A kind of alkyl salicylate as additive of lubricant oil
The present invention relates to a kind of alkyl salicylate as additive of lubricant oil, especially relate to the alkyl salicylate as additive of lubricant oil that a kind of compatibility performance improves and antioxidant capacity improves, belong to the lubricating oil field.
Along with the fast development of automotive industry, more and more higher specification of quality has been proposed lubricating oil additive.With multiple metal detergent compound and the allotment recombiner oneself become the main flow of lubricating oil additive Application Areas.
Usually, if do not influence each other between each additive component, just play a role independently, then the various performances of recombiner should be the mean value of this kind performance of component additive by the concentration weighting.But in fact have different interactions between each additive component and produce synergy or antagonistic action each other, sometimes even produce co-precipitation.Composite precipitation is the most extreme a kind of form of antagonistic action performance.
Alkylsalicylate and sulfonate are the main additive in the detergent for lubricating oil.Their compound uses will produce co-precipitation under certain condition.For improving the consistency of alkylsalicylate and sulfonate: forefathers carried out some research reports.The Heldeweg of Ying He Shell Co. Ltd, Rudolf, Frank etc. vulcanize the salicylate product, product after the sulfuration have the consistency improved (EP 168,880,168,110), but do not report that Acid Thiosalicylique salt and sulfonate have or not sedimentary problem after compound.Also there is the synthesis technique of people's p-sulfonic acid salt to carry out improvement, it is reported and improved its use properties, but also do not see the test of itself and salicylate convergent improvement effect.
Alkylsalicylate and sulfonate composite precipitation problem find early in China, and origin are for a long time own.The existence of this problem make lubricant oil metal detergent in recombiner development and in using difficulty bigger, it has also limited sulfonate and alkylsalicylate promoting the use of at home.This problem is since finding, oneself carried out a large amount of basic research work forefathers.Zhou Xiangzhai etc. once write articles and thought that co-precipitation partly was the material based on carbonate and tensio-active agent, used ashless dispersant can make it to spread out again and may not influence the use properties of product.In experiment,, also improved the consistency of salicylate really with sulfonate by calling in a certain amount of ashless dispersant.But still have the co-precipitation material, experiment does not fundamentally solve the problem of compound co-precipitation.
Purpose of the present invention will provide a kind of alkyl salicylate as additive of lubricant oil exactly, alkyl salicylate additive of the present invention has fabulous compatibility performance, thereby can solve the problem of alkylsalicylate and sulfonate composite precipitation effectively, and this additive performance is suitable with the salicylate performance that does not add tensio-active agent.
The object of the present invention is achieved like this: after designing one group of tensio-active agent and alkyl salicylate mixing, produce salicylate by the processing method of producing alkylsalicylate, the consistency of investigating itself and sulfonate then is co-precipitation quantity (percentage ratio).
Alkyl salicylate additive preparation method of the present invention is as follows: with boiling range is that 80~130 ℃ straight-run spirit and methyl alcohol joins in the reactor, mixes to stir and heats up; After temperature rises to 40~60 ℃, add calcium oxide, add metering water then, slaking 10-15 minute.After slaking reaction was finished, alkyl salicylate that adding mixes in advance and specific tensio-active agent carried out neutralization reaction 1 hour; Feed carbonic acid gas then, high basicity reaction 90 minutes.After reaction finishes, be warming up to 105 ℃, steam dehydration, methyl alcohol, add the gasoline dilution, centrifugal, steam desolventizing at last and get product.
The present invention relates to the alkyl salicylate as additive of lubricant oil that a kind of compatibility performance has improved.Add some tensio-active agent in its preparation process, as sulfonic acid, alkenyl succinic acid ester.Synthetic alkyl sodium salicylates such as polyisobutene-maleic anhydride can suppress sedimentary generation to a certain extent significantly after compound with sulfonate; By adjusting consumption, use the alkenyl succinic acid ester can solve the problem of salicylate with the sulfonate composite precipitation.
A kind of alkyl salicylate as additive of lubricant oil is characterized in that this additive prepares with following method: the solvent of metering and methyl alcohol are dropped into to heat up in the reactor be stirred to 40~60 ℃, add calcium oxide; Added water cure 10~15 minutes, and then alkyl salicylate and tensio-active agent were joined in the reactor together, neutralization reaction 1 hour fed carbonic acid gas 90 minutes then, reaction is warming up to 105 ℃ after finishing, and steams dehydration, methyl alcohol, the solubilizing agent dilution is centrifugal, removes slag, and steams desolventizing and gets product.It is characterized in that said tensio-active agent can be an alkyl benzene sulphonate (ABS), alkylbenzene sulfonate, dodecenylsuccinic acid ester or polyisobutene-maleic anhydride or polyisobutene succinimide.It is characterized in that described dodecenylsuccinic acid ester molecule formula is:
Wherein, R is the laurylene base, and R ' can be C
8~15Alkyl, preferably C
10~12Straight chained alkyl.The add-on that it is characterized in that described tensio-active agent can be 5.0~20.0% (m/m), is preferably within 10~15% (m/m).It is characterized in that adding the alkylsalicylate of the above dodecenylsuccinic acid ester of 7% (m/m).
Advantage of the present invention and effect can be seen by the following examples, but those skilled in the art should be understood that, the following examples just further specify of the present invention, rather than the restriction scope of the invention, any change that does not exceed spirit and scope of the invention, all within the scope of the present invention.
Embodiment 1, in the 500ml there-necked flask that installs electronic stirring and condensation water trap, drop into the straight-run spirit 150ml of 80~130 ℃ of boiling ranges, industrial methanol 95ml, stirring is warming up to 50~55 ℃, adds calcium oxide 10.0g (purity 95%m/m), stirs 15 minutes, the warm water 6.0ml that slowly adds 70 ℃ then carried out slaking reaction 10~15 minutes.After reaction is finished, (acid number is 66.2mgKOH/g to add the alkyl salicylate that mixes, contain 90%) and dodecenylsuccinic acid ester (half ester, containing 10%) mixture 100.0g is in reactor, carried out neutralization reaction about 60 minutes, and fed carbonic acid gas with 150ml/min speed then and carry out the about 90min of metallization reaction.After reaction finishes, add the dilution of 100ml gasoline, centrifugal removing slag under 3000 rev/mins of rotating speeds steamed desolventizing then and got product.The product calcium contents is 5.31%, and base number is 150mgKOH/g.
Embodiment 2, press the operation of embodiment 1, are the tensio-active agent synthesis of alkyl salicylate that tensio-active agent alkenyl succinic acid ester is changed consumption or change other into, and its character sees Table I.(tensio-active agent drops into percentage amounts by adding total amount of surfactant).
Table I synthesis of alkyl salicylate character
Sequence number | Calcium contents (%) | Base number (mgKOH/g) | Remarks |
Examination-1 | ????5.31 | ?????150 | Add the alkenyl succinic acid ester, 7% |
Examination-2 | ????5.93 | ?????169 | Add the alkenyl succinic acid ester, 14% |
Examination-3 | ????5.32 | ?????150 | Add the alkenyl succinic acid ester, 5% |
Examination-4 | ????5.50 | ?????153 | Add the alkenyl succinic acid ester, 3% |
Examination-5 | ????5.60 | ?????156 | Add alkyl benzene sulphonate (ABS) 10% (TAN=113.0mgKOH/g) |
Examination-6 | ????5.30 | ?????148 | Add low basicity calcium sulphonate, 10% |
Examination-7 | ????5.23 | ?????143 | Add polyisobutene dicarboxylic anhydride (MW=1320), 10% |
Examination-8 | ????5.22 | ?????141 | Add single polyisobutene horse imide, 10% hung |
Embodiment 3, in the 100ml beaker, accurately take by weighing each 2.5 ± 0.1g of alkyl salicylate and sulfonate, add 45.0g 300SN base oil.Stir-concoction is 15 minutes under 80 ℃ of temperature, oil solution is poured into be with (its least reading is 0.01ml, capacity 50ml) in the graduated taper sedimentation pipe.One group in storage at normal temperature, and one group places 100 ℃ of storages of high temperature in the baking oven, record period of storage and the relation that generates the sediment amount.The results are shown in Table II.
In the Table II, T-109 is that alkyl sodium salicylate is produced in blue refining, and Ca% is 6.0, and base number is 160mgKOH/g; HE-600 is U.S.'s ethyl corporation sulfonate, and Ca%12.11, base number are 293.7mgKOH/g; On-202C is that factory of shanghai refinery produces sulfonate, and Ca%o 11.17, and base number is 282.0mgKOH/g.
From the Table II test-results as can be seen: the synthetic salicylate is followed successively by from small to large with sulfonate co-precipitation amount:
Examination-1, examination-2<examination-6<examination 7, examination-8<examination-5<examination-4<examination-3<T-109.
That is to say, in salicylate salt process, add a certain amount of other tensio-active agents and all can reduce the co-precipitation amount to a certain extent, that is to say, can slow down antagonistic effect therebetween to a certain extent.Particularly when dodecenylsuccinic acid ester addition greater than 7.0% the time, no co-precipitation generates, and has solved salicylate with the sulfonate sedimentary problem that coexists.
Under the identical condition of addition, during equal 10% (m/m), can improve salicylate and be followed successively by: dodecenylsuccinic acid ester (half ester)>low alkali value calcium sulphonate>polyisobutylene butanedioic anhydride or polyisobutene succinimide (the single extension)>alkyl benzene sulphonate (ABS) with the tensio-active agent of sulfonate coexistence precipitation or antagonistic effect.
Salicylate performance and T-109 performance that compatibility performance has improved relatively see Table III.As can be seen, the resistance of oxidation of adding tensio-active agent synthetic products such as alkenyl succinic acid ester, polyisobutene maleic anhydride and Phenylsulfonic acid is greatly improved from Table III; Dispersiveness has some improvement, and more with product dispersing property raising after adding polyisobutene-maleic anhydride tensio-active agent, and lacquering plate performance also has certain improvement or suitable.
Table II alkylsalicylate and sulfonate composite testing result
Alkylsalicylate | Overbased sulfonate | Shelf test (sinkability, %) |
Normal temperature, 30d | ?100℃,24h | ?100℃,48h | ?100℃,4d | ?100℃,7d |
?T-109 | ?HE-611 | ??0.00 | ????0.22 | ????0.44 | ????0.60 | ????0.80 |
On-202C | ??0.00 | ????0.10 | ????0.24 | ????0.48 | ????0.48 |
Examination-1 | ?HE-811 | ??0.00 | ????0.00 | ????0.00 | ????0.00 | ????0.00 |
On-202C | ??0.00 | ????0.00 | ????0.00 | ????0.00 | ????0.00 |
Examination-2 | ?HE-811 | ??0.00 | ????0.00 | ????0.00 | ????0.00 | ????0.00 |
On-202C | ??0.00 | ????0.00 | ????0.00 | ????0.00 | ????0.00 |
Examination-3 | ?HE-611 | ??0.00 | ????0.00 | ????0.00 | ????0.06 | ????0.08 |
On-202C | ??0.00 | ????0.00 | ????0.06 | ????0.10 | ????0.10 |
Examination-4 | ?HE-611 | ??0.00 | ????0.00 | ????0.16 | ????0.36 | ????0.36 |
On-202C | ??0.00 | ????0.00 | ????0.18 | ????0.30 | ????0.30 |
Examination-5 | ?HE-611 | ??0.00 | ????0.60 | ????0.30 | ????0.30 | ????0.30 |
On-202C | ??0.00 | ????0.00 | ????0.06 | ????0.16 | ????0.16 |
Examination-6 | ?HE-611 | ??0.00 | ????0.00 | ????0.02 | ????0.02 | ????0.02 |
On-202C | ??0.00 | ????0.00 | ????0.04 | ????0.06 | ????0.06 |
Examination-7 | ?HE-611 | ??0.00 | ????0.02 | ????0.06 | ????0.06 | ????0.06 |
On-202C | ??0.00 | ????0.02 | ????0.04 | ????0.12 | ????0.12 |
Examination-8 | ?HE-611 | ??0.00 | ????0.02 | ????0.04 | ????0.04 | ????0.06 |
On-202C | ??0.00 | ????0.04 | ????0.06 | ????0.12 | ????0.12 |
The salicylate that the Table III compatibility performance has improved with the T-109 performance relatively
Annotate: base oil: 300ZN, additive add-on 2% (m/m); PW-1 bench testing oil product total dose is 5.5%, contains bigcatkin willow hydrochlorate 1.5% (m/m); The SDT distributed test is 1.0g agent+9.0g.Greasy filth+10.0g base oil drips and puts on the filter paper, calculates greasy filth loop diameter and scraper ring diameter ratio.