 | 1988-05-10 | Mobil Oil Corporation | Grease compositions containing phenolic- or thio-amine borates and hydroxy-containing soap thickeners |
| CN1161970A (en) * | 1996-04-05 | 1997-10-15 | 中国石化兰州炼油化工总厂 | Preparation method for lubricating oil additive |
| CN102061214A (en) * | 2009-11-13 | 2011-05-18 | 中国科学院兰州化学物理研究所 | Water-soluble lubricating additive and preparation method thereof |
-
2012
- 2012-09-27 CN CN201210370454.9A patent/CN102850396B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4743386A (en) * | 1983-01-10 | 1988-05-10 | Mobil Oil Corporation | Grease compositions containing phenolic- or thio-amine borates and hydroxy-containing soap thickeners |
| CN1161970A (en) * | 1996-04-05 | 1997-10-15 | 中国石化兰州炼油化工总厂 | Preparation method for lubricating oil additive |
| CN102061214A (en) * | 2009-11-13 | 2011-05-18 | 中国科学院兰州化学物理研究所 | Water-soluble lubricating additive and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104818101A (en) * | 2015-03-19 | 2015-08-05 | 柳州市永益机械制造有限公司 | Preparation method for wire electrical discharge machining working fluid |
| CN104818102A (en) * | 2015-03-19 | 2015-08-05 | 柳州市永益机械制造有限公司 | Wire electrical discharge machining working fluid |
| CN115820329A (en) * | 2022-12-30 | 2023-03-21 | 太原理工大学 | Lubricating oil with layered boron phosphate amine compound as additive and preparation method thereof |
| CN115820329B (en) * | 2022-12-30 | 2023-10-31 | 太原理工大学 | Lubricating oil with lamellar borophosphate amine compound as additive and preparation method thereof |
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