CN1216974C - Preparation method of antioxidation antifriction lubricating oil additive - Google Patents
Preparation method of antioxidation antifriction lubricating oil additive Download PDFInfo
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- CN1216974C CN1216974C CN 03121155 CN03121155A CN1216974C CN 1216974 C CN1216974 C CN 1216974C CN 03121155 CN03121155 CN 03121155 CN 03121155 A CN03121155 A CN 03121155A CN 1216974 C CN1216974 C CN 1216974C
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Abstract
The present invention provides a making method of an oxidation-resistant and wear-resistant additive, which comprises: a shielding phenol reacts with 2-mercapto-5-alkylthio 1, 3, 4 thiadiazole in the presence of formaldehyde and an acid catalyst in a condensation mode at 40 to 150DEG C so as to obtain the sulfurous phenol oxidation-resistant and wear-resistant additive; the products contains the compound in the structure disclosed in the specification, wherein R1 is C4 to C16 alkyls. The oxidation-resistant and wear-resistant additive can obviously enhance the oxidation stability and the wear resistance of oil products, and does not have free chlorine, corrosiveness or ash. The oxidation-resistant and wear-resistant additive is suitable for industrial lubricating oil and internal combustion engine oil.
Description
Technical field
The present invention relates to a kind of preparation process lubricant oil additive of sulfur-bearing shielding phenol structure.
Technical background
Should be able to satisfy service requirements as lubricating oil product, need lubricate when mechanical means is moved usually so that reduce friction.During use, lubricating oil product is subjected to factor affecting deterioration by oxidation such as oxygen and metal catalytic effect in envrionment temperature, the air, generate alcohols, ester class, ketone, these low-molecular-weight small molecules of acid compounds, further generate high molecular weight polymers, form settling, cause oil viscosity rising lubricity variation through polycondensation, wearing and tearing increase, even understand the heavy corrosion mechanical means, and reduce the function of lubricating oil greatly, shorten the work-ing life of oil product.Therefore, the oil oxidation stability is a particularly important index of oil property, almost concerning lubricating oil product, all must be added with antioxidant component.Because in the free-radical oxidn process, free radical (R. or ROO.) and superoxide (ROOH) are the two class important activity particles that quicken the oil ageing reaction, the effect of oxidation inhibitor is promptly being eliminated free radical or hydroperoxide decomposition, make it loss of activity or be converted into nonactive particle, thereby reach the oxidising process that inhibition slows down oil product, significantly improve the oil product purpose in work-ing life.Also meet the environmental requirement of present strictness.According to oil ageing mechanism, oil product oxidation inhibitor commonly used has, and radical chain terminator is as, phenol, amine type compound.Peroxide decomposer as, sulfide, contain sulfur phosphorus compound.At present, dialkyl group thiophosphoric acid (ZDDP) oxidation inhibitor that uses in the I. C. engine oil is that a kind of multipurpose additive has outstanding antioxidant effect and outstanding abrasion resistance.But because environmental requirement, oil product is tending towards low ash, low phosphatization, and this agent consumption is restricted, and influenced by this, and oil oxidation stability and oil product abrasion resistance can not guarantee.
In order to guarantee that oil oxidation stability and resistance to abrasion have enough assurances, new compound substitutes or active development of the alternative ZDDP research work of part.The sulfur-bearing shield phenol type antioxidant is the very outstanding oxidation inhibitor of a class result of use.US.6096695 (applicant Ethyl.Co.) discloses sulfur-bearing phenol type antioxidant preparation technology, the preparation of this compound is by mixed phenol (Ethyl4733) and elementary sulfur, having in the presence of solvent and the alkali formula promotor, 85-100 ℃ of reaction forms, this compound sulphur content 10.4w%, liquid under the room temperature, in the low-phosphorous prescription of 5w/30,, evaluate by program IIIE engine pedestal with the 1.0w% consumption.Viscosity increased by 17% in 64 hours.The rotten test-results 1a of ASDM-130 copper level shows the copper corrosion influence very little.
US.4,225,450 (applicant Ciba.Corp.) disclose a kind of alkyl and have replaced chloromethylation phenol and the reaction of alkyl dithiocar-bamate, obtain a kind of polysulfide shielding phenol oxidation inhibitor, and antioxidant effect and wear-resistant effect are preferably arranged.
US.6,100,406 (applicant Ciba.Corp.) disclose the synthetic method of a kind of antioxygen and wear preventive additive, by 3,5-di-t-butyl 4-hydroxy phenyl propionyl chloride and 2, two propyl alcohol sulfo-1,3, the 4 thiadiazoles reactions of 5-, obtain containing shielding phenol thiophene dithiazole derivative, its antioxygen and anti-wear effect are outstanding, can obviously improve the oil product polishing machine.
US 5,414, wear-resistant/antioxidant additive synthetic method that 90 (applicant Texaco.Inc) openly introduce a kind of oil product, be by 2,5-dimercapto 1,3,4 thiadiazoles, a kind of epoxy compounds, formaldehyde and 4, the reaction of 4-isopropylidene diphenol obtains product.Has obvious result of use through ROBT oxidation test and four-ball wear test proof.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of novel sulfurized shielding phenol antioxygen wear preventive additive.
The preparation method of antioxygen wear preventive additive provided by the invention comprises: make shielding phenol and 2-sulfydryl-5-alkylthio 1,3,4 thiadiazoles in the presence of formaldehyde and acid catalyst, carry out condensation reaction at 40-150 ℃, obtain sulfur-bearing shielding phenol antioxygen wear preventive additive, wherein alkyl is C
4-C
16Alkyl, preferred C
6-C
14Alkyl.
Specifically, will shield phenol, formaldehyde, 2-sulfydryl-5-alkylthio 1,3,4 thiadiazoles and acid catalysts, join in the reaction flask, reaction flask is equipped with and stirs and condenser, and stirring heating is warming up to 40-150 ℃, preferably 80-120 ℃, reacted preferred 4-8 hour 2-10 hour.After reaction finishes, neutralization, extracting, washing separates, and distillation obtains product.Wherein, shielding phenol, aldehyde and 2-sulfydryl-5-alkylthio 1,3,4 thiadiazoles react according to chemical dose, but react completely the preferably suitable excessive 30-50% of aldehyde for making.
Said shielding phenol is 2,6-di-tert-butylphenol or contain 2, and the mixing shielding phenol of 6-di-tert-butylphenol, other shielding phenol in the mixed phenol can be 2-tert-butyl phenol, 4-tert-butyl phenol etc.Mainly contain 2-(3,5-di-t-butyl 4-hydroxybenzyl) sulfo--5-alkyl dithio 1,3,4 thiadiazoles, i.e. structure shown in (I) formula in the product that the present invention obtains; If raw material is a mixed phenol, also can contain a small amount of 2-(3-tertiary butyl-4-hydroxy benzyl) sulfo--5-alkyl dithio 1,3,4 thiadiazoles in the product, and/or 2-(3-tertiary butyl 6-hydroxybenzyl) sulfo--5-alkyl dithio 1,3,4 thiadiazoles.
Said reaction reagent formaldehyde can be Paraformaldehyde 96.
Said acid catalyst is organic acid or mineral acid, for example sulfuric acid, tosic acid etc., and preferred tosic acid, its consumption is the 0.1-0.5% of 2-sulfydryl-5-alkylthio 1,3,4 thiadiazoles weight.
Said 2-sulfydryl-5-alkyl dithio 1,3,4 thiadiazoles can be made by oneself according to ordinary method, that is, and and with 2,5 dimercaptos, 1,3,4 thiadiazoles and C
4-C
16Alkyl sulfhydryl, preferred C
6-C
14Alkyl sulfhydryl joins in the organic solvent, drips hydrogen peroxide down at 30-50 ℃, rises to reflux temperature after dripping, and reacts after 1-5 hour, and extracting separates, and washing obtains the thick liquid product, is 2-sulfydryl-5-alkyl dithio 1,3,4 thiadiazoles.Said organic solvent can be methyl alcohol, ethanol, Virahol etc., preferred alcohol.Wherein 2,5 dimercaptos, 1,3,4 thiadiazoles can be the commercial goods, also can be according to known ordinary method self-control; The structural formula of 2-sulfydryl-5-alkyl dithio 1,3,4 thiadiazoles is:
Product of the present invention is used in the lubricating oil with the 0.1-2% mass percent, can significantly improve oil oxidation stability and resistance to abrasion, and this product do not have free chlorine, non-corrosiveness, ashless, is particularly suitable for using in industrial lubricant and I. C. engine oil.This product is liquid, is easy to dissolving, with other functional additives, and as oxidation inhibitor such as amine, phenols, ZDDP, alkenyl succinic acid or half ester rust-preventive agent, Ashless butyl diimide dispersant, sulfonate or alkylthio phenates purification agent have compatibility preferably.
Embodiment
The preparation of embodiment 1:2-sulfydryl-uncle's 5-dodecyl dithio 1,3,4 thiadiazoles
According to ordinary method, preparation 2,5 dimercaptos 1,3,4 thiadiazoles (DMTD).Add 12 gram sodium hydroxide in 100 milliliters there-necked flask, 20 gram water and 15 grams, 50% hydrazine hydrate stir and make dissolution of sodium hydroxide, add 28.5 gram dithiocarbonic anhydride, be heated to 46 ℃, holding temperature reaction 1.5 hours, after be warming up to 80 ℃, reacted 2 hours, obtain 64.5 gram yellow-green solns, this solution is moved as in 500 milliliters of there-necked flasks, add 48 milliliters of hcl acidifyings, produce white solid, be DMTD.
In DMTD, add 30 gram uncle lauryl mercaptans, 100 milliliters of ethanol, drip 20 gram hydrogen peroxide down at 40 ℃, drip the back temperature in 1 hour and rise to reflux temperature, reacted 2 hours, add the industrial naptha extracting, change 250 milliliters of separating funnel static layering over to, divide the sub-cloud water to add 50 ml waters, wash three times to neutrality, carry out normal, underpressure distillation removal solvent, obtain 49 gram thick liquid products, be 2-sulfydryl-uncle's 5-dodecyl dithio 1,3,4 thiadiazoles, sulphur content 35.5%, theoretical sulphur content are 36.7%.
The preparation of embodiment 2:2-sulfydryl-5-n-octyl dithio-1,3,4 thiadiazoles
Method with reference to embodiment 1, use uncle's lauryl mercaptan in the example 1 instead n-octyl mercaptan, preparation 2-sulfydryl-5-n-octyl dithio-1,3,4 thiadiazoles, obtain 41 gram thickness liquid products, be 2-sulfydryl-5-n-octyl dithio-1,3,4 thiadiazoles, its sulphur content 42.8%, theoretical sulphur content 43.2%.
The preparation of embodiment 3:2-(3, the 5-di-tert-butyl-4-hydroxyl benzyl) sulfo--uncle's 5-dodecyl dithio 1,3,4 thiadiazoles
Take by weighing 24.7 gram (0.12mol) 2, the 6-di-tert-butylphenol, 4.2 gram (0.14mol) Paraformaldehyde 96,42.2 gram (0.12mol) example 1 product and 0.3 gram tosic acid, add successively respectively in three mouthfuls of reaction flasks of 250ml, reaction flask is equipped with and stirs and condenser, and stirring heating is warming up to 110 ℃, reacts 6 hours, after reaction finishes, add 10 milliliter of 10% sodium bicarbonate aqueous solution neutralization, add 60ml industrial naptha and 50ml water extractive reaction product again, shift the extractive reaction product then to the 500ml separating funnel, each with the washing of 50m1 water, static layering, branch vibration layer repeats secondary washing and is neutral up to water layer.The solution that washing is good changes in the 250ml matrass, often carries out, and petrolic solvent is removed in underpressure distillation, obtains the amber thickness liquid product of 66.3 grams.The product sulfur content 21.81%, theoretical value 22.53%.
Embodiment 4:2-(3, the 5-di-tert-butyl-4-hydroxyl benzyl) sulfo--5-n-octyl dithio 1,3,4 thiadiazoles preparation
Take by weighing 24.8 gram (0.12mol) 2, the 6-di-tert-butylphenol, 3.6 gram (0.12mol) Paraformaldehyde 96,35.5 gram (0.12mol) example 2 products and 0.3 gram tosic acid, add successively respectively in three mouthfuls of reaction flasks of 250ml, reaction flask is equipped with and stirs and condenser, and stirring heating is warming up to 120 ℃, reacts 5 hours, after reaction finishes, add 10 milliliter of 10% sodium bicarbonate aqueous solution neutralization, add 60ml industrial naptha and 50ml water extractive reaction product again, shift the extractive reaction product then to the 500ml separating funnel, each with the washing of 50ml water, static layering, branch vibration layer repeats secondary washing and is neutral up to water layer.The solution that washing is good changes in the 250ml matrass, often carries out, and petrolic solvent is removed in underpressure distillation, obtains the amber thickness liquid product of 58.6 grams.Product yield 95%, sulphur content 23.81%, theoretical value 24.90%.
Embodiment 5: the lubricating oil oxidation stability evaluation
Adopt rotating bomb oxidation test assessment method (SH/T0193), measure synthetic this test method of sulfur-bearing shielding phenol oxidation inhibitor effect, 150 ℃ of test temperatures, the copper wire catalyzer, sample 50 grams also add 5ml water.The oxygen initial pressure is measured oil oxidation inductive phase, and the test-results time is long more, illustrates that the oxidation inhibitor antioxidant effect is good more.The synthetic specimen test the results are shown in Table 1.
Table 1 synthetic sample antioxidant property result
| Sample | Add dosage % | Oxidation induction period (min) |
| The HVIS150SN of Dalian Petrochemical Industry Company | - | 25 |
| HVIS150SN+ example 3 | 0.5 | 241 |
| HVIS150SN+ example 4 | 0.5 | 286 |
| HVIS150SN+L-115 * | 0.5 | 173 |
| HVIS150SN+L-118 ** | 0.5 | 166 |
*For Ciba.Co. sulfur-bearing shielding phenol (chemical structure is:
)
*For Ciba.Co. sulfur-bearing shielding phenol (chemical structure is:
)
Table 1 result shows that the synthetic sample can obviously improve the oxidation stability of oil product, and its antioxidant effect is significantly better than the Ciba.Co. sample.
Embodiment 6:TFOUT (engine oil film olivetoric acid) ASTM-4742
Adopt TFOUT test evaluation method, the antioxidant effect of evaluation in gasoline engine oil, these test sample 1.5 grams, 160 ℃ of test temperatures are used special catalyzer, 0.03 gram water, the complex loop alkyl salt of 0.06 gram, the nitrated fuel of 0.06 gram oxidation.The oxidation induction period of test determination oil sample, its test-results and MS program IIID testing of engine have good corresponding relationship.Synthetic sample adds in the 10w/30 turbine oil prescription with 0.5% dosage, ZDDP consumption 1.2% in the prescription, total dose 7.7%.Test-results sees Table 2.
Table 2 synthetic sample antioxidant property result
| Sample | Add dosage % | Oxidation induction period (min) |
| Test oil * | - | 78 |
| HVIS150SN+ example 3 | 0.5 | 159 |
| HVIS150SN+ example 4 | 0.5 | 162 |
| HVIS150SN+L-115 * | 0.5 | 82 |
*ZDDP consumption 1.2% in the test oil
Table 2 result shows that oil oxidation obviously improves inductive phase, and its result is better than external sample.
Embodiment 7: the lubricating oil Bearing Capacity Evaluation
Measure according to the GB/T3142 method.The supporting capacity of lubricating oil is evaluated in employing on four-ball extreme pressure tester, comprise last non seizure load P
B, sintering load P
D, three indexs of integrated abrasion value ZMZ.The synthetic sample test-results sees Table 3.
Table 3 synthetic sample abrasion resistance test-results
| Sample | Add dosage % | P B，Kg | P D，Kg | ZMZ，Kg |
| The HVIS150SN of Dalian Petrochemical Industry Company | - | 45 | 160 | 28.27 |
| HVIS150SN+ example 3 | 1 | 70 | 200 | 37.32 |
| HVIS150SN+ example 4 | 1 | 80 | 200 | 36.89 |
| HVIS150SN+L-115 * | 1 | 45 | 160 | 26.97 |
Table 3 is the result show, synthetic sample removes has tangible antioxidant effect effect, and abrasion resistance also has performance preferably.
Claims (9)
1. the preparation method of antioxygen wear preventive additive provided by the invention comprises: make shielding phenol and 2-sulfydryl-5-alkylthio 1,3,4 thiadiazoles in the presence of formaldehyde and acid catalyst, carry out condensation reaction at 40-150 ℃, obtain sulfur-bearing shielding phenol antioxygen wear preventive additive, wherein, the acid catalyst consumption is the 0.1-0.5% of thiadiazoles weight, and the alkyl in the thiadiazoles is C
4-C
16Alkyl.
2. according to the described preparation method of claim 1, it is characterized in that alkyl is C
6-C
14Alkyl.
3. according to the described preparation method of claim 1, it is characterized in that, contain the compound of following structure in the product, wherein R
1Be C
4-C
16Alkyl:
4. according to the described preparation method of claim 1, it is characterized in that temperature of reaction is 80-120 ℃.
5. according to the described preparation method of claim 1, it is characterized in that the reaction times is 2-10 hour.
6. according to the described preparation method of claim 5, it is characterized in that the reaction times is 4-8 hour.
7. according to the described preparation method of claim 1, it is characterized in that said shielding phenol is 2, the 6-di-tert-butylphenol, or contain 2, the mixing shielding phenol of 6-di-tert-butylphenol.
8. according to the described preparation method of claim 1, it is characterized in that said acid catalyst is organic acid or mineral acid.
9. according to claim 1 or 8 described preparation methods, it is characterized in that said acid catalyst is sulfuric acid or tosic acid.
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