CN104560283B - Sulfonate, preparation method thereof, lubricating grease containing sulfonate and preparation method of lubricating grease - Google Patents
Sulfonate, preparation method thereof, lubricating grease containing sulfonate and preparation method of lubricating grease Download PDFInfo
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Abstract
The invention provides sulfonate, a preparation method thereof, lubricating grease containing the sulfonate and a preparation method of the lubricating grease. The sulfonate has the structure as shown in the specification, wherein M1, M2 and M3 are respectively a single metal or a mixed metal in alkaline metals or alkaline earth metals; n1, n2 and n3 are respectively valences of M1, M2 and M3; x, y and z are respectively an integer ranging from 1 to 4; R1, R2 and R3 are respectively an alkyl; the sum of carbon number in the R1 alkyl and x is 8-28; the sum of carbon number in the R2 alkyl and y is 7-27; the sum of carbon number in the R3 alkyl and z is 9-29; R4 and R5 are respectively C5-C30 alkyls; e, q, r, u and d are respectively an integer ranging from 1 to 20000; t is an integer ranging from 0 to 20000; and OCP is abbreviated from an ethylene-propylene copolymer. The sulfonate obtained by the invention is high in alkaline value and is particularly suitable for preparing the lubricating grease. When the lubricating grease is prepared, amorphous carbonate is completely converted into crystallized carbonate, the conversion time is relatively short, and the lubricating grease containing the converted sulfonate has excellent high-temperature resistance, water resistance, colloidal stability and wear resistance.
Description
Technical field
The present invention relates to a kind of sulfonate, more particularly to a kind of over base sulfosalt suitable for grease.
Background technology
Complex calcium sulfonate grease is the new grease of a class, with excellent extreme pressure property, abrasion resistance, water resistant
Performance, resistance to saltfog energy and Corrosion Protection, and dropping point height, heat stability are good, are widely used in automobile, iron and steel, mine, papermaking
Etc. industry.
Complex calcium sulfonate grease adopts newton body sulfoacid calcium for raw material, and non newtonian is converted in the presence of active hydrogen
Body sulfoacid calcium.Calcium Carbonate wherein in newton body sulfoacid calcium is unbodied, and the Calcium Carbonate in complex calcium sulfonate grease
For calcite type, therefore to prepare the process of grease be actually to be converted into the unformed Calcium Carbonate in newton body sulfoacid calcium
Calcite type calcium carbonate, and the process of non-newtonian fluid sulfoacid calcium is ultimately formed, therefore, select suitable newton body sulfoacid calcium very
It is important.
Patent with regard to preparing the calcium sulfonate with high base number and overbased sulfoacid calcium of newton body is very more, such as US4, and 427,
559、US4,604,219、US4,879,053、US4,929,373、US4,810,396、EP0,515,062、EP0,949,322、
US6,015,778, US4,560,489 etc., its preparation method is generally：With alkyl benzene sulphonate or alkyl benzene calcium sulfonate as original
Material, adopts all kinds of low mass molecule alcohols for accelerator, and being passed through carbon dioxide carries out carbonation reaction, and reaction heats up after terminating and is dehydrated, Jing
Post processing obtains calcium sulfonate with high base number.Calcium sulfonate with high base number in above-mentioned patent（Base number is more than 300mgKOH/g）With it is overbased
Sulfoacid calcium（Base number is more than 395mgKOH/g）, it is mainly used in I. C. engine oil and iundustrial oil, plays solubilising, dispersion, neutralization, anti-
The effect such as rust.
Grease sulfoacid calcium requires that the Calcium Carbonate in sulfoacid calcium is unformed, is easy to conversion under certain condition, obtains
Grease has preferable high and low temperature performance, extreme pressure anti-wear, colloidal stability and water-resistance.And the sulphur used in lubricating oil
Sour calcium is required with excellent detergency, dispersibility and acid neutralization performance.Two kinds of products are different for the requirement of sulfoacid calcium,
Therefore, prepare grease with the existing newton body sulfoacid calcium in lubricating oil to there are problems that, for example：Sulfoacid calcium turns
Change speed is slow or changing effect is bad, and the high-temperature behavior and other performance of the grease after conversion can not meet requirement, so
Limit sulfoacid calcium further applying in grease.
The content of the invention
The invention provides a kind of sulfonate, its preparation method and the grease comprising the sulfonate and preparation method thereof.
The structure of sulfonate of the present invention is：
Wherein M1、M2、M3Single metal or hybrid metal respectively in alkali and alkaline earth metal ions, n1、n2、n3Respectively
M1、M2、M3Quantivalence, x, y, z be respectively 1～4 between integer, R1、R2、R3Respectively alkyl, and R1Carbon number in alkyl
It is 8～28, R with x sums2Carbon number in alkyl is 7～27, R with y sums3Carbon number in alkyl is 9～29, R with z sums4、R5
Respectively C5～C30Alkyl, e, q, r, u, d be respectively 1～20000 between integer, t is the integer between 0～20000,
OCP is the abbreviation of ethylene-propylene copolymer molecule.
Described M1、M2、M3Can be with identical, it is also possible to different, the one kind in preferred alkaline-earth metal, most preferably magnesium, calcium and barium
Or it is various；n1、n2、n3Respectively M1、M2、M3Quantivalence, value be 1～2, preferably 2；
Integer of the x, y, z respectively between 1～4, preferably 2 or 3；
R1、R2、R3Respectively alkyl, and R1Carbon number in alkyl is 8～28, R with x sums2Carbon number in alkyl and y sums
For 7～27, R3Carbon number in alkyl is 9～29 with z sums, preferred R1Carbon number in alkyl is 10～18, R with x sums2Alkyl
In carbon number and y sums be 9～17, R3Carbon number in alkyl is 11～19 with z sums；
R4、R5Respectively C5～C30Alkyl, preferred C10～C30Alkyl；
E, q, r, u, d are respectively the integer between 1～20000, the integer preferably between 1～10000；T is 0～20000
Between integer, the integer preferably between 1～10000.
The preparation method of sulfonate of the present invention is：
（1）C10～C30Alhpa olefin and sulfonating agent there is sulfonating reaction and generate C10～C30Sulfonic acid and sultone, then with alkali
There is neutralization reaction in the hydroxide of metal and/or alkaline-earth metal, collect the C for generating10～C30The alkali metal and/or alkali of sulfonic acid
The mixture of earth metal salt and sultone；
（2）By neutral oil, ethylene-propylene copolymer, varsol, C1～C4Alcohol, calcium oxide, water, step（1）Middle C10～C30Sulphur
The mixture and non-essential C of the alkali metal and/or alkali salt and sultone of acid5～C30The alkali metal of alkyl benzene sulphonate
And/or alkali salt mixing, carbon dioxide is passed through, carbonation reaction is carried out under 0.4MPa～2.0MPa pressure, removing alcohol,
Water, varsol and solid residue, obtain sulfonate product.
In step（1）In, the C10～C30The preferred C of alhpa olefin10～C30Straightαolefin, most preferably C12～C20Straight chain alpha
Alkene；
The sulfonating agent is one or more in sulfur trioxide, concentrated sulphuric acid and oleum, preferred sulfur trioxide；
The sulfonating agent and the C10～C30The mol ratio of alhpa olefin be：1.0～1.5：1, preferably 1.05～1.1：1；
The temperature of the sulfonating reaction is 0～60 DEG C, preferably 20～40 DEG C；Response time be 1～10 hour, preferably 1～4
Hour；
Solvent can be added in the sulfonating reaction, such as petroleum ether, benzene, toluene, solvent is preferably added to.
The C10～C30Alhpa olefin and sulfonating agent there is sulfonating reaction and generate C10～C30Sulfonic acid and sultone mixing
Thing, the C10～C30Sulfonic acid include thiazolinyl monosulfonic acid, thiazolinyl disulfonic acid, the C10～C30Sultone include a sultone,
Disultone.
With sulfur trioxide and C18Alhpa olefin occur sulfonating reaction as a example by, the two reaction generate thiazolinyl monosulfonic acid, a sultone and
A small amount of thiazolinyl disulfonic acid, the mixture of disultone.
The example equation formula of the sulfonating reaction is：
In step（1）Described in sulfonating reaction and/or neutralization reaction in can add neutral oil, it is also possible in being added without
Property oil, be preferably added to neutral oil.Preferably 100 DEG C kinematic viscositys of the neutral oil are 2～6mm2The lubricating base oil of/s, most preferably
One or more in 100SN, 150SN, 100N and 150N.
Step（1）Described in neutralization reaction be by C10～C30Sulfonic acid and sultone and alkali metal and/or alkaline-earth metal
There is neutralization reaction in hydroxide, collect the C for generating10～C30The alkali metal and/or alkali salt of sulfonic acid and sultone and
The mixture of the neutral oil being preferably added to.The molal quantity of the hydroxide of the alkali metal and/or alkaline-earth metal is the C10~
C301.2～2 times of alhpa olefin molal quantity, reaction temperature are 50 DEG C～70 DEG C, and the response time is 10～40 minutes.The alkali metal
And/or the hydroxide of alkaline-earth metal can be single hydroxide, or mixed hydroxides, preferred alkaline-earth metal
One or more in hydroxide, most preferably magnesium hydroxide, calcium hydroxide and barium hydroxide.
Step（1）Described in neutralization reaction can also first by C10～C30Sulfonic acid and sultone and alkali-metal hydroxide
C generated and neutralization reaction in thing there is10～C30The alkali metal salt and sultone of sulfonic acid, then there is subdivision with soluble alkaline earth salt
Solution reaction, collects the C for generating10～C30The alkali metal and/or alkali salt of sulfonic acid and sultone and the neutrality being preferably added to
The mixture of oil.The C10～C30Sulfonic acid and sultone and alkali-metal hydroxide there is the condition of neutralization reaction and be：Institute
The molal quantity for stating alkali-metal hydroxide is the C10～C301.2～2 times of alhpa olefin molal quantity, reaction temperature be 50 DEG C～
70 DEG C, the response time is 10～40 minutes.The condition of the metathesis reaction is：The molal quantity of the soluble alkaline earth salt
It is the C10～C300.3～2.0 times of alhpa olefin molal quantity, reaction temperature are 60～90 DEG C, and the response time is 1～4 hour.Institute
State the one kind or many in soluble alkaline earth salt preferably calcium chloride, magnesium chloride, barium chloride, calcium nitrate, magnesium nitrate and barium nitrate
Kind.
Step（1）Described in neutralization reaction complete after preferred pair product carry out washing, filter, it is more pure to obtain
Net C10～C30The mixture of the alkali metal and/or alkali salt of sulfonic acid and sultone and the neutral oil being preferably added to.
In step（2）In, the same step of the neutral oil（1）In the neutral oil that is preferably added to, be 100 DEG C of kinematic viscositys be 2
～6mm2One or more in the lubricating base oil of/s, most preferably 100SN, 150SN, 100N and 150N；
The ethylene-propylene copolymer is the copolymerization product of ethylene and propylene, and optimal ethylene content is 40%～60%（Quality hundred
Fraction）Between ethylene-propylene copolymer, the number-average molecular weight of the ethylene-propylene copolymer preferably exists between 5000～100000
Between 10000～60000.The ethylene-propylene copolymer is dope or solids in room temperature, to make step（2）Reaction be easy to into
OK, preferably ethylene-propylene copolymer is dissolved in neutral oil.The structure of the ethylene-propylene copolymer is：
Wherein a, b are respectively the integer between 0～6000, and wherein at least one is not 0.The structure of the ethylene-propylene copolymer
It is abbreviated as OCP.
The varsol can be alkane, may also be aromatic hydrocarbon, preferred boiling range 60 DEG C～180 DEG C alkane and/or
The one kind or many of aromatic hydrocarbon, most preferably normal octane, benzene,toluene,xylene and boiling range in 60 DEG C～180 DEG C of direct steaming gasoline
Kind；
The C1～C4Alcohol can be from one or more in methanol, ethanol, propanol, butanol and ethylene glycol, preferred methanol
And C3～C4The mixture of alcohol, the methanol and C3～C4The mass ratio of alcohol is 2:1～10:1, preferably 2:1～4:1.In the present invention
In method, the C1～C4Alcohol enables to mass transfer rate in reactant mixture between gas, liquid, solid three-phase faster, oil phase and water
Mix uniformly, make reaction be easy to carry out；
In step（2）In can add C5～C30The alkali metal and/or alkali salt of alkyl benzene sulphonate, it is also possible to be not added with
Enter C5～C30The alkali metal and/or alkali salt of alkyl benzene sulphonate, is preferably added to C5～C30The alkali metal of alkyl benzene sulphonate and/
Or alkali salt.
The C5～C30The structure of the alkali metal and/or alkali salt of alkyl benzene sulphonate is：
Wherein M3For alkali metal and/or alkaline-earth metal, n3For alkali metal and/or the quantivalence of alkaline-earth metal, R4、R5Wherein
One of be C5～C30Alkyl, another be H or both at C5～C30Alkyl, R4、R5It is one of preferably wherein C10～C30
Alkyl, another be H or both at C10～C30Alkyl.
The C5～C30The alkali metal and/or alkali salt of alkyl benzene sulphonate is by C5～C30Alkyl benzene sulphonate and alkali gold
There is neutralization reaction and obtain in the hydroxide of category and/or alkaline-earth metal, its preparation method is that the two is carried out at 70 DEG C～100 DEG C
Neutralization reaction, the water of intensification elimination reaction generation, filtration after reacting 1～3 hour, that is, be obtained C5～C30The alkali gold of alkyl benzene sulphonate
Category and/or alkali salt, are preferably added to neutral oil in here reaction so as to C is obtained5～C30The alkali metal of alkyl benzene sulphonate and/
Or the mixture of alkali salt and neutral oil.
The C5～C30Alkyl benzene sulphonate can select C20～C28Alkyl benzene sulphonate and/or carbon number are C5～C24Height boiling
Thing sulfonic acid, the C20～C28Sulfonic acid can be used by C20～C28There is benzene alkylation reaction, sulphur occur with sulfonating agent again in alhpa olefin
Change the alkyl benzene sulphonate that reaction is obtained, the carbon number is C5～C24High-boiling components sulfonic acid produce detergent alkylate when obtain
By-product high-boiling components sulfonic acid, the carbon number of this high-boiling components sulfonic acid is C5～C24, mainly contain dialkyl benzene sulfonic acids, monoalkyl benzene sulphur
Acid.
When in step（2）Middle addition C5～C30When the alkali metal and/or alkali salt of alkyl benzene sulphonate, the step
（1）Middle C10～C30The mixture and the C of the alkali metal and/or alkali salt and sultone of sulfonic acid5～C30Alkyl benzene sulphonate
Alkali metal and/or alkali salt consumption ratio be 0.3～3：1～3, preferably 0.3～1：1～2.
In step（2）In, with the step（1）Middle C10～C30The alkali metal and/or alkali salt of sulfonic acid and sultone
Mixture and non-essential C5～C30The consumption of the alkali metal and/or alkali salt of alkyl benzene sulphonate is calculated for 100 parts,
The total amount of neutral oil is 50～400 parts, preferably 100～300 parts, including the neutrality that added during dissolving ethylene-propylene copolymer
Oil, preparation C10～C30Neutral oil that the alkali metal and/or alkali salt of sulfonic acid and sultone are preferably added to, prepare C5～C30
The neutral oil being preferably added to when the alkali metal and/or alkali salt of alkyl benzene sulphonate；The consumption of the ethylene-propylene copolymer is
0.5～50 part, preferably 1～10 part；C1～C4The consumption of alcohol is 20～200 parts, preferably 30～100 parts；The consumption of varsol
For 50～1000 parts, preferably 100～500 parts；The consumption of the calcium oxide is 50～400 parts, preferably 50～100 parts；Water
Consumption be 10～150 parts, preferably 10～50 parts.
In step（2）In, the molal quantity for being passed through carbon dioxide for calcium oxide molal quantity 50%～120%, preferably
80%～100%；The temperature of the carbonation reaction is 50 DEG C～200 DEG C, preferably 80 DEG C～180 DEG C；Reaction pressure is 0.4MPa
～2.0MPa, preferred 0.5MPa～1.5MPa.
In step（2）In, the sultone can be hydrolyzed to olefin sulfonic acid and hydroxyl sulfoacid, and give birth to calcium oxide, water reaction
Into alkenyl sulphonate and hydroxy sulfonate, these sulfonate meetings and step（1）Middle C10～C30The alkali metal and/or alkaline earth of sulfonic acid
Slaine and non-essential C5～C30The alkali metal and/or alkali salt of alkyl benzene sulphonate, ethylene-propylene copolymer are coated together
Around Calcium Carbonate.After carbonation reaction terminates, intensification desolvation, solid slag is isolated, obtain the sulfonate of the present invention.
There is the example equation formula of hydrolysis, generation alkenyl sulphonate and hydroxy sulfonate in the sultone：
In step（2）It is middle prepare sulfonate of the present invention example equation formula be：
The grease of the present invention includes the quality of above-mentioned sulfonate and lubricating base oil, the sulfonate and lubricating base oil
Than for 30～70：70～30, preferably 40～60：60～40.Other additives, such as antioxygen can also be added in the grease
Agent, thickening agent, antiwear additive.The lubricating base oil can be from API I, II, III, IV, V class lubricating base oils
Plant or various, one or more in preferred API I, II, Group III lubricating base oil, most preferably 90BS, 120BS, 150BS.
The preparation of greases method is：
Lubricating base oil, sulfonate of the present invention are mixed at 100～150 DEG C, while the carbonic acid in p-sulfonic acid salt
Calcium carries out infrared detection, when its infrared absorption peak is by 863.1cm-1881.5cm is transferred to gradually-1When, it is believed that in sulfonate
The Calcium Carbonate of cladding is gradually converted into calcite type crystal by unformed, and grease product is collected after conversion completely.
Prepared grease product is non-newtonian fluid.
Over base sulfosalt of the prior art, is mainly used in I. C. engine oil and iundustrial oil, play solubilising, dispersion,
Neutralization, antirust etc. are acted on, and can be there are problems that during with its synthetic grease, and such as newton body sulfonate conversion rate is slow or converts
Effect is bad, and after conversion, the properties of grease are good etc..
Sulfonate base number obtained by the present invention is high, is particularly useful for making grease.It is when grease is prepared, amorphous
Carbonate is fully converted to crystal type carbonate, and transformation time is shorter, the sulfonate grease after conversion have excellent high temperature,
Water repelling property, colloidal stability, abrasion resistance.
Specific embodiment
The present invention is further illustrated below by way of example, but is not limited the invention.
Unless stated otherwise, percentage ratio mentioned below is mass percent.
The analysis method for being adopted：
Sulfonic acid composition analysis：1）HP6890 gas chromatograies（Agilent companies）, HP-5 chromatographic columns, fid detector, sample introduction
Temperature：300 DEG C, split ratio 10:1；2）Waters companies liquid chromatograph, C8 silicagel columns, mobile phase are normal octane, and detector is purple
External detector and refractive index detection device 2414.
Olefin(e) centent is analyzed：Nuclear magnetic resonance chemical analyser, model：INOVA500, the sulfonic acid content analysis of Varian companies of the U.S.：
The measure of sulfonic acid content in alkyl benzene sulphonate（RIPP48-90）Product base number is analyzed：SH/T0251 oil product base number algoscopys
（Perchloric acid potentiometric titration）Product viscosity is analyzed：GB/T265 oil product dynamic viscosity algoscopys and dynamic viscosity calculating method.
It is raw materials used：60～90 DEG C of petroleum ether, sulfur trioxide, sodium hydroxide, No. 120 industrial napthas, dimethylbenzene, methanol,
Isopropanol, n-butyl alcohol, isobutanol, distilled water, calcium oxide, carbon dioxide, C18Alhpa olefin, C12～C18Alhpa olefin, high-boiling components sulfonic acid
Calcium, C20～C28Alkyl benzene calcium sulfonate, ethylene-propylene copolymer, 150SN, 150N, 150BS neutral oil.
Embodiment 1C18The preparation of alhpa olefin sulfoacid calcium and sultone
101 grams of C are added in the 1000mL there-necked flasks with stirring and cooling/heating apparatus18Alhpa olefin (molecular weight 252,
0.397mol, purchased from Chevron companies, purity 99%), 100 grams of petroleum ether（60～90 DEG C）, after stirring, form solution, Ran Houtong
Enter 34.94 grams of sulfur trioxide gas sulfonating agents（0.437mol）, now there is sulfonating reaction, heat release is violent, controlling reaction temperature
At 30 DEG C～35 DEG C, now sulfur trioxide and alhpa olefin sulfonating reaction 2 hours, generate thiazolinyl monosulfonic acid, a sultone, thiazolinyl two
The mixture such as sulfonic acid and disultone.
After sulfonating reaction terminates, in sulfonic acid-petroleum ether solution 30% 64 grams of sodium hydroxide solution is added to be neutralized instead
Should, wherein containing sodium hydroxide 0.48mol, reaction temperature is 60 DEG C, react 20 minutes, now olefin sulfonic acid generation olefin sulfonic acid
Sodium, cools to 40 DEG C of dischargings, separates water layer in being put into separatory funnel after reaction, obtain by about 229 grams of lurid oil reservoir, by which
It is transferred in there-necked flasks of the 1000mL with stirring and temperature control, adds 40 grams of 150SN neutral oils, be stirring evenly and then adding into 20%
200 grams of calcium chloride solution, wherein containing calcium chloride 0.36mol, controlling reaction temperature is 70 DEG C, is reacted 2 hours, is steamed after reaction
Distilled water is washed twice, solution layering is stood, water layer is separated, retains oil reservoir, then by oil reservoir distillation abjection petroleum ether, obtains C18
The mixture of α olefin sulfonic acids calcium and sultone and neutral oil amounts to 174.5 grams, and wherein active matter content is 77.1%, active matter
In the calcium salt containing 48% thiazolinyl monosulfonic acid, 49% sultone, the calcium salt of 2% thiazolinyl disulfonic acid and 1% disultone.
Embodiment 2C12～C18The preparation of α olefin sulfonic acids calcium and sultone
100 grams of C are added in the 1000mL there-necked flasks with stirring and cooling/heating apparatus12～C18Alhpa olefin（Average mark
Son amount 224,0.393mol, purchased from Lanzhou Lu Borun additives company, purity 88%）, it is firstly added 90 grams of petroleum ether（90～120
℃）, solution is formed after stirring, 34.58 grams of sulfur trioxide gas sulfonating agents are then passed to（0.432mol）, now sulfonating reaction send out
It is raw, heat release acutely, controlling reaction temperature at 30～35 DEG C, now sulfur trioxide and alhpa olefin sulfonating reaction generate thiazolinyl monosulfonic acid,
The mixture such as one sultone, thiazolinyl disulfonic acid and disultone.
After sulfonating reaction terminates, in sulfonic acid-petroleum ether solution 25% 75 grams of sodium hydroxide solution is added to be neutralized instead
Should, wherein containing sodium hydroxide 0.47mol, reaction temperature is controlled at 60 DEG C, react 10 minutes, now olefin sulfonic acid generation thiazolinyl
Sodium sulfonate, after reaction terminates, separates water layer in being put into separatory funnel, obtains, by about 213 grams of lurid oil reservoir, being transferred into
During 1000mL has the there-necked flask of stirring and temperature control, 39 grams of 150N neutral oils are added, 15% calcium chloride is stirring evenly and then adding into
267 grams of solution, wherein the molal quantity 0.36mol containing calcium chloride, controlling reaction temperature is 70 DEG C, reacts 2 hours, steams after reaction
After distilled water is washed twice, water layer is separated, retain oil reservoir, then by oil reservoir distillation abjection petroleum ether, obtain C12～C18α olefin sulfonic acids
The mixture of calcium and sultone and neutral oil amounts to 174.1 grams, and the content of wherein active matter is 77.6%, is contained in the active matter
There are the calcium salt of 49% thiazolinyl monosulfonic acid, 47% sultone, the calcium salt of 2.6% thiazolinyl disulfonic acid and 1.4% disultone.
Embodiment 3
With high-boiling components sulfoacid calcium, C18Alhpa olefin sulfoacid calcium and sultone prepare calcium sulfonate with high base number for raw material
In 500 milliliters of autoclaves with motor agitators and temperature control facility, 2 grams of ethylene-propylene copolymers are added（Wherein
Ethylene contents 55%, number-average molecular weight are 55238）With 34 grams of the mixture of 32 grams of 150SN neutral oils, No. 120 solvent vapour are added
100 grams of oil（Industrial goods）, add 20 grams of methanol, 5 grams of normal propyl alcohol, 10 grams of distilled water, 37 grams of calcium oxide, high-boiling components sulfoacid calcium with
50 grams of the mixture of 150SN neutral oils（It is prepared with calcium hydroxide and 150SN neutral oils by high-boiling components sulfonic acid, sulfoacid calcium contains
Measure as 61.6%）, the product that embodiment 1 is obtained（Containing olefin sulfonic acid calcium, sultone and neutral oil, active matter content 77.1%）16
Gram, 145 DEG C are warming up to, and are passed through carbon dioxide, and reaction pressure are controlled in 0.9～1.2MPa, when carbon dioxide absorption amount is oxygen
When changing the 92% of calcium molal quantity, stop ventilation, then blood pressure lowering is warmed up to 120 DEG C of dealcoholysis, water.100 millis are added in the material for obtaining
Gasoline is risen, is then placed in medical centrifuge, be centrifuged with rotating speed 4000rpm, the flash distillation thing after centrifugation be put into and set with decompression
In the alembic applied, be warmed up to 120 DEG C of air-distillations first, then carry out vacuum distillation, finally obtain sepia it is sticky 146
Gram sulfonic acid calcium product, the base number=395mgKOH/g of the product, 100 DEG C of dynamic viscosity=201mm2/s。
Embodiment 4
With C20～C28Alkyl benzene calcium sulfonate, C12～C18Alhpa olefin sulfoacid calcium and sultone prepare calcium sulfonate with high base number for raw material
In 500 milliliters of autoclaves with motor agitators and temperature control facility, 2 grams of ethylene-propylene copolymers are added（Wherein
Ethylene contents are 52%, and its number-average molecular weight is 48690）With 28 grams of the mixture of 26 grams of 150N neutral oils, dimethylbenzene 150 is added
Milliliter（Chemistry is pure）, 16 grams of methanol, 8 grams of n-butyl alcohol, 38 grams of calcium oxide, 12 grams of distilled water, C20～C28Alkyl benzene calcium sulfonate is with
Property oil 51 grams of mixture（It is prepared with calcium hydroxide and 150SN neutral oils by alkyl benzene sulphonate, alkyl benzene calcium sulfonate contains
Measure as 61.8%）, the product that embodiment 2 is obtained（C12～C18The mixture of α olefin sulfonic acid calcium, sultone and neutral oil, activity
Thing content 77.6%）In 21 grams of addition autoclaves, be warming up to 146 DEG C, be passed through carbon dioxide, and control reaction pressure 0.9～
1.1MPa, when carbon dioxide absorption amount reaches the 91% of calcium oxide molal quantity, stops ventilation, and then blood pressure lowering is warmed up to 120 DEG C
Dealcoholysis, water.100 milliliters of gasoline are added in the material for obtaining, is then placed in medical centrifuge, be centrifuged with rotating speed 4000rpm, will
Flash distillation thing after centrifugation is put in the alembic with decompression facility, is warmed up to 120 DEG C of air-distillations first, is then entered to system
Row vacuum distillation, finally obtains 147 grams of sticky sulfoacid calciums of sepia, the base number=389mgKOH/g of the product, 100 DEG C of product
Dynamic viscosity=197mm2/s。
Embodiment 5
With high-boiling components sulfoacid calcium, C12～C18Alhpa olefin sulfoacid calcium and sultone prepare calcium sulfonate with high base number for raw material
In 500 milliliters of autoclaves with motor agitators and temperature control facility, 1.8 grams of ethylene-propylene copolymers are added（Its
Middle ethylene contents are 55%, and its number-average molecular weight is 55238）With 31.8 grams of the mixture of 30 grams of 150SN neutral oils, 120 are added
Number 100 grams of industrial naptha（Industrial goods）, add 22 grams of methanol, 8 grams of isobutanol, 10 grams of distilled water, 39 grams of calcium oxide, high-boiling components sulphur
44 grams of the mixture of sour calcium and neutral oil（It is prepared with calcium hydroxide and 150SN neutral oils by high-boiling components sulfonic acid, wherein sulfonic acid
The content of calcium is 61.6%）, 22 grams of the product that embodiment 2 is obtained（C12～C18α olefin sulfonic acid calcium, sultone and neutral oil
Mixture, active matter content 77.6%）, it is added in autoclave, is warming up to 138 DEG C, is passed through carbon dioxide, and controls reactor
Pressure when carbon dioxide absorption amount reaches the 93% of calcium oxide molal quantity, stops ventilation, is then warmed up in 0.9～1.2MPa
120 DEG C of dealcoholysis, water.In the material for obtaining add 100 milliliters of gasoline, be then placed in medical centrifuge, with rotating speed 4000rpm from
The heart, the flash distillation thing after centrifugation is put in the alembic with decompression facility, is warmed up to 120 DEG C of air-distillations, Ran Houjin first
Row vacuum distillation, finally obtains 149 grams of sticky sulfonic acid calcium products of sepia, the base number=391mgKOH/g of the product, 100 DEG C
Dynamic viscosity=199mm2/s。
Embodiment 6 is with C18Alhpa olefin sulfoacid calcium and sultone prepare calcium sulfonate with high base number for raw material
In 500 milliliters of autoclaves with motor agitators and condensing tube, 42 grams of 150SN neutral oils and 2 grams are added
Ethylene-propylene copolymer（Wherein ethylene contents are 55%, and its number-average molecular weight is 55238）44 grams of mixture, add No. 120 solvents
100 grams of gasoline（Industrial goods）, 20 grams of methanol of addition, 5 grams of normal propyl alcohol, 11 grams of distilled water, 40 grams of calcium oxide, what embodiment 1 was obtained
Product（C18The mixture of α olefin sulfonic acid calcium, sultone and neutral oil, active matter content 77.1%）56 grams, add to autoclave
In, 145 DEG C are warming up to, and are passed through carbon dioxide, and reaction pressure are controlled in 0.9～1.2MPa, when carbon dioxide absorption amount is oxygen
When changing the 92% of calcium molal quantity, stop ventilation, then blood pressure lowering is warmed up to 120 DEG C of dealcoholysis, water.100 millis are added in the material for obtaining
Gasoline is risen, is then placed in medical centrifuge, be centrifuged with rotating speed 4000rpm, the flash distillation thing after centrifugation be put into and set with decompression
In the alembic applied, be warmed up to 120 DEG C of air-distillations first, then carry out vacuum distillation, finally obtain sepia it is sticky 138
Gram sulfoacid calcium, the base number=335mgKOH/g of the product, 100 DEG C of dynamic viscosity=187mm of product2/s。
Comparative example 1,2,3 repeats the operation of embodiment 3 respectively, and ethylene-propylene copolymer is added without in comparative example 1, and comparative example 2 exists
After carbonation reaction, ability and ethylene-propylene copolymer mechanical mixture, are added without alhpa olefin sulfoacid calcium and sultone, comparative example 4 in comparative example 3
Calcium sulfonate with high base number is prepared using synthesis under normal pressure.
Comparative example 1 is with high-boiling components sulfoacid calcium, C18Alhpa olefin sulfoacid calcium and sultone prepare calcium sulfonate with high base number for raw material
In 500 milliliters of autoclaves with motor agitators and temperature control facility, 34 grams of 150SN neutral oils are added（In
Petrochemical industry Yanshan Petrochemical company of state produces）, add 100 grams of No. 120 industrial napthas（Industrial goods）, add 20 grams of methanol, normal propyl alcohol 5
Gram, 10 grams of distilled water, 37 grams of calcium oxide, 50 grams of the mixture of high-boiling components sulfoacid calcium and 150SN neutral oils（By high-boiling components sulfonic acid with
Calcium hydroxide and 150SN neutral oils are prepared, and wherein the content of sulfoacid calcium is 61.6%）, the product that embodiment 1 is obtained（Contain
C18α olefin sulfonic acids calcium and sultone and neutral oil, active matter content 77.1%）16 grams, 145 DEG C are warming up to, titanium dioxide is passed through
Carbon, and reaction pressure is controlled in 0.9～1.2MPa, when carbon dioxide absorption amount for calcium oxide molal quantity 92%, stop logical
Then gas, blood pressure lowering are warmed up to 120 DEG C of dealcoholysis, water.100 milliliters of gasoline are added in the material for obtaining, medical centrifuge is then placed in
In, it is centrifuged with rotating speed 4000rpm, the flash distillation thing after centrifugation is put in the alembic with decompression facility, 120 are warmed up to first
DEG C air-distillation, then carries out vacuum distillation, finally obtains 149 grams of sticky sulfonic acid calcium products of sepia, and the base number of the product=
398mgKOH/g, 100 DEG C of dynamic viscosity=167mm2/s。
Comparative example 2
2 grams of ethylene-propylene copolymers are added in product in comparative example 1（Wherein ethylene contents are 55%, and its number-average molecular weight is
55238）, stir 2 hours in 100 DEG C of constant temperature, obtain sticky brown colour additive.
Comparative example 3 prepares calcium sulfonate with high base number as raw material with high-boiling components sulfoacid calcium
In 500 milliliters of autoclaves with motor agitators and temperature control facility, 32 grams of 150SN neutral oils and 2 are added
Gram ethylene-propylene copolymer（Wherein ethylene contents are 55%, and its number-average molecular weight is 55238）34 grams of mixture, add No. 120 it is molten
100 grams of agent gasoline（Industrial goods）, add 20 grams of methanol, 5 grams of normal propyl alcohol, 10 grams of distilled water, 37 grams of calcium oxide, high-boiling components sulfoacid calcium
With 66 grams of the mixture of 150SN neutral oils（It is prepared with calcium hydroxide and 150SN neutral oils by high-boiling components sulfonic acid, wherein sulphur
Sour calcium content is 65.8%）, add and be warming up to 145 DEG C, be passed through carbon dioxide, and to control reaction pressure in 0.9～1.2MPa,
When carbon dioxide absorption amount for calcium oxide molal quantity 92%, stop ventilation, then blood pressure lowering is warmed up to 120 DEG C of dealcoholysis, water.
To material in add 100 milliliters of gasoline, be then placed in medical centrifuge, with rotating speed 4000rpm be centrifuged, by the sudden strain of a muscle after centrifugation
Steam thing to be put in the alembic with decompression facility, be warmed up to 120 DEG C of air-distillations first, then carry out vacuum distillation, finally
Obtain tan 147 grams of sticky additives.Base number=the 391mgKOH/g of product, product viscosity=206mm2/s。
Comparative example 4
With high-boiling components sulfoacid calcium, C18Alhpa olefin sulfoacid calcium and sultone are raw material, and synthesis under normal pressure prepares calcium sulfonate with high base number
In 500 milliliters of there-necked flasks with motor agitators and condensing tube, 32 grams of 150SN neutral oils and 2 are added
Gram ethylene-propylene copolymer（Wherein ethylene contents are 55%, and its number-average molecular weight is 55238）34 grams of mixture, add No. 120 it is molten
100 grams of agent gasoline（Industrial goods）, add 20 grams of methanol, 5 grams of normal propyl alcohol, 2 grams of distilled water, 13 grams of calcium oxide, high-boiling components sulfoacid calcium
With 50 grams of the mixture of neutral oil（It is prepared with calcium hydroxide and 150SN neutral oils by high-boiling components sulfonic acid, sulfonic acid calcium content is
61.6%）, the product that embodiment 1 is obtained（C18The mixture of α olefin sulfonic acid calcium, sultone and neutral oil）16 grams, control after addition
Reaction temperature processed is passed through carbon dioxide at 45 DEG C～50 DEG C, when carbon dioxide absorption rate for calcium oxide molal quantity 90%, plus
Enter 25 grams of calcium oxide, 8 grams of distilled water continue to be passed through carbon dioxide, when carbon dioxide absorption amount is the 92% of calcium oxide molal quantity
When, stopping ventilation, then blood pressure lowering is warmed up to 120 DEG C of dealcoholysis, water.100 milliliters of gasoline are added in the material for obtaining, is then placed in
In medical centrifuge, it is centrifuged with rotating speed 4000rpm, the flash distillation thing after centrifugation is put in the alembic with decompression facility, it is first
120 DEG C of air-distillations are first warmed up to, vacuum distillation is then carried out, 143 grams of sticky sulfoacid calciums of sepia, the product is finally obtained
Base number=362mgKOH/g, 100 DEG C of viscosity=199mm of product2/s。
Using commercially available sulfoacid calcium T107（400TBN calcium sulfonate with high base number）5 sulfonate as a comparison case.
Embodiment 7～11 and the comparative example 6～10 of grease
The sulfonate for being utilized respectively embodiment 3～6 and comparative example 1～5 mixes, prepares the reality of grease with lubricating base oil
Apply example 7～11 and comparative example 6～10.The lubricating base oil for being used is 150BS.
The commercially available sulfoacid calcium used by the sulfonate that synthesizes embodiment 3～6 and comparative example 1～4 respectively, comparative example 5 with
Lubricating base oil mixes at 100～150 DEG C, while the Calcium Carbonate in p-sulfonic acid salt carries out infrared detection, when its infrared absorption peak
By 863.1cm-1881.5cm is transferred to gradually-1When, it is believed that the Calcium Carbonate coated in sulfonate is gradually by unformed conversion
For calcite type crystal, grease product after conversion completely, is collected, obtain the embodiment 7～11 and comparative example 6 of grease product
～10.The sulphur that wherein grease of embodiment 7～10 and comparative example 6～10 is prepared by embodiment 3～6 and comparative example 1～5 respectively
Sour calcium conversion is obtained, and sulfoacid calcium is 42 with lubricating base oil mass ratio:58；The grease of embodiment 11 is prepared by embodiment 3
Sulfoacid calcium conversion is obtained, and sulfoacid calcium is 51 with lubricating base oil mass ratio：49.
Properties test is carried out with comparative example 6～10 to the embodiment 7～11 of grease product respectively, test result is shown in
Table 1.
The assessment of performance of 1 grease product of table
Find out from above example, the transformation time of grease of the present invention is shorter, with preferable high-temperature behavior, water-resistance
Energy, colloidal stability, abrasion resistance.
Claims (17)
1. a kind of sulfonate, its structure is：
Wherein M1、M2、M3Single metal or hybrid metal respectively in alkali and alkaline earth metal ions, n1、n2、n3Respectively M1、
M2、M3Quantivalence, x, y, z be respectively 1～4 between integer, R1、R2、R3Respectively alkyl, and R1Carbon number and x in alkyl
Sum is 8～28, R2Carbon number in alkyl is 7～27, R with y sums3Carbon number in alkyl is 9～29, R with z sums4、R5Point
Wei not C5～C30Alkyl, e, q, r, u, d be respectively the integer between 1～20000, and t is the integer between 0～20000, OCP
It is the abbreviation of ethylene-propylene copolymer molecule.
2. according to the sulfonate described in claim 1, it is characterised in that：Described M1、M2、M3For alkaline-earth metal；n1、n2、n3Take
It is worth for 2；X, y, z is respectively 2 or 3；R1Carbon number in alkyl is 10～18, R with x sums2Carbon number in alkyl and y sums be 9～
17、R3Carbon number in alkyl is 11～19 with z sums；R4、R5Respectively C10～C30Alkyl；E, q, r, u, d, t be respectively 1～
Integer between 10000.
3. a kind of preparation method of sulfonate, including：
(1)C10～C30Alhpa olefin and sulfonating agent there is sulfonating reaction and generate C10～C30Sulfonic acid and sultone, then with alkali metal
And/or the hydroxide of alkaline-earth metal occurs neutralization reaction, the C for generating is collected10～C30The alkali metal of sulfonic acid and/or alkaline earth gold
The mixture of category salt and sultone；The sulfonating agent and the C10～C30The mol ratio of alhpa olefin be：1.0～1.5：1；It is described
The molal quantity of the hydroxide of alkali metal and/or alkaline-earth metal is the C10～C301.2～2 times of alhpa olefin molal quantity；
(2) by neutral oil, ethylene-propylene copolymer, varsol, C1～C4C in alcohol, calcium oxide, water, step (1)10～C30Sulfonic acid
The mixture and non-essential C of alkali metal and/or alkali salt and sultone5～C30The alkali metal of alkyl benzene sulphonate and/
Or alkali salt mixing, be passed through carbon dioxide, carry out carbonation reaction under 0.4MPa～2.0MPa pressure, removing alcohol, water,
Varsol and solid residue, obtain sulfonate product；With C in the step (1)10～C30The alkali metal and/or alkaline earth of sulfonic acid
The mixture and non-essential C of slaine and sultone5～C30The use of the alkali metal and/or alkali salt of alkyl benzene sulphonate
Measure and calculate for 100 mass parts, the total amount of neutral oil is 50～400 parts；The consumption of ethylene-propylene copolymer is 0.5～50 part；C1～C4Alcohol
Consumption be 20～200 parts；The consumption of varsol is 50～1000 parts；The consumption of calcium oxide is 50～400 parts；The consumption of water
For 10～150 parts；The molal quantity for being passed through carbon dioxide for calcium oxide molal quantity 50%～120%；The carbonating is anti-
The temperature answered is 50 DEG C～200 DEG C；Reaction pressure is 0.4MPa～2.0MPa.
4. in accordance with the method for claim 3, it is characterised in that in step (1), the C10～C30Alhpa olefin be C10~
C30Straightαolefin.
5. in accordance with the method for claim 3, it is characterised in that the sulfonating reaction and/or neutralization described in step (1) is anti-
Neutral oil should be added middle.
6. in accordance with the method for claim 3, it is characterised in that in step (1), the temperature of the sulfonating reaction be 0～
60℃；Response time is 1～10 hour.
7. in accordance with the method for claim 3, it is characterised in that described in step (1) in neutralization reaction, reaction temperature is
50 DEG C～70 DEG C, the response time is 10～40 minutes.
8. in accordance with the method for claim 3, it is characterised in that in step (1), the alkali metal and/or alkaline-earth metal
Hydroxide be single hydroxide or mixed hydroxides.
9. in accordance with the method for claim 3, it is characterised in that neutralization reaction described in step (1) is first by C10～C30's
C generated and neutralization reaction with alkali-metal hydroxide in sulfonic acid and sultone there is10～C30The alkali metal salt and sultone of sulfonic acid,
There is metathesis reaction with soluble alkaline earth salt again, collect the C for generating10～C30The alkali metal and/or alkaline-earth metal of sulfonic acid
The mixture of salt and sultone.
10. in accordance with the method for claim 9, it is characterised in that the C10～C30Sulfonic acid and sultone with it is alkali-metal
There is the condition of neutralization reaction in hydroxide：The molal quantity of the alkali-metal hydroxide is the C10～C30Alhpa olefin
1.2～2 times of molal quantity, reaction temperature are 50 DEG C～70 DEG C, and the response time is 10～40 minutes；The bar of the metathesis reaction
Part is：The molal quantity of the soluble alkaline earth salt is the C10～C300.5～2.0 times of alhpa olefin molal quantity, reaction
Temperature is 60～90 DEG C, and the response time is 1～4 hour.
11. in accordance with the method for claim 9, it is characterised in that the soluble alkaline earth salt is selected from calcium chloride, chlorination
One or more in magnesium, barium chloride, calcium nitrate, magnesium nitrate and barium nitrate.
12. in accordance with the method for claim 3, it is characterised in that in step (2), and the neutral oil is that 100 DEG C of motions are viscous
Spend for 2～6mm2The lubricating base oil of/s, the ethylene-propylene copolymer be ethylene contents 40%～60% (mass percent) it
Between ethylene-propylene copolymer, its number-average molecular weight is 5000～100000, and the varsol is alkane and/or aromatic hydrocarbon.
13. in accordance with the method for claim 3, it is characterised in that C is added in step (2)5～C30The alkali of alkyl benzene sulphonate
Metal and/or alkali salt, the C5～C30The structure of the alkali metal and/or alkali salt of alkyl benzene sulphonate is：
Wherein M3For alkali metal and/or alkaline-earth metal, n3For alkali metal and/or the quantivalence of alkaline-earth metal, R4、R5One of them is
C5～C30Alkyl, another be H or both at C5～C30Alkyl.
14. in accordance with the method for claim 13, it is characterised in that in step (2), C in the step (1)10～C30Sulphur
The mixture and the C of the alkali metal and/or alkali salt and sultone of acid5～C30The alkali metal of alkyl benzene sulphonate and/or
The mass ratio of alkali salt is 0.3～3：1～3.
15. according to the method described in one of claim 3-14, it is characterised in that in step (2), the C1～C4Alcohol
For methanol and C3～C4The mixture of alcohol, the methanol and C3～C4The mass ratio of alcohol is 2:1～10:1.
A kind of 16. greases, including one of them described sulfonate of claim 1～2 or according to claim 3～14 wherein
The mass ratio of the sulfonate and lubricating base oil prepared by any claim, the sulfonate and lubricating base oil be 30～
70：70～30.
Preparation of greases method described in 17. claim 16, including：By lubricating base oil, described sulfonate 100～
150 DEG C of mixing, while the Calcium Carbonate in p-sulfonic acid salt carries out infrared detection, when its infrared absorption peak is by 863.1cm-1It is transferred to
881.5cm-1When, the Calcium Carbonate coated in sulfonate is converted into calcite type crystal by unformed, collects grease product.
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| JP6465536B2 (en) * | 2017-02-22 | 2019-02-06 | 株式会社Ｓｏｎｏｄａ | Lubricating oil additive and method for producing lubricating oil additive |
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| CN1872968A (en) * | 2005-05-31 | 2006-12-06 | 中国石油化工股份有限公司 | Compound grease of calcium sulfonic acid, and preparation method |
| EP1749875A1 (en) * | 2005-07-29 | 2007-02-07 | Chevron Oronite S.A. | Overbased alkaline earth metal alkylhydroxybenzoates having low crude sediment |
| CN101318915A (en) * | 2008-06-20 | 2008-12-10 | 辽宁天合精细化工股份有限公司 | Method for preparing high-alkali value (TBN400) synthesized calcium alkyl benzene sulfonate |
| CN102757845A (en) * | 2011-04-28 | 2012-10-31 | 中国石油化工股份有限公司 | Low-noise lithium-based lubricating grease composition and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1872968A (en) * | 2005-05-31 | 2006-12-06 | 中国石油化工股份有限公司 | Compound grease of calcium sulfonic acid, and preparation method |
| EP1749875A1 (en) * | 2005-07-29 | 2007-02-07 | Chevron Oronite S.A. | Overbased alkaline earth metal alkylhydroxybenzoates having low crude sediment |
| CN101318915A (en) * | 2008-06-20 | 2008-12-10 | 辽宁天合精细化工股份有限公司 | Method for preparing high-alkali value (TBN400) synthesized calcium alkyl benzene sulfonate |
| CN102757845A (en) * | 2011-04-28 | 2012-10-31 | 中国石油化工股份有限公司 | Low-noise lithium-based lubricating grease composition and preparation method thereof |
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