阅读说明：本技术 聚醚胺及其制备方法和应用 (Polyether amine and preparation method and application thereof ) 是由 张瑞军 张建荣 黄作鑫 于 2020-03-16 设计创作，主要内容包括：本发明提供一种聚醚胺及其制备方法和应用。该制备方法包括：将催化剂SO-4～(-2)/ZrO-2加入到聚醚中,之后加入环氧氯丙烷进行环氧化反应,得到反应液；对所述反应液进行分离,回收所述催化剂SO-4～(-2)/ZrO-2和环氧氯丙烷,得到氯醇中间产物；向所述氯醇中间产物中加入固体碱进行闭环反应,得到粗环氧基封端聚醚；对所述粗环氧基聚醚进行过滤后,向滤液中加入中和剂中和,再加入吸附剂,得到精制环氧基封端聚醚；将所述精制环氧基封端聚醚与有机胺和/或无机铵进行胺化反应,得到聚醚胺。本发明采用SO-4～(-2)/ZrO-2作为开环反应的催化剂,其选择性高、副产物少、对设备无腐蚀性,反应结束后易分离,具有很好的工业化应用价值；同时环氧基封端聚醚的胺化具有反应速度快、生产成本低的优点。(The invention provides polyether amine and a preparation method and application thereof. The preparation method comprises the following steps: adding catalyst SO 4 ‑2 /ZrO 2 Adding the mixture into polyether, and then adding epoxy chloropropane to perform epoxidation reaction to obtain reaction liquid; separating the reaction solution 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 terminated polyether; filtering the crude epoxy polyether, adding a neutralizing agent into the filtrate for neutralization, and then addingAdding an adsorbent to obtain refined epoxy terminated polyether; and carrying out amination reaction on the refined epoxy-terminated polyether and organic amine and/or inorganic ammonium to obtain polyether amine. In the invention, SO is used 4 ‑2 /ZrO 2 As a catalyst for ring-opening reaction, the catalyst has high selectivity, few byproducts, no corrosion to equipment, easy separation after the reaction is finished, and good industrial application value; meanwhile, the amination of the epoxy-terminated polyether has the advantages of high reaction speed and low production cost.)

1. The preparation method of the polyether amine is characterized by comprising the following steps:

adding catalyst SO₄ ^-2/ZrO₂Adding the mixture into polyether, and then adding epoxy chloropropane to perform epoxidation reaction to obtain reaction liquid;

separating the reaction solution and recovering the catalyst SO₄ ^-2/ZrO₂And epichlorohydrin to obtain a chlorohydrin intermediate;

adding solid alkali into the chlorohydrin intermediate product to carry out ring-closure reaction to obtain crude epoxy terminated polyether;

filtering the crude epoxy polyether, adding a neutralizer into the filtrate for neutralization, and then adding an adsorbent to obtain refined epoxy terminated polyether; and

and carrying out amination reaction on the refined epoxy-terminated polyether and organic amine and/or inorganic ammonium to obtain polyether amine.

2. The method according to claim 1, wherein the polyether has a structure represented by the following formula (I),

wherein R is₀Selected from hydrogen atoms and optionally substituted C_1-50Preferably selected from hydrogen atoms, C_1-20Straight or branched chain alkyl, substituted by one or more C_1-20Straight or branched alkyl substituted C_6-10Monocyclic or polycyclic aryl and substituted by one or more C_1-20Straight or branched alkyl substituted C_3-20Monocyclic or polycyclic cycloalkyl radicals, more preferably selected from hydrogen atoms, C_5-15Straight or branched chain alkyl and substituted by one or more C_5-15Straight or branched chain alkyl substituted phenyl;

R_ueach independently selected from C_2-24Straight or branched alkylene, preferably each independently selected from C_2-12Straight or branched alkylene, more preferably each independently selected from C_2-6Straight or branched alkylene, more preferably each independently selected from-CH₂-CH₂-and-CH₂-CH(CH₃) -; and

n is selected from 1 to 100, preferably from 1 to 50, and more preferably from 5 to 25.

3. Preparation process according to claim 1, characterized in that the catalyst SO is₄ ^-2/ZrO₂The preparation method comprises the following steps:

ZrOCl₂·8H₂Dissolving O in distilled water to obtain saturated zirconium salt-water solution;

dropwise adding dilute ammonia water while stirring to adjust the pH value of the saturated zirconium salt-water solution to 9-10, standing and aging, and then performing suction filtration to obtain a filter cake;

drying the filter cake, grinding the filter cake into powder, adding the powder into a sulfuric acid solution for soaking, and then filtering, drying and drying the solution to obtain the catalyst SO₄ ^-2/ZrO₂。

4. Preparation process according to claim 1, characterized in that the catalyst SO is₄ ^-2/ZrO₂The addition amount of the epoxy chloropropane is 0.2-4% of the total mass of the polyether and the epoxy chloropropane, the molar ratio of the polyether to the epoxy chloropropane is 1: 1-1.5, the reaction time of the epoxidation reaction is 1-2.5 h, and the reaction temperature is 40-80 ℃.

5. The preparation method according to claim 1, wherein the molar ratio of the polyether to the solid base is 1: 1-1.5, the ring-closure reaction is carried out for 2-3 h, and the reaction temperature is 30-50 ℃.

6. The preparation 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 neutralized filtrate is 5-7.

7. The preparation method according to claim 1, wherein the adsorbent is one or more selected from clay, diatomite and activated carbon, and the addition amount of the adsorbent is 1-5% of the mass of the polyether.

8. According to the claimsThe process according to claim 1, wherein the organic amine is selected from the group consisting of polyene polyamine and C₁-C₃₀And the inorganic ammonium is selected from one or more of ammonia gas, ammonia water and inorganic ammonium salt.

9. The preparation method according to claim 1, wherein the amination reaction is carried out at a temperature of 90 to 180 ℃ for 2 to 8 hours.

10. The method according to claim 1, wherein the amination further comprises adding a catalyst and/or a solvent, wherein the solvent is C₁-C₈Alcohol, and the catalyst is tertiary amine or phenolic substance.

11. The process according to claim 10, wherein the tertiary amine is selected from the group consisting of trimethylamine, triethylamine, tripropylamine, N-dimethylethylamine, N-dimethylpropylamine, N-dimethylbutylamine, N-diethylpropylamine, N-dipropyl-1-propylamine, N-diethylbutylamine, N-dimethyl-1, 2-ethylenediamine, N-dimethyl-1, 3-propanediamine, N-dimethylpentylamine, N-dimethylhexylamine, N-dimethylheptylamine, N-dimethyloctylamine, N-dimethylnonylamine, N-dimethyldecylamine, N-dimethylundecylamine, N-dimethyldodecylamine, N-dimethyldodecylamine, One or more of N, N-diethylpentylamine, N-diethylhexylamine, N-diethylheptylamine, N-diethyloctylamine, N-diethylnonylamine, N-diethyldecylamine, N-diethylundecylamine, N-diethyldodecylamine, N-dipropylbutylamine, N-dipropylpentylamine, N-dipropylhexylamine, N-dipropylheptylamine, N-dipropyloctylamine, N-dipropylnonylamine, N-dipropyldecylamine, N-dipropylundecylamine, N-dipropyldodecylamine, triphenylamine, and N, N-dimethylbenzylamine.

12. The method of claim 10, wherein the phenolic substance is selected from one or more of phenol, sodium phenolate, hydroquinone, sodium hydroquinone, o-cresol, m-cresol, p-cresol and p-cresol, 2, 4-xylenol, 2,4, 6-tricresol, ethylphenol, sodium ethylphenol, 2, 4-diethylphenol, 2,4, 6-triethylphenol, p-methoxyphenol, m-methoxyphenol, o-methoxyphenol, p-methoxyphenol, m-methoxyphenol, o-methoxyphenol, phenylphenol and sodium phenylphenol.

13. Polyetheramine, characterized in that it is obtained by the preparation process according to any one of claims 1 to 12.

14. Use of the polyetheramine of claim 13 in a fuel detergent.

Technical Field

The invention relates to the field of petrochemical industry, in particular to polyether amine for a fuel detergent, and a preparation method and application thereof.

Background

The automobile gasoline in China has high content of unsaturated hydrocarbons, sulfur and nitrogen compounds, and is easily oxidized to form colloid in the storage and use processes, so that carbon deposits are easily formed at positions such as 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 quantity of automobiles kept in China, air pollution caused by the emission of automobile exhaust pollutants is increasingly serious, and the elimination of the environmental protection problem caused by the emission of the automobile exhaust pollutants is still difficult. Domestic and foreign researches show that adding a detergent into gasoline is a practical and effective measure for improving the quality of gasoline, improving the combustion efficiency of gasoline and realizing energy conservation and emission reduction.

The gasoline detergent is a surface active substance, and can disperse and solubilize potential deposits formed by oxidation in gasoline in the gasoline and prevent the potential deposits from depositing in key parts of an engine. For the sediments formed at the parts, the detergent can be stripped from the metal surface, and the sediments are dispersed and peptized in the gasoline, so that the engine recovers the normal working state, the gasoline is fully combusted, the emission of automobile exhaust pollutants is effectively reduced, the air pollution is reduced, and the effect of saving the gasoline is also achieved.

The main components of gasoline detergents are usually organic high molecular amine compounds, mainly polyisobutylene amines and polyether amines. The polyether amine is a generic name of a chemical substance, and the molecular structure of the polyether amine comprises polyether and amine structures. Compared with polyisobutene amine, ether bonds in polyether amine are easy to crack at high temperature, and the deposit of a fuel nozzle and an air inlet valve is effectively controlled, and meanwhile, the carbon deposit in a combustion chamber is remarkably reduced. Therefore, in recent years, the development and application of the polyetheramine detergent are more and more emphasized by researchers at home and abroad, and the polyetheramine detergent is a hot spot for developing new products of fuel detergents.

The synthesis method of the polyether amine mainly comprises a high-pressure catalytic ammoniation method, a leaving group method, an amino phenoxy method, a hydrolysis method, a nitrile alkylation method and the like. The catalytic reduction ammoniation method is a main method for industrial synthesis of polyether amine at present, and the catalytic reduction ammoniation method is mostly adopted for industrial production of the foreign polyether amine. The method starts with the terminal hydroxyl group of polyether polyol, and replaces the terminal hydroxyl group with an amino (amine) group by aminolysis reaction. The catalytic reduction ammoniation method has high product conversion rate and good quality, but the used noble metal catalyst is expensive, needs high-temperature and high-pressure reaction, has higher equipment investment and operation cost, and is only suitable for large-scale industrial production. The leaving group process is generally carried out in two steps: starting with active hydrogen of hydroxyl at the tail end of polyether polyol, and carrying out end capping by using a compound (p-toluenesulfonic acid vinyl, acyl chloride, halogen, carboxyl, aldehyde group and the like) with an easy-to-leave group or an unsaturated group and the active hydrogen; and 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 polyether amine has the defects that a large amount of alkali is needed during the product post-treatment, the environment is easily polluted, and particularly, chlorine, sulfur and other impurities are introduced into the product polyether amine, so that the corrosion performance of the gasoline detergent is not good. The aminophenoxy process is also based on the active hydrogen of the terminal hydroxyl groups of the polyether polyols, with unsaturated groups (-NCO, -CN, -NO)₂Etc.) with active hydrogen, and then obtaining the polyether amine after corresponding treatment. The method has simple process route, but in the reaction process of the polyether glycol and the compound with unsaturated groups, the side reaction is more, so the method has strict requirements on reaction conditions and difficult actual operation. The hydrolysis method has wide applicability, but a small amount of chain extension reaction exists in the reaction process, urethane groups exist in the product, and the viscosity of the product is higher than that of the initial polyether polyol. The polyether nitrile alkylation method for preparing the polyether amine has high cost andthe acrylonitrile as a reaction raw material is extremely toxic and is rarely applied to industry.

Currently, there are two main epoxy-terminated polyether methods:

the first is a one-step process, i.e. phase transfer: polyether and epoxy chloropropane are used as raw materials and react in the presence of a phase transfer catalyst and solid or solution of alkali such as sodium hydroxide or potassium hydroxide to directly generate a target product. In the synthesis process of the method, epichlorohydrin is easy to generate ring-opening polymerization side reaction under alkaline conditions, so that the reaction efficiency is low, the number of oligomers in the product is large, and the color of the product is easy to deepen.

The second is a two-step process: polyether and epichlorohydrin are used as raw materials, ring opening reaction is carried out in the presence of acid catalysts (such as concentrated sulfuric acid, boron trifluoride ether, anhydrous stannic chloride, stannous dichloride, anhydrous aluminum chloride and the like) to obtain a chlorohydrin intermediate, and then alkali is used to carry out ring-closing reaction on the intermediate in an alkaline environment to remove hydrogen chloride, so as to obtain a target product.

Because the one-step method is difficult to control and the by-products of the products are more, the epoxy-terminated polyether is mainly produced by a ring-opening and ring-closing two-step method at home and abroad at present. The catalyst is generally Lewis acid catalyst such as titanium tetrachloride, boron trifluoride 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, is inconvenient to use and is difficult to recycle; the selectivity is poor in the ring-opening reaction, and the intermediate product contains more byproducts, so that the epoxy value of the final product is low, and the using effect is poor.

Chinese patent CN103191761A discloses a solid phase catalyst which is prepared by loading boron trifluoride on modified active carbon and can be used for preparing fatty acid glycidyl ether; chinese patent CN104592166A discloses a molecular sieve immobilized catalytic synthesis method of allyl glycidyl ether; chinese patent CN101805446A discloses an epoxy terminated polyether and a synthesis method and application thereof, which mainly comprises adding strong base to prepare the epoxy terminated polyether; chinese patent CN101070380A discloses a glycidyl ether group end-capped long-chain polyether silane coupling agent and a synthesis method thereof, which mainly adopts Lewis acid or Lewis acidThe Si-base is used as a catalyst for reaction, and then the glycidyl ether-based allyl polyether is obtained through post-treatment by inorganic base ring-closing reaction; chinese patent CN101811007A discloses the application of epoxy propyl terminated polyether in defoaming agent, adding strong base into polyether to react, then adding epichlorohydrin to prepare epoxy propyl terminated polyether; chinese patent CN105330836A adopts solid super acid WO₃/Al₂O₃The 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)₂Or Al (ClO)₄)₃As a catalyst, polyether and epichlorohydrin are subjected to ring-opening reaction in a microchannel reactor, and then subjected to ring-closing reaction in the presence of solid alkali to obtain epoxy-terminated polyether.

The patents disclosed so far are mainly terminated single molecules, but there has not been any report on synthesizing long-chain high-molecular-weight epoxy-terminated polyether or aminating the epoxy-terminated polyether to prepare polyether amine.

It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute 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 near or international advanced use effect.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of polyether amine comprises the following steps:

adding catalyst SO₄ ^-2/ZrO₂Adding the mixture into polyether, and then adding epoxy chloropropane to perform epoxidation reaction to obtain reaction liquid;

separating the reaction solution and recovering the catalyst SO₄ ^-2/ZrO₂And epichlorohydrin to obtain a chlorohydrin intermediate；

Adding solid alkali into the chlorohydrin intermediate product to carry out ring-closure reaction to obtain crude epoxy terminated polyether;

filtering the crude epoxy polyether, adding a neutralizer into the filtrate for neutralization, and then adding an adsorbent to obtain refined epoxy terminated polyether; and

and carrying out amination reaction on the refined epoxy-terminated polyether and organic amine and/or inorganic ammonium to obtain polyether amine.

In some embodiments, the polyether has the structure shown in formula (I),

wherein R is₀Selected from hydrogen atoms and optionally substituted C_1-50Preferably selected from hydrogen atoms, C_1-20Straight or branched chain alkyl, substituted by one or more C_1-20Straight or branched alkyl substituted C_6-10Monocyclic or polycyclic aryl and substituted by one or more C_1-20Straight or branched alkyl substituted C_3-20Monocyclic or polycyclic cycloalkyl radicals, more preferably selected from hydrogen atoms, C_5-15Straight or branched chain alkyl and substituted by one or more C_5-15Straight or branched chain alkyl substituted phenyl;

R_ueach independently selected from C_2-24Straight or branched alkylene, preferably each independently selected from C_2-12Straight or branched alkylene, more preferably each independently selected from C_2-6Straight or branched alkylene, more preferably each independently selected from-CH₂-CH₂-and-CH₂-CH(CH₃) -; and

n is selected from 1 to 100, preferably from 1 to 50, and more preferably from 5 to 25.

In some embodiments, the catalyst SO₄ ^-2/ZrO₂The preparation method comprises the following steps:

ZrOCl₂·8H₂Dissolving O in distilled water to obtain saturated zirconium salt-water solution;

dropwise adding dilute ammonia water while stirring to adjust the pH value of the saturated zirconium salt-water solution to 9-10, standing and aging, and then performing suction filtration to obtain a filter cake;

drying the filter cake, grinding the filter cake into powder, adding the powder into a sulfuric acid solution for soaking, and then filtering, drying and drying the solution to obtain the catalyst SO₄ ^-2/ZrO₂。

In some embodiments, the catalyst SO₄ ^-2/ZrO₂The addition amount of the epoxy chloropropane is 0.2-4% of the total mass of the polyether and the epoxy chloropropane, the molar ratio of the polyether to the epoxy chloropropane 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: 1-1.5, the ring-closure reaction is performed for 2-3 hours, and the reaction temperature is 30-50 ℃.

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 neutralized filtrate is 5-7.

In some embodiments, the adsorbent is selected from one or more of clay, diatomite and activated carbon, and the addition amount of the adsorbent is 1-5% of the mass of the polyether.

In some embodiments, the organic amine is selected from the group consisting of a polyene polyamine and C₁-C₃₀And the inorganic ammonium is selected from one or more of ammonia gas, ammonia water and inorganic ammonium salt.

In some embodiments, the amination reaction is carried out at a temperature of 90-180 ℃ for 2-8 hours.

In some embodiments, the amination reaction further comprises adding a catalyst and/or a solvent, wherein the solvent is C₁-C₈Alcohol, and 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-dimethylbutylamine, N-diethylpropylamine, N-dipropyl-1-propylamine, N-diethylbutylamine, N-dimethyl-1, 2-ethylenediamine, N-dimethyl-1, 3-propanediamine, N-dimethylpentylamine, N-dimethylhexylamine, N-dimethylheptylamine, N-dimethyloctylamine, N-dimethylnonylamine, N-dimethyldecylamine, N-dimethylundecylamine, N-dimethyldodecylamine, N-diethylpentylamine, N-dimethylpropylamine, N-dimethylbutylamine, N-dimethylpentylamine, N-dimethyldodecylamine, N-diethylpentylamine, N-dimethyldodecylamine, N-propylamine, N-dimethyldodecylamine, N-diethylpentylamine, N-dimethylbutylamine, N-1-ethylenediamine, N-dimethylbutylamine, N-1, N-ethylenediamine, N-dimethylbutylamine, N-dimethylbutylamine, N-dimethylbutylamine, N-dimethylbutylamine, N-dimethylbutylamine, and a, One or more of N, N-diethylhexylamine, N-diethylheptylamine, N-diethyloctylamine, N-diethylnonylamine, N-diethyldecylamine, N-diethylundecylamine, N-diethyldodecylamine, N-dipropylbutylamine, N-dipropylpentylamine, N-dipropylhexylamine, N-dipropylheptylamine, N-dipropyloctylamine, N-dipropylnonylamine, N-dipropyldecylamine, N-dipropylundecylamine, N-dipropyldodecylamine, triphenylamine, and N, N-dimethylbenzylamine.

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 p-cresol, 2, 4-xylenol, 2,4, 6-tritolyl, ethylphenol, sodium ethylphenol, 2, 4-diethylphenol, 2,4, 6-triethylphenol, p-methoxyphenol, m-methoxyphenol, o-methoxyphenol, sodium o-methoxyphenol, phenyl phenol and sodium phenyl phenolate.

In another aspect, the invention also provides a polyether amine prepared by the preparation method.

In still another aspect, the present invention also provides the use of the above polyetheramine in a fuel detergent.

The invention adopts solid super acidic SO₄ ^-2/ZrO₂The catalyst used for the ring-opening reaction has high selectivity and few byproducts, is non-corrosive to equipment, 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-terminated polyether, and compared with the existing technology of catalytically aminating hydroxyl-terminated polyether, the method has the advantages of high reaction speed and low production cost; and can also be effectiveThe formation of engine deposits is suppressed, and an excellent effect is achieved.

Detailed Description

The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to 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 same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.

When the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or a synonym thereof, directed to a material, substance, method, step, device, or component, the subject matter from which the heading is derived encompasses those conventionally used in the art as presented in the present application, but also includes those not currently in use, but which would become known in the art to be suitable for a similar purpose.

In the context of the present specification, anything or things which are not mentioned, except where explicitly stated, are directly applicable to those known in the art without any changes. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or concepts resulting therefrom are considered part of the original disclosure or original disclosure of the invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such a combination to be clearly unreasonable.

All features disclosed in this invention may be combined in any combination and such combinations are understood to be disclosed or described herein unless a person skilled in the art would consider such combinations to be clearly unreasonable. The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

Unless otherwise expressly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise not in accordance with the conventional knowledge of those 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 polyetheramines comprising the steps of:

adding catalyst SO₄ ^-2/ZrO₂Adding the mixture into polyether, and then adding epoxy chloropropane to perform epoxidation reaction to obtain reaction liquid;

separating the reaction liquid and recovering the catalyst SO₄ ^-2/ZrO₂And epichlorohydrin to obtain a chlorohydrin intermediate;

adding solid alkali into the chlorohydrin intermediate product to carry out ring-closing reaction to obtain crude epoxy-terminated polyether;

filtering the crude epoxy polyether, adding a neutralizing agent into the filtrate for neutralization, and then adding an adsorbent to obtain refined epoxy terminated polyether; and

and carrying out amination reaction on the refined epoxy-terminated polyether and organic amine and/or inorganic ammonium to obtain polyether amine.

The invention firstly takes polyether as an initial raw material to react with epichlorohydrin to obtain epoxy-terminated polyether, and the epoxy-terminated polyether further generates ring-opening reaction with amine to generate polyether amine, namely the epoxy-terminated polyether mainly comprises the epoxidation of the polyether and the amination of the epoxy polyether, wherein the epoxidation of the polyether comprises the epoxidation reaction, catalyst and raw material separation, ring-closing reaction and neutralization/adsorption.

The raw material polyether used by the invention has a structure shown in the following formula (I),

wherein R is₀Selected from hydrogen atoms and optionally substituted C_1-50Preferably selected from hydrogen atoms, C_1-20Straight or branched chain alkyl, substituted by one or more C_1-20Straight or branched alkyl substituted C_6-10Monocyclic or polycyclic aryl and substituted by one or more C_1-20Straight or branched alkyl substituted C_3-20Monocyclic or polycyclic cycloalkyl radicals, more preferably selected from hydrogen atoms, C_5-15Straight or branched chain alkyl and substituted by one or more C_5-15Straight or branched chain alkyl substituted phenyl; r_uEach independently selected from C_2-24Straight or branched alkylene, preferably each independently selected from C_2-12Straight or branched alkylene, more preferably each independently selected from C_2-6Straight or branched alkylene, more preferably each independently selected from-CH₂-CH₂-and-CH₂-CH(CH₃) -; n represents the average polymerization degree of the polyether segment and is selected from any value between 1 and 100, preferably from any value between 1 and 50, and more preferably from any value between 5 and 25.

In the epoxidation reaction, epichlorohydrin is slowly added to polyether under the protection of inert gas such as nitrogen, preferably in a dropwise manner.

The catalyst used in the epoxidation reaction is a solid super acidic catalyst SO₄ ^-2/ZrO₂The preparation method can be used for preparing the following components:

a certain amount of ZrOCl₂·8H₂Dissolving O in distilled water to obtain saturated zirconium salt-water solution;

dropwise adding dilute ammonia water (volume fraction is 10-15%) under rapid stirring to adjust the pH of the saturated zirconium salt-water solution to 9-10, standing and aging for about 24h, and performing suction filtration until filtrate is subjected to 0.1mol/L AgNO₃Detecting the solution to obtain a filter cake, wherein chloride ions cannot be generated in the solution;

drying the filter cake for 12h, grinding, and screening (1.05-1.5) x 10⁵Adding nm powder into sulfuric acid solution for soaking, filtering to remove residual solution, drying the powder, and baking in a muffle furnace for 3h to obtain SO catalyst₄ ^-2/ZrO₂。

Catalyst SO₄ ^-2/ZrO₂The addition amount of the polyether is 0.2-4% of the total mass of the polyether and the epoxy chloropropane, the molar ratio of the polyether to the epoxy chloropropane is 1: 1-1.5, the reaction time of the epoxidation reaction is 1-2.5 h, and the reaction temperature is 40-80 ℃.

After the epoxidation reaction is finished, separating the reaction liquid, filtering and recovering the catalyst SO₄ ^-2/ZrO₂And carrying out reduced pressure distillation to recover the epichlorohydrin to obtain a chlorohydrin intermediate product.

And then adding solid alkali to perform ring-closure reaction on the chlorohydrin intermediate product, wherein the solid alkali used in the method is NaOH or KOH, the molar ratio of polyether to the solid alkali is 1: 1-1.5, the ring-closure reaction time is 2-3 h, and the reaction temperature is 30-50 ℃.

After the ring-closing reaction is finished, filtering the crude epoxy polyether, and then neutralizing and adsorbing to obtain refined epoxy terminated polyether, wherein the used 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 neutralized filtrate is controlled within the range of 5-7; the used adsorbent is selected from one or more of argil, diatomite and activated carbon, and the addition amount of the adsorbent is 1-5% of the mass of the polyether.

The amination of epoxy polyether is to carry out amination reaction on refined epoxy-terminated polyether and organic amine and/or inorganic ammonium to obtain polyether amine, wherein the organic amine is selected from polyene polyamine and C₁-C₃₀The amination reaction is carried out at the temperature of 90-180 ℃ for 2-8h, and the used inorganic ammonium is one or more selected from ammonia gas, ammonia water and inorganic ammonium salt.

In the amination, a catalyst and/or a solvent can also be added, wherein the solvent is C₁-C₈Alcohol, and tertiary amine or phenolic catalyst.

The tertiary amine as catalyst is selected from the group consisting of trimethylamine, triethylamine, tripropylamine, N-dimethylethylamine, N-dimethylpropylamine, N-dimethylbutylamine, N-diethylpropylamine, N-dipropyl-1-propylamine, N-diethylbutylamine, N-dimethyl-1, 2-ethylenediamine, N-dimethyl-1, 3-propanediamine, N-dimethylpentylamine, N-dimethylhexylamine, N-dimethylheptylamine, N-dimethyloctylamine, N-dimethylnonylamine, N-dimethyldecylamine, N-dimethylundecylamine, N-dimethyldodecylamine, N-diethylpentylamine, N, one or more of N-diethylhexylamine, N-diethylheptylamine, N-diethyloctylamine, N-diethylnonylamine, N-diethyldecylamine, N-diethylundecylamine, N-diethyldodecylamine, N-dipropylbutylamine, N-dipropylpentylamine, N-dipropylhexylamine, N-dipropylheptylamine, N-dipropyloctylamine, N-dipropylnonylamine, N-dipropyldecylamine, N-dipropylundecylamine, N-dipropyldodecylamine, triphenylamine, and N, N-dimethylbenzylamine.

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 p-cresol, 2, 4-xylenol, 2,4, 6-tritolyl, ethylphenol, sodium ethylphenol, 2, 4-diethylphenol, 2,4, 6-triethylphenol, p-methoxyphenol, m-methoxyphenol, o-methoxyphenol, phenyl phenol and sodium phenyl phenolate.

The invention adopts solid super acidic SO₄ ^-2/ZrO₂The catalyst used for the ring-opening reaction has high selectivity and few byproducts, is non-corrosive to equipment, 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, the polyether amine is obtained by further aminating the epoxy-terminated polyether, and compared with the existing technology of catalytically aminating the hydroxyl-terminated polyether, 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 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 economy, and can reduce tail gas pollutant emission.

The present invention is further illustrated by the following specific examples, which describe preferred embodiments, but which are not to be construed as limiting the invention, and any person skilled in the art may, by applying the above teachings, modify the equivalent embodiments equally.

Examples

The epoxy value of the intermediate epoxy polyether was determined in the examples by the method described in GBT1677-1981, and the blocking ratio in the examples was defined as follows: the end capping ratio of the epoxy-capped polyether is 100% x the actually measured epoxy value/theoretical epoxy value.

Example 1 solid super acidic catalyst SO₄ ^-2/ZrO₂Preparation of

Weighing ZrOCl₂·8H₂Dissolving O15 g (to 0.0001g) in distilled water to obtain saturated zirconium salt-water solution.

Under the condition of rapid stirring, dropwise adding dilute ammonia water with the volume fraction of 10% -15% to adjust the pH of the solution to 9-10, standing and aging for 24h, carrying out suction filtration, washing with deionized water until filtrate is washed with 0.1mol/L AgNO₃The solution was checked for chloride ion.

Drying the filter cake for 12h, grinding and screening (1.05-1.5) x 10⁵Soaking nm powder 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 acidic catalyst SO₄ ^-2/ZrO₂。

EXAMPLE 2 preparation of polyetheramines

1) And (3) epoxidation of polyether.

500g of nonylphenol polyoxypropylene ether and 2.5g of SO₄ ^-2/ZrO₂Adding the catalyst into a 1000ml four-neck flask, starting stirring under the protection of nitrogen, starting dropwise adding 55.5g of epichlorohydrin after 10min, heating to 60 ℃ after finishing dropwise adding within 1h, and maintaining the temperature for reacting for 2.5 h.

After the reaction is finished, cooling to room temperature, filtering and separating the catalyst, and carrying out reduced pressure distillation to recover the epichlorohydrin 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 ℃, the reaction is carried out for 3h, and the temperature is reduced to room temperature, so as to obtain the crude epoxy-terminated polyether.

Filtering the crude epoxy polyether, collecting filtrate, adding oxalic acid to neutralize the filtrate to be neutral, adding 10g of acid clay to perform adsorption refining for 1 hour, and performing rotary evaporation dehydration filtration to obtain the refined epoxy terminated polyether. The polyether capping rate was 95.4%.

2) Amination of the epoxy polyether.

And adding the obtained epoxy polyether into an amination reaction kettle, adding 10-20g of liquid ammonia and 3g of triethylamine, and reacting at the temperature of 150 ℃ for 2-8 h. And (4) performing rotary evaporation on the product to obtain a final polyether amine product.

EXAMPLE 3 preparation of polyetheramines

1) And (3) epoxidation of polyether. 500g of nonylphenol polyoxypropylene ether and 2.5g of SO₄ ^-2/ZrO₂Adding the catalyst into a 1000ml four-neck flask, starting stirring under the protection of nitrogen, starting dropwise adding 55.5g of epichlorohydrin after 10min, heating to 60 ℃ after finishing dropwise adding within 1h, and maintaining the temperature for reacting for 2.5 h.

After the reaction is finished, cooling to room temperature, filtering and separating the catalyst, and carrying out reduced pressure distillation to recover the epichlorohydrin 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 ℃, the reaction is carried out for 3h, and the temperature is reduced to room temperature, so as to obtain the crude epoxy-terminated polyether.

Filtering the crude epoxy polyether, collecting filtrate, adding oxalic acid to neutralize the filtrate to be neutral, adding 10g of acid clay to perform adsorption refining for 1 hour, and performing rotary evaporation dehydration filtration to obtain the refined epoxy terminated polyether. The polyether capping rate was 95.4%.

2) Amination of the epoxy polyether. Adding the epoxy polyether into an amination reaction kettle, adding 36.6g of ethanolamine and 5g of triethylamine, reacting at 160 ℃ for 2-8 h. And (4) performing rotary evaporation on the product to obtain a final polyether amine product.

EXAMPLE 4 preparation of polyetheramines

1) And (3) epoxidation of polyether. 300g of methoxypolyoxyethylene allyl ether and 2g of SO₄ ^-2/ZrO₂Adding the catalyst into a 1000ml four-neck flask, starting stirring under the protection of nitrogen, starting dropwise adding 27.8g of epichlorohydrin after 20min, heating to 70 ℃ after finishing dropwise adding within 1h, and maintaining the temperature for reacting for 3 h.

After the reaction is finished, cooling to room temperature, filtering and separating the catalyst, and carrying out reduced pressure distillation to recover the epichlorohydrin 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 ℃, the reaction is carried out for 3h, and the temperature is reduced to room temperature, so as to obtain the crude epoxy-terminated polyether.

And filtering the crude epoxy terminated polyether, collecting filtrate, adding oxalic acid to neutralize the filtrate to be neutral, adding 8g of acid clay to perform adsorption refining for 1 hour, and performing rotary evaporation dehydration filtration to obtain the refined epoxy terminated polyether. The obtained polyether has a capping rate of 90.23%.

2) Amination of the epoxy polyether. Adding the obtained epoxy polyether into an amination reaction kettle, adding 43.86 tetraethylenetriamine and 1g triethylamine, and reacting at 150 ℃ for 2-7 h. And (4) performing rotary evaporation on the product to obtain a final polyether amine product.

EXAMPLE 5 preparation of polyetheramines

1) And (3) epoxidation of polyether. 1466g Butaneth (molecular weight 1466) and 9.8g SO₄ ^-2/ZrO₂Adding the catalyst into a 2000ml four-neck flask, stirring under the protection of nitrogen, dropwise adding 94g of epichlorohydrin after 20min, heating to 60 ℃ after completing dropwise adding within 1h, and maintaining the temperature for reaction for 3 h.

After the reaction is finished, cooling to room temperature, filtering and separating the catalyst, and carrying out reduced pressure distillation to recover the epichlorohydrin 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 3h, and the temperature is reduced to room temperature, so that crude epoxy-terminated polyether is obtained.

And filtering the crude epoxy terminated polyether, collecting filtrate, adding oxalic acid to neutralize the filtrate to be neutral, adding 30g of acid clay to perform adsorption refining for 1 hour, and performing rotary evaporation dehydration filtration to obtain the refined epoxy terminated polyether. The obtained polyether had a capping rate of 97.2%.

2) Amination of the epoxy polyether. And adding the epoxy polyether into an amination reaction kettle, adding 66.11g of ethylenediamine and 7.5g of triethylamine, and reacting at the temperature of 150 ℃ for 2-7 h. And (4) performing rotary evaporation on the product to obtain a final polyether amine product.

Comparative example 1

The compound of comparative example 1 was a commercial polyetheramine host (FL1000 polyetheramine) from hensmei, usa, which was prepared from nonylphenol polyether with ammonia and hydrogen at high temperature and pressure, and a noble metal catalyst was also required.

Evaluation experiment for detergency simulation

The cleaning performance of the example and comparative compounds was 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 fed back and forth to the deposit collecting plate at a rate of 1.54ml/min, the deposit collecting plate temperature being 175 ℃. After the experiment was completed, the sediment collection plates were handled and weighed. The smaller the deposit collector plate weight gain, the greater the deposit reduction rate, indicating the better performance of the gasoline detergent in inhibiting intake valve deposit formation, and the deposit collector plate weight gain data is shown in table 1.

TABLE 1

Evaluation results of detergency	Weight gain/mg of deposit collection plate	Reduction of the sediment/%)
			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 detergency of the polyetheramine compound of the present invention is close to that of the commercial polyetheramine, the formation of gasoline deposits can be effectively reduced, and the reaction process is mild, the end-capping rate of the epoxidation reaction is high, and the raw materials are easily available.

It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.