CN104560283A - 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, particularly relate to a kind of over base sulfosalt being applicable to lubricating grease.
Background technology
Complex calcium sulfonate grease is the novel lubricating grease of a class, there is excellent extreme pressure property, abrasion resistance, water repelling property, salt fog resistance performance and Corrosion Protection, and dropping point is high, Heat stability is good, is widely used in the industries such as automobile, iron and steel, mine, papermaking.
Complex calcium sulfonate grease all adopts newton's body calcium sulphonate to be raw material, is converted into non-newtonian fluid calcium sulphonate when reactive hydrogen exists.Calcium carbonate wherein in newton's body calcium sulphonate is unbodied, and the calcium carbonate in complex calcium sulfonate grease is calcite type, unformed calcium carbonate in newton's body calcium sulphonate is converted into calcite type calcium carbonate by process in fact exactly that therefore prepare lubricating grease, and the final process forming non-newtonian fluid calcium sulphonate, therefore, select suitable newton's body calcium sulphonate extremely important.
Patent about the calcium sulfonate with high base number and overbased calcium sulphonate of preparing newton's body is very many, 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 (ABS) or alkyl benzene calcium sulfonate for raw material, adopt all kinds of low mass molecule alcohol to be promotor, pass into carbonic acid gas and carry out carbonation reaction, reaction terminates rear intensification dehydration, obtains calcium sulfonate with high base number through aftertreatment.Calcium sulfonate with high base number (base number is greater than 300mgKOH/g) in above-mentioned patent and overbased calcium sulphonate (base number is greater than 395mgKOH/g), be mainly used in I. C. engine oil and technical oils, plays solubilising, dispersion, neutralization, the effect such as antirust.
Lubricating grease calcium sulphonate requires that the calcium carbonate in calcium sulphonate is unformed, and be easy under certain condition transform, the lubricating grease obtained has good high and low temperature performance, extreme pressure anti-wear, colloidal stability and water resisting property.And the calcium sulphonate used in lubricating oil requires to have in excellent detergency, dispersiveness and acid and performance.Two kinds of products are different for the requirement of calcium sulphonate, therefore, prepare lubricating grease for the newton's body calcium sulphonate in lubricating oil can there are some problems with existing, such as: calcium sulphonate conversion rate is slow or changing effect is bad, high-temperature behavior and other performance of lubricating grease after conversion can not meet the demands, and so just limit the further application of calcium sulphonate in lubricating grease.
Over base sulfosalt of the prior art, be mainly used in I. C. engine oil and technical oils, play solubilising, dispersion, neutralization, the effect such as antirust, some problems can be there are with during its synthetic grease, as slow in newton's body sulfonate conversion rate or changing effect is bad, after transforming, the properties of lubricating grease is good etc.
The sulfonate base number that the present invention obtains is high, is particularly useful for making lubricating grease.When preparing lubricating grease, decolorizing carbon hydrochlorate is converted into crystal type carbonate completely, and transformation time is shorter, and the sulfonate lubricating grease after conversion has excellent high temperature, water repelling property, colloidal stability, abrasion resistance.
Summary of the invention
The invention provides a kind of sulfonate, its preparation method and the lubricating grease comprising this sulfonate and preparation method thereof.
The structure of sulfonate of the present invention is:
Wherein M
1, M
2, M
3be respectively the single metal in alkali and alkaline earth metal ions or hybrid metal, n
1, n
2, n
3be respectively M
1, M
2, M
3valency, x, y, z is respectively the integer between 1 ~ 4, R
1, R
2, R
3be respectively alkyl, and R
1carbon number in alkyl and x sum are 8 ~ 28, R
2carbon number in alkyl and y sum are 7 ~ 27, R
3carbon number in alkyl and z sum are 9 ~ 29, R
4, R
5be respectively C
5~ C
30alkyl, e, q, r, u, d are respectively the integer between 1 ~ 20000, and t is the integer between 0 ~ 20000, and OCP is the abbreviation of ethylene-propylene copolymer molecule.
Described M
1, M
2, M
3can be identical, also can be different, preferred bases earth metals, one or more most preferably in magnesium, calcium and barium; n
1, n
2, n
3be respectively M
1, M
2, M
3valency, value is 1 ~ 2, preferably 2;
X, y, z is respectively the integer between 1 ~ 4, and preferably 2 or 3;
R
1, R
2, R
3be respectively alkyl, and R
1carbon number in alkyl and x sum are 8 ~ 28, R
2carbon number in alkyl and y sum are 7 ~ 27, R
3carbon number in alkyl and z sum are 9 ~ 29, preferred R
1carbon number in alkyl and x sum are 10 ~ 18, R
2carbon number in alkyl and y sum are 9 ~ 17, R
3carbon number in alkyl and z sum are 11 ~ 19;
R
4, R
5be respectively C
5~ C
30alkyl, preferred C
10~ C
30alkyl;
E, q, r, u, d are respectively the integer between 1 ~ 20000, the integer preferably between 1 ~ 10000; T is the integer between 0 ~ 20000, the integer preferably between 1 ~ 10000.
The preparation method of sulfonate of the present invention is:
(1) C
10~ C
30alhpa olefin and sulphonating agent generation sulfonation reaction generate C
10~ C
30sulfonic acid and sultone, then with the oxyhydroxide generation neutralization reaction of basic metal and/or alkaline-earth metal, collect the C generated
10~ C
30the mixture of the basic metal of sulfonic acid and/or alkaline earth salt and sultone;
(2) by neutral oil, ethylene-propylene copolymer, varsol, C
1~ C
4c in alcohol, calcium oxide, water, step (1)
10~ C
30the mixture of the basic metal of sulfonic acid and/or alkaline earth salt and sultone and non-essential C
5~ C
30the basic metal of alkyl benzene sulphonate (ABS) and/or alkaline earth salt mixing, pass into carbonic acid gas, under 0.4MPa ~ 2.0MPa pressure, carry out carbonation reaction, remove alcohol, water, varsol and solid residue, obtain sulfonate product.
In step (1), described C
10~ C
30the preferred C of alhpa olefin
10~ C
30straightαolefin, most preferably C
12~ C
20straightαolefin;
Described sulphonating agent is one or more in sulphur trioxide, the vitriol oil and oleum, preferred sulphur trioxide;
Described sulphonating agent and described C
10~ C
30the mol ratio of alhpa olefin be: 1.0 ~ 1.5:1, preferably 1.05 ~ 1.1:1;
The temperature of described sulfonation reaction is 0 ~ 60 DEG C, preferably 20 ~ 40 DEG C; Reaction times is 1 ~ 10 hour, preferably 1 ~ 4 hour;
Can solvent be added in described sulfonation reaction, as sherwood oil, benzene, toluene, preferably add solvent.
Described C
10~ C
30alhpa olefin and sulphonating agent generation sulfonation reaction generate C
10~ C
30sulfonic acid and the mixture of sultone, described C
10~ C
30sulfonic acid comprise thiazolinyl monosulfonic acid, thiazolinyl disulfonic acid, described C
10~ C
30sultone comprise a sultone, disultone.
With sulphur trioxide and C
18alhpa olefin generation sulfonation reaction is example, and the two reaction generates the mixture of thiazolinyl monosulfonic acid, a sultone and a small amount of thiazolinyl disulfonic acid, disultone.
The example equation formula of described sulfonation reaction is:
Can neutral oil be added in sulfonation reaction described in step (1) and/or neutralization reaction, also can not add neutral oil, preferably add neutral oil.Described neutral oil preferably 100 DEG C of kinematic viscosity is 2 ~ 6mm
2the lubricating base oil of/s, one or more most preferably in 100SN, 150SN, 100N and 150N.
Described in step (1), neutralization reaction is by C
10~ C
30sulfonic acid and the oxyhydroxide generation neutralization reaction of sultone and basic metal and/or alkaline-earth metal, collect the C generated
10~ C
30the basic metal of sulfonic acid and/or alkaline earth salt and sultone and the mixture of neutral oil preferably added.The mole number of the oxyhydroxide of described basic metal and/or alkaline-earth metal is described C
10~ C
301.2 ~ 2 times of alhpa olefin mole number, temperature of reaction is 50 DEG C ~ 70 DEG C, and the reaction times is 10 ~ 40 minutes.The oxyhydroxide of described basic metal and/or alkaline-earth metal can be single oxyhydroxide, also can be the oxyhydroxide of mixed hydroxides, preferred bases earth metals, one or more most preferably in magnesium hydroxide, calcium hydroxide and hydrated barta.
Described in step (1), neutralization reaction also can first by C
10~ C
30sulfonic acid and sultone and alkali-metal oxyhydroxide generation neutralization reaction generate C
10~ C
30an alkali metal salt of sulfonic acid and sultone, then with soluble alkaline earth salt generation replacement(metathesis)reaction, collect generate C
10~ C
30the basic metal of sulfonic acid and/or alkaline earth salt and sultone and the mixture of neutral oil preferably added.Described C
10~ C
30sulfonic acid and the condition of sultone and alkali-metal oxyhydroxide generation neutralization reaction be: the mole number of described alkali-metal oxyhydroxide is described C
10~ C
301.2 ~ 2 times of alhpa olefin mole number, temperature of reaction is 50 DEG C ~ 70 DEG C, and the reaction times is 10 ~ 40 minutes.The condition of described replacement(metathesis)reaction is: the mole number of described soluble alkaline earth salt is described C
10~ C
300.3 ~ 2.0 times of alhpa olefin mole number, temperature of reaction is 60 ~ 90 DEG C, and the reaction times is 1 ~ 4 hour.One or more in described soluble alkaline earth salt preferably calcium chloride, magnesium chloride, bariumchloride, nitrocalcite, magnesium nitrate and nitrate of baryta.
Preferably reaction product washed after neutralization reaction described in step (1) completes, filter, to obtain more pure C
10~ C
30the basic metal of sulfonic acid and/or alkaline earth salt and sultone and the mixture of neutral oil preferably added.
In step (2), the neutral oil preferably added in the same step of described neutral oil (1) is 100 DEG C of kinematic viscosity is 2 ~ 6mm
2the lubricating base oil of/s, one or more most preferably in 100SN, 150SN, 100N and 150N;
Described ethylene-propylene copolymer is the copolymerization product of ethene and propylene, optimal ethylene content is at 40% ~ 60%(mass percent) between ethylene-propylene copolymer, the number-average molecular weight of described ethylene-propylene copolymer between 5000 ~ 100000, preferably between 10000 ~ 60000.Described ethylene-propylene copolymer is dope or solids in room temperature, reacting and being easy to carry out, being preferably dissolved in neutral oil by ethylene-propylene copolymer for making step (2).The structure of described 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 described ethylene-propylene copolymer is abbreviated as OCP.
Described varsol can be alkane, may also be aromatic hydrocarbon, preferred boiling range at the alkane of 60 DEG C ~ 180 DEG C and/or aromatic hydrocarbon, most preferably one or more in the straight-run spirit of 60 DEG C ~ 180 DEG C of octane, benzene,toluene,xylene and boiling range;
Described C
1~ C
4alcohol can select in methyl alcohol, ethanol, propyl alcohol, butanols and ethylene glycol one or more, particular methanol and C
3~ C
4the mixture of alcohol, described methyl alcohol and C
3~ C
4the mass ratio of alcohol is 2:1 ~ 10:1, preferred 2:1 ~ 4:1.In the methods of the invention, described C
1~ C
4alcohol can make the rate of mass transfer in reaction mixture between gas, liquid, solid three-phase faster, and oil phase and aqueous phase mix, and make reaction be easy to carry out;
C can be added in step (2)
5~ C
30the basic metal of alkyl benzene sulphonate (ABS) and/or alkaline earth salt, also can not add C
5~ C
30the basic metal of alkyl benzene sulphonate (ABS) and/or alkaline earth salt, preferably add C
5~ C
30the basic metal of alkyl benzene sulphonate (ABS) and/or alkaline earth salt.
Described C
5~ C
30the basic metal of alkyl benzene sulphonate (ABS) and/or the structure of alkaline earth salt are:
Wherein M
3for basic metal and/or alkaline-earth metal, n
3for the valency of basic metal and/or alkaline-earth metal, R
4, R
5one of them is C
5~ C
30alkyl, another for H or the two be C
5~ C
30alkyl, R
4, R
5preferably one of them is C
10~ C
30alkyl, another for H or the two be C
10~ C
30alkyl.
Described C
5~ C
30the basic metal of alkyl benzene sulphonate (ABS) and/or alkaline earth salt are by C
5~ C
30the oxyhydroxide generation neutralization reaction of alkyl benzene sulphonate (ABS) and basic metal and/or alkaline-earth metal and obtaining, its preparation method is that the two is carried out neutralization reaction at 70 DEG C ~ 100 DEG C, and reacting heated up after 1 ~ 3 hour removes water that reaction generates, filtration, i.e. obtained C
5~ C
30the basic metal of alkyl benzene sulphonate (ABS) and/or alkaline earth salt, preferably add neutral oil thus obtained C in this reaction
5~ C
30the mixture of the basic metal of alkyl benzene sulphonate (ABS) and/or alkaline earth salt and neutral oil.
Described C
5~ C
30alkyl benzene sulphonate (ABS) can select C
20~ C
28alkyl benzene sulphonate (ABS) and/or carbon number are C
5~ C
24high boiling material sulfonic acid, described C
20~ C
28sulfonic acid can use by C
20~ C
28alhpa olefin generation benzene alkylation reaction, the alkyl benzene sulphonate (ABS) obtained with sulphonating agent generation sulfonation reaction again, described carbon number is C
5~ C
24high boiling material sulfonic acid be the by product high boiling material sulfonic acid that obtains when producing dodecylbenzene, the carbon number of this high boiling material sulfonic acid is C
5~ C
24, mainly containing dialkyl benzene sulfonic acids, monoalkylbenzene.
When adding C in step (2)
5~ C
30when the basic metal of alkyl benzene sulphonate (ABS) and/or alkaline earth salt, C in described step (1)
10~ C
30the mixture of the basic metal of sulfonic acid and/or alkaline earth salt and sultone and described C
5~ C
30the ratio of the basic metal of alkyl benzene sulphonate (ABS) and/or the consumption of alkaline earth salt is 0.3 ~ 3:1 ~ 3, preferably 0.3 ~ 1:1 ~ 2.
In step (2), with C in described step (1)
10~ C
30the mixture of the basic metal of sulfonic acid and/or alkaline earth salt and sultone and non-essential C
5~ C
30the basic metal of alkyl benzene sulphonate (ABS) and/or the consumption of alkaline earth salt are 100 parts of calculating, and the total amount of neutral oil is 50 ~ 400 parts, are preferably 100 ~ 300 parts, comprising the neutral oil added when dissolving ethylene-propylene copolymer, preparation C
10~ C
30the neutral oil that the basic metal of sulfonic acid and/or alkaline earth salt and sultone preferably add, preparation C
5~ C
30the neutral oil preferably added when the basic metal of alkyl benzene sulphonate (ABS) and/or alkaline earth salt; The consumption of described ethylene-propylene copolymer is 0.5 ~ 50 part, preferably 1 ~ 10 part; C
1~ C
4the consumption of alcohol is 20 ~ 200 parts, is preferably 30 ~ 100 parts; The consumption of varsol is 50 ~ 1000 parts, is preferably 100 ~ 500 parts; The consumption of described calcium oxide is 50 ~ 400 parts, is preferably 50 ~ 100 parts; The consumption of water is 10 ~ 150 parts, is preferably 10 ~ 50 parts.
In step (2), described in pass into carbonic acid gas mole number be 50% ~ 120% of calcium oxide mole number, preferably 80% ~ 100%; The temperature of described 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), described sultone can be hydrolyzed to olefin sulfonic acid and hydroxyl sulfoacid, and reacts with calcium oxide, water and generate alkenyl sulphonate and hydroxy sulfonate, these sulfonate can with C in step (1)
10~ C
30the basic metal of sulfonic acid and/or alkaline earth salt and non-essential C
5~ C
30the basic metal of alkyl benzene sulphonate (ABS) and/or alkaline earth salt, ethylene-propylene copolymer are coated on around calcium carbonate together.After carbonation reaction terminates, intensification desolvation, isolate solid slag, obtain sulfonate of the present invention.
The example equation formula of described sultone generation hydrolysis reaction, generation alkenyl sulphonate and hydroxy sulfonate is:
In step (2), the example equation formula of preparation sulfonate of the present invention is:
Lubricating grease of the present invention comprises above-mentioned sulfonate and lubricating base oil, and the mass ratio of described sulfonate and lubricating base oil is 30 ~ 70:70 ~ 30, preferably 40 ~ 60:60 ~ 40.Other additive can also be added, such as antioxidant, thickening material, anti-wear agent in described lubricating grease.Described lubricating base oil can select in API I, II, III, IV, V class lubricating base oil one or more, one or more in preferred API I, II, III class lubricating base oil, most preferably 90BS, 120BS, 150BS.
Described preparation of greases method is:
By lubricating base oil, sulfonate of the present invention 100 ~ 150 DEG C of mixing, the calcium carbonate simultaneously in p-sulfonic acid salt carries out infrared detection, when its infrared absorption peak is by 863.1cm
-1transfer to 881.5cm gradually
-1time, can think that coated calcium carbonate is converted into calcite type crystal by unformed gradually in sulfonate, transform completely and collect grease product.
Prepared grease product is non-newtonian fluid.
Embodiment
Further illustrate the present invention below by way of example, but do not limit the invention.
Unless stated otherwise, the per-cent below mentioned is mass percent.
The analytical procedure adopted:
Sulfonic acid compositional analysis: 1) HP6890 gas-chromatography (Agilent company), HP-5 chromatographic column, fid detector, injector temperature: 300 DEG C, splitting ratio 10:1; 2) Waters company liquid chromatography, C8 silicagel column, moving phase is octane, and detector is UV-detector and refractive index detection device 2414.
Olefin(e) centent is analyzed: nuclear magnetic resonance spectrometer, model: INOVA500, Varian company of U.S. sulfonic acid content is analyzed: in alkyl benzene sulphonate (ABS), mensuration (RIPP48-90) the product base number of sulfonic acid content is analyzed: SH/T0251 petroleum products base number assay method (perchloric acid potentiometric titration) product viscosity is analyzed: GB/T265 petroleum products kinematic viscosity assay method and coefficient of dynamic viscosity computing method.
Raw materials used: 60 ~ 90 DEG C of sherwood oils, sulphur trioxide, sodium hydroxide, No. 120 industrial napthas, dimethylbenzene, methyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, distilled water, calcium oxide, carbonic acid gas, C
18alhpa olefin, C
12~ C
18alhpa olefin, high boiling material calcium sulphonate, C
20~ C
28alkyl benzene calcium sulfonate, ethylene-propylene copolymer, 150SN, 150N, 150BS neutral oil.
Embodiment 1C
18the preparation of alhpa olefin calcium sulphonate and sultone
101 grams of C are added in the 1000mL there-necked flask with stirring and cooling/heating apparatus
18alhpa olefin (molecular weight 252,0.397mol, purchased from Chevron company, purity 99%), 100 grams of sherwood oils (60 ~ 90 DEG C), form solution after stirring, then 34.94 grams of sulfur trioxide gas sulphonating agents (0.437mol) are passed into, now sulfonation reaction occurs, heat release is violent, controls temperature of reaction at 30 DEG C ~ 35 DEG C, now sulphur trioxide and alhpa olefin sulfonation reaction 2 hours, generates the mixtures such as thiazolinyl monosulfonic acid, a sultone, thiazolinyl disulfonic acid and disultone.
After sulfonation reaction terminates, the sodium hydroxide solution 64 grams adding 30% in sulfonic acid-petroleum ether solution carries out neutralization reaction, wherein containing sodium hydroxide 0.48mol, temperature of reaction is 60 DEG C, react 20 minutes, now olefin sulfonic acid generates sodium olefin sulfonate, 40 DEG C of dischargings are cooled to after reaction, put into separating funnel point water-yielding stratum, obtain about 229 grams, lurid oil reservoir, being transferred to 1000mL has in the there-necked flask of stirring and temperature control, add 40 grams of 150SN neutral oils, the calcium chloride solution 200 grams of 20% is added after stirring, wherein containing calcium chloride 0.36mol, controlling temperature of reaction is 70 DEG C, react 2 hours, distilled water washing twice after reaction, solution layering is left standstill, divide water-yielding stratum, retain oil reservoir, then sherwood oil is deviate from oil reservoir distillation, obtain C
18the mixture of α olefin sulfonic acid calcium and sultone and neutral oil amounts to 174.5 grams, and wherein active matter content is 77.1%, the calcium salt containing the thiazolinyl monosulfonic acid of 48% in actives, a sultone of 49%, the calcium salt of thiazolinyl disulfonic acid of 2% and the disultone of 1%.
Embodiment 2C
12~ C
18the preparation of α olefin sulfonic acid calcium and sultone
100 grams of C are added in the 1000mL there-necked flask with stirring and cooling/heating apparatus
12~ C
18alhpa olefin (molecular-weight average 224,0.393mol, purchased from Lanzhou Lu Borun additive company, purity 88%), first add 90 grams of sherwood oils (90 ~ 120 DEG C), solution is formed after stirring, then pass into 34.58 grams of sulfur trioxide gas sulphonating agents (0.432mol), now sulfonation reaction occurs, and heat release is violent, control temperature of reaction at 30 ~ 35 DEG C, now sulphur trioxide and alhpa olefin sulfonation reaction generate the mixtures such as thiazolinyl monosulfonic acid, a sultone, thiazolinyl disulfonic acid and disultone.
After sulfonation reaction terminates, the sodium hydroxide solution 75 grams adding 25% in sulfonic acid-petroleum ether solution carries out neutralization reaction, wherein containing sodium hydroxide 0.47mol, temperature of reaction controls at 60 DEG C, react 10 minutes, now olefin sulfonic acid generates sodium olefin sulfonate, after reaction terminates, put into separating funnel point water-yielding stratum, obtain about 213 grams, lurid oil reservoir, being transferred to 1000mL has in the there-necked flask of stirring and temperature control, add 39 grams of 150N neutral oils, the calcium chloride solution 267 grams of 15% is added after stirring, mole number 0.36mol wherein containing calcium chloride, controlling temperature of reaction is 70 DEG C, react 2 hours, after reaction rear distillation washing twice, divide water-yielding stratum, retain oil reservoir, then sherwood oil is deviate from oil reservoir distillation, obtain C
12~ C
18the mixture of α olefin sulfonic acid calcium and sultone and neutral oil amounts to 174.1 grams, wherein the content of actives is 77.6%, calcium salt containing the thiazolinyl monosulfonic acid of 49% in this actives, a sultone of 47%, the calcium salt of thiazolinyl disulfonic acid of 2.6% and the disultone of 1.4%.
Embodiment 3
With high boiling material calcium sulphonate, C
18alhpa olefin calcium sulphonate and sultone are that calcium sulfonate with high base number prepared by raw material
In 500 milliliters of autoclaves with motor agitators and temperature control facility, add 2 grams of ethylene-propylene copolymers (wherein ethylene content 55%, number-average molecular weight is 55238) and 34 grams, the mixture of 32 grams of 150SN neutral oils, add No. 120 industrial napthas 100 grams (industrial goods), add methyl alcohol 20 grams, n-propyl alcohol 5 grams, distilled water 10 grams, 37 grams, calcium oxide, 50 grams, the mixture of high boiling material calcium sulphonate and 150SN neutral oil (is prepared by high boiling material sulfonic acid and calcium hydroxide and 150SN neutral oil and is obtained, calcium sulphonate content is 61.6%), the product that embodiment 1 obtains is (containing olefin sulfonic acid calcium, sultone and neutral oil, active matter content 77.1%) 16 grams, be warming up to 145 DEG C, pass into carbonic acid gas, and control reaction pressure at 0.9 ~ 1.2MPa, when carbon dioxide absorption amount is 92% of calcium oxide mole number, stop ventilation, step-down, then 120 DEG C of dealcoholysis are warmed up to, water.100 milliliters of gasoline are added in the material obtained, then medical centrifuge is put into, centrifugal with rotating speed 4000rpm, flash distillation thing after centrifugal is put into the matrass with decompression facility, first 120 DEG C of air distillations are warmed up to, then carry out underpressure distillation, finally obtain 146 grams of calcium sulphonate products of brown thickness, the base number=395mgKOH/g of this product, 100 DEG C of kinematic viscosity=201mm
2/ s.
Embodiment 4
With C
20~ C
28alkyl benzene calcium sulfonate, C
12~ C
18alhpa olefin calcium sulphonate and sultone are that calcium sulfonate with high base number prepared by raw material
In 500 milliliters of autoclaves with motor agitators and temperature control facility, (wherein ethylene content is 52% to add 2 grams of ethylene-propylene copolymers, its number-average molecular weight is 48690) and 28 grams, the mixture of 26 grams of 150N neutral oils, add dimethylbenzene 150 milliliters (chemical pure), methyl alcohol 16 grams, propyl carbinol 8 grams, 38 grams, calcium oxide, distilled water 12 grams, C
20~ C
2851 grams, the mixture (prepared by alkyl benzene sulphonate (ABS) and calcium hydroxide and 150SN neutral oil and obtained, the content of alkyl benzene calcium sulfonate is 61.8%) of alkyl benzene calcium sulfonate and neutral oil, the product (C that embodiment 2 obtains
12~ C
18the mixture of α olefin sulfonic acid calcium, sultone and neutral oil, active matter content 77.6%) 21 grams add in autoclave, be warming up to 146 DEG C, pass into carbonic acid gas, and control reaction pressure at 0.9 ~ 1.1MPa, when carbon dioxide absorption amount reaches 91% of calcium oxide mole number, stop ventilation, step-down, is then warmed up to 120 DEG C of dealcoholysis, water.100 milliliters of gasoline are added in the material obtained, then medical centrifuge is put into, centrifugal with rotating speed 4000rpm, flash distillation thing after centrifugal is put into the matrass with decompression facility, first be warmed up to 120 DEG C of air distillations, then carry out underpressure distillation to system, finally obtain 147 grams of calcium sulphonate of brown thickness, base number=the 389mgKOH/g of this product, product 100 DEG C of kinematic viscosity=197mm
2/ s.
Embodiment 5
With high boiling material calcium sulphonate, C
12~ C
18alhpa olefin calcium sulphonate and sultone are that calcium sulfonate with high base number prepared by raw material
In 500 milliliters of autoclaves with motor agitators and temperature control facility, (wherein ethylene content is 55% to add 1.8 grams of ethylene-propylene copolymers, its number-average molecular weight is 55238) and 31.8 grams, the mixture of 30 grams of 150SN neutral oils, add No. 120 industrial napthas 100 grams (industrial goods), add methyl alcohol 22 grams, isopropylcarbinol 8 grams, distilled water 10 grams, 39 grams, calcium oxide, 44 grams, the mixture of high boiling material calcium sulphonate and neutral oil (is prepared by high boiling material sulfonic acid and calcium hydroxide and 150SN neutral oil and is obtained, wherein the content of calcium sulphonate is 61.6%), the product that embodiment 2 obtains 22 grams of (C
12~ C
18the mixture of α olefin sulfonic acid calcium, sultone and neutral oil, active matter content 77.6%), join in autoclave, be warming up to 138 DEG C, pass into carbonic acid gas, and control reactor pressure at 0.9 ~ 1.2MPa, when carbon dioxide absorption amount reaches 93% of calcium oxide mole number, stop ventilation, be then warmed up to 120 DEG C of dealcoholysis, water.100 milliliters of gasoline are added in the material obtained, then medical centrifuge is put into, centrifugal with rotating speed 4000rpm, flash distillation thing after centrifugal is put into the matrass with decompression facility, first 120 DEG C of air distillations are warmed up to, then carry out underpressure distillation, finally obtain 149 grams of calcium sulphonate products of brown thickness, the base number=391mgKOH/g of this product, 100 DEG C of kinematic viscosity=199mm
2/ s.
Embodiment 6 is with C
18alhpa olefin calcium sulphonate and sultone are that calcium sulfonate with high base number prepared by raw material
With in 500 milliliters of autoclaves of motor agitators and prolong, (wherein ethylene content is 55% to add 42 grams of 150SN neutral oils and 2 grams of ethylene-propylene copolymers, its number-average molecular weight is 55238) 44 grams, mixture, add No. 120 industrial napthas 100 grams (industrial goods), add methyl alcohol 20 grams, n-propyl alcohol 5 grams, distilled water 11 grams, 40 grams, calcium oxide, the product (C that embodiment 1 obtains
18the mixture of α olefin sulfonic acid calcium, sultone and neutral oil, active matter content 77.1%) 56 grams, be added in autoclave, be warming up to 145 DEG C, pass into carbonic acid gas, and control reaction pressure at 0.9 ~ 1.2MPa, when carbon dioxide absorption amount is 92% of calcium oxide mole number, stop ventilation, step-down, is then warmed up to 120 DEG C of dealcoholysis, water.100 milliliters of gasoline are added in the material obtained, then medical centrifuge is put into, centrifugal with rotating speed 4000rpm, flash distillation thing after centrifugal is put into the matrass with decompression facility, first be warmed up to 120 DEG C of air distillations, then carry out underpressure distillation, finally obtain 138 grams of calcium sulphonate of brown thickness, base number=the 335mgKOH/g of this product, product 100 DEG C of kinematic viscosity=187mm
2/ s.
Comparative example 1,2,3 repeats the operation of embodiment 3 respectively, ethylene-propylene copolymer is not added in comparative example 1, comparative example 2 is ability and ethylene-propylene copolymer mechanically mixing after carbonation reaction, and do not add alhpa olefin calcium sulphonate and sultone in comparative example 3, comparative example 4 adopts synthesis under normal pressure to prepare calcium sulfonate with high base number.
Comparative example 1 is with high boiling material calcium sulphonate, C
18alhpa olefin calcium sulphonate and sultone are that calcium sulfonate with high base number prepared by raw material
In 500 milliliters of autoclaves with motor agitators and temperature control facility, add 150SN neutral oil 34 grams (production of Sinopec Yanshan Petrochemical company), add No. 120 industrial napthas 100 grams (industrial goods), add methyl alcohol 20 grams, n-propyl alcohol 5 grams, distilled water 10 grams, 37 grams, calcium oxide, 50 grams, the mixture of high boiling material calcium sulphonate and 150SN neutral oil (is prepared by high boiling material sulfonic acid and calcium hydroxide and 150SN neutral oil and is obtained, wherein the content of calcium sulphonate is 61.6%), the product that embodiment 1 obtains is (containing C
18α olefin sulfonic acid calcium and sultone and neutral oil, active matter content 77.1%) 16 grams, be warming up to 145 DEG C, pass into carbonic acid gas, and control reaction pressure at 0.9 ~ 1.2MPa, when carbon dioxide absorption amount is 92% of calcium oxide mole number, stop ventilation, step-down, is then warmed up to 120 DEG C of dealcoholysis, water.100 milliliters of gasoline are added in the material obtained, then medical centrifuge is put into, centrifugal with rotating speed 4000rpm, flash distillation thing after centrifugal is put into the matrass with decompression facility, first 120 DEG C of air distillations are warmed up to, then carry out underpressure distillation, finally obtain 149 grams of calcium sulphonate products of brown thickness, the base number=398mgKOH/g of this product, 100 DEG C of kinematic viscosity=167mm
2/ s.
Comparative example 2
In comparative example 1, in product, add 2 grams of ethylene-propylene copolymers (wherein ethylene content is 55%, and its number-average molecular weight is 55238), stir 2 hours at 100 DEG C of constant temperature, obtain the brown additive of thickness.
Comparative example 3 with high boiling material calcium sulphonate for calcium sulfonate with high base number prepared by raw material
In 500 milliliters of autoclaves with motor agitators and temperature control facility, (wherein ethylene content is 55% to add 32 grams of 150SN neutral oils and 2 grams of ethylene-propylene copolymers, its number-average molecular weight is 55238) 34 grams, mixture, add No. 120 industrial napthas 100 grams (industrial goods), add methyl alcohol 20 grams, n-propyl alcohol 5 grams, distilled water 10 grams, 37 grams, calcium oxide, 66 grams, the mixture of high boiling material calcium sulphonate and 150SN neutral oil (is prepared by high boiling material sulfonic acid and calcium hydroxide and 150SN neutral oil and is obtained, wherein calcium sulphonate content is 65.8%), add and be warming up to 145 DEG C, pass into carbonic acid gas, and to control reaction pressure at 0.9 ~ 1.2MPa, when carbon dioxide absorption amount is 92% of calcium oxide mole number, stop ventilation, step-down, then 120 DEG C of dealcoholysis are warmed up to, water.100 milliliters of gasoline are added in the material obtained, then medical centrifuge is put into, centrifugal with rotating speed 4000rpm, flash distillation thing after centrifugal is put into the matrass with decompression facility, first 120 DEG C of air distillations are warmed up to, then carry out underpressure distillation, finally obtain 147 grams of additives of tan thickness.Base number=the 391mgKOH/g of product, product viscosity=206mm
2/ s.
Comparative example 4
With high boiling material calcium sulphonate, C
18alhpa olefin calcium sulphonate and sultone are raw material, and synthesis under normal pressure prepares calcium sulfonate with high base number
With in 500 milliliters of there-necked flasks of motor agitators and prolong, (wherein ethylene content is 55% to add 32 grams of 150SN neutral oils and 2 grams of ethylene-propylene copolymers, its number-average molecular weight is 55238) 34 grams, mixture, add No. 120 industrial napthas 100 grams (industrial goods), add methyl alcohol 20 grams, n-propyl alcohol 5 grams, distilled water 2 grams, 13 grams, calcium oxide, 50 grams, the mixture of high boiling material calcium sulphonate and neutral oil (is prepared by high boiling material sulfonic acid and calcium hydroxide and 150SN neutral oil and is obtained, calcium sulphonate content is 61.6%), the product (C that embodiment 1 obtains
18the mixture of α olefin sulfonic acid calcium, sultone and neutral oil) 16 grams, add rear control temperature of reaction at 45 DEG C ~ 50 DEG C, pass into carbonic acid gas, when carbon dioxide absorption rate is 90% of calcium oxide mole number, add 25 grams of calcium oxide, 8 grams of distilled water, continue to pass into carbonic acid gas, when carbon dioxide absorption amount is 92% of calcium oxide mole number, stop ventilation, step-down, is then warmed up to 120 DEG C of dealcoholysis, water.100 milliliters of gasoline are added in the material obtained, then medical centrifuge is put into, centrifugal with rotating speed 4000rpm, flash distillation thing after centrifugal is put into the matrass with decompression facility, first be warmed up to 120 DEG C of air distillations, then carry out underpressure distillation, finally obtain 143 grams of calcium sulphonate of brown thickness, base number=the 362mgKOH/g of this product, product 100 DEG C of viscosity=199mm
2/ s.
Adopt commercially available calcium sulphonate T107(400TBN calcium sulfonate with high base number) as a comparison case 5 sulfonate.
Embodiment 7 ~ 11 and the comparative example 6 ~ 10 of lubricating grease
Utilize the sulfonate of embodiment 3 ~ 6 and comparative example 1 ~ 5 to mix with lubricating base oil respectively, prepare the embodiment 7 ~ 11 of lubricating grease and comparative example 6 ~ 10.The lubricating base oil used is 150BS.
The commercially available calcium sulphonate that sulfonate embodiment 3 ~ 6 and comparative example 1 ~ 4 synthesized respectively, comparative example 5 use mixes at 100 ~ 150 DEG C with lubricating base oil, and the calcium carbonate simultaneously in p-sulfonic acid salt carries out infrared detection, when its infrared absorption peak is by 863.1cm
-1transfer to 881.5cm gradually
-1time, can think that coated calcium carbonate is converted into calcite type crystal by unformed gradually in sulfonate, transform completely and collect grease product, obtain embodiment 7 ~ 11 and the comparative example 6 ~ 10 of grease product.The calcium sulphonate that wherein embodiment 7 ~ 10 and the lubricating grease of comparative example 6 ~ 10 are prepared by embodiment 3 ~ 6 and comparative example 1 ~ 5 respectively transforms and obtains, and calcium sulphonate and lubricating base oil mass ratio are 42:58; The calcium sulphonate conversion that the lubricating grease of embodiment 11 is prepared by embodiment 3 obtains, and calcium sulphonate and lubricating base oil mass ratio are 51:49.
Carry out properties test to the embodiment 7 ~ 11 of grease product and comparative example 6 ~ 10 respectively, test result is in table 1.
The assessment of performance of table 1 grease product
Find out from above embodiment, the transformation time of lubricating grease of the present invention is shorter, has good high-temperature behavior, water repelling property, colloidal stability, abrasion resistance.
Claims (19)
1. a sulfonate, its structure is:
Wherein M
1, M
2, M
3be respectively the single metal in alkali and alkaline earth metal ions or hybrid metal, n
1, n
2, n
3be respectively M
1, M
2, M
3valency, x, y, z is respectively the integer between 1 ~ 4, R
1, R
2, R
3be respectively alkyl, and R
1carbon number in alkyl and x sum are 8 ~ 28, R
2carbon number in alkyl and y sum are 7 ~ 27, R
3carbon number in alkyl and z sum are 9 ~ 29, R
4, R
5be respectively C
5~ C
30alkyl, e, q, r, u, d are respectively the integer between 1 ~ 20000, and t is the integer between 0 ~ 20000, and OCP is the abbreviation of ethylene-propylene copolymer molecule.
2. according to sulfonate according to claim 1, it is characterized in that: described M
1, M
2, M
3for alkaline-earth metal; n
1, n
2, n
3value is 2; X, y, z is respectively 2 or 3; R
1carbon number in alkyl and x sum are 10 ~ 18, R
2carbon number in alkyl and y sum are 9 ~ 17, R
3carbon number in alkyl and z sum are 11 ~ 19; R
4, R
5be respectively C
10~ C
30alkyl; E, q, r, u, d, t are respectively the integer between 1 ~ 10000.
3. a preparation method for sulfonate, comprising:
(1) C
10~ C
30alhpa olefin and sulphonating agent generation sulfonation reaction generate C
10~ C
30sulfonic acid and sultone, then with the oxyhydroxide generation neutralization reaction of basic metal and/or alkaline-earth metal, collect the C generated
10~ C
30the mixture of the basic metal of sulfonic acid and/or alkaline earth salt and sultone;
(2) by neutral oil, ethylene-propylene copolymer, varsol, C
1~ C
4c in alcohol, calcium oxide, water, step (1)
10~ C
30the mixture of the basic metal of sulfonic acid and/or alkaline earth salt and sultone and non-essential C
5~ C
30the basic metal of alkyl benzene sulphonate (ABS) and/or alkaline earth salt mixing, pass into carbonic acid gas, under 0.4MPa ~ 2.0MPa pressure, carry out carbonation reaction, remove alcohol, water, varsol and solid residue, obtain sulfonate product.
4. in accordance with the method for claim 3, it is characterized in that, in step (1), described C
10~ C
30alhpa olefin be C
10~ C
30straightαolefin.
5. in accordance with the method for claim 3, it is characterized in that, in sulfonation reaction described in step (1) and/or neutralization reaction, add neutral oil.
6. in accordance with the method for claim 3, it is characterized in that, in step (1), described sulphonating agent and described C
10~ C
30the mol ratio of alhpa olefin be: 1.0 ~ 1.5:1, the temperature of described sulfonation reaction is 0 ~ 60 DEG C; Reaction times is 1 ~ 10 hour.
7. in accordance with the method for claim 3, it is characterized in that, in step (1) in described neutralization reaction, the mole number of the oxyhydroxide of described basic metal and/or alkaline-earth metal is described C
10~ C
301.2 ~ 2 times of alhpa olefin mole number, temperature of reaction is 50 DEG C ~ 70 DEG C, and the reaction times is 10 ~ 40 minutes.
8. in accordance with the method for claim 3, it is characterized in that, in step (1), the oxyhydroxide of described basic metal and/or alkaline-earth metal is single oxyhydroxide or mixed hydroxides.
9. in accordance with the method for claim 3, it is characterized in that, described in step (1), neutralization reaction is first by C
10~ C
30sulfonic acid and sultone and alkali-metal oxyhydroxide generation neutralization reaction generate C
10~ C
30an alkali metal salt of sulfonic acid and sultone, then with soluble alkaline earth salt generation replacement(metathesis)reaction, collect generate C
10~ C
30the mixture of the basic metal of sulfonic acid and/or alkaline earth salt and sultone.
10. in accordance with the method for claim 9, it is characterized in that, described C
10~ C
30sulfonic acid and the condition of sultone and alkali-metal oxyhydroxide generation neutralization reaction be: the mole number of described alkali-metal oxyhydroxide is described C
10~ C
301.2 ~ 2 times of alhpa olefin mole number, temperature of reaction is 50 DEG C ~ 70 DEG C, and the reaction times is 10 ~ 40 minutes; The condition of described replacement(metathesis)reaction is: the mole number of described soluble alkaline earth salt is described C
10~ C
300.5 ~ 2.0 times of alhpa olefin mole number, temperature of reaction is 60 ~ 90 DEG C, and the reaction times is 1 ~ 4 hour.
11. in accordance with the method for claim 9, it is characterized in that, described soluble alkaline earth salt be selected from calcium chloride, magnesium chloride, bariumchloride, nitrocalcite, magnesium nitrate and nitrate of baryta one or more.
12. in accordance with the method for claim 3, it is characterized in that, in step (2), described neutral oil is 100 DEG C of kinematic viscosity is 2 ~ 6mm
2the lubricating base oil of/s, described ethylene-propylene copolymer is the ethylene-propylene copolymer of ethylene content between 40% ~ 60% (mass percent), and its number-average molecular weight is 5000 ~ 100000, and described varsol is alkane and/or aromatic hydrocarbon.
13. in accordance with the method for claim 3, it is characterized in that, in step (2), add C
5~ C
30the basic metal of alkyl benzene sulphonate (ABS) and/or alkaline earth salt, described C
5~ C
30the basic metal of alkyl benzene sulphonate (ABS) and/or the structure of alkaline earth salt are:
Wherein M
3for basic metal and/or alkaline-earth metal, n
3for the valency of basic metal and/or alkaline-earth metal, R
4, R
5one of them is C
5~ C
30alkyl, another for H or the two be C
5~ C
30alkyl.
14. in accordance with the method for claim 13, it is characterized in that, C in described step (1)
10~ C
30the mixture of the basic metal of sulfonic acid and/or alkaline earth salt and sultone and described C
5~ C
30the ratio of the basic metal of alkyl benzene sulphonate (ABS) and/or the consumption of alkaline earth salt is 0.3 ~ 3:1 ~ 3.
15., according to the method for claim 3-14 described in one of them, is characterized in that, in step (2), with C in described step (1)
10~ C
30the mixture of the basic metal of sulfonic acid and/or alkaline earth salt and sultone and non-essential C
5~ C
30the basic metal of alkyl benzene sulphonate (ABS) and/or the consumption of alkaline earth salt are 100 parts of calculating, and the total amount of neutral oil is 50 ~ 400 parts; The consumption of described ethylene-propylene copolymer is 0.5 ~ 50 part; C
1~ C
4the consumption of alcohol is 20 ~ 200 parts; The consumption of varsol is 50 ~ 1000 parts; The consumption of described calcium oxide is 50 ~ 400 parts; The consumption of water is 10 ~ 150 parts.
16. in accordance with the method for claim 15, it is characterized in that, described C
1~ C
4alcohol is methyl alcohol and C
3~ C
4the mixture of alcohol, described methyl alcohol and C
3~ C
4the mass ratio of alcohol is 2:1 ~ 10:1.
17. in accordance with the method for claim 15, it is characterized in that, in step (2), described in pass into carbonic acid gas mole number be 50% ~ 120% of calcium oxide mole number; The temperature of described carbonation reaction is 50 DEG C ~ 200 DEG C; Reaction pressure is 0.4MPa ~ 2.0MPa.
18. 1 kinds of lubricating grease, comprise the sulfonate of claim 1 ~ 2 described in one of them or according to the sulfonate of claim 3 ~ 17 wherein prepared by arbitrary claim and lubricating base oil, the mass ratio of described sulfonate and lubricating base oil is 30 ~ 70:70 ~ 30.
Preparation of greases method described in 19. claims 18, comprising: by lubricating base oil, described sulfonate 100 ~ 150 DEG C of mixing, and the calcium carbonate simultaneously in p-sulfonic acid salt carries out infrared detection, when its infrared absorption peak is by 863.1cm
-1transfer to 881.5cm
-1time, calcium carbonate coated in sulfonate is converted into calcite type crystal by unformed, collects grease product.
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| WO2017209118A1 (en) * | 2016-05-31 | 2017-12-07 | 花王株式会社 | Liquid detergent composition for textile products |
| CN110300796A (en) * | 2017-02-22 | 2019-10-01 | 株式会社Ｓｏｎｏｄａ | The manufacturing method of lube oil additive and lube oil additive |
| US11053456B2 (en) | 2016-05-31 | 2021-07-06 | Kao Corporation | Detergent composition for textile products |
| US11124743B2 (en) | 2016-05-31 | 2021-09-21 | Kao Corporation | Liquid detergent composition for textile products |
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| EP1749875A1 (en) * | 2005-07-29 | 2007-02-07 | Chevron Oronite S.A. | Overbased alkaline earth metal alkylhydroxybenzoates having low crude sediment |
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| US11053456B2 (en) | 2016-05-31 | 2021-07-06 | Kao Corporation | Detergent composition for textile products |
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