CN107118823A - Porous nano particle in lubricating oil as Inorganic antioxidant application - Google Patents
Porous nano particle in lubricating oil as Inorganic antioxidant application Download PDFInfo
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- CN107118823A CN107118823A CN201710208510.1A CN201710208510A CN107118823A CN 107118823 A CN107118823 A CN 107118823A CN 201710208510 A CN201710208510 A CN 201710208510A CN 107118823 A CN107118823 A CN 107118823A
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- lubricating oil
- meso
- antioxidant
- parts
- dios
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/26—Compounds containing silicon or boron, e.g. silica, sand
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/10—Metal oxides, hydroxides, carbonates or bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/08—Resistance to extreme temperature
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Fats And Perfumes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A kind of application the present invention relates to porous nano particle in lubricating oil as inorganic antioxidant.The porous nano particle is meso-porous alumina or mesoporous silicon oxide.Specifically, using when, meso-porous alumina is added directly into lubricating oil, both weights are：0.25-2 parts of meso-porous alumina, 98-99 parts of lubricating oil.The inorganic porous nano particle for the features such as present invention is with high specific surface area, regular pore passage structure, narrow pore-size distribution is incorporated into antioxidant system, make it during oil ageing, the increase of its viscosity and acid number is delayed to a certain extent, so as to improve its antioxidant capacity, good antioxygenic property and high thermal stability is made it have.
Description
Technical field
The invention belongs to lube oil additive technical field, and in particular to a kind of porous nano particle conduct in lubricating oil
The application of Inorganic antioxidant.
Background technology
Lubricating oil under the influence of the factors such as air, metal, can be oxidized to alcohol, carboxylic acid, ketone etc. during use
Low molecular compound, and then may occur condensation and form polymer, so that viscosity and the acid number increase of system, the lubrication of oil product
Degradation, or even can etching mechanism parts, reduction of service life.Therefore during lubricating oil use, it is necessary to addition pair
Oil oxidation can play delay or inhibitory action antioxidant, to extend the working life of lubricating oil.
At present, the antioxidant for lubricant oil of various documents and patent report is mainly organic kind antioxidant, such as alkane both at home and abroad
The arylamine type such as base diphenylamines, alkyl naphthylamines, alkyl phenthazine antioxidant is used alone or collaboration is used, and such as Yao Junbing et al. passes through
Oxidative coupling alkyl diphenylamine and alkyl naphthylamines and being cooperateed with thiocarbamate is used, so as to extend amine antioxidants
Oxidation induction time, and realize the control to acidity and viscosity build.United States Patent (USP) patent 6426324, patent
3509214 report diphenylamines and alkyl naphthylamines is polymerized in oligomer structure, reaction product except there is aniline with certain proportion
Beyond the polymer of naphthylamines, also aniline and aniline, the polymer architecture of naphthylamines and naphthylamines, this mixed structure is at 220 DEG C
Under still have good antioxidant capacity.Existing lubricating oil antioxidant is mainly organic based on arylamine type antioxidant in a word
Compound, but amine antioxidants are generally more costly, toxicity is big, and pollution is easily caused to environment.
The content of the invention
Present invention aims to overcome that prior art defect there is provided a kind of porous nano particle in lubricating oil as inorganic
The application of antioxidant, the porous nano particle belongs to environmentally friendly high temperature inorganic antioxidant, after being added in lubricating oil
Antioxygenic property is good, and high thermal stability is good.
To achieve the above object, the present invention is adopted the following technical scheme that：
Porous nano particle in lubricating oil as Inorganic antioxidant application.
Specifically, in above-mentioned application, the porous nano particle is meso-porous alumina or mesoporous two prepared by feather weight
Silica, can be prepared according to this area conventional method.
Using when, meso-porous alumina can be added directly into lubricating oil, to improve the service life of lubricating oil.Both
Weight is：
0.25-2 parts of meso-porous alumina,
98-99 parts of lubricating oil.
Using when, can also be by meso-porous alumina and commercial antioxidant 3,5- di-t-butyl -4- hydroxyl phenol methyl propionates（Letter
Claim 3,5- methyl esters）It is added to after compound in lubricating oil, to improve the service life of lubricating oil.The weight of three is：
0.1-0.8 parts of meso-porous alumina,
3,5- 0.5-1.5 parts of methyl esters,
97-99 parts of lubricating oil.
Using when, mesoporous silicon oxide and commercial antioxidant 3 can be added in lubricating oil after 5- methyl esters is compound, with
Improve the service life of lubricating oil.The weight of three is：
0.1-0.5 parts of mesoporous silicon oxide,
3,5- 0.5-1.5 parts of methyl esters,
98-99 parts of lubricating oil.
Using when, can also by mesoporous silicon oxide and antioxidant 3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid it is multiple
It is added to after conjunction in lubricating oil, to improve the service life of lubricating oil.The weight of three is：
0.1-0.5 parts of mesoporous silicon oxide,
0.5-1.5 parts of 3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid,
98-99 parts of lubricating oil.
In the present invention, inorganic porous nano particle is added to lubricating oil（Such as Plexol 201, abbreviation DIOS；Poly- a
Alkene, abbreviation PAO）In, for example, meso-porous alumina can not only be used separately as antioxidant, and can be anti-with commercialization
Oxygen agent compound use, works well.Mesoporous silicon oxide and commercial antioxidant also have cooperative effect, can extend the oxygen of oil product
Change induction time.Wherein oxidation induction time is measured using rotary oxygen bomb tester and pressure differential scanning calorimetry.Profit
The change of oil product color, viscosity and acid number with oxidization time is investigated with baking oven oxidation experiment.
Compared to the prior art, the invention has the advantages that：
The features such as present invention is with high specific surface area, regular pore passage structure, narrow pore-size distribution it is inorganic many
Hole nano particle is incorporated into antioxidant system, makes it during oil ageing, delayed to a certain extent its viscosity and
The increase of acid number, so as to improve its antioxidant capacity, makes it have good antioxygenic property and high thermal stability.
Brief description of the drawings
Fig. 1 is that the rotary oxygen bomb test result after not same amount meso-porous alumina is added in DIOS；
Fig. 2 is the sample optical photograph after baking oven oxidation experiment in embodiment 1, and a DIOS base oils, b is added with meso-porous alumina
Oil product；
Fig. 3 is the viscosity B coefficent a DIOS base oils of the sample after baking oven oxidation experiment in embodiment 1, and b is added with mesoporous oxidation
The oil product of aluminium；
Fig. 4 is the sample optical photograph after baking oven oxidation experiment in embodiment 3, and a DIOS base oils, b is added with 0.5wt% 3,
The oil product of the oil product of 5- methyl esters, c addition 0.5wt% 3,5- methyl esters and the inorganic antioxidant meso-porous aluminas of 0.5wt%；
Fig. 5 is the sample optical photograph after baking oven oxidation experiment in embodiment 5, and a DIOS base oils, b is added with 0.5wt% 3,
The oil product of the oil product of 5- methyl esters, c addition 0.5wt% 3,5- methyl esters and the inorganic antioxidant mesoporous silicon oxides of 0.15wt%；
Fig. 6 is the sample acid number change after baking oven oxidation experiment in embodiment 5, and a DIOS base oils, b is added with 0.5wt% 3,
The oil product of the oil product of 5- methyl esters, c addition 0.5wt% 3,5- methyl esters and the inorganic antioxidant mesoporous silicon oxides of 0.15wt%.
Embodiment
The present invention is specifically described with reference to specific embodiment, it is necessary to it is pointed out here that be that the present embodiment is only used
It is further described in the present invention, it is impossible to be interpreted as limiting the scope of the invention.Those skilled in the art according to
The content of the invention described above makes some nonessential modifications and adaptations, is accordingly to be regarded as within the scope of the present invention.
In following embodiments, each raw material dosage is in parts by weight.Wherein, meso-porous alumina is with PEO-polycyclic
Ethylene Oxide-PEO is template, and ethanol is reaction medium, and aluminium isopropoxide prepares for silicon source（Specifically it can refer to：
Zhang K, Xu L L, Jiang J G, et al. Facile Large-Scale Synthesis of
Monodisperse Mesoporous Silica Nanospheres with Tunable Pore Structure [J].
Journal of the American Chemical Society, 2013,135(7):2427）.Mesoporous silicon oxide is with ten
Six alkyl trimethyl ammonium bromides are template, and water is reaction medium, and tetraethyl orthosilicate prepares for silicon source（Specifically it can refer to：
Yuan Q, Yin A X, Luo C, et al. Facile synthesis for ordered mesoporous gamma-
aluminas with high thermal stability [J]. Journal of the American Chemical
Society, 2008,130(11):3465-3472.）.
Embodiment 1
Lubricating oil Plexol 201 is added to using meso-porous alumina as antioxidant（DIOS）In, surveyed using rotary bomb oxidation test
Determine its oxidation induction time at 150 DEG C.Fig. 1 is rotary oxygen bomb test result, as can be seen from Figure 1：Base oil DIOS
Oxidation induction time be 44min；And add after 0.5 wt % meso-porous aluminas, the antioxygen time increases to 79min.
Fig. 2 is to be aoxidized in 150 DEG C of air dry ovens, oil based on the optical photograph of sample, a after being sampled every 24 hours
DIOS samples with oxidation number of days color change, b for addition the inorganic antioxidant meso-porous aluminas of 0.5wt% after DIOS samples with
Aoxidize the color change of number of days.As can be seen from Figure 2：Base oil DIOS samples are bright with the extension color change of oxidization time
It is aobvious, inhibit the increasing of oil product color deep to a certain extent after inorganic antioxidant meso-porous alumina is added.Fig. 3 is through different time
The viscosity B coefficent of sample after oxidation, as can be seen from Figure 3：The addition of inorganic antioxidant meso-porous alumina is suppressing to a certain degree
The increases of DIOS oil viscosities.
Embodiment 2
It is added to using meso-porous alumina as antioxidant in lubricating oil in esters DIOS, addition is 0.75 wt %, utilizes Rotary Oxygen
Bullet method determines its oxidation induction time at 150 DEG C.Fig. 1 is mesoporous to add the not inorganic antioxidant of same amount in Esters oil DIOS
The rotary oxygen bomb test result of aluminum oxide.As can be seen from Figure 1：Base oil DIOS oxidation induction time is 44min；With
The increase of meso-porous alumina addition, the antioxygen time is consequently increased.When inorganic antioxidant meso-porous alumina addition is
During 0.75wt%, the antioxygen time increases to 81min.
Embodiment 3
Meso-porous alumina and commercial antioxidant 3,5- methyl esters is combined, and investigating its oxidation in DIOS using rotary bomb oxidation test lures
Lead the time.Individually addition 0.5wt% 3,5- methyl esters, can make DIOS oxidation induction time extend to 85.5min from 44min.
3,5- methyl esters additions is in 0.5wt% DIOS systems, addition 0.5wt% meso-porous alumina can make oxidation induction time
Extend to 165min.
Fig. 4 is to be aoxidized in 150 DEG C of air dry ovens, the optical photograph of sample after being sampled every 24 hours, and a is to be not added with
DIOS base oil samples with the color change of oxidation number of days, b is addition 0.5% 3, and the DIOS samples of 5- methyl esters are with oxidation number of days
Color change, c is 0.5 wt % 3 of addition, and the DIOS samples of 5- methyl esters and the inorganic antioxidant meso-porous aluminas of 0.5wt% are with oxygen
Change the color change of number of days.As can be seen from Figure 4：Oil product when being not added with oxidization time extension color change the most
Substantially, after 3,5- methyl esters and inorganic antioxidant meso-porous alumina are compound, the change of oil product color is inhibited to a certain extent, is imitated
Fruit is substantially.
Embodiment 4
Meso-porous alumina and commercial antioxidant 3,5- methyl esters is combined, and it is investigated at 150 DEG C DIOS's using rotary bomb oxidation test
Oxidation induction time.Individually addition 0.5wt% 3,5- methyl esters, can be such that DIOS oxidation induction time is extended to from 44min
85.5min.In 3,5- methyl esters addition in 0.5wt% DIOS systems, addition 0.3wt% meso-porous alumina can make oxygen
Change induction time and extend to 120min.
Embodiment 5
Mesoporous silicon oxide and commercial antioxidant 3,5- methyl esters is combined, and it is investigated at 150 DEG C in DIOS using rotary bomb oxidation test
Oxidation induction time.Individually addition 0.5wt% 3,5- methyl esters, can be such that DIOS oxidation induction time is extended to from 44min
85.5min.In 3,5- methyl esters addition in 0.5wt% DIOS systems, addition 0.15wt% mesoporous silicon oxide can make
Oxidation induction time extends to 162min.
Fig. 5 is to be aoxidized in 150 DEG C of air dry ovens, the optical photograph of sample after being sampled every 24 hours, and a is to be not added with
DIOS base oil samples with the color change of oxidation number of days, b is addition 0.5wt% 3, and the DIOS samples of 5- methyl esters are with oxidation day
Several color changes, c is addition 0.5wt% 3,5- methyl esters and the inorganic antioxidant mesoporous silicon oxides of 0.15wt% DIOS samples
With the color change of oxidation number of days.As can be seen from Figure 6：Oil product is when being not added with the extension color change of oxidization time
The most substantially, after 3,5- methyl esters and inorganic antioxidant mesoporous silicon oxide are compound, oil product color is inhibited to a certain extent
Change, effect is obvious.The viscosity B coefficent of sample after three kinds of systems are aoxidized through different time is determined, inorganic antioxidant mesoporous two is found
After silica and 3,5- methyl esters are compound, the viscosity increase of oil product is minimum.Fig. 6 is sample after three kinds of systems are aoxidized through different time
Acid number changes, as can be seen from Figure 6：After inorganic antioxidant mesoporous silicon oxide and 3,5- methyl esters are compound, the acid number of oil product increases
Plus it is minimum, illustrate that after inorganic antioxidant mesoporous silicon oxide and 3,5- methyl esters are compound the oxygen of oil product can be suppressed to a certain extent
Change.
Embodiment 6
Mesoporous silicon oxide and commercial antioxidant 3,5- methyl esters is combined, and it is investigated at 150 DEG C in DIOS using rotary bomb oxidation test
Oxidation induction time.Individually addition 1.5wt% 3,5- methyl esters, can be such that DIOS oxidation induction time is extended to from 44min
196min.In 3,5- methyl esters addition in 1.5wt% DIOS systems, addition 0.6wt% meso-porous alumina can make oxidation
Induction time extends to 196min.
Embodiment 7
Mesoporous silicon oxide and antioxidant 3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid are combined, rotary bomb oxidation test is utilized
Investigate 150 DEG C at its DIOS oxidation induction time.Individually add 0.5wt% 3- (3,5- di-tert-butyl-hydroxy phenyls)
Propionic acid, can make DIOS oxidation induction time extend to 110.5min from 44min.In 3- (3,5- di-t-butyl -4- hydroxy benzenes
Base) propionic acid addition for 0.5wt% DIOS systems in, add 0.6wt% mesoporous silicon oxide, oxidation induction time can be made
Extend to 196min.
Embodiment 8
Mesoporous silicon oxide and commercial antioxidant 3,5- methyl esters is combined, and utilizes pressure differential scanning calorimetry（PDSC, oxygen stream
Fast 100mL/min）It is determined in polyalphaolefin -6（Abbreviation PAO6）In oxidation induction time.180 DEG C, 3.5MPa high pressures it is pure
Under the conditions of oxygen, un-added PAO6 oxidation induction time is 6.0min, can individually be made after addition 0.5wt% 3,5- methyl esters
PAO6 oxidation induction time extends to 23min.In the PAO6 systems that 3,5- methyl esters addition is 0.5wt%, addition
0.15wt% mesoporous silicon oxide, can make oxidation induction time extend to 25.8min.
Embodiment 9
Mesoporous silicon oxide and commercial antioxidant 3,5- methyl esters is combined, and utilizes pressure differential scanning calorimetry（PDSC, oxygen stream
Fast 100mL/min）Determine its oxidation induction time in DIOS.Under the conditions of 190 DEG C, 3.5MPa pure oxygen in high pressure, it is not added with
DIOS oxidation induction time be 3.1min, individually addition 0.5wt% 3,5- methyl esters after can make DIOS oxidation induction time
Extend to 6.6min.In 3,5- methyl esters addition in 0.5wt% DIOS systems, to add 0.15wt% mesoporous silicon oxide,
Oxidation induction time can be made to extend to 8.1min.
Embodiment 10
Mesoporous silicon oxide and commercial antioxidant 3,5- methyl esters is combined, and utilizes pressure differential scanning calorimetry（PDSC, oxygen stream
Fast 100mL/min）Determine its oxidation induction time in DIOS.Under the conditions of 170 DEG C, 3.5MPa pure oxygen in high pressure, it is not added with
DIOS oxidation induction time be 13.3min, individually addition 0.5wt% 3,5- methyl esters after can make DIOS oxidation induce when
Between extend to 25.8min.In the DIOS systems that 3,5- methyl esters addition is 0.5wt %, 0.15wt% meso-porous titanium dioxide is added
Silicon, can make oxidation induction time extend to 28.3min.
Claims (6)
1. porous nano particle in lubricating oil as Inorganic antioxidant application.
2. application as claimed in claim 1, it is characterised in that the porous nano particle is meso-porous alumina or mesoporous dioxy
SiClx.
3. application as claimed in claim 2, it is characterised in that when applying, meso-porous alumina is added directly into lubricating oil,
Both weight is：
0.25-2 parts of meso-porous alumina,
98-99 parts of lubricating oil.
4. application as claimed in claim 2, it is characterised in that when applying, by meso-porous alumina and commercial antioxidant 3,5- first
It is added to after ester is compound in lubricating oil, the weight of three is：
0.1-0.8 parts of meso-porous alumina,
3,5- 0.5-1.5 parts of methyl esters,
97-99 parts of lubricating oil.
5. application as claimed in claim 2, it is characterised in that when applying, by mesoporous silicon oxide and commercial antioxidant 3,5-
It is added to after methyl esters is compound in lubricating oil, the weight of three is：
0.1-0.5 parts of mesoporous silicon oxide,
3,5- 0.5-1.5 parts of methyl esters,
98-99 parts of lubricating oil.
6. application as claimed in claim 2, it is characterised in that when applying, by mesoporous silicon oxide and antioxidant 3- (3,5- bis-
Tert-butyl-hydroxy phenyl) it is added in lubricating oil after propionic acid is compound, the weight of three is：
0.1-0.5 parts of mesoporous silicon oxide,
0.5-1.5 parts of 3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid,
98-99 parts of lubricating oil.
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| CN201710208510.1A CN107118823B (en) | 2017-03-31 | 2017-03-31 | Application of porous nanoparticles as inorganic antioxidant in lubricating oil |
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| CN201710208510.1A CN107118823B (en) | 2017-03-31 | 2017-03-31 | Application of porous nanoparticles as inorganic antioxidant in lubricating oil |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206432A (en) * | 2010-03-31 | 2011-10-05 | 中国科学院化学研究所 | Nano-silica surface-grafted with antioxidant molecule and preparation method and application thereof |
| CN102947429A (en) * | 2010-03-26 | 2013-02-27 | 爱思开润滑油株式会社 | Lubricating oil composition for reducing friction comprising nanoporous particles |
| CN104817727A (en) * | 2015-04-17 | 2015-08-05 | 广州合成材料研究院有限公司 | Carried antioxygen and preparation method thereof |
-
2017
- 2017-03-31 CN CN201710208510.1A patent/CN107118823B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102947429A (en) * | 2010-03-26 | 2013-02-27 | 爱思开润滑油株式会社 | Lubricating oil composition for reducing friction comprising nanoporous particles |
| CN102206432A (en) * | 2010-03-31 | 2011-10-05 | 中国科学院化学研究所 | Nano-silica surface-grafted with antioxidant molecule and preparation method and application thereof |
| CN104817727A (en) * | 2015-04-17 | 2015-08-05 | 广州合成材料研究院有限公司 | Carried antioxygen and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 毛新建: ""介孔硅纳米微粒在酯类油中抗氧协同效应及其摩擦学性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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