CN105623783B - Breaker composition, lubricant oil composite and the method for improving lubricating oil demulsification performance - Google Patents
Breaker composition, lubricant oil composite and the method for improving lubricating oil demulsification performance Download PDFInfo
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Abstract
The present invention provides a kind of breaker composition, the lubricant oil composite comprising the breaker composition and the methods for improving lubricating oil demulsification performance.The breaker composition of the present invention, including：1) copolymer of alkyl acrylate and α olefin sulfonic acids；2) four (4 hydroxy phenyl) porphyrins and propylene oxide, the polymeric reaction product of ethylene oxide；Therebetween mass ratio is 1~10：10~1.The breaker composition of present invention stability in lubricating oil is good, has excellent oil-water separation, demulsification effect, is particularly suitable for the separation of minor amount of water in lubricating oil, especially suitable for industrial gear oil, steam turbine oil, crank axle for vessel case oil.
Description
Technical field
It is more particularly to a kind of to be suitable for the broken of I. C. engine oil and industrial lubricant the present invention relates to a kind of breaker composition
Emulsion composition.
Background technology
I. C. engine oil and industrial lubricant have been frequently run onto occasion existing for water in use, these lubricating oil are easy
The emulsification system of Water-In-Oil is formed with water, especially when containing additive with surface-active, emulsification of lubricating oils situation
It is more serious.If water-oil separating cannot be realized in time, oil lubrication situation will be changed, the lighter can influence the shape of oil film
Into reduction lubricating ability, severe one can cause mechanical corrosion and abrasion or even damage equipment, influence production and safety.Therefore,
The demulsification of lubricating oil is an important physical and chemical index.
Lubricating oil breaking method mainly has chemical demulsification method, physical demulsification method, biological demulsifying method, joint demulsification method, film to break
Newborn method etc..Wherein, addition demulsifying agent makes the chemical demulsification method of the grease quick separating of lubricating oil, does not need to additionally increase and sets
It is standby, both facilitated, is simple, is economical, while generally having no adverse effects to the physicochemical property of oil product, and being a kind of method of first choice.Therefore
Development for demulsifier, there are many research reports.
US 2979528 describes nitrogenous Pluronic F-127, propylene oxide composition detersive, wherein to be no more than 6
The nitrogenous compound of carbon atom is starting reaction raw materials, these nitrogenous compounds can be ammonia, secondary amine, alkenyl polyamine, hydramine, piperazine
Piperazine, alkyl-substituted piperazine, ammonium hydroxide, phenol amine, wherein oxygen propyl group chain are connected with connecting the atom of reactive hydrogen, oxyethylene chain and oxygen third
Alkenyl chain end connects.The average molecular weight of oxygen propyl group chain is 900~25000, and oxyethylene chain accounts for the 20%~90% of compound.
There is the compound of more than structure, there is excellent detergency.
CN 100516116C describe a kind of synthetic method of multi block copolyether emulsion resistant agent, wherein using mesoporous silicon
Oxide carried potassium or silicon-Zirconium oxide load potassium catalyst, use monohydric alcohol, dihydric alcohol, polyalcohol as initiator, with epoxy
Ethane, propylene oxide carry out block copolymerization reaction, are then post-processed to obtain object.The more blocks of product that this method obtains
Copolyether emulsion resistant agent is copolymerized, molecular weight is 4800~5500, overall excellent demulsification performance, and production application cost is relatively low, is applicable in profit
Lubricating oil oil product is in extensive range, structure-controllable, it is low blistering, it is less toxic, efficient, environmentally friendly.
Patent CN 101255354 describes a kind of non-polyether type thick oil demulsifying agent and preparation method thereof, proposes with acrylic acid
Butyl ester and acrylic acid are raw material, and solution copolymerization prepares non-polyether type demulsifying agent, and the present invention improves monomer using solution polymerization process
Activated monomer acrylic acid is added in batch or continuously once to feed intake in feed way, butyl acrylate in the course of the polymerization process.It is this common
Polymers has good amphipathic property, and demulsification is good, is particularly suitable for viscous crude.
CN 101721841 describes a kind of lubrication oil composite type demulsifier, is made of anti-foaming agent, demulsifier and solvent, with
Composite demulsifying agent total weight is 100% meter, and anti-foaming agent mass percent is 0.5%~15%, and demulsifier mass percent is
1%~25%, solvent quality percentage is 60%~98%, wherein described anti-foaming agent is silicone oil, fluorine containing silicone oil and acrylic acid
One or more in ester copolymer, demulsifier is polyethers demulsifier.Anti-foaming agent and demulsifier are used in combination the present invention, fill
The advantages of the two, is waved in distribution, further improves the demulsification performance of oil product.
Although the demulsifier of Yi Shang patent introduction can be used for lubricating oil demulsification, there are still demulsification is effective
Fruit is bad, the problem of needing to add in more demulsifier.In addition, some demulsifiers, particularly polyethers demulsifier is due to containing
Hydrophilic radical and easily separated with oil phase, the production cost of lubricating oil is not only caused to rise, at the same also be not easy ensure lubricating oil
Quality.Therefore, existing lubricating oil demulsifier still has limitation, requires further improvement.
Invention content
The present invention provides a kind of breaker composition, the lubricant oil composite comprising the breaker composition and improve profit
The method of lubricating oil demulsification performance.
The breaker composition of the present invention, including：1) copolymer of alkyl acrylate and α-olefin sulfonic acid；2) four (4-
Hydroxy phenyl) porphyrin and propylene oxide, ethylene oxide polymeric reaction product；Therebetween mass ratio is 1~10：10~1,
It is preferred that 1~5：5~1, most preferably 1~3：3~1.
The structure of the first demulsifier is in breaker composition of the present invention：
Wherein R is C4~C18 alkyl or its mixed alkyl, preferably C4~C15 alkyl or its mixed alkyl, most preferably C5~
C10 alkyl or its mixed alkyl；Wherein A1 is hydrogen or methyl, and A2 is hydrogen or C1~C4 alkyl, preferably hydrogen, methyl, ethyl or third
Base, most preferably hydrogen, methyl or ethyl, x be 0~4 integer, preferably 0~3 integer, most preferably 0~2 integer；When A2 is hydrogen
When, x is positive integer；M be 1~50 integer, preferably 5~50, most preferably 10~30, n be 1~50 integer, preferably 5~50,
Most preferably 10~20.
The molecular weight of the first demulsifier is between 1000~15000, preferably 1500~10000, most preferably 2000
~8000.
The preparation method of the first demulsifier, including：Alkyl acrylate and α-olefin sulfonic acid are copolymerized instead
Should, collect product.
The structure of the alkyl acrylate is：
Wherein R is C4~C18 alkyl or its mixed alkyl, preferably C4~C15 alkyl or its mixed alkyl, most preferably C5~
C10 alkyl or its mixed alkyl；A1 is hydrogen or methyl.
The alkyl acrylate is to be obtained by methacrylic acid or acrylic acid with alkylol by esterification, and esterification is anti-
It is the acidic catalysts such as the concentrated sulfuric acid, acid-exchange resin to answer common catalyst.
The structure of the α-olefin sulfonic acid is：
Wherein A2 is hydrogen or C1~C4 alkyl, and preferably hydrogen, methyl, ethyl or propyl, most preferably hydrogen, methyl or ethyl, x is
0~4 integer, preferably 0~3 integer, most preferably 0~2 integer；When A2 is hydrogen, x is positive integer.
α-the olefin sulfonic acid is that alpha-olefin and sulfonating agent sulfonating reaction occur and obtains.The alpha-olefin is C3~C10
Alkene, for example, can select it is one or more in propylene, butylene, amylene, hexene, heptene, octene, nonene and decene, preferably
C3~C8 alkene, most preferably C3~C6 alkene.The sulfonating agent can select oleum and/or sulfur trioxide.
When sulfonating reaction occurs for alpha-olefin and sulfonating agent, solvent, preferably hydrocarbon solvent, the hydrocarbon solvent can be added in
It is preferred that C5~C10 alkane or its mixture.The 20%~200% of the preferred alpha-olefin quality of addition of the solvent, in sulfonation
Solvent is removed after reaction.
The reaction pressure of sulfonating reaction occurs for the alpha-olefin and sulfonating agent preferably between 0.1~4MPa, and most preferably 0.3
~3MPa, reaction temperature is preferably between 0~30 DEG C, most preferably between 0~20 DEG C, preferably 0.1~8 hour reaction time,
Most preferably 0.3~5 hour.
The molar ratio of the alpha-olefin and sulfonating agent preferably 1：1~1.5, more preferable 1：1~1.2.
In the product of the sulfonating reaction alkyl acrylate is cannot participate in containing α-olefin sulfonic acid, sultone, sultone
With the copolyreaction of α-olefin sulfonic acid.
Molar ratio between the alkyl acrylate and α-olefin sulfonic acid is 1~50：50~1, preferably 1~10：10~
1, most preferably 1~3：2~1.
The copolyreaction of the alkyl acrylate and α-olefin sulfonic acid preferably carries out in a solvent, and the solvent is preferably fragrant
It is one or more in hydrocarbon solvent, such as benzene, toluene and dimethylbenzene；Preferably 20~200 DEG C of reaction temperature, more preferable 30~150
DEG C, most preferably 40~120 DEG C, preferably 1~20 hour time of polymerization, more preferable 2~15 hours, most preferably 3~10 hours.
The alkyl acrylate and α-olefin sulfonic acid add in initiator when being copolymerized, addition is alkyl acrylate
The 0.1%~10% of base ester and α-olefin sulfonic acid gross mass, preferably 0.1%~6%；The preferred azo compound of the initiator
And/or peroxide, such as azodiisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, peroxidating bay can be selected
Acyl, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, di-t-butyl peroxide, cumyl peroxide, perbenzoic acid uncle
Butyl ester, peroxidating trimethylacetic acid tertiary butyl ester, methyl ethyl ketone peroxide, cyclohexanone peroxide, di-isopropyl peroxydicarbonate and mistake
Aoxidize one or more in two dicyclohexyl carbonates, preferably azo diisobutyl and/or benzoyl peroxide, most preferably azo
Bis-isobutyronitrile.
When preparing the first demulsifier, material is washed with water after the copolyreaction, removes unreacted sulphur
Lactone and initiator；If adding solvent when being copolymerized, removing solvent is needed.
Neutral oil can be added in the first demulsifier obtained through copolyreaction, the addition of the neutral oil is described
The 50%~150% of polymer quality.The neutral oil preferred solvent refined oil and/or poly alpha olefine synthetic oil, such as can
To select HVI150, No. 6 hydrogenated oils, PAO4, PAO6,100 DEG C of dynamic viscosities of the neutral oil are in 1~8mm2Between/s.
Second of demulsifier is produced for the polymerisation of four (4- hydroxy phenyls) porphyrins and propylene oxide, ethylene oxide
Object, structure are：
Wherein j be 5~50 between integer, preferably 10~40, most preferably 10~30；K is the integer between 5~40, excellent
Select 5~30, most preferably 5~20.
Described four (4- hydroxy phenyls) porphyrin, structure are：
Described four (4- hydroxy phenyls) porphyrin is to be obtained by the reaction by parahydroxyben-zaldehyde and pyrroles using Adler methods, that is, is used
Directly synthesis obtains in propionic acid medium by parahydroxyben-zaldehyde and pyrroles, and dimethyl sulfoxide may be used as solvent, can also use
The mixed solvent of propionic acid and dimethyl sulfoxide, to improve the yield of four (4- hydroxy phenyls) porphyrins.Specific reaction equation is as follows：
Preparing the described four more preferred methods of (4- hydroxy phenyls) porphyrin is：Para hydroxybenzene first is added in reaction vessel
Aldehyde, solvent in 125 DEG C~130 DEG C reflux, are added dropwise to the pyrroles of molal quantity identical with parahydroxyben-zaldehyde, back flow reaction 1h, cold
But；It is recrystallized by crystalline solid propionic acid wash, then with absolute ethyl alcohol, by 100 mesh silica gel post separations, obtains purple section, steam
Solvent, and crystallized with absolute ethyl alcohol to obtain purple four (4- hydroxy phenyls) porphyrin.
The preparation method of second of demulsifier, including：Four (4- hydroxy phenyls) porphyrins are first occurred with propylene oxide
Polymerisation, then polymerisation occurs with ethylene oxide, collect product.
Four (4- hydroxy phenyls) porphyrin is 1 with propylene oxide molar ratio：20~200, preferably 1：40~160, it is optimal
Select 1：40~120.
Pressure when polymerisation occurs with propylene oxide for four (4- hydroxy phenyls) porphyrin is 0.1~1MPa, preferably
0.1~0.8MPa, most preferably 0.2~0.6MPa；Reaction temperature be 80 DEG C~200 DEG C, preferably 100 DEG C~160 DEG C, most preferably
120 DEG C~140 DEG C；Reaction time is 1~10 hour, preferably 2~8 hours, most preferably 2~4 hours.
The molar ratio of four (4- hydroxy phenyls) porphyrin and ethylene oxide is 1：20~160, preferably 1：20~120, most
It is preferred that 1：20~80.
After with propylene oxide polymerisation occurs for four (4- hydroxy phenyls) porphyrin, it polymerize again with ethylene oxide
The pressure of reaction is 0.1~1MPa, most preferably preferably 0.1~0.8MPa, 0.2~0.6MPa；Reaction temperature is 80 DEG C~200
DEG C, preferably 100 DEG C~160 DEG C, most preferably 120 DEG C~140 DEG C；Reaction time is 1~10 hour, preferably 2~8 hours, optimal
It selects 2~4 hours.
Molar ratio preferably 1~5 between the propylene oxide and ethylene oxide：1, most preferably 1~2.5：1.
Alkali metal hydroxide, most preferably potassium hydroxide and/or sodium hydroxide are preferably added in the polymerisation.
The molar ratio of the alkali metal hydroxide and four (4- hydroxy phenyls) porphyrins is 1~20：1, preferably 1~10：1,
Most preferably 1~4：1.
When adding alkali metal hydroxide in the polymerisation, nothing is added in into reaction product after the completion of reaction
Machine acid, neutralization reaction product to neutrality, the sulfuric acid solution of the inorganic acid preferably 10%~20%.
Solvent is preferably added to after the polymerisation, is preferably added to the inert organic solvents that boiling range is 100 DEG C~160 DEG C,
For example, toluene, dimethylbenzene, petroleum ether, steam solvent after pickling, the polymer of the present invention is obtained.
The invention also provides a kind of lubricant oil composite, the composition includes above-mentioned breaker composition and lubrication base
Oil, the breaker composition account for the 0.001%~1% of lubricant oil composite gross mass.
The invention also provides a kind of methods for improving lubricating oil demulsification performance, which is characterized in that by above-mentioned demulsifier group
It closes object to be added in lubricating oil, the breaker composition accounts for the 0.001%~1% of lubricating oil gross mass.
The breaker composition of present invention stability in lubricating oil is good, has excellent oil-water separation, demulsification
Effect is particularly suitable for the separation of minor amount of water in lubricating oil, especially suitable for industrial gear oil, steam turbine oil, crank axle for vessel case
Oil.
Specific embodiment
It further illustrates the present invention rather than limits the invention by the following examples.
Test method and experiment raw material
7305 oil of 1.GB/T and Synthesis liquid resistance to emulsion pipette method；
Specific method is；By sample and each 40mL of distilled water be packed into as defined in graduated cylinder, under measuring temperature, with 1500r/
It keeps standing, and start timing after the rotating speed stirring 5min of min, record Synthesis liquid, water and remaining emulsified body product respectively reach
40mL, 37mL, 3mL either 40mL, 40mL, 0mL when time, the time used is shorter, illustrates that the resistance to emulsion of oil product is better.
If left standing for 30min (test temperature is 54 ± 1 DEG C) or 1h (when test temperature is 82 ± 1 DEG C, oil and water still cannot separate,
Then report the milliliter number of oil either Synthesis liquid, water and remaining emulsion volume.Reach 40-37-3 to be basically separated qualification, reach
To 40-40-0 to be kept completely separate.
2. raw materials used physical index
The physical and chemical index of 1 lube base oil of table
2 lube oil additive type of table and producer
| Additive | Title | Source |
| T102 | Middle base number calcium mahogany sulfonate | Sinopec Shanghai additive factory |
| T307 | D2EHDTPA amine salt | Liaoning Tianhe Fine Chemical Co., Ltd. |
| T321 | Sulfide isobutene | Liaoning Tianhe Fine Chemical Co., Ltd. |
| T405 | Sulfurized olefin cotton oil | Liaoning Tianhe Fine Chemical Co., Ltd. |
| T451 | Phosphate | Jiangsu Hai'an petrochemical plant |
| T502A | Liquid mixed type shields phenol | Liaoning Tianhe Fine Chemical Co., Ltd. |
| T613 | Ethylene-propylene copolymer tackifier | Lanzhou Petrochemical Company |
| T803 | Polyalphaolefin pour-point depressant | Lanzhou Lu Borun additives Co., Ltd |
| T1001 | Amine and epoxide condensation product | Jinzhou Kangtai Lube Additive Co., Ltd. |
| DL-32 | Ethylene oxide and propylene oxide copolymers | Wuxi south petroleum additive factory |
The preparation of 1 propene sulfonic acid mixture of embodiment
With stirring, heating, 80 grams of 30 DEG C~60 DEG C petroleum ethers of addition in the 500mL autoclaves of cryostat, then close
Reaction kettle opens stirring, and is passed through cryostat and carries out temperature control, then squeezes into propylene 40 grams (0.952mol) into kettle with high-pressure pump,
And high pure nitrogen is passed through, control reactor pressure controls the temperature of reaction kettle that will be stored at 0~10 DEG C between 0.8~1MPa
The steel cylinder for having sulfur trioxide heats, and is placed in measuring on electronic scale, then heating temperature is controlled to cause sulfur trioxide steel cylinder pressure
More than autoclave pressure, and sulfur trioxide steel cylinder outlet valve is opened, gas is passed through in the snorkel of autoclave, is then passed to
Sulfonating reaction is carried out into the liquid phase of autoclave, sulfur trioxide intake is 77.7 grams (0.971mol), controls reaction kettle at this time
For middle pressure between 0.8~1.2MPa, the reaction time is 3.2 hours, after reaction, continuously decreases the pressure of reactor, when
After pressure reaches normal pressure, stop stirring, then solvent distillation, obtains 115.8 grams of propene sulfonic acid mixture, analysis is found；The production
Containing 54% propene sulfonic acid in product, 46% propene sultone, the acid value of mixture is 260.8mgKOH/g.
The preparation of 2 butylene azochlorosulfonate acid mixture of embodiment
With stirring, heating, 70 grams of n-hexanes of addition in the 500mL autoclaves of cryostat, then capping kettle, is opened
Stirring, and be passed through cryostat and carry out temperature control, butylene 38 grams (0.679mol) is then squeezed into kettle with high-pressure pump, and be passed through High Purity Nitrogen
Gas, control reactor pressure control the temperature of reaction kettle that will store sulfur trioxide at 0~10 DEG C between 0.8~1MPa
Steel cylinder heats, and is placed in measuring on electronic scale, then controls heating temperature that sulfur trioxide steel cylinder pressure is caused to be more than autoclave pressure
Power, and sulfur trioxide steel cylinder outlet valve is opened, gas is passed through in the snorkel of autoclave, then passes to the liquid of autoclave
Sulfonating reaction is carried out in phase, sulfur trioxide intake is 54.88 grams (0.686mol), at this time control reaction kettle in pressure 0.8
Between~1.2MPa, the reaction time is 2.8 hours, after reaction, continuously decreases the pressure of reactor, when pressure reaches normal pressure
Afterwards, stop stirring, then solvent distillation, obtains 91.25 grams of butylene azochlorosulfonate acid mixture, contain 53% butylene sulphur in the product
Acid, 47% butene sultone, the acid value of mixture is 225.3mgKOH/g.
The synthesis of embodiment 3 four (4- hydroxy phenyls) porphyrin
With reflux and stirring, temperature control device three-necked flask in add in 10 grams of parahydroxyben-zaldehyde (M=122.12,
0.0819mol), propionic acid 160ml and dimethyl sulfoxide (DMSO) 10ml mixed solvents, are warming up to 125~130 DEG C and flow back, then drip
Add 5.5 grams of pyrroles (M=67.09,0.0819mol), reflux time is 140 minutes, and material then is imported beaker, is put into
Refrigerator is cooled to 2~4 DEG C, is filtered after placing 10 hours, obtains blue colored crystal, then by this crystalline solid propionic acid wash, then use
Absolute ethyl alcohol recrystallizes, and by 100 mesh silica gel post separations, obtains bluish violet section, steams solvent, and crystallize to obtain with absolute ethyl alcohol
Four 4.5 grams of (4- hydroxy phenyls) porphyrins.
Structural characterization is carried out to product：From its ultraviolet spectrogram as can be seen that at 422nm (Soret bands), 517,553,
There is absorption peak at 594,651nm (Q bands)；Infrared analysis the result shows that, 3398cm-1Corresponding to the phenolic hydroxyl group stretching vibration on phenyl ring
Absorption peak, 3370cm-1Corresponding is pyrroles's N-H stretching vibration peaks, 1100~1200cm on the big ring of porphyrin-1Between there is porphyrin
The vibration absorption peak of ring, 1249cm-1It is the stretching vibration peak of phenyl ring C-O, l608cm-1、l508cm-1、l473cm-1It is phenyl ring bone
Frame stretching vibration peak, more than analysis result show that the product of synthesis is really four (4- hydroxy phenyls) porphyrins.
The synthesis of 4 acrylic acid C5 ester butylene sulfonic acid copolymers P1 of embodiment
In the 500mL three-necked flasks with motor agitators and condenser pipe, 110 grams of toluene, 63.9 grams of propylene are added in
Sour C5 esters (0.45mol, M=142) add in 0.08 gram of azodiisobutyronitrile, introduce nitrogen protection, open and stir and be warming up to 70
DEG C, observing response object has apparent heat release at this time, and controlling reaction temperature is 90 DEG C, and polymerisation 1 hour adds embodiment 2
64 grams of the butylene azochlorosulfonate acid mixture (containing 53% butylene sulfonic acid, 0.25mol, M=136) of preparation, 0.05 gram of two isobutyl of azo
Nitrile is gradually heating to 105 DEG C and carries out copolyreaction 4 hours.Twice, then reaction product is washed respectively with 200 grams of distilled water
60 grams of HVI150 (production of Sinopec Yanshan Petrochemical branch company) are added in, material is warming up to 125 DEG C and is evaporated under reduced pressure, is obtained
Acrylic acid C5 ester butylene sulfonic acid copolymer 157.6 grams (P1).Infrared analysis the result shows that：In 1721cm-1、1160cm-1Nearby have
Strong absworption peak, and illustrate to contain ester type compound in product, 1184cm-1、1053cm-1、3650cm-1The spike at place shows there is sulphur
Acid groups exist, 1640cm-1Locate non-telescope vibration peak to occur, there is no double bond presence in compound, it is propylene to illustrate the compound
Sour C5 esters butylene sulfonic acid copolymer；Gpc analysis shows that the number-average molecular weight of copolymer is being 5130, wherein the content of copolymer
It is 61.92%, the content of flux oil is 38.02%, and the content of acrylic acid C5 esters is 65.47% in copolymer, butylene sulfonic acid
Content is 34.53%.
The synthesis of 5 methacrylic acid C8 ester propene sulfonic acids copolymer p 2 of embodiment
In the 500mL three-necked flasks with motor agitators and condenser pipe, 100 grams of dimethylbenzene, 73.6 grams of first are added in
Base acrylic acid C8 esters (0.38mol, M=196) add in 0.07 gram of azodiisobutyronitrile, introduce nitrogen protection, open and stir and rise
Temperature is to 75 DEG C, and observing response object has apparent heat release at this time, and controlling reaction temperature is 95 DEG C, and polymerisation 1.5 hours adds
90.37 grams of propene sulfonic acid mixture (containing 54% propene sulfonic acid, 0.4mol, M=122) prepared by embodiment 1,0.06 gram of idol
Nitrogen bis-isobutyronitrile is gradually heating to 108 DEG C and carries out copolyreaction 5 hours.Two are washed with 200 grams of distilled water respectively to reaction product
It is secondary, 80 grams of 150N (production of Sinopec Shanghai Gaoqiao petrochemical industry branch company) are then added in, material is warming up to 125 DEG C and is depressurized
Distillation, obtains methacrylic acid C8 ester propene sulfonic acids copolymer 201 grams (P2).Infrared analysis the result shows that：In 1721cm-1、
1160cm-1Nearby there is strong absworption peak, and illustrate to contain ester type compound in product, 1184cm-1、1053cm-1、3650cm-1Place
Spike shows with the presence of sulfonic acid group, 1640cm-1Locate non-telescope vibration peak to occur, there is no double bond presence in compound, illustrate this
Compound is methacrylic acid C8 ester propene sulfonic acid copolymers；Gpc analysis shows that the number-average molecular weight of copolymer is 3860,
The content of middle copolymer is 60.2%, and the content of flux oil is 39.8%, and the content of methacrylic acid C8 esters is in copolymer
60.83%, the content of propene sulfonic acid is 39.17%.
The synthesis of 6 acrylic acid C6~C8 ester butylene sulfonic acid copolymers P3 of embodiment
In the 500mL three-necked flasks with motor agitators and condenser pipe, 100 grams of toluene, 34.32 grams of propylene are added in
Sour C6 esters (0.22mol, M=156), 40.48 grams of acrylic acid C8 esters (0.22mol, M=184) add in 0.07 gram of two isobutyl of azo
Nitrile introduces nitrogen protection, opens and stir and be warming up to 80 DEG C, observing response object has apparent heat release, controlling reaction temperature at this time
It it is 96 DEG C, polymerisation 1.8 hours adds 89.8 grams of the butylene azochlorosulfonate acid mixture of the preparation of embodiment 2 (containing 53% propylene
Sulfonic acid, 0.35mol, M=136), 0.07 gram of azodiisobutyronitrile is gradually heating to 112 DEG C and carries out copolyreaction 6 hours, obtains
The liquid of brown.Reaction product with 200 grams of distilled water is washed twice respectively, then adds in 78 grams of HVI150 (Sinopec swallows
Mountain petrochemical industry branch company produces), material is warming up to 125 DEG C and is evaporated under reduced pressure, acrylic acid C6~C8 ester butylene sulfonic acid is obtained and is total to
Polymers 201 grams (P3).Infrared analysis the result shows that：In 1721cm-1、1160cm-1Nearby there is strong absworption peak, and illustrate in product
Contain ester type compound, 1184cm-1、1053cm-1、3650cm-1The spike at place shows with the presence of sulfonic acid group, 1640cm-1Locate nothing
Stretching vibration peak occurs, and does not have double bond presence in compound, it is acrylic acid C6~C8 ester butylene sulfonic acid copolymerizations to illustrate the compound
Object；Gpc analysis shows that the number-average molecular weight of copolymer is 4660, and the wherein content of copolymer is 60.70%, and flux oil contains
It is 39.30% to measure, and the content of acrylic acid C6~C8 esters is 61.12% in copolymer, and the content of butylene sulfonic acid is 38.88%.
The synthesis of (4- hydroxy phenyls) the porphyrin SYNPERONIC PE/F68 of embodiment 7 four N1
In 250 milliliters of autoclaves with motor agitators and condensation, heating mantle, four (4- hydroxy benzenes are added in
Base) porphyrin 4.5 grams (M=678.7,0.0066mol), 1.5 grams of potassium hydroxide (0.027mol) are added in, then three after nitrogen displacement
90 DEG C are warming up to after secondary；Start that 30 grams of propylene oxide (0.52mol) are added dropwise into autoclave, control reaction pressure 0.6MPa, instead
It is 125 DEG C to answer temperature, is reacted 3 hours；Ethylene oxide 14 grams (0.32mol) is added dropwise into autoclave, controls reaction pressure
0.5MPa, reaction temperature are 125 DEG C, are reacted 2 hours；10 grams of toluene is added in after reaction, transfers the material into 200ml beakers
In, remaining potassium hydroxide in 10% 50 milliliters of neutralization reaction products of sulfuric acid solution is added in, and be washed with deionized twice,
Until reaction product is in neutrality；Oil reservoir in material is put into vacuum distillation apparatus, thick liquid is obtained after steaming solvent toluene
47.8 grams, ultra-violet analysis the result shows that：There is absorption peak at 424nm (Soret bands), 521,561,599,659 (Q bands) nm.
Copolymer infrared analysis the result shows that：3350cm-1Corresponding to the hydroxyl on polyethers, 3370cm-1Corresponding is pyrrole on the big ring of porphyrin
Cough up N-H stretching vibration peaks, 1100~1200cm-1Between there is the vibration absorption peak of porphyrin ring, 1249cm-1It is stretching for phenyl ring C-O
Contracting vibration peak, 1608cm-1、1508cm-1、1473cm-1It is phenyl ring skeleton stretching vibration peak, shows that the big ring of porphyrin and tetraphenyl take
For the presence of unit structure, in addition in 1060~1150cm-1Between there is the stretching vibration peak of alkyl ehter bond, in 2900cm-1It is attached
Closely there is methyl and methylene stretching vibration peak, show polyether structure occur on the big ring of porphyrin, closed by thinking
Into being four (4- hydroxy phenyls) porphyrin propylene oxide ethylene oxide polyether compounds, pass through its number average molecular weight of gpc analysis
It is 7353.
The synthesis of (4- hydroxy phenyls) the porphyrin SYNPERONIC PE/F68 of embodiment 8 four N2
In 250 milliliters of autoclaves with motor agitators and condensation, heating mantle, four (4- hydroxy phenyls) porphins are added in
Quinoline 5 grams (M=678.7,0.0074mol), 1.25 grams of sodium hydroxides (0.031mol), heats up afterwards three times after then being replaced with nitrogen
To 90 DEG C；20 grams of propylene oxide (0.34mol) are added dropwise into autoclave, control reaction pressure 0.6MPa, reaction temperature 122
DEG C, it reacts 2.5 hours；Ethylene oxide 10.5 grams (0.24mol) is added dropwise into autoclave, controls reaction pressure 0.5MPa, reaction
Temperature is 125 DEG C, is reacted 2 hours；20 grams of dimethylbenzene are added in after reaction, are transferred the material into 200ml beakers, are added in
Remaining sodium hydroxide in 10% 50 milliliters of neutralization reaction products of sulfuric acid solution, and be washed with deionized twice, until anti-
Product is answered to be in neutrality；Oil reservoir in material is put into vacuum distillation apparatus, thick liquid 34.69 is obtained after steaming solvent xylene
Gram.Ultra-violet analysis the result shows that：There is absorption peak at 426nm (Soret bands), 522,564,599,661 (Q bands) nm.Infrared point
Analysis the result shows that：3350cm-1Corresponding to the hydroxyl on polyethers, 3370cm-1Corresponding is that pyrroles N-H stretches and shakes on the big ring of porphyrin
Dynamic peak, 1100~1200cm-1Between there is the vibration absorption peak of porphyrin ring, 1249cm-1It is the stretching vibration peak of phenyl ring C-O,
1608cm-1、1508cm-1、1473cm-1It is phenyl ring skeleton stretching vibration peak, shows the big ring of porphyrin and tetraphenyl substituent group structure
Presence, in addition in 1060~1150cm-1Between there is the stretching vibration peak of alkyl ehter bond, in 2900cm-1Nearby there is first
Base and methylene stretching vibration peak show polyether structure occur on the big ring of porphyrin, by thinking that synthesized is four (4-
Hydroxy phenyl) porphyrin propylene oxide ethylene oxide polyether compound, by gpc analysis, its number average molecular weight is 4810.
The synthesis of (4- hydroxy phenyls) the porphyrin SYNPERONIC PE/F68 of embodiment 9 four N3
Four (4- hydroxy benzenes are added in 250 milliliters of autoclaves with motor agitators and condensation, heating mantle
Base) porphyrin 4.4 grams (M=678.7,0.0065mol), 1.6 grams of potassium hydroxide are then added in, are warming up to afterwards three times after nitrogen displacement
90℃；35 grams of propylene oxide (0.60mol) are added dropwise into autoclave, control reaction pressure 0.6MPa, reaction temperature is 126 DEG C,
Reaction 3.5 hours；Ethylene oxide 12 grams (0.27mol) is added dropwise into autoclave, controls reaction pressure 0.5MPa, reaction temperature is
It 125 DEG C, reacts 2.5 hours；90 DEG C~120 DEG C petroleum ethers are added in after reaction, are transferred the material into 200ml beakers, are added
Enter remaining potassium hydroxide in 10% 50 milliliters of neutralization reaction products of sulfuric acid solution, and be washed with deionized twice, until
Reaction product is in neutrality；Oil reservoir in material is put into vacuum distillation apparatus, thick liquid is obtained after steaming solvent petroleum ether
50.9 grams.Ultra-violet analysis the result shows that：There is absorption peak at 423nm (Soret bands), 522,562,599,658 (Q bands) nm.It is red
Outer analysis the result shows that：3350cm-1Corresponding to the hydroxyl on polyethers, 3370cm-1Corresponding is that pyrroles N-H stretches on the big ring of porphyrin
Contracting vibration peak, 1100~1200cm-1Between there is the vibration absorption peak of porphyrin ring, 1249cm-1It is the stretching vibration of phenyl ring C-O
Peak, 1608cm-1、1508cm-1、1473cm-1It is phenyl ring skeleton stretching vibration peak, shows the big ring of porphyrin and tetraphenyl substituent group
The presence of structure, in addition infrared analysis result be shown in 1060~1150cm-1Between there is the stretching vibration peak of alkyl ehter bond,
2900cm-1Nearby there is methyl and methylene stretching vibration peak, show polyether structure, as four occur on the big ring of porphyrin
(4- hydroxy phenyls) porphyrin propylene oxide ethylene oxide polyether compound, by gpc analysis, its number average molecular weight is 7862.
The synthesis of 1 acrylic acid C5 ester acrylic copolymers D1 of comparative example
In the 500mL three-necked flasks with motor agitators and condenser pipe, 110 grams of toluene, 63.9 grams of propylene are added in
Sour C5 esters (0.45mol, M=142) add in 0.08 gram of azodiisobutyronitrile, introduce nitrogen protection, open and stir and be warming up to 70
DEG C, observing response object has apparent heat release at this time, and controlling reaction temperature is 90 DEG C, and polymerisation 1 hour adds acrylic acid 18
Gram (0.25mol, M=72), 0.05 gram of azodiisobutyronitrile are gradually heating to 105 DEG C and carry out copolyreaction 4 hours.To reaction
Product is washed twice respectively with 200 grams of distilled water, then adds in 52 grams of HVI150 (production of Sinopec Yanshan Petrochemical branch company),
Material is warming up to 125 DEG C to be evaporated under reduced pressure, obtains acrylic acid C5 esters acrylic copolymer 135 grams (D2).Analysis result table
It is bright：The number-average molecular weight of copolymer is 4938, and wherein the content of copolymer is 61.48%, and the content of flux oil is 38.52%,
The content of acrylic acid C5 esters is 78.02% in copolymer, and the content of acrylic acid is 22.98%.
2 ethylene glycol of comparative example and propylene oxide, ethylene oxide copolymer D2
In 250 milliliters of autoclaves with motor agitators and condensation, heating mantle, 0.5 gram of solid hydrogen is added in
Sodium oxide molybdena (0.0125mol), ethylene glycol 0.4 gram (0.0066mol) are then warming up to 90 DEG C afterwards three times after nitrogen displacement；Start
30 grams of propylene oxide (0.52mol) are added dropwise into autoclave, control reaction pressure 0.6MPa, reaction temperature is 125 DEG C, reaction 3
Hour；Ethylene oxide 14 grams (0.32mol) is added dropwise into autoclave, controls reaction pressure 0.5MPa, reaction temperature is 125 DEG C,
Reaction 2 hours；Reaction pressure 0.5MPa is controlled, reaction temperature is 125 DEG C, is reacted 2 hours；It transfers the material into after reaction
In 200ml beakers, remaining sodium hydroxide in 10% 50 milliliters of neutralization reaction products of sulfuric acid solution is added in, and use deionized water
Twice of washing, until reaction product is in neutrality；Oil reservoir in material is put into vacuum distillation apparatus, steam obtain after solvent it is purplish red
44.89 grams of the thick liquid of color, infrared analysis the result shows that：3350cm-1Corresponding to the hydroxyl on polyethers, 1060~
1150cm-1Between there is the stretching vibration peak of alkyl ehter bond, in 2900cm-1Nearby there is methyl and methylene stretching vibration
Peak shows there are polyether structure, as ethylene glycol propylene oxide ethylene oxide polyether compound, its number is divided equally by gpc analysis
Protonatomic mass is 6729.
Embodiment 10
The demulsifier synthesized above according to following combination is allocated, forms the breaker composition of following table.
The proportioning of 3 breaker composition of the present invention of table
Embodiment 11~26 and comparative example 3~30
Be separately added into 0.5% T502A antioxidant, 0.1% T551 metal deactivators, 0.1% T746 antirust agent,
0.01% or 0.02% breaker composition or comparison demulsifier, the base oil for then adding in surplus is prepared to obtain L-TSA32
The embodiment 11~18 of steam turbine oil and comparative example 3~16, the base oil be by mass ratio be 1：1 HVI 200N and HVI
150 modulate and obtain.The type and addition of demulsifier in the embodiment 11~18 of L-TSA32 steam turbine oils and comparative example 3~16
It is shown in Table 4.
Be separately added into 1.2% T321,1.5% T307,0.1% T405,0.1% T451,0.06% T102,
Then the breaker composition of 0.05% T502A, 0.02% or 0.03% or comparison demulsifier add in the base oil of surplus,
Preparation obtains the embodiment 19~26 of L-CKD N220 industrial gear oils and comparative example 17~30, wherein the base oil is
It is 7 by mass ratio：3 HVI750 and 150BS is modulated and is obtained.The embodiment 19~26 of L-CKD N220 industrial gear oils and right
The type of demulsifier and addition are shown in Table 5 in ratio 17~30.
Demulsibility test, experiment knot are carried out according to 7305 methods of GB/T to above-mentioned steam turbine oil, Industrial gear oil composition
Fruit is same to be shown in Table 4,5.
By table 4,5 as can be seen that with alkyl acrylate and α olefin sulfonic acids copolymer and four (4- hydroxy phenyls) porphyrins
The demulsification of compound breaker composition is best with propylene oxide, ethylene oxide polymer, and better than T1001 demulsifiers.
The emulsion resistance result ((40-37-3,54 DEG C)/min) of table 4L-TSA32 steam turbine oils
| Embodiment | Demulsifier | Additive amount/% | Water-separating time/min |
| Blank | - | 0 | 29 |
| Embodiment 11 | Demulsifier 1 | 0.01 | 2.1 |
| Embodiment 12 | Demulsifier 2 | 0.01 | 2.2 |
| Embodiment 13 | Demulsifier 3 | 0.01 | 2.1 |
| Embodiment 14 | Demulsifier 4 | 0.01 | 2.3 |
| Comparative example 3 | 100%P1 | 0.01 | 3.5 |
| Comparative example 4 | 100%P3 | 0.01 | 3.5 |
| Comparative example 5 | 100%D1 | 0.01 | 6.5 |
| Comparative example 6 | 100%D2 | 0.01 | 6.1 |
| Comparative example 7 | 50%D1+50%P1 | 0.01 | 4.8 |
| Comparative example 8 | 50%P3+50%D2 | 0.01 | 4.6 |
| Comparative example 9 | T1001 | 0.01 | 8.1 |
| Embodiment 15 | Demulsifier 1 | 0.02 | 1.0 |
| Embodiment 16 | Demulsifier 2 | 0.02 | 1.1 |
| Embodiment 17 | Demulsifier 3 | 0.02 | 1.0 |
| Embodiment 18 | Demulsifier 4 | 0.02 | 1.2 |
| Comparative example 10 | 100%P1 | 0.02 | 1.8 |
| Comparative example 11 | 100%P3 | 0.02 | 1.9 |
| Comparative example 12 | 100%D1 | 0.02 | 4.3 |
| Comparative example 13 | 100%D2 | 0.02 | 3.9 |
| Comparative example 14 | 50%D1+50%P1 | 0.02 | 3.8 |
| Comparative example 15 | 50%P3+50%D2 | 0.02 | 2.9 |
| Comparative example 16 | T1001 | 0.02 | 5.9 |
The emulsion resistance result ((40-37-3,82 DEG C)/min) of table 5L-CKD N220 industrial gear oils
Claims (15)
1. a kind of breaker composition, including：1) copolymer of the first demulsifier, alkyl acrylate and α-olefin sulfonic acid；
2) second of demulsifier, four (4- hydroxy phenyls) porphyrins and propylene oxide, the polymeric reaction product of ethylene oxide；Therebetween
Mass ratio is 1~10：10~1；
The structure of the first demulsifier is：
Wherein R is C4~C18 alkyl or its mixed alkyl；A1 is hydrogen or methyl, and A2 is hydrogen or C1~C4 alkyl, and x is 0~4
Integer；When A2 is hydrogen, x is positive integer；M is 1~50 integer, and n is 1~50 integer；
The structure of second of demulsifier is：
Wherein j is the integer between 5~50；K is the integer between 5~40.
2. breaker composition described in accordance with the claim 1, which is characterized in that the R is C4~C15 alkyl or its mixing alkane
Base；A2 is hydrogen, methyl, ethyl or propyl, and x is 0~3 integer；M is 5~50 integer, and n is 5~50 integer.
3. breaker composition described in accordance with the claim 1, which is characterized in that the molecular weight of the first demulsifier exists
Between 1000~15000.
4. breaker composition described in accordance with the claim 1, which is characterized in that the preparation method of the first demulsifier is
Alkyl acrylate and α-olefin sulfonic acid are copolymerized, collect product.
5. according to the breaker composition described in claim 4, which is characterized in that
The structure of the alkyl acrylate is：
Wherein R is C4~C18 alkyl or its mixed alkyl；A1 is hydrogen or methyl；
The structure of the α-olefin sulfonic acid is：
A2 is hydrogen or C1~C4 alkyl, and x is 0~4 integer；When A2 is hydrogen, x is positive integer.
6. according to the breaker composition described in claim 4, which is characterized in that the alkyl acrylate and α-olefin sulfonic acid
Between molar ratio be 1~50：50~1.
7. according to the breaker composition described in claim 4, which is characterized in that the alkyl acrylate and α-olefin sulfonic acid
The temperature being copolymerized is 20~200 DEG C, and the time of polymerization is 1~20 hour.
8. according to the breaker composition described in claim 4, which is characterized in that the alkyl acrylate and α-olefin sulfonic acid
Initiator is added in when being copolymerized, addition is the 0.1%~10% of alkyl acrylate and α-olefin sulfonic acid gross mass；
The initiator is azo compound and/or peroxide.
9. breaker composition described in accordance with the claim 1, which is characterized in that the structure of described four (4- hydroxy phenyls) porphyrin
For：
10. breaker composition described in accordance with the claim 1, which is characterized in that the preparation method of second of demulsifier
It is that polymerisation is first occurred into for four (4- hydroxy phenyls) porphyrins and propylene oxide, then polymerisation occurs with ethylene oxide, collects
Product.
11. according to breaker composition according to any one of claims 10, which is characterized in that four (4- hydroxy phenyls) porphyrin and ring
Ethylene Oxide molar ratio is 1：20~200, pressure during polymerisation occurs with propylene oxide for four (4- hydroxy phenyls) porphyrin
For 0.1~1MPa；Reaction temperature is 80 DEG C~200 DEG C；Reaction time is 1~10 hour.
12. according to breaker composition according to any one of claims 10, which is characterized in that four (4- hydroxy phenyls) porphyrin and ring
The molar ratio of oxidative ethane is 1：20~160；After with propylene oxide polymerisation occurs for four (4- hydroxy phenyls) porphyrin, with ring
The pressure that polymerisation occurs again for oxidative ethane is 0.1~1MPa；Reaction temperature is 80 DEG C~200 DEG C；Reaction time is 1~10
Hour.
13. according to breaker composition according to any one of claims 10, which is characterized in that between the propylene oxide and ethylene oxide
Molar ratio be 1~5：1.
14. a kind of lubricant oil composite, including the breaker composition and lubricating base oil described in one of claim 1-13, institute
State breaker composition accounts for lubricant oil composite gross mass 0.001%~1%.
A kind of 15. method for improving lubricating oil demulsification performance, which is characterized in that by the demulsifier described in one of claim 1-13
Composition is added in lubricating oil, and the breaker composition accounts for the 0.001%~1% of lubricating oil gross mass.
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| CN101352666A (en) * | 2007-07-26 | 2009-01-28 | 中国石油化工股份有限公司 | Compound demulsifying agent and method of use thereof |
| CN102634402A (en) * | 2011-02-10 | 2012-08-15 | 中国石油化工股份有限公司 | Demulsifier composition and lubricating oil |
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| US4529527A (en) * | 1984-05-14 | 1985-07-16 | Exxon Research And Engineering Co. | Method for controlling viscosity of lubricating oils |
| CN101352666A (en) * | 2007-07-26 | 2009-01-28 | 中国石油化工股份有限公司 | Compound demulsifying agent and method of use thereof |
| CN102634402A (en) * | 2011-02-10 | 2012-08-15 | 中国石油化工股份有限公司 | Demulsifier composition and lubricating oil |
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