CN105733745A - Preparation method of boriding crystalline calcium sulfonate clearing agent - Google Patents
Preparation method of boriding crystalline calcium sulfonate clearing agent Download PDFInfo
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Abstract
A preparation method of a boriding crystalline calcium sulfonate clearing agent sequentially comprises the following steps of: mixing 100 parts by mass of an amorphous calcium sulfonate clearing agent and 10- 60 parts by mass of a base oil or a non-polar solvent; stirring a mixture for 5-30 minutes at the temperature between 40 DEG C and 70 DEG C; then adding 20-100 parts by mass of a polar solvent and 1-10 parts by mass of a boron reagent in order; stirring a mixture for 5-30 minutes at the temperature between 40 DEG C and 60 DEG C; then heating the mixture to the temperature between 70 DEG C and 120 DEG C and performing reaction for 0.5 to 5 hours; and continuously heating the mixture to the temperature between 120 DEG C and 200 DEG C after the reaction ends, performing distillation and removing the solvent, and obtaining the boriding crystalline calcium sulfonate clearing agent. The boriding crystalline calcium sulfonate clearing agent has a strong extreme pressure antiwear effect, can be used in the field of engine lubrication, solves the dependence of antiwear performance in oils on ZDDP, and alleviates the limitation of environmental emissions to S and P additives. The preparation method is green and environmental friendly, is high efficient and convenient, and is easy for industrialization.
Description
Technical field
The preparation method that the present invention relates to a kind of boronation crystal type calcium sulfonate detergents.
Background technology
Along with the popularization day by day of high-power, high load capacity, rev-happy engine, I. C. engine oil is also progressively superior and multipolarity.In order to adapt to this lubrication needs, modern lubricating oil often to add the additive of the wear-resistant elements such as more sulfur-bearing, phosphorus to reduce fretting wear.The element such as sulfur, phosphorus is given again strict restriction by harsh environment emission request day by day on the other hand, the antiwear additive zinc dialkyl dithiophosphate (ZDDP) of tradition multiple-effect is faced with challenge, finds ZDDP succedaneum or other additive carries out wear-resistant multiple-effectization has become a urgent task.
Sulfonic acid calcium salt detersive is a current the most widely used type lubricating oil additive both at home and abroad.Its raw material is easy to get, with low cost, non-oil-soluble solid granule (gathering such as flue dust, carbon granule, resin-like thing, greasy filth, scoriform thing and slaine forms) is disperseed except having removing, neutralize acidic oxidation material (oxyacid and asphalitine etc.) outward, also there is certain wear-resistant effect, be a multi-functional additive of class.Research shows, calcium sulfonate detergents is the stable colloidal dispersion system formed by alkyl benzene calcium sulfonate surfactant, calcium carbonate and a certain amount of base oil.Calcium carbonate is positioned at the core of colloid, its outer alkyl sulfonic acid calcium parcel that is with, and the localized hyperthermia that during intermetallic friction, surface of friction pair produces makes calcium carbonate discharge; it is deposited on rubbing surface, forms protecting film, play wear-resistant effect (TribologyLetter; 2004,17:715-721).In calcium sulfonate detergents, the existing forms of nanometer core calcium carbonate mainly has amorphous and crystal type (calcite, vaterite and aragonite) two kinds, calcium carbonate in the sulfonate detergent of conventional basic, normal, high base number is impalpable structure, because of aragonite and vaterite poor stability, therefore usually said crystal type product refers generally to calcite structure.Research shows: amorphous calcium sulfonate detergents can obtain crystal type by chemical conversion, and crystal type sulfonate detergent can form thicker protecting film between friction pair, and therefore, anti-wear effect further enhances.It is known that the boron element wear-resistant element that to be a class important, organic boric acid ester, Calcium pyroborate etc. are respectively provided with stronger wear-resistant effect.The crystal type sulfonic acid calcium salt detersive of exploitation boracic is the important channel improving detersive abrasion resistance, is also solve abrasion resistance to one of effective means that ZDDP relies on.
As far back as 1985, US Patent No. 4560489 just reports a kind of high performance crystal type (calcite) sulfoacid calcium complex grease, its preparation method has two kinds, one is two-step method, first sulfoacid calcium (the TBN of Newtonian fluid is prepared, 400mgKOH/g), then as raw material, add C12-C40 alkyl fatty acid, certain viscosity index improver etc., the grease of non-Newtonian fluid can be obtained under certain condition, another is with chain alkyl benzenesulfonic acid, CaO for raw material, passes into CO2In carbonating simultaneously, add C12-C40 alkyl fatty acid and certain viscosity index improver etc., one-step method directly obtains crystal type sulfoacid calcium complex grease, sulfoacid calcium grain diameter prepared by above two method relatively big (about 500nm), base number (TBN, mgKOH/g), about 400, is only applicable to grease field.
(the TribologyLetter such as Liu, 2012,45:265-273) also report a kind of crystal type (calcite) high performance sulfoacid calcium complex grease and preparation method thereof, with amorphous sulfoacid calcium (TBN, 400mgKOH/g) for raw material, transformation of crystal can be realized under long-chain fatty acid effect, no matter crystal type grease after conversion is from the coefficient of friction (f) of SRV rattling machine test, or the extreme pressure property (PB) of four-ball tester (Four-ball) is superior to impalpable structure.
US6107259 reports a kind of method for transforming agent, amorphous sulfoacid calcium being converted into crystal type (calcite) with acetic acid or calcium acetate, crystal type sulfoacid calcium product total base number (TBN) that it is prepared is general at about 260mgKOH/g, (RSO3)2The content of Ca is 12.5%.Performance test shows, when product consumption is 5%, mill class's diameter (d) of Four-ball experiment is 0.4mm, adding dosage when being 1%, ladder nurse agree OK value that (Timken) test more than 12h, and the maximum failure load of method Simon Rex (Falex) is 45001bs, show prominent abrasion resistance, and this product has less grain diameter (about 100nm), stability is better, recommended is applied in engine lubricating oil.
All reporting a kind of vaterite sulfoacid calcium and preparation method thereof in US7422999 and CN102295971, US7422999, with amorphous calcium carbonate detersive for raw material, is continually fed into CO2Carry out transformation of crystal, it is thus achieved that vaterite-type sulfoacid calcium.CN102295971, then with alkyl benzene sulphonate and CaO for raw material, adds heptane and CaCl2, next footwork of dicyandiamide solution at first alcohol and water directly prepares the sulfoacid calcium of this crystal formation, but product stability is poor, all fails to use as lube oil additive.
Summary of the invention
The preparation method that it is an object of the invention to provide boronation crystal type calcium sulfonate detergents.
The object of the present invention is achieved like this: the preparation method of a kind of boronation crystal type calcium sulfonate detergents, comprise the following steps successively: the base oil of the amorphous calcium sulfonate detergents of 100 mass parts and 10-60 mass parts or non-polar solven are mixed, stir 5-30 minute in 40-70 DEG C, sequentially add the polar solvent of 20-100 mass parts and the borane reagent of 1-10 mass parts, stir 5-30 minute in 40-60 DEG C, it is warming up to 70-120 DEG C afterwards to react 0.5-5 hour, it is continuously heating to 120-200 DEG C after end and solvent is distilled off, obtain boronation crystal type calcium sulfonate detergents.
Wherein, described amorphous calcium sulfonate detergents includes amorphous calcium carbonate, surfactant and base oil, and calcium content is 2-20wt%, and base number is 50-500mgKOH/g, and the mean diameter of calcium carbonate nano core is 10-200nm.
Wherein, described amorphous calcium sulfonate detergents includes amorphous calcium carbonate, surfactant and base oil, and calcium content is 12-15wt%, and base number is 350-420mgKOH/g, and the mean diameter of calcium carbonate nano core is 30-50nm.
Wherein, described surfactant is C12-C15 chain-like alkyl sulfoacid calcium surfactant.
Wherein, described base oil is I class in American Petroleum Institute's classification, II class, III class, IV class or V class base oil.
Wherein, described base oil is II class in American Petroleum Institute's classification or III class base oil.
Wherein, described non-polar solven is normal hexane, normal heptane, benzene,toluene,xylene, octane, 120# solvent naphtha, 180# solvent naphtha or petroleum ether.
Wherein, described non-polar solven is 120#Solvent naphtha or petroleum ether.
Wherein, described polar solvent is the mixture of one or more in water, methanol, ethanol, isopropanol, butanol or amylalcohol.
Wherein, described polar solvent is the mixture of first alcohol and water.
Wherein, the mass ratio of described first alcohol and water is 1:3-5:1.
Wherein, described borane reagent is boric acid, sodium borate, Calcium pyroborate, Firebrake ZB, "Antifungin"., barium borate, sodium metaborate, calcium metaborate, barium metaborate, zinc metaborate, first boric acid, phenylboric acid or organic boric acid ester.
Wherein, described borane reagent is boric acid or first boric acid.
Product particle particle diameter is had considerable influence by dicyandiamide solution and the consumption of borane reagent in preparation method of the present invention, it it is the principal element determining product appearance and stability, conversion process needs strict control, in addition charging sequence, experimental temperature and response time also can have a certain impact, and also need corresponding control.
The method have the benefit that the present invention prepares crystal type calcium sulfonate detergents with the method for transformation of crystal, the condition that de novo synthesis both can have been avoided complicated controls, and simplifies production technology, can meet again harsh environment assessment requirement, be comparatively efficiently feasible method.Prepared product is Newtonian fluid, there is less nano-scale (30-100nm), higher base number (> 100mgKOH/g), oil-soluble and good stability, not free settling, abrasion resistance is strong, and developing this series products is solve abrasion resistance to one of effective ways of restriction of pollution element such as S, P, and the high-grade engine lubricating oil of exploitation is also significant.
Accompanying drawing explanation
Fig. 1 a is Fourier (FTIR) infrared spectrum of embodiment 1 Raw；
Fig. 1 b is Fourier (FTIR) infrared spectrum of product in embodiment 1；
Fig. 2 is the laser particle analyzer spectrogram of embodiment 1 product；
Fig. 3 a is transmission electron microscope (TEM) spectrogram of embodiment 1 Raw；
Fig. 3 b is transmission electron microscope (TEM) spectrogram of product in embodiment 1.
Detailed description of the invention
Following embodiment is further illustrating the present invention, rather than to the restriction that the present invention carries out, the spirit and scope of the present invention is listed in claims.
A kind of preparation method of boronation crystal type calcium sulfonate detergents, comprise the following steps successively: the base oil of the amorphous calcium sulfonate detergents of 100 mass parts and 10-60 mass parts or non-polar solven are mixed, stir 5-30 minute in 40-70 DEG C, sequentially add the polar solvent of 20-100 mass parts and the borane reagent of 1-10 mass parts, stir 5-30 minute in 40-60 DEG C, it is warming up to 70-120 DEG C afterwards to react 0.5-5 hour, it is continuously heating to 120-200 DEG C after end and solvent is distilled off, obtain boronation crystal type calcium sulfonate detergents.
Wherein, described amorphous calcium sulfonate detergents includes amorphous calcium carbonate, surfactant and base oil, and calcium content is 2-20wt%, and base number is 50-500mgKOH/g, and the mean diameter of calcium carbonate nano core is 10-200nm.
Wherein, described amorphous calcium sulfonate detergents includes amorphous calcium carbonate, surfactant and base oil, and calcium content is 12-15wt%, and base number is 350-420mgKOH/g, and the mean diameter of calcium carbonate nano core is 30-50nm.
Wherein, described surfactant is C12-C15 chain-like alkyl sulfoacid calcium surfactant.
Wherein, described base oil is I class in American Petroleum Institute's classification, II class, III class, IV class or V class base oil.
Wherein, described base oil is II class in American Petroleum Institute's classification or III class base oil.
Wherein, described non-polar solven is normal hexane, normal heptane, benzene,toluene,xylene, octane, 120# solvent naphtha, 180# solvent naphtha or petroleum ether.
Wherein, described non-polar solven is 120#Solvent naphtha or petroleum ether.
Wherein, described polar solvent is the mixture of one or more in water, methanol, ethanol, isopropanol, butanol or amylalcohol.
Wherein, described polar solvent is the mixture of first alcohol and water.
Wherein, the mass ratio of described first alcohol and water is 1:3-5:1.
Wherein, described borane reagent is boric acid, sodium borate, Calcium pyroborate, Firebrake ZB, "Antifungin"., barium borate, sodium metaborate, calcium metaborate, barium metaborate, zinc metaborate, first boric acid, phenylboric acid or organic boric acid ester.
Wherein, described borane reagent is boric acid or first boric acid.
Embodiment 1
Equipped with in the 1L there-necked flask of mechanical agitator and reflux condensing tube, add calcium sulfonate detergents (TBN400mgKOH/g, 400g) with 150N base oil (200g), it is warming up to 50-60 DEG C to stir 10 minutes, is subsequently adding methanol-water (150ml-150ml) and boric acid (10g), continue stirring 15min, it is warming up to 70-75 DEG C to react 2 hours, after end, it is warming up to 150 DEG C and solvent is evaporated off, obtain brown viscous shape product.
Infrared spectrum is as the instrument of qualitative and quantitative analysis calcium carbonate crystalline structure.IR spectrogram (see Fig. 1 a and Fig. 1 b, wherein Fig. 1 a is raw material IR figure, Fig. 1 b is product I R figure) after analyzing embodiment 1 Raw and converting can find: 722cm-1And 860cm-1Absworption peak move to 711cm respectively-1And 883cm-1, 1400cm-1Locating strong absworption peak and also become sharp-pointed, these typical characteristic peak data show that raw material is converted into crystal type (calcite) from amorphous state.
Laser particle analyzer test result is (see Fig. 2, test temperature: 25 DEG C, solvent: normal hexane；Solvent refractive index: 1.426) display, the mean diameter of product less (38nm) in embodiment 1, particle size distribution narrower (30-100nm), transmission electron microscope can be visually observed that the morphology change (as shown in Figure 3 a and Figure 3 b shows) converting front and back calcium carbonate, contrast the transmission electron microscope graph discovery of the two, in the front calcium sulfonate detergents of conversion, calcium carbonate is without solid shape, particle diameter is generally at 10-30nm, the not only shape side of becoming bar shaped after conversion, and particle diameter generally increases to 40-80nm.
Embodiment 2
Equipped with in the 1L there-necked flask of mechanical agitator and reflux condensing tube, add calcium sulfonate detergents (TBN400mgKOH/g, 400g) with 100N base oil (150g), it is warming up to 50-60 DEG C to stir 10 minutes, is subsequently adding methanol-water (150ml-150ml) and boric acid (15g), continue stirring 15min, it is warming up to 70-75 DEG C to react 2 hours, after end, it is warming up to 150 DEG C and solvent is evaporated off, obtain brown viscous shape product.
Embodiment 3
Equipped with in the 1L there-necked flask of mechanical agitator and reflux condensing tube, add calcium sulfonate detergents (TBN400mgKOH/g, 400g) with 120# solvent naphtha (50g), it is warming up to 50-60 DEG C of stirring 10min, it is subsequently adding methanol-water (150ml-150ml) and boric acid (10g), continue stirring 15min, it is warming up to 70-75 DEG C to react 2 hours, after end, it is warming up to 150 DEG C and solvent is evaporated off, add 70N base oil (150g) dilution, obtain brown viscous shape product.
Embodiment 4
Equipped with in the 1L there-necked flask of mechanical agitator and reflux condensing tube, add calcium sulfonate detergents (TBN400mgKOH/g, 400g) with 70N base oil (150g), it is warming up to 50-60 DEG C to stir 10 minutes, is subsequently adding methanol-water (100ml-200ml) and boric acid (10g), continue stirring 15min, it is warming up to 70-75 DEG C to react 2 hours, after end, it is warming up to 150 DEG C and solvent is evaporated off, obtain brown viscous shape product.
Embodiment 5
Equipped with in the 1L there-necked flask of mechanical agitator and reflux condensing tube, add calcium sulfonate detergents (TBN300mgKOH/g, 400g) with 150N base oil (150g), it is warming up to 50-60 DEG C to stir 10 minutes, is subsequently adding methanol-water (200ml-200ml) and boric acid (5g), continue stirring 15min, temperature rising reflux reacts 2 hours, after end, it is warming up to 120 DEG C and solvent is evaporated off, then decompression is distilled off residual solvent and namely obtains brown viscous shape product.
In embodiment 1-5, product physicochemical property and frictional behavior data are in Table 1.
Table 1
Note: JTU, WSD, PB, f mensuration in add dosage and be 2%, base oil is 150N.
Comparative example 1
Experiment condition is identical with embodiment 1 with consumption, is different in that, is added without borane reagent in reaction, and after reaction terminates, IR collection of illustrative plates is unchanged with raw material, it was shown that the unrealized transformation of crystal of product, and this example illustrates that borane reagent is the necessary reagent participating in converting.
Comparative example 2
Equipped with in the 1L there-necked flask of mechanical agitator and reflux condensing tube, add calcium sulfonate detergents (TBN400mgKOH/g, 400g) with 150N base oil (200g), it is warming up to 50-60 DEG C to stir 10 minutes, is subsequently adding methanol-water (150ml-150ml) and acetic acid (10g), continue stirring 15min, it is warming up to 70-75 DEG C to react 2 hours, after end, it is warming up to 150 DEG C and solvent is evaporated off, obtain brown viscous shape product.
Comparative example 3
Equipped with in the 1L there-necked flask of mechanical agitator and reflux condensing tube, add calcium sulfonate detergents (TBN400mgKOH/g, 400g) with 150N base oil (200g), it is warming up to 50-60 DEG C to stir 10 minutes, it is subsequently adding methanol-water (150ml-150ml) and chain alkyl benzenesulfonic acid (M.W450-500,10g), continue stirring 15min, it is warming up to 70-75 DEG C to react 2 hours, after end, it is warming up to 150 DEG C and solvent is evaporated off, obtain brown viscous shape product.
In comparative example 1-3, product physicochemical property and frictional behavior data are in Table 2.
Table 2
| Project | Comparative example 1 | Comparative example 2 | Comparative example 2 | Method 3 |
| Conversion ratio (%) | - | ≥98 | ≥98 | IR peak area (A880/(A860+A880)) |
| Base number (TBN, mg KOH/g) | - | 256 | 262 | SH/T 0251 |
| Mean diameter (d, nm) | - | 67 | 150 | Particle size analyzer |
| Viscosity (100 DEG C, mm2/s) | - | 336 | Do not flow | GB/T 265 |
| Ca content (%) | - | 7.2 | 7.3 | GB/T 17476 |
| Turbidity (JTU, mg/L) | - | 30.00 | >1000 | SH/T 0028 |
| Wear scar diameter (WSD, mm) | - | 0.66 | 0.71 | SH/T 0189 |
| PB(N) | - | 630 | 590 | GB/T 3142 |
| Coefficient of friction (f) | - | 0.14 | 0.14 | SRV testing machine |
Note: JTU, WSD, PB, f mensuration in add dosage and be 2%, base oil is 150N.
Data in analytical table 2, it can be seen that when transforming agent is acetic acid or sulfonic acid, raw material also achieves transformation of crystal under similarity condition, obtain calcite type product, and conversion ratio are more than 98%.In comparative example 1, product finds, the particle diameter changing the product prepared by transforming agent significantly increases, turbidity substantially increases, and its abrasion resistance also slightly declines, above comparative example fully shows, the effect that borane reagent participates in converting is substantially better than other transforming agent, and the product abrasion resistance that borane reagent converts is more excellent.
Above example and data fully show, method is simple to prepare crystal type calcium sulfonate detergents in the present invention, efficient quick, and the complex conditions both having avoided de novo synthesis controls, again will not to environment.Prepared sulfoacid calcium product turbidity is low, and oil-soluble is good, and anti-wear effect is notable, it is possible to be applied in engine lubricating oil, is solve abrasion resistance to one of effective way that S, P class additive ZDDP relies on.
Claims (13)
1. the preparation method of a boronation crystal type calcium sulfonate detergents, it is characterized in that, comprise the following steps successively: the base oil of the amorphous calcium sulfonate detergents of 100 mass parts and 10-60 mass parts or non-polar solven are mixed, stir 5-30 minute in 40-70 DEG C, sequentially add the polar solvent of 20-100 mass parts and the borane reagent of 1-10 mass parts, stir 5-30 minute in 40-60 DEG C, it is warming up to 70-120 DEG C afterwards to react 0.5-5 hour, it is continuously heating to 120-200 DEG C after end and solvent is distilled off, obtain boronation crystal type calcium sulfonate detergents.
2. the preparation method of boronation crystal type calcium sulfonate detergents according to claim 1, it is characterized in that, described amorphous calcium sulfonate detergents includes amorphous calcium carbonate, surfactant and base oil, calcium content is 2-20wt%, base number is 50-500mgKOH/g, and the mean diameter of calcium carbonate nano core is 10-200nm.
3. the preparation method of boronation crystal type calcium sulfonate detergents according to claim 1, it is characterized in that, described amorphous calcium sulfonate detergents includes amorphous calcium carbonate, surfactant and base oil, calcium content is 12-15wt%, base number is 350-420mgKOH/g, and the mean diameter of calcium carbonate nano core is 30-50nm.
4. the preparation method of the boronation crystal type calcium sulfonate detergents according to any one of Claims 2 or 3, it is characterised in that described surfactant is C12-C15 chain-like alkyl sulfoacid calcium surfactant.
5. the preparation method of boronation crystal type calcium sulfonate detergents according to claim 1, it is characterised in that described base oil is I class in American Petroleum Institute's classification, II class, III class, IV class or V class base oil.
6. the preparation method of boronation crystal type calcium sulfonate detergents according to claim 1, it is characterised in that described base oil is II class in American Petroleum Institute's classification or III class base oil.
7. the preparation method of boronation crystal type calcium sulfonate detergents according to claim 1, it is characterised in that described non-polar solven is normal hexane, normal heptane, benzene,toluene,xylene, octane, 120# solvent naphtha, 180# solvent naphtha or petroleum ether.
8. the preparation method of boronation crystal type calcium sulfonate detergents according to claim 1, it is characterised in that described non-polar solven is 120#Solvent naphtha or petroleum ether.
9. the preparation method of boronation crystal type calcium sulfonate detergents according to claim 1, it is characterised in that described polar solvent is the mixture of one or more in water, methanol, ethanol, isopropanol, butanol or amylalcohol.
10. the preparation method of boronation crystal type calcium sulfonate detergents according to claim 1, it is characterised in that described polar solvent is the mixture of first alcohol and water.
11. the preparation method of boronation crystal type calcium sulfonate detergents according to claim 10, it is characterised in that the mass ratio of described first alcohol and water is 1:3-5:1.
12. the preparation method of boronation crystal type calcium sulfonate detergents according to claim 1, it is characterized in that, described borane reagent is boric acid, sodium borate, Calcium pyroborate, Firebrake ZB, "Antifungin"., barium borate, sodium metaborate, calcium metaborate, barium metaborate, zinc metaborate, first boric acid, phenylboric acid or organic boric acid ester.
13. the preparation method of boronation crystal type calcium sulfonate detergents according to claim 1, it is characterised in that described borane reagent is boric acid or first boric acid.
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Cited By (4)
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| CN110295079A (en) * | 2019-07-19 | 2019-10-01 | 中国科学院兰州化学物理研究所 | A kind of preparation and application of low-temperature lubrication oil additive |
| CN111164191A (en) * | 2017-10-20 | 2020-05-15 | 雪佛龙日本有限公司 | Low viscosity lubricating oil composition |
| CN111808664A (en) * | 2020-07-09 | 2020-10-23 | 嘉兴顺诚精细化工有限公司 | Plant fat high-viscosity stainless steel chlorine-free forming agent and preparation method thereof |
| CN113652280A (en) * | 2021-08-10 | 2021-11-16 | 希玛石油制品（镇江）有限公司 | Environment-friendly chlorine-free titanium alloy cutting oil and preparation method thereof |
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|---|---|---|---|---|
| CN111164191A (en) * | 2017-10-20 | 2020-05-15 | 雪佛龙日本有限公司 | Low viscosity lubricating oil composition |
| CN110295079A (en) * | 2019-07-19 | 2019-10-01 | 中国科学院兰州化学物理研究所 | A kind of preparation and application of low-temperature lubrication oil additive |
| CN111808664A (en) * | 2020-07-09 | 2020-10-23 | 嘉兴顺诚精细化工有限公司 | Plant fat high-viscosity stainless steel chlorine-free forming agent and preparation method thereof |
| CN111808664B (en) * | 2020-07-09 | 2022-08-16 | 嘉兴顺诚精细化工有限公司 | Plant fat high-viscosity stainless steel chlorine-free forming agent and preparation method thereof |
| CN113652280A (en) * | 2021-08-10 | 2021-11-16 | 希玛石油制品（镇江）有限公司 | Environment-friendly chlorine-free titanium alloy cutting oil and preparation method thereof |
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