CN105567382B - Breaker composition and lubricant oil composite - Google Patents
Breaker composition and lubricant oil composite Download PDFInfo
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- CN105567382B CN105567382B CN201410586678.2A CN201410586678A CN105567382B CN 105567382 B CN105567382 B CN 105567382B CN 201410586678 A CN201410586678 A CN 201410586678A CN 105567382 B CN105567382 B CN 105567382B
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Abstract
The present invention provides a kind of breaker composition and include the lubricant oil composite of the breaker composition.The breaker composition of the present invention, including：1) copolymer of alkyl acrylate and α olefin sulfonic acids；2) copolymer of sulfenyl phenolate and propylene oxide, ethylene oxide；Mass ratio between the two 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, can be used for industrial gear oil, steam turbine oil, crank axle for vessel case oil.
Description
Technical field
The present invention relates to a kind of breaker compositions, more particularly to are suitable for the breaker composition of lubricating oil.
Background technology
Steam turbine oil, industrial gear oil, maritime applications system lubricating oil etc. have been frequently run onto field existing for water in use
It closing, these lubricating oil are easy to form the emulsification system of Water-In-Oil with water, especially when containing additive with surface-active,
Emulsification of lubricating oils situation is more serious.If water-oil separating cannot be realized in time, it will deteriorate oil lubrication situation, less serious case
The formation of oil film can be influenced, lubricating ability is reduced, severe one can cause the corrosion and abrasion of machinery, or even damage equipment, influence to give birth to
Production and safety.Therefore, the demulsification resistance 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 broken
Newborn method etc..Wherein, addition demulsifying agent makes the chemical demulsification method of the grease quick separating of lubricating oil, need not additionally increase and set
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 the atom for connecting 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,
Compound with the above structure has preferable detergency.
The study found that various demulsifiers, which are applied in combination, reaches preferable demulsification, such as：CN 1013502B are described
A kind of anti-emulsifying compound additive for lubricant is the four poly- trimethylene derivative of alkylene diamine by average molecular weight 2000~10000
With selected from C10~C20Alkenyl succinic acid, C10~C36Carboxylic acid dimerization, C10~C22One kind of saturated or unsaturated aliphatic acid has
Machine carboxylic acid composition forms.The anti-emulsifying compound agent is used as the lubricating oil component including steam turbine oil, gear oil, hydraulic oil,
Its demulsification performance and rustless property can be effectively improved.
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.
Although the demulsifier of the above patent introduction can be used for lubricating oil demulsification, there are still demulsification is effective
Fruit is bad, the problem of needing that more demulsifier is added.In addition, some demulsifiers, especially polyethers demulsifier is due to containing
Hydrophilic radical and be easy separated with oil phase, not only cause the production cost of lubricating oil to rise, at the same also be not easy guarantee 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 and include the lubricant oil composite of the breaker composition.
The breaker composition of the present invention, including：1) copolymer of alkyl acrylate and α-olefin sulfonic acid；2) vulcanize alkane
The copolymer of base phenol and propylene oxide, ethylene oxide；Mass ratio between the two is 1~10：10~1, preferably 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 R1 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 be hydrogen or methyl, A2 be hydrogen or C1~C4 alkyl, preferably hydrogen, methyl, ethyl or
Propyl, most preferably hydrogen, methyl or ethyl, the integer that x is 0~4, preferably 0~3 integer, most preferably 0~2 integer；When A2 is
When hydrogen, x is positive integer；The integer that m is 1~50, preferably 5~50, the integer that most preferably 10~30, n is 1~50, 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
It answers, collects product.
The structure of the alkyl acrylate is：
Wherein R1 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 obtained by esterification with alkylol by methacrylic acid or acrylic acid, 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 sulfonating reaction is occurred for alpha-olefin and sulfonating agent and is obtained.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
It is preferred that or mixtures thereof C5~C10 alkane.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.
Initiator is added in the alkyl acrylate and α-olefin sulfonic acid when being copolymerized, addition is alkyl acrylate
The 0.05%~5% of base ester and α-olefin sulfonic acid gross mass, preferably 0.05%~3%；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 20%~100% 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.
The structure of second of demulsifier is：
Wherein X group isA be 10~100 between integer, preferably 15~80, it is optimal
It is the integer between 5~100, preferably 5~60, most preferably 10~40 to select 20~60, b；K be 1~10 between integer, preferably 1
~6, most preferably 1~2；J is the integer between 1~10, and the j on each sulphur bridge can be the same or different, preferably 1~6, most
It is preferred that 1~4；R2 is C1~C18 alkyl or its mixed alkyl, preferably C3~C15 alkyl or its mixed alkyl, most preferably C3~
C10 alkyl or its mixed alkyl.
The preparation method of second of demulsifier includes：By sulfenyl phenolate first with Polymerization of Propylene Oxide, again with epoxy
Ethane polymerize, and collects product.
The sulfenyl phenolate is vulcanization C1~C18 alkyl phenols, preferably vulcanizes C3~C15 alkyl phenols, most preferably vulcanizes C3
~C12 aligns alkyl phenol；The sulfenyl phenolate is obtained by the reaction by alkyl phenol and vulcanizing agent, and the vulcanizing agent can select sulphur
One or more in sulphur, sulfur chloride and sulfur dichloride, the molar ratio of the alkyl phenol and the vulcanizing agent is 1~3：3~1.
The temperature of vulcanization is room temperature to 200 DEG C.The sulfur content of sulfenyl phenolate obtained is 5%~20%.
The molar ratio of phenolic hydroxyl group and propylene oxide in the sulfenyl phenolate is 1：10~100, preferably 1：15~80, most
It is preferred that 1：20~60；The molar ratio of phenolic hydroxyl group and ethylene oxide in the sulfenyl phenolate is 1：5~100, preferably 1：5~
60, most preferably 1：10~40.
When preparing second of demulsifier of the present invention, it is preferably added to solvent, the solvent preferred aromatic hydrocarbons solvent, most preferably
Dimethylbenzene and/or toluene, the mass ratio preferably 1 of the sulfenyl phenolate and the solvent：0.1~50, more preferable 1：0.2~
20, most preferably 1：0.5~10.
When preparing second of demulsifier of the present invention, it is preferably added to catalyst, the catalyst preferred as alkali hydrogen-oxygen
Compound, most preferably potassium hydroxide and/or sodium hydroxide, the molar ratio preferably 1 of the sulfenyl phenolate and the catalyst：1~
20, more preferable 1：1~10, most preferably 1：3~8.
The sulfenyl phenolate and propylene oxide, ethylene oxide polymerization reaction pressure be 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℃；Reaction time is 1~10 hour, preferably 2~8 hours, most preferably 2~4 hours.
When preparing second of demulsifier of the present invention, after the polymerisation, it is added 60 into reaction product~
90 DEG C of petroleum ethers, 10% sulfuric acid solution, neutralization reaction product to neutrality, divide water, it is dry after, neutral oil is added, steams solvent,
Obtain sulfenyl phenolate propylene oxide ethylene oxide polymer.
The molecular weight of second of demulsifier of the invention is 1000~30000, preferably 5000~20000, most preferably 10000~
20000。
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 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 lubricant oil composite 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, can be used for industrial gear oil, steam turbine oil, crank axle for vessel case oil.
Specific implementation mode
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：Sample and each 40mL of distilled water are packed into defined graduated cylinder, under measuring temperature, with 1500r/
It keeps standing after the rotating speed stirring 5min of min, and starts timing, 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 stand 30min (test temperature be 54 ± 1 DEG C) or 1h (it is oily still to be separated with water when test temperature be 82 ± 1 DEG C,
Then report oil either Synthesis liquid, the ml of water and remaining emulsion volume.It is to be basically separated qualification to reach 40-37-3, is reached
It is to be kept completely separate to 40-40-0.
The physico-chemical analysis data of 1 lube base oil of table
2. raw material sources
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. |
| T551 | Benzotriazole derivative | Liaoning Tianhe Fine Chemical Co., Ltd. |
| T746 | Alkenyl succinic acid | Liaoning Tianhe Fine Chemical Co., Ltd. |
| T1001 | Ethylenediamine propylene oxide polyether compound | Jinzhou Kangtai Lube Additive Co., Ltd. |
The preparation of 1 propene sulfonic acid mixture of embodiment
With stirring, heating, cryostat the corrosion-resistant autoclaves of 500mL in be added 80 grams of 30 DEG C~60 DEG C petroleum ethers, so
Rear enclosed reaction kettle opens stirring, and is passed through cryostat and carries out temperature control, then squeezes into 40 grams of propylene into kettle with high-pressure pump
(0.952mol), and be passed through high pure nitrogen, control reactor pressure between 0.8~1MPa, control the temperature of reaction kettle 0~
10 DEG C, the steel cylinder for storing sulfur trioxide is heated, is placed on electronic scale and measures, then controlled heating temperature and make three oxidations
Sulphur steel cylinder pressure is more than autoclave pressure, and opens sulfur trioxide steel cylinder outlet valve, and gas is passed through to the snorkel of autoclave
In, it then passes to and carries out sulfonating reaction in the liquid phase of autoclave, sulfur trioxide intake is 77.7 grams (0.971mol), at this time
Controlling pressure in reaction kettle, between 0.8~1.2MPa, the reaction time is 3.2 hours, after reaction, continuously decreases reactor
Pressure, after pressure reaches normal pressure, stop stirring, then solvent distillation, obtains 115.8 grams of propene sulfonic acid mixture, analysis
It was found that；Containing 54% propene sulfonic acid in the product, the acid value of 46% propene sultone, mixture is 260.8mgKOH/g.
The preparation of 2 butylene azochlorosulfonate acid mixture of embodiment
With stirring, heating, cryostat 500mL autoclaves in 70 grams of n-hexanes are added, 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 at 0~10 DEG C, will store sulfur trioxide between 0.8~1MPa
Steel cylinder heats, and is placed on electronic scale and measures, and then controls heating temperature and sulfur trioxide steel cylinder pressure is made 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, the liquid of autoclave is then passed to
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, stopping stirring, then solvent distillation obtains 91.3 grams of butylene azochlorosulfonate acid mixture, containing 53% butylene sulfonic acid in the product,
The acid value of 47% butene sultone, mixture is 225.3mgKOH/g.
The synthesis of 3 sulfenyl phenolate A of embodiment
Nonyl phenol 100 grams (0.455mol), 100mL are added in the 500ml three-necked flasks with temperature control and water cooling, stirring
N-decane is added sulphur 35 grams (1.09mol), is then gradually heating to 160 DEG C, with nitrogen protection reaction mass, while will be anti-
Tail gas is answered to be passed through 10% sodium hydroxide solution, with the hydrogen sulfide gas that absorbing reaction generates, nonyl phenol is by colourless gradual change at this time
For dark brown, black liquor is eventually become, after reacting 4 hours, vacuum distillation obtains controlled at 165 DEG C after steaming desolventizing
Sulfenyl phenolate A, it is 23.9% to measure sulfur content.It is measured with VPO methods, the average molecular weight of vulcanization nonyl phenol A is 881 (equivalent
Contain 3 alkyl phenols in each molecule, 3.5) average value of k 1, number of sulfur atoms j are.
The synthesis of 4 sulfenyl phenolate B of embodiment
Dodecylphenol 100 grams (0.382mol) is added in the 500ml three-necked flasks with temperature control and water cooling, stirring,
60~90 DEG C of petroleum ethers of 100ml, controlled at 25~35 DEG C, then be added dropwise sulfur monochloride 36 grams (0.267mol), then by
160 DEG C are gradually warming up to, with nitrogen protection reaction mass, while reaction end gas is passed through 10% sodium hydroxide solution, it is anti-to absorb
The hydrogen chloride gas that should be generated, at this time dodecylphenol gradually become dark brown by colourless, black liquor is eventually become, by 5
It is dripped off after hour, then heats to 100 DEG C, removed solvent, obtain sulfenyl phenolate B, it is 14.7% to measure sulfur content.Use VPO
The average molecular weight of method measurement, vulcanization dodecylphenol B (converts into each molecule containing 3 alkyl phenols, k 1, sulphur original for 912
2) subnumber j is.
The synthesis of 5 sulfenyl phenolate C of embodiment
Nonyl phenol 100 grams (0.455mol), 100mL are added in the 500ml three-necked flasks with temperature control and water cooling, stirring
N-decane is added sulfur dichloride 35.1 grams (0.34mol), is then gradually heating to 160 DEG C, with nitrogen protection reaction mass, together
When reaction end gas is passed through 10% sodium hydroxide solution, with the hydrogen chloride gas that absorbing reaction generates, nonyl phenol is by colourless at this time
Dark brown is gradually become, black liquor is eventually become, after reacting 4 hours, vacuum distillation steams desolventizing controlled at 165 DEG C
After obtain sulfenyl phenolate C, it is 10.2% to measure sulfur content, is measured with VPO methods, and the average molecular weight of vulcanization nonyl phenol A is 970
It (converts into and contains 4 alkyl phenols in each molecule, 1) k 2, number of sulfur atoms j are.
The synthesis of 6 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
0.08 gram of azodiisobutyronitrile is added in sour C5 esters (0.45mol, M=142), introduces nitrogen protection, opens and stirs and be warming up to 70
DEG C, it is 90 DEG C that observing response object, which has apparent heat release, controlling reaction temperature, at this time, 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 with 200 grams of distilled water respectively
60 grams of HVI150 (production of Sinopec Yanshan Petrochemical branch company) are added, 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 illustrates to contain ester type compound in product, 1184cm-1、1053cm-1, 3650cm-1Neighbouring spike shows there is sulphur
Acid groups exist, 1640cm-1Nearby non-telescope vibration peak occurs, and does not have double bond presence in compound, illustrates that the compound is third
Olefin(e) acid C5 ester butylene sulfonic acid copolymers；Gpc analysis shows that the number-average molecular weight of copolymer is being 5130, and wherein copolymer contains
Amount is 61.92%, and 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 be 34.53%.
The synthesis of 7 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
0.07 gram of azodiisobutyronitrile is added in base acrylic acid C8 esters (0.371mol, M=198), introduces nitrogen protection, opens stirring simultaneously
75 DEG C are warming up to, it is 95 DEG C that observing response object, which has apparent heat release, controlling reaction temperature, at this time, polymerisation 1.5 hours, then is added
Enter embodiment 1 preparation 90.37 grams of propene sulfonic acid mixture (containing 54% propene sulfonic acid, 0.4mol, M=122), 0.06 gram
Azodiisobutyronitrile is gradually heating to 108 DEG C and carries out copolyreaction 5 hours.Reaction product is washed with 200 grams of distilled water respectively
Twice, then be added 80 grams of 6# base oils (production of Sinopec Shanghai Gaoqiao petrochemical industry branch company), by material be warming up to 125 DEG C into
Row vacuum distillation, obtains methacrylic acid C8 ester propene sulfonic acids copolymer 201 grams (P2).Infrared analysis the result shows that：
1721cm-1、1160cm-1Nearby there is strong absworption peak, illustrates to contain ester type compound in product, 1184cm-1、1053cm-1,
3650cm-1Neighbouring spike shows with the presence of sulfonic acid group, 1640cm-1Nearby non-telescope vibration peak occurs, and does not have in compound
Double bond exists, and illustrates that the compound is methacrylic acid C8 ester propene sulfonic acid copolymers；Gpc analysis shows that the number of copolymer is equal
Molecular weight is 3860, and wherein the content of copolymer is 60.2%, and the content of flux oil is 39.8%, methacrylic acid in copolymer
The content of C8 esters is 60.83%, and the content of propene sulfonic acid is 39.17%.
The synthesis of 8 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
0.07 gram of two isobutyl of azo is added in sour C6 esters (0.22mol, M=156), 40.48 grams of acrylic acid C8 esters (0.22mol, M=184)
Nitrile introduces nitrogen protection, opens and stirs 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.To anti-
Product is answered to be washed twice with 200 grams of distilled water respectively, 78 grams of HVI150 are then added, and (Sinopec Yanshan Petrochemical branch company gives birth to
Production), material is warming up to 125 DEG C and is evaporated under reduced pressure, acrylic acid C6~C8 ester butylene sulfonic acid copolymer 201 grams (P3) is obtained.
Infrared analysis the result shows that：In 1721cm-1、1160cm-1Nearby there is strong absworption peak, illustrate to contain ester type compound in product,
1184cm-1、1053cm-1、3650cm-1Neighbouring spike shows with the presence of sulfonic acid group, 1640cm-1Neighbouring non-telescope vibration peak
Occur, there is no double bond presence in compound, illustrate that the compound is acrylic acid C6~C8 ester butylene sulfonic acid copolymers；Gpc analysis
Show that the number-average molecular weight of copolymer is 4660, the wherein content of copolymer is 60.70%, and the content of flux oil is
39.30%, the content of acrylic acid C6~C8 esters is 61.12% in copolymer, and the content of butylene sulfonic acid is 38.88%.
The preparation of 9 sulfenyl phenolate propylene oxide ethylene oxide polymer M1 of embodiment
In 250 milliliters of autoclaves with motor agitators and condensation, heating mantle, sulfenyl phenolate A 3.4 is added
Gram (0.0039mol contains 0.012mol phenolic hydroxyl groups), 5 grams of dimethylbenzene, 1 gram of solid potassium hydroxide (0.0179mol) are then used
Nitrogen displacement is warming up to 90 DEG C afterwards three times；30 grams of propylene oxide (0.517mol) are added dropwise into autoclave, control reaction pressure
0.6MPa, reaction temperature are 122 DEG C, are reacted 2.5 hours；Ethylene oxide 12 grams (0.272mol), control are added dropwise into autoclave
Reaction pressure 0.5MPa, reaction temperature are 125 DEG C, are reacted 2 hours；It transfers the material into 200ml beakers, adds after reaction
Enter 60~90 DEG C of 30 grams of petroleum ethers, 50 milliliters of 10% sulfuric acid solution, remaining potassium hydroxide in neutralization reaction product, and spends
Ion water washing, until reaction product is in neutrality；12 grams of HVI150 neutral oils are added, the oil reservoir in material is put into vacuum distillation
Device obtains 53.3 grams of product after steaming solvent, as vulcanizes nonyl phenol propylene oxide ethylene oxide polymer M1, infrared analysis
The result shows that 723cm in product-1Neighbouring peak corresponds to the stretching vibration peak of S -- S, 1500cm-1、1249cm-1Neighbouring peak corresponds to
In the stretching vibration peak of aromatic ring and hydroxyl oxygen, in 1060~1150cm-1Nearby there is the stretching vibration peak of alkyl ehter bond,
2900cm-1Neighbouring peak corresponds to methyl and methylene stretching vibration peak, shows that the compound generated is sulfenyl phenolate epoxy third
Alkane ethylene oxide polymer, determination of elemental analysis sulfur content are 1.56%, and by gpc analysis, its number average molecular weight is 11094.
The preparation of 10 sulfenyl phenolate propylene oxide ethylene oxide polymer M2 of embodiment
In 250 milliliters of autoclaves with motor agitators and condensation, heating mantle, sulfenyl phenolate B 4.25 is added
Gram (0.00467mol contains 0.014mol phenolic hydroxyl groups), 6 grams of dimethylbenzene, 1.2 grams of solid potassium hydroxides (0.0214mol), then
It is warming up to 90 DEG C afterwards three times with nitrogen displacement；28 grams of propylene oxide (0.483mol) are added dropwise into autoclave, control reaction pressure
0.6MPa, reaction temperature are 122 DEG C, are reacted 2.5 hours；Ethylene oxide 17 grams (0.386mol), control are added dropwise into autoclave
Reaction pressure 0.5MPa, reaction temperature are 125 DEG C, are reacted 3 hours；It transfers the material into 200ml beakers, adds after reaction
Enter 60~90 DEG C of 40 grams of petroleum ethers, remaining potassium hydroxide in 10% 50 milliliters of neutralization reaction products of sulfuric acid solution is added, and
It is washed with deionized, until reaction product is in neutrality；10 grams of 6# base oils are added, the oil reservoir in material is put into vacuum distillation
Device obtains 58.8 grams of thick liquid after steaming solvent, as vulcanizes dodecylphenol propylene oxide ethylene oxide polymer M2,
Infrared analysis the result shows that, 723cm in product-1Neighbouring peak corresponds to the stretching vibration peak of S -- S, 1500cm-1、1249cm-1It is attached
Nearly peak corresponds to the stretching vibration peak of aromatic ring and hydroxyl oxygen, in 1060~1150cm-1Nearby there is the stretching vibration of alkyl ehter bond
Peak, in 2900cm-1Neighbouring peak corresponds to methyl and methylene stretching vibration peak, shows that the compound generated is sulfenyl phenolate ring
Ethylene Oxide ethylene oxide polymer, determination of elemental analysis sulfur content are 1.06%, and by gpc analysis, its number average molecular weight is
10366。
The preparation of 11 sulfenyl phenolate propylene oxide ethylene oxide polymer M3 of embodiment
In 250 milliliters of autoclaves with motor agitators and condensation, heating mantle, sulfenyl phenolate C 3.0 is added
Gram (0.0031mol contains 0.0124mol phenolic hydroxyl groups) 5 grams of dimethylbenzene, 1.3 grams of solid potassium hydroxides (0.0232mol), then
It is warming up to 90 DEG C afterwards three times with nitrogen displacement；22 grams of propylene oxide (0.38mol) are added dropwise into autoclave, control reaction pressure
0.6MPa, reaction temperature are 122 DEG C, are reacted 2.5 hours；Ethylene oxide 20 grams (0.455mol), control are added dropwise into autoclave
Reaction pressure 0.5MPa, reaction temperature are 125 DEG C, are reacted 3 hours；It transfers the material into 200ml beakers, adds after reaction
Enter 60~90 DEG C of 35 grams of petroleum ethers, remaining potassium hydroxide in 10% 50 milliliters of neutralization reaction products of sulfuric acid solution is added, and
It is washed with deionized, until reaction product is in neutrality；9 grams of HVI150 oil is added, the oil reservoir in material is put into vacuum distillation
Device obtains 54.6 grams of thick liquid after steaming solvent, as vulcanization nonyl phenol propylene oxide ethylene oxide polymer M3, infrared
Analysis result shows 723cm-1Neighbouring peak corresponds to the stretching vibration peak of S -- S, 1500cm-1、1249cm-1Neighbouring peak corresponds to
The stretching vibration peak of aromatic ring and hydroxyl oxygen, in 1060~1150cm-1Between peak correspond to alkyl ehter bond stretching vibration peak,
2900cm-1Neighbouring peak corresponds to methyl and methylene stretching vibration peak, shows that the compound generated is sulfenyl phenolate epoxy third
Alkane ethylene oxide polymer, determination of elemental analysis sulfur content are 0.57%, and by gpc analysis, its number average molecular weight is 14353.
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
0.08 gram of azodiisobutyronitrile is added in sour C5 esters (0.45mol, M=142), introduces nitrogen protection, opens and stirs and be warming up to 70
DEG C, it is 90 DEG C that observing response object, which has apparent heat release, controlling reaction temperature, at this time, 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 with 200 grams of distilled water respectively, and 52 grams of HVI150 (production of Sinopec Yanshan Petrochemical branch company) are then added,
Material is warming up to 125 DEG C to be evaporated under reduced pressure, obtains acrylic acid C5 esters acrylic copolymer 135 grams (D1).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 21.98%.
The synthesis of 2 alkyl phenol propylene oxide ethylene oxide polymer N1 of comparative example
In 250 milliliters of autoclaves with motor agitators and condensation, heating mantle, 2.8 grams of nonyl phenol is added
(0.0127mol contains 0.0127mol phenolic hydroxyl groups), 1 gram of solid potassium hydroxide (0.0179mol) rise after then being replaced with nitrogen
Temperature is to 92 DEG C；30 grams of propylene oxide (0.517mol) are added dropwise into autoclave, control reaction pressure 0.6MPa, reaction temperature is
It 125 DEG C, reacts 2.5 hours；Ethylene oxide 12 grams (0.272mol) is added dropwise into autoclave, controls reaction pressure 0.5MPa, instead
It is 125 DEG C to answer temperature, is reacted 2 hours；It transfers the material into after reaction in 200ml beakers, 60~90 DEG C of petroleum ethers is added
50 grams, remaining potassium hydroxide in 10% 50 milliliters of neutralization reaction products of sulfuric acid solution, and be washed with deionized, until anti-
Product is answered to be in neutrality；12 grams of HVI150 neutral oils are added, the oil reservoir in material is put into vacuum distillation apparatus, are obtained after steaming solvent
To 55.6 grams of thick liquid, infrared analysis the result shows that, 1500cm-1、1249cm-1Neighbouring peak corresponds to aromatic ring and hydroxyl oxygen
Stretching vibration peak, 1060~1150cm-1Between peak correspond to the stretching vibration peak of alkyl ehter bond, in 2900cm-1Neighbouring peak corresponds to
Methyl and methylene stretching vibration peak show that the compound generated is nonyl phenol propylene oxide ethylene oxide polymer N1, pass through
Its number average molecular weight of gpc analysis is 3561.
Embodiment 12
The demulsifier synthesized above is allocated according to following combination, forms the breaker composition of following table.
The proportioning of 3 breaker composition of the present invention of table
Embodiment 13~28 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 that surplus is then added is prepared to obtain L-TSA32
The embodiment 13~20 and comparative example 3~16 of steam turbine oil, it is 1 that the base oil, which is by mass ratio,：1 HVI 200N and HVI
150SN is modulated and is obtained.The type of demulsifier and addition in the embodiment 13~20 and comparative example 3~16 of L-TSA32 steam turbine oils
Amount is shown in Table 4.
Be separately added into 1.2% T321,1.5% T307,0.1% T405,0.1% T451,0.06% T102,
The breaker composition or comparison demulsifier of 0.05% T502A, 0.02% or 0.03%, are then added the base oil of surplus,
Preparation obtains the embodiment 21~28 and comparative example 17~30 of L-CKD N220 industrial gear oils, wherein the base oil is
It is 7 by mass ratio：3 HVI750 and 150BS is modulated and is obtained.The embodiment 21~28 of L-CKD N220 industrial gear oils and right
The type and addition of demulsifier 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 alkenyl sulfonic acid copolymers and sulfenyl phenolate and epoxy third
The demulsification of the compound breaker composition of alkane, ethylene oxide polymer is best, and is better than T1001 demulsifiers.
The emulsion resistance result ((40-37-3,54 DEG C)/min) of 4 L-TSA32 steam turbine oils of table
| Embodiment | Demulsifier | Additive amount/% | Water-separating time/min |
| Blank | - | 0 | 29 |
| Embodiment 13 | Demulsifier 1 | 0.01 | 1.9 |
| Embodiment 14 | Demulsifier 2 | 0.01 | 2.2 |
| Embodiment 15 | Demulsifier 3 | 0.01 | 2.2 |
| Embodiment 16 | Demulsifier 4 | 0.01 | 2.3 |
| Comparative example 3 | 100%P1 | 0.01 | 3.5 |
| Comparative example 4 | 100%M2 | 0.01 | 3.1 |
| Comparative example 5 | 100%D1 | 0.01 | 6.5 |
| Comparative example 6 | 100%N1 | 0.01 | 4.1 |
| Comparative example 7 | 50%D1+50%M1 | 0.01 | 4.4 |
| Comparative example 8 | 50%P2+50%N1 | 0.01 | 3.9 |
| Comparative example 9 | T1001 | 0.01 | 8.1 |
| Embodiment 17 | Demulsifier 1 | 0.02 | 0.9 |
| Embodiment 18 | Demulsifier 2 | 0.02 | 1.0 |
| Embodiment 19 | Demulsifier 3 | 0.02 | 1.2 |
| Embodiment 20 | Demulsifier 4 | 0.02 | 1.1 |
| Comparative example 10 | 100%P1 | 0.02 | 1.8 |
| Comparative example 11 | 100%M2 | 0.02 | 2.0 |
| Comparative example 12 | 100%D1 | 0.02 | 4.3 |
| Comparative example 13 | 100%N1 | 0.02 | 3.7 |
| Comparative example 14 | 50%D1+50%M1 | 0.02 | 3.8 |
| Comparative example 15 | 50%P2+50%N1 | 0.02 | 3.1 |
| Comparative example 16 | T1001 | 0.02 | 5.9 |
The emulsion resistance result ((40-37-3,82 DEG C)/min) of 5 L-CKD N220 industrial gear oils of table
| Embodiment | Additive | Additive amount/% | Water-separating time/min |
| Blank | - | 0 | 35-36-9 |
| Embodiment 21 | Demulsifier 1 | 0.02 | 2.3 |
| Embodiment 22 | Demulsifier 2 | 0.02 | 2.0 |
| Embodiment 23 | Demulsifier 3 | 0.02 | 2.2 |
| Embodiment 24 | Demulsifier 4 | 0.02 | 2.4 |
| Comparative example 17 | 100%P1 | 0.02 | 2.6 |
| Comparative example 18 | 100%M2 | 0.02 | 3.5 |
| Comparative example 19 | 100%D1 | 0.02 | 6.8 |
| Comparative example 20 | 100%N1 | 0.02 | 5.7 |
| Comparative example 21 | 50%D1+50%M1 | 0.02 | 6.3 |
| Comparative example 22 | 50%P2+50%N1 | 0.02 | 5.1 |
| Comparative example 23 | T1001 | 0.02 | 7.1 |
| Embodiment 25 | Demulsifier 1 | 0.03 | 1.2 |
| Embodiment 26 | Demulsifier 2 | 0.03 | 1.1 |
| Embodiment 27 | Demulsifier 3 | 0.03 | 1.2 |
| Embodiment 28 | Demulsifier 4 | 0.03 | 1.3 |
| Comparative example 24 | 100%P1 | 0.03 | 2.2 |
| Comparative example 25 | 100%M2 | 0.03 | 2.4 |
| Comparative example 26 | 100%D1 | 0.03 | 4.7 |
| Comparative example 27 | 100%N1 | 0.03 | 3.9 |
| Comparative example 28 | 50%D1+50%M1 | 0.03 | 4.3 |
| Comparative example 29 | 50%P2+50%N1 | 0.03 | 3.8 |
| Comparative example 30 | T1001 | 0.03 | 5.3 |
Claims (19)
1. a kind of breaker composition, including：1) the first demulsifier, the copolymer of alkyl acrylate and α-olefin sulfonic acid；
2) copolymer of second of demulsifier, sulfenyl phenolate and propylene oxide, ethylene oxide；Mass ratio between the two is 1~10：
10~1；
The structure of the first demulsifier is：
Wherein R1 is each independently selected from C4~C18 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；The integer that m is 1~50, the integer that n is 1~50；
The structure of second of demulsifier is：
Wherein X group is
A is the integer between 10~100, and b is the integer between 5~100；K is the integer between 1~10；Between j is 1~10
Integer, the j on each sulphur bridge can be the same or different；R2 is each independently selected from C1~C18 alkyl.
2. breaker composition described in accordance with the claim 1, which is characterized in that wherein R1 is each independently selected from C4~C15
Alkyl；A2 is hydrogen, methyl, ethyl or propyl, the integer that x is 0~3；The integer that m is 5~50, the integer that n is 5~50.
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
It is：Alkyl acrylate and α-olefin sulfonic acid are copolymerized, product is collected.
5. breaker composition according to claim 4, which is characterized in that the structure of the alkyl acrylate is：
Wherein R1 is each independently selected from C4~C18 alkyl；A1 is hydrogen or methyl.
6. breaker composition according to claim 4, which is characterized in that the structure of the α-olefin sulfonic acid is：
Wherein A2 is hydrogen or C1~C4 alkyl, the integer that x is 0~4；When A2 is hydrogen, x is positive integer.
7. breaker composition according to claim 4, which is characterized in that the alkyl acrylate and α-olefin sulfonic acid
Between molar ratio be 1~50：50~1.
8. breaker composition according to claim 4, which is characterized in that the alkyl acrylate and α-olefin sulfonic acid
The temperature of copolyreaction be 20~200 DEG C, time of reaction is 1~20 hour.
9. breaker composition according to claim 4, which is characterized in that the alkyl acrylate and α-olefin sulfonic acid
Initiator is added when being copolymerized；The initiator is azo compound and/or peroxide.
10. breaker composition according to claim 9, which is characterized in that the initiator is different selected from azo two
Butyronitrile, azobisisoheptonitrile, benzoyl peroxide, lauroyl peroxide, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, mistake
Aoxidize di-t-butyl, cumyl peroxide, peroxidized t-butyl perbenzoate, peroxidating trimethylacetic acid tertiary butyl ester, peroxidating first
It is one or more in ethyl ketone, cyclohexanone peroxide, di-isopropyl peroxydicarbonate and di-cyclohexylperoxy di-carbonate.
11. breaker composition described in accordance with the claim 1, which is characterized in that the preparation method of second of demulsifier
Including：Sulfenyl phenolate is first collected into product with Polymerization of Propylene Oxide, again with ethylene oxide polymerization.
12. breaker composition according to claim 11, which is characterized in that the sulfenyl phenolate be vulcanization C1~
C18 alkyl phenols.
13. breaker composition according to claim 11, which is characterized in that phenolic hydroxyl group in the sulfenyl phenolate with
The molar ratio of propylene oxide is 1：10~100；The molar ratio of phenolic hydroxyl group and ethylene oxide in the sulfenyl phenolate is 1：5~
100。
14. breaker composition according to claim 11, which is characterized in that when preparing second of demulsifier,
Catalyst is added, the catalyst is alkali metal hydroxide.
15. breaker composition according to claim 11, which is characterized in that the sulfenyl phenolate and propylene oxide,
The reaction pressure of ethylene oxide polymerization is 0.1~1MPa；Reaction temperature is 80 DEG C~200 DEG C；Reaction time is 1~10 hour.
16. breaker composition according to claim 11, which is characterized in that the molecular weight of second of demulsifier is
1000~30000.
17. breaker composition described in accordance with the claim 1, which is characterized in that the first described demulsifier and the two are broken
The mass ratio of emulsion is 1~5：5~1.
18. the breaker composition described in one of a kind of lubricant oil composite, including claim 1-17 and lubricating base oil.
19. a kind of method improving lubricating oil demulsification performance, which is characterized in that by the demulsifier described in one of claim 1-17
Composition is added in lubricating oil.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4529527A (en) * | 1984-05-14 | 1985-07-16 | Exxon Research And Engineering Co. | Method for controlling viscosity of lubricating oils |
| US4973764A (en) * | 1986-10-24 | 1990-11-27 | Exxon Research And Engineering Company | Alkylphenols and derivatives thereof via phenol alkylation by cracked petroleum distillates |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4529527A (en) * | 1984-05-14 | 1985-07-16 | Exxon Research And Engineering Co. | Method for controlling viscosity of lubricating oils |
| US4973764A (en) * | 1986-10-24 | 1990-11-27 | Exxon Research And Engineering Company | Alkylphenols and derivatives thereof via phenol alkylation by cracked petroleum distillates |
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