CN109970899B - Copolymer and preparation method thereof, antistatic agent containing copolymer and application of antistatic agent - Google Patents
Copolymer and preparation method thereof, antistatic agent containing copolymer and application of antistatic agent Download PDFInfo
- Publication number
- CN109970899B CN109970899B CN201910158498.7A CN201910158498A CN109970899B CN 109970899 B CN109970899 B CN 109970899B CN 201910158498 A CN201910158498 A CN 201910158498A CN 109970899 B CN109970899 B CN 109970899B
- Authority
- CN
- China
- Prior art keywords
- copolymer
- parts
- compound
- acrylamide
- antistatic agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a copolymer and a preparation method thereof, an antistatic agent containing the copolymer and application thereof. The raw materials for preparing the copolymer comprise: maleic acid derivatives, alkenyl carboxylate compounds, acrylamide compounds, ethylene and alpha-olefins. The molar ratio of the raw materials is 1 to (0-5) to (15-30) to (5-15); wherein the maleic acid derivative is obtained by reacting maleic anhydride with an amine compound. The above copolymer has: slow conductivity decay, good antistatic effect, strong applicability, no need of antistatic stabilizer, good oil solubility, good water separation performance and the like. An antistatic agent containing the copolymer comprises the following components in parts by weight: 20 to 40 parts of copolymer, 10 to 20 parts of fatty acid amide, 5 to 15 parts of poly fatty acid ester, 0 to 10 parts of imide compound and 40 to 70 parts of diluent. The antistatic agent has slow conductivity decay, good water separation characteristic, good oil product applicability and small environmental pollution.
Description
Technical Field
The invention relates to the field of oil additives, in particular to a copolymer and a preparation method thereof, an antistatic agent and a preparation method and application thereof.
Background
The main component of the aviation kerosene is hydrocarbon compound, the insulating property is strong, and due to the special application of the aviation kerosene, the requirements on the contents of sulfur and nitrogen are lower, and the conductivity of the aviation kerosene is poorer than that of common fuel. Therefore, when aviation kerosene is produced, stored and transported, especially when aviation kerosene is added with oil in the air, charges are easy to separate due to friction between media, and if the charges are accumulated to a certain degree, serious safety accidents such as fire and explosion can happen. The addition of the antistatic agent into the aviation kerosene can lead the charge to be quickly dissipated, prevent the charge from being accumulated and generate high voltage, and is a feasible method for ensuring the use safety of the aviation kerosene.
The antistatic agent for aviation kerosene is divided into two types of ash type antistatic agents and ash-free type antistatic agents, wherein the ash type antistatic agents (such as ASA-3 produced by Shell company, domestic T1501 and the like) have the problems of rapid conductivity attenuation, obviously reduced water separation index after the antistatic agent is added, chromium pollution after combustion and the like, and are rarely produced and used. Ashless antistatic agents (e.g., ST450 available from DuPont, T1502 available from China) have good conductivity and excellent water separation characteristics, but have problems in use: (1) the sensitivity difference of aviation kerosene oil products of different processes is large; (2) the conductivity decays rapidly; (3) after the aviation kerosene is added with the antistatic agent, the phenomenon that the water separation index does not reach the standard often occurs; (4) the main components of the traditional antistatic agent are polysulfone, polyamine or a composition thereof, the polysulfone has a complex production process and contains sulfur elements, and environmental pollution is easily caused after combustion.
Disclosure of Invention
Therefore, the antistatic agent has slow conductivity decay, good water separation characteristic, good oil product applicability and environmental protection.
In addition, a copolymer and a preparation method thereof, an antistatic agent containing the copolymer and application thereof are also provided.
A copolymer is prepared from raw materials including maleic acid derivatives, carboxylic acid alkene ester compounds, acrylamide compounds, ethylene and alpha-olefin; wherein:
the molar ratio of the maleic acid derivative to the alkenyl carboxylate compound to the acrylamide compound to the ethylene to the alpha-olefin is 1: 0 to 5: 15 to 30: 5 to 15;
the maleic acid derivative is obtained by reacting maleic anhydride with an amine compound, wherein the amine compound is one selected from diamine and alcohol amine, and the number of carbon atoms of the amine compound is 3-18;
the carboxylic acid allyl ester compound is at least one of vinyl formate, acrylic formate, vinyl acetate, acrylic acetate, 3-butylene acetate, 3-hexylene acetate and pent-2-en-1-yl acetate;
the acrylamide compound is at least one selected from acrylamide, 2-methacrylamide, diacetone acrylamide and N-alkyl acrylamide, wherein the carbon atom number of an alkyl group in the N-alkyl acrylamide is 1-18;
the number of carbon atoms of the alpha-olefin is 3-24.
In one embodiment, the molar ratio of the maleic acid derivative, the alkenyl carboxylate compound, the acrylamide compound, the ethylene and the alpha-olefin is 1: 1-3: 2-4: 20-25: 8-12; and/or the amine compound has 5-10 carbon atoms; and/or the number of carbon atoms of the alpha-olefin is 8-12; and/or the number average molecular weight of the copolymer is 5000-50000.
A method of preparing a copolymer comprising the steps of:
carrying out copolymerization reaction on raw materials in a first solvent to obtain a copolymer precursor solution, wherein the raw materials comprise maleic acid derivatives, carboxylic acid alkene ester compounds, acrylamide compounds, ethylene and alpha-olefin, and the molar ratio of the maleic acid derivatives, the carboxylic acid alkene ester compounds, the acrylamide compounds, the ethylene and the alpha-olefin is 1: 0-5: 15-30: 5-15; the maleic acid derivative is obtained by reacting maleic anhydride with an amine compound, wherein the amine compound is one selected from diamine and alcohol amine, and the number of carbon atoms of the amine compound is 3-18; the carboxylic acid allyl ester compound is at least one of vinyl formate, acrylic formate, vinyl acetate, acrylic acetate, 3-butylene acetate, 3-hexylene acetate and pent-2-en-1-yl acetate; the acrylamide compound is at least one selected from acrylamide, 2-methacrylamide, diacetone acrylamide and N-alkyl acrylamide, wherein the carbon number of an alkyl group in the N-alkyl acrylamide is 1-18, and the carbon number of the alpha-olefin is 3-24;
and hydrolyzing, separating and purifying the copolymer precursor in the copolymer precursor solution to obtain the copolymer.
In one embodiment, the step of reacting maleic anhydride with an amine compound to obtain the maleic acid derivative specifically comprises: adding the maleic anhydride into a second solvent, heating to dissolve, adding the amine compound, continuously heating to 90-130 ℃, carrying out acylation reaction for 3-10 hours, and carrying out desolventizing; wherein the molar ratio of the maleic anhydride to the amine compound is 1: 1.1-2.2.
In one embodiment, the step of copolymerizing the raw materials in the first solvent to obtain the copolymer precursor solution specifically includes: adding the maleic acid derivative, the carboxylic acid alkenyl ester compound, the acrylamide compound, the ethylene and the alpha-olefin into a first solvent, heating to 45-50 ℃ under a protective atmosphere, adding an initiator, continuously heating to 70-100 ℃, and reacting for 3-10 hours; wherein the initiator is selected from at least one of dibenzoyl peroxide, azobisisobutyronitrile, di-tert-butyl peroxide and cumene hydroperoxide, and the mass of the initiator is 0.1-1% of the total mass of the maleic acid derivative, the carboxylic acid alkene ester compound, the acrylamide compound, the ethylene and the alpha-olefin.
In one embodiment, the step of hydrolyzing, separating and purifying the copolymer precursor in the copolymer precursor solution to obtain the copolymer specifically includes: adding 10-20 wt% sodium hydroxide solution into the copolymer precursor solution, hydrolyzing at 60-90 deg.c for 10-60 min, neutralizing, water washing, drying and desolventizing.
The hydrolysis reaction of the copolymer precursor is mainly to hydrolyze an ester in the carboxylic acid alkene ester monomer into an alcohol and a part of amide into a carboxylic acid, and the obtained copolymer contains various polar groups such as a hydroxyl group, a carboxyl group, an amino group, an amide group, an ester group and the like.
The antistatic agent comprises the following components in parts by weight:
20 to 40 parts of the copolymer or the copolymer prepared by the preparation method of the copolymer, 10 to 20 parts of fatty acid amide, 5 to 15 parts of poly fatty acid ester, 0 to 10 parts of imide compound and 40 to 70 parts of diluent.
In one embodiment, the fatty acid amide is selected from at least one of myristamidopropyldimethyl tertiary amine, palmitamidopropyldimethyl tertiary amine, stearamidoethyldiethyl tertiary amine, and stearamidopropyldimethyl tertiary amine; and/or the poly fatty acid ester is selected from at least one of poly glycerol laurate, poly glycerol palmitate, poly glycerol monostearate, polyoxyethylene sorbitan monolaurate and polyoxyethylene monopalmitate; and/or the imide compound is selected from at least one of bis-succinimide, alkyl succinimide, polyisobutylene bis-succinimide and polyisobutylene succinimide, wherein the alkyl succinimide has 8-16 alkyl carbon atoms; and/or the diluent is an aromatic hydrocarbon solvent with 8-15 carbon atoms.
The antistatic agent is applied to aviation kerosene as an additive.
In one embodiment, the additive is added in a mass concentration of 1ppm to 10ppm of the aviation kerosene.
The above copolymer has the following effects: (1) the conductivity decay is slow. Because the copolymer forms intramolecular hydrogen bonds, polar groups are adducted, and the molecular surface is mostly nonpolar groups, the copolymer is not easy to be adsorbed on the inner wall of a container or the surface of a pipeline, so that the conductivity decay is slow; (2) the antistatic effect is good. The copolymer is rich in amide groups with strong polarity, intramolecular hydrogen bond bonds formed by the amide groups are short and long, and are further ionized into positive and negative ions to generate dipole electric field strength, so that the electric pressure generated by an external electrostatic field is offset, and the antistatic property is good; (3) the applicability is strong. On one hand, a leakage charge channel is formed through the ion conduction of polar groups or ionized groups, and static charges are dissipated; on the other hand, intramolecular hydrogen bonds with various types and bond lengths are formed, and the generated anti-electric field can be matched with almost all electrostatic fields, especially strong electrostatic fields; (4) no antistatic stabilizer is required. The polar group of the copolymer can form intramolecular hydrogen bond, the antistatic mechanism is between ionic type and nonionic type, the stable antistatic effect and conductivity can be kept without adding a stabilizer, and the cost is reduced; (5) good oil solubility and good water separation performance. The copolymer introduces alpha-olefin, and polar groups are adducted, so that the molecular surface active groups are few, the oil solubility is good, and the water separation performance is good; (6) has the additional functions of pour point depression, ice prevention and the like. The ethylene and alpha-olefin long chains in the polymer play a role of providing crystal seeds for wax crystallization, and the polar groups are adsorbed on the surface of wax crystals to play a role of poisoning the wax crystals, so that the condensation point of the aviation kerosene can be reduced, and the problem of low-temperature fluidity possibly occurring in the high-altitude use process of the aviation kerosene is solved; in addition, the polymer has certain water binding capacity and certain anti-icing effect due to a large number of polar groups.
Through the test: the antistatic agent containing the copolymer has slow conductivity decay, good water separation characteristic and good oil product applicability. In addition, the antistatic agent does not contain heavy metal, sulfur, phosphorus and other elements in the traditional antistatic agent, and no metal ash is generated after combustion, so that the environmental pollution is small.
Drawings
FIG. 1 is a flow chart of a method of preparing a copolymer according to one embodiment.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
An embodiment of a copolymer is prepared from starting materials comprising: maleic acid derivatives, alkenyl carboxylate compounds, acrylamide compounds, ethylene and alpha-olefins;
wherein: the molar ratio of the maleic acid derivative to the alkenyl carboxylate compound to the acrylamide compound to the ethylene to the alpha-olefin is 1: 0 to 5: 15 to 30: 5 to 15;
the maleic acid derivative is obtained by reacting maleic anhydride with an amine compound, wherein the amine compound is selected from one of diamine and alcohol amine; the amine compound has 3 to 18 carbon atoms.
The carboxylic acid allyl ester compound is at least one of vinyl formate, acrylic formate, vinyl acetate, acrylic acetate, 3-butylene acetate, 3-hexylene acetate and pent-2-en-1-yl acetate; further, the carboxylic acid alkene ester compound is at least one selected from vinyl acetate, acrylic ester and 3-butylene acetate.
The acrylamide compound is at least one selected from acrylamide, 2-methacrylamide, diacetone acrylamide and N-alkyl acrylamide, wherein the carbon number of an alkyl group in the N-alkyl acrylamide is 1-18; further, the acrylamide compound is acrylamide or 2-methacrylamide.
The alpha-olefin has 3 to 24 carbon atoms.
In one embodiment, the molar ratio of the maleic acid derivative, the alkenyl carboxylate compound, the acrylamide compound, the ethylene and the alpha-olefin is 1: 1-3: 2-4: 20-25: 8-12; and/or the amine compound has 5 to 10 carbon atoms; and/or the alpha-olefin has 8 to 12 carbon atoms; and/or; the number average molecular weight of the copolymer is 5000-50000.
The above copolymer has at least the following effects: (1) the conductivity decay is slow. Because the copolymer forms intramolecular hydrogen bonds, polar groups are adducted, and the molecular surface is mostly nonpolar groups, the copolymer is not easy to be adsorbed on the inner wall of a container or the surface of a pipeline, so that the conductivity decay is slow; (2) the antistatic effect is good. The copolymer is rich in amide groups with strong polarity, intramolecular hydrogen bond bonds formed by the amide groups are short and long, and are further ionized into positive and negative ions to generate dipole electric field strength, so that the electric pressure generated by an external electrostatic field is offset, and the antistatic property is good; (3) the applicability is strong. On one hand, a leakage charge channel is formed through the ion conduction of polar groups or ionized groups, and static charges are dissipated; on the other hand, intramolecular hydrogen bonds with various types and bond lengths are formed, and the generated anti-electric field can be matched with almost all electrostatic fields, especially strong electrostatic fields; (4) no antistatic stabilizer is required. The polar group of the copolymer can form intramolecular hydrogen bond, the antistatic mechanism is between ionic type and nonionic type, the stable antistatic effect and conductivity can be kept without adding a stabilizer, and the cost is reduced; (5) good oil solubility and good water separation performance. The copolymer introduces alpha-olefin, and polar groups are adducted, so that the molecular surface active groups are few, the oil solubility is good, and the water separation performance is good; (6) has the additional functions of pour point depression, ice prevention and the like. The ethylene and alpha-olefin long chains in the polymer play a role of providing crystal seeds for wax crystallization, and the polar groups are adsorbed on the surface of wax crystals to play a role of poisoning the wax crystals, so that the condensation point of the aviation kerosene can be reduced, and the problem of low-temperature fluidity possibly occurring in the high-altitude use process of the aviation kerosene is prevented; in addition, the polymer has certain water binding capacity and certain anti-icing effect due to a large number of polar groups.
As shown in fig. 1, a method for preparing a copolymer according to an embodiment includes the steps of:
step S110: carrying out copolymerization reaction on the raw materials in a first solvent to obtain a copolymer precursor solution.
The raw materials in the step S110 comprise maleic acid derivatives, carboxylic acid alkene ester compounds, acrylamide compounds, ethylene and alpha-olefin, wherein the molar ratio of the maleic acid derivatives, the carboxylic acid alkene ester compounds, the acrylamide compounds, the ethylene and the alpha-olefin is 1: 0-5: 15-30: 5-15; the maleic acid derivative is obtained by reacting maleic anhydride with an amine compound, wherein the amine compound is one selected from diamine and alcohol amine, and the number of carbon atoms of the amine compound is 3-18; the carboxylic acid allyl ester compound is at least one of vinyl formate, acrylic formate, vinyl acetate, acrylic acetate, 3-butylene acetate, 3-hexylene acetate and pent-2-en-1-yl acetate; the acrylamide compound is at least one selected from acrylamide, 2-methacrylamide, diacetone acrylamide and N-alkyl acrylamide, wherein the carbon number of an alkyl group in the N-alkyl acrylamide is 1-18; the alpha-olefin has 3 to 24 carbon atoms. Further, the carboxylic acid alkene ester compound is at least one selected from vinyl acetate, acrylic ester and 3-butylene acetate. Further, the acrylamide compound is acrylamide or 2-methacrylamide.
In one embodiment, the molar ratio of the maleic acid derivative, the alkenyl carboxylate compound, the acrylamide compound, the ethylene and the alpha-olefin is 1: 1-3: 2-4: 20-25: 8-12; and/or the amine compound has 5 to 10 carbon atoms; and/or the alpha-olefin has 8 to 12 carbon atoms; and/or; the number average molecular weight of the copolymer is 5000-50000.
In one embodiment, the step of reacting maleic anhydride with an amine compound to obtain the maleic acid derivative specifically includes: adding maleic anhydride into a second solvent, heating to dissolve, adding the amine compound, continuously heating to 90-130 ℃, carrying out acylation reaction for 3-10 hours, and carrying out desolventizing; wherein the molar ratio of the maleic anhydride to the amine compound is 1: 1.1-2.2; preferably, the molar ratio of the maleic anhydride to the amine compound is 1: 2. It will be appreciated that the maleic acid derivative described above, if a commercially available finished product is purchased, need not be synthesized by itself and this step may be omitted.
In one embodiment, the first solvent is at least one selected from petroleum ether, toluene, xylene, trimethylbenzene and tetramethylbenzene, and the amount of the first solvent added is 0.5 to 2 times the total mass of the maleic acid derivative, the alkenyl carboxylate compound, the acrylamide compound, ethylene and the α -olefin.
In one embodiment, the second solvent is at least one selected from petroleum ether, toluene, xylene, mixed trimethylbenzene and mixed tetramethylbenzene, and the addition amount of the second solvent is 0.5 to 2 times of the total mass of the maleic anhydride and the amine compound.
Specifically, step S110 includes: adding the maleic acid derivative, the carboxylic acid alkenyl ester compound, the acrylamide compound, the ethylene and the alpha-olefin into a first solvent, heating to 45-50 ℃ under a protective atmosphere, adding an initiator, continuously heating to 70-100 ℃, and reacting for 3-10 hours; wherein the initiator is at least one selected from dibenzoyl peroxide, azobisisobutyronitrile, di-tert-butyl peroxide and cumene hydroperoxide, and the mass of the initiator is 0.1-1% of the total mass of maleic acid derivatives, carboxylic acid alkene ester compounds, acrylamide compounds, ethylene and alpha-olefin.
Step S120: and hydrolyzing, separating and purifying the copolymer precursor in the copolymer precursor solution to obtain the copolymer.
Specifically, step S120 includes: adding 10-20 wt% sodium hydroxide solution into the copolymer precursor solution, hydrolyzing at 60-90 deg.c for 10-60 min, neutralizing, water washing, drying and desolventizing.
The hydrolysis reaction of the copolymer precursor is mainly a hydrolysis reaction of an ester in the alkenyl carboxylate monomer to an alcohol and a hydrolysis reaction of a part of an amide to a carboxylic acid, and the resulting copolymer contains a plurality of polar groups such as a hydroxyl group, a carboxyl group, an amino group, an amide group, and an ester group.
It is understood that the neutralization, water washing, drying and desolventizing treatment in step S120 are conventional separation and purification operations in the art, and the purpose of the neutralization, water washing, drying and desolventizing treatment is to remove impurities such as sodium chloride and the like and solvents in the hydrolyzed solution, thereby obtaining a relatively pure copolymer. In one embodiment, the separation and purification operations are: after the hydrolysis reaction is finished, cooling to room temperature, neutralizing with hydrochloric acid solution until the pH value is 6-7, washing with water for 2-3 times in an amount which is 0.5-2 times the mass of the reaction raw materials, and then using anhydrous Na2SO4Drying and finally desolventizing.
The antistatic agent of one embodiment comprises the following components in parts by weight:
20 to 40 parts of the copolymer or the copolymer prepared by the preparation method of the copolymer, 10 to 20 parts of fatty acid amide, 5 to 15 parts of poly fatty acid ester, 0 to 10 parts of imide compound and 40 to 70 parts of diluent.
In one embodiment, the fatty acid amide is at least one selected from the group consisting of myristylamidopropyl dimethyl tertiary amine, palmitylamidopropyl dimethyl tertiary amine, stearamidoethyl diethyl tertiary amine, and stearamidopropyl dimethyl tertiary amine; and/or the poly fatty acid ester is selected from at least one of poly glycerol laurate, poly glycerol palmitate, poly glycerol monostearate, polyoxyethylene sorbitan monolaurate and polyoxyethylene monopalmitate; and/or the imide compound is selected from at least one of bis-succinimide, alkyl succinimide, polyisobutylene bis-succinimide and polyisobutylene succinimide, wherein the alkyl succinimide has 8-16 alkyl carbon atoms; and/or the diluent is an aromatic hydrocarbon solvent with 8-15 carbon atoms.
Further, the fatty acid amide is selected from one of stearamidoethyldiethyltertiary amine and stearamidopropyldimethyltertiary amine.
Further, the number average molecular weight of the poly fatty acid ester is 1000-10000; preferably, the poly fatty acid ester is selected from the group consisting of polyglycerol laurate having a number average molecular weight of 2000 to 5000 or polyglycerol palmitate having a number average molecular weight of 2000 to 5000.
Further, the number average molecular weight of the polyisobutylene bis-succinimide or polyisobutylene succinimide is 500-2000; further, the imide compound is selected from the group consisting of bis-succinimide and polyisobutylene bis-succinimide having a number average molecular weight of 1000 to 1200.
Further, the diluent is at least one selected from xylene, mixed trimethylbenzene, mixed tetramethylbenzene and heavy aromatic hydrocarbon; further, trimethylbenzene or tetramethylbenzene is preferable.
The antistatic agent preferably comprises the following components in parts by weight:
25 to 35 parts of the copolymer or the copolymer prepared by the preparation method of the copolymer, 12 to 18 parts of fatty acid amide, 8 to 12 parts of poly fatty acid ester, 4 to 8 parts of imide compound and 50 to 60 parts of diluent.
The fatty acid amide plays a supporting role, so that the long-chain side group of the copolymer is in a stretching state, the stability and the antistatic effect of the copolymer are improved, and a dipole ion pair can be formed with the macromolecular copolymer in the presence of an external electrostatic field, the intensity of the external electrostatic field is reduced, and the antistatic effect of a product is enhanced; in addition, the fatty acid amide also has a corrosion inhibition effect, and can inhibit the corrosion of acidic substances in the oil products to engine parts.
The imide compound and the copolymer have synergistic antistatic property, and simultaneously have cleaning and dispersing effects, so that the accumulation and deposition of high-temperature oxidation products of the fuel can be prevented, the harm of the high-temperature oxidation products of the fuel can be effectively reduced, and the high-temperature thermal oxidation stability of the aviation kerosene can be improved.
The poly fatty acid ester in the above components provides antistatic performance, and also has solubilizing and anti-wear effects.
The antistatic agent is applied to aviation kerosene as an additive.
In one embodiment, the additive is added in a mass concentration of 1ppm to 10ppm of the aviation kerosene. Preferably, the mass concentration of the additive in the aviation kerosene is 2 ppm-5 ppm of the aviation kerosene.
Through the test: the antistatic agent containing the copolymer has slow conductivity decay, good water separation characteristic and good oil product applicability. In addition, the antistatic agent does not contain heavy metal, sulfur, phosphorus and other elements in the traditional antistatic agent, and no metal ash is generated after combustion, so that the environmental pollution is small.
The following is an example section:
in the following examples, unless otherwise specified, components not specifically indicated except for inevitable impurities are not contained; unless otherwise specified, the parts of the raw materials in each example and comparative example are parts by mass.
Example 1
The antistatic agent of this example was prepared as follows:
1. preparation of the copolymer
(1) Adding 0.1mol of maleic anhydride and xylene (equivalent to the total mass of the reaction raw materials in the step) into a reaction kettle, heating to dissolve, adding a mol of amine compound A (A is abbreviated as A in Table 1), continuously heating to 90 ℃, carrying out acylation reaction for 4 hours, and carrying out desolventization to obtain the maleic acid derivative.
(2) Adding the maleic acid derivative, ethylene and 1-nonene into dimethylbenzene (the molar ratio is equal to the total mass of the reaction raw materials in the step) according to the molar ratio of 1: 15: 5, heating to 45 ℃ under the protection of nitrogen, adding azobisisobutyronitrile accounting for 0.2 percent of the total mass of the reaction raw materials, continuously heating to 90 ℃, and reacting for 5 hours to obtain a copolymer precursor solution.
(3) Adding 15 percent by mass of sodium hydroxide aqueous solution, heating to 70 ℃, carrying out hydrolysis reaction for 30 minutes, neutralizing, washing with water, drying, and carrying out desolventizing treatment to obtain the copolymer.
2. Preparation of antistatic agent
30 parts of the copolymer prepared above, 10 parts of palmitoylamidopropyl dimethyl tertiary amine, 10 parts of polyglycerol laurate and 45 parts of mesitylene were mixed and stirred at 50 ℃ for 1 hour to prepare antistatic agents, which were designated as antistatic agents #1 to # 14.
3. Effect testing
(1) Conductivity testing of antistatic agents
The antistatic agents #1 to #14 prepared in the above way are respectively added into aviation kerosene distillate oil (the conductivity is 2S/m) of Daqing hydrocracking process according to the dosage of 5ppm, the mixture is stirred for 1 hour at the temperature of 30 ℃, the conductivity of the aviation kerosene containing the antistatic agents is measured after the mixture is stabilized for 12 hours, a test instrument is an MAIHAK MLA 900 digital conductivity measuring instrument, and the test method is GB/T6539 'aviation fuel and distillate fuel conductivity measuring method'. The results are shown in Table 1.
(2) Water separation index of antistatic agent
The antistatic agents #1 to #14 prepared above were added to aviation kerosene distillate oil (water separation index 96) of Daqing hydrocracking process at 5ppm, respectively, stirred at 30 ℃ for 1 hour, and the water separation index of aviation kerosene containing the antistatic agent was measured according to GB/11129-89 jet fuel water separation index measurement method, and the test instrument was a model 1104 CRC measurement instrument. The results are shown in Table 1.
TABLE 1
| Numbering | A | a1(mol) | Number average molecular weight | Conductivity (pS/m) | Index of water separation |
| 1 | Octanediamine | 0.11 | 22000 | 339 | 73 |
| 2 | Octanediamine | 0.15 | 23000 | 358 | 73 |
| 3 | Octanediamine | 0.2 | 25000 | 374 | 77 |
| 4 | Octanediamine | 0.22 | 25000 | 370 | 75 |
| 5 | Propane diamine | 0.2 | 19000 | 354 | 75 |
| 6 | Pentanediamine | 0.2 | 23000 | 373 | 76 |
| 7 | Decamethylenediamine | 0.2 | 24000 | 374 | 78 |
| 8 | Dodecanediamine | 0.2 | 25000 | 366 | 75 |
| 9 | Octadecanediamine | 0.2 | 26000 | 345 | 74 |
| 10 | N-propanolamine | 0.2 | 18000 | 349 | 75 |
| 11 | 5-amino-1-pentanol | 0.2 | 20000 | 372 | 77 |
| 12 | 8-amino-1-octanol | 0.2 | 21000 | 373 | 78 |
| 13 | 10-amino-1-decanols | 0.2 | 22000 | 372 | 77 |
| 14 | 12-amino-1-dodecanol | 0.2 | 22000 | 363 | 74 |
From the data in table 1, it can be seen that: firstly, when the molar ratio of the maleic anhydride to the amine compound is 1: 2, the antistatic agent has better effect; the diamine is preferably pentanediamine, octanediamine or decamethylenediamine; the alcohol amine is preferably 5-amino-1-pentanol, 8-amino-1-octanol or 10-amino-1-decanol.
Example 2
1. Preparation of the copolymer
(1) Dissolving 0.1mol of maleic acid derivative corresponding to antistatic agent #3 in example 1, B2 mol of carboxylic acid alkenyl ester compound B (abbreviated as B in Table 2), C2 mol of acrylamide compound C (abbreviated as C in Table 2), d 2mol of ethylene and E2 mol of alpha-olefin (abbreviated as E in Table 2) in trimethylbenzene (equivalent to the total mass of the reaction raw materials in the step), heating to 45 ℃ under the protection of nitrogen, adding dibenzoyl peroxide accounting for 0.3 percent of the total mass of the reaction raw materials, continuously heating to 100 ℃, and reacting for 3 hours to obtain a copolymer precursor solution;
(2) adding 20 percent sodium hydroxide aqueous solution by mass fraction, heating to 60 ℃, carrying out hydrolysis reaction for 50 minutes, neutralizing, washing with water, drying, and carrying out desolventizing treatment to obtain the copolymer.
2. Preparation of antistatic agent
25 parts of the copolymer prepared above, 15 parts of stearamidoethyl diethyl tertiary amine, 8 parts of polyglycerol laurate and 50 parts of durene were mixed and stirred at 50 ℃ for 1 hour to prepare antistatic agents #15 to # 45.
3. Effect testing
The antistatic agents #15 to #45 prepared above were added to the aviation kerosene distillate oil of daqing hydrocracking process in an amount of 4ppm, respectively, and the other evaluation conditions were the same as in example 1, and the conductivity and water separation index of the aviation kerosene were measured, and the results are shown in table 2.
TABLE 2
As can be seen from the data in table 2: the antistatic agent has a good effect when the molar ratio of the maleic acid derivative to the carboxylic acid alkenyl ester compound to the acrylamide compound to the ethylene to the alpha-olefin is 1 to (1-3) to (2-4) to (20-25) to (8-12); the carboxylic acid alkenyl ester compound is preferably vinyl acetate, acrylic ester acetate or 3-butylene acetate; the acrylamide compound is preferably acrylamide or 2-methacrylamide; the alpha-olefin is preferably octene or 1-dodecene.
Example 3
1. Preparation of the copolymer
(1) Dissolving 0.1mol of maleic acid derivative corresponding to antistatic agent #3 in example 1, 0.2mol of vinyl acetate, 0.3mol of acrylamide, 2mol of ethylene and 1mol of octene in tetramethylbenzene (corresponding to the total mass of the reaction raw materials in the step), heating to 50 ℃ under the protection of nitrogen, adding azobisisobutyronitrile accounting for f% of the total mass of the reaction raw materials, continuously heating to T ℃, and reacting for T hours to obtain a copolymer precursor solution;
(2) adding 10% sodium hydroxide aqueous solution, heating to 80 deg.C for hydrolysis reaction for 40 min, neutralizing, washing with water, drying, and desolventizing to obtain copolymer.
2. Preparation of antistatic agent
20 parts of the prepared copolymer, 20 parts of myristyl amido propyl dimethyl tertiary amine, 12 parts of polyglycerol monostearate, 4 parts of bis-succinimide and 60 parts of heavy aromatic hydrocarbon are mixed and stirred for 1 hour at the temperature of 50 ℃, and antistatic agents #46 to #58 are prepared.
3. Effect testing
The antistatic agents #46 to #58 prepared above were added to the aviation kerosene distillate of daqing hydrocracking process in an amount of 3ppm, respectively, and the conductivity and water separation index of the aviation kerosene were measured under the same other evaluation conditions as in example 1. The results are shown in Table 3.
TABLE 3
From the data in table 3, it can be seen that: the mass of the initiator is 0.3-0.5% of the total mass of the reaction raw materials, the reaction temperature is 80-90 ℃, the reaction time is 5-7 hours, and the prepared antistatic agent has good effect.
Example 4
1. Preparation of antistatic agent
Antistatic agents #59 to #87 were prepared by mixing and stirring H1 parts of the copolymer used in preparation of antistatic agent #53 in example 3, H2 parts of fatty acid amide F (abbreviated as F in Table 4), H3 parts of poly fatty acid ester G (abbreviated as G in Table 4), H4 parts of imide compound H (abbreviated as H in Table 4), and H5 parts of diluent J (abbreviated as J in Table 4) at 50 ℃ for 2 hours.
2. Effect testing
The antistatic agents #59 to #87 obtained by the above preparation were added to the aviation kerosene distillate oil of daqing hydrocracking process in an amount of 2ppm, respectively, and the conductivity and water separation index of the aviation kerosene were measured under the same other evaluation conditions as in example 1. The results are shown in Table 4.
TABLE 4
Note: the number average molecular weight of polyglycerol laurate, polyglycerol palmitate and polyglycerol monostearate in table 4 was 2000; the number average molecular weight of the polyisobutylene bis-succinimide and polyisobutylene succinimide is 1000.
From the data in table 4, it can be seen that: firstly, when the mass parts of the copolymer, the fatty acid amide, the poly fatty acid ester, the imide compound and the diluent are respectively 25 to 35 parts, 12 to 18 parts, 8 to 12 parts, 4 to 8 parts and 50 to 60 parts, the antistatic agent has better effect; the fatty acid amide is preferably stearamidoethyl diethyl tertiary amine or stearamidopropyl dimethyl tertiary amine; ③ the poly fatty acid ester is preferably poly glycerol laurate (number average molecular weight 2000) or poly glycerol palmitate (number average molecular weight 2000); the imide compound is preferably selected from the group consisting of bis-succinimide and polyisobutylene bis-succinimide (number average molecular weight 1000); the diluent is preferably mixed trimethylbenzene or mixed tetramethylbenzene.
Example 5
The #56, #63 and #86 antistatic agents were added to the aviation kerosene distillate oil of daqing hydrocracking process in respective dosages of 1ppm, 2ppm, 5ppm, 7ppm and 10ppm, and the conductivity and water separation index of the aviation kerosene after standing for 0h, 12h, 24h, 4 days, 15 days and 30 days were respectively measured, and other evaluation conditions were the same as in example 1. The antistatic effect of the antistatic product ST450 of the imported aviation kerosene is taken as comparison data, and the result is shown in Table 5.
TABLE 5
From the data in table 5, it can be seen that: compared with an imported antistatic product ST450, the aviation kerosene added with the antistatic agent has higher conductivity and higher water separation index when the dosage is the same; secondly, after standing for the same time, the conductivity of the aviation kerosene added with the antistatic agent is increased quickly and attenuated slowly, and the water separation index is stable; the conductivity of the aviation kerosene added with the ST450 antistatic agent is slowly increased and quickly attenuated, so that the conductivity and the water separation index of the aviation kerosene possibly cannot meet the requirements of GB 6537-2006 (the ex-factory conductivity is 150 pS/m-450 pS/m, and the water separation index is not lower than 70) after the aviation kerosene is stored for a long time.
Example 6
Adding antistatic agents #73 and #78 to hydrocracking process (daqing) aviation kerosene (conductivity 2pS/m, water separation index 96), straight run process (shijiazhuang) aviation kerosene (conductivity 12pS/m, water separation index 97) and hydrogenation process (swallow) aviation kerosene (conductivity 0pS/m, water separation index 95) respectively according to the addition amount of 3ppm, and testing the conductivity and the water separation index of the aviation kerosene under the same other evaluation conditions as in example 1; and the antistatic effect of the antistatic product ST450 of the imported aviation kerosene is taken as a comparative example, and the test results are shown in Table 6.
TABLE 6
From the data in table 6, it can be seen that: the antistatic agent has good applicability to aviation kerosene of different processes, and the conductivity and the water separation index of the antistatic agent can reach the national standards of aviation kerosene execution.
From the test results of the above examples, it can be seen that the antistatic agent of the present invention or the antistatic agent prepared by the preparation method described in the present invention has slow conductivity decay, good water separation characteristics, and good oil applicability.
In addition, the antistatic agent does not contain heavy metal, sulfur, phosphorus and other elements in the traditional antistatic agent, and no metal ash is generated after combustion, so that the environmental pollution is small.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The copolymer is characterized in that raw materials for preparing the copolymer comprise maleic acid derivatives, carboxylic acid alkene ester compounds, acrylamide compounds, ethylene and alpha-olefin; wherein:
the molar ratio of the maleic acid derivative, the carboxylic acid alkenyl ester compound, the acrylamide compound, the ethylene and the alpha-olefin is 1 (1-3): 2-4): 20-25): 8-12;
the maleic acid derivative is obtained by reacting maleic anhydride with an amine compound, wherein the amine compound is one selected from diamine and alcohol amine, and the number of carbon atoms of the amine compound is 5-10;
the carboxylic acid allyl ester compound is at least one of vinyl formate, acrylic formate, vinyl acetate, acrylic acetate, 3-butylene acetate, 3-hexylene acetate and pent-2-en-1-yl acetate;
the acrylamide compound is at least one selected from acrylamide, 2-methacrylamide, diacetone acrylamide and N-alkyl acrylamide, wherein the carbon atom number of an alkyl group in the N-alkyl acrylamide is 1-18;
the carbon atom number of the alpha-olefin is 8-12; the number average molecular weight of the copolymer is 5000-50000;
the preparation of the copolymer comprises the following steps:
carrying out copolymerization reaction on the raw materials in a first solvent to obtain a copolymer precursor solution; and
and hydrolyzing, separating and purifying the copolymer precursor in the copolymer precursor solution to obtain the copolymer.
2. A method for preparing a copolymer, comprising the steps of:
carrying out copolymerization reaction on raw materials in a first solvent to obtain a copolymer precursor solution, wherein the raw materials comprise maleic acid derivatives, carboxylic acid alkenyl ester compounds, acrylamide compounds, ethylene and alpha-olefin, and the molar ratio of the maleic acid derivatives, the carboxylic acid alkenyl ester compounds, the acrylamide compounds, the ethylene and the alpha-olefin is 1 (1-3) to (2-4) to (20-25) to (8-12); the maleic acid derivative is obtained by reacting maleic anhydride with an amine compound, wherein the amine compound is one selected from diamine and alcohol amine, and the number of carbon atoms of the amine compound is 5-10; the carboxylic acid allyl ester compound is at least one of vinyl formate, acrylic formate, vinyl acetate, acrylic acetate, 3-butylene acetate, 3-hexylene acetate and pent-2-en-1-yl acetate; the acrylamide compound is at least one selected from acrylamide, 2-methacrylamide, diacetone acrylamide and N-alkyl acrylamide, wherein the carbon atom number of an alkyl group in the N-alkyl acrylamide is 1-18; the carbon atom number of the alpha-olefin is 8-12; the number average molecular weight of the copolymer is 5000-50000;
and hydrolyzing, separating and purifying the copolymer precursor in the copolymer precursor solution to obtain the copolymer.
3. The method for preparing the copolymer according to claim 2, wherein the step of reacting the maleic acid derivative with the amine compound comprises: adding the maleic anhydride into a second solvent, heating to dissolve, adding the amine compound, continuously heating to 90-130 ℃, carrying out acylation reaction for 3-10 hours, and carrying out desolventizing; wherein the molar ratio of the maleic anhydride to the amine is 1 (1.1-2.2).
4. The method for preparing the copolymer according to claim 2, wherein the step of copolymerizing the raw materials in the first solvent to obtain the copolymer precursor solution specifically comprises: adding the maleic acid derivative, the carboxylic acid alkenyl ester compound, the acrylamide compound, the ethylene and the alpha-olefin into the first solvent, heating to 45-50 ℃ under a protective atmosphere, adding an initiator, continuously heating to 70-100 ℃, and reacting for 3-10 hours; the initiator is selected from at least one of dibenzoyl peroxide, azobisisobutyronitrile, di-tert-butyl peroxide and cumene hydroperoxide, and the mass of the initiator is 0.1% -1% of the total mass of the maleic acid derivative, the carboxylic acid alkene ester compound, the acrylamide compound, the ethylene and the alpha-olefin.
5. The method for preparing the copolymer according to claim 4, wherein the step of hydrolyzing, separating and purifying the copolymer precursor in the copolymer precursor solution to obtain the copolymer specifically comprises: adding 10-20% by mass of sodium hydroxide solution into the copolymer precursor solution, carrying out hydrolysis reaction for 10-60 minutes at 60-90 ℃, and then carrying out neutralization, water washing, drying and desolventizing treatment.
6. The antistatic agent is characterized by comprising the following components in parts by weight:
20 to 40 parts of the copolymer according to claim 1 or the copolymer prepared by the method according to any one of claims 2 to 5, 10 to 20 parts of fatty acid amide, 5 to 15 parts of poly fatty acid ester, 0 to 10 parts of imide compound and 40 to 70 parts of diluent; the fatty acid amide is at least one selected from myristylamidopropyl dimethyl tertiary amine, palmitylamidopropyl dimethyl tertiary amine, stearamidoethyl diethyl tertiary amine and stearamidopropyl dimethyl tertiary amine; the poly fatty acid ester is selected from at least one of poly glycerol laurate, poly glycerol palmitate and poly glycerol monostearate.
7. The antistatic agent according to claim 6, wherein the imide compound is at least one selected from the group consisting of a bissuccinimide, an alkyl succinimide, a polyisobutylene bissuccinimide, and a polyisobutylene succinimide, wherein the alkyl succinimide has an alkyl group having 8 to 16 carbon atoms; and/or the diluent is an aromatic hydrocarbon solvent with 8-15 carbon atoms.
8. The antistatic agent according to claim 6 or 7, characterized in that it comprises the following components in parts by mass: 25-35 parts of the copolymer, 12-18 parts of the fatty acid amide, 8-12 parts of the poly fatty acid ester, 4-8 parts of the imide compound and 50-60 parts of the diluent.
9. Use of an antistatic agent as claimed in any one of claims 6 to 8 as an additive in jet fuel.
10. The application of the antistatic agent as an additive in aviation kerosene according to claim 9, wherein the additive is added in a mass concentration of 1 ppm-10 ppm of the aviation kerosene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910158498.7A CN109970899B (en) | 2019-03-01 | 2019-03-01 | Copolymer and preparation method thereof, antistatic agent containing copolymer and application of antistatic agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910158498.7A CN109970899B (en) | 2019-03-01 | 2019-03-01 | Copolymer and preparation method thereof, antistatic agent containing copolymer and application of antistatic agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109970899A CN109970899A (en) | 2019-07-05 |
| CN109970899B true CN109970899B (en) | 2021-08-10 |
Family
ID=67077771
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910158498.7A Active CN109970899B (en) | 2019-03-01 | 2019-03-01 | Copolymer and preparation method thereof, antistatic agent containing copolymer and application of antistatic agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109970899B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111500204A (en) * | 2020-06-15 | 2020-08-07 | 杭州福斯特应用材料股份有限公司 | Adhesive film, composition for forming the same, and electronic device |
| WO2024050715A1 (en) * | 2022-09-07 | 2024-03-14 | 广东香与生物科技有限公司 | Amide compounds having amino groups on both ends, preparation method therefor, and use thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1420135A (en) * | 2001-11-15 | 2003-05-28 | 中日合成化学股份有限公司 | Antistatic material and mfg. method thereof |
| BRPI0506110A (en) * | 2005-11-10 | 2007-08-14 | Braskem Sa | antistatic composition useful in polymerization or copolymerization of suspended olefins, polymerization or copolymerization process of suspended olefins, and olefin polymer or copolymer |
| CN105400555B (en) * | 2015-12-11 | 2017-08-25 | 广昌达新材料技术服务（深圳）股份有限公司 | A kind of environmentally friendly oil antistatic agent and its application method |
| CN108192004B (en) * | 2017-12-28 | 2021-01-26 | 深圳市广昌达石油添加剂有限公司 | Quadripolymer, preparation method thereof and application thereof in crude oil pour point depressant |
| CN108997521A (en) * | 2018-06-20 | 2018-12-14 | 深圳市广昌达石油添加剂有限公司 | A kind of multiple copolymer and preparation method thereof as pour point depression of crude oil thinner |
-
2019
- 2019-03-01 CN CN201910158498.7A patent/CN109970899B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109970899A (en) | 2019-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109970899B (en) | Copolymer and preparation method thereof, antistatic agent containing copolymer and application of antistatic agent | |
| US3440029A (en) | Gasoline containing anti-icing additive | |
| CN101691510B (en) | Novel compound gasoline antiknock agent | |
| CN102363735B (en) | Preparation method of alcohol ether boric acid ester type DOT4 braking fluid | |
| JPS63179996A (en) | Novel reaction product and ori suppressing car fuel composition | |
| KR20070104274A (en) | Additives for minimizing injector fouling and valve deposits and their uses | |
| PL172553B1 (en) | Polyfunctional detergent additive to petrols | |
| US4581040A (en) | Polyoxyisopropylenediamine-acid anhydride-polyamine reaction product and motor fuel composition containing same | |
| US4643738A (en) | Polyoxyisopropylenediamine-acid anhydride-n-alkyl-alkylene diamine reaction product and motor fuel composition containing same | |
| CN111500328B (en) | Methanol fuel composite additive | |
| CN102888259A (en) | Efficient compound additive of methanol gasoline and preparation method thereof | |
| CN103695050B (en) | Vehicle methanol gasoline composite additive | |
| CN113862050A (en) | Multifunctional fuel oil additive and preparation method thereof | |
| CN107573986A (en) | A kind of electric power electrical apparatus conserves protective agent and its production and use online | |
| CN106498405B (en) | Oil-soluble inhibitor and preparation method thereof | |
| CN108315061A (en) | Automobile exhaust detergent | |
| US4944770A (en) | Motor fuel additive and ori-inhibited motor fuel composition | |
| US4865622A (en) | ORI-inhibited and deposit-resistant motor fuel composition | |
| CN109082311B (en) | Green and environment-friendly gasoline additive | |
| CN111394141A (en) | Environment-friendly energy-saving automobile detergent and preparation method thereof | |
| US4869728A (en) | Motor fuel additive and ORI-inhibited motor fuel composition | |
| US4981493A (en) | ORI-Inhibited and deposit-resistant motor fuel composition | |
| JP4986355B2 (en) | Fuel additive | |
| US4865621A (en) | Ori-inhibited and deposit-resistant motor fuel composition | |
| KR101697877B1 (en) | Esters of alkoxylated quaternary ammonium salts and fuels containing them |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Chen Ao Inventor after: Yan Bin Inventor after: Xiong Jing Inventor after: Hu Taoying Inventor before: Hu Taoying Inventor before: Chen Ao Inventor before: Yan Bin Inventor before: Xiong Jing |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |