CN102061214A - Water-soluble lubricating additive and preparation method thereof - Google Patents
Water-soluble lubricating additive and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a water-soluble lubricating additive and a preparation method thereof. The additive is a water-soluble thiophosphite compound; and by a molecular design method, a water-soluble group (CH2CH2O), active elements S and P and an adsorbent group -OH are introduced into the compound structure for synthesis, and the additive has good tribological properties.
Description
Technical field
The present invention relates to a kind of water-soluble lubricant additive and its production and use.
Background technology
Water base lubricant fires, cleans plurality of advantages such as low pollution, wide material sources with its excellent cooling performance and difficulty; obtained paying close attention to widely in this century; based on the purpose of saving petroleum resources and protection environment; each developed country of the world is all greatly developing water base lubricant; especially at hydraulic liquid and metal manufacture field, obtained no small progress.Water-based metal working fluid has occupied nearly 50% metal working fluid market at present, and has obtained using widely in the hydraulic power actuating system that advantage that the contour water-base hydraulic fluid of water-ethylene glycol also fires with its difficulty is worked under the high-risk environment of some fire.But because water is different from many characteristics of oil, water is difficult to play the same lubricant effect of oil, and water self easy-to-rust metal, thereby the problem of existing water base lubricant ubiquity oilness and rust-preventing characteristic difference, this has limited the development and the practical application of water base lubricant to a great extent.Therefore, research and develop high performance water-soluble lubricant additive and have important use value.
Have the report of much synthetic and tribological Properties in recent years about water-soluble lubricant additive; as (Y.J.Gao such as Gao; Y.S.Jing; Z.J.Zhang; G.X.Chen; Q.J.Xue.Tribological properties of aqueous solution of imidazoline borates.Wear; 2002; 253; 576) reported a kind of water-soluble imidazoline boric acid ester; US Patent 6228818 has synthesized a kind of boric acid ester water based lubrication additive; (W.J.Huang such as Huang; J.X.Dong; F.F.Li; B.S.Chen.Study of the tribological behavior of S-(carboxylpropyl)-N-alkyl dithiocarbamic acid as additives in water-based fluid.Wear; 2002; 252; 306) three kinds of water-soluble dithiocarbamate derivatives have been prepared as water base additive; US Patent 6852678 is that part has prepared a series of soft metals complex compound as water base additive with the dithiocarbamic acid derivative; US Patent 4729839 has reported a kind of water-soluble lubricant additive of sulfur-bearing; US Patent 6617288 has reported a kind of water-soluble phosphorothioate compound, Jiang Haizhen (Jiang Haizhen. the research of the antirust wear-resistant multifunction additive of new type water-solubility. Shanghai University's Ph D dissertation 2006) etc. robot system studied tribological property and the rustless property of N-acylamino acid as water-soluble additive.Though these compounds as additive can both be in various degree the tribological property of raising water-based lubricating liquid, but it is often water-soluble limited, need be with surface active agent solubilization, and it is also not obvious to the raising of water-based lubricating liquid antiwear and antifriction overall performance, to metal existence corrosion in various degree, be difficult to be applied in practice.
Summary of the invention
The object of the present invention is to provide a kind of water-soluble lubricant additive and preparation method thereof.
The present invention realizes by following measure:
For solving the above problems, we have prepared the water-soluble lubricant additive that a kind of lubricity excellence, preparation method are easy, can improve the whole antiwear and friction reduction property of water base lubricant, by molecule design method, in compound structure, introduce water soluble group (CH2CH2O)
n, active element S, P and adsorptivity group-OH, synthesized a kind of water-soluble cpds that contains sulphur, phosphorus, it is as the good tribological property of having of water-soluble lubricant additive.
A kind of water-soluble lubricant additive is characterized in that additive is water-soluble thiophosphorous acid ester cpds, with general formula (VI) expression, R in the formula (VI)
1, R
2Be straight chained alkyl or the alkyl-substituted phenyl of identical or different C8～C18, R
3Be the straight or branched alkyl of H, phenyl or C1～C8, n is 10～20 integer,
The preparation method of general formula (VI) compound: fatty alcohol-polyoxyethylene ether or alkylphenol polyoxyethylene or the mixture of the two and di-n-butyl phosphite are carried out transesterification reaction under the condition that catalyzer exists, add the sulfuration of sulphur powder then and make thiophosphite, further carry out the Mannich condensation, promptly get the water-soluble cpds of sulfur-bearing, phosphorus with diethanolamine and aldehyde.
A kind of water-soluble lubricant additive specifically comprises three reactions steps of A, B and C:
A uses fatty alcohol-polyoxyethylene ether or the alkylphenol polyoxyethylene of formula (II) or the di-n-butyl phosphite of mixture of the two and formula (III) of formula (I), in the presence of catalyzer, in 120～160 ℃ of decompression reactions 4～10 hours, the ester exchange offspring of production (IV), adopt reliever to remove the by product propyl carbinol in the whole process, R ' is the straight or branched alkyl of C8～C18 in the formula (I), R in the formula (II) " be C2～C12 straight or branched alkyl;
120～160 ℃ of reactions 4～10 hours under nitrogen atmosphere of the phosphorous acid ester that B uses formula (IV) and sulphur powder, the thiophosphite of generation formula V:
The thiophosphite of C use formula V and diethanolamine and aldehyde generate the water-soluble thiophosphite compound product of general formula (VI) 80～120 ℃ of reactions 4～8 hours, and wherein R3 is H, the straight chained alkyl of phenyl or C1～C8 or branched-chain alkyl;
Among the method steps A of preparation general formula (VI), the mol ratio of fatty alcohol-polyoxyethylene ether or alkylphenol polyoxyethylene or mixture of the two and di-n-butyl phosphite is 2.0～2.3: 1.
Among the method steps A of preparation general formula (VI), the catalyzer that uses is sodium methylate, sodium ethylate or potassium tert.-butoxide, and the usage quantity of catalyzer is 0.5%～1% of a reactant total mass.
Among the method steps C of preparation general formula (VI), the aldehyde that uses is formaldehyde, phenyl aldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, hexanal, enanthaldehyde or octanal.
The water-soluble thiophosphorous acid ester cpds of general formula (VI) can be used as water-soluble lubricant additive and uses, especially in water-based metal working fluid, high water base fluid hydraulic fluid or drilling fluid, use, have excellent lubricating property, and ferrous metal is had good antirust function.
Formula of the present invention (VI) compound adds in water, water and ethylene glycol mixture, water and the polyoxyethylene glycol mixed solution and constitutes lubricating system, can obtain excellent antifriction performance, good supporting capacity, and ferrous metal had good rust-proof effect.
When formula of the present invention (VI) compound used in water-based metal working fluid, high water base fluid hydraulic fluid or drilling fluid as water-soluble lubricant additive, its addition was 1%～10% of a water base fluid quality.
Formula of the present invention (VI) compound is the water-soluble lubricant additive of excellent performance, simultaneously ferrous metal is had good antirust function.Compare with existing water-soluble lubricant additive, synthetic water-soluble additive of the present invention has good solubility in water, dissolving back system clear, and has excellent stability, long-term storage inclusion-free or precipitation are separated out, extremely low addition can obtain excellent antiwear and antifriction effect, is specially adapted to fields such as water-based metal working fluid, high water base fluid hydraulic fluid or drilling fluid.
Description of drawings
Fig. 1～Fig. 6 is respectively 1%, 2% for concentration, the aqueous solution of 3%, 4%, 5%, 6% embodiment 1 product on the little vibration friction abrasion testing machine of SRV-IV in 25 ℃, frequency 50Hz, the relation curve of The friction coefficient load change under the operating mode of amplitude 1mm.
Fig. 7～Figure 12 is respectively 1%, 2% for concentration, the aqueous solution of 3%, 4%, 5%, 6% embodiment 1 product at the little vibration friction abrasion testing machine of SRV-IV in 25 ℃, frequency 50Hz, amplitude 1mm, the frictional coefficient under the operating mode of load 300N during long mill 20min.
Embodiment
Embodiment 1
In three mouthfuls of round-bottomed flasks of the 500mL that mechanical stirring, thermometer and vacuum distillation apparatus are housed, add the 0.2mol di-n-butyl phosphite, 0.42mol octyl phenyl Soxylat A 25-7 (n=10, M=646.85g/mol), the 2g potassium tert.-butoxide, begin the decompression reaction after being warming up to 140 ℃ under the agitation condition, after this entire reaction course system is in the decompression state of 0.08MPa, steams stopped reaction to no coupling product.Wait to be cooled to 60 ℃ and add 0.2mol sulphur powder, feed N
2, be warming up to 150 ℃ and react to the system clarification, stopped reaction, obtaining faint yellow transparent thick liquid is the intermediate thiophosphite.
In three mouthfuls of round-bottomed flasks of the 500mL that mechanical stirring, thermometer and prolong are housed, add 0.2mol diethanolamine and 0.22mol formaldehyde (37% solution), stirred 1.5 hours at 60 ℃, slowly add the thiophosphite intermediate that 0.2mol has prepared then, be warming up to 110 ℃ of reactions 5 hours, low-boiling point material is removed in underpressure distillation, obtain the reddish-brown thick liquid and be phosphorous acid ester Mannich condensation product shown in the general formula (VI), its concrete structure is:
Embodiment 2
In three mouthfuls of round-bottomed flasks of the 500mL that mechanical stirring, thermometer and vacuum distillation apparatus are housed, add the 0.2mol di-n-butyl phosphite, 0.42mol dodecyl Soxylat A 25-7 (n=10, M=626.98g/mol), the 2g potassium tert.-butoxide, begin the decompression reaction after being warming up to 140 ℃ under the agitation condition, after this entire reaction course system is in the decompression state of 0.08MPa, steams stopped reaction to no coupling product.Wait to be cooled to 60 ℃ and add 0.2mol sulphur powder, feed N
2, be warming up to 150 ℃ and react to the system clarification, stopped reaction, obtaining light yellow viscous liquid is the intermediate thiophosphite.
In three mouthfuls of round-bottomed flasks of the 500mL that mechanical stirring, thermometer and prolong are housed, add 0.2mol diethanolamine and 0.2mol phenyl aldehyde, stirred 1.5 hours at 60 ℃, slowly add the thiophosphite intermediate that 0.2mol has prepared then, be warming up to 110 ℃ of reactions 6 hours, low-boiling point material is removed in underpressure distillation, obtain the reddish-brown thick liquid and be phosphorous acid ester Mannich condensation product shown in the general formula (VI), its concrete structure is:
Embodiment 3
In three mouthfuls of round-bottomed flasks of the 500mL that mechanical stirring, thermometer and division box are housed, add the 0.2mol di-n-butyl phosphite, 0.21mol dodecyl Soxylat A 25-7 (n=10, M=626.98g/mol), 0.21mol nonyl phenyl Soxylat A 25-7 (n=10, M=660.85g/mol), begin the decompression reaction after being warming up to 160 ℃ under the 3g potassium tert.-butoxide, agitation condition, after this entire reaction course system is in the decompression state of 0.08MPa, stopped reaction when no coupling product is told.Wait to be cooled to 60 ℃ and add 0.2mol sulphur powder, feed N
2, be warming up to 150 ℃ and react to the system clarification, stopped reaction, obtaining light yellow viscous liquid is the intermediate thiophosphite.
In three mouthfuls of round-bottomed flasks of the 500mL that mechanical stirring, thermometer and prolong are housed, add 0.2mol diethanolamine and 0.2mol butyraldehyde-n, stirred 1.5 hours at 60 ℃, slowly add the thiophosphite intermediate that 0.2mol has prepared then, be warming up to 110 ℃ of reactions 6 hours, low-boiling point material is removed in underpressure distillation, obtain red thick liquid and be phosphorous acid ester Mannich condensation product shown in the general formula (VI), its concrete structure is:
The tribological property evaluation of product:
The bi-ester of phosphite of embodiment 1 preparation is dissolved in the distilled water, and being mixed with concentration is 1%, 2%, 3%, 4%, 5%, 6% the aqueous solution, and its tribological property of comprehensive evaluation:
1. according to the GB-3142-82 standard, adopt Britain to produce Shell-Steta Four Ball EP lubricant Tester test concentrations and be respectively 1%, 2%, 3%, 4%, the PB of 5%, 6% embodiment 1 product water solution, the PD value, testing used steel ball is the GCr15 bearing steel secondary standard steel ball that Lanzhou Berings Factory produces, its hardness is 59～61HRC, and test is at room temperature carried out, and rotating speed is 1450rpm.The results are shown in table 1:
The last non seizure load (PB) of table 1 different concns water base lubricant and the test result of sintering load (PD)
By data in the table as can be known, this compound can significantly promote the supporting capacity and the extreme pressure property of water as additive, adds and the last non seizure load of water can be promoted to nearly 600N from not enough 100N with 1%, after concentration further increases, PB increases gradually, and sintering load also rises to 2452N.
2. the little vibration friction abrasion testing machine test concentrations of SRV-IV that adopts German Optimol grease company to produce is respectively 1%, 2%, 3%, the aqueous solution of 4%, 5%, 6% embodiment 1 product is at 25 ℃, frequency 50Hz, frictional coefficient f is with the relation curve of load change under the operating mode of amplitude 1mm, and testing used steel ball is the GCr15 bearing steel of Φ=10mm, the GCr15 bloom that following sample is Φ 24 * 8mm.The results are shown in accompanying drawing 1～6.As seen from the figure, in the program loading procedure, this additive shows excellent antiwear and friction reduction property, although load increases step by step, the highest 1100N that increases to, but frictional coefficient shows comparatively stablely in the whole process, and average friction coefficient and has with load and increases and downward trend about 0.100.
3. the little vibration friction abrasion testing machine test concentrations of SRV-IV that adopts German Optimol grease company to produce is respectively 1%, 2%, 3%, 4%, 5%, the aqueous solution of 6% embodiment 1 product is at 25 ℃, frequency 50Hz, amplitude 1mm, the frictional coefficient f under the operating mode of load 300N during long mill 20min, testing used steel ball is the GCr15 bearing steel of Φ=10mm, the GCr15 bloom that following sample is Φ 24 * 8mm.The results are shown in accompanying drawing 7～12.As seen from the figure, at the high frequency of 50Hz, during 300N load lower slip, this compound can well lubricate steel-steel-steel pair as additive, and frictional coefficient shows very steadily, is stabilized in about 0.100, and friction reducing effect is very obvious.
Claims (5)
1. a water-soluble lubricant additive is characterized in that additive is water-soluble thiophosphorous acid ester cpds, with general formula (VI) expression, R in the formula (VI)
1, R
2Be straight chained alkyl or the alkyl-substituted phenyl of identical or different C8～C18, R
3Be the straight or branched alkyl of H, phenyl or C1～C8, n is 10～20 integer,
2. the preparation method of water-soluble lubricant additive according to claim 1 is characterized in that this method comprises A, B and three reactions steps of C:
A uses fatty alcohol-polyoxyethylene ether or the alkylphenol polyoxyethylene of formula (II) or the di-n-butyl phosphite of mixture of the two and formula (III) of formula (I), in the presence of catalyzer, in 120～160 ℃ of decompression reactions 4～10 hours, the ester exchange offspring of production (IV), adopt reliever to remove the by product propyl carbinol in the whole process, R ' is the straight or branched alkyl of C8～C18 in the formula (I), R in the formula (II) " be C2～C12 straight or branched alkyl;
120～160 ℃ of reactions 4～10 hours under nitrogen atmosphere of the phosphorous acid ester that B uses formula (IV) and sulphur powder, the thiophosphite of generation formula V:
The thiophosphite of C use formula V and diethanolamine and aldehyde generate the water-soluble thiophosphite compound product of general formula (VI), wherein R 80～120 ℃ of reactions 4～8 hours
3Be H, the straight chained alkyl of phenyl or C1～C8 or branched-chain alkyl;
3. method as claimed in claim 2 is characterized in that: in steps A, the mol ratio of fatty alcohol-polyoxyethylene ether or alkylphenol polyoxyethylene or mixture of the two and di-n-butyl phosphite is 2.0～2.3: 1.
4. method as claimed in claim 2 is characterized in that: in steps A, the catalyzer that uses is sodium methylate, sodium ethylate or potassium tert.-butoxide, and the usage quantity of catalyzer is 0.5%～1% of a reactant total mass.
5. method as claimed in claim 2 is characterized in that: in step C, the aldehyde that uses is formaldehyde, phenyl aldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, hexanal, enanthaldehyde or octanal.
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| CN102850396A (en) * | 2012-09-27 | 2013-01-02 | 沈阳工业大学 | Amido boron phosphate and preparation method of amido boron phosphate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102850396A (en) * | 2012-09-27 | 2013-01-02 | 沈阳工业大学 | Amido boron phosphate and preparation method of amido boron phosphate |
| CN102850396B (en) * | 2012-09-27 | 2016-05-25 | 沈阳工业大学 | A kind of amido boron phosphonate ester and preparation method thereof |
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Application publication date: 20110518 Assignee: Lanzhou Kekailu lubrication and Protection Technology Co. Ltd. Assignor: Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences Contract record no.: 2014620000014 Denomination of invention: Water-soluble lubricating additive and preparation method thereof Granted publication date: 20131002 License type: Common License Record date: 20140619 |
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