CN102850396B - A kind of amido boron phosphonate ester and preparation method thereof - Google Patents
A kind of amido boron phosphonate ester and preparation method thereof Download PDFInfo
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- CN102850396B CN102850396B CN201210370454.9A CN201210370454A CN102850396B CN 102850396 B CN102850396 B CN 102850396B CN 201210370454 A CN201210370454 A CN 201210370454A CN 102850396 B CN102850396 B CN 102850396B
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Abstract
<b>The present invention relates to a kind of amido boron phosphonate ester, its component is:</b><b>Organic amine: dibutyl phosphite: formaldehyde: boronating agent=1</b><b>: 2</b><b>～3</b><b>: 2</b><b>～3</b><b>: 1</b><b>; Its preparation method is: a.</b><b>Dibutyl phosphite and formaldehyde are added in reactor, then under agitation organic amine is all added drop-wise in reactor, control reactor temperature≤30</b><b>DEG C, in the time that no longer rising, continues temperature in the kettle to stir 1</b><b>～2h</b><b>; B.</b><b>Boronating agent is added in reactor, open division box, heat to 110</b><b>～130</b><b>DEG C back flow reaction 3</b><b>～5h</b><b>, when in water knockout drum, the liquid level of water no longer increases, reaction finishes, and is cooled to room temperature, obtains target product. The synthetic amido boron phosphonate ester of the present invention is a kind of B-N-P</b><b>The multi-functional Y of type</b><b>Lube oil additive, is added to anti-corrosive properties and the rust-preventing characteristic that in water-based metal working fluid, not only can improve working fluid, can also increase the lubricity of water-based metal working fluid.</b>
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 phosphonate esterAnd preparation method thereof.
Background technology
Lubricated and antirust is the important performance of metal working fluid, and the focus of Ye Shi various countries scientific worker research is askedTopic. In recent years, along with the enhancing of people's environmental consciousness and constantly raising up of oil price, entirely synthesize and narrowBecome the use amount of lubricating oil more and more, aspect metal processing, the range of application of water-base cutting fluid also more and moreExtensively, therefore lubricated more outstanding with antirust problem. , semi-synthetic lubricating oil complete synthetic in order to solve and water base goldBelong to lubricity and the rust-preventing characteristic of working fluid, scientific research person both domestic and external aspect exploitation antirust agent, dropped into a large amount ofEnergy.
Owing to being subject to the impact of healthy and environmental protection problem, nitrite, sulfonate and alkenyl succinic acid class are anti-Rust agent is restricted in use, and from 20 century 70s, the emphasis of various countries' development work is mainConcentrate on the exploitation aspect of multi-functional antirust agent, if the people such as the Horodysky of Mobil company are at US4522734In mention 1,2-epoxy cetyl borate, it is by anti-with boric acid again after 1,2-epoxy hexadecane hydrolysisThe product of answering, this borate has good antifriction quality, but such borate is except B, does not contain other workProperty element, function is relatively single, and its typical structural formula is (1); In order to improve the wear-resistant of boratePerformance, the more effective characteristic such as heat-resisting, wear-resisting, antibacterial of utilizing boron element, Mobil after US4522734The people such as the Horodysky of company have synthesized again a kind of phosphate ester-containing ammonia salt structure in its patent US4557844Borate, this borate is except having anti-wear and wear-resistant performance, also has antioxygen and suppresses corrosion of copper alloyEtc. multiple efficacies, almost can be used in any lubricating oil, its typical structural formula is (2); LubrizolThe people such as the Schwind of company have also introduced a kind of sulphur-phosphorus-boron type borate, this borate in US228818
Because also having active element S and P except having antifriction, wear resistence, also there is fabulous extreme pressure property, can be extensiveBe used as the lubricating additive of oil base or water-based metal working fluid, its typical structural formula is (3); State in 1994The people such as interior Yao Junbing, utilize the chemism of boron element to synthesize a kind of N-S-B type additive, this interpolationThe antifriction antiwear of agent is also fine, and its structural formula is (4); Even to this day be most study containing N borate,
One of organic boride, because N atom can form various joining with the B atom of electron deficient with lone electron pairPosition key, thus the resistant to hydrolysis ability of borate is strengthened, as the people such as the JohnP.Doner of Mobil company existThe amido borate of reporting in US4743386, it is by first synthetic alkalescence of Mannich reaction by phenol, aldehyde, amineThing, and then carry out esterification with boric acid and the product that obtains, its structural formula is (5).
Above-mentioned various containing B additive except formula (5), the B atom in other each molecule is all with the knot of B-O keyStructure is combined on molecule, and less stable in the environment that this structure exists at water, particularly at heating conditionLower B-O key very easily ruptures and is hydrolyzed, and cannot realize the designing requirement of properties of product. Patent US4743386Utilize Mannich reaction in molecule, to form B-N bond structure, this B-N key resistant to hydrolysis energy force rate B-O key is strong,Its product can be used in complete synthetic, semi-synthetic and water-based metal working fluid as anti-friction agent, but this products moleculeIn only contain N and two kinds of active elements of B are functional not strong, cannot meet the lubricated of water-based metal working fluid withAntirust requirement. Therefore, develop a kind of resistant to hydrolysis ability strong, there is again lubricated, antirust, extreme pressure, antibacterial etc.The multi-functional boron-containing compound of effect is very important.
Summary of the invention:
The deficiency that the object of the invention is to overcome above-mentioned various organic boric acid esters of the prior art, provides onePlant amido boron phosphonate ester, in this amido boron phosphonate ester molecule, not only have B-N bond structure, also contain N, P and BIsoreactivity element, has fabulous antifriction, antioxygen, antirust and lubricity, and resistant to hydrolysis ability is strong, adds waterIn Base Metal working fluid, can improve lubricity and the rust-preventing characteristic of working fluid, simultaneously also can improve working fluidExtreme pressure property and service life. It is a kind of well multifunctional water-soluble additive.
Another object of the present invention is to provide the preparation method of this amido boron phosphonate ester.
For achieving the above object, the present invention is achieved in that
A kind of amido boron phosphonate 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 ethylenediamine or diethylenetriamine.
Described boronating agent is boric acid.
A preparation method for amido boron phosphonate ester, carries 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, adds dibutyl phosphite and formaldehyde in reactor, then under agitation organic amine is all drippedBe added in reactor, control reactor temperature≤30 DEG C, continuation stirring 1 in the time that temperature in the kettle no longer rises～2h；
B. the boronating agent of formula ratio is added in the reactor of step a, open division box, heat to110～130 DEG C of back flow reaction 3～5h, when in water knockout drum, the liquid level of water no longer increases, reaction finishes, and is cooled toRoom temperature, obtains target product.
Reaction principle of the present invention:
First under the condition lower than≤30 DEG C, there is Mannich anti-in dibutyl phosphite and formaldehyde and organic amineN and P should be attached in molecule; Then Mannich reaction products is carried out condensation reaction by B with boronating agent againIntroduce in molecular structure, obtain amido boron phosphonate ester, typical chemical equation is as follows:
Compared with prior art, the invention has the beneficial effects as follows: the B-N key in molecular structure is more anti-than B-O keyHydrolysis ability is stronger; Contain N, two kinds of active elements of P than the lubricity of additive formula (5) and extreme pressure property moreGood, table 1 is hydrolytic stability and the lubricity testing result of product of the present invention and several existing borates.
The Performance Ratio of table 1 amido boron phosphonate ester and other borate
Note: hydrolytic stability is measured with uncovered observation: get dry 25ml glass, respectively add 10mlContaining the paraffin oil solution of 1.0% borate, under identical experiment condition, observe liquid and start the time that becomes muddy(become muddy represent be hydrolyzed into the boric acid that is insoluble to paraffin oil), and judge the hydrolysis of borate with this timeSpeed; Lubricity is measured with four ball methods: undertaken by GB3142-82.
The test result of table 1 shows, its hydrolytic stability of amido boron phosphonate ester of the present invention and structural formula (5)Quite, but than unazotized common borate and high a lot of containing the borate of hindered phenol group, and significantly better thanThree iso-octyl borate ammonium salts of outer coordinate bond, meanwhile, four ball methods tests show, the antifriction of product of the present invention,Wear resistence and lubricity have clear improvement and improve than nitrogen-containing borate with than common borate.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the invention will be further described.
Embodiment 1
The formaldehyde (16.7g, 0.2mol) of dibutyl phosphite (38.8g, 0.2mol) and 36% is added insteadAnswer in still, under agitation ethylenediamine (6.1g, 0.1mol) is added drop-wise in reactor gradually, control reaction1.5h is continued to stir in temperature in the kettle≤30 DEG C in the time that temperature in the kettle no longer rises; And then by boric acid (6.1g,0.1mol) add in above-mentioned reactor, open division box, heat to 110 DEG C of back flow reaction 4h,When in water knockout drum, the liquid level of water no longer increases, reaction finishes, and is cooled to room temperature, obtains target product, chemistryReaction equation is as follows:
Embodiment 2
The formaldehyde (25.0g, 0.3mol) of dibutyl phosphite (58.2g, 0.3mol) and 36% is added insteadAnswer in still, under agitation diethylenetriamine (10.3g, 0.1mol) is added drop-wise in reactor gradually, control2h is continued to stir in reactor temperature≤30 DEG C processed in the time that temperature in the kettle no longer rises; And then by boric acid(6.1g, 0.1mol) adds in above-mentioned reactor, opens division box, heats to 130 DEG C of backflowsReaction 5h, when in water knockout drum, the liquid level of water no longer increases, reaction finishes, and is cooled to room temperature, obtains target and producesThing, typical chemical equation is as follows:
Organic synthesis is a complicated chemical reaction process, and with regard to embodiment 2, its boronation reaction can obtainTo the amido boron phosphonic acid ester material of monobasic and two kinds of structures of binary, each amount number mainly joined by raw materialThan (being mol ratio) and reaction process conditions determine, mask work is very difficult. The present invention synthesizesAmido boron phosphonate ester is also the mixture of a kind of monobasic and binary boride, but taking monobasic boride as main, producesThe technical indicator of product is as follows:
Outward appearance: salmon liquid; PH:5～6;
Working substance content: >=70%; Total phosphorus content (in P): 10%～12%.
Above-mentioned amido boron phosphonate ester product confirms there be stretching of B-N key at 1401cm-1 place through infrared spectrum analysisContracting vibration absorption peak, has the characteristic absorption peak of B-O key at 1374cm-1 place, and 660cm-1 placeBoron skeleton vibration performance absworption peak. Illustrate that by B element after Mannich and boronation reaction be the knot with B-N keyStructure is combined in molecule, and resistant to hydrolysis ability strengthens.
The Performance Detection of amido boron phosphonate ester
1, measure the anticorrosive property of amido boron phosphonate ester by weight-loss method
Taking 45# steel disc as test material, measure the Corrosion Protection of amido boron phosphonate ester under variable concentrations, detectThe results are shown in Table 2.
The anticorrosive property result of the test of table 2 amido boron phosphonate ester
Note: experiment condition is: 3cm × 5cm45# steel disc, static immersing 10 days.
From the test data in table 2, amido boron phosphonate ester has good corrosion mitigating effect to 45# steel disc,In the time that concentration reaches 4%, corrosion inhibition rate is 98.5%, continues to increase the concentration of amido boron phosphonate ester, and corrosion inhibition rate changesVery little, illustrate and in the time that concentration is 4%, formed the uniform adsorbed film of one deck on test piece surface.
2, the rust-preventing characteristic of cast iron monolithic experimental test amido boron phosphonate ester
Test is undertaken by GB/T6144-85, measures the rust-preventing characteristic of amido boron phosphonate ester under variable concentrations, detectsThe results are shown in Table 3.
The rust-preventing characteristic result of the test of table 3 amido boron phosphonate ester
Amido boron phosphonate ester has good rust-preventing characteristic to cast iron as can be seen from Table 3, in the time that content reaches 5%Monolithic can reach 5 days stainless, can meet the antirust requirement of water-base metal processing technology completely.
3, test the lubricity of amido boron phosphonate ester with four-ball tester
Test is undertaken by GB3142-82 " load carrying capacity of lubricant determination method (four ball methods) ", and test(ing) liquid is5% water-based metal working fluid, measures the lubricity of amido boron phosphonate ester under different dosages, and testing result is in table 4.
The lubricity test result of table 4 amido boron phosphonate ester
As can be seen from Table 4, add after amido boron phosphonate ester, under same concentrations water-based metal working fluidLarge nothing card is stung load PBValue increases, P in the time that content reaches 6%BMore than value reaches 500N, can meet largeThe processing technology requirement of most metal materials. The synthetic amido boron phosphonate ester of the present invention is that a kind of B-N-P type is manyFunction lube oil additive, is added to and in water-based metal working fluid, not only can be improved the anticorrosion of working fluidProperty and rust-preventing characteristic, can also increase the lubricity of water-based metal working fluid, be that a kind of well boracic class is lubricatedOil additive.
Claims (1)
1. an amido boron phosphonate product, is characterized in that:
This amido boron phosphonate product is by the formaldehyde 16.7g of dibutyl phosphite 38.8g and 36% is added in reactor, under agitation ethylenediamine 6.1g is added drop-wise in reactor gradually, control reactor temperature≤30 DEG C, in the time that no longer rising, continues temperature in the kettle to stir 1.5h, and then boric acid 6.1g is added in above-mentioned reactor, open division box, heat to 110 DEG C of back flow reaction 4h, when in water knockout drum, the liquid level of water no longer increases, reaction finishes, and is cooled to room temperature and obtains target product and be prepared from;
Or
This amido boron phosphonate product is by the formaldehyde 25.0g of dibutyl phosphite 58.2g and 36% is added in reactor, under agitation diethylenetriamine 10.3g is added drop-wise in reactor gradually, control reactor temperature≤30 DEG C, in the time that no longer rising, continues temperature in the kettle to stir 2h, and then boric acid 6.1g is added in above-mentioned reactor, open division box, heat to 130 DEG C of back flow reaction 5h, when in water knockout drum, the liquid level of water no longer increases, reaction finishes, and is cooled to room temperature and obtains target product and be prepared from.
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| 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 |
| 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 |
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 |
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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 |
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