CN105985471B - The preparation method and application of phosphor boronation ashless dispersant - Google Patents
The preparation method and application of phosphor boronation ashless dispersant Download PDFInfo
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- CN105985471B CN105985471B CN201510090043.8A CN201510090043A CN105985471B CN 105985471 B CN105985471 B CN 105985471B CN 201510090043 A CN201510090043 A CN 201510090043A CN 105985471 B CN105985471 B CN 105985471B
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Abstract
The present invention relates to a kind of preparation method and application of phosphor boronation ashless dispersant, include the following steps：First, aminated compounds and epoxy prapanol are subjected to ring-opening reaction and prepare intermediate product amine；Then, polyisobutene maleic anhydride and base oil and above-mentioned intermediate product amine are reacted, obtains polyisobutene succinimide；Finally, polyisobutene succinimide reacts jointly with the mixture of boron-containing compound, solvent, phosphorous acid and phosphite ester prepares phosphor boronation ashless dispersant.Phosphor boronation ashless dispersant prepared by the technique has many advantages, such as that friction coefficient low and high temperature cleansing performance is good, low temperature greasy filth dispersion performance is strong, extreme pressure property is strong, and the additive can improve the sound frictional behavior of oil product, can be used in the oil products such as I. C. engine oil, gear oil and transmission fluid.
Description
Technical field
The present invention relates to the preparation method and application of lube oil additive field, especially phosphor boronation ashless dispersant.
Background technology
There is ashless dispersant excellent low temperature greasy filth dispersion performance to be widely used in lubricating oil, commonly
Ashless dispersant is polyisobutene succinimide.It is right as mechanical equipment constantly develops to high speed, heavy duty and high temperature resistant direction
The requirement of I. C. engine oil and industrial lubricant is increasingly harsh, especially to oil product oxidation resistance at high temperature, antiwear and antifriction
Performance and detergent-dispersant performance energy, it is proposed that higher requirement.
Phosphor boronation ashless dispersant not only has good low temperature greasy filth dispersion performance, also has better high-temperature oxidation resistant
Ability, antiwear and friction reduction property and detergent-dispersant performance energy can improve the sound frictional behavior of oil product, in I. C. engine oil, gear
More and more applications have been obtained in the oil products such as oil and transmission fluid.
In the shift process of automobile, the speed of transmission clutch piece gradually increases from zero, in order to smoothly grasp
Make, lubricating oil needs stable friction coefficient, to ensure that clutch being capable of smooth transfer power.Quiet this requires oil product rubs
Wiping coefficient is relatively low, and the coefficient of kinetic friction of oil product can be stablized, and the coefficient of kinetic friction crosses conference and increases abrasion, the coefficient of kinetic friction
Cannot be too low, the too low transmission that will influence power.Phosphor boronation ashless dispersant can effectively reduce the confficient of static friction of oil product,
And the coefficient of kinetic friction of oil product can be kept, more applications have been obtained in gear box oil.
Currently, the synthetic method for usually preparing phosphor boronation ashless dispersant be by tetraethylenepentamine or polyamines polyene with gather it is different
Polyisobutene succinimide ashless dispersant is prepared in the reaction of butylene maleic anhydride, then with boron-containing compound, phosphorus-containing compound
Phosphor boronation ashless dispersant is prepared in reaction.
Li Yong has carried out the research of phosphor boronation ashless dispersant, by ashless dispersant, phosphor-included additive, boric acid, ethyoxyl
Change fatty amine, water and fatty alcohol mixing, mixed at 70~100 DEG C, is gradually warming up to 110 DEG C, reaction a period of time
Afterwards, removing solvent obtains phosphor boronation ashless dispersant, and the phosphor boronation ashless dispersant of development has the effect of wear-resistant.
Helen T.Ryan et al. have studied a kind of synthetic method of oil-soluble phosphor boronation ashless dispersant.It prepared
Journey：First using number-average molecular weight be 1300 polyisobutene prepare polyisobutene maleic anhydride, then with tetraethylenepentamine
With 1.8：1 molar ratio is mixed, and is heated to 165 DEG C~170 DEG C and is reacted 4 hours, addition is equivalent to tetraethylenepentamine 0.35
Times mole maleic anhydride, reacted at 165 DEG C~170 DEG C 1.5 hours, be then equivalent to tetraethylenepentamine in 105 DEG C of additions
1.21~1.6 moles of boric acid and phosphorous acid, the reaction was continued 2 hours, is heated to 155 DEG C, vacuum distillation removes moisture, is produced
Product.
Papay et al. has studied a kind of preparation method of phosphor boronation ashless dispersant, by Phos and boron-containing compound and
Phosphor boronation ashless dispersant, preparation process are prepared in ashless dispersant reaction：260 parts of Hitec644 ashless dispersants with
100 parts of aromatic solvent, 8 parts of phosphorous acid, 8 parts of boric acid and the mixing of 3 parts of water, are heated 2 hours at 100 DEG C, until all
Solid material dissolving, be warming up to 110 DEG C, decompression slowly distills out moisture, obtains an oil-soluble limpid product.
Max J.Wisotsky et al. have studied polyisobutene succinic amide or the polyisobutene succinic amide and oil of boronation
The sulfur-bearing of dissolubility or phosphorous carboxylic acid reaction react ashless dispersant with boron-containing compound, then again with it is oil-soluble phosphorous
Phosphor boronation ashless dispersant is prepared in compound reaction, and product has preferable dispersion performance in diesel engine oil.
The present invention with epoxy prapanol react using aminated compounds prepares intermediate products amine, is prepared using the amine poly-
Isobutene succimide, then react jointly with the mixture of boride, phosphorous acid and phosphite ester prepare phosphorus boronation gather it is different
Butylene succimide.Hydroxyl there are two containing in the structure of the intermediate products amine, obtains with the reactivity of boric acid, phosphorous acid
It improves, since hydroxyl has preferable friction reducing effect, the friction coefficient of the phosphor boronation ashless dispersant of preparation is relatively low, uses Asia
The mixture of phosphoric acid and phosphite ester reacts jointly, and obtained product can either improve the film strength of oil product, and can improve
The anti-caking power of oil product.
The product that the present invention develops has the following advantages：(1) friction coefficient is less than commercially available polyisobutene succinimide；
(2) high temperature detergent performance of product is good, and the coking amount of coking plate is less than 10mg；(3) the low temperature greasy filth good dispersion of product, greasy filth
Spot dispersion value is more than 70%；(4) extreme pressure property of product is strong, with 3% plus dosage be added in base oil, can significantly carry
The film strength of higher baseline oil and anti-caking power；(5) product can improve the sound frictional behavior of oil product, call in energy in oil product
It enough effectively reduces the confficient of static friction of oil product and improves the coefficient of kinetic friction of oil product.
Invention content
The purpose of the present invention is developing a kind of phosphor boronation ashless dispersant product, product has friction coefficient low and high temperature clear
Net performance is good, low temperature greasy filth good dispersion, the features such as extreme pressure property is strong.
The present invention provides a kind of preparation method of phosphor boronation ashless dispersant, includes the following steps：
First, aminated compounds and epoxy prapanol are subjected to ring-opening reaction and prepare intermediate product amine；
Then, polyisobutene maleic anhydride and base oil and above-mentioned intermediate product amine are reacted, obtains polyisobutene fourth
Imidodicarbonic diamide；
Finally, the mixture of polyisobutene succinimide and boron-containing compound, solvent, phosphorous acid and phosphite ester is common
Phosphor boronation ashless dispersant is prepared in reaction.
The preparation method of phosphor boronation ashless dispersant of the present invention, wherein aminated compounds preferably at least contains three
A nitrogen-atoms.
The preparation method of phosphor boronation ashless dispersant of the present invention, wherein aminated compounds is preferably divinyl three
One or more of amine, triethylene tetramine, tetraethylenepentamine, pentaethylene hexamine and polyamines polyene, more preferably four ethylene
Five amine and polyamines polyene.
The preparation method of phosphor boronation ashless dispersant of the present invention, wherein ring-opening reaction, aminated compounds and epoxy
The molar ratio of propyl alcohol is preferably 1：0.2~1：2, the more preferably molar ratio of aminated compounds and epoxy prapanol is 1：0.5~
1：1.5, reaction temperature is preferably 0~80 DEG C, more preferably 5~30 DEG C, and the reaction time is preferably 2~8 hours.
The preparation method of phosphor boronation ashless dispersant of the present invention, wherein preferably by aminated compounds and ring
Oxygen propyl alcohol carries out ring-opening reaction, and epoxy prapanol is first dissolved in solvent.
The preparation method of phosphor boronation ashless dispersant of the present invention, wherein solvent is preferably in water, methanol and ethyl alcohol
One or more.
The preparation method of phosphor boronation ashless dispersant of the present invention, wherein the dosage of solvent is preferably epoxy prapanol
3~5 times of quality.
The preparation method of phosphor boronation ashless dispersant of the present invention, wherein the dosage of polyisobutenyl maleic anhydride
Preferably 20~40 times of epoxy prapanol quality, the dosage of the base oil are preferably 5~15 times of epoxy prapanol quality, are gathered different
Cyclobutenyl maleic anhydride number-average molecular weight is preferably 800-2500, and more preferably 1000~1500, polyisobutene maleic anhydride
Saponification number is preferably greater than 20mgKOH/g.
The preparation method of phosphor boronation ashless dispersant of the present invention, wherein boron-containing compound dosage is preferably poly- different
0.1~0.5 times of butylene maleic anhydride quality.
The preparation method of boronation ashless dispersant of the present invention, wherein boron-containing compound is preferably inorganic boracic
Close object and/or organic boric acid ester.
The preparation method of phosphor boronation ashless dispersant of the present invention, wherein inorganic boron containing compound is preferably boric acid
Or diboron trioxide, more preferably boric acid；Organic boric acid ester is preferably butyl borate, triphenyl borine acid esters or triethanolamine boron
Acid esters, more preferably butyl borate.
The preparation method of phosphor boronation ashless dispersant of the present invention, wherein polyisobutene succinimide and boracic
The mixture reaction of compound, solvent, phosphorous acid and phosphite ester prepares solvent described in boronation ashless dispersant and is preferably
Butanol, solvent dosage are preferably 0.1~0.3 times of polyisobutene maleic anhydride quality.
The preparation method of phosphor boronation ashless dispersant of the present invention, wherein preferably comprised in the phosphite ester certainly
Few 8 or more carbon atoms.
The preparation method of phosphor boronation ashless dispersant of the present invention, wherein the phosphite ester is preferably phosphorous acid
One or more of dibutyl ester, dioctyl phosphite and phosphorous acid two (dodecyl) fat.
The preparation method of phosphor boronation ashless dispersant of the present invention, wherein the mixture of phosphorous acid and phosphite ester
The mixed proportion of phosphorous acid and phosphite ester is preferably 1：0.2~1：5, it is prepared using the mixture of phosphorous acid and phosphite ester
Phosphor boronation ashless dispersant, the film strength of oil product can either be improved, and the anti-caking power of oil product can be improved.
The preparation method of phosphor boronation ashless dispersant of the present invention, wherein polyisobutene maleic anhydride and base oil
It reacts with intermediate product amine and is preferably reacted 4~12 hours at 70~160 DEG C.
The preparation method of phosphor boronation ashless dispersant of the present invention, wherein polyisobutene succinimide and boracic
The mixture reaction of compound, solvent, phosphorous acid and phosphite ester is preferably reacted 2~10 hours at 100 DEG C~160 DEG C.
Ashless dispersant is in I. C. engine oil, gear made from the preparation method of phosphor boronation ashless dispersant of the present invention
Application in oil and transmission fluid oil product.
The present invention can sketch：
A kind of preparation method and application of phosphor boronation ashless dispersant are anti-by aminated compounds and epoxy prapanol progress open loop
Intermediate product amine should be prepared, polyisobutene maleic anhydride is reacted with the amine, prepares polyisobutene succinimide, then
It is reacted jointly with the mixture of boron-containing compound, phosphorous acid and phosphite ester and prepares phosphor boronation ashless dispersant.Party's legal system
Standby phosphor boronation ashless dispersant is good with friction coefficient low and high temperature cleansing performance, low temperature greasy filth dispersion performance is strong, extreme pressure property
The advantages that strong, and the additive can improve the sound frictional behavior of oil product, product can be applied to I. C. engine oil, gear oil and biography
In the oil products such as hydrodynamic.
Aminated compounds is added in reaction kettle, epoxy prapanol is dissolved in solvent and is added drop-wise in reaction kettle, 0~80
After DEG C reaction 2~8 hours, polyisobutene maleic anhydride and base oil is added, after react 4~12 hours at 70~160 DEG C, addition
Boride, phosphorous acid, phosphite ester and solvent, after being reacted 2~10 hours at 100 DEG C~160 DEG C, vacuum distillation removes remaining molten
Agent obtains phosphor boronation ashless dispersant after filtering.
Product friction coefficient prepared by the technique is less than commercially available polyisobutene succinimide, the high temperature detergent performance of product
Good, the coking amount of coking plate is less than 10mg, the low temperature greasy filth good dispersion of product, and greasy filth spot dispersion value is more than 70%, product
Extreme pressure property it is strong, with 3% plus dosage be added in base oil, the film strength of base oil and anti-sintering can be significantly improved
Ability, product can improve the sound frictional behavior of oil product, and the confficient of static friction of oil product can be effectively reduced by calling in oil product
With the coefficient of kinetic friction for improving oil product.
Description of the drawings
Fig. 1：The preparation method flow chart of the phosphor boronation ashless dispersant of embodiment；
Fig. 2：The friction coefficient of ashless dispersant compares；
Fig. 3：The sound frictional behavior of ashless dispersant compares.
Specific implementation mode
It elaborates below to the embodiment of the present invention：The present embodiment is carried out lower based on the technical solution of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
Aminated compounds：
In the present invention, aminated compounds being not particularly limited, usual aminated compounds at least contains there are three nitrogen-atoms,
It can be in the group that diethylenetriamine, triethylene tetramine, tetraethylenepentamine, pentaethylene hexamine and polyamines polyene are constituted
It is at least one.
The molar ratio of aminated compounds and epoxy prapanol：
In the present invention, the molar ratio of aminated compounds and epoxy prapanol is not particularly limited, usual ring-opening reaction, amine
Class compound and the molar ratio of epoxy prapanol are 1：0.2~1：2, the molar ratio of preferably aminated compounds and epoxy prapanol is
1：0.5~1：1.5；
If the molar ratio of aminated compounds and epoxy prapanol is less than 1：2, since aminated compounds dosage is very few, cause to produce
The nitrogen quantity of product declines, and product low temperature greasy filth dispersion performance declines, and the molar ratio of aminated compounds and epoxy prapanol is more than 1：
0.2, since aminated compounds dosage is excessive, cause the addition of epoxy prapanol too low, the boron content of product declines.
Ring-opening reaction condition：
In the present invention, divided ring reaction condition is not particularly limited, and when usual ring-opening reaction, reaction temperature is 0~80
DEG C, preferably reaction temperature is 5~30 DEG C, and the reaction time is 2~8 hours.
If reaction temperature is less than 0 DEG C, since reaction temperature is too low, reaction speed is caused to decline, reaction is incomplete, and anti-
It is more than 80 DEG C to answer temperature, since temperature is excessively high, causes side reaction more, and product storage stability is deteriorated.
If the reaction time is less than 2 hours, since the time is too short, cause reaction incomplete, and the reaction time is more than 8 small
When, due to overlong time, temporal waste is caused, has no other advantageous effects.
Solvent：
In the present invention, solvent is not particularly limited, aminated compounds and epoxy prapanol is usually subjected to ring-opening reaction
When, epoxy prapanol is first dissolved in solvent, and the solvent can be enumerated as one or more of water, methanol and ethyl alcohol.
The dosage of solvent：
In the present invention, the dosage of solvent is not particularly limited, the dosage of the usual solvent is epoxy prapanol quality
3~5 times.
If the dosage of solvent is less than 3 times of epoxy prapanol quality, since solvent dosage is very few, when causing to react in temperature
It rises comparatively fast, reaction temperature is not easy to control, and the dosage of solvent is caused more than 5 times of epoxy prapanol quality since solvent dosage is excessive
Waste, has no other advantageous effects.
The dosage of polyisobutenyl maleic anhydride：
In the present invention, the dosage of polyisobutenyl maleic anhydride is not particularly limited, usual polyisobutenyl Malaysia
The dosage of acid anhydrides is 20~40 times of epoxy prapanol quality；
If the dosage of polyisobutenyl maleic anhydride is less than 20 times of epoxy prapanol quality, since dosage is very few, cause
Reaction is incomplete, and product appearance is muddy, and storage stability is deteriorated；And the dosage of polyisobutenyl maleic anhydride is more than epoxy prapanol
40 times of quality, since dosage is excessive, the nitrogen content of product declines, and product low temperature greasy filth dispersion performance is deteriorated.
The dosage of base oil：
In the present invention, the dosage of base oil is not particularly limited, the dosage of usual base oil is epoxy prapanol quality
5~15 times；
If the dosage of base oil is less than 5 times of epoxy prapanol quality, since dosage is very few, product viscosity is caused to become larger,
Product is not easy to use；And the dosage of base oil is more than 15 times of epoxy prapanol quality, since dosage is excessive, under the nitrogen content of product
Drop, product low temperature greasy filth dispersion performance are deteriorated.
The number-average molecular weight of polyisobutenyl maleic anhydride：
In the present invention, the number-average molecular weight of polyisobutenyl maleic anhydride is not particularly limited, usual polyisobutene
The number-average molecular weight of base maleic anhydride is 800~2500, and preferably polyisobutenyl maleic anhydride number-average molecular weight is 1000
~1500；
If the number-average molecular weight of polyisobutenyl maleic anhydride is less than 800, since molecular weight is too small, the low of product is caused
Warm greasy filth dispersion performance is deteriorated, and the number-average molecular weight of polyisobutenyl maleic anhydride is more than 2500, since molecular weight is excessive, makes
It is excessive at product viscosity, have no other beneficial effects.
The saponification number of polyisobutene maleic anhydride：
In the present invention, the saponification number of polyisobutene maleic anhydride is not particularly limited, usual polyisobutene maleic acid
The saponification number of acid anhydride is more than 20mgKOH/g, if the saponification number of polyisobutene maleic anhydride is less than 20mgKOH/g, due to poly- isobutyl
The saponification number of alkene maleic anhydride is too small, causes product low temperature greasy filth dispersibility to be deteriorated, the boron content of product declines.
Boron-containing compound dosage：
In the present invention, boron-containing compound dosage is not particularly limited, usual boron-containing compound dosage is polyisobutene
0.1~0.5 times of maleic anhydride quality；If boron-containing compound dosage is less than 0.1 times of polyisobutene maleic anhydride quality, by
It is very few in dosage, cause the boron content of product to decline；And boron-containing compound dosage is more than the 0.5 of polyisobutene maleic anhydride quality
Times, it since dosage is excessive, causes to waste, and product is not easy to filter, and has no other beneficial effects.
Boron-containing compound type：
In the present invention, boron-containing compound type is not particularly limited, usual boron-containing compound is inorganic boracic chemical combination
Object and/or organic boric acid ester, inorganic boron containing compound can be enumerated as boric acid or diboron trioxide；Organic boric acid ester can be enumerated
For butyl borate, triphenyl borine acid esters or triethanolamine borate.
Institute during polyisobutene succinimide is reacted with the mixture of boron-containing compound, solvent, phosphorous acid and phosphite ester
State solvent：
In the present invention, polyisobutene succinimide and boron-containing compound, solvent, phosphorous acid and phosphite ester are mixed
It closes solvent described in object reaction to be not particularly limited, usual polyisobutene succinimide and boron-containing compound, solvent, phosphorous acid
Be butanol with solvent described in the reaction of the mixture of phosphite ester, solvent dosage be polyisobutene maleic anhydride quality 0.1~
0.3 times；
If solvent dosage is less than 0.1 times of polyisobutene maleic anhydride quality, since dosage is very few, the boron of product is caused
Content declines；And solvent dosage is more than 0.3 times of polyisobutene maleic anhydride quality, since dosage is excessive, causes to waste, have no
Other beneficial effects.
Phosphite ester：
In the present invention, phosphite ester is not particularly limited, it is former containing the carbon from 8 or more less in usual phosphite ester
Son can be enumerated as one or more of dibutyl phosphite, dioctyl phosphite and phosphorous acid two (dodecyl) fat.
Phosphorous acid and the mixture phosphorous acid of phosphite ester and the mixed proportion of phosphite ester：
In the present invention, the mixed proportion of the mixture phosphorous acid to phosphorous acid and phosphite ester and phosphite ester has no
It is particularly limited to, the mixture phosphorous acid of usual phosphorous acid and phosphite ester and the mixed proportion of phosphite ester are 1：0.2~1：
5；
If the mixed proportion of the mixture phosphorous acid and phosphite ester of phosphorous acid and phosphite ester is less than 1：5, due to
The dosage of phosphorous acid is very few, and the extreme pressure property of product is caused to be deteriorated；And the mixture phosphorous acid of phosphorous acid and phosphite ester and
The mixed proportion of phosphite ester is more than 1：0.2, since phosphorous acid dosage is excessive, cause the acid value of product to increase, the corrosion of product
Property increase.
Polyisobutene maleic anhydride and base oil and intermediate product amine reaction condition：
In the present invention, polyisobutene maleic anhydride and base oil are not particularly limited with intermediate product amine reaction condition,
Usual polyisobutene maleic anhydride and base oil are reacted with intermediate product amine to be reacted 4~12 hours at 70~160 DEG C；
If reaction temperature is less than 70 DEG C, since reaction temperature is too low, cause reaction incomplete, and reaction temperature is more than
160 DEG C, since temperature is excessively high, cause side reaction excessive, the appearance color of product deepens；
If the reaction time is less than 4 hours, since the time is too short, cause reaction incomplete, and the reaction time is more than 12 small
When, it causes the time to waste, has no other advantageous effects.
Polyisobutene succinimide and the mixture reaction condition containing boride, solvent, phosphorous acid and phosphite ester：
In the present invention, to polyisobutene succinimide and the mixing containing boride, solvent, phosphorous acid and phosphite ester
Object reaction condition is not particularly limited, usual polyisobutene succinimide with contain boride, solvent, phosphorous acid and phosphite ester
Mixture reaction be to be reacted 2~10 hours at 100 DEG C~160 DEG C；
If reaction temperature is less than 100 DEG C, since reaction temperature is too low, cause reaction incomplete, and reaction temperature is more than
160 DEG C, since temperature is excessively high, product colour is caused to deepen, has no other advantageous effects；
If the reaction time is less than 2 hours, since the time is too short, cause reaction incomplete, and the reaction time is more than 10 small
When, it causes the time to waste, has no other advantageous effects.
Embodiment 1
26 parts of tetraethylenepentamine are added in reaction bulb, 10 parts of epoxy prapanols are dissolved in 40 parts of ethyl alcohol by constant temperature to 10 DEG C,
It is added drop-wise in reaction bulb, after reacting 5 hours, the polyisobutene maleic anhydride that 300 number average molecular weights are 1300,90 parts of bases is added
Plinth oil is warming up to 140 DEG C of reaction 6h, cools to 60 DEG C, 32 parts of boric acid, 16 parts of phosphorous acid, 30 parts of phosphorous acid two is added
Monooctyl ester, 32 parts of butanol, 110 DEG C are reacted 6 hours, and vacuum distillation removes solvent, and phosphor boronation ashless dispersant is obtained after filtering.
Embodiment 2
26 parts of polyamines polyenes are added in reaction bulb, 10 parts of epoxy prapanols are dissolved in 40 parts of ethyl alcohol by constant temperature to 10 DEG C, are dripped
It is added in reaction bulb, after reacting 5 hours, the polyisobutene maleic anhydride that 300 number average molecular weights are 1300,90 parts of bases is added
Oil is warming up to 140 DEG C of reaction 6h, cools to 60 DEG C, 32 parts of boric acid, 16 parts of phosphorous acid, 12 parts of two fourth of phosphorous acid is added
Ester, 32 parts of butanol, 110 DEG C are reacted 6 hours, and vacuum distillation removes solvent, and phosphor boronation ashless dispersant is obtained after filtering.
Embodiment 3
26 parts of tetraethylenepentamine are added in reaction bulb, 10 parts of epoxy prapanols are dissolved in 40 parts of ethyl alcohol by constant temperature to 10 DEG C,
It is added drop-wise in reaction bulb, after reacting 5 hours, the polyisobutene maleic anhydride that 300 number average molecular weights are 1300,90 parts of bases is added
Plinth oil is warming up to 140 DEG C of reaction 6h, cools to 60 DEG C, 110 parts of butyl borate, 16 parts of phosphorous acid, 12 parts of Asia is added
Dibutylphosphoric acid ester, 50 parts of butanol, 110 DEG C are reacted 6 hours, and vacuum distillation removes solvent, and boronation ashless dispersion is obtained after filtering
Agent.
Embodiment 4
10 parts of tetraethylenepentamine, 10 parts of diethylenetriamines are added in reaction bulb, constant temperature is molten by 4 parts of epoxy prapanols to 0 DEG C
It in 12 parts of ethyl alcohol, is added drop-wise in reaction bulb, after reacting 8 hours, the polyisobutene horse that 160 number average molecular weights are 800 is added
Carry out acid anhydrides, 60 parts of base oils are warming up to 70 DEG C of reaction 2h, are warming up to 120 DEG C and react 10 hours, cool to 60 DEG C, be added 24 parts
Boric acid, 20 parts of phosphorous acid, 4 parts of dibutyl phosphite, 24 parts of butanol, 100 DEG C react 10 hours, vacuum distillation remove
Solvent obtains boronation ashless dispersant after filtering.
Embodiment 5
40 parts of diethylenetriamines are added in reaction bulb, 20 parts of epoxy prapanols are dissolved in 100 parts of water by constant temperature to 80 DEG C,
It is added drop-wise in reaction bulb, after reacting 2 hours, the polyisobutene maleic anhydride that 800 number average molecular weights are 800,100 parts of bases is added
Plinth oil is warming up to 70 DEG C of reaction 2h, is warming up to 120 DEG C and reacts 10 hours, cool to 60 DEG C, 80 parts of boric acid is added, 20 parts
Phosphorous acid, 100 parts of dioctyl phosphite, 80 parts of butanol, 100 DEG C are reacted 10 hours, and vacuum distillation removes solvent, after filtering
Obtain boronation ashless dispersant.
Embodiment 6
10 parts of diethylenetriamines are added in reaction bulb, constant temperature is dissolved in 100 parts of methanol to 40 DEG C, by 20 parts of epoxy prapanols
In, it is added drop-wise in reaction bulb, after reacting 6 hours, the polyisobutene maleic anhydride that 400 number average molecular weights of addition are 2500,100
Part base oil is warming up to 160 DEG C of reaction 4h, cools to 60 DEG C, is added 200 parts of butyl borate, 20 parts of phosphorous acid, 20 parts
Dibutyl phosphite, 120 parts of butanol, be warming up to 160 DEG C react 2 hours, vacuum distillation remove solvent, obtain boron after filtering
Change ashless dispersant.
The low temperature greasy filth dispersion performance of product can be evaluated by the distributed test of greasy filth spot.Greasy filth spot dispersing method
Brief introduction：In the 50ml beakers of wash clean, standard used oil 9g, HVI150 base oil 10g, tested sample 1g are weighed.It will be above-mentioned
Beaker is put into the oil bath of constant temperature to 150 ± 1 DEG C, after fixed, starts blender, after stirring 90min, stops stirring.It makes even whole
Qualitative filter paper one open, its is smooth horizontal aerial, with the clean dried pipette of 1ml, draw 0.2ml samples.Vertical natural
Sample is dripped on above-mentioned sizing filter paper, allows after its natural diffuseness 5min, filter paper is moved into constant temperature in 80 ± 2 DEG C of baking oven
Interior, constant temperature spreads 120min.Filter paper, slightly cold 1min are taken out, setting-out immediately obtains the straight of inner ring greasy filth circle and outer ring oil stain circle
The percentage of diameter, inner ring greasy filth loop diameter and outer ring oil stain loop diameter is the spot dispersion value (SDT) of ashless dispersant.SDT
Numerical value it is bigger, illustrate that the low temperature greasy filth dispersion performance of oil product is better.
Embodiment product and commercially available ashless dispersant T151, T152 and T161 are carried out low temperature greasy filth dispersion performance to comment
Fixed, evaluation result is shown in Table 1.
The low temperature greasy filth dispersion performance of 1 ashless dispersant of table compares
| Sample ID | Spot dispersion value, % |
| Embodiment 1 | 72.3 |
| Embodiment 2 | 72.9 |
| Embodiment 3 | 72.2 |
| Embodiment 4 | 72.8 |
| Embodiment 5 | 72.1 |
| Embodiment 6 | 72.9 |
| T151 | 68.7 |
| T152 | 62.4 |
| T161 | 64.2 |
The spot dispersion value that can be seen that embodiment product from the data in table 1 is all higher than 70%, is better than commercially available no ash content
Powder.
The high temperature detergent performance of product can use I. C. engine oil coke test method to evaluate.Method brief introduction：By ashless dispersants with
3% dosage is added in 150SN base oils, is mixing uniformly to form experiment oil, and 310ml experiment oil is taken to be added to the examination of coking plate
It tests in the oil box of machine, is covered with polishing and weighted experiment aluminium sheet on oil box, experiment aluminium sheet is heated to 320 DEG C, by experiment oil
150 DEG C are heated to, the oil splasher in firing test oil splashes oil on hot test aluminium sheet with the rotational speed of 1000r/min
Coke and paint film are formed, after 2 hours, experiment aluminium sheet is removed, oil stain remaining in plate face and deposit is washed with petroleum ether, is dried in the air
It weighs after dry.The difference that plate after experiment subtracts the plate weight before experiment again is the coking amount of coking plate, and coking amount is lower to be shown
The high temperature detergent performance of ashless dispersant is better.
Embodiment product and commercially available ashless dispersant T151, T152 and T161 are subjected to high temperature detergent performance evaluation, commented
Surely 2 be the results are shown in Table.
The high temperature detergent performance of 2 ashless dispersant of table compares
| Sample ID | Coking amount, mg |
| Embodiment 1 | 6.2 |
| Embodiment 2 | 5.6 |
| Embodiment 3 | 5.6 |
| Embodiment 4 | 6.8 |
| Embodiment 5 | 5.9 |
| Embodiment 6 | 6.3 |
| T151 | 45.6 |
| T152 | 35.8 |
| T161 | 26.3 |
The coking plate coking amount that can be seen that embodiment product from the data in table 2 is less than 10mg, and high temperature detergent performance is excellent
In commercially available ashless dispersant.
The extreme pressure property of product can with lubricator bearing capacity measuring method be evaluated.Method brief introduction：In four-ball tester, four
Steel ball by equilateral tetrahedral arrangement, and upper ball rotates under 1400~1500 revs/min, below three balls be fixed on one with oil box
It rises, load is from bottom to top applied to steel ball by lever.During the test, the contact point of four steel balls is immersed in lubricating oil
In, each test period is 10 seconds, and the grinding defect diameter of steel ball in oil box is measured after experiment, according to regulation program repeat experiment, directly
To finding out the deliberated index for representing lubricating oil bearing capacity.Common deliberated index is PB values and PD values, and PB values are maximum without card
Load is stung, i.e., seizing maximum load does not occur under test conditions, it represents film strength, and PB values are bigger, and film strength is got over
By force.PD values are to make the minimum load that steel ball is sintered under test conditions, it represents the maximal work ability of lubricant, PD values
Bigger, extreme pressure property is better.
Embodiment product and commercially available ashless dispersant T151, T152 and T161 are added to base oil with 3% dosage
Middle progress extreme pressure property evaluation, evaluation result are shown in Table 3.
The extreme pressure property of 3 ashless dispersant of table compares
| Sample ID | PB, N | PD, N |
| Embodiment 1 | 833.6 | 1961.3 |
| Embodiment 2 | 882.6 | 1961.3 |
| Embodiment 3 | 882.6 | 1961.3 |
| Embodiment 4 | 833.6 | 1961.3 |
| Embodiment 5 | 833.6 | 1961.3 |
| Embodiment 6 | 882.6 | 1961.3 |
| T151 | 509.9 | 1235.6 |
| T152 | 490.3 | 1235.6 |
| T161 | 539.4 | 1235.6 |
| Base oil | 411.9 | 1235.6 |
The PB values of embodiment product are can be seen that from the data in table 3 and PD values are all higher than commercially available ashless dispersant, explanation
Embodiment product has more preferable film strength and anti-caking power.
The friction coefficient of oil product can be evaluated by four-ball tester, by embodiment 1 and commercially available ashless dispersant T151,
T152 and T161 is added to progress friction coefficient evaluation, evaluation result in base oil with 3% dosage and sees Fig. 2.
As it is clear from fig. 2 that the friction coefficient of embodiment 1 is less than commercially available ashless dispersant.
The sound frictional behavior of oil product can be evaluated using TE92M clutch frictions testing machine.By embodiment 1 and commercially available
Ashless dispersant T151, T152 and T161 progress sound frictional behavior evaluation, evaluation are added in base oil with 3% dosage
As a result see Fig. 3.
It can be seen from figure 3 that the increase of ashless dispersant T151, T152 and T161 with rotating speed, friction coefficient decline rapidly, and
The friction coefficient when rotating speed is relatively low of embodiment 1 is smaller, when rotating speed increases, friction coefficient has the tendency that rising, i.e. embodiment 1
Confficient of static friction is relatively low, and the coefficient of kinetic friction keeps preferable, has preferable sound frictional behavior.
Only several embodiments of the present invention are expressed for embodiment described above, the description thereof is more specific and detailed, but
It cannot be construed as a limitation to the scope of the present invention.It should be pointed out that for the ordinary skill people of this field
For member, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the present invention's
Protection domain.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (18)
1. a kind of preparation method of phosphor boronation ashless dispersant, includes the following steps：
First, aminated compounds and epoxy prapanol are subjected to ring-opening reaction and prepare intermediate product amine；
Then, polyisobutene maleic anhydride and base oil and above-mentioned intermediate product amine are reacted, obtains polyisobutene succinyl
Imines；
Finally, polyisobutene succinimide reacts jointly with the mixture of boron-containing compound, solvent, phosphorous acid and phosphite ester
Prepare phosphor boronation ashless dispersant；
The boron-containing compound is boric acid or butyl borate.
2. the preparation method of phosphor boronation ashless dispersant as described in claim 1, which is characterized in that the aminated compounds is extremely
Few nitrogen-atoms containing there are three.
3. the preparation method of phosphor boronation ashless dispersant as claimed in claim 2, which is characterized in that the aminated compounds is
One or more of diethylenetriamine, triethylene tetramine, tetraethylenepentamine, pentaethylene hexamine and polyamines polyene.
4. the preparation method of phosphor boronation ashless dispersant as described in claim 1, which is characterized in that the ring-opening reaction, amine
Class compound and the molar ratio of epoxy prapanol are 1：0.2~1：2, reaction temperature is 0~80 DEG C, and the reaction time is 2~8 hours.
5. the preparation method of phosphor boronation ashless dispersant as claimed in claim 4, which is characterized in that the ring-opening reaction, amine
Class compound and the molar ratio of epoxy prapanol are 1：0.5~1：1.5, the temperature of reaction is 5~30 DEG C.
6. such as the preparation method of Claims 1 to 5 any one of them phosphor boronation ashless dispersant, which is characterized in that by amine
Compound carries out ring-opening reaction with epoxy prapanol, and epoxy prapanol is first dissolved in solvent.
7. the preparation method of phosphor boronation ashless dispersant as claimed in claim 6, which is characterized in that the solvent is water, first
One or more of alcohol and ethyl alcohol.
8. the preparation method of phosphor boronation ashless dispersant as claimed in claim 7, which is characterized in that the dosage of the solvent is
3~5 times of epoxy prapanol quality.
9. such as the preparation method of Claims 1 to 5 any one of them phosphor boronation ashless dispersant, which is characterized in that described poly-
The dosage of isobutenyl maleic anhydride is 20~40 times of epoxy prapanol quality, and the dosage of the base oil is epoxy prapanol quality
5~15 times, polyisobutenyl maleic anhydride number-average molecular weight is 800-2500, and the saponification number of polyisobutene maleic anhydride is more than
20mgKOH/g。
10. the preparation method of phosphor boronation ashless dispersant as claimed in claim 9, which is characterized in that polyisobutenyl Malaysia
Acid anhydrides number-average molecular weight is 1000~1500.
11. such as the preparation method of Claims 1 to 5 any one of them phosphor boronation ashless dispersant, which is characterized in that described to contain
Boron compound dosage is 0.1~0.5 times of polyisobutene maleic anhydride quality.
12. such as the preparation method of Claims 1 to 5 any one of them phosphor boronation ashless dispersant, which is characterized in that poly- isobutyl
Alkene succimide is reacted with the mixture of boron-containing compound, solvent, phosphorous acid and phosphite ester prepares boronation ashless dispersion
Solvent described in agent is butanol, and solvent dosage is 0.1~0.3 times of polyisobutene maleic anhydride quality.
13. such as the preparation method of Claims 1 to 5 any one of them phosphor boronation ashless dispersant, which is characterized in that the Asia
Contain the carbon atom from 8 or more less in phosphate.
14. the preparation method of phosphor boronation ashless dispersant as claimed in claim 13, which is characterized in that the phosphite ester is
One or more of dibutyl phosphite, dioctyl phosphite and phosphorous acid two (dodecyl) ester.
15. such as the preparation method of Claims 1 to 5 any one of them phosphor boronation ashless dispersant, which is characterized in that phosphorous acid
It is 1 with the mixture phosphorous acid of phosphite ester and the mixed proportion of phosphite ester：0.2~1：5.
16. such as the preparation method of Claims 1 to 5 any one of them phosphor boronation ashless dispersant, which is characterized in that poly- isobutyl
Alkene maleic anhydride and base oil are reacted with intermediate product amine to be reacted 4~12 hours at 70~160 DEG C.
17. such as the preparation method of Claims 1 to 5 any one of them phosphor boronation ashless dispersant, which is characterized in that poly- isobutyl
It is that 2 are reacted at 100 DEG C~160 DEG C that alkene succimide is reacted with the mixture containing boride, solvent, phosphorous acid and phosphite ester
~10 hours.
18. ashless dispersant exists made from the preparation method of claim 1~17 any one of them phosphor boronation ashless dispersant
Application in I. C. engine oil, gear oil and transmission fluid oil product.
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