CN110982582A - Preparation method of lubricating oil antiwear agent - Google Patents
Preparation method of lubricating oil antiwear agent Download PDFInfo
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- CN110982582A CN110982582A CN201911227688.6A CN201911227688A CN110982582A CN 110982582 A CN110982582 A CN 110982582A CN 201911227688 A CN201911227688 A CN 201911227688A CN 110982582 A CN110982582 A CN 110982582A
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- 239000010687 lubricating oil Substances 0.000 title claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 25
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 18
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 18
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 12
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000012989 trithiocarbonate Substances 0.000 claims abstract description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000002091 cationic group Chemical group 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000008096 xylene Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 238000005292 vacuum distillation Methods 0.000 claims description 18
- 238000010992 reflux Methods 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 6
- 230000001502 supplementing effect Effects 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 239000004705 High-molecular-weight polyethylene Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000000654 additive Substances 0.000 description 24
- 230000000996 additive effect Effects 0.000 description 11
- 230000001050 lubricating effect Effects 0.000 description 9
- 239000003921 oil Substances 0.000 description 8
- 238000011160 research Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- -1 benzothiazole ester Chemical class 0.000 description 5
- 230000006698 induction Effects 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 239000002199 base oil Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N cyclobenzothiazole Natural products C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
- C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
- C10M145/14—Acrylate; Methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
Abstract
A process for preparing antiwear agent of lubricating oil includes such steps as polymerizing n-butyl acrylate as raw material, azodiisobutyronitrile as trigger, s ' -bis (α ' -methyl- α ' -acetic acid) trithiocarbonate as chain transfer agent in the presence of solvent, vacuum distilling to remove solvent to obtain polymer A, esterifying and capping polymer A with ethanolamine and cationic resin as catalyst to obtain the product containing-NH2A polymer B of groups; C. heating the polymer B and molybdenum trioxide to 127-135 ℃ in the presence of N, N-dimethylformamide and xyleneRefluxing for 4-5h, cooling to 60-80 deg.C, adding hydrazine hydrate, stirring for 2-3h until the reaction substrate is blue-green or dark green, distilling under reduced pressure to remove xylene, and filtering. The lubricating oil antiwear agent prepared by the method has good compatibility stability.
Description
Technical Field
The invention belongs to the technical field of lubricating compositions characterized by reaction product additives with unknown or incompletely determined structures, and particularly relates to a preparation method of a lubricating oil antiwear agent.
Background
Along with the improvement of the industrial automation degree of modern production, the automation degree, the accuracy and the reliability degree of automation equipment are higher and higher, and the requirements on the lubricating effect of mechanical equipment are higher and higher (the application of a ball screw and hydraulic transmission on the equipment, Wangming, Henan science and technology, 2011, 16 th, page 64, abstract, line 1, published 2011, 12 and 31 days; "lubricating management of shallow-analysis mining equipment", Liuyunhua and the like, the automation application, 2018, 10 th, page 135, abstract, lines 1 and 2, and 2018, 12 and 31 days). To meet the increasingly severe working conditions, more and more complex additives are required to be added to the lubricating oil, and the lubricating performance of the lubricating oil is improved through the synergistic effect of the additives.
However, the molecular structure of the lubricant additive is complex, and various problems such as compatibility and stability difference exist among different additives, which bring adverse effects on the production and use of the lubricant. Therefore, the development of multifunctional lubricating oil additives becomes an important research direction in the field of tribology ("the synthesis and tribology performance research of novel boron-containing benzothiazole ester derivative lubricating additives", Youjianwei et al, the Master academic thesis of the university of south and Central university, 2010, abstract line 1, published day 2011, 05 and 31; "the current situation and development trend of lubricating oil additives", Voxisheng et al, automotive technology and materials, 2005, 5 th, page 1, left column, 1 st paragraph 1, lines 1-15, published day 2005, 12 and 31).
In which, Xiadei of the academy of logistical engineering, etc. uses a self-made organic Molybdenum (MSN) multifunctional additive to investigate the solubility, corrosion resistance, oxidation resistance, friction reduction and extreme pressure resistance of the additive in the formulated oil. Experiments show that the multifunctional organic molybdenum additive has more excellent performance than the common additive under the same conditions (the performance research of oil soluble organic molybdenum as the multifunctional lubricating oil additive, Xiadei, functional materials, No. 47, No. 2 in 2016, No. 1-4 in abstract page 2154, and No. 2016, No. 06, No. 29). The multifunctional boric acid ester containing sulfur and nitrogen is synthesized by experiments and the performance of the boric acid ester is researched by Huangweijiu and the like of Chongqing institute of Industrial science and engineering. Research shows that the multifunctional sulfur-nitrogen-containing borate additive has the same anti-wear performance as ZDDP, and also has better anti-corrosion performance and thermal stability ("performance research of multifunctional sulfur-nitrogen-containing borate", Huangweijiu et al, synthetic lubricating material, No. 28, No. 2, page 11, abstract, lines 1-4, published 2001, 12 months and 31). The hindered phenol multifunctional lubricating additive is synthesized by Livemin and the like of Lanzhou chemical and physical research institute of Chinese academy of sciences, and compared with a common single additive, the hindered phenol multifunctional lubricating additive has better friction resistance and antioxidant performance (preparation and performance research of the hindered phenol derivative multifunctional lubricating additive, Livemin and the like, lubricating oil, No. 2 of volume 27 in 2012, No. 1-3 of abstract on page 30, and 30 of 04 and 30 of published date 2012).
However, the above lubricating oil additives have problems of unstable compatibility of raw materials, such as poor compatibility with some components, which may cause precipitation.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of a lubricating oil antiwear agent with good raw material compatibility stability.
The parts are all parts by mass unless otherwise specified.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the preparation method of the lubricating oil antiwear agent comprises the following steps:
A. carrying out polymerization reaction by using n-butyl acrylate as a raw material, azobisisobutyronitrile as an initiator and s, s ' -bis (α ' -methyl- α ' -acetic acid) trithiocarbonate as a chain transfer agent in the presence of a solvent, and then distilling under reduced pressure to remove the solvent to obtain a polymer A;
B. using cation resin as catalyst, using ethanolamine to make esterification capping of polymer A to obtain the product containing-NH2A polymer B of groups;
C. heating the polymer B and molybdenum trioxide to 127-135 ℃ in the presence of N, N-dimethylformamide and xylene, refluxing for 4-5h, cooling to 60-80 ℃, supplementing hydrazine hydrate, continuously stirring for 2-3h until a reaction substrate is blue-green or dark green, distilling under reduced pressure to remove the xylene, and filtering to obtain the high-performance low-temperature-resistant high-molecular-weight polyethylene glycol.
The inventor unexpectedly finds that the method comprises the following steps:
A. carrying out polymerization reaction by using n-butyl acrylate as a raw material, azobisisobutyronitrile as an initiator and s, s ' -bis (α ' -methyl- α ' -acetic acid) trithiocarbonate as a chain transfer agent in the presence of a solvent, and then distilling under reduced pressure to remove the solvent to obtain a polymer A;
B. using cation resin as catalyst, using ethanolamine to make esterification capping of polymer A to obtain the product containing-NH2A polymer B of groups;
C. heating the polymer B and molybdenum trioxide to 127-135 ℃ in the presence of N, N-dimethylformamide and xylene, refluxing for 4-5h, cooling to 60-80 ℃, supplementing hydrazine hydrate, continuously stirring for 2-3h until a reaction substrate is blue-green or dark green, distilling under reduced pressure to remove the xylene, and filtering to obtain the high-performance liquid crystal;
the lubricating oil antiwear agent prepared by the method has good compatibility stability.
Further, in the step A, the mass ratio of the n-butyl acrylate, the azobisisobutyronitrile, the solvent and the s, s ' -bis (α ' -methyl- α ' -acetic acid) trithiocarbonate is 100:0.5-1.0: 1.5-2.0: 80-100.
Further, in step a, the solvent comprises ethyl acetate.
Further, in the step A, the temperature of the polymerization reaction is 70-75 ℃, and the reaction time is 8-10 h.
Further, the temperature of the reduced pressure distillation in the step A is 60-65 ℃, the pressure is 80-1000Pa, and the time is 2-2.5 h.
Further, the weight average molecular weight of the polymer A was 15000-29500.
Further, in the step B, the mass ratio of the polymer A, the ethanolamine and the cationic resin is 100:30-35: 2.0-4.0.
Further, in the step B, the reaction is carried out by reduced pressure distillation at 80-95 ℃ for 6-8h, the reduced pressure distillation temperature is increased to 140-150 ℃, then the reduced pressure distillation is continued for 3-4 h, and the cationic resin is removed by filtration.
Further, in the step C, the mass fraction of hydrazine monohydrate in the hydrazine hydrate is 80%.
Further, in the step C, the mass ratio of the polymer B, the molybdenum trioxide, the N, N-dimethylformamide, the xylene and the hydrazine hydrate is 100:10.0-15.0:1.0-1.2:80-100: 2.0-4.0.
Further, the temperature of the reduced pressure distillation in the step C is 90-95 ℃, the pressure is 800-1000Pa, and the time is 2-2.5 h.
The invention has the beneficial effects that:
the lubricating oil antiwear agent prepared by the method has good compatibility stability.
The lubricating oil antiwear agent prepared by the method has higher viscosity and viscosity index, and the kinematic viscosity of the 15# industrial asphalt can be improved by 15mm at 40 DEG C2·s-1To 18.5-19.9mm2·s-1The viscosity index is increased from 6 to 13-16.
The lubricating oil antiwear agent prepared by the method has a lower friction coefficient and a higher sintering load, the addition amount of 1 wt% can reduce the friction coefficient of No. 15 industrial asphalt to 0.052-0.067, and the sintering load is improved to 2450-2945N.
The lubricating oil antiwear agent prepared by the method has better oxidation stability, and the addition proportion of 1 wt% can improve the oxidation induction time of 15# industrial asphalt to 62-83 min.
Detailed Description
The examples are provided for better illustration of the present invention, but the present invention is not limited to the examples. Therefore, those skilled in the art should make insubstantial modifications and adaptations to the embodiments of the present invention in light of the above teachings and remain within the scope of the invention.
The following s, s ' -bis (α ' -methyl- α ' -acetic acid) trithiocarbonate (RAFT reagent) was prepared by Xinjiang academy of sciences in China;
the following weight average molecular weight was measured by permeation gel chromatography under the following test conditions: RID (parallax refraction) detectors, temperature 40 ℃; tetrahydrofuran is used as a mobile phase, the column temperature is 40 ℃, and the flow rate is 0.5 mL/min;
the following functional groups were determined by fourier infrared spectroscopy, test conditions: by KBr coating method, the wave number scanning range is 400-4000cm-1；
The following friction coefficients were measured according to SH/T0762-2005 lubricating oil friction coefficient measurement method (four-ball method).
Test on four ball machine-sintering load PDThe test was carried out according to GB/T3142-1982 method for measuring the load-carrying capacity of lubricants (four-ball method);
the following kinematic viscosities were measured according to GB/T265 and 1998 kinematic viscosity measurements and kinetic viscosity calculations of petroleum products;
the following viscosity index calculations were performed according to GB/T1995-1998 viscosity index calculation method for petroleum products;
the following oxidative induction period (150 ℃) was examined according to SH/T0209-.
The following determination method of the compatibility of the additive is as follows: the two different additives are simultaneously stirred and dissolved in the base oil, and the mixture is kept stand for 30 days at room temperature and then observed by naked eyes.
Example 1
The lubricating oil antiwear agent is prepared by the following steps:
A. adding 100 parts of n-butyl acrylate, 0.5 part of azodiisobutyronitrile AIBN serving as an initiator and 80 parts of ethyl acetate serving as a solvent into a reaction kettle with a stirrer and a condenser, adding 1.5 parts of s, s ' -bis (α ' -methyl- α ' -acetic acid) trithiocarbonate (RAFT reagent) under the stirring condition, heating to 70 ℃ for reflux reaction for 8 hours, and after the reaction is finished, distilling under reduced pressure for 2 hours under the conditions of 60 ℃ and 800Pa to remove the ethyl acetate serving as the solvent to obtain an inserted polymer A (the weight average molecular weight Mw is measured to be 29500);
B. 100 parts of polymer A are put into a vacuum distillation reaction kettle with stirring, 30 parts of ethanolamine and 2.0 parts of catalyst DOO1 cationic resin are put into the vacuum distillation reaction kettle, the vacuum distillation reaction is carried out for 8 hours at the temperature of 80 ℃, the vacuum distillation temperature is increased to 140 ℃, the vacuum distillation is continued for 4 hours, the catalyst DOO1 is filtered to obtain polymer B (measured by a Fourier infrared spectrometer at 3300--1Shows an N-H absorption peak and proves that the compound contains-NH2Functional groups);
C. putting 100 parts of polymer B into a reaction kettle with a stirrer and a reflux condenser, adding 10.0 parts of molybdenum trioxide, 1.0 part of N, N-dimethylformamide and 100 parts of dimethylbenzene, heating to 127 ℃, refluxing for 4 hours, cooling to 80 ℃, supplementing 2.0 parts of hydrazine hydrate with the mass fraction of 80% of hydrazine monohydrate, continuously stirring for 3 hours at 60 ℃ until a reaction substrate is blue-green, distilling under reduced pressure for 2 hours at 90 ℃ and under the vacuum pressure of 800Pa to remove the dimethylbenzene, and filtering to remove solid impurities to obtain the catalyst.
Example 2
The lubricating oil antiwear agent is prepared by the following steps:
A. adding 100 parts by mass of n-butyl acrylate, 1.0 part by mass of azobisisobutyronitrile AIBN serving as an initiator and 100 parts by mass of ethyl acetate serving as a solvent into a reaction kettle with a stirrer and a condenser, adding 2.0 parts by mass of s, s ' -bis (α ' -methyl- α ' -acetic acid) trithiocarbonate (RAFT reagent) under stirring, heating to 75 ℃ for reflux reaction for 8 hours, and after the reaction is finished, distilling under reduced pressure for 2.5 hours under the conditions of 65 ℃ and 1000Pa to remove the ethyl acetate serving as the solvent to obtain a polymer A (the measured weight average molecular weight Mw is 15000);
B. 100 parts of polymer A are put into a vacuum distillation reaction kettle with stirring, 30 parts of ethanolamine and 2.0 parts of catalyst DOO1 cationic resin are put into the vacuum distillation reaction kettle, the vacuum distillation reaction is carried out for 6 hours at the temperature of 95 ℃, the vacuum distillation temperature is increased to 150 ℃, the vacuum distillation is continued for 3 hours, the catalyst DOO1 is filtered to obtain polymer B (measured by a Fourier infrared spectrometer at 3300--1Shows an N-H absorption peak and proves that the compound contains-NH2Functional groups);
C. putting 100 parts of polymer B into a reaction kettle with a stirrer and a reflux condenser, adding 15.0 parts of molybdenum trioxide, 1.0 part of N, N-dimethylformamide and 100 parts of dimethylbenzene, heating to 135 ℃, refluxing for 5 hours, cooling to 60 ℃, supplementing 4.0 parts of hydrazine hydrate with the mass fraction of 80% of hydrazine monohydrate, continuously stirring for 2-3 hours at 80 ℃ until a reaction substrate is dark green, controlling the vacuum pressure of 1000Pa and the distillation temperature of 95 ℃, distilling under reduced pressure for 2.5 hours to remove the dimethylbenzene, and filtering to remove solid impurities to obtain the catalyst.
Example 3
The lubricating oil antiwear agent is prepared by the following steps:
A. adding 100 parts of n-butyl acrylate, 0.8 part of azodiisobutyronitrile AIBN serving as an initiator and 90 parts of ethyl acetate serving as a solvent into a reaction kettle with a stirrer and a condenser, adding 1.8 parts of s, s ' -bis (α ' -methyl- α ' -acetic acid) trithiocarbonate (RAFT reagent) under the stirring condition, heating to 72 ℃ for reflux reaction for 9 hours, controlling the temperature to be 62.5 ℃ after the reaction is finished, and distilling under reduced pressure for 2 hours under the vacuum pressure of 900Pa to remove the ethyl acetate serving as the solvent to obtain a block polymer A (the weight average molecular weight Mw measured by molecular permeation gel chromatography is 22700);
B. 100 parts of polymer A are put into a vacuum distillation reaction kettle with stirring, 30 parts of ethanolamine and 2.0 parts of catalyst DOO1 cationic resin are put into the vacuum distillation reaction kettle, the vacuum distillation reaction is carried out for 7 hours at the temperature of 90 ℃, the vacuum distillation temperature is increased to 145 ℃, the vacuum distillation is continued for 3.5 hours, the catalyst cationic resin DOO1 is filtered out to obtain polymer B (measured by a Fourier infrared spectrometer at 3300-3500 cm)-1Shows an N-H absorption peak and proves that the compound contains-NH2Functional groups);
C. putting 100 parts of polymer B into a reaction kettle with a stirrer and a reflux condenser, adding 13.0 parts of molybdenum trioxide, 1.0 part of N, N-dimethylformamide and 100 parts of dimethylbenzene, heating to 132 ℃, refluxing for 4.5 hours, cooling to 70 ℃, supplementing 3.0 parts of hydrazine hydrate with the mass fraction of 80% of hydrazine monohydrate, continuously stirring for 2.5 hours at 70 ℃ until a reaction substrate is blue-green, controlling the temperature to be 92 ℃, controlling the vacuum pressure to be 900Pa, carrying out reduced pressure distillation for 2 hours to remove the dimethylbenzene, and filtering to remove solid impurities to obtain the catalyst.
Performance detection
The antiwear agents for lubricating oils prepared in examples 1 to 3 were added to No. 15 technical white oil (manufactured by Clarity oil refinery) in an amount of 1 wt% to measure the kinematic viscosity (40 ℃), viscosity index, friction coefficient, sintering load (Pd), oxidation induction time, etc., and were blank-compared with No. 15 technical white oil to which no antiwear agent was added, and the results are shown in Table 1.
1 wt% of the lubricating oil anti-wear agent obtained in examples 1 to 3, T106 (calcium petroleum sulfonate, emerging from jin Petroleum additives, Inc.), T109 (calcium alkyl salicylate, emerging from jin Petroleum additives, Inc.), T321 (sulfurized isobutylene, emerging from jin Tianhe chemical Co., Ltd., jin, N.P.) and T203 (zinc dialkyl dithiophosphate, emerging from jin Tianhe chemical Co., Ltd., N.P.) were added to 15# technical white oil as a base oil to conduct a dissolution stability test, and the results are shown in Table 2.
Table 1 results of performance testing
| Detecting items | Blank control group | Example 1 | Example 2 | Example 3 |
| Kinematic viscosity (40 ℃ C.)/(mm)2·s-1) | 15.8 | 19.9 | 18.5 | 19.1 |
| Viscosity index | 6 | 16 | 13 | 15 |
| Coefficient of friction | 0.116 | 0.067 | 0.052 | 0.061 |
| Sintering load Pd/N | 1180 | 2450 | 2945 | 2750 |
| Oxidative induction time (150 deg.C)/min | 26 | 62 | 83 | 71 |
As can be seen from Table 1, when 1 wt% of the antiwear agent prepared in examples 1-3 was added to No. 15 industrial white oil, the kinematic viscosity and viscosity index at 40 ℃ were both significantly improved, and at the same time, the sintering load was increased from 1180N to 2450-2945N, and the oxidation induction time was increased from 26min to 62-83 min. Therefore, the lubricating oil antiwear agent prepared by the method disclosed by the invention has an antiwear function, and can be used for remarkably improving the viscosity and viscosity index and remarkably prolonging the oxidation resistance time of base oil.
TABLE 2 compatibility test results
As can be seen from Table 2, the antiwear agents prepared in examples 1 to 3 and 1 wt% of other additives were added to 15% of a technical white oil as a base oil, and the mixture was allowed to stand at room temperature for 30 days after dissolution without separation and precipitation. Therefore, the lubricating oil antiwear agent prepared by the method has good compatibility with the additives.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. The preparation method of the lubricating oil antiwear agent is characterized by comprising the following steps:
A. carrying out polymerization reaction by using n-butyl acrylate as a raw material, azobisisobutyronitrile as an initiator and s, s ' -bis (α ' -methyl- α ' -acetic acid) trithiocarbonate as a chain transfer agent in the presence of a solvent, and then distilling under reduced pressure to remove the solvent to obtain a polymer A;
B. using cation resin as catalyst, using ethanolamine to make esterification capping of polymer A to obtain the product containing-NH2A polymer B of groups;
C. heating the polymer B and molybdenum trioxide to 127-135 ℃ in the presence of N, N-dimethylformamide and xylene, refluxing for 4-5h, cooling to 60-80 ℃, supplementing hydrazine hydrate, continuously stirring for 2-3h until a reaction substrate is blue-green or dark green, distilling under reduced pressure to remove the xylene, and filtering to obtain the high-performance low-temperature-resistant high-molecular-weight polyethylene glycol.
2. The process according to claim 1, wherein in step A, the mass ratio of n-butyl acrylate, azobisisobutyronitrile, solvent and s, s '-bis (α' -methyl- α "-acetic acid) trithiocarbonate is 100:0.5-1.0: 1.5-2.0: 80-100.
3. The method according to claim 1 or 2, wherein in step a, the solvent comprises ethyl acetate.
4. The process according to any one of claims 1 to 3, wherein in the step A, the polymerization temperature is 70 to 75 ℃ and the reaction time is 8 to 10 hours.
5. The process according to any one of claims 1 to 4, wherein the reduced pressure distillation in step A is carried out at a temperature of 60 to 65 ℃ and a pressure of 80 to 1000Pa for a period of 2 to 2.5 hours.
6. The production method according to any one of claims 1 to 5, wherein the weight average molecular weight of the polymer A is 15000-29500.
7. The production method according to any one of claims 1 to 6, wherein in the step B, the mass ratio of the polymer A, the ethanolamine and the cationic resin is 100:30 to 35:2.0 to 4.0.
8. The method according to any one of claims 1-7, wherein in step B, the reaction is performed by vacuum distillation at 80-95 ℃ for 6-8h, the vacuum distillation temperature is increased to 140-150 ℃, then the vacuum distillation is continued for 3-4 h, and the cationic resin is removed by filtration.
9. A method according to any one of claims 1 to 8, wherein in step C, the mass fraction of hydrazine monohydrate in the hydrazine hydrate is 80%.
10. The production method according to any one of claims 1 to 9, wherein in the step C, the mass ratio of the polymer B, molybdenum trioxide, N-dimethylformamide, xylene, and hydrazine hydrate is 100:10.0 to 15.0:1.0 to 1.2:80 to 100:2.0 to 4.0.
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| US20080004461A1 (en) * | 2000-02-16 | 2008-01-03 | Lai John T | S-S'-bis-(Alpha, Alpha'-Disubstituted-Alpha"-Acetic Acid) - Trithiocarbonates and Derivatives as Initiator - Chain Transfer Agent - Terminator for Controlled Radical Polymerizations and the Process for Making the Same |
| CN103113502A (en) * | 2013-02-20 | 2013-05-22 | 中国科学院新疆理化技术研究所 | Preparation method of wear resistance viscosity index improver |
| CN106221862A (en) * | 2016-08-18 | 2016-12-14 | 江西福安路润滑材料有限公司 | Molybdenum modifiers dispersants, its preparation method and application |
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| US20080004461A1 (en) * | 2000-02-16 | 2008-01-03 | Lai John T | S-S'-bis-(Alpha, Alpha'-Disubstituted-Alpha"-Acetic Acid) - Trithiocarbonates and Derivatives as Initiator - Chain Transfer Agent - Terminator for Controlled Radical Polymerizations and the Process for Making the Same |
| CN103113502A (en) * | 2013-02-20 | 2013-05-22 | 中国科学院新疆理化技术研究所 | Preparation method of wear resistance viscosity index improver |
| CN106221862A (en) * | 2016-08-18 | 2016-12-14 | 江西福安路润滑材料有限公司 | Molybdenum modifiers dispersants, its preparation method and application |
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