CN103725357B - Low-alkali detergent, preparation method of detergent and lubricating oil composition containing detergent - Google Patents
Low-alkali detergent, preparation method of detergent and lubricating oil composition containing detergent Download PDFInfo
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Abstract
The invention provides a low-alkali detergent, a preparation method of the detergent and a lubricating oil composition containing the detergent. The preparation method comprises the following steps: conducting a saponification reaction of organic sulfur phosphonic acid, alkali metal and/or alkaline-earth metal oxide, water and alkyl salicylic acid with an inorganic acid and/or aryl carboxylic acid accelerant at the same time or successively, and collecting products. The low-alkali detergent and the lubricating oil containing the same are excellent in detergency and dispersibility, oxidation resistance and thermal stability.
Description
Technical field
The present invention relates to a kind of low alkali value purification agent, specifically a kind of multi-functional purification agent with peace and quiet, dispersion, anti-oxidant and abrasion resistance.
Background technology
At present, on China's Lube Oil Market, metal detergent is mainly sulfonate, alkylsalicylate and alkyl phenate, three kinds of purification agents respectively have relative merits, wherein sulfonate is cheap, dispersed and oil soluble is better, although alkylsalicylate and alkyl phenate performance are slightly well, price is higher, and performance is not comprehensive.It is general that these two kinds of additives often only have high temperature detergency, anti-oxidative stability and dispersing property and oil soluble, can not meet the needs of high performance lubricating oil.
Polyisobutene phosphine sulfide salt additives develops a class purification agent comparatively early, and traditional phosphine sulfide hydrochlorate take barium salt as metal, and product has detergency dispersed and certain preferably, but its thermostability is general, affects it and use.
Research report about phosphine sulfide hydrochlorate purification agent is more, such as GB 1,039,732 preparation methods describing polyisobutene phosphine sulfide hydrochlorate purification agent, at the alkyl containing sulphur of acidity with containing in the compound of phenol and inert solvent, add and be less than stoichiometric basic metal or alkaline earth metal alkali, in high temperature, then pass into carbonic acid gas form colloidal-carbon hydrochlorate, need water in carbonation reaction, add sulphur after carbonation reaction terminates and carry out vulcanization reaction.
GB 1,004,401 and US 3,377,282 describes the preparation method of phosphine sulfide acid barium; Mixing phosphine sulfide polyisobutene and alkylphenol or sulfenyl phenolate, then with oxide compound or the oxyhydroxide reaction of divalent metal.Wherein the alkyl of alkylphenol sulfide or alkylphenol aromatic ring has 5-20 carbon atom.The molecular weight of polyisobutene is 500-3500.
US 3,321,399 describes the preparation of oil-soluble metal carbonate.Comprise with phosphine sulfide polyolefine, nonyl phenol, calcium hydroxide, urea, mineral oil, water for raw material reaction, wherein the ratio of calcium hydroxide and tensio-active agent is 6.3.
Although the standby product of above patent system has certain detergency, its performance is general, and does not also solve the poor problem of polyisobutene phosphine sulfide hydrochlorate thermostability.
Summary of the invention
The invention provides a kind of low alkali value purification agent, its preparation method and comprise the lubricating oil composition of this purification agent.
Low alkali value purification agent provided by the invention, its preparation method comprises: the oxide compound of organic sulfur phosphonic, basic metal and/or alkaline-earth metal, water, alkyl salicylate and mineral acid and/or aryl carboxylic acid promotor saponification reaction are occurred simultaneously or successively, collects product.
The structure of described organic sulfur phosphonic is:
Wherein R
1for the alkyl of number-average molecular weight between 500-5000, preferred 700-3500, most preferably 850-2500; X is O atom or S atom, and wherein at least one X is S atom, the preferred S atom of X.
Organic sulfur phosphonic is obtained by reacting by polyolefine generation phosphine sulfide, and namely polyolefine and thiophosphoric anhydride and/or sulphur phosphatase reaction obtain.Described polyolefine is by ethene, propylene, C
4-c
10alkene is polymerized separately or copolymerization and the polyolefine obtained, described C
4-c
10alkene can select in n-butene, iso-butylene, positive amylene, n-hexylene, positive octene and positive decene one or more, preferred polyisobutene.Described polyolefinic number-average molecular weight is 500-5000, preferred 700-3500, most preferably 850-2500.The temperature of described phosphine sulfideization reaction is between 100-300 DEG C, and preferred 150-250 DEG C, the reaction times is 5h ~ 20h, preferred 12h ~ 18h.
The oxide compound of the oxide compound preferred bases earth metals of described basic metal and/or alkaline-earth metal, such as, in calcium oxide, magnesium oxide, strontium oxide and barium oxide one or more, most preferably calcium oxide and/or magnesium oxide.
The structure of described alkyl salicylate is:
Wherein R
2for C4-C20 alkyl, preferred C8-C18 alkyl, most preferably C10-C16 alkyl, be connected to the neighbour/contraposition of hydroxyl carbon atom.
The preferred C4-C20 alkene of described alkyl salicylate and phenol generation alkylated reaction generate alkylphenol, then obtain through saponification, kobe reaction, acidifying.
Described mineral acid promotor can select in sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid one or more, preferably sulfuric acid; Described aryl carboxylic acid promotor comprises aryl monoprotic acid and/or aryl diprotic acid, described aryl is phenyl and/or naphthyl, aryl dicarboxylic acid comprise neighbour, contraposition aryl dicarboxylic acid, phenylformic acid, naphthoic acid, phthalic acid, m-phthalic acid, terephthalic acid, adjacent naphthalic acid, a naphthalic acid and to one or more in naphthalic acid can be selected.
When there is saponification reaction in the oxide compound of organic sulfur phosphonic, basic metal and/or alkaline-earth metal, water, alkyl salicylate and mineral acid and/or aryl carboxylic acid promotor simultaneously, mol ratio between described organic sulfur phosphonic and alkyl salicylate is 1:10-10:1, preferred 1:5-5:1, most preferably 1:3-3:1; Mol ratio between the oxide compound of described organic sulfur phosphonic and described basic metal and/or alkaline-earth metal is 1:0.2-1:10, preferred 1:0.4-1:7, most preferably 1:1-1:5; The oxide compound of described basic metal and/or alkaline-earth metal and the mol ratio of water are 1:0.5-1:10, preferred 1:0.8-1:5, most preferably 1:1-1:3; Described mineral acid and/or aryl carboxylic acid promotor account for the 0.1-10% of organic sulfur phosphonic and alkyl salicylate quality sum, preferred 0.5-6%, most preferably 1-3%; The temperature of described reaction is 20 ~ 200 DEG C, preferably 40 ~ 160 DEG C, most preferably 60 ~ 120 DEG C; The time of described reaction is 1-20h, preferred 1-12h, most preferably 1-8h.
After described saponification reaction terminates, by material filtering, refining obtain low alkali value purification agent.
It is carry out according to the following steps that the oxide compound of described organic sulfur phosphonic, basic metal and/or alkaline-earth metal, water, alkyl salicylate and mineral acid and/or aryl carboxylic acid promotor successively saponification reaction occur:
1) by oxide compound, the water generation saponification reaction of organic sulfur phosphonic and basic metal and/or alkaline-earth metal;
2) by step (1) product and alkylated salicylamide acid-respons, then add the oxide compound of basic metal and/or alkaline-earth metal, water, mineral acid and/or aryl carboxylic acid promotor and further saponification reaction occurs, collect product.
Mol ratio between the oxide compound of basic metal and/or alkaline-earth metal described in organic sulfur phosphonic described in step (1) and step (1) is 1:0.2-1:5, preferred 1:0.4-1:4, most preferably 1:1-1:3.5.
The mol ratio of the oxide compound of basic metal and/or alkaline-earth metal described in step (1) and the middle water of step (1) is 1:0.5-1:10, preferred 1:0.8-1:5, most preferably 1:1-1:3.
Described in step (1), the temperature of saponification reaction is 20 ~ 200 DEG C, preferably 40 ~ 160 DEG C, most preferably 60 ~ 120 DEG C.
The time of saponification reaction described in step (1) is 1-20h, preferred 1-10h, most preferably 1-6h.
Mol ratio described in alkyl salicylate described in step (2) and step (1) between organic sulfur phosphonic is 1:10-10:1, preferred 1:5-5:1, most preferably 1:3-3:1.
In step (2), the temperature of step (1) product and alkylated salicylamide acid-respons is 20-200 DEG C, preferred 40-160 DEG C, most preferably 60-120 DEG C, and the time of reaction is 5-50 minute, preferred 10-40 minute, most preferably 15-30 minute.
Mol ratio between the oxide compound of basic metal and/or alkaline-earth metal described in alkyl salicylate described in step (2) and step (2) between 1:0.2-1:2, preferred 1:0.4-1:1.4, most preferably 1:0.6-1:1.6.
The mol ratio of the oxide compound of basic metal and/or alkaline-earth metal described in step (2) and the middle water of step (2) is 1:0.5-1:10, preferred 1:0.8-1:8, most preferably 1:1-1:4.
Described in step (2), mineral acid and/or aryl carboxylic acid promotor account for the 0.1-10% of organic sulfur phosphonic and alkyl salicylate quality sum, preferred 0.5-6%, most preferably 1-3%.
Described in step (2), the temperature of saponification reaction is 20-200 DEG C, preferred 40-160 DEG C, most preferably 60-120 DEG C, and the reaction times is 1-10 hour, preferred 1-8 hour, most preferably 1-5 hour.
After saponification reaction terminates described in step (2), by material filtering, refining obtain low alkali value purification agent.
Can not solvent be added in described saponification reaction, also can add solvent, preferably add solvent.Described solvent is the varsol of boiling range between 80-200 DEG C, and such as normal heptane, octane, No. 120 solvent oils, No. 200 solvent oils, boiling range are the sherwood oil of 90-120 DEG C.The add-on of described solvent is the 30-250% of organic sulfur phosphonic quality, preferred 50-180%, most preferably 60-150%.When successively there is saponification reaction in the oxide compound of described organic sulfur phosphonic, basic metal and/or alkaline-earth metal, water, alkyl salicylate and mineral acid and/or aryl carboxylic acid promotor, described solvent can add when step (1) is reacted, and also can add when step (2) is reacted.Described solvent steams and removes after saponification reaction completes.
Preferably thinning oil is added in described saponification reaction or after saponification reaction.Described thinning oil is 100 DEG C of kinematic viscosity is 2-10mm
2one or more in API I, II, III, IV and V class lubrication base of/s, preferred API I, II, III class base oil, most preferably API I, II class base oil.The add-on of described thinning oil is the 10-150% of organic sulfur phosphonic and alkyl salicylate quality sum, preferred 20-120%, most preferably 50-100%.When successively there is saponification reaction in the oxide compound of described organic sulfur phosphonic, basic metal and/or alkaline-earth metal, water, alkyl salicylate and mineral acid and/or aryl carboxylic acid promotor, described thinning oil can add when step (1) is reacted, and also can add when step (2) is reacted.
Present invention also offers the lubricating oil composition comprising above-mentioned purification agent.Lubricating oil composition of the present invention comprises lubricating base oil and this purification agent, and wherein this purification agent accounts for the 0.1-10% of lubricating oil composition total mass, preferred 0.3-8%, most preferably 0.5-5%.Wherein said lubricating base oil be selected from API I, II, III, IV, V class lubricating base oil one or more, preferred API I, II, III class base oil, most preferably API I, II class base oil.Lubricating oil composition of the present invention can also add the additive of other kind, as dispersion agent, oxidation inhibitor, viscosity index improver, anti-wear agent, pour point depressant, kilfoam etc.
Low alkali value purification agent of the present invention and the lubricating oil composition comprising this purification agent have excellent detergent-dispersant performance, oxidation-resistance and thermostability.
Embodiment
Further describe the present invention below by example, but the present invention is not limited to this.
Unless stated otherwise, the per-cent below mentioned is mass percent.
The raw material used and source:
Alkyl salicylate, company of Lanzhou Lu Borun additive company of CNPC produces, industrial goods, and its acid number is 72mgKOH/g, and molecular weight is 345, and wherein the content of alkyl salicylate is 44.4%;
The high-activity polyisobutene of number-average molecular weight 1000,2300, CNPC's Jilin Chemical Industry Company is produced;
T109, middle basicity alkyl calcium salicylate, base number; 165mgKOH/g, Lanzhou Lu Borun additive company of CNPC produces;
T108, sulfur phosphorization polyisobutylene titanate salt, base number; 135mgKOH/g, Lanzhou Lu Borun additive company of CNPC produces;
Thinning oil, 150SN, 100 DEG C of kinematic viscosities are 5.66mm
2/ s, Dalian Petrochemical Industry Company produces.
The preparation of organic sulfur phosphonic A
In the there-necked flask being provided with electric stirring, add the polyisobutene 1000 grams that number-average molecular weight is 1000, add P
2s
5168 grams, be warmed up to 210 DEG C gradually from room temperature, heat-up rate is 30 DEG C/h, and 210 DEG C of isothermal reactions 12 hours, now material gradually became brown from colourless, passes into 8.5 grams of water vapors and reacts, and carry out aftertreatment.The sulphur content of the polyisobutene phosphine sulfide acid obtained is 5.2%, and phosphorus content is 2.2%, is designated as organic sulfur phosphonic A.
The preparation of organic sulfur phosphonic B
In the there-necked flask being provided with electric stirring, add the polyisobutene 1000 grams of number-average molecular weight 2300, add P
2s
5158 grams, be warmed up to 225 DEG C gradually from room temperature, heat-up rate is 30 DEG C/h, and 225 DEG C of constant temperature 12 hours, now material gradually became brown from colourless, passes into 8 grams of water vapors and reacts, and carry out aftertreatment.The sulphur content of the polyisobutene phosphine sulfide acid obtained is 4.9%, and phosphorus content is 1.8%, is designated as organic sulfur phosphonic B.
Embodiment 1
The mol ratio of raw material organic sulfur phosphonic A and alkyl salicylate is 1:1.5 in embodiment 1, and the mode adopting raw material once to add carries out saponification reaction.
Organic sulfur phosphonic A60 gram of (molecular weight=1112 are added in the 500ml there-necked flask being provided with temperature control system and electric stirring, 0.054mol) with alkyl salicylate 62.72 grams (0.081mol), add 120ml No. 200 industrial napthas again, stir 5 minutes, then 9.9 grams of calcium oxide (0.177mol) are added, add 5 grams of water (0.278mol), 2.2 gram of 98% vitriol oil, then 95 DEG C of reactions 6.5 hours are warmed up to, now material becomes brown liquid, 105 grams of thinning oils are added after reaction, then water is steamed, material is cooled to 50 DEG C, at rotating speed be 2000rpm whizzer on centrifugal 30 minutes, distill after removing slag, obtain low alkali value purification agent Ga-1, its base number is 68.1mgKOH/g, sulphur content is 1.15%, phosphorus content is 0.52%.
Embodiment 2
The mol ratio of raw material organic sulfur phosphonic A and alkyl salicylate is 1:1.5 in example 2, and the mode adopting raw material secondary to add carries out saponification reaction.
In the 500ml there-necked flask being provided with temperature control system and electric stirring, (molecular weight is 1112 to add organic sulfur phosphonic A60 gram, 0.054mol), add 100ml No. 200 industrial napthas again, stir 5 minutes, then add 5 grams of calcium oxide (0.089mol), add 3 grams of water (0.17mol), stir 25 minutes, be warmed up to 95 DEG C of reactions 3 hours, now material becomes brown liquid.Then add alkyl salicylate 62.72 grams (0.081mol) and react 15 minutes, then 4.9 grams of calcium oxide (0.088mol) are added, 2 grams of water (0.111mol), 2.2 gram of 98% vitriol oil, 105 grams of thinning oils, controlling temperature of reaction is 95 DEG C of reactions 3.5 hours, then water is steamed, material is cooled to 50 DEG C, at rotating speed be 2000rpm whizzer on centrifugal 30 minutes, distill after removing slag, obtain low alkali value purification agent Ga-2, its base number is 75.2mgKOH/g, sulphur content is 1.23%, and phosphorus content is 0.52%.
Embodiment 3
The mol ratio of raw material organic sulfur phosphonic B and alkyl salicylate is 1:2.3 in embodiment 3, and the mode adopting raw material once to add carries out saponification reaction.
Organic sulfur phosphonic B80 gram of (molecular weight=2341 are added in the 500ml there-necked flask being provided with temperature control system and electric stirring, 0.034mol), alkyl salicylate 61 grams (0.079mol), add 150ml No. 200 industrial napthas again, stir 5 minutes, then add 8.2 grams of calcium oxide (0.146mol), add 3.6 grams of water (0.2mol), 2.5 grams of phenylformic acid, be then warmed up to 93 DEG C of reactions 5.5 hours, now material becomes brown liquid.Add 115 grams of thinning oils after reaction, then steam water, material is cooled to 50 DEG C, at rotating speed be 2000rpm whizzer on centrifugal 30 minutes, except distillation after removing slag, obtain low alkali value purification agent Ga-3, its base number is 55.2mgKOH/g, and sulphur content is 1.42%, and phosphorus content is 0.44%.
Embodiment 4
The mol ratio of raw material organic sulfur phosphonic B and alkyl salicylate is 1:2.3 in example 4, and the mode adopting raw material secondary to add carries out saponification reaction.
Organic sulfur phosphonic B 80 grams of (molecular weight=2341 are added in the 500ml there-necked flask being provided with temperature control system and electric stirring, 0.034mol), add 150ml No. 200 industrial napthas again, stir 5 minutes, then add 4.3 grams of calcium oxide (0.077mol), add 1.8 grams of water (0.1mol), stir 15 minutes, be warmed up to 93 DEG C of reactions 3 hours, now material becomes brown liquid.Then add alkyl salicylate 61 grams (0.079mol) and react 20 minutes, then 3.9 grams of calcium oxide (0.070mol) are added, 2 grams of water (0.1mol), 2.5 grams of phenylformic acid, controlling temperature of reaction is 96 DEG C of reactions 2.5 hours, 115 grams of thinning oils are added after reaction, then water is steamed, material is cooled to 50 DEG C, at rotating speed be 2000rpm medical centrifuge on centrifugal 30 minutes, except distillation after removing slag, obtain low alkali value purification agent Ga-4, its base number is 60.7_mgKOH/g, and sulphur content is 1.43%, and phosphorus content is 0.45%.
Embodiment 5
Be 2.04:1 in the mol ratio of embodiment 5 Raw organic sulfur phosphonic A and alkyl salicylate, the mode adopting raw material secondary to add carries out saponification reaction.
Organic sulfur phosphonic A 105 grams of (molecular weight=1112 are added in the 500ml there-necked flask being provided with temperature control system and electric stirring, 0.094mol), add 120ml No. 120 industrial napthas again, stir 5 minutes, then 5.4 grams of magnesium oxide (0.135mol), 3.2 grams of water (0.178mol) are added, stir 30 minutes, be warmed up to 96 DEG C of reactions 3 hours, now material becomes brown liquid.Then add alkyl salicylate 36 grams (0.046mol) and react 15 minutes, add 1.8 grams of magnesium oxide (0.045mol), 1.6 grams of water (0.089mol), 2.2 grams of phthalic acids, controlling temperature of reaction is 95 DEG C, react 2.5 hours, add 115 grams of thinning oils after reaction, then steam water, material is cooled to 50 DEG C, at rotating speed be 2000rpm whizzer on centrifugal 30 minutes, distill after removing slag, obtain low alkali value purification agent Mg-1, its base number is 70.9mgKOH/g, sulphur content is 1.88%, and phosphorus content is 0.78%.
Embodiment 6
Be 1.6:1 in the mol ratio of embodiment 6 Raw organic sulfur phosphonic A and alkyl salicylate, the mode adopting raw material secondary to add carries out saponification reaction.
Organic sulfur phosphonic A100 gram of (molecular weight=1112 are added in the 500ml there-necked flask being provided with temperature control system and electric stirring, 0.090mol), add 100ml octane again, stir 5 minutes, then add 8.2 grams of calcium oxide (0.146mol), add 3.6 grams of water (0.2mol), stir 30 minutes, be warmed up to 98 DEG C of reactions 3 hours, now material becomes brown liquid.Then add alkyl salicylate 42.74 grams (0.055mol) and react 15 minutes, then 2.6 grams of calcium oxide (0.046) are added, 2 grams of water (0.111), 2.0 gram of 98% vitriol oil, controlling temperature of reaction is 96 DEG C of reactions 2.6 hours, 95 grams of thinning oils are added after reaction, then water is steamed, material is cooled to 50 DEG C, at rotating speed be 2000rpm whizzer on centrifugal 30 minutes, slagging-off after distillation, obtain low alkali value purification agent Ga-5, its base number is 81.4mgKOH/g, and sulphur content is 1.98%, and phosphorus content is 0.82%.
Comparative example 1
Comparative example 1 does not adopt promotor, and other reaction conditions is with embodiment 1.
Organic sulfur phosphonic A60 gram of (molecular weight=1112 are added in the 500ml there-necked flask being provided with temperature control system and electric stirring, 0.054mol) with alkyl salicylate 62.72 grams (0.082mol), add 120ml No. 200 industrial napthas again, stir 5 minutes, then 9.9 grams of calcium oxide (0.177mol) are added, add 5 grams of water (0.278mol), then 95 DEG C of reactions 6.5 hours are warmed up to, now material becomes brown liquid, 105 grams of thinning oils are added after reaction, then water is steamed, material is cooled to 50 DEG C, at rotating speed be 2000rpm whizzer on centrifugal 30 minutes, distill after removing slag, obtain low alkali value purification agent DGa-1, its base number is 48.3mgKOH/g, sulphur content is 1.13%, phosphorus content is 0.51%.
Comparative example 2
Comparative example 2 adopts methyl alcohol as promotor, and other reaction conditions is with embodiment 1.
Organic sulfur phosphonic A60 gram of (molecular weight=1112 are added in the 500ml there-necked flask being provided with temperature control system and electric stirring, 0.054mol) with alkyl salicylate 62.72 grams (0.082mol), add 120ml No. 200 industrial napthas again, stir 5 minutes, then 9.9 grams of calcium oxide (0.177mol) are added, add 5 grams of water (0.278mol), 10ml methyl alcohol, then 95 DEG C of reactions 6.5 hours are warmed up to, now material becomes brown liquid, 105 grams of thinning oils are added after reaction, then water is steamed, material is cooled to 50 DEG C, at rotating speed be 2000rpm whizzer on centrifugal 30 minutes, distill after removing slag, obtain low alkali value purification agent DGa-2, its base number is 53.2mgKOH/g, sulphur content is 1.13%, phosphorus content is 0.51%.
Comparative example 3
Comparative example 3 adopts methyl alcohol as promotor, and other reaction conditions is with embodiment 2.
Organic sulfur phosphonic A60 gram of (molecular weight=1112 are added in the 500ml there-necked flask being provided with temperature control system and electric stirring, 0.054mol), add 100ml200 industrial naptha again, stir 5 minutes, then add 5 grams of calcium oxide (0.089mol), add 3 grams of water (0.167mol), stir 20 minutes, be warmed up to 95 DEG C of reactions 3 hours, now material becomes brown liquid.Then add alkyl salicylate 62.72 grams (0.082mol) and react 15 minutes, then 4.9 grams of calcium oxide (0.077mol) are added, 2 grams of water (0.111mol), 10ml methyl alcohol, 105 grams of thinning oils, control temperature is 95 DEG C of reactions 3.5 hours, then water is steamed, material is cooled to 50 DEG C, at rotating speed be 2000rpm whizzer on centrifugal 30 minutes, slagging-off distillation, obtain low alkali value purification agent DGa-3, its base number is 62.3mgKOH/g, sulphur content is 1.15%, and phosphorus content is 0.52%.
Comparative example 4
Comparative example 4 adopts methyl alcohol as promotor, and other reaction conditions is with embodiment 3.
Organic sulfur phosphonic B80 gram of (molecular weight=2341 are added in the 500ml there-necked flask being provided with temperature control system and electric stirring, 0.034mol), alkyl salicylate 61 grams (0.078mol), add 150ml No. 200 industrial napthas again, stir 5 minutes, then add 8.2 grams of calcium oxide (0.146mol), add 3.6 grams of water (0.2mol), 10ml methyl alcohol, be then warmed up to 93 DEG C of reactions 5.5 hours, now material becomes brown liquid.Add 115 grams of thinning oils after reaction, then steam water, material is cooled to 50 DEG C, at rotating speed be 2000rpm whizzer on centrifugal 30 minutes, except distillation after removing slag, obtain low alkali value purification agent DGa-4, its base number is 45.3mgKOH/g, and sulphur content is 1.41%, and phosphorus content is 0.42%.
Comparative example 5
Comparative example 5 adopts methyl alcohol as promotor, and other reaction conditions is with embodiment 4.
Organic sulfur phosphonic B80 gram of (molecular weight=2341 are added in the 500ml there-necked flask being provided with temperature control system and electric stirring, 0.034mol), add 150ml No. 200 industrial napthas again, stir 5 minutes, then add 4.3 grams of calcium oxide (0.077mol), add 1.8 grams of water (0.1mol), stir 15 minutes, be warmed up to 95 DEG C of reactions 3 hours, now material becomes brown liquid.Then add alkyl salicylate 61 grams (0.078mol) and react 20 minutes, then 3.9 grams of calcium oxide (0.070mol) are added, 2 grams of water (0.11mol), 5ml methyl alcohol, controlling temperature of reaction is 96 DEG C of reactions 2.5 hours, 115 grams of thinning oils are added after reaction, then water is steamed, material is cooled to 50 DEG C, at rotating speed be 2000rpm whizzer on centrifugal 30 minutes, except distillation after removing slag, obtain low alkali value purification agent DGa-5, its base number is 51.9mgKOH/g, and sulphur content is 1.42%, and phosphorus content is 0.45%.
Comparative example 6
Comparative example 6 adopts methyl alcohol as promotor, and other reaction conditions is with embodiment 5.
Organic sulfur phosphonic A105 gram of (molecular weight=1112 are added in the 500ml there-necked flask being provided with temperature control system and electric stirring, 0.094mol), add 120ml No. 120 industrial napthas again, stir 5 minutes, then 5.4 grams of magnesium oxide (0.135mol), 3.2 grams of water (0.178mol) are added, stir 30 minutes, be warmed up to 96 DEG C of reactions 3 hours, now material becomes brown liquid.Then add alkyl salicylate 36 grams (0.046mol) and react 15 minutes, then 1.8 grams of magnesium oxide (0.045mol) are added, 1.6 grams of water (0.089mol), 5ml gram of methyl alcohol, controlling temperature of reaction is 95 DEG C, react 2.5 hours, add 115 grams of thinning oils after reaction, then steam water, material is cooled to 50 DEG C, at rotating speed be 2000rpm whizzer on centrifugal 30 minutes, distill after removing slag, obtain low alkali value purification agent DMg-1, its base number is 59.7mgKOH/g, sulphur content is 1.88%, and phosphorus content is 0.76%.
The heat stability test of embodiment and comparative example purification agent
The method of evaluation purification agent thermostability is DSC test, and this test is carried out on TA 5000 DSC 2910 thermal analyzer, test conditions: heat-up rate is 100 DEG C/min, constant temperature 60min.Thermostability DSC test is carried out to the purification agent of embodiment 1-6 and comparative example 1-6.Evaluation result is in table 1.
As can be seen from table 1 result, the heat decomposition temperature of embodiment purification agent is higher than the heat decomposition temperature of the comparative example purification agent of correspondence, and, the heat decomposition temperature of embodiment 2, embodiment 4, all higher than the heat decomposition temperature of embodiment 1,3, illustrates that two steps in the present invention add the thermostability of purification agent prepared by raw material better.
Table 1 heat stability test result
| Embodiment | Purification agent | DSC heat decomposition temperature/DEG C | Comparative example | Purification agent | DSC heat decomposition temperature/DEG C |
| 1 | Ca-1 | 256 | 1 | DCa-1 | 245 |
| 2 | Ca-2 | 261 | 2 | DCa-2 | 247 |
| 3 | Ca-3 | 259 | 3 | DCa-3 | 251 |
| 4 | Ca-4 | 263 | 4 | DCa-4 | 251 |
| 5 | Mg-1 | 258 | 5 | DCa-5 | 255 |
| 6 | Ca-5 | 260 | 6 | DMg-1 | 249 |
The embodiment 7-12 of lubricating oil composition and comparative example 7-14
By 150SN, 500SN, 150BS by 14: 5:1 mass ratio be modulated into lubricating base oil, respectively by the purification agent in embodiment 1-6 and the purification agent in comparative example 1-6 and contrast commercial purification agent T109, T108 with 2% add-on add in above-mentioned lubricating base oil, allotment obtains embodiment 7-12 and the comparative example 7-14 of lubricating oil composition.
The embodiment of these lubricating oil compositions and comparative example are carried out to the qualification test of high temperature detergency, anti-oxidative stability, dispersing property.Evaluation result is in table 2.
The method of evaluation high temperature detergency is lacquering and QZX experiment, and this test is carried out on L-1 plate-type coking device or L-A type detergency tester.L-1 plate-type coking device oil droplet speed be 1.0ml/min, coke test condition is: plate temperature/oil temperature=320 DEG C/100 DEG C, time 2 h, stop/ETAD expected time of arrival and departure=45 second/15 seconds, lacquering test conditions is: plate temperature/oil temperature=300 DEG C/150 DEG C, time 2 h, carries out continuously.The oil droplet speed of L-A type detergency tester is 1.0ml/min, plate temperature/oil temperature=300 DEG C/100 DEG C, 1 hour time, stop/ETAD expected time of arrival and departure=40 second/20 seconds.
The method of evaluation anti-oxidative stability is PDSC test, and this test carries out on TA 5000 DSC 2910 thermal analyzer, test conditions: heat-up rate is 100 DEG C/min, constant temperature 60min, 3.5MPa.
The method of evaluation dispersing property be by massfraction be the black dispersion of 2.5% in lubricating oil, after high-speed stirring, at 50 DEG C of constant temperature 18h, oil dripping, measure the diameter of greasy filth circle and scraper ring, both calculating ratio, the larger expression dispersiveness of its value is better.
As can be seen from Table 2, the coking of the lubricating oil composition of embodiment 7-11, lacquering value are all less than coking, the lacquering value of corresponding comparative example 7-12, and oxidation induction period is longer than the oxidation induction period of corresponding comparative example, dispersion value is greater than corresponding comparative example, illustrates that low alkali value purification agent of the present invention has good high temperature detergency, anti-oxidative stability, dispersiveness, thermostability.In addition, compared with 8 by embodiment 7, embodiment 9 compares discovery with 10, coking, the lacquering value of the lubricating oil composition of the purification agent adopting two step feed way to prepare reduce further, oxidation induction period extends further, dispersion value improves a little, employing two step charging technology is described, the product of preparation is the better lubricating oil additive of performance.
The high temperature detergency of table 2 lubricating oil, PDSC test, distributed test result
Claims (13)
1. a low alkali value purification agent, its preparation method comprises: the oxide compound of organic sulfur phosphonic, basic metal and/or alkaline-earth metal, water, alkyl salicylate and mineral acid and/or aryl carboxylic acid promotor saponification reaction are occurred simultaneously, collects product;
The structure of described organic sulfur phosphonic is:
Wherein R
1for the alkyl of number-average molecular weight between 500-5000; X is O atom or S atom, and wherein at least one X is S atom;
The structure of described alkyl salicylate is:
Wherein R
2for C4-C20 alkyl;
Described mineral acid promotor be selected from sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid one or more; Described aryl carboxylic acid promotor comprises aryl monoprotic acid and/or aryl diprotic acid, and described aryl is phenyl and/or naphthyl;
Mol ratio between described organic sulfur phosphonic and alkyl salicylate is 1:10-10:1; Mol ratio between the oxide compound of described organic sulfur phosphonic and described basic metal and/or alkaline-earth metal is 1:0.2-1:10; The oxide compound of described basic metal and/or alkaline-earth metal and the mol ratio of water are 1:0.5-1:10;
Described mineral acid and/or aryl carboxylic acid promotor account for the 0.1-10% of organic sulfur phosphonic and alkyl salicylate quality sum.
2. a low alkali value purification agent, its preparation method comprises: the oxide compound of organic sulfur phosphonic, basic metal and/or alkaline-earth metal, water, alkyl salicylate and mineral acid and/or aryl carboxylic acid promotor successively saponification reaction are occurred, collects product;
The structure of described organic sulfur phosphonic is:
Wherein R
1for the alkyl of number-average molecular weight between 500-5000; X is O atom or S atom, and wherein at least one X is S atom;
The structure of described alkyl salicylate is:
Wherein R
2for C4-C20 alkyl;
Described mineral acid promotor be selected from sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid one or more; Described aryl carboxylic acid promotor comprises aryl monoprotic acid and/or aryl diprotic acid, and described aryl is phenyl and/or naphthyl;
It is carry out according to the following steps that the oxide compound of described organic sulfur phosphonic, basic metal and/or alkaline-earth metal, water, alkyl salicylate and mineral acid and/or aryl carboxylic acid promotor successively saponification reaction occur:
1) by oxide compound, the water generation saponification reaction of organic sulfur phosphonic and basic metal and/or alkaline-earth metal; Mol ratio between the oxide compound of described organic sulfur phosphonic and described basic metal and/or alkaline-earth metal is 1:0.2-1:5; The oxide compound of described basic metal and/or alkaline-earth metal and the mol ratio of water are 1:0.5-1:10;
2) by step (1) product and alkylated salicylamide acid-respons, then add the oxide compound of basic metal and/or alkaline-earth metal, water, mineral acid and/or aryl carboxylic acid promotor and further saponification reaction occurs, collect product; Mol ratio described in described alkyl salicylate and step (1) between organic sulfur phosphonic is 1:10-10:1; Mol ratio between the oxide compound of basic metal and/or alkaline-earth metal described in described alkyl salicylate and step (2) is between 1:0.2-1:2; The mol ratio of the oxide compound of basic metal and/or alkaline-earth metal described in step (2) and the middle water of step (2) is 1:0.5-1:10; Described in step (2), mineral acid and/or aryl carboxylic acid promotor account for the 0.1-10% of organic sulfur phosphonic and alkyl salicylate quality sum.
3., according to the purification agent described in claim 1 or 2, it is characterized in that, described basic metal and/or the oxide compound of alkaline-earth metal be selected from calcium oxide, magnesium oxide, strontium oxide and barium oxide one or more.
4. according to the purification agent described in claim 1 or 2, it is characterized in that, described aryl carboxylic acid promotor selects phenylformic acid, naphthoic acid, phthalic acid, m-phthalic acid, terephthalic acid, adjacent naphthalic acid, a naphthalic acid and to one or more in naphthalic acid.
5. according to purification agent according to claim 1, it is characterized in that, the temperature of described reaction is 20 ~ 200 DEG C, and the time of described reaction is 1-20h.
6. according to purification agent according to claim 2, it is characterized in that, described in step (1), the temperature of saponification reaction is 20 ~ 200 DEG C, and the time of saponification reaction is 1-20h.
7. according to purification agent according to claim 2, it is characterized in that, in step (2), the temperature of step (1) product and alkylated salicylamide acid-respons is 20-200 DEG C, and the time of reaction is 5-50 minute.
8. according to purification agent according to claim 2, it is characterized in that, described in step (2), the temperature of saponification reaction is 20-200 DEG C, and the reaction times is 1-10 hour.
9. according to the purification agent described in claim 1 or 2, it is characterized in that, add solvent in described saponification reaction, described solvent is the varsol of boiling range between 80-200 DEG C, and the add-on of described solvent is the 30-250% of organic sulfur phosphonic quality.
10. according to the purification agent described in claim 1 or 2, it is characterized in that, in described saponification reaction or after saponification reaction, preferably add thinning oil, described thinning oil is 100 DEG C of kinematic viscosity is 2-10mm
2one or more in APII, II, III, IV and V class lubrication base of/s, the add-on of described thinning oil is the 10-150% of organic sulfur phosphonic and alkyl salicylate quality sum.
The preparation method of 11. 1 kinds of low alkali value purification agents, comprising: the oxide compound of organic sulfur phosphonic, basic metal and/or alkaline-earth metal, water, alkyl salicylate and mineral acid and/or aryl carboxylic acid promotor saponification reaction are occurred simultaneously, collects product;
The structure of described organic sulfur phosphonic is:
Wherein R
1for the alkyl of number-average molecular weight between 500-5000; X is O atom or S atom, and wherein at least one X is S atom;
The structure of described alkyl salicylate is:
Wherein R
2for C4-C20 alkyl;
Described mineral acid promotor be selected from sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid one or more; Described aryl carboxylic acid promotor comprises aryl monoprotic acid and/or aryl diprotic acid, and described aryl is phenyl and/or naphthyl;
Mol ratio between described organic sulfur phosphonic and alkyl salicylate is 1:10-10:1; Mol ratio between the oxide compound of described organic sulfur phosphonic and described basic metal and/or alkaline-earth metal is 1:0.2-1:10; The oxide compound of described basic metal and/or alkaline-earth metal and the mol ratio of water are 1:0.5-1:10;
Described mineral acid and/or aryl carboxylic acid promotor account for the 0.1-10% of organic sulfur phosphonic and alkyl salicylate quality sum.
The preparation method of 12. 1 kinds of low alkali value purification agents, comprising: the oxide compound of organic sulfur phosphonic, basic metal and/or alkaline-earth metal, water, alkyl salicylate and mineral acid and/or aryl carboxylic acid promotor successively saponification reaction are occurred, collects product;
The structure of described organic sulfur phosphonic is:
Wherein R
1for the alkyl of number-average molecular weight between 500-5000; X is O atom or S atom, and wherein at least one X is S atom;
The structure of described alkyl salicylate is:
Wherein R
2for C4-C20 alkyl;
Described mineral acid promotor be selected from sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid one or more; Described aryl carboxylic acid promotor comprises aryl monoprotic acid and/or aryl diprotic acid, and described aryl is phenyl and/or naphthyl;
It is carry out according to the following steps that the oxide compound of described organic sulfur phosphonic, basic metal and/or alkaline-earth metal, water, alkyl salicylate and mineral acid and/or aryl carboxylic acid promotor successively saponification reaction occur:
1) by oxide compound, the water generation saponification reaction of organic sulfur phosphonic and basic metal and/or alkaline-earth metal; Mol ratio between the oxide compound of described organic sulfur phosphonic and described basic metal and/or alkaline-earth metal is 1:0.2-1:5; The oxide compound of described basic metal and/or alkaline-earth metal and the mol ratio of water are 1:0.5-1:10;
2) by step (1) product and alkylated salicylamide acid-respons, then add the oxide compound of basic metal and/or alkaline-earth metal, water, mineral acid and/or aryl carboxylic acid promotor and further saponification reaction occurs, collect product; Mol ratio described in described alkyl salicylate and step (1) between organic sulfur phosphonic is 1:10-10:1; Mol ratio between the oxide compound of basic metal and/or alkaline-earth metal described in described alkyl salicylate and step (2) is between 1:0.2-1:2; The mol ratio of the oxide compound of basic metal and/or alkaline-earth metal described in step (2) and the middle water of step (2) is 1:0.5-1:10; Described in step (2), mineral acid and/or aryl carboxylic acid promotor account for the 0.1-10% of organic sulfur phosphonic and alkyl salicylate quality sum.
13. 1 kinds of lubricating oil compositions, the purification agent one of to comprise in lubricating base oil and claim 1-10, wherein this purification agent accounts for the 0.1-10% of lubricating oil composition total mass, described lubricating base oil be selected from APII, II, III, IV, V class lubricating base oil one or more.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2496100A1 (en) * | 2004-03-10 | 2005-09-10 | Afton Chemical Corporation | Power transmission fluids with enhanced extreme pressure characteristics |
| CN102066391A (en) * | 2008-06-27 | 2011-05-18 | 科聚亚公司 | Phosphite stabilizer for lubricating base stocks and thermoplastic polymers |
| CN102071085A (en) * | 2009-11-19 | 2011-05-25 | 中国石油化工股份有限公司 | High-base number metal detergent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2496100A1 (en) * | 2004-03-10 | 2005-09-10 | Afton Chemical Corporation | Power transmission fluids with enhanced extreme pressure characteristics |
| CN102066391A (en) * | 2008-06-27 | 2011-05-18 | 科聚亚公司 | Phosphite stabilizer for lubricating base stocks and thermoplastic polymers |
| CN102071085A (en) * | 2009-11-19 | 2011-05-25 | 中国石油化工股份有限公司 | High-base number metal detergent and preparation method thereof |
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