CN107312597B

CN107312597B - Triple composite film wear-resistant energy-saving engine oil

Info

Publication number: CN107312597B
Application number: CN201710530968.9A
Authority: CN
Inventors: 赫常山
Original assignee: Beijing Yashike Laien Petroleum Chemical Co ltd
Current assignee: Beijing Yashike Laien Petroleum Chemical Co ltd
Priority date: 2017-06-30
Filing date: 2017-06-30
Publication date: 2021-12-03
Anticipated expiration: 2037-06-30
Also published as: CN107312597A

Abstract

The invention relates to a triple composite membrane anti-wear energy-saving engine oil, in particular to a triple composite membrane anti-wear energy-saving engine diesel oil and/or gasoline engine oil, wherein the engine oil is prepared by taking base oil, a complexing agent, a tackifier and an additive as raw materials, the base oil is a mixture at least comprising polyester base oil, the additive at least comprises organic molybdenum and polytetrafluoroethylene additives, and under different working conditions of an engine, the polyester base oil, the organic molybdenum and the polytetrafluoroethylene respectively form a polar adsorption membrane, a chemical reaction membrane and a physical deposition membrane on the surface of an engine friction pair and provide lubrication anti-wear protection for the engine through the synergistic effect of the triple composite membrane. The triple composite membrane anti-wear energy-saving engine oil provided by the invention has good anti-wear and anti-friction properties, can effectively prolong the oil change period, improves the fuel economy, and meets the requirements of modern engine technology on engine oil.

Description

Triple composite film wear-resistant energy-saving engine oil

Technical Field

The invention relates to the field of lubricating oil, in particular to triple composite membrane anti-wear energy-saving engine oil.

Background

In the automotive industry, tribological behavior is the main cause of mechanical failure and energy consumption of automobiles. According to the typical automobile energy distribution measured by the united states environmental protection agency, 62% of the fuel energy is consumed due to inevitable heat dissipation, and the friction loss of various parts consumed in the automobile accounts for 10.5% of the remaining 38% of the available mechanical energy. The fact proves that: reducing the energy loss due to friction of engine components is an important factor in achieving reduced fuel consumption in automobiles. Improvements in engine design and improvements in engine oil formulation technology both directly improve the fuel economy of automobiles, but the cost of improving fuel economy by improving engine oil formulations is much lower than the cost of developing new engines.

With the development of engine technology and the increasing perfection of environmental regulations, the requirements for engine oil are becoming more stringent. Improvements in engine design and emission control technology have placed greater demands on engine oil quality, namely, engine oil energy conservation, environmental protection, and extended oil change periods. This is not only a test for the quality of base oil as a main component of engine oil, but also a limitation on the contents of sulfur and phosphorus in engine oil, and most importantly, requires engine oil having better high-temperature oxygen resistance and antiwear and antifriction properties.

The current more commonly used high-efficiency wear-resistant antifriction agent is organic molybdenum containing sulfur and phosphorus. The organic molybdenum additive serving as a friction modifier can effectively reduce the friction resistance of an engine so as to improve the fuel economy of a vehicle, but the high-level molybdenum in the anti-wear and anti-friction agent can cause the corrosion and the abrasion of the engine and shorten the service life of the engine; at the same time, when the molybdenum content is too high, the oxidation of the oil product is accelerated. On the other hand, if active elements such as sulfur and phosphorus are not added into the organic molybdenum, the wear resistance of the organic molybdenum is low; however, high levels of sulfur, phosphorus and ash in engine oils can negatively impact exhaust emission treatment devices.

Chinese patent (publication No. CN103497815A) discloses an antifriction energy-saving engine lubricating oil. The lubricating oil is composed of the following components in percentage by weight: 50-60% of hydroisomerization dewaxing III base oil, 25-30% of poly alpha olefin PAO, and 10-25% of a lubricating oil additive. The lubricating oil additive component comprises: 1 to 2 percent of antiwear agent; 2-3% of a detergent dispersant; 1.5-2% of antioxidant and corrosion inhibitor; 0.3-0.7% of pour point depressant; 6-15% of a viscosity index improver; 0.01 percent of defoaming agent. The antiwear agent of the lubricating oil is compounded by molybdenum-dithiocarbamate and molybdenum-dithiophosphate, so that the lubricating oil has very obvious antifriction and antiwear effects, engine silencing effects and oil saving effects, and the lubricating oil can better protect an engine system, prolong the service life and save fuel under the full load condition and harsh road condition of a large heavy-duty vehicle. However, the lubricating oil provided by the patent has at least the following defects: the lubricating oil improves the anti-wear and anti-friction effects of the lubricating oil only through the organic molybdenum anti-wear agent, so that the use amount of organic molybdenum is too high, the cleanliness of oil products is not high, the requirements of modern environmental protection on the lubricating oil are not met, and meanwhile, the high-level molybdenum causes the corrosion and wear of an engine and shortens the service life of the engine; on the other hand, the lubricating oil realizes the anti-wear and anti-friction effects of the lubricating oil only through the organic molybdenum anti-wear agent, the anti-wear agent has limited action, so that the service cycle of the lubricating oil is short, the fuel economy of an oil product is low, the oil needs to be frequently replaced with new oil, and the requirements of modern engine technology on the lubricating oil are not met.

On the other hand, polytetrafluoroethylene has been regarded as a friction modifier for lubricating oils in recent years because of its excellent chemical stability, high and low temperature resistance, corrosion resistance, and particularly excellent tribological properties; however, polytetrafluoroethylene has a strong self-adsorption capacity, is easy to agglomerate, and has the defects of poor dispersion stability and easy precipitation in a lubricating oil system, thereby limiting the application of polytetrafluoroethylene. Therefore, a novel anti-wear and anti-friction agent is urgently needed, and the anti-wear and anti-friction effects of the lubricating oil are realized through the synergistic effect of various formula components, so that the lubricating oil can still maintain excellent anti-wear and anti-friction performance and long oil change period while the content of organic molybdenum is reduced.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a triple composite membrane engine oil, in particular to a triple composite membrane anti-wear energy-saving engine oil, wherein under different working conditions of an engine, a polyester base oil in the engine oil forms a polar adsorption film on a metal friction surface through a polar ester group contained in the polyester base oil, organic molybdenum forms a chemical reaction film through a chemical reaction on the metal friction surface, polytetrafluoroethylene forms a physical deposition film through adsorption, deposition, melting and solidification on the metal friction surface, so that the engine oil provides lubrication anti-wear protection for the engine through the synergistic effect of the polar adsorption film, the chemical reaction film and the physical deposition film. The different working conditions refer to cold start, low-speed running, high-speed running, braking and stopping of the engine.

The polytetrafluoroethylene used in the invention is submicron polytetrafluoroethylene, and the granularity is 0.05-0.5 μm. The submicron polytetrafluoroethylene can be adsorbed and deposited on the surface of the friction pair to form a layer of physical protective film at low temperature and low load, so that the metal surface is effectively protected. With the temperature rise and the load increase, the polytetrafluoroethylene particles are melted and solidified at the local high temperature of the convex peak contact to form a physical film of a polymolecular layer, so that the friction surface is protected. Meanwhile, the organic molybdenum and the surface of the friction pair can generate chemical reaction to form a layer of chemical protective film, so that the abrasion of the metal surface is further reduced. The molecular structure of the polyester base oil contains polar ester groups, and a thick and firm polar adsorption film can be always kept on the metal surface due to the special polar structure and the high-temperature oxidation resistance. Therefore, the oil product is ensured to always keep excellent wear resistance and friction reduction in the whole process from starting to normal running and stopping of the engine in a low-temperature environment through the synergistic effect of the submicron polytetrafluoroethylene, the organic molybdenum and the polyester base oil, so that the engine is comprehensively protected.

According to a preferred embodiment, the engine oil is prepared from 82.7-87.2 wt% of base oil, 7.5-9.5 wt% of complexing agent, 4.6-8.3 wt% of tackifier and 0.7 wt% of additive, wherein the sum of the wt% of the base oil, the complexing agent, the tackifier and the additive is 100%. Preferably, the base oil is 82.7-84.8% of diesel engine oil or 85.1-87.2% of gasoline engine oil.

According to a preferred embodiment, the 0.7% additive comprises 0.1-0.5% pour point depressant, 0.1% organic molybdenum and 0.1-0.5% polytetrafluoroethylene by weight percentage. The triple composite film wear-resistant energy-saving engine oil disclosed by the invention is low in organic molybdenum content, can effectively reduce the content of sulfur and phosphorus in oil products, improves the cleanness of the oil products, and meets the requirements of modern environmental protection on the engine oil.

According to a preferred embodiment, the polytetrafluoroethylene is submicron polytetrafluoroethylene and the particle size of the submicron polytetrafluoroethylene is submicron ultrafine powder of 0.05 to 0.5 μm. The submicron ultrafine powder polytetrafluoroethylene used in the invention has high dispersibility. In the using process, the polytetrafluoroethylene of the submicron ultrafine powder has small molecular particle size and weak binding force, can be stably dispersed in lubricating oil, and improves the dispersion stability of the polytetrafluoroethylene in a lubricating oil system, thereby improving the service performance of the polytetrafluoroethylene.

According to a preferred embodiment, the organo-molybdenum is one or more of sulphur phosphorus molybdenum, phosphorus free molybdenum and sulphur and phosphorus free molybdenum. Preferably, the organic molybdenum is one or more of molybdenum dialkyl dithiophosphate, molybdenum dialkyl dithiocarbamate, molybdenum disulfide, molybdenum amine complex, molybdenum naphthenate and molybdenum alkyl salicylate. The organic molybdenum is added into the triple composite film anti-wear energy-saving engine oil, so that the engine oil can achieve the functions of friction reduction, wear resistance and lubrication.

According to a preferred embodiment, the pour point depressant is polymethacrylate. Preferably, the molecular weight of the polymethacrylate is 10000-200000. The polymethacrylate is prepared from hexadecyl methacrylate, styrene and maleic anhydride according to the proportion of 2-10: 1-5. The polymethacrylate has the advantages of high purity, good pour point depressing effect and wide selection range of base oil. The pour point depressant is added into the triple composite film wear-resistant energy-saving engine oil, so that the low-temperature fluidity of the engine oil can be well improved.

According to a preferred embodiment, the base oil is a mixture of a group ii base oil and/or a group iii base oil with a polyester base oil, the weight percentage of the polyester base oil in the total amount of the base oil not exceeding 25%. Preferably, the group II base oil and the group III base oil used in the present invention are bright stock 150BS, and hydroisomerization 500N. The polyester base oil is one or a mixture of more than two of diisooctyl sebacate, diisooctyl adipate, trimethylolpropane fatty acid ester and pentaerythritol fatty acid ester.

According to a preferred embodiment, the complexing agent is a diesel oil complexing agent or a gasoline oil complexing agent. Preferably, the diesel engine oil complexing agent is prepared from base oil, an oxidation and corrosion inhibitor, a detergent, a dispersant and a metal deactivator. The gasoline and engine oil complexing agent is prepared from a detergent, a dispersant, an oxidation and corrosion inhibitor, an oxygen promoter and an antifoaming agent as raw materials.

According to a preferred embodiment, the tackifier is an ethylene-propylene copolymer or a hydrogenated styrene isoprene copolymer. Preferably, the tackifier may also be one or two of polyester, polyisobutylene and polyethylene wax.

According to a preferred embodiment, the engine oil is prepared by: and adding one half of the base oil into a blending kettle, heating to 80-90 ℃, adding the tackifier and the pour point depressant, and circularly stirring for 0.5-1.5 hours. And adding the residual base oil into the blending kettle, keeping the temperature in the blending kettle at 60 ℃, adding the complexing agent, and continuously and circularly stirring for 0.2-1 h. Adding polytetrafluoroethylene and organic molybdenum into a blending kettle, continuously and circularly stirring for 2-3 h, and cooling to obtain the product. Preferably, the tackifier and the pour point depressant are added and then stirred circularly for 1 hour. Continuously circularly stirring for 0.5h after the complexing agent is added. The preparation method of the triple composite membrane anti-wear energy-saving engine oil provided by the invention has the advantages of simple process and strong operability, and is suitable for large-scale batch production.

According to a preferred embodiment, the triple-composite-membrane anti-wear energy-saving engine oil is prepared by compounding 68.7% of II-type and/or III-type base oil, 15% of polyester base oil, 9.5% of diesel oil complexing agent D3384, 6.1% of tackifier, 0.3% of pour point depressant, 0.1% of organic molybdenum and 0.3% of polytetrafluoroethylene; or the triple composite membrane anti-wear energy-saving engine oil is prepared by compounding 71.2 percent of II and/or III base oil, 15 percent of polyester base oil, 7.5 percent of gasoline oil complexing agent H9325G, 5.6 percent of tackifier, 0.3 percent of pour point depressant, 0.1 percent of organic molybdenum and 0.3 percent of polytetrafluoroethylene. The II-type base oil and/or the III-type base oil are (is) 500N and/or 150BS (bright stock) in hydroisomerization with the viscosity index of 90-100, the content of saturated hydrocarbon more than 98% and the content of sulfur less than 0.03%. The polyester base oil has a kinematic viscosity of 8-20 mm at 40 DEG C²(ii) diisooctyl sebacate and diisooctyl adipate with an acid value of less than 0.1mgKOH/g, or the kinematic viscosity at 40 ℃ is 15-68 mm²(ii)/s, acid value of less than 0.1mgKOH/g trimethylolpropane fatty acid ester and pentaerythritol fatty acid ester. The tackifier is polymethacrylate VISCOPLEX8-450, low molecular polyisobutylene PB1300 or PB2400 and/or ethylene propylene copolymer T612 or T614. The pour point depressant is polymethacrylate with the molecular weight of 10000-200000. The organic molybdenum is one or more of molybdenum dialkyl dithiophosphate, molybdenum dialkyl dithiocarbamate, molybdenum disulfide, molybdenum amine complex, molybdenum naphthenate and molybdenum alkyl salicylate. The polytetrafluoroethylene is submicron polytetrafluoroethylene with the granularity of 0.05-0.5 mu m. The triple composite film anti-wear energy-saving engine oil of diesel oil and/or gasoline adopts proper proportionUnder different working conditions, the polar adsorption film, the chemical reaction film and the physical deposition film cooperate to provide lubrication and wear resistance protection for the engine, so that the noise of the engine can be reduced, fuel oil can be saved, and the oil change period can be greatly prolonged; meanwhile, the content of a tackifier in the engine oil can be effectively reduced, and the cleanliness of the oil product of the triple composite film wear-resistant energy-saving engine oil is improved, so that the triple composite film wear-resistant energy-saving engine oil meets the requirements of modern environmental protection on the engine oil.

The triple composite film wear-resistant energy-saving engine oil provided by the invention has at least the following advantages:

(1) the triple composite membrane anti-wear energy-saving engine oil provided by the invention has good anti-wear and anti-friction properties, can effectively prolong the oil change period, improves the fuel economy, and meets the requirements of modern engine technology on engine oil.

(2) The triple composite membrane anti-wear energy-saving engine oil provided by the invention improves the anti-wear antifriction property and extreme pressure property of the engine oil while reducing the content of organic molybdenum, can effectively reduce the content of sulfur and phosphorus in the oil product, improves the cleanness of the oil product, and meets the requirements of modern environmental protection on the engine oil.

(3) The addition of submicronic polytetrafluoroethylene in the engine oil can improve the wear resistance and friction reduction of the engine oil, and due to the stable physical and chemical properties of the polytetrafluoroethylene, the engine oil can still maintain excellent wear resistance and friction reduction performance even if used under severe conditions, thereby effectively saving fuel and prolonging the service cycle of oil products.

Detailed Description

The following examples are given for illustrative purposes.

Aiming at the defects of the prior art, the invention provides triple composite membrane anti-wear energy-saving engine oil which is prepared by taking base oil, a complexing agent, a tackifier and an additive as raw materials. The base oil is a mixture containing at least a polyester base oil. The additive at least comprises organic molybdenum and polytetrafluoroethylene additive. Under different working conditions of the engine, the polyester base oil, the organic molybdenum and the polytetrafluoroethylene respectively form a polar adsorption film, a chemical reaction film and a physical deposition film on the surface of a friction pair of the engine, and the engine is lubricated and protected against wear through the synergistic effect of the triple composite films. Under different working conditions, the polar adsorption film, the chemical reaction film and the physical deposition film are formed and provide lubrication and wear resistance protection for the engine through the triple composite film.

The judgment standards of different working conditions are the normal rotating speed of the engine or the economic speed per hour and the operation condition, and different vehicle types are different. More than low speed per hour or stop and start can be regarded as low speed working condition, and more than high speed per hour, violent driving and highway driving can be regarded as high speed working condition. When the automobile runs, the automobile mainly meets the working conditions of cold start, low-speed running, high-speed running, deceleration braking and the like. The temperature of the engine is different under different working conditions, such as cold start and low-speed running, the temperature of the engine is lower, organic molybdenum in the engine oil can not effectively play a role at the temperature, and the polar adsorption film formed by polyester base oil and the physical deposition film formed by polytetrafluoroethylene which play roles in resisting wear and reducing friction can form an adsorption film at the lower temperature, so that the engine is protected. When the automobile normally runs, the temperature of the engine is in a normal state, namely the temperature is moderate, the organic molybdenum can form a chemical reaction film on the metal surface at a certain temperature, and at the moment, the polar adsorption film formed by the polyester base oil, the physical deposition film formed by the polytetrafluoroethylene and the chemical reaction film formed by the organic molybdenum act together in a synergistic manner to protect the engine from abrasion. When the automobile runs at high speed, the temperature of the engine is high, and the polar adsorption film formed by the polyester base oil, the physical deposition film formed by the polytetrafluoroethylene and the chemical reaction film formed by the organic molybdenum play a role in resisting wear and reducing wear, particularly the advantages of the chemical reaction film formed by the organic molybdenum and the physical deposition film formed by the polytetrafluoroethylene under the severe high-temperature condition are more obvious compared with the polar adsorption film formed by the polyester base oil under the high-temperature condition.

The polytetrafluoroethylene has excellent chemical stability and tribological performance, the molecular structure of the polytetrafluoroethylene is in symmetrical arrangement, the whole molecule is in weak polarity, the acting force between adjacent molecular chains is Van der Waals force, the mutual attraction is small, the mechanical shearing strength is weak, and a uniform and continuous transfer film is easy to form on a contact surface. The film forming reason is mainly that the molecules have no branched chain, and the molecules are only bonded by Van der Waals force and are easy to transfer along the sliding direction; the other is the tendency of complexing with metal, and metal fluoride and metal complex are formed on the surface of the friction metal.

The polytetrafluoroethylene used in the invention is submicron polytetrafluoroethylene, has high crystallinity and high dispersibility, can be uniformly blended with other materials, and can greatly improve the dispersibility of the polytetrafluoroethylene, thereby improving the service performance of the polytetrafluoroethylene. When submicron polytetrafluoroethylene particles dispersed in engine oil flow into the friction surface along with the engine oil, the submicron polytetrafluoroethylene particles are soaked, adsorbed and deposited on superfine gaps and rough machining points on the friction surface, and a polishing effect is achieved on the friction surface; meanwhile, submicron polytetrafluoroethylene particles form an adhered particle layer at a peak part of the friction surface, when a peak contact slides, the contact is plastically deformed to generate local instantaneous temperature of hundreds of degrees, and the adhered polytetrafluoroethylene particle layer is in a molten state and is solidified at the peak contact to form a multi-molecular-layer covering film. Because the polytetrafluoroethylene molecular structures are symmetrically arranged, the whole molecules are weak in polarity, acting force between adjacent molecular chains is Van der Waals force, the mutual attraction force is small, the mechanical shear strength is weak, and the friction coefficient is extremely small, so that physical films formed by adsorbing, depositing, melting and solidifying polytetrafluoroethylene on the metal surface are spaced between the friction surfaces, the friction between the sliding surfaces and the frequency of direct contact between the sliding surfaces are reduced, the excellent wear resistance and friction reduction are shown, the oil temperature of engine oil is reduced, the wear of an engine is reduced, and the wear resistance and the load capacity of the engine are improved. The polytetrafluoroethylene reduces friction by virtue of a physical film formed on the surface of the metal, does not need reaction, and has good lubricating effect even at low temperature.

The organic molybdenum compound used in the invention can perform chemical reaction on the surface of the friction pair under certain temperature and load conditions to form a chemical reaction film, thereby showing excellent anti-wear and anti-friction effects. The non-active organic molybdenum has good wear resistance and friction reduction under medium and low loads, and the active organic molybdenum has excellent wear resistance and extreme pressure resistance under high loads. The organic molybdenum and the submicron polytetrafluoroethylene coexist in the same engine oil system to generate a synergistic complementary effect, and the physical film and the chemical reaction film perform combined action, so that the high temperature resistance, the wear resistance and the friction reduction of the oil product can be greatly improved, the oil temperature of the oil product is kept relatively low in the using process, and the service cycle of the oil product is effectively prolonged. On the other hand, the synergistic effect of the organic molybdenum and the submicron polytetrafluoroethylene improves the anti-wear and friction-reducing effects of the compound in oil products, and simultaneously reduces the molybdenum content in the oil products, so that the oil products still have good wear resistance and friction reduction and extreme pressure properties under the condition of low sulfur and phosphorus content or even no sulfur and phosphorus, the oil change period is effectively prolonged, and the fuel economy is improved.

The high-viscosity polyester used in the invention is a novel lubricating material, and the molecular structure of the high-viscosity polyester contains polar ester groups, so that the solubility of the additive can be improved, the effect of the additive is fully exerted, the high-viscosity polyester also has strong adsorption capacity, and the high-viscosity polyester can be adsorbed on the surface of metal friction to form a thick and firm polar adsorption film as a base oil component of engine oil. The polar adsorption film can still provide enough oil film protection under the condition of high-temperature and high-speed running of an engine.

The triple composite membrane wear-resistant energy-saving engine oil disclosed by the invention ensures that the excellent wear-resistant and friction-reducing properties of an oil product are always kept in the whole process from starting to normal running and stopping of an engine in a low-temperature environment through the synergistic action of a physical membrane, a chemical reaction membrane and a polar adsorption membrane formed by the submicron polytetrafluoroethylene, the organic molybdenum and the polyester base oil, so that the engine is comprehensively protected.

According to a preferred embodiment, the 0.7% additive comprises 0.1-0.5% pour point depressant, 0.1% organic molybdenum and 0.1-0.5% polytetrafluoroethylene by weight. The triple composite film wear-resistant energy-saving engine oil disclosed by the invention is low in organic molybdenum content, can effectively reduce the content of sulfur and phosphorus in oil products, improves the cleanness of the oil products, and meets the requirements of modern environmental protection on the engine oil.

According to a preferred embodiment, the polytetrafluoroethylene is submicron polytetrafluoroethylene micropowder. The particle size of the submicron polytetrafluoroethylene ultrafine powder is 0.05-0.5 mu m. The submicron polytetrafluoroethylene has high crystallinity and high dispersibility, can be uniformly blended with other materials, and can greatly improve the dispersibility of the polytetrafluoroethylene, thereby improving the service performance of the submicron polytetrafluoroethylene. The submicronic polytetrafluoroethylene can effectively solve the defects of poor dispersion stability and easy precipitation of polytetrafluoroethylene in an engine oil system in the prior art.

According to a preferred embodiment, the organo-molybdenum is one or more of sulphur phosphorus molybdenum, phosphorus free molybdenum and sulphur and phosphorus free molybdenum. Preferably, the organo-molybdenum is one or more of molybdenum dialkyldithiophosphate, molybdenum dialkyldithiocarbamate, molybdenum disulfide, molybdenum amine complex, molybdenum naphthenate, and molybdenum alkylsalicylate. The organic molybdenum is added into the triple composite film anti-wear energy-saving engine oil, so that the engine oil can achieve the functions of friction reduction, wear resistance and lubrication. The lubricating and friction reducing mechanism of organic molybdenum is mainly related to the polished surface of friction pair, and on the surface of friction pair, at every point of high load pressure, the tip can produce chemical reaction to promote organic molybdenum to decompose and decompose MOS₂And certain phosphides, sulfides, nitrides and the like, dispersed in an oil solvent, adsorbed and deposited on friction surfaces, MOS₂The formed film is covered on the anti-wear layer, thereby achieving the functions of friction reduction, wear resistance and lubrication.

According to a preferred embodiment, the polymethacrylate pour point depressant is prepared as follows: (1) synthesis of the Polymer: adding cetyl methacrylate, styrene and maleic anhydride into a three-neck flask with a magnet according to the proportion of 2-10: 1-5. Toluene is used as solvent, initiator benzoyl peroxide is added, and the temperature is raised to completely dissolve reactants. Starting stirring, maintaining the internal temperature of the three-neck flask to be 65-90 ℃, and reacting for 4-8 h. (2) And (3) removing toluene by reduced pressure distillation: and connecting a circulating water type vacuum multi-purpose pump to a closed distillation device, starting the vacuum pump, and carrying out reduced pressure distillation to remove the toluene. The water bath is started, the temperature is about 45 ℃, toluene begins to be evaporated, and the temperature is gradually increased to about 70 ℃ along with the slow evaporation speed of the toluene until the toluene is almost completely removed. And cooling the decompressed product at room temperature to obtain viscous light yellow liquid, namely the polymethacrylate pour point depressant.

According to a preferred embodiment, the base oil is a group ii base oil and/or a mixture of a group iii base oil and a polyester base oil. The weight percentage of the polyester base oil in the total amount of the base oil is not more than 25%. Preferably, the group II base oil and the group III base oil used in the present invention are bright stock 150BS, and hydroisomerization 500N. The polyester base oil is one or more of diisooctyl sebacate, diisooctyl adipate, trimethylolpropane fatty acid ester and pentaerythritol fatty acid ester. Preferably, the adopted hydroisomerization 500N and bright stock 150BS have the viscosity index of 90-100, the content of saturated hydrocarbon is more than 98 percent, and the content of sulfur is less than 0.03 percent. The adopted diisooctyl sebacate and diisooctyl adipate have the kinematic viscosity of 8-20 mm2/s at 40 ℃ and the acid value of less than 0.1mgKOH/g, and the trimethylolpropane fatty acid ester and pentaerythritol fatty acid ester have the kinematic viscosity of 15-68 mm2/s at 40 ℃ and the acid value of less than 0.1 mgKOH/g.

The invention preferentially adopts II and III base oil as main base oil, namely bright stock 150BS and hydroisomerization 500N, and has the function of providing enough oil film on the friction surface to play a role of lubrication. The polyester base oil is adopted as polar base oil, and the polar adsorption effect of the polyester base oil is utilized to reduce the friction coefficient of a friction surface and improve the dissolving capacity of the additive in the base oil. The base oil selected by the invention is hydroisomerized mineral oil and polyester synthetic oil, the antioxidant stability of the base oil is good, the evaporation loss is low, and the oil change period of the engine oil can be prolonged.

According to a preferred embodiment, the complexing agent is a diesel oil complexing agent or a gasoline oil complexing agent. Preferably, the diesel engine oil complexing agent is prepared from base oil, an oxidation and corrosion inhibitor, a detergent, a dispersant and a metal deactivator. The gasoline and engine oil complexing agent is prepared from a detergent, a dispersant, an oxidation and corrosion inhibitor, an oxygen promoter and an antifoaming agent as raw materials. The diesel engine oil complexing agent has excellent high-temperature performance and good cleaning dispersibility at high temperature; the diesel engine oil complexing agent also has excellent extreme pressure wear resistance and effectively reduces the friction on the metal surface. The gasoline engine oil complexing agent has excellent high-temperature and low-temperature detergency and dispersibility, oxidation resistance, corrosion resistance, rust resistance and other performances. The invention can keep the engine oil with excellent high temperature performance, cleaning and dispersing performance and extreme pressure wear resistance by adding the diesel oil complexing agent or the gasoline oil complexing agent into the triple composite film wear-resistant energy-saving engine oil.

According to a preferred embodiment, the diesel oil complexing agent is D3384 in combination with a wetting agent. The Runzi D3384 is a high-performance heavy-load diesel engine oil complexing agent. Can be prepared into various viscosities in various base oils, can meet the API oil products with various performance grades, and can meet the requirements of various OEM oil specifications. The performance indexes of the RunYing combination D3384 are as follows: density (15 ℃): 974kg/m 3. Flash point: 180 ℃ is carried out. Kinematic viscosity (100 ℃): 164 cSt. Calcium content: 1.07 wt%. The content of magnesium: 1.01 wt%. Nitrogen content: 0.72 wt%. Phosphorus content: 1.21 wt%. Zinc content: 1.41 wt%. Total base number: 93.5mg KOH/g. Appearance: brown viscous liquid.

According to a preferred embodiment, the gasoline engine oil complexing agent is jaffon H9325G. The performance indexes of Yafuton H9325G are: density (15 ℃): 0.998kg/m 3. Flash point: 160 ℃. Kinematic viscosity (100 ℃): 125 cSt. Calcium content: 3.41 wt%. Nitrogen content: 0.98 wt%. Phosphorus content: 1.47 wt%. Zinc content: 1.62 wt%. Total base number: 112mg KOH/g. Appearance: brown viscous liquid.

According to a preferred embodiment, the tackifier is an ethylene-propylene copolymer or a hydrogenated styrene isoprene copolymer. Preferably, the tackifier may also be one or both of polyester, polyisobutylene and polyethylene wax. Preferably, the polyester is polymethacrylate VISCOPLEX 8-450. The polyisobutylene adopts low molecular polyisobutylene PB1300 or PB 2400. The ethylene-propylene copolymer adopts an ethylene-propylene copolymer T612 or T614. The function of adding the tackifier into the engine oil is as follows: firstly, the viscosity of the base oil in the triple composite film wear-resistant energy-saving engine oil is improved; the adhesive capacity of the triple composite film wear-resistant energy-saving engine oil on the metal surface is improved; and thirdly, the low temperature of the triple composite film wear-resistant energy-saving engine oil is improved.

According to a preferred embodiment, the engine oil is prepared by: and adding one half of the base oil into a blending kettle, heating to 80-90 ℃, adding the tackifier and the pour point depressant, and circularly stirring for 0.5-1.5 hours. And adding the residual base oil into the blending kettle, keeping the temperature in the blending kettle at 60 ℃, adding the complexing agent, and continuously and circularly stirring for 0.2-1 h. Adding polytetrafluoroethylene and organic molybdenum into a blending kettle, continuously and circularly stirring for 2-3 h, and cooling to obtain the product. The preparation method of the triple composite membrane anti-wear energy-saving engine oil provided by the invention has the advantages of simple process and strong operability, and is suitable for batch production.

Comparative example 1

81.5% of the group II base oil and/or group III base oil was added in two portions to a blending kettle. Firstly, adding half of base oil into a blending kettle, heating to 80-90 ℃, adding 8.3% of ethylene-propylene copolymer type tackifier and 0.6% of polymethacrylate, and stirring for 1 hour. Adding the rest base oil, keeping the temperature in the blending kettle at 60 ℃, adding 9.5% of D3384 diesel engine oil complexing agent, continuously stirring for 30min, adding 0.1% of organic molybdenum, continuously circularly stirring for 2-3 h, and cooling to obtain the finished product.

Example 1

A mixture of 72.7% of a group II base oil and/or a group III base oil and 10% of a polyester base oil was added in two portions to a blending kettle. Firstly, adding half of base oil into a blending kettle, heating to 80-90 ℃, adding 7.1% of ethylene-propylene copolymer type tackifier and 0.5% of polymethacrylate, and stirring for 1 hour. Adding the rest base oil, keeping the temperature in the blending kettle at 60 ℃, adding 9.5% of D3384 diesel engine oil complexing agent, continuously stirring for 30min, adding 0.1% of polytetrafluoroethylene powder and 0.1% of organic molybdenum, continuously and circularly stirring for 2-3 h, and cooling to obtain the finished product.

Example 2

A mixture of 68.7% of a group II base oil and/or a group III base oil and 15% of a polyester base oil was added in two portions to a blending kettle. Firstly, adding half of base oil into a blending kettle, heating to 80-90 ℃, adding 6.1% of ethylene-propylene copolymer type tackifier and 0.3% of polymethacrylate, and stirring for 1 hour. Adding the rest base oil, keeping the temperature in the blending kettle at 60 ℃, adding 9.5% of D3384 diesel engine oil complexing agent, continuously stirring for 30min, adding 0.3% of polytetrafluoroethylene powder and 0.1% of organic molybdenum, continuously and circularly stirring for 2-3 h, and cooling to obtain the finished product.

Example 3

A mixture of 64.8% of a group II base oil and/or a group III base oil and 20% of a polyester base oil was added in two portions to a blending kettle. Firstly, adding half of base oil into a blending kettle, heating to 80-90 ℃, adding 5% of ethylene-propylene copolymer type tackifier and 0.1% of polymethacrylate, and stirring for 1 hour. Adding the rest base oil, keeping the temperature in the blending kettle at 60 ℃, adding 9.5% of D3384 diesel engine oil complexing agent, continuously stirring for 30min, adding 0.5% of polytetrafluoroethylene powder and 0.1% of organic molybdenum, continuously and circularly stirring for 2-3 h, and cooling to obtain the finished product.

Comparative example 2

83.8% of group II base oil and/or group III base oil was added in two portions to a blending kettle. Firstly, adding half of base oil into a blending kettle, heating to 80-90 ℃, adding 8% of hydrogenated styrene-isoprene copolymer type tackifier and 0.6% of polymethacrylate, and stirring for 1 hour. Adding the rest base oil, keeping the temperature in the mixing kettle at 60 ℃, adding 7.5% of H9325G gasoline oil complexing agent, continuously stirring for 30min, adding 0.1% of organic molybdenum, continuously circularly stirring for 2-3H, and cooling to obtain the finished product.

Example 4

A mixture of 75.1% of a group II base oil and/or a group III base oil and 10% of a polyester base oil was added in two portions to a blending kettle. Firstly, adding half of base oil into a blending kettle, heating to 80-90 ℃, adding 6.7% of hydrogenated styrene-isoprene copolymer type tackifier and 0.5% of polymethacrylate, and stirring for 1 h. Adding the rest base oil, keeping the temperature in the blending kettle at 60 ℃, adding 7.5% of H9325 gasoline oil complexing agent, continuously stirring for 30min, adding 0.1% of polytetrafluoroethylene powder and 0.1% of organic molybdenum, continuously and circularly stirring for 2-3H, and cooling to obtain the finished product.

Example 5

A mixture of 71.2% of a group II base oil and/or a group III base oil and 15% of a polyester base oil was added in two portions to a blending kettle. Firstly, adding half of base oil into a blending kettle, heating to 80-90 ℃, adding 5.6% of hydrogenated styrene-isoprene copolymer type tackifier and 0.3% of polymethacrylate, and stirring for 1 h. Adding the rest base oil, keeping the temperature in the blending kettle at 60 ℃, adding 7.5% of H9325 gasoline oil complexing agent, continuously stirring for 30min, adding 0.3% of polytetrafluoroethylene powder and 0.1% of organic molybdenum, continuously and circularly stirring for 2-3H, and cooling to obtain the finished product.

Example 6

A mixture of 67.2% of a group II base oil and/or a group III base oil and 20% of a polyester base oil was added in two portions to a blending kettle. Firstly, adding half of base oil into a blending kettle, heating to 80-90 ℃, adding 4.6% of hydrogenated styrene-isoprene copolymer type tackifier and 0.1% of polymethacrylate, and stirring for 1 h. Adding the rest base oil, keeping the temperature in the blending kettle at 60 ℃, adding 7.5% of H9325 gasoline oil complexing agent, continuously stirring for 30min, adding 0.5% of polytetrafluoroethylene powder and 0.1% of organic molybdenum, continuously and circularly stirring for 2-3H, and cooling to obtain the finished product.

Tables 1 and 2 show the amounts of the raw materials used in comparative example 1 and examples 1 to 3 and comparative example 2 and examples 4 to 6, respectively.

TABLE 1 raw material consumption table for comparative example 1 and examples 1-3

TABLE 2 raw material consumption table for comparative example 2 and examples 4-6

The oil products of the examples and the comparative examples are compared by an anti-wear and anti-friction test.

Test equipment: a four-ball friction tester MS-10A type produced by Xiamen sky machine automation company Limited uses steel balls with the diameter of 12.7mm, II-grade bearing steel balls conforming to GB/T308-2002 standard, the material is GCrl5, and the hardness HRC is 64-66.

The test method comprises the following steps: SH/T0189-92 METHOD FOR MEASURING ABRASION RESISTANCE OF LUBRICANT (FOUR BALL METHOD).

The test conditions are as follows: the ball feeding revolution is 1500 r/min; the oil temperature is 40 ℃; the time is 60 min; the load was 392N.

The abrasion resistance and the antifriction performance of the oil product are evaluated by measuring the diameter of the abrasion spots, the friction coefficient and the friction resistance through the test.

After the test is finished, the electron microscope is used for measuring the wear-scar diameters of the bottom balls, the arithmetic mean value of the three bottom ball wear-scar diameters is used for representing the wear resistance, the smaller the wear-scar diameter is, the better the wear resistance is, the average friction coefficient is used for evaluating the friction reduction capability, and the smaller the friction coefficient is, the better the friction reduction performance is. The test results are shown in tables 3 and 4.

TABLE 3 table of results of the abrasion and friction reducing performance tests of comparative example 1 and examples 1 to 3

TABLE 4 table of results of the anti-wear and anti-friction performance test of comparative example 2 and examples 4 to 6

From the results of the anti-wear and anti-friction tests in tables 3 and 4, it can be seen that: the wear resistance and friction reduction performance of the examples 1 to 6 is obviously better than that of the comparative example. It can be known by combining table 1 and table 2 that in examples 1 to 3 and 4 to 6, the wear-resistant and friction-reducing performance of the triple composite film wear-resistant energy-saving engine oil of the present invention can be effectively improved by adding the polyester base oil, the organic molybdenum and the polytetrafluoroethylene, and meanwhile, the content of the organic molybdenum and the tackifier in the engine oil can be effectively reduced, and the cleanliness of the oil product of the triple composite film wear-resistant energy-saving engine oil of the present invention can be improved, so that the oil product meets the requirements of modern environmental protection on the engine oil. By comparison, examples 2 and 5 are optimal, i.e. the preferred polyester addition is 15%, polytetrafluoroethylene addition is 0.3%, and organomolybdenum addition is 0.1%.

The oil products of comparative example 1 and example 2 are used on the same long-distance truck, the noise of the engine is tested by a decibel meter at different driving mileage stages, the oil quality condition is tested by a GB/T7607-2010 method, and the oil consumption is recorded to test the oil saving condition. The test results are shown in table 5.

TABLE 5 oil Performance test results of comparative example 1 and example 2

From the test results of table 5, it can be seen that: when the oil of example 2 was used, the engine noise was significantly less than when the oil of comparative example 1 was used, and the oil consumption was also significantly less than when the oil of comparative example 1 was used. In the aspect of oil quality, according to the national standard of GB/T7607-2010 diesel engine oil change indexes, the viscosity change rate of used oil at 100 ℃ is +/-20%, and if the viscosity change rate exceeds the value, the oil should be changed. The oil of comparative example 1, which had a viscosity change of more than 20% after 18000Km running, was used and the oil was replaced with fresh oil, whereas the oil of example 2, which had a viscosity change of not more than 20% even after 20000Km running, was used continuously without replacing the fresh oil. Thus, the oil of example 2 reduced engine noise, saved fuel, and greatly extended the oil change cycle compared to the oil of comparative example 1.

The oil products of the comparative example 2 and the example 5 are used on the same popular taxi, the noise of the engine is tested by a decibel meter at different driving mileage stages, the oil quality condition is tested by a filter paper spot method, and the oil consumption is recorded to test the oil saving condition. The test results are shown in table 6.

TABLE 6 oil performance test results of comparative example 2 and example 5

From the test results of table 6, it can be seen that: the engine noise was significantly less when the oil of example 5 was used than when the oil of comparative example 2 was used, and the fuel consumption was also significantly less than when the oil of comparative example 2 was used. In terms of oil quality, the oil of comparative example 2 was unevenly black after 10000Km driving and required to be replaced with fresh oil, while the oil of example 5 was not black even after 12500Km driving and could be used without replacing fresh oil. Thus, the oil of example 5 reduced engine noise, saved fuel, and greatly extended the oil change cycle compared to the oil of comparative example 2.

In addition, drivers using the oils showed that the noise was significantly reduced, the speed increased, and the acceleration was powerful when using the oils of the examples as compared to the oils of the comparative examples. The test data and the actual use data show that the triple composite membrane anti-wear energy-saving engine oil provided by the invention has excellent anti-wear and anti-friction performance, can reduce the noise of the engine, saves fuel oil and can greatly prolong the oil change period.

It should be noted that the above-mentioned embodiments are exemplary, and that those skilled in the art, having benefit of the present disclosure, may devise various arrangements that are within the scope of the present disclosure and that fall within the scope of the invention. It is to be understood by persons skilled in the art that the present description is illustrative and not restrictive of the claims. The scope of the invention is defined by the claims and their equivalents.

Claims

1. A triple composite membrane antiwear energy-saving engine oil, especially a triple composite membrane antiwear energy-saving engine diesel oil and/or gasoline engine oil, characterized by that, under different working conditions of the engine, the polyester base oil in the engine oil forms a polar adsorption film on the metal friction surface through the polar ester group contained therein, organic molybdenum forms a chemical reaction film through the chemical reaction on the metal friction surface, and polytetrafluoroethylene forms a physical deposition film through the adsorption, deposition, melting and solidification on the metal friction surface, so that the engine oil provides lubrication antiwear protection for the engine through the synergistic effect of the polar adsorption film, the chemical reaction film and the physical deposition film;

the engine oil is prepared from 82.7-87.2 wt% of base oil, 7.5-9.5 wt% of complexing agent, 4.6-8.3 wt% of tackifier and 0.7 wt% of additive, wherein the base oil is 82.7-84.8 wt% of diesel engine oil or 85.1-87.2 wt% of gasoline engine oil,

the sum of the weight percentages of the base oil, the complexing agent, the tackifier and the additive is 100 percent;

the 0.7% additive comprises 0.1-0.5% pour point depressant, 0.1% organic molybdenum and 0.1-0.5% polytetrafluoroethylene by weight percentage, wherein the organic molybdenum is one or more of molybdenum dialkyl dithiophosphate, molybdenum dialkyl dithiocarbamate, molybdenum amine complex, molybdenum naphthenate and molybdenum alkyl salicylate;

the polytetrafluoroethylene is submicron polytetrafluoroethylene, and the particle size of the submicron polytetrafluoroethylene is 0.05-0.5 mu m;

the pour point depressant is polymethacrylate, the polymethacrylate is prepared from cetyl methacrylate, styrene and maleic anhydride according to the proportion of 2-10: 1-5, wherein,

the polymethacrylate pour point depressant is prepared as follows: (1) synthesis of the Polymer: adding cetyl methacrylate, styrene and maleic anhydride into a three-neck flask with a magnet according to the proportion of 2-10: 1-5, taking toluene as a solvent, adding an initiator benzoyl peroxide, heating to completely dissolve reactants, starting stirring, maintaining the internal temperature of the three-neck flask at 65-90 ℃, and reacting for 4-8 hours,

(2) and (3) removing toluene by reduced pressure distillation: connecting a circulating water type vacuum multi-purpose pump to a closed distillation device, starting a vacuum pump, carrying out reduced pressure distillation to remove toluene, starting a water bath, starting toluene evaporation at about 45 ℃, gradually raising the temperature to about 70 ℃ along with the slow speed of toluene evaporation until toluene is completely removed, and cooling a product after pressure reduction at room temperature to obtain viscous light yellow liquid, namely the polymethacrylate pour point depressant;

the tackifier is an ethylene-propylene copolymer or a hydrogenated styrene isoprene copolymer;

the base oil is a mixture of II-type base oil and/or III-type base oil and polyester base oil, and the weight percentage of the polyester base oil in the total amount of the base oil is not more than 25%;

the II-class base oil and the III-class base oil are bright stock 150BS and are subjected to hydroisomerization by 500N, and the polyester base oil is one or a mixture of more than two of diisooctyl sebacate, diisooctyl adipate, trimethylolpropane fatty acid ester and pentaerythritol fatty acid ester;

the engine oil is prepared by the following steps:

adding one half of the base oil into a blending kettle, heating to 80-90 ℃, adding the tackifier and the pour point depressant, circularly stirring for 0.5-1.5 h,

adding the residual base oil into the blending kettle, keeping the temperature in the blending kettle at 60 ℃, adding the complexing agent, continuously and circularly stirring for 0.2-1 h,

adding polytetrafluoroethylene and organic molybdenum into the blending kettle, continuously circularly stirring for 2-3 h, and cooling to obtain a product;

the composite agent is a diesel oil composite agent or a gasoline oil composite agent according to different prepared engine oils, wherein the addition amount of polyester is 15%, the addition amount of polytetrafluoroethylene is 0.3%, and the addition amount of organic molybdenum is 0.1%, and the composite agent is a diesel oil composite agent or a gasoline oil composite agent, wherein the brand number of the diesel oil composite agent is D3384, and the brand number of the gasoline oil composite agent is H9325G.