CN110862855B - Anti-foam methanol automobile engine lubricating oil - Google Patents
Anti-foam methanol automobile engine lubricating oil Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M147/00—Lubricating compositions characterised by the additive being a macromolecular compound containing halogen
- C10M147/04—Monomer containing carbon, hydrogen, halogen and oxygen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/04—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen
Abstract
The invention relates to an anti-foam methanol automobile engine lubricating oil, which is characterized in that perfluoro straight-chain hexanol and palladium nitrate are taken to prepare a colloidal solution a, and acrylic acid is added to generate perfluoro hexyl acrylate containing palladium ions; taking perfluoro straight-chain decanol, taking palladium nitrate, preparing a colloidal solution b, and adding acrylic acid to generate perfluoro decyl acrylate containing palladium ions; perfluorohexyl acrylate and perfluorodecyl acrylate are mixed and added with an initiator, and the product is subjected to synthetic reaction with methanol fuel engine lubricating oil produced according to the enterprise standard Q/LSY005-2018 of Liaoning Santa petrochemical company Limited, thereby forming the anti-foam methanol automobile engine lubricating oil. The invention can quickly convert formic acid and formaldehyde diffused to the auxiliary surface of the methanol fuel engine into carbon dioxide and water and quickly discharge the carbon dioxide and water out of a lubricating oil layer of the engine.
Description
Technical Field
The invention relates to the technical field of lubricating oil, in particular to anti-foam methanol automobile engine lubricating oil.
Background
According to the energy structure and the current market situation of China, China is supposed to walk the way of energy diversification to relieve the challenge of energy safety. Improving the air environment quality and promoting the sustainable development of the economic health of China.
According to the current technology and test analysis results, the methanol fuel can be used as one of alternative energy sources of the internal combustion engine, so that the energy sources of the internal combustion engine are more selected, the energy sources are more diversified, the air environment quality can be improved, and the sustainable development of the economic health of China is promoted. When the methanol is used as the fuel of the automobile engine, under ideal conditions, the methanol is completely combusted and converted into carbon dioxide and water, and simultaneously energy is released to power the automobile. However, the current automobile engine using methanol as fuel cannot completely convert methanol into carbon dioxide and water. A part of formic acid and formaldehyde are generated due to incomplete combustion of methanol in an engine and are diffused to the surface of an engine auxiliary, so that the phenomena of turbidity, emulsification and foaming can occur when the methanol engine uses the original automobile engine lubricating oil, and the service performance and the service life of the methanol engine are influenced.
According to the requirement of using the methanol fuel as the alternative energy of the internal combustion engine, the lubricating oil suitable for the methanol fuel engine needs to be produced in a matching way. Liaoning Santa petrochemical company has preliminarily established the enterprise standard of methanol fuel engine lubricating oil, Q/LSY 005-2018. And part of products are produced by the original technology according to the standard, and the probation shows that the phenomena of turbidity, emulsification and foaming of the products are improved, but the performance can not completely meet the requirement of the methanol fuel engine lubricating oil. Therefore, a methanol automobile engine lubricating oil with anti-foaming performance and a preparation method of the lubricating oil are needed.
Disclosure of Invention
Object of the Invention
The invention aims to produce anti-foaming methanol automobile engine lubricating oil which is used for a methanol fuel engine and can reduce the phenomena of turbidity, emulsification and foaming of the lubricating oil.
Technical scheme
An anti-foam methanol automobile engine lubricating oil is prepared by carrying out synthetic reaction on a low molecular weight polymer obtained by mixing and polymerizing perfluoro-n-hexyl acrylate containing palladium ions and perfluoro-n-decyl acrylate and a methanol fuel engine lubricating oil produced according to the standard Q/LSY005-2018 of Liaoning Santa petrochemical company, Inc.;
the molecular structural formula of the low molecular weight polymer obtained by mixing and polymerizing the perfluoro-n-hexyl acrylate and the perfluoro-n-decyl acrylate is as follows:
n represents the degree of polymerization, and n is a positive integer of 2, 3, 4 and 5; z is a handle group, Z is Z1Or Z2Or Z1And Z2N ═ n1+n2，n1Represents Z1Number of radicals, n2Represents Z2Number of radicals, n1And n2Is a positive integer;
Z1represents perfluoro-n-hexyl, Z2Represents a perfluoro-n-decyl group,
Z1the molecular structural formula is:
Z2the molecular structural formula is:
e is a reaction product after the initiation reaction of a peroxy or azo initiator.
E in the molecular structural formula of the low molecular weight polymer obtained by mixing and polymerizing the perfluoro-n-hexyl acrylate and the perfluoro-n-decyl acrylate is a reaction product obtained after initiation reaction of p-methyl benzoyl peroxide, azodiisobutyronitrile or tert-butyl hydroperoxide.
A method for preparing the anti-foaming methanol automobile engine lubricating oil comprises the following steps:
taking a raw material A1: perfluoro-linear hexanol, catalyst B: and (3) palladium nitrate, adding the two into a colloid mill to prepare a colloid solution a, and adding the raw material C: acrylic acid, controlling the reaction temperature, reacting under stirring, discharging the byproduct water after the reaction is completed, and generating a product D1: product D1Is perfluorohexyl acrylate containing palladium ions;
taking a raw material A2: taking perfluoro-straight-chain decanol, taking a catalyst B: and (3) palladium nitrate, adding the two into a colloid mill to prepare a colloid solution b, and adding the raw material C: acrylic acid, controlling the reaction temperature, reacting under stirring, discharging the byproduct water after the reaction is completed, and generating a product D2: product D2Is perfluorodecyl acrylate containing palladium ions;
subjecting the product D to1And product D2Mixing, controlling the reaction temperature under vacuum condition and adding an initiator under stirring condition to perform polymerization reaction, wherein the polymerization product is a product P: a low molecular weight polymer obtained by mixing and polymerizing perfluoro-n-hexyl acrylate containing palladium ions and perfluoro-n-decyl acrylate;
and (3) carrying out synthetic reaction on the product P and the methanol fuel engine lubricating oil produced according to the enterprise standard Q/LSY005-2018 of Liaoning Santa petrochemical company, namely company Limited, controlling the reaction temperature under a vacuum condition and stirring for a period of time to obtain a product G, wherein the product G forms the anti-foaming methanol automobile engine lubricating oil.
The raw material A1The mol ratio of the catalyst A to the catalyst B is controlled to be 1000:1 to 100000:1, and the raw material A1The molar ratio of the raw material C to the raw material C is controlled to be 2:1 to 1: 2; the raw material A2The mol ratio of the catalyst A to the catalyst B is controlled to be 1000:1 to 100000:1, and the raw material A2The molar ratio to the raw material C is controlled to be 2:1 to 1: 2.
The reaction temperature of the colloidal solution a and the raw material C is 20-100 ℃, the reaction pressure is 133Pa-760 x 133Pa, and the reaction time is more than or equal to 2 h; the reaction temperature of the colloidal solution b and the raw material C is 20-100 ℃, the reaction pressure is 133Pa-760 x 133Pa, and the reaction time is more than or equal to 2 h.
The product D1And product D2The mixture of (A) is added with an initiator under the condition of the reaction temperature of 40-130 ℃, and the product D1And product D2The molar ratio of the sum of the mole numbers of the mixture of (A) and (B) to the initiator is controlled to be 100:1 to 10000:1, the polymerization reaction time is more than or equal to 2h, and a product D1And product D2In a molar ratio of 1:10 to 10: 1.
The mass ratio of the product P to the methanol fuel engine lubricating oil produced according to the enterprise standard Q/LSY005-2018 of Liaoning Santa petrochemical company Limited is 1:1000 to 1:100000, and the synthetic reaction time is more than or equal to 1 h.
After the colloidal solution a and the colloidal solution b are respectively prepared, respectively transferring the colloidal solution a and the colloidal solution b into the reactor a to independently react with the raw material C; reactor an is kettle-type reactor, reactor an includes kettle-type reactor main part, shell and tube cooler and accessory substance water receiver, kettle-type reactor main part is equipped with feed inlet and discharge gate, the agitator has been inserted to kettle-type reactor main part, the agitator is connected with the motor, kettle-type reactor main part outside is equipped with presss from both sides the cover, it is equipped with heat carrier entry and heat carrier export to press from both sides the cover, there is shell and tube cooler the inside of kettle-type reactor main part through the pipe connection, accessory substance water receiver connects in shell and tube cooler's lower extreme, shell and tube cooler is equipped with cooling water export and cooling water entry, vacuum system is connected to shell and tube cooler's upper end.
And a vacuum balance pipe is arranged outside the tube type cooler and the byproduct water receiver and is used for communicating the tube type cooler and the byproduct water receiver.
The product D1And product D2The mixture of (A) and (B) is polymerized in a reactor (b), and the product P is mixed with a methanol fuel engine lubricating oil mixture produced according to the Liaoning Santa petrochemical company, Inc. enterprise standard Q/LSY005-2018The formation reaction also takes place the synthesis reaction in reactor b, reactor b is kettle-type reactor, reactor b's kettle-type reactor main part is equipped with feed inlet and discharge gate, the agitator has been inserted to kettle-type reactor main part, the agitator is connected with the motor, the kettle-type reactor main part outside is equipped with presss from both sides the cover, it is equipped with heat carrier entry and heat carrier export to press from both sides the cover, kettle-type reactor main part inner wall cloth has the cooling tube, the cooling water entry and the cooling water export of cooling tube wear out from the lateral wall of kettle-type reactor main part, kettle-type reactor main part still passes through pipe connection vacuum system.
Advantages and effects
The low molecular weight polymer obtained by mixing and polymerizing the perfluoro-n-hexyl acrylate and the perfluoro-n-decyl acrylate containing palladium ions can quickly convert formic acid and formaldehyde diffused to the secondary surface of a methanol fuel engine into carbon dioxide and water and quickly discharge the generated carbon dioxide and water out of an engine lubricating oil layer.
Drawings
FIG. 1 is a schematic view of the structure of reactor a;
FIG. 2 is a schematic view of the structure of reactor b.
Description of reference numerals:
1. the reactor comprises a kettle type reactor body, 2 tubular coolers, 3 byproduct water receivers, 4 feed inlets, 5 discharge outlets, 6 stirrers, 7 motors, 8 jackets, 9 heat carrier inlets, 10 heat carrier outlets, 11 cooling water outlets, 12 cooling water inlets, 13 vacuum balance pipes, 14 cooling pipes, 15 cooling water inlets and 16 cooling water outlets.
Detailed Description
The technical solutions of the present invention will be described in further detail with reference to the accompanying drawings, and all the parts of the present invention that are not described in detail are the prior art.
As shown in fig. 1, reactor a is a kettle reactor, reactor a includes kettle reactor main body 1, shell and tube cooler 2 and accessory substance water receiver 3, kettle reactor main body 1 is equipped with feed inlet 4 and discharge gate 5, kettle reactor main body 1 has inserted agitator 6, agitator 6 is connected with motor 7, kettle reactor main body 1 outside is equipped with jacket 8, jacket 8 is equipped with heat carrier entry 9 and heat carrier export 10, kettle reactor main body 1's inside has shell and tube cooler 2 through the pipe connection, accessory substance water receiver 3 is connected in shell and tube cooler 2's lower extreme, shell and tube cooler 2 is equipped with cooling water export 11 and cooling water entry 12, the upper end of shell and tube cooler 2 connects the vacuum system vacuum pump. The shell and tube cooler 2 and the by-product water receiver 3 are also provided with a vacuum balance pipe 13, and the shell and tube cooler 2 and the by-product water receiver 3 are communicated through the vacuum balance pipe 13 to ensure the vacuum balance of the shell and tube cooler 2 and the by-product water receiver 3.
As shown in fig. 2, the reactor b is a tank reactor, a tank reactor body 1 of the reactor b is provided with a feed inlet 4 and a discharge outlet 5, a stirrer 6 is inserted into the tank reactor body 1, the stirrer 6 is connected with a motor 7, a jacket 8 is arranged on the outer side of the tank reactor body 1, the jacket 8 is provided with a heat carrier inlet 9 and a heat carrier outlet 10, cooling pipes 14 are distributed on the inner wall of the tank reactor body 1, cooling water inlets 15 and cooling water outlets 16 of the cooling pipes 14 penetrate out of the side wall of the tank reactor body 1, and the tank reactor body 1 is further connected with a vacuum pump of a vacuum system through a pipeline.
Example 1
A method for preparing the anti-foaming methanol automobile engine lubricating oil comprises the following steps: 1) taking a raw material A1: perfluoro linear hexanol of the formula: c6F13OH, molecular weight: in 336, the molecular structural formula is:
taking a catalyst B: palladium nitrate, Pd (NO)3)2The molecular weight is 230.41, and the colloidal solution a is prepared by adding the two into a colloid mill and is transferred into a reactor a. Adding raw material C under stirring: acrylic acid, molecular weight 72.06, molecular formula: c3H4O2The molecular structural formula is as follows:
controlling the reaction temperature at 20-100 ℃ and the pressure at 133 Pa-760X 133Pa under stirring, reacting for 2h, discharging the generated by-product water out of the main body of the reactor a through a tubular cooler. Formation of product D1: perfluorohexyl acrylate containing palladium ions, the formula of perfluorohexyl acrylate: c9F13O2H3Molecular weight: 390, molecular structural formula of perfluorohexyl acrylate:
starting materials A1The mol ratio of the catalyst A to the catalyst B is controlled to be 1000:1, and the raw material A1The molar ratio to C was controlled at 2: 1. Subjecting the product D to1Transferring out of the reactor a to a container for storage and standby.
2) Taking a raw material A2: perfluoro-linear decanol, molecular formula: c10F21OH, molecular weight: in 536, the molecular structural formula is as follows:
taking a catalyst B: palladium nitrate, Pd (NO)3)2The molecular weight is 230.41, and the colloidal solution b is prepared by adding the two into a colloid mill and is transferred into a reactor a. Adding raw material C under stirring: acrylic acid, molecular weight 72.06, molecular formula: c3H4O2The molecular structural formula is as follows:
controlling the reaction temperature at 20-100 ℃ and the pressure at 133 Pa-760X 133Pa under stirring, reacting for 2h, discharging the generated by-product water out of the main body of the reactor a through a tubular cooler. Formation of product D2: perfluoro decyl acrylate containing palladium ion, perfluoro acrylateThe molecular formula of decyl ester is: c13F21O2H3Molecular weight: 590, structural formula of perfluorodecyl acrylate molecule:
starting materials A2The mol ratio of the catalyst A to the catalyst B is controlled to be 1000:1, and the raw material A2The molar ratio to C was controlled at 2: 1. Subjecting the product D to2Is transferred out of the reactor a to the product D1Storing in different containers for standby.
Feeding product D to reactor b1While feeding product D to reactor b2Stirring, product D1And product D2At a molar ratio of 1:10, controlling the reaction temperature at 40-130 deg.C, adding an initiator (preferably, the initiator is a peroxy or azo initiator, such as p-toluyl peroxide, azobisisobutyronitrile or tert-butyl hydroperoxide) to obtain the product D1And product D2Mixed polymerization reaction occurs, the polymerization reaction time is 5h, the molecular weight of the polymerization product is controlled between 390X 2 and 590X 5, the polymerization product is called product P, and the product P contains Pd2+Ion, molecular structural formula:
n represents the degree of polymerization, and n is a positive integer of 2, 3, 4 and 5; z is a handle group, Z is Z1Or Z2Or Z1And Z2N ═ n1+n2，n1Represents Z1Number of radicals, n2Represents Z2Number of radicals, n1And n2Is a positive integer; product D1And product D2The molar ratio of the sum of the number of moles to the initiator is controlled at 100: 1. E in the molecular structural formula of the low molecular weight polymer obtained by mixing and polymerizing the perfluoro-n-hexyl acrylate and the perfluoro-n-decyl acrylate is a reaction product obtained after initiation reaction of p-methyl benzoyl peroxide, azodiisobutyronitrile or tert-butyl hydroperoxide. Z1Represents perfluoro-n-hexyl, Z2Represents a perfluoro-n-decyl group,Z1the molecular structural formula is:
Z2the molecular structural formula is:
e is a reaction product after the initiation reaction of p-methyl benzoyl peroxide, azodiisobutyronitrile or tert-butyl hydroperoxide.
Taking the product P and methanol fuel engine lubricating oil produced by Liaoning Santa petrochemical company Limited according to the enterprise standard Q/LSY005-2018 according to the proportion, simultaneously adding the mixture into a reactor b, controlling the reaction temperature to be 80-130 ℃, stirring for 20min, and carrying out synthetic reaction to obtain a product G. The mass ratio is controlled to be 1:1000, and the synthesis reaction time is 1 h. The product G constitutes the anti-foaming methanol automobile engine lubricating oil.
Example 2
A method for preparing the anti-foaming methanol automobile engine lubricating oil comprises the following steps: 1) taking a raw material A1: perfluoro linear hexanol of the formula: c6F13OH, molecular weight: in 336, the molecular structural formula is:
taking a catalyst B: palladium nitrate, Pd (NO)3)2The molecular weight is 230.41, and the colloidal solution a is prepared by adding the two into a colloid mill and is transferred into a reactor a. Adding raw material C under stirring: acrylic acid, molecular weight 72.06, molecular formula: c3H4O2The molecular structural formula is as follows:
controlling the reaction temperature at 20-100 ℃ and the pressure at 133 Pa-760X 133Pa under stirring, reacting for 3h, discharging the generated by-product water out of the main body of the reactor a through a tubular cooler. Formation of product D1: perfluorohexyl acrylate containing palladium ions, the formula of perfluorohexyl acrylate: c9F13O2H3Molecular weight: 390, molecular structural formula of perfluorohexyl acrylate:
starting materials A1The mol ratio of the catalyst A to the catalyst B is controlled to be 10000:1, and the raw material A1The molar ratio to C was controlled at 1: 1. Subjecting the product D to1Transferring out of the reactor a to a container for storage and standby.
2) Taking a raw material A2: perfluoro-linear decanol, molecular formula: c10F21OH, molecular weight: in 536, the molecular structural formula is as follows:
taking a catalyst B: palladium nitrate, Pd (NO)3)2The molecular weight is 230.41, and the colloidal solution b is prepared by adding the two into a colloid mill and is transferred into a reactor a. Adding raw material C under stirring: acrylic acid, molecular weight 72.06, molecular formula: c3H4O2The molecular structural formula is as follows:
controlling the reaction temperature at 20-100 ℃ and the pressure at 133 Pa-760X 133Pa under stirring, reacting for 3h, discharging the generated by-product water out of the main body of the reactor a through a tubular cooler. Formation of product D2: perfluoro decyl acrylate containing palladium ions, the molecular formula of the perfluoro decyl acrylate is as follows: c13F21O2H3Is divided intoAnd (2) sub-amount: 590, structural formula of perfluorodecyl acrylate molecule:
starting materials A2The mol ratio of the catalyst A to the catalyst B is controlled to be 10000:1, and the raw material A2The molar ratio to C was controlled at 1: 1. Subjecting the product D to2Is transferred out of the reactor a to the product D1Storing in different containers for standby.
Feeding product D to reactor b1While feeding product D to reactor b2Stirring, product D1And product D2At a molar ratio of 1:1, controlling the reaction temperature at 40-130 deg.C, adding an initiator (preferably, the initiator is a peroxy or azo initiator, such as p-toluyl peroxide, azobisisobutyronitrile or tert-butyl hydroperoxide) to obtain the product D1And product D2Mixed polymerization reaction is carried out for 2h, the molecular weight of the polymerization product is controlled between 390X 2 and 590X 5, the polymerization product is called product P, and the product P contains Pd2+Ion, molecular structural formula:
n represents the degree of polymerization, and n is a positive integer of 2, 3, 4 and 5; z is a handle group, Z is Z1Or Z2Or Z1And Z2N ═ n1+n2，n1Represents Z1Number of radicals, n2Represents Z2Number of radicals, n1And n2Is a positive integer; product D1And product D2The molar ratio of the sum of the mole numbers to the initiator is controlled to be 1000: 1. E in the molecular structural formula of the low molecular weight polymer obtained by mixing and polymerizing the perfluoro-n-hexyl acrylate and the perfluoro-n-decyl acrylate is a reaction product obtained after initiation reaction of p-methyl benzoyl peroxide, azodiisobutyronitrile or tert-butyl hydroperoxide. Z1Represents perfluoro-n-hexyl, Z2Represents perfluoro-n-decyl, Z1The molecular structural formula is:
Z2the molecular structural formula is:
e is a reaction product after the initiation reaction of p-methyl benzoyl peroxide, azodiisobutyronitrile or tert-butyl hydroperoxide.
Taking the product P and methanol fuel engine lubricating oil produced by Liaoning Santa petrochemical company Limited according to the enterprise standard Q/LSY005-2018 according to the proportion, simultaneously adding the mixture into a reactor b, controlling the reaction temperature to be 80-130 ℃, stirring for 20min, and carrying out synthetic reaction to obtain a product G. The mass ratio is controlled to be 1:10000, and the synthesis reaction time is 2 h. The product G constitutes the anti-foaming methanol automobile engine lubricating oil.
Example 3
A method for preparing the anti-foaming methanol automobile engine lubricating oil comprises the following steps: 1) taking a raw material A1: perfluoro linear hexanol of the formula: c6F13OH, molecular weight: in 336, the molecular structural formula is:
taking a catalyst B: palladium nitrate, Pd (NO)3)2The molecular weight is 230.41, and the colloidal solution a is prepared by adding the two into a colloid mill and is transferred into a reactor a. Adding raw material C under stirring: acrylic acid, molecular weight 72.06, molecular formula: c3H4O2The molecular structural formula is as follows:
under stirring, the reaction temperature is controlled at 20-100 deg.C and pressure133Pa to 760X 133Pa, and the by-product water produced by the reaction for 4 hours was discharged outside the main body of the reactor a through a tubular cooler. Formation of product D1: perfluorohexyl acrylate containing palladium ions, the formula of perfluorohexyl acrylate: c9F13O2H3Molecular weight: 390, molecular structural formula of perfluorohexyl acrylate:
starting materials A1The molar ratio of the catalyst A to the catalyst B is controlled to be 100000:1, and the raw material A1The molar ratio to C was controlled at 1: 2. Subjecting the product D to1Transferring out of the reactor a to a container for storage and standby.
2) Taking a raw material A2: perfluoro-linear decanol, molecular formula: c10F21OH, molecular weight: in 536, the molecular structural formula is as follows:
taking a catalyst B: palladium nitrate, Pd (NO)3)2The molecular weight is 230.41, and the colloidal solution b is prepared by adding the two into a colloid mill and is transferred into a reactor a. Adding raw material C under stirring: acrylic acid, molecular weight 72.06, molecular formula: c3H4O2The molecular structural formula is as follows:
controlling the reaction temperature at 20-100 ℃ and the pressure at 133 Pa-760X 133Pa under stirring, reacting for 4h, discharging the generated by-product water out of the main body of the reactor a through a tubular cooler. Formation of product D2: perfluoro decyl acrylate containing palladium ions, the molecular formula of the perfluoro decyl acrylate is as follows: c13F21O2H3Molecular weight: 590, structural formula of perfluorodecyl acrylate molecule:
starting materials A2The molar ratio of the catalyst A to the catalyst B is controlled to be 100000:1, and the raw material A2The molar ratio to C was controlled at 1: 2. Subjecting the product D to2Is transferred out of the reactor a to the product D1Storing in different containers for standby.
Feeding product D to reactor b1While feeding product D to reactor b2Stirring, product D1And product D2At a molar ratio of 10:1, controlling the reaction temperature at 40-130 ℃, adding an initiator (preferably, the initiator is a peroxy or azo initiator, such as p-toluyl peroxide, azobisisobutyronitrile or tert-butyl hydroperoxide) to obtain a product D1And product D2Mixed polymerization reaction is carried out for 3h, the molecular weight of the polymerization product is controlled between 390X 2 and 590X 5, the polymerization product is called product P, and the product P contains Pd2+Ion, molecular structural formula:
n represents the degree of polymerization, and n is a positive integer of 2, 3, 4 and 5; z is a handle group, Z is Z1Or Z2Or Z1And Z2N ═ n1+n2，n1Represents Z1Number of radicals, n2Represents Z2Number of radicals, n1And n2Is a positive integer; product D1And product D2The molar ratio of the sum of the number of moles to the initiator is controlled to 10000: 1. E in the molecular structural formula of the low molecular weight polymer obtained by mixing and polymerizing the perfluoro-n-hexyl acrylate and the perfluoro-n-decyl acrylate is a reaction product obtained after initiation reaction of p-methyl benzoyl peroxide, azodiisobutyronitrile or tert-butyl hydroperoxide. Z1Represents perfluoro-n-hexyl, Z2Represents a perfluoro-n-decyl group,
Z1the molecular structural formula is:
Z2the molecular structural formula is:
e is a reaction product after the initiation reaction of p-methyl benzoyl peroxide, azodiisobutyronitrile or tert-butyl hydroperoxide.
Taking the product P and methanol fuel engine lubricating oil produced by Liaoning Santa petrochemical company Limited according to the enterprise standard Q/LSY005-2018 according to the proportion, simultaneously adding the mixture into a reactor b, controlling the reaction temperature to be 80-130 ℃, stirring for 20min, and carrying out synthetic reaction to obtain a product G. The mass ratio is controlled to be 1:100000, and the synthesis reaction time is 3 h. The product G constitutes the anti-foaming methanol automobile engine lubricating oil.
And (3) quality detection:
the product G produced by the method of the above example 1-3 is tested according to the enterprise standard of methanol fuel engine lubricating oil, Q/LSY005-2018, established by Liaoning Santa petrochemical company Limited, and all quality indexes are in accordance with the standard.
And (3) comparison test:
a comparison test is carried out on two specified dual-fuel M100 methanol engines which are newly assembled, a unit A is formed by using methanol fuel engine lubricating oil produced by an original factory according to enterprise standards Q/LSY005-2018, and a unit B is formed by using anti-foaming methanol fuel engine lubricating oil produced by the method, and a 100-hour durability comparison test is respectively carried out. And sampling, analyzing and examining the lubricating oil sample at the same test time. The foam of unit B was only 40% of unit a.
The parts of this patent not referred to in detail are the same as or can be implemented using prior art. The above-mentioned embodiments are only preferred embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and their concepts should be equivalent or changed within the technical scope of the present invention.
Claims (10)
1. An anti-foaming methanol automobile engine lubricating oil is characterized in that: the lubricating oil is anti-foam methanol automobile engine lubricating oil obtained by carrying out synthetic reaction on a low molecular weight polymer obtained by mixing and polymerizing perfluoro-n-hexyl acrylate and perfluoro-n-decyl acrylate containing palladium ions and methanol fuel engine lubricating oil produced according to the standard Q/LSY005-2018 of Liaoning Santa petrochemical company, Inc.;
the molecular structural formula of the low molecular weight polymer obtained by mixing and polymerizing the perfluoro-n-hexyl acrylate and the perfluoro-n-decyl acrylate is as follows:
n represents the degree of polymerization, and n is a positive integer of 2, 3, 4 and 5; z is a handle group, Z is Z1Or Z2Or Z1And Z2N ═ n1+n2，n1Represents Z1Number of radicals, n2Represents Z2Number of radicals, n1And n2Is a positive integer;
Z1represents perfluoro-n-hexyl, Z2Represents a perfluoro-n-decyl group,
Z1the molecular structural formula is:
Z2the molecular structural formula is:
e is a reaction product after initiation reaction of a peroxy or azo initiator;
the preparation method of the anti-foaming methanol automobile engine lubricating oil comprises the following steps:
taking a raw material A1: perfluoro-linear hexanol, catalyst B: and (3) palladium nitrate, adding the two into a colloid mill to prepare a colloid solution a, and adding the raw material C: acrylic acid, controlling the reaction temperature, reacting under stirring, discharging the byproduct water after the reaction is completed, and generating a product D1: product D1Is perfluorohexyl acrylate containing palladium ions;
taking a raw material A2: taking perfluoro-straight-chain decanol, taking a catalyst B: and (3) palladium nitrate, adding the two into a colloid mill to prepare a colloid solution b, and adding the raw material C: acrylic acid, controlling the reaction temperature, reacting under stirring, discharging the byproduct water after the reaction is completed, and generating a product D2: product D2Is perfluorodecyl acrylate containing palladium ions;
subjecting the product D to1And product D2Mixing, controlling the reaction temperature under vacuum condition and adding an initiator under stirring condition to perform polymerization reaction, wherein the polymerization product is a product P: a low molecular weight polymer obtained by mixing and polymerizing perfluoro-n-hexyl acrylate containing palladium ions and perfluoro-n-decyl acrylate;
taking the product P and methanol fuel engine lubricating oil produced according to the enterprise standard Q/LSY005-2018 of Liaoning Santa petrochemical company, namely company Limited, to carry out synthetic reaction, controlling the reaction temperature under vacuum condition and stirring for a period of time to obtain a product G, wherein the product G forms the anti-foam methanol automobile engine lubricating oil;
the raw material A1The mol ratio of the catalyst A to the catalyst B is controlled to be 1000:1 to 100000:1, and the raw material A1The molar ratio of the raw material C to the raw material C is controlled to be 2:1 to 1: 2; the raw material A2The mol ratio of the catalyst A to the catalyst B is controlled to be 1000:1 to 100000:1, and the raw material A2The molar ratio of the raw material C to the raw material C is controlled to be 2:1 to 1: 2;
the product D1And product D2The mixture of (A) is added with an initiator under the condition of the reaction temperature of 40-130 ℃, and the product D1And product D2The molar ratio of the sum of the mole numbers of the mixture of (A) and (B) to the initiator is controlled to be 100:1 to 10000:1, the polymerization reaction time is more than or equal to 2h, and a product D1And product D2In a molar ratio of 1:10 to 10: 1.
2. The foam-resistant methanol automobile engine lubricating oil according to claim 1, characterized in that: e in the molecular structural formula of the low molecular weight polymer obtained by mixing and polymerizing the perfluoro-n-hexyl acrylate and the perfluoro-n-decyl acrylate is a reaction product obtained after initiation reaction of p-methyl benzoyl peroxide, azodiisobutyronitrile or tert-butyl hydroperoxide.
3. A method of preparing the anti-foaming methanol automotive engine lubricating oil of claim 1, characterized in that: the method comprises the following steps:
taking a raw material A1: perfluoro-linear hexanol, catalyst B: and (3) palladium nitrate, adding the two into a colloid mill to prepare a colloid solution a, and adding the raw material C: acrylic acid, controlling the reaction temperature, reacting under stirring, discharging the byproduct water after the reaction is completed, and generating a product D1: product D1Is perfluorohexyl acrylate containing palladium ions;
taking a raw material A2: taking perfluoro-straight-chain decanol, taking a catalyst B: and (3) palladium nitrate, adding the two into a colloid mill to prepare a colloid solution b, and adding the raw material C: acrylic acid, controlling the reaction temperature, reacting under stirring, discharging the byproduct water after the reaction is completed, and generating a product D2: product D2Is perfluorodecyl acrylate containing palladium ions;
subjecting the product D to1And product D2Mixing, controlling the reaction temperature under vacuum condition and adding an initiator under stirring condition to perform polymerization reaction, wherein the polymerization product is a product P: a low molecular weight polymer obtained by mixing and polymerizing perfluoro-n-hexyl acrylate containing palladium ions and perfluoro-n-decyl acrylate;
and (3) carrying out synthetic reaction on the product P and the methanol fuel engine lubricating oil produced according to the enterprise standard Q/LSY005-2018 of Liaoning Santa petrochemical company, namely company Limited, controlling the reaction temperature under a vacuum condition and stirring for a period of time to obtain a product G, wherein the product G forms the anti-foaming methanol automobile engine lubricating oil.
4. The method for preparing the anti-foaming methanol automobile engine lubricating oil according to claim 3, characterized in that: the raw material A1The mol ratio of the catalyst A to the catalyst B is controlled to be 1000:1 to 100000:1, and the raw material A1The molar ratio of the raw material C to the raw material C is controlled to be 2:1 to 1: 2; the raw material A2The mol ratio of the catalyst A to the catalyst B is controlled to be 1000:1 to 100000:1, and the raw material A2The molar ratio to the raw material C is controlled to be 2:1 to 1: 2.
5. The method for preparing the anti-foaming methanol automobile engine lubricating oil according to claim 3, characterized in that: the reaction temperature of the colloidal solution a and the raw material C is 20-100 ℃, the reaction pressure is 133Pa-760 x 133Pa, and the reaction time is more than or equal to 2 h; the reaction temperature of the colloidal solution b and the raw material C is 20-100 ℃, the reaction pressure is 133Pa-760 x 133Pa, and the reaction time is more than or equal to 2 h.
6. The method for preparing the anti-foaming methanol automobile engine lubricating oil according to claim 3, characterized in that: the product D1And product D2The mixture of (A) is added with an initiator under the condition of the reaction temperature of 40-130 ℃, and the product D1And product D2The molar ratio of the sum of the mole numbers of the mixture of (A) and (B) to the initiator is controlled to be 100:1 to 10000:1, the polymerization reaction time is more than or equal to 2h, and a product D1And product D2In a molar ratio of 1:10 to 10: 1.
7. The method for preparing the anti-foaming methanol automobile engine lubricating oil according to claim 3, characterized in that: the mass ratio of the product P to the methanol fuel engine lubricating oil produced according to the enterprise standard Q/LSY005-2018 of Liaoning Santa petrochemical company Limited is 1:1000 to 1:100000, and the synthetic reaction time is more than or equal to 1 h.
8. The method for preparing the anti-foaming methanol automobile engine lubricating oil according to claim 3, characterized in that: after the colloidal solution a and the colloidal solution b are respectively prepared, respectively transferring the colloidal solution a and the colloidal solution b into the reactor a to independently react with the raw material C; the reactor a is a kettle type reactor, the reactor a comprises a kettle type reactor main body (1), tubular cooler (2) and accessory substance water receiver (3), kettle-type reactor main part (1) is equipped with feed inlet (4) and discharge gate (5), kettle-type reactor main part (1) has inserted agitator (6), agitator (6) are connected with motor (7), kettle-type reactor main part (1) outside is equipped with and presss from both sides cover (8), it is equipped with heat carrier entry (9) and heat carrier export (10) to press from both sides cover (8), there are tubular cooler (2) inside of kettle-type reactor main part (1) through the pipe connection, accessory substance water receiver (3) are connected in the lower extreme of tubular cooler (2), tubular cooler (2) are equipped with cooling water outlet (11) and cooling water inlet (12), vacuum system is connected to the upper end of tubular cooler (2).
9. The method of preparing a foam-resistant methanol automotive engine lubricating oil according to claim 8, characterized in that: the shell and tube cooler (2) and the byproduct water receiver (3) are also provided with a vacuum balance tube (13) outside, and the shell and tube cooler (2) and the byproduct water receiver (3) are communicated through the vacuum balance tube (13).
10. The method for preparing the anti-foaming methanol automobile engine lubricating oil according to claim 3, characterized in that: the product D1And product D2The mixture of (1) is subjected to polymerization reaction in a reactor b, the synthetic reaction of a product P and the methanol fuel engine lubricating oil produced according to the enterprise standard Q/LSY005-2018 of Santong petrochemical company Limited is also subjected to synthetic reaction in the reactor b, the reactor b is a kettle-type reactor, a kettle-type reactor main body (1) of the reactor b is provided with a feeding hole (4) and a discharging hole (5), a stirrer (6) is inserted into the kettle-type reactor main body (1), the stirrer (6) is connected with a motor (7), a jacket (8) is arranged on the outer side of the kettle-type reactor main body (1), and the jacket (8) is provided with a heat carrier inlet (9)) And a heat carrier outlet (10), cooling pipes (14) are distributed on the inner wall of the kettle type reactor main body (1), a cooling water inlet (15) and a cooling water outlet (16) of each cooling pipe (14) penetrate out of the side wall of the kettle type reactor main body (1), and the kettle type reactor main body (1) is further connected with a vacuum system through a pipeline.
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