CN113402705B - Polyether amine and preparation method and application thereof - Google Patents
Polyether amine and preparation method and application thereof Download PDFInfo
- Publication number
- CN113402705B CN113402705B CN202010180314.XA CN202010180314A CN113402705B CN 113402705 B CN113402705 B CN 113402705B CN 202010180314 A CN202010180314 A CN 202010180314A CN 113402705 B CN113402705 B CN 113402705B
- Authority
- CN
- China
- Prior art keywords
- polyether
- reaction
- catalyst
- amine
- epoxy
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/338—Polymers modified by chemical after-treatment with inorganic and organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/325—Polymers modified by chemical after-treatment with inorganic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/33306—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33396—Polymers modified by chemical after-treatment with organic compounds containing nitrogen having oxygen in addition to nitrogen
-
- 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
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
- C10L1/2387—Polyoxyalkyleneamines (poly)oxyalkylene amines and derivatives thereof (substituted by a macromolecular group containing 30C)
-
- 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
- C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
Abstract
The invention provides polyether amine and a preparation method and application thereof. The preparation method comprises the following steps: catalyst SO 4 ‑2 /ZrO 2 Adding the epoxy chloropropane into polyether, and then adding the epoxy chloropropane to perform epoxidation reaction to obtain a reaction solution; separating the reaction liquid and recovering the catalyst SO 4 ‑2 /ZrO 2 And epichlorohydrin to obtain a chlorohydrin intermediate; adding solid alkali into the chlorohydrin intermediate product to carry out ring closure reaction to obtain crude epoxy group end-capped polyether; filtering the crude epoxy polyether, adding a neutralizing agent into the filtrate for neutralization, and then adding an adsorbent to obtain refined epoxy capped polyether; and (3) subjecting the refined epoxy group end capped polyether and organic amine and/or inorganic ammonium to amination reaction to obtain polyether amine. The invention adopts SO 4 ‑2 /ZrO 2 As a catalyst for ring-opening reaction, the catalyst has high selectivity, few byproducts, no corrosiveness to equipment and easy separation after the reaction is finished, and has good industrial application value; meanwhile, the amination of the epoxy group end capped polyether has the advantages of high reaction speed and low production cost.
Description
Technical Field
The invention relates to the field of petrochemical industry, in particular to polyether amine for a fuel oil detergent, and a preparation method and application thereof.
Background
Unsaturated hydrocarbons, sulfur and nitrogen compounds in the automotive gasoline in China are more, and the automotive gasoline is easy to oxidize to form colloid in the storage and use processes, so that carbon deposits are easy to form at the positions of a nozzle, an air inlet valve, a combustion chamber and the like in the combustion process of the gasoline, further the problems of unsmooth oil supply, incomplete combustion, reduced maneuvering performance, increased oil consumption and the like of an engine are caused, and a large amount of harmful tail gas is discharged. In recent years, with the continuous increase of the keeping amount of domestic automobiles, the air pollution caused by the emission of automobile exhaust pollutants is more serious, and the elimination of the environmental protection problem caused by the emission is not enough. Research at home and abroad shows that adding the detergent into the gasoline is a practical and effective measure for improving the quality of the gasoline, improving the combustion efficiency of the gasoline and realizing energy conservation and emission reduction.
The gasoline detergent is a surface active substance which can disperse and solubilize potential sediments formed by oxidation in gasoline into the gasoline to prevent the potential sediments from depositing on key parts of an engine. For the sediments formed at the parts, the detergent can be peeled off from the metal surface and dispersed and peptized in the gasoline, so that the engine is recovered to a normal working state, and the gasoline is fully combusted, thereby effectively reducing the emission of automobile exhaust pollutants, reducing air pollution and simultaneously achieving the effect of saving the gasoline.
The components that play a major role in gasoline detergents are typically organic polymeric amines, mainly polyisobutylene amines and polyether amines. Polyetheramines are a generic term for a class of chemical substances whose molecular structure comprises polyether and amine structures. Compared with polyisobutene amine, ether bond in polyether amine is easy to crack at high temperature, and can effectively control the sediments of a fuel nozzle and an air inlet valve and obviously reduce the carbon deposit generation of a combustion chamber. Therefore, the development and application of polyether amine detergents in recent years are increasingly paid attention to by researchers at home and abroad, and are hot spots for developing new products of fuel detergents.
The synthesis method of polyether amine mainly comprises a high-pressure catalytic ammonification method, a leaving group method, an aminophenoxy method, a hydrolysis method, a nitrile alkylation method and the like. The catalytic reduction ammonification method is a main method for industrial synthesis of polyether amine at present, and the industrial production of foreign polyether amine mostly adopts the catalytic reduction ammonification method. The process starts with polyether polyols whose terminal hydroxyl groups are replaced by amino (amine) groups by ammonolysis. High conversion rate and high quality of catalytic reduction ammonification methodThe noble metal catalyst is good, but the price is high, high-temperature and high-pressure reaction is needed, the equipment investment and the operation cost are high, and the catalyst is only suitable for large-scale industrial production. The leaving group method is generally divided into two steps: starting from the active hydrogen of the hydroxyl at the tail end of polyether polyol, and blocking by using a compound (p-toluenesulfonic acid acetate, acyl chloride, halogen, carboxyl, aldehyde and the like) with an easy leaving group or an unsaturated group and the active hydrogen; and then carrying out amination reaction, and reacting the product obtained in the first step with amine (monoamine or polyamine) to obtain polyether amine. The method for synthesizing the polyetheramine has the defects that a large amount of alkali is needed during the post-treatment of the product, the environment is easy to pollute, and particularly, the corrosion performance of the gasoline detergent is not good due to the fact that chlorine, sulfur and other impurities are introduced into the polyetheramine. Aminophenoxy is also carried out by starting from the active hydrogen of the terminal hydroxyl groups of polyether polyols, using compounds having unsaturated groups (-NCO, -CN, -NO) 2 Etc.) are blocked with active hydrogen and then treated accordingly to give polyetheramines. The method has simple process route, but has a plurality of side reactions in the reaction process of polyether polyol and compound with unsaturated groups, so the method has strict requirements on reaction conditions and is difficult to actually operate. Hydrolysis is widely applicable, but there is a small amount of chain extension reaction in the reaction process, and urethane groups are present in the product, and the viscosity of the product is greater than that of the original polyether polyol. The polyether nitrile alkylation method for preparing polyether amine has high cost, and the reaction raw material acrylonitrile is extremely toxic and is rarely applied in industry.
At present, the epoxy-terminated polyether method mainly comprises the following two steps:
the first is a one-step process, namely a phase transfer process: polyether and epichlorohydrin are used as raw materials, and the target product is directly produced by reaction in the presence of a phase transfer catalyst and solid or solution of alkali such as sodium hydroxide or potassium hydroxide. In the synthetic process, epoxy chloropropane is easy to generate ring-opening polymerization side reaction under alkaline condition, so that the reaction efficiency is low, the oligomers in the product are more, and the color of the product is easy to deepen.
The second is a two-step process: polyether and epoxy chloropropane are used as raw materials, ring-opening reaction is carried out in the presence of an acid catalyst (such as concentrated sulfuric acid, boron trifluoride diethyl ether, anhydrous stannic chloride, stannous dichloride, anhydrous aluminum chloride and the like) to obtain a chlorohydrin intermediate, and then ring-opening reaction is carried out on the intermediate in an alkaline environment by using alkali to remove hydrogen chloride, so that a target product is obtained.
Because the one-step method is difficult to control, the byproducts of the product are more, and the open-loop and closed-loop two-step method is mainly adopted for producing the epoxy polyether at home and abroad at present. The catalyst is generally Lewis acid catalyst such as titanium tetrachloride, boron trifluoride diethyl ether and the like or protonic acid such as concentrated sulfuric acid, perchloric acid and the like, and the acidic catalyst can corrode reaction equipment and is inconvenient to use and difficult to recycle; the selectivity in the ring-opening reaction is poor, and the intermediate product contains more byproducts, so that the epoxy value of the final product is low, and the use effect is poor.
Chinese patent CN103191761a discloses a solid phase catalyst for loading boron trifluoride on modified activated carbon, which can be used for preparing fatty acid glycidyl ether; chinese patent CN104592166a discloses a molecular sieve supported catalytic synthesis method of allyl glycidyl ether; chinese patent CN101805446a discloses an epoxy group-capped polyether, its synthesis method and application, which is mainly prepared by adding strong base; chinese patent CN101070380a discloses a long-chain polyether type silane coupling agent capped with glycidyl ether group and its synthesis method, which mainly uses lewis acid or lewis base as catalyst to react, then performs ring-closure reaction with inorganic base, and obtains glycidyl ether allyl polyether through post-treatment; chinese patent CN101811007a discloses the use of epoxypropyl-capped polyether in defoamers, wherein strong base is added to the polyether for reaction, and epichlorohydrin is added thereto, thereby producing epoxypropyl-capped polyether; chinese patent CN105330836A adopts solid super acid WO 3 /Al 2 O 3 The method is to impregnate concentrated sulfuric acid and trifluoromethanesulfonic acid together on a molecular sieve as a solid phase catalyst. Chinese patent CN109369902A adopts self-made solid acid Zn (ClO) 4 ) 2 Or Al (ClO) 4 ) 3 As a catalyst, polyether and epichlorohydrin are subjected to ring-opening reaction in a microchannel reactor, and then are subjected to closing reaction in the presence of solid alkaliThe epoxy group end capped polyether is obtained through the ring reaction.
The presently disclosed patent is mainly end capped single molecules, but there is no report of synthesizing long chain large molecular weight end epoxy polyether or aminating end epoxy polyether to prepare polyether amine.
It is noted that the information disclosed in the foregoing background section is only for enhancement of understanding of the background of the invention and therefore it may contain information that does not form the prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the polyether amine which has the advantages of simple production process, low equipment requirement, less three-waste discharge and use effect close to or reaching the international leading level.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for preparing polyetheramine, comprising the steps of:
catalyst SO 4 -2 /ZrO 2 Adding the epoxy chloropropane into polyether, and then adding the epoxy chloropropane to perform epoxidation reaction to obtain a reaction solution;
separating the reaction liquid and recovering the catalyst SO 4 -2 /ZrO 2 And epichlorohydrin to obtain a chlorohydrin intermediate;
adding solid alkali into the chlorohydrin intermediate product to carry out ring closure reaction to obtain crude epoxy group end-capped polyether;
filtering the crude epoxy polyether, adding a neutralizing agent into the filtrate for neutralization, and then adding an adsorbent to obtain refined epoxy capped polyether; and
and (3) subjecting the refined epoxy group end capped polyether and organic amine and/or inorganic ammonium to amination reaction to obtain polyether amine.
In some embodiments, the polyether has a structure represented by formula (I),
wherein R is 0 Selected from hydrogen atoms and optionally substituted C 1-50 Preferably selected from hydrogen atoms, C 1-20 Linear or branched alkyl, substituted by one or more C' s 1-20 C substituted by straight-chain or branched alkyl groups 6-10 Monocyclic or polycyclic aryl groups and substituted by one or more C' s 1-20 C substituted by straight-chain or branched alkyl groups 3-20 Monocyclic or polycyclic cycloalkyl groups, more preferably selected from hydrogen atoms, C 5-15 Straight-chain or branched alkyl and substituted by one or more C' s 5-15 Phenyl substituted by straight chain or branched alkyl;
R u each independently selected from C 2-24 Linear or branched alkylene groups, preferably each independently selected from C 2-12 Linear or branched alkylene groups, more preferably each independently selected from C 2-6 Linear or branched alkylene groups, more preferably each independently selected from-CH 2 -CH 2 -and-CH 2 -CH(CH 3 ) -; and
n is selected from 1 to 100, preferably from 1 to 50, more preferably from 5 to 25.
In some embodiments, the catalyst SO 4 -2 /ZrO 2 The preparation method comprises the following steps:
ZrOCl 2 ·8H 2 O is dissolved in distilled water to obtain saturated zirconium salt-water solution;
dropwise adding dilute ammonia water under stirring to adjust the pH value of the saturated zirconium salt-water solution to 9-10, standing for ageing, and performing suction filtration to obtain a filter cake;
drying the filter cake, grinding into powder, soaking in sulfuric acid solution, filtering, drying and oven drying to obtain the catalyst SO 4 -2 /ZrO 2 。
In some embodiments, the catalyst SO 4 -2 /ZrO 2 The addition amount of the catalyst is 0.2-4% of the total mass of the polyether and the epichlorohydrin, the mol ratio of the polyether to the epichlorohydrin is 1:1-1.5, the reaction time of the epoxidation reaction is 1-2.5 h, and the reaction temperature is 40-80 ℃.
In some embodiments, the molar ratio of the polyether to the solid base is 1:1 to 1.5, the reaction time of the ring closure reaction is 2 to 3 hours, and the reaction temperature is 30 to 50 ℃.
In some embodiments, the neutralizing agent is selected from one or more of phosphoric acid, sulfuric acid, oxalic acid and glacial acetic acid, and the pH value of the filtrate after neutralization is 5-7.
In some embodiments, the adsorbent is selected from one or more of clay, diatomaceous earth, and activated carbon, and the adsorbent is added in an amount of 1 to 5% by mass of the polyether.
In some embodiments, the organic amine is selected from the group consisting of polyene polyamines and C 1 -C 30 And (2) one or more of primary amine, secondary amine and alcohol amine, wherein the inorganic ammonium is selected from one or more of ammonia, ammonia water and inorganic ammonium salt.
In some embodiments, the amination reaction is carried out at a reaction temperature of 90 to 180 ℃ for a reaction time of 2 to 8 hours.
In some embodiments, the amination reaction further comprises adding a catalyst and/or a solvent, wherein the solvent is C 1 -C 8 And alcohol, wherein the catalyst is tertiary amine or phenolic substance.
In some embodiments, the tertiary amine is selected from the group consisting of trimethylamine, triethylamine, tripropylamine, N-dimethylethylamine, N-dimethylpropylamine, N, N-dimethylbutylamine, N-diethylpropylamine, N-dipropyl-1-propylamine, N-diethylbutylamine, N-dimethyl-1, 2-ethylenediamine, N, N-dimethylbutylamine, N-diethylpropylamine, N-dipropyl-1-propylamine, N, N-diethyl butylamine, N-dimethyl-1, 2-ethylenediamine, N, N-diethylpentylamine, N-diethylhexylamine, N-diethylheptylamine, N-diethyloctylamine, N-diethylnonylamine, N, N-diethyldecylamine, N-diethylundecylamine, N-diethyldodecylamine, N-dipropylbutylamine, N-dipropylpentylamine, N, N-diethyl decylamine, N-diethyl undecylamine, N-diethyl dodecylamine, N, N-dipropylbutylamine, N-dipropylpentylamine, N.
In some embodiments, the phenolic material is selected from one or more of phenol, sodium phenolate, hydroquinone, sodium hydroquinone, o-cresol, sodium o-cresol, m-cresol, sodium m-cresol, p-cresol and sodium p-cresol, 2, 4-xylenol, 2,4, 6-trimethylphenol, ethylphenol, sodium ethylbenzene phenol, 2, 4-diethylphenol, 2,4, 6-triethylphenol, p-methoxyphenol, m-methoxyphenol, o-methoxyphenol, sodium p-methoxyphenol, sodium m-methoxyphenol, sodium o-methoxyphenol, phenylphenol, and sodium phenylphenol.
In another aspect, the invention also provides a polyetheramine, which is prepared by the preparation method.
In still another aspect, the invention also provides the use of the polyetheramine described above in a fuel detergent.
The invention adopts solid super acid SO 4 -2 /ZrO 2 The catalyst used for the ring-opening reaction has high selectivity and less byproducts, the catalyst has no corrosiveness to equipment, and the catalyst is easy to separate from reactants after the reaction is finished and can be recycled, so that the catalyst has good industrial application value; meanwhile, polyether amine is obtained by further aminating epoxy group-terminated polyether, and compared with the existing technology for aminating hydroxyl-terminated polyether in a catalytic manner, the method has the advantages of high reaction speed and low production cost; but also can effectively inhibit the generation of engine sediment, thereby achieving excellent effect.
Detailed Description
The technical scheme of the invention is further described below according to specific embodiments. The scope of the invention is not limited to the following examples, which are given for illustrative purposes only and do not limit the invention in any way.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the meaning commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, definitions, will control.
When the specification derives materials, substances, methods, steps, devices, or elements, etc. with the word "known to those skilled in the art", "prior art", or its synonyms, the word "derived" is intended to cover those conventionally used in the art at the time of the application, but also includes those which are not currently commonly used but which would become known in the art to be suitable for similar purposes.
In the context of this specification, any matters or matters not mentioned are directly applicable to those known in the art without modification except as explicitly stated. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are all deemed to be part of the original disclosure or original description of the present invention, and should not be deemed to be a new matter which has not been disclosed or contemplated herein, unless such combination is clearly unreasonable by those skilled in the art.
All of the features disclosed in this invention may be combined in any combination which is understood to be disclosed or described in this invention unless the combination is obviously unreasonable by those skilled in the art. The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Unless explicitly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise clear to the routine knowledge of a person skilled in the art.
Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.
According to a first aspect of the present invention, there is provided a process for the preparation of polyetheramine comprising the steps of:
catalyst SO 4 -2 /ZrO 2 Adding the epoxy chloropropane into polyether, and then adding the epoxy chloropropane to perform epoxidation reaction to obtain a reaction solution;
separating the reaction liquid and recovering the catalyst SO 4 -2 /ZrO 2 And epichlorohydrin to obtain a chlorohydrin intermediate;
adding solid alkali into the chlorohydrin intermediate product to carry out ring closure reaction to obtain crude epoxy group end-capped polyether;
filtering the crude epoxy polyether, adding a neutralizing agent into the filtrate for neutralization, and then adding an adsorbent to obtain refined epoxy capped polyether; and
and (3) subjecting the refined epoxy group end capped polyether to amination reaction with organic amine and/or inorganic ammonium to obtain polyether amine.
Firstly, polyether is used as a starting material and reacts with epichlorohydrin to obtain epoxy group end capped polyether, and the epoxy group end capped polyether further reacts with amine to generate polyether amine through ring opening reaction, namely the polyether amine mainly comprises epoxidation of polyether and amination of epoxy polyether, wherein the epoxidation of polyether comprises epoxidation reaction, catalyst and raw material separation, ring opening reaction and neutralization/adsorption.
The raw polyether used in the invention has a structure shown in the following formula (I),
wherein R is 0 Selected from hydrogen atoms and optionally substituted C 1-50 Preferably selected from hydrogen atoms, C 1-20 Linear or branched alkyl, substituted by one or more C' s 1-20 C substituted by straight-chain or branched alkyl groups 6-10 Monocyclic or polycyclic aryl groups and substituted by one or more C' s 1-20 C substituted by straight-chain or branched alkyl groups 3-20 Monocyclic or polycyclic cycloalkyl groups, more preferably selected from hydrogen atoms, C 5-15 Straight-chain or branched alkyl and substituted by one or more C' s 5-15 Phenyl substituted by straight chain or branched alkyl; r is R u Each independently selected from C 2-24 Linear or branched alkylene groups, preferably each independently selected from C 2-12 Linear or branched alkylene groups, more preferably each independently selected from C 2-6 Linear or branched alkylene groups, more preferably each independently selected from-CH 2 -CH 2 -and-CH 2 -CH(CH 3 ) -; n represents the average degree of polymerization of the polyether segment and is selected from any number between 1 and 100, preferably from any number between 1 and 50, more preferably from any number between 5 and 25.
In the epoxidation reaction, epichlorohydrin is slowly added to the polyether under the protection of an inert gas such as nitrogen, preferably by dropwise addition.
The catalyst used in the epoxidation reaction is a solid superacid catalyst SO 4 -2 /ZrO 2 It can be prepared by the following method:
a certain amount of ZrOCl 2 ·8H 2 O is dissolved in distilled water to obtain saturated zirconium salt-water solution;
dropwise adding dilute ammonia water (volume fraction is 10-15%) under rapid stirring, regulating pH of saturated zirconium salt-water solution to 9-10, standing and aging for about 24 hr, and suction filtering until filtrate is treated with AgNO of 0.1mol/L 3 The solution is inspected to obtain a filter cake;
drying the filter cake for 12h, grinding, and screening (1.05-1.5) multiplied by 10 5 nm powder, soaking in sulfuric acid solution, filtering to remove residual solution, drying the powder, and baking in muffle furnace for 3 hr to obtain catalyst SO 4 -2 /ZrO 2 。
Catalyst SO 4 -2 /ZrO 2 The addition amount of the catalyst is 0.2-4% of the total mass of polyether and epichlorohydrin, the mol ratio of polyether to epichlorohydrin is 1:1-1.5, the reaction time of epoxidation reaction is 1-2.5 h, and the reaction temperature is 40-80 ℃.
After the epoxidation reaction is finished, the reaction solution is separated, and the catalyst SO is recovered by filtration 4 -2 /ZrO 2 And (3) distilling under reduced pressure to recover epoxy chloropropane to obtain a chlorohydrin intermediate product.
Then adding solid alkali to make chlorohydrin intermediate product undergo the process of ring-closing reaction, the solid alkali used in the invention is NaOH or KOH, the mole ratio of polyether and solid alkali is 1:1-1.5, the reaction time of ring-closing reaction is 2-3 h, and the reaction temperature is 30-50 deg.C.
After the ring closure reaction is finished, filtering the crude epoxy polyether, and then neutralizing and adsorbing to obtain refined epoxy capped polyether, wherein the neutralizing agent is one or more selected from phosphoric acid, sulfuric acid, oxalic acid and glacial acetic acid, and the pH value of the neutralized filtrate is controlled within the range of 5-7; the adsorbent is one or more selected from clay, diatomite and active carbon, and the adding amount of the adsorbent is 1-5% of the mass of the polyether.
The amination of epoxy polyether is to make the refined epoxy end capped polyether undergo the process of amination reaction with organic amine and/or inorganic ammonium to obtain polyether amine, in which the organic amine is selected from polyene polyamine and C 1 -C 30 The inorganic ammonium is selected from one or more of ammonia, ammonia water and inorganic ammonium salt, the reaction temperature of amination reaction is 90-180 ℃, and the reaction time is 2-8h.
In the amination reaction, a catalyst and/or a solvent can be added, wherein the solvent is C 1 -C 8 The alcohol and the catalyst are tertiary amine or phenols.
The tertiary amine used as the catalyst is selected from trimethylamine, triethylamine, tripropylamine, N-dimethylethylamine, N-dimethylpropylamine, N, N-dimethylbutylamine, N-diethylpropylamine, N-dipropyl-1-propylamine, N-diethylbutylamine, N-dimethyl-1, 2-ethylenediamine, N, N-dimethylbutylamine, N-diethylpropylamine, N-dipropyl-1-propylamine, N, N-diethyl butylamine, N-dimethyl-1, 2-ethylenediamine, N, N-diethylpentylamine, N-diethylhexylamine, N-diethylheptylamine, N-diethyloctylamine, N-diethylnonylamine, N, N-diethyldecylamine, N-diethylundecylamine, N-diethyldodecylamine, N-dipropylbutylamine, N-dipropylpentylamine, N, N-diethyl decylamine, N-diethyl undecylamine, N-diethyl dodecylamine, N, N-dipropylbutylamine, N-dipropylpentylamine, N.
The phenolic substance used as the catalyst is selected from one or more of phenol, sodium phenolate, hydroquinone, sodium hydroquinone, o-cresol, sodium o-cresol, m-cresol, sodium m-cresol, p-cresol and sodium p-cresol, 2, 4-xylenol, 2,4, 6-trimethylphenol, ethylphenol, sodium ethylbenzene, 2, 4-diethylphenol, 2,4, 6-triethylphenol, p-methoxyphenol, m-methoxyphenol, o-methoxyphenol, sodium p-methoxyphenol, sodium m-methoxyphenol, sodium o-methoxyphenol, phenylphenol and sodium phenylphenol.
The invention adopts solid super acid SO 4 -2 /ZrO 2 The catalyst used for the ring-opening reaction has high selectivity and less byproducts, the catalyst has no corrosiveness to equipment, and the catalyst is easy to separate from reactants after the reaction is finished and can be recycled, so that the catalyst has good industrial application value; meanwhile, polyether amine is obtained by further aminating epoxy group-terminated polyether, and compared with the existing technology for aminating hydroxyl-terminated polyether in a catalytic manner, the method has the advantages of high reaction speed and low production cost.
The polyether amine prepared by the preparation method can be used as a fuel oil detergent, can inhibit and clean carbon deposition of an air inlet valve, a nozzle and a combustion chamber of a gasoline engine, can improve fuel oil economy, and can reduce exhaust pollutant emission.
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the preferred embodiments and not limiting of the invention, and any equivalent examples of equivalent variations are possible by those skilled in the art using the teachings set forth above.
Examples
The epoxy value of the intermediate epoxy polyether was determined in the examples using the method described in GBT1677-1981, and the end-capping rate in the examples is defined as follows: end-capping ratio of epoxy-capped polyether = 100% ×actual measured epoxy value/theoretical epoxy value.
Example 1 solidSuper acid catalyst SO 4 -2 /ZrO 2 Is prepared from
Weighing ZrOCl 2 ·8H 2 O15 g (accurate to 0.0001 g) was dissolved in distilled water to prepare a saturated zirconium salt-water solution.
Dropwise adding 10-15% of diluted ammonia water with volume fraction to adjust pH of the solution to 9-10 under rapid stirring, standing and aging for 24h, filtering, washing with deionized water until the filtrate is washed with 0.1mol/L AgNO 3 The solution was checked for no chloride ions.
Grinding and screening the dried filter cake for 12 hours, and taking (1.05-1.5) multiplied by 10 5 nm powder, soaking in sulfuric acid solution, filtering to remove residual solution, drying the powder, and baking in a muffle furnace for 3 hr to obtain solid super acid catalyst SO 4 -2 /ZrO 2 。
Example 2 preparation of polyetheramines
1) Epoxidation of polyethers.
500g of nonylphenol polyoxypropylene ether and 2.5g of SO 4 -2 /ZrO 2 The catalyst was added to a 1000ml four-necked flask, stirring was started under nitrogen protection, after 10min, the addition of epichlorohydrin was started to 55.5g, after 1h, the temperature was raised to 60℃and the reaction was continued for 2.5h.
After the reaction is finished, cooling to room temperature, filtering and separating the catalyst, and recovering epoxy chloropropane by reduced pressure distillation to obtain an intermediate product. Under the protection of nitrogen, 24g of sodium hydroxide particles are added into the intermediate product, the temperature is raised to 40 ℃ for reaction for 3 hours, and the temperature is reduced to room temperature, so that crude epoxy-terminated polyether is obtained.
Filtering the coarse end epoxy polyether, collecting filtrate, adding oxalic acid into the filtrate to neutralize the filtrate, adding 10g of acid clay to adsorb and refine the filtrate for 1h, and performing spin-steaming dehydration filtration to obtain the refined epoxy end capped polyether. The end capping rate of the obtained polyether is 95.4%.
2) Amination of epoxy polyethers.
Adding the epoxy polyether into an amination reaction kettle, adding 10-20g of liquid ammonia and 3g of triethylamine, and reacting at 150 ℃ for 2-8h. And (5) carrying out rotary steaming on the product to obtain the final polyether amine product.
Example 3 preparation of polyetheramines
1) Epoxidation of polyethers. 500g of nonylphenol polyoxypropylene ether and 2.5g of SO 4 -2 /ZrO 2 The catalyst was added to a 1000ml four-necked flask, stirring was started under nitrogen protection, after 10min, the addition of epichlorohydrin was started to 55.5g, after 1h, the temperature was raised to 60℃and the reaction was continued for 2.5h.
After the reaction is finished, cooling to room temperature, filtering and separating the catalyst, and recovering epoxy chloropropane by reduced pressure distillation to obtain an intermediate product. Under the protection of nitrogen, 24g of sodium hydroxide particles are added into the intermediate product, the temperature is raised to 40 ℃ for reaction for 3 hours, and the temperature is reduced to room temperature, so that crude epoxy-terminated polyether is obtained.
Filtering the coarse end epoxy polyether, collecting filtrate, adding oxalic acid into the filtrate to neutralize the filtrate, adding 10g of acid clay to adsorb and refine the filtrate for 1h, and performing spin-steaming dehydration filtration to obtain the refined epoxy end capped polyether. The end capping rate of the obtained polyether is 95.4%.
2) Amination of epoxy polyethers. Adding the epoxy polyether obtained in the above into an amination reaction kettle, adding 36.6g of ethanolamine and 5g of triethylamine, and reacting at 160 ℃ for 2-8 hours. And (5) carrying out rotary steaming on the product to obtain the final polyether amine product.
Example 4 preparation of polyetheramines
1) Epoxidation of polyethers. 300g of methoxypolyoxyethylene propylene ether and 2g of SO 4 -2 /ZrO 2 The catalyst was added to a 1000ml four-necked flask, stirring was started under nitrogen protection, after 20min, the addition of epichlorohydrin was started to 27.8g, after 1h, the temperature was raised to 70℃and the reaction was continued for 3h.
After the reaction is finished, cooling to room temperature, filtering and separating the catalyst, and recovering epoxy chloropropane by reduced pressure distillation to obtain an intermediate product. Under the protection of nitrogen, 12g of sodium hydroxide particles are added into the intermediate product, the temperature is raised to 40 ℃ for reaction for 3 hours, and the temperature is reduced to room temperature, so that crude epoxy-terminated polyether is obtained.
Filtering the coarse end epoxy polyether, collecting filtrate, adding oxalic acid into the filtrate to neutralize the filtrate, adding 8g of acid clay to adsorb and refine the filtrate for 1h, and performing spin-steaming dehydration filtration to obtain the refined epoxy end capped polyether. The end capping rate of the obtained polyether is 90.23%.
2) Amination of epoxy polyethers. Adding the epoxy polyether obtained in the above into an amination reaction kettle, adding 43.86 tetraethylenetriamine and 1g triethylamine, and reacting at 150 ℃ for 2-7h. And (5) carrying out rotary steaming on the product to obtain the final polyether amine product.
Example 5 preparation of polyetheramines
1) Epoxidation of polyethers. 1466g of butanol polyether (molecular weight 1466) and 9.8g of SO 4 -2 /ZrO 2 The catalyst was added to a 2000ml four-necked flask, stirring was started under nitrogen protection, after 20min, the addition of 94g of epichlorohydrin was started, and after 1h the addition was completed, the temperature was raised to 60℃and the temperature was maintained for reaction for 3h.
After the reaction is finished, cooling to room temperature, filtering and separating the catalyst, and recovering epoxy chloropropane by reduced pressure distillation to obtain an intermediate product. Under the protection of nitrogen, 58.5g of sodium hydroxide particles are added into the intermediate product, the temperature is raised to 35 ℃ for reaction for 3 hours, and the temperature is reduced to room temperature, so that crude epoxy-terminated polyether is obtained.
Filtering the coarse end epoxy polyether, collecting filtrate, adding oxalic acid into the filtrate to neutralize the filtrate, adding 30g of acid clay to adsorb and refine the filtrate for 1h, and performing spin-steaming dehydration filtration to obtain the refined epoxy end capped polyether. The end capping rate of the obtained polyether was 97.2%.
2) Amination of epoxy polyethers. The epoxy polyether obtained above is added into an amination reaction kettle, 66.11g of ethylenediamine and 7.5g of triethylamine are added, the reaction temperature is 150 ℃, and the reaction time is 2-7 hours. And (5) carrying out rotary steaming on the product to obtain the final polyether amine product.
Comparative example 1
The compound of comparative example 1 was a commercial polyetheramine main agent (FL 1000 polyetheramine) produced by Henschel, USA, and was prepared from nonylphenol polyether, ammonia gas and hydrogen gas under high temperature and high pressure conditions, and a noble metal catalyst was also required for the preparation process.
Detergency simulation evaluation experiment
The detergent properties of the compounds of the examples and comparative examples were evaluated on an L-2 gasoline engine intake valve deposit simulation tester. The polymers of examples and comparative examples were dissolved in base gasoline to prepare gasoline compositions having a polymer content of 300ppm, respectively.
These gasoline compositions were each continuously reciprocated at a flow rate of 1.54ml/min to a deposit collecting plate having a deposit collecting plate temperature of 175 ℃. The sediment collection panels were treated and weighed after the end of the experiment. The smaller the deposit collector plate weight gain, the greater the deposit reduction, indicating that the better the gasoline detergent performs to inhibit intake valve deposit formation, the deposit collector plate weight gain data is shown in table 1.
TABLE 1
| Cleaning performance evaluation results | Sediment trap weight gain/mg | Deposit decline rate/% |
| Comparative example (blank) | 10.7 | —— |
| Comparative example 1 | 0.9 | 91.60 |
| Example 2 | 1.2 | 88.79 |
| Example 3 | 2.0 | 81.31 |
| Example 4 | 1.0 | 90.65 |
| Example 5 | 1.3 | 87.85 |
As can be seen from Table 1, the polyether amine compound of the invention has the detergency close to that of commercial polyether amine, can effectively reduce the generation of gasoline sediment, and has the advantages of mild reaction process, high end-capping rate of epoxidation reaction and easily obtained raw materials.
It will be appreciated by persons skilled in the art that the embodiments described herein are merely exemplary and that various other alternatives, modifications and improvements may be made within the scope of the invention. Thus, the present invention is not limited to the above-described embodiments, but only by the claims.
Claims (13)
1. The preparation method of the polyether amine applied to the fuel oil detergent is characterized by comprising the following steps of:
catalyst SO 4 -2 /ZrO 2 Adding the epoxy chloropropane into polyether, and then adding the epoxy chloropropane to perform epoxidation reaction to obtain a reaction solution;
the polyether has a structure shown in the following formula (I),
wherein R is 0 Selected from hydrogen atoms and optionally substituted C 1-50 Is a hydrocarbon group of (2);
R u each independently selected from C 2-24 Linear or branched alkylene; and
n is selected from 1 to 100;
separating the reaction liquid and recovering the catalyst SO 4 -2 /ZrO 2 And epichlorohydrin to obtain chlorohydrin intermediateA material;
adding solid alkali into the chlorohydrin intermediate product to carry out ring closure reaction to obtain crude epoxy group end-capped polyether;
filtering the crude epoxy polyether, adding a neutralizing agent into the filtrate for neutralization, and then adding an adsorbent to obtain refined epoxy capped polyether; and
subjecting the refined epoxy group end capped polyether and organic amine and/or inorganic ammonium to amination reaction to obtain polyether amine;
the amination reaction further comprises the step of adding a catalyst, wherein the catalyst is tertiary amine;
the catalyst SO 4 -2 /ZrO 2 The preparation method comprises the following steps:
ZrOCl 2 ·8H 2 O is dissolved in distilled water to obtain saturated zirconium salt-water solution;
dropwise adding dilute ammonia water under stirring to adjust the pH value of the saturated zirconium salt-water solution to 9-10, standing for ageing, and performing suction filtration to obtain a filter cake;
drying the filter cake, grinding into powder, soaking in sulfuric acid solution, filtering, drying and oven drying to obtain the catalyst SO 4 -2 /ZrO 2 。
2. The method according to claim 1, wherein,
wherein R is 0 Selected from hydrogen atoms, C 1-20 Linear or branched alkyl, substituted by one or more C' s 1-20 C substituted by straight-chain or branched alkyl groups 6-10 Monocyclic or polycyclic aryl groups and substituted by one or more C' s 1-20 C substituted by straight-chain or branched alkyl groups 3-20 Monocyclic or polycyclic cycloalkyl groups, more preferably selected from hydrogen atoms, C 5-15 Straight-chain or branched alkyl and substituted by one or more C' s 5-15 Phenyl substituted by straight chain or branched alkyl;
R u each independently selected from C 2-12 Linear or branched alkylene; and
n is selected from 1 to 50.
3. Root of Chinese characterThe process according to claim 1, wherein the catalyst SO 4 -2 /ZrO 2 The addition amount of the catalyst is 0.2-4% of the total mass of the polyether and the epichlorohydrin, the mol ratio of the polyether to the epichlorohydrin is 1:1-1.5, the reaction time of the epoxidation reaction is 1-2.5 h, and the reaction temperature is 40-80 ℃.
4. The preparation method according to claim 1, wherein the molar ratio of the polyether to the solid base is 1:1-1.5, the reaction time of the ring-closure reaction is 2-3 h, and the reaction temperature is 30-50 ℃.
5. The method according to claim 1, wherein the neutralizing agent is one or more selected from phosphoric acid, sulfuric acid, oxalic acid and glacial acetic acid, and the pH value of the filtrate after neutralization is 5 to 7.
6. The preparation method according to claim 1, wherein the adsorbent is one or more selected from clay, diatomaceous earth and activated carbon, and the amount of the adsorbent added is 1 to 5% by mass of the polyether.
7. The process according to claim 1, wherein the organic amine is selected from the group consisting of polyene polyamines and C 1 -C 30 And (2) one or more of primary amine, secondary amine and alcohol amine, wherein the inorganic ammonium is selected from one or more of ammonia, ammonia water and inorganic ammonium salt.
8. The preparation method according to claim 1, wherein the amination reaction is carried out at a reaction temperature of 90-180 ℃ for a reaction time of 2-8 hours.
9. The process according to claim 1, wherein the amination reaction further comprises adding a catalyst and/or a solvent, wherein the solvent is C 1 -C 8 And alcohol, wherein the catalyst is tertiary amine.
10. The process according to claim 9, wherein the tertiary amine is selected from the group consisting of trimethylamine, triethylamine, tripropylamine, N-dimethylethylamine, N, N-dimethylpropylamine, N-dimethylbutylamine, N-diethylpropylamine, N-dipropyl-1-propylamine, N-diethylbutylamine, N, N-dimethylpropylamine, N-dimethylbutylamine, N-diethylpropylamine, N, N-dipropyl-1-propylamine, N-diethyl butylamine, N, N-dimethyldodecylamine, N-diethylpentylamine, N-diethylhexylamine, N-diethylheptylamine, N-diethyloctylamine, N, N-diethyl-nonanamine, N-diethyl-decane amine, N-diethyl-undecane amine, N-diethyl-dodecyl-amine, N-dipropyl-butylamine, N, N-diethyl-nonylamine, N-diethyl-decylamine, N-diethyl-undecylamine, N, N-diethyl-dodecyl amine, N-dipropyl butylamine, N.
11. The method of claim 9, wherein the phenolic is selected from one or more of phenol, sodium phenolate, hydroquinone, sodium hydroquinone, o-cresol, sodium o-cresol, m-cresol, sodium m-cresol, p-cresol and sodium p-cresol, 2, 4-xylenol, 2,4, 6-trimethylphenol, ethylphenol, sodium ethylbenzene phenolate, 2, 4-diethylphenol, 2,4, 6-triethylphenol, p-methoxyphenol, m-methoxyphenol, o-methoxyphenol, sodium p-methoxyphenol, sodium m-methoxyphenol, sodium o-methoxyphenol, phenylphenol and sodium phenylphenol.
12. Polyetheramine, characterized in that it is obtainable by the process according to any one of claims 1 to 11.
13. Use of the polyetheramine of claim 12 in a fuel detergent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010180314.XA CN113402705B (en) | 2020-03-16 | 2020-03-16 | Polyether amine and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010180314.XA CN113402705B (en) | 2020-03-16 | 2020-03-16 | Polyether amine and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113402705A CN113402705A (en) | 2021-09-17 |
| CN113402705B true CN113402705B (en) | 2023-05-05 |
Family
ID=77675985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010180314.XA Active CN113402705B (en) | 2020-03-16 | 2020-03-16 | Polyether amine and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113402705B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114249894B (en) * | 2021-11-29 | 2022-10-14 | 四川大学 | Ether-containing polymer containing active group and preparation method and application thereof |
| CN114874431B (en) * | 2022-06-13 | 2023-03-28 | 江南大学 | Preparation method of tertiary amine-terminated polyether type nonionic surfactant |
| CN115926140B (en) * | 2022-12-24 | 2023-07-25 | 江南大学 | N, N-dibutyl polyether amine nonionic surfactant, preparation thereof, tetrabutylammonium hydroxide developer based on N, N-dibutyl polyether amine nonionic surfactant and preparation thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106543447A (en) * | 2016-10-23 | 2017-03-29 | 中海油天津化工研究设计院有限公司 | A kind of preparation method of hyper-branched type high water-content crude oil demulsifier |
| CN109369902A (en) * | 2018-10-23 | 2019-02-22 | 扬州晨化新材料股份有限公司 | A kind of synthetic method of epoxy radicals end-blocking polyethers |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7423112B2 (en) * | 2004-05-27 | 2008-09-09 | Bayer Materialscience Llc | Polyether polyols containing pendant amine groups and a process for their preparation |
-
2020
- 2020-03-16 CN CN202010180314.XA patent/CN113402705B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106543447A (en) * | 2016-10-23 | 2017-03-29 | 中海油天津化工研究设计院有限公司 | A kind of preparation method of hyper-branched type high water-content crude oil demulsifier |
| CN109369902A (en) * | 2018-10-23 | 2019-02-22 | 扬州晨化新材料股份有限公司 | A kind of synthetic method of epoxy radicals end-blocking polyethers |
Non-Patent Citations (1)
| Title |
|---|
| 固体酸SO42-/ZrO2催化合成大豆油基多元醇;李楠等;《中国油脂》;20120620;第37卷(第6期);第67-71页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113402705A (en) | 2021-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113402705B (en) | Polyether amine and preparation method and application thereof | |
| CN103374085B (en) | A kind of Mannich base, its manufacture method and application thereof | |
| CN104761718B (en) | A kind of novel polyether amine and its synthetic method as gasoline cleaning agent | |
| DE19947631A1 (en) | Process for the preparation of highly branched polyols based on glycidol | |
| CN113061242B (en) | Polyether amine compound, preparation method and application thereof | |
| WO2020133062A1 (en) | Method for preparing reactive sealant resin | |
| CN101343358A (en) | End capping polyether prepared with end hydroxyl radical polyether and preparation thereof | |
| CN112028787A (en) | Beta-hydroxyalkylamide curing agent and preparation method and application thereof | |
| CN1740139A (en) | Hydrogenation of methylenedianiline | |
| CN107915836B (en) | Polyether amine and preparation method thereof | |
| CN110283315B (en) | Method for producing hydroxyl silicone oil by using methyl chlorosilane by-product | |
| CN114437334B (en) | Polyether amine compound, preparation method and application thereof | |
| EP1112994B1 (en) | Method of removing boron from polyalkyl hydroxyaromatics | |
| CN112521595B (en) | Synthetic method for preparing amino-terminated polyether polyol through hydrogen catalytic amination | |
| CN113444237B (en) | Quaternized polyether reverse demulsifier and preparation method thereof | |
| CN116041690A (en) | Polyether amine gasoline detergent and synthetic method thereof | |
| CN110484315B (en) | Gasoline detergent and preparation method thereof | |
| CN1046730A (en) | The preparation method of polyether polyhydroxy-compound | |
| CN100590110C (en) | Production method for vinyl ethers | |
| CN109970572B (en) | Synthetic method of double-bond end-capping compound | |
| EP3385299B1 (en) | Amine polymer and preparation method and use thereof. | |
| CN1052017C (en) | A fuel composition containing alkylphenyl poly(oxyalkylene) polyamine polyamine acid ester | |
| CN114805649B (en) | Synthesis method of main agent Mannich base of gasoline detergent | |
| CN116284738A (en) | Polyether amine and preparation method and application thereof | |
| CN1142194C (en) | Process to make aminated polyolefins |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |