CN101153237B - Compound energy-saving antiwear agent of organic boron and method of producing the same - Google Patents
Compound energy-saving antiwear agent of organic boron and method of producing the same Download PDFInfo
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Abstract
The invention relates to the anti-abrasion agent field, in particular to an organic boron complex energy saving anti-abrasion agent and a preparation process thereof. The compositions by weight percentage of the organic boron complex energy saving anti-abrasion agent are as follows: organic boron: 40 to 80 percent; petroleum sulfonate of barium: 5 to 15 percent; isobutylene boride: 10 to 30 percent; sulfurized isobutylene: 5 to 15 percent. The organic boron complex energy saving anti-abrasion agent has scientific formula, reasonable design and good anti-abrasion, water-resistant and anti-rustperformance, can form a boronization laminated film with elasticity and strong adhesive force by being absorbed on the friction surfaces to play a role of apparent abrasion reduction and abrasion resistance, can be widely used in the lubricating systems of various machines, equipment and vehicles, and has good maintenance effect and certain energy saving effect.
Description
Technical field
The present invention relates to the anti-wear agent field, especially a kind of compound energy-saving antiwear agent of organic boron and preparation method thereof.
Background technology
Anti-wear agent can make the protected machinery resistance of reducing friction significantly, practices thrift power source, prolonged mechanical life-span at double.Along with the development of sulphur-phosphorus gear oil and hydraulicefficiency oil, boron-containing additive begins to be applied in such oil product, and borate is the extreme pressure anti-wear additives of the friendly type of a kind of novel environmental.Research shows: its extreme pressure property, wear resistance, thermal oxidation stability ability, high-temperature corrosion-resistance performance and airtight performance all are superior to the extreme pressure agent of some other types; As the heat resisting temperature of sulphur phosphorus agent be about 130 ℃, and boratory heat resisting temperature is 150 ℃.In addition, the nontoxic and easy degraded of borate.
The borate extreme pressure anti-wear additives began to be used for gear oil in 1974 by Chevron Corporation, under the condition of not sneaking into water, used, and can prolong the oil draining period significantly, wheel casing turn(a)round and good abrasion resistance and resistance to marring are arranged, and can reduce frictional coefficient; When same viscosity, it is than sulphur-phosphorus type gear oil fuel economy 1%～3%, and particularly extreme pressure property and Heat stability is good do not produce corrosion.But because borate is water-soluble, and it needs certain crystal water that best extreme pressure property is just arranged, so can not be used for the lubricated of water breakthrough position.When having water to exist, less water can change boratory crystal water content, thereby reduces performance; Excessive water can make the very fast approach exhaustion of borate again.Through changing the molecular structure of organoboron compound, just possibly under the condition that keeps extreme pressure property, improve its hydrolysis stability.For example: US3303130, US3082169 and CN1191258C have reported ring-type or four part organoboron compounds; Its hydrolysis stability has some improvement, need a kind of make reaction more rationally, easy handling, be convenient to the respond well energy-saving antiwear agent of suitability for industrialized production.
Summary of the invention
The present invention is the deficiency that overcomes prior art; A kind of compound energy-saving antiwear agent of organic boron and preparation method thereof is provided; Made compound energy-saving antiwear agent of organic boron has overcome the water funk shortcoming of borate and can have elasticity and the very strong boronation composite package of adhesive power plays the wear-resistant effect of anti-attrition through being adsorbed on to form on the friction surface; And the preparation method who is adopted is simple to operation, is convenient to suitability for industrialized production.
The present invention realizes through following technical scheme:
A kind of compound energy-saving antiwear agent of organic boron is characterized in that: the component of this compound energy-saving antiwear agent of organic boron and weight percent are:
Organic boron: 40～80%;
Barium mahogany sulfonate: 5～15%;
Boronation iso-butylene: 10～30%;
Sulfide isobutene: 5～15%;
Described organic boron is made up of dialkyl group curing phosphoric acid boron oxide and dialkyl group curing di(2-ethylhexyl)phosphate polymers, and their structural formula is respectively:
R wherein
1Be sec.-propyl or normal-butyl or isobutyl-or sec.-amyl sec-pentyl secondary amyl or Zhong Yiji or secondary octyl or iso-octyl; R
2Be sec.-amyl sec-pentyl secondary amyl or Zhong Yiji or secondary octyl or iso-octyl; R
1With R
2Equivalence ratio is 1: 1～1.2.
And described barium mahogany sulfonate substitutes with dinonyl naphthalene sulfonate barium.
A kind of preparation method of compound energy-saving antiwear agent of organic boron is characterized in that:
The preparation method of this compound energy-saving antiwear agent of organic boron may further comprise the steps:
(1) sulfur phosphatization reaction: with thiophosphoric anhydride and one or both single hydroxyl alcohols, by 1: 4～4.8 mixed in molar ratio, under 90 ± 2 ℃ of conditions, isothermal reaction 3～5h generates dialkyl group curing phosphoric acid, and its molecular formula is (R
1O) (R
2O) PSSH, the H that produces in the reaction process
2S gas is used the NaOH solution absorption, the Na of generation
2S and NaHS collect subsequent use;
(2) boronation reaction: boric acid or boric anhydride are added entry and reaction promotor, and reaction promotor and water are warming up to 55～65 ℃ after being 1: 0.1～0.5 mixing by volume, and again by 0.5～1: 1: 1 equivalence ratio adds above-mentioned Na
2S and NaHS mixture stir 15～25min; Temperature is brought down below 40～50 ℃; The sulfuric acid or the hydrochloric acid that add 0.5 times of boric acid or boric anhydride molar weight again react, and the equivalence ratio 1.5～2.0: 1 of pressing boric acid or boric anhydride behind 15～25min again adds above-mentioned dialkyl group curing phosphoric acid, generate dialkyl group curing di(2-ethylhexyl)phosphate polymers and dialkyl group curing phosphoric acid boron oxide at 75～100 ℃ of reaction 4～6h; Under 50～70 ℃ of conditions, divide the phase of anhydrating; Volume ratio by 1: 1～1.5 is divided water after stirring and adding the sherwood oil dilution down once more, washes secondary again, through distillation sherwood oil, unreacting alcohol, reaction promotor and residual water is steamed again;
(3) hybrid modulation: above-mentioned reactant dialkyl group curing di(2-ethylhexyl)phosphate polymers and dialkyl group curing phosphoric acid boron oxide mixture 40～80% and barium mahogany sulfonate or dinonyl naphthalene sulfonate barium 5～15%, boronation iso-butylene 10～30%, sulfide isobutene 5～15% are stirred 30～60min and promptly make compound energy-saving antiwear agent of organic boron under 50～70 ℃ of conditions.
And described single hydroxyl alcohol is C
4～C
8Primary alconol or secondary alcohol.
And described reaction promotor is C
1～C
5Lower alcohol.
And described reaction promotor is ethanol, Virahol, propyl carbinol or terepthaloyl moietie.
And described sulfur phosphatization reaction and boronation are reflected at and feed N
2Protective condition is reaction down.
And the boric anhydride in the described boronation reactions step adopts boron trioxide.
Beneficial effect of the present invention and advantage are:
1. this compound energy-saving antiwear agent of organic boron formula compatibility science, reasonable in design; Form by organic boron and barium mahogany sulfonate, boronation iso-butylene, sulfide isobutene; Organic boron has good extreme-pressure anti-wear Harmony; The synergistic effect and the complex effect of organic boron strengthened in the adding of other reagent; Make compound energy-saving antiwear agent of organic boron have good wear-resistant, waterproof, rust protection performance, can have elasticity and the very strong boronation composite package of adhesive power plays the wear-resistant effect of obvious anti-attrition through being adsorbed on to form on the friction surface.
2. the preparation method that this compound energy-saving antiwear agent of organic boron adopted is simple to operation; Be convenient to suitability for industrialized production; The compound energy-saving antiwear agent of organic boron of being produced can be widely used in the oiling system in various machineries, equipment, the vehicle, and it is had good maintenance effect and certain energy-conservation effect.
Embodiment
The present invention further details through following examples, but is not limited to present embodiment.
This compound energy-saving antiwear agent of organic boron is made up of organic boron and barium mahogany sulfonate (or dinonyl naphthalene sulfonate barium), boronation iso-butylene, sulfide isobutene.
Wherein said organic boron is made up of dialkyl group curing phosphoric acid boron oxide and dialkyl group curing di(2-ethylhexyl)phosphate polymers; Dialkyl group curing phosphoric acid boron oxide and dialkyl group curing di(2-ethylhexyl)phosphate polymers have good extreme-pressure anti-wear Harmony, and being added in of other reagent is wear-resistant, waterproof, rust protection aspect of performance all have good synergistic effect and complex effect.
Following embodiment 1, embodiment 2, embodiment 3, embodiment 4 are the embodiment of organic boron preparation, and prepared organic boron 40～80% and barium mahogany sulfonate or dinonyl naphthalene sulfonate barium 5～15%, boronation iso-butylene 10～30%, sulfide isobutene 5～15% stir 30～60min and can make compound energy-saving antiwear agent of organic boron under 50～70 ℃ of conditions.
Embodiment 5, embodiment 6, embodiment 7, embodiment 8 are the embodiment of organic boron performance measurement.
Embodiment 9 is the embodiment of compound energy-saving antiwear agent of organic boron performance measurement.
Embodiment 1
(1) sulfur phosphatization reaction: be equipped with in the four-hole reaction flask of whisking appliance, TM and gas tube and gas absorbing device, at first add sec.-amyl alcohol 176g (2mol) and 2-Ethylhexyl Alcohol 260g (2mol), stir and feed N
2Under the protective condition, drip thiophosphoric anhydride 222g (1mol), the control rate of addition to be avoiding temperature rise too fast in batches, and controlled temperature is at 90 ± 2 ℃, isothermal reaction 3～5h.The H2S gas that reaction produces imports the absorption bottle that 178g30% concentration NaOH solution (1.33mol) is housed, and is converted into Na after reaction finishes
2S and NaHS mixed solution 212g are subsequent use.Reactant cooled and filtered in the four-hole bottle obtains sec.-amyl sec-pentyl secondary amyl iso-octyl phosphorodithioic acid dusky transparent liquid, heavy 612g, and yield 98.1%, acid number 146mgKOH/g, S% are 19.84 (theoretical values 20.51), P% is 9.85 (theoretical values 9.94).
(2) boronation reaction: be furnished with in three mouthfuls of reaction flasks of 1000mL of whisking appliance, TM, tap funnel, reflux condensing tube and gas tube one, adding boric acid is 24.8g (0.6mol), tap water 500mL, and propyl carbinol 100mL imports N
2, stirring to pulp when being warming up to 60 ℃, drips the above-mentioned Na of 95.3g
2(B: Na=1: 2 equivalence ratios), behind the stirring 20min, temperature is brought down below 45 ℃ for S and NaHS mixed solution; Drip 48% sulfuric acid 34mL (0.3mol), behind the 20min, drip above-mentioned synthetic sec.-amyl sec-pentyl secondary amyl iso-octyl phosphorodithioic acid 374.4g (1.2mol); Heat up backflow 5h simultaneously.The shift reaction mixture divides sub-cloud blue look water to separating funnel, adds then with volume sherwood oil (60～90 ℃ of boiling points) and fully divides water once more after the dilution; Use again with the water of volume washing secondary, cut most water after, underpressure distillation removes and desolvates, unreacting alcohol, promotor and residual water etc.; Promptly obtain the brown mixed solution of dialkyl group curing phosphoric acid boron oxide and dialkyl group curing di(2-ethylhexyl)phosphate polymers, gross weight 376.5g, yield 96.5%; Acid number 99.82mgKOH/g; S is 19.87%, and P is 7.53%, and B is 5.42%.
Embodiment 2
(1) sulfur phosphatization reaction: be equipped with in the four-hole reaction flask of whisking appliance, TM and gas tube and gas absorbing device, at first add isooctyl alcohol 520g (4mol), stir and feed N
2Under the protective condition, drip thiophosphoric anhydride 222g (1mol), the control rate of addition to be avoiding temperature rise too fast in batches, and controlled temperature is at 90 ± 2 ℃, isothermal reaction 3～5h.The H that reaction produces
2S gas imports the absorption bottle that 178g30% concentration NaOH solution (1.33mol) is housed, and is converted into Na after reaction finishes
2S and NaHS mixed solution 212g are subsequent use.The reactant cooled and filtered obtains diisooctyl phosphorodithioic acid dusky transparent liquid, heavy 688g, and yield 98.0%, acid number 140mgKOH/g, S are 19.4%, P is 9.55%.
(2) boronation reaction: be furnished with in three mouthfuls of reaction flasks of 1000mL of whisking appliance, TM, tap funnel, reflux condensing tube and gas tube one, adding boric acid is 24.8g (0.6mol), tap water 500mL, and propyl carbinol 100mL imports N
2, stirring to pulp when being warming up to 60 ℃, drips the above-mentioned Na of 95.3g
2(B: Na=1: 2 equivalence ratios), behind the stirring 20min, temperature is brought down below 45 ℃, drips 48% sulfuric acid 34mL (0.3mol), behind the 20min, drips above-mentioned synthetic diisooctyl phosphorodithioic acid 424.8g (1.2mol), heats up backflow 5h simultaneously for S and NaHS mixed solution.The shift reaction mixture divides sub-cloud blue look water to separating funnel, adds then with volume sherwood oil (60～90 ℃ of boiling points) and fully divides water once more after the dilution; Use washing secondary again with volume, cut most water after, underpressure distillation removes and to desolvate, unreacting alcohol, promotor and residual water etc.; Promptly obtain the brown mixed solution of dialkyl group curing phosphoric acid boron oxide and dialkyl group curing di(2-ethylhexyl)phosphate polymers, gross weight 435g, yield 96.1%; Acid number 97.6mgKOH/g; S is 17.82%, and P is 7.81%, and B is 5.35%.
Embodiment 3
(1) sulfur phosphatization reaction: be equipped with in the four-hole reaction flask of whisking appliance, TM and gas tube and gas absorbing device, at first add sec.-amyl alcohol 352g (4mol), stir and feed N
2Under the protective condition, drip thiophosphoric anhydride 222g (1mol), the control rate of addition to be avoiding temperature rise too fast in batches, and controlled temperature is at 90 ± 2 ℃, isothermal reaction 3～5h.The H that reaction produces
2S gas imports the absorption bottle that 178g30% concentration NaOH solution (1.33mol) is housed, and is converted into Na after reaction finishes
2S and NaHS mixed solution 212g are subsequent use.The reactant cooled and filtered obtains di-sec-amyl phosphorodithioic acid dusky transparent liquid, and heavy 542.8g receives 98.1%, and acid number 98.82mgKOH/g, S are 19.85%, and P is 9.89%.
(2) boronation reaction: be furnished with in three mouthfuls of reaction flasks of 1000mL of whisking appliance, TM, tap funnel, reflux condensing tube and gas tube one, adding boron (acid) acid anhydride is 23.5g (0.6mol), tap water 500mL, and propyl carbinol 100mL imports N
2, stirring to pulp when being warming up to 60 ℃, drips the above-mentioned Na of 95.3g
2(B: Na=1: 2 equivalence ratios), behind the stirring 20min, temperature is brought down below 45 ℃, drips 48% sulfuric acid 34mL (0.3mol), behind the 20min, drips above-mentioned synthetic di-sec-amyl phosphorodithioic acid 324g (1.2mol), heats up backflow 5h simultaneously for S and NaHS mixed solution.The shift reaction mixture divides sub-cloud blue look water to separating funnel, adds then with volume sherwood oil (60～90 ℃ of boiling points) and fully divides water once more after the dilution; Use washing secondary again with volume, cut most water after, underpressure distillation removes and to desolvate, unreacting alcohol, promotor and residual water etc.; Promptly obtain the brown mixed solution of di-sec-amyl curing phosphoric acid boron oxide and di-sec-amyl curing di(2-ethylhexyl)phosphate polymers, gross weight 328.6g, yield 96.9%; Acid number 99.85mgKOH/g; S is 19.52%, and P is 7.74%, and B is 5.56%.
Embodiment 4
(1) sulfur phosphatization reaction: be equipped with in the four-hole reaction flask of whisking appliance, TM and gas tube and gas absorbing device, at first add sec.-amyl alcohol 176g (2mol) and 2-Ethylhexyl Alcohol 260g (2mol), stir and feed N
2Under the protective condition, drip thiophosphoric anhydride 222 (1mol), the control rate of addition to be avoiding temperature rise too fast in batches, and controlled temperature is at 90 ± 2 ℃, isothermal reaction 3～5h.The H that reaction produces
2S gas imports the absorption bottle that 178g30% concentration NaOH solution (1.33mol) is housed, and is converted into Na after reaction finishes
2S and NaHS mixed solution 212g are subsequent use.The reactant cooled and filtered obtains sec.-amyl sec-pentyl secondary amyl iso-octyl phosphorodithioic acid dusky transparent liquid, heavy 613g, and yield 98.3%, acid number 98.8KOH/g, S% are 19.81, P% is 9.82.
(2) boronation reaction: be furnished with in three mouthfuls of reaction flasks of 1000mL of whisking appliance, TM, tap funnel, reflux condensing tube and gas tube one, adding boron (acid) acid anhydride is 23.5g (0.6mol), tap water 500mL, and propyl carbinol 100mL imports N
2, stirring to pulp when being warming up to 60 ℃, drips the above-mentioned Na of 95.3g
2(B: Na=1: 2 equivalence ratios), behind the stirring 20min, temperature is brought down below 45 ℃ for S and NaHS mixed solution; Drip 48% sulfuric acid 34mL (0.3mol), behind the 20min, drip above-mentioned synthetic sec.-amyl sec-pentyl secondary amyl iso-octyl phosphorodithioic acid 374.4g (1.2mol); Heat up backflow 5h simultaneously.The shift reaction mixture divides sub-cloud blue look water to separating funnel, adds then with volume sherwood oil (60～90 ℃ of boiling points) and fully divides water once more after the dilution; Use again with the water of volume washing secondary, cut most water after, underpressure distillation removes and desolvates, unreacting alcohol, promotor and residual water etc.; Promptly obtain the brown mixed solution of dialkyl group curing phosphoric acid boron oxide and dialkyl group curing di(2-ethylhexyl)phosphate polymers, gross weight 375.2g, yield 96.2%; Acid number 98.5mgKOH/g; S is 17.73%, and P is 7.45%, and B is 5.25%.
Embodiment 5
Four kinds of sample JQ with embodiment 1, embodiment 2, embodiment 3, embodiment 4
1, JQ
2, JQ
3, JQ
4Add respectively in the 500SN base oil by 1% weight, carry out four-ball test (GB/T3142) and blank oil and compare the result and see table-1:
Table-1 endurance check result
| Sample | JQ 1 | JQ 2 | JQ 3 | JQ 4 | Blank |
| D 441N 30min(mm) | 0.48 | 0.47 | 0.49 | 0.48 | 0.55 |
| P B N | 1078 | 1100 | 1056 | 1078 | 960 |
Table-1 result shows that the abrasion resistance of organic boron of the present invention all is significantly improved.
Embodiment 6
Four kinds of sample JQ with embodiment 1, embodiment 2, embodiment 3, embodiment 4
1, JQ
2, JQ
3, JQ
4Add respectively in the 500SN base oil by 2% weight, the soundness test that is hydrolyzed (SH/T0301) compares the result with blank oil and sees table-2:
Table-2 hydrolysis stability test-results
| Sample | JQ 1 | JQ 2 | JQ 3 | JQ 4 | Blank |
| The weightless mg/cm of copper sheet 2 | 0.114 | 0.286 | 0.320 | 0.126 | 0.822 |
| Water layer acidity mgKOH/g | 6.65 | 2.32 | 4.50 | 7.45 | 27.82 |
| Copper sheet outward appearance level | 3b | 2C | 3b | 3b | 3b |
The stability performance of table-2 hydrolysis stability test-results tables organic boron of the present invention all is significantly improved.
Embodiment 7
Four kinds of sample JQ with embodiment 1, embodiment 2, embodiment 3, embodiment 4
1, JQ
2, JQ
3, JQ
4Add respectively in the 500SN base oil by 1% weight, carry out liquid-phase corrosion test (GB/T11143A) and blank oil and compare the result and see table-3:
Table-3 liquid-phase corrosion test results
| Sample | JQ 1 | JQ 2 | JQ 3 | JQ 4 | Blank |
| The corrosion rank | Rustless | Rustless | Rustless | Rustless | Light rust |
| The corrosion form | Rustless | Rustless | Rustless | Rustless | Spot corrosion |
Table is-3 liquid-phase corrosion test results show, the liquid phase rust protection performance of organic boron of the present invention all is superior to blank oil.The result of table-1, table-2, table-3 shows that also dialkyl group curing di(2-ethylhexyl)phosphate polymers and dialkyl group curing phosphoric acid boron oxide have good extreme-pressure anti-wear Harmony.
Embodiment 8
Examine or check the compound wear resistant performance of organic boron anti-wear agent and sulfocompound, with four kinds of sample JQ of embodiment 1, embodiment 2, embodiment 3, embodiment 4
1, JQ
2, JQ
3, JQ
4Add respectively in the 500SN base oil by 1% weight, again sulfide isobutene (Ps) 2% added respectively and carry out carrying out in four kinds of samples and the blank oil sample four its results of ball simultaneous test (GB/T3142) and see table-4:
Table-4 compound wear resistant results of property
| Sample | JQ 1+Ps | JQ 2+Ps | JQ 3+Ps | JQ 4+Ps | Blank+Ps |
| D 441N 30min(mm) | 0.46 | 0.45 | 0.46 | 0.47 | 0.52 |
| P B N | 1127 | 1127 | 1127 | 1078 | 1027 |
Table-4 four ball comparative test result show that the sulfide isobutene of organoboron compound and sulfur-bearing has the synergism of compound wear resistant performance.
Embodiment 9
For synergistic effect and the complex effect of strengthening organic boron anti-wear agent, organic boron anti-wear agent 60% that embodiment 1 is made and barium mahogany sulfonate or dinonyl naphthalene sulfonate barium 10%, boronation iso-butylene 20%, sulfide isobutene 10% stir 30～60min and promptly make compound energy-saving antiwear agent of organic boron under 50～70 ℃ of conditions.Salient features is following:
Table-5 energy-saving antiwear agents test-results in IC engine oil
| Test oil | P B(kg) | P D(kg) | ZMZ |
| J15W/40SJ | 54 | 252 | 25.98 |
| J15W/40SJ+ compound wear resistant agent 2% | 91 | 316 | 41.02 |
Four kinds of sample JQ with embodiment 1, embodiment 2, embodiment 3, embodiment 4
1, JQ
2, JQ
3, JQ
4Under 50～70 ℃ of conditions, stir 30～60min and promptly make compound energy-saving antiwear agent of organic boron with barium mahogany sulfonate or dinonyl naphthalene sulfonate barium 10%, boronation iso-butylene 20%, sulfide isobutene 10% by 60% respectively, the gained compound energy-saving antiwear agent of organic boron adds in No. 20 turbine oils salient features by 0.2% respectively and sees table-6 as follows:
Table-6 energy-saving antiwear agents test-results in No. 20 turbine oils
Table-5, table-6 results show that the compound energy-saving antiwear agent with organic boron production of the present invention's preparation all has good synergistic effect and complex effect at wear-resistant, waterproof, rust protection aspect of performance.
Claims (8)
1. compound energy-saving antiwear agent of organic boron, it is characterized in that: the component of this compound energy-saving antiwear agent of organic boron and weight percent are:
Organic boron: 40～80%;
Barium mahogany sulfonate: 5～15%;
Boronation iso-butylene: 10～30%;
Sulfide isobutene: 5～15%;
Described organic boron is made up of dialkyl group curing phosphoric acid boron oxide and dialkyl group curing di(2-ethylhexyl)phosphate polymers, and their structural formula is respectively:
R wherein
1Be sec.-propyl or normal-butyl or isobutyl-or sec.-amyl sec-pentyl secondary amyl or Zhong Yiji or secondary octyl or iso-octyl; R
2Be sec.-amyl sec-pentyl secondary amyl or Zhong Yiji or secondary octyl or iso-octyl; R
1With R
2Equivalence ratio is 1: 1～1.2.
2. a kind of compound energy-saving antiwear agent of organic boron according to claim 1 is characterized in that: described barium mahogany sulfonate substitutes with dinonyl naphthalene sulfonate barium.
3. the preparation method of an a kind of compound energy-saving antiwear agent of organic boron as claimed in claim 1 is characterized in that:
The preparation method of this compound energy-saving antiwear agent of organic boron may further comprise the steps:
(1) sulfur phosphatization reaction: with thiophosphoric anhydride and one or both single hydroxyl alcohols, by 1: 4～4.8 mixed in molar ratio, under 90 ± 2 ℃ of conditions, isothermal reaction 3～5h generates dialkyl group curing phosphoric acid, and its molecular formula is (R
1O) (R
2O) PSSH, the H that produces in the reaction process
2S gas is used the NaOH solution absorption, the Na of generation
2S and NaHS collect subsequent use;
(2) boronation reaction: boric acid or boric anhydride are added entry and reaction promotor, and reaction promotor and water are warming up to 55～65 ℃ after being 1: 0.1～0.5 mixing by volume, and again by 0.5～1: 1: 1 equivalence ratio adds above-mentioned Na
2S and NaHS mixture stir 15～25min; Temperature is brought down below 40～50 ℃; The sulfuric acid or the hydrochloric acid that add 0.5 times of boric acid or boric anhydride molar weight again react, and the equivalence ratio 1.5～2.0: 1 of pressing boric acid or boric anhydride behind 15～25min again adds above-mentioned dialkyl group curing phosphoric acid, generate dialkyl group curing di(2-ethylhexyl)phosphate polymers and dialkyl group curing phosphoric acid boron oxide at 75～100 ℃ of reaction 4～6h; Under 50～70 ℃ of conditions, divide the phase of anhydrating; Volume ratio by 1: 1～1.5 is divided water after stirring and adding the sherwood oil dilution down once more, washes secondary again, through distillation sherwood oil, unreacting alcohol, reaction promotor and residual water is steamed again;
(3) hybrid modulation: above-mentioned reactant dialkyl group curing di(2-ethylhexyl)phosphate polymers and dialkyl group curing phosphoric acid boron oxide mixture 40～80% and barium mahogany sulfonate or dinonyl naphthalene sulfonate barium 5～15%, boronation iso-butylene 10～30%, sulfide isobutene 5～15% are stirred 30～60min and promptly make compound energy-saving antiwear agent of organic boron under 50～70 ℃ of conditions.
4. the preparation method of a kind of compound energy-saving antiwear agent of organic boron according to claim 3, it is characterized in that: described single hydroxyl alcohol is C
4～C
8Primary alconol or secondary alcohol.
5. the preparation method of a kind of compound energy-saving antiwear agent of organic boron according to claim 3, it is characterized in that: described reaction promotor is C
1～C
5Lower alcohol.
6. the preparation method of a kind of compound energy-saving antiwear agent of organic boron according to claim 5, it is characterized in that: described reaction promotor is ethanol, Virahol, propyl carbinol or terepthaloyl moietie.
7. the preparation method of a kind of compound energy-saving antiwear agent of organic boron according to claim 3 is characterized in that: described sulfur phosphatization reaction and boronation are reflected at and feed N
2Protective condition is reaction down.
8. the preparation method of a kind of compound energy-saving antiwear agent of organic boron according to claim 3 is characterized in that: the boric anhydride employing boron trioxide in the described boronation reactions step.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5885943A (en) * | 1997-12-18 | 1999-03-23 | Exxon Chemical Patents Inc. | Sulfur boron antiwear agents for lubricating compositions |
| CN1393539A (en) * | 2001-06-29 | 2003-01-29 | 中国石油化工股份有限公司 | Extreme pressure antiwear agent made of organic boron and its preparing process |
-
2006
- 2006-09-27 CN CN2006100160006A patent/CN101153237B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5885943A (en) * | 1997-12-18 | 1999-03-23 | Exxon Chemical Patents Inc. | Sulfur boron antiwear agents for lubricating compositions |
| CN1393539A (en) * | 2001-06-29 | 2003-01-29 | 中国石油化工股份有限公司 | Extreme pressure antiwear agent made of organic boron and its preparing process |
Non-Patent Citations (1)
| Title |
|---|
| 王明江等.国内有机硼抗磨剂的研究进展.《合成润滑材料》.2005,第32卷(第4期),15-18. * |
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|---|---|
| CN101153237A (en) | 2008-04-02 |
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