阅读说明：本技术 一种用于汽油清净剂的聚醚胺类化合物及其制备方法 (Polyether amine compound for gasoline detergent and preparation method thereof ) 是由 李厚成 于 2021-11-06 设计创作，主要内容包括：本发明公开了一种聚醚胺类化合物的制备方法,属于汽油发动机清净剂技术领域。以两端均为羟基的聚醚为原料,与对苯二醌反应得到端位为苯酚的聚醚,接着再与二胺和醛进行曼尼希反应得到端位为酚基胺的聚醚胺。该方法原料便宜易得,容易操作,反应温度低,得到的聚醚胺有优良油溶性,不沉淀不分层,可改善油品性能,使燃料在气缸中更加完全充分燃烧,增加车辆动力性能,减少车辆磨损,降低汽车发动机噪音；聚醚胺结构中同时具有聚醚主链和端位胺基酚基团,可在部件表面形成漆膜,胺基极性基团具有吸附积炭、微尘和沉积物形成胶束作用,聚醚主链将其包裹具有更好的油溶性,同时防止积炭进一步氧化和聚集,不溶在油品中的分散和悬浮胶束通过过滤器除去,达到理想清洗。(The invention discloses a preparation method of a polyether amine compound, belonging to the technical field of gasoline engine detergents. Polyether with two hydroxyl ends is used as a raw material, the raw material reacts with p-phenylenediamine to obtain polyether with phenol at the end position, and then the polyether with diamine and aldehyde are subjected to Mannich reaction to obtain polyether amine with phenol amine at the end position. The method has the advantages of cheap and easily-obtained raw materials, easy operation and low reaction temperature, and the obtained polyether amine has excellent oil solubility, does not precipitate or delaminate, can improve the performance of an oil product, enables fuel to be more completely combusted in a cylinder, increases the dynamic performance of a vehicle, reduces the abrasion of the vehicle and reduces the noise of an automobile engine; the polyether amine structure simultaneously has a polyether main chain and terminal amino phenol groups, a paint film can be formed on the surface of a component, the amino polar groups have the function of adsorbing deposited carbon, micro dust and sediments to form micelles, the polyether main chain wraps the deposited carbon, the deposited carbon is better in oil solubility and is prevented from being further oxidized and aggregated, and dispersed and suspended micelles insoluble in oil are removed through a filter, so that ideal cleaning is achieved.)

1. The polyether amine compound has the following structure:

wherein: x is an integer of 0 to 25, Y is an integer of 0 to 30, and Z is 0 or 1; r is hydrogen or methyl; r₁Is hydrogen, methyl, ethyl or phenyl, and n is an integer of 2 to 6.

2. A process for the synthesis of polyetheramine compounds according to claim 1, characterized in that: polyether with two hydroxyl ends is used as a raw material and reacts with p-benzoquinone to obtain polyether with the end position of phenol, and then Mannich reaction is carried out on the polyether with diamine and aldehyde to obtain polyether amine with the end position of phenol amine; the reaction equation is as follows:

wherein: x is an integer of 0 to 25, Y is an integer of 0 to 30, and Z is 0 or 1; r is hydrogen or methyl; r₁Is hydrogen, methyl, ethyl or phenyl, and n is an integer of 2-6;

the method comprises the following steps:

1) mixing polyether with two hydroxyl ends, p-benzoquinone and catalyst; heating the reaction solution to 80-120 ℃ for reaction;

2) after the reaction is finished, cooling to 60-90 ℃, adding water, raising the temperature, distilling with steam to remove redundant p-phenylenediamine, and then cooling to room temperature; carrying out reduced pressure concentration to obtain the terminal phenol polyether;

3) mixing the terminal phenol polyether with a solvent to obtain a uniform solution; then adding aldehyde and diamine; controlling the temperature of the reaction liquid to be 40-110 ℃ for reaction;

4) and after the reaction is finished, carrying out reduced pressure concentration to obtain the terminal phenol amino polyether amine.

3. The method for synthesizing polyetheramine compound according to claim 2, wherein: in the step 1), the mole ratio of the p-benzoquinone to the polyether with both ends of hydroxyl is 2.2-3.5: 1; the molar ratio of the catalyst to the polyether with both ends being hydroxyl is 0.5-5.0: 100.

4. the method for synthesizing polyetheramine compound according to claim 2, wherein: in the step 1), the catalyst is methanesulfonic acid, ethylsulfonic acid, p-toluenesulfonic acid monohydrate or trifluoromethanesulfonic acid.

5. The method for synthesizing polyetheramine compound according to claim 2, wherein: in the step 1), the reaction temperature is 90-110 ℃; the reaction time is 4-10 hours.

6. The method for synthesizing polyetheramine compound according to claim 2, wherein: in the step 2), the temperature reduction is controlled at 70-80 ℃.

7. The method for synthesizing polyetheramine compound according to claim 2, wherein: in the step 3), the solvent is water, methanol, ethanol, toluene or xylene; the aldehyde is 37% formaldehyde aqueous solution, trioxymethylene or paraformaldehyde.

8. The method for synthesizing polyetheramine compound according to claim 2, wherein: in the step 3), the mass ratio of the solvent to the polyether with hydroxyl at both ends in the step 1 is 2-6: 1; the molar ratio of the diamine to the polyether with both ends being hydroxyl in the step 1 is 2.0-2.1: 1.

9. the method for synthesizing polyetheramine compound according to claim 2, wherein: in the step 3), the molar ratio of the aldehyde to the polyether with hydroxyl at both ends in the step 1 is 2.0-2.4: 1; the temperature of the reaction liquid is 60-80 ℃; the reaction time is 2-6 hours.

10. The use of polyetheramine compounds of claim 1 in gasoline detergents.

Technical Field

The invention belongs to the technical field of gasoline engine detergents, and particularly relates to a polyether amine compound and a preparation method thereof.

Background

The incomplete combustion of gasoline in the engine results in great amount of carbon deposit in the combustion chamber, fuel nozzle, air inlet valve and other parts, and this results in environment pollution and shortened engine life. The gasoline detergent can effectively control the generation of sediments and keep an engine clean, and becomes an indispensable component of modern clean gasoline.

The gasoline detergent includes, as a main component, polyisobutylene amine, polyisobutylene phenol mannich base, and polyether amine. There is a great difference in the backbone structure of polyisobutylene amines and polyetheramines detergents. Polyisobutene amine detergent with main chain made of medium carbon (- (CH)₂-C(CH₃)₂) -) bond, although the problem of fuel nozzle and intake valve deposit can be solved well, the polyisobutylene main chain has higher thermal stability and incomplete combustion in a combustion chamber; the main chain of the polyether amine is composed of medium carbon oxygen carbon (-C-O-C-) bonds, so that the polyether amine is easy to thermally crack, and can remarkably reduce the deposits in a combustion chamber while effectively controlling the deposits of a fuel nozzle and an air inlet valve.

The polyetheramine detergent (Amine-Terminated Polyether, short for ATPE) has a flexible Polyether chain skeleton as the main molecular chain and Terminated primary or secondary Amine group as the terminal group. The polyether amine detergent has excellent dispersing, washing, solubilizing, corrosion inhibiting and antioxidant performance. The material can not only remove the deposits of an engine oil nozzle, an intake valve and a combustion chamber, but also reduce or inhibit the generation of the deposits at the parts, and simultaneously does not increase the deposits of the combustion chamber, thereby being widely applied to the cleaning of automobile engines.

In order to further improve the performances of oxidation resistance, dispersion, cleaning and the like of the polyetheramine, aiming at exploring the polyetheramine with a novel structure, the invention introduces aminophenol into the end position of the polyether to prepare a novel polyetheramine detergent, and the oxidation resistance of the polyetheramine can be further improved due to the introduction of phenol; the amino substituent group on the phenol group can keep the wetting, dispersing and penetrating properties of the polyether amine and improve the cleaning effect; the novel polyether amine compound can be used as an intermediate of a fuel additive, prevents carbon deposit from being further oxidized and condensed, and reduces deposition; and the detergent can be directly used as a fuel detergent, and has great advantages in removing deposits in an internal combustion engine oil system, an oil nozzle and a spark plug, and maintaining the thermal stability and the oxidation resistance of the fuel. And the addition of minor amounts of auxiliary additives to the detergent may be reduced or avoided.

Disclosure of Invention

The invention aims to provide a terminal amino phenol modified polyether amine fuel additive material and a preparation method thereof. Polyether with two hydroxyl ends is used as a raw material, the raw material reacts with p-phenylenediamine to obtain phenol polyether with the end position, and then the phenol polyether with the end position is obtained through Mannich reaction with diamine and aldehyde. The material can be used as a gasoline cleaning agent, has multiple performances of oxidation resistance, dispersion and cleaning on the basis of adding a small amount of the material, can reduce the emission of automobile exhaust, improve the fuel economy and the anti-explosion performance, and can also improve the performance of removing deposits in an internal combustion engine oil system, an oil nozzle and a spark plug.

The structure of the polyether amine compound is as follows:

wherein: x is an integer of 0 to 25, Y is an integer of 0 to 30, and Z is 0 or 1; r is hydrogen or methyl; r₁Is hydrogen, methyl, ethyl or phenyl, and n is an integer of 2 to 6.

The polyether with both ends being hydroxyl is a main raw material of polyether amine, and the average molecular weight is about 230-2000; the structural formula is as follows:

wherein X is an integer of 0 to 25, Y is an integer of 0 to 30, and Z is 0 or 1.

The structure of the p-phenylene benzoquinone serving as a terminal phenolic group raw material is as follows:wherein R is hydrogen or methyl;

the diamine is used as an amination raw material and has the structure as follows:wherein R is₁Is hydrogen, methyl,Ethyl or phenyl, n is an integer of 2 to 6.

The synthesis of the polyether amine compound is realized by the following technical scheme:

polyether with two hydroxyl ends is used as a raw material to react with p-benzoquinone to obtain polyether with a phenol end position, and then the polyether with diamine and aldehyde are subjected to Mannich reaction to obtain polyether amine with a phenol amine end position, wherein the reaction equation is as follows:

the method comprises the following steps:

1) mixing polyether with two hydroxyl ends, p-benzoquinone and catalyst; heating the reaction solution to 80-120 ℃ for reaction;

2) after the reaction is finished, cooling to 60-90 ℃, adding water, raising the temperature, distilling with steam to remove redundant p-phenylenediamine, and then cooling to room temperature; carrying out reduced pressure concentration to obtain the terminal phenol polyether;

3) mixing the terminal phenol polyether with a solvent to obtain a uniform solution; then adding aldehyde and diamine; controlling the temperature of the reaction liquid to be 40-110 ℃ for reaction;

4) and after the reaction is finished, carrying out reduced pressure concentration to obtain the terminal phenol amino polyether amine.

Further, in the step 1), the mole ratio of the p-benzoquinone to the polyether with both hydroxyl groups is 2.2-3.5: 1, preferably the mole ratio of the p-benzoquinone to the polyether with both ends being hydroxyl is 2.6: 1.

further, in the above step 1), the catalyst is methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid monohydrate, or trifluoromethanesulfonic acid, preferably trifluoromethanesulfonic acid.

Further, in the step 1), the molar ratio of the catalyst to the polyether with hydroxyl groups at both ends is 0.5-5.0: 100, preferably the molar ratio of catalyst to polyether having hydroxyl groups at both ends is 2.0: 100.

further, in the step 1), the reaction temperature is 90-110 ℃; the reaction time is 4 to 10 hours, preferably 5 to 8 hours.

Further, in the step 2), the temperature of the temperature reduction is controlled to be 70-80 ℃.

Further, in the above step 3), the solvent is water, methanol, ethanol, toluene or xylene, preferably methanol.

Further, in the step 3), the mass ratio of the solvent to the polyether with hydroxyl groups at both ends in the step 1) is 2-6: 1, preferably, the mass ratio of the solvent to the polyether with both ends of hydroxyl in the step 1) is 3-4: 1.

further, in the step 3), the aldehyde is 37% formaldehyde aqueous solution, trioxymethylene or paraformaldehyde, and is preferably trioxymethylene.

Further, in the step 3), the molar ratio of the aldehyde to the polyether with hydroxyl groups at both ends in the step 1) is 2.0-2.4: 1, preferably in an aldehyde to polyether molar ratio of 2.1: 1.

further, in the step 3), the molar ratio of the diamine to the polyether with hydroxyl groups at both ends in the step 1) is 2.0-2.1: 1, preferably the molar ratio of diamine to polyether having hydroxyl groups at both ends in step 1) is 2.02: 1.

further, in the step 3), the temperature of the reaction solution is 60-80 ℃; the reaction time is 2 to 6 hours, preferably 4 to 10 hours.

The invention also provides application of the polyether amine compound in a gasoline cleaning agent.

The invention has the beneficial effects that:

1. the polyether amine has excellent oil solubility, does not precipitate and is not layered, the performance of an oil product can be improved, fuel can be more completely combusted in a cylinder, the dynamic performance of a vehicle is improved, the abrasion of the vehicle is reduced, and the noise of an automobile engine is reduced.

2. The polyether amine has the structure that the polyether amine simultaneously has a polyether main chain and amino phenol groups at end positions, a paint film can be formed on the surface of a component, the amino polar groups have the function of adsorbing deposited carbon, micro dust and sediments to form micelles, the polyether main chain wraps the deposited carbon to form better oil solubility, the deposited carbon is prevented from being further oxidized and aggregated, and dispersed and suspended micelles insoluble in oil are removed through a filter, so that the ideal cleaning purpose is achieved.

3. The structure of the polyether amine of the invention has a terminal phenol group, and the oxidation resistance and the explosion resistance of the polyether amine can be further improved due to the introduction of phenol.

4. According to the preparation method, cheap polyether is selected as a raw material and benzoquinone are synthesized into the phenol-terminated polyether, and the phenol-terminated polyether, formaldehyde and diamine are subjected to Mannich reaction to obtain the product. The method has the advantages of cheap and easily available raw materials, easy operation and low reaction temperature.

Drawings

FIG. 1 is an infrared spectrum of the polyether raw material in example 1:

FIG. 2 is an IR spectrum of the end group phenol polyether intermediate and polyetheramine product of example 1:

FIG. 3 is a view of the endoscope detection air inlet valve prior to cleaning;

FIG. 4 is an endoscopic examination of air intake valves after cleaning with polyetheramine as the detergent.

Detailed Description

The invention is illustrated by way of example. The specific material ratios, process conditions and results described in the examples are merely illustrative of the invention and the invention should not be, nor should it be limited by the examples.

Example 1

1) 230 grams of polyether (average molecular weight 230), p-phenylene benzoquinone (281 grams) and methanesulfonic acid (1.9 grams) were added to a reaction flask; controlling the temperature of the reaction solution at 90 ℃ and reacting for 5 hours;

2) after the reaction is finished, adding water, heating up steam for distillation to remove redundant benzoquinone, and then cooling to room temperature; concentrating the residual reaction solution under reduced pressure to obtain a product, namely the terminal phenol polyether; the infrared spectrum of the end phenol polyether intermediate product (shown in figure 1) is 1180cm^-1Is asymmetric stretching vibration of phenolic hydroxyl at 1650cm^-1Stretching vibration in the C ═ C (benzene ring) structure indicates that phenol has been introduced at the end position of the polyether.

3) Adding the terminal phenol polyether into a reaction kettle, and adding 690 g of methanol to obtain a solution; trioxymethylene (63 g) and N-methylethylenediamine (149.5 g) were added; controlling the temperature of the kettle at 60 ℃, and continuing to react for 4 hours;

4) after the reaction is finished, the reaction product is decompressed and concentrated to obtain the product, namely the terminal phenol amino polyether amine.

The infrared spectrums of the polyether raw material, the end-phenol polyether and the product polyether amine (see attached figures 1 and 2). As shown in FIG. 1, the polyether raw material is at 3460cm^-1The peak is the stretching vibration absorption peak of alcoholic hydroxyl group O-H, 2972cm^-12928cm from C-H shock absorption peak at methyl^-1And 2870cm^-1A C-H vibration absorption peak of methylene at a polyether chain segment; as shown in FIG. 2, 1450-1620 cm^-1The component (A) is a vibration absorption peak of a benzene ring skeleton, and the polyether is at 3470cm^-1The strong stretching vibration absorption broad peak of phenolic hydroxyl (Ar-OH) appears at 1012cm^-1And the position is a C-O stretching vibration absorption peak in Ar-O-C, and the existence of the characteristic absorption peaks indicates that the synthesized intermediate is the end phenol-based polyether. Reacting the end phenol polyether with diamine to generate polyether amine, wherein the polyether amine is 3470cm^-1The strong stretching vibration absorption broad peak of the phenolic hydroxyl group (Ar-OH) is not changed, and in addition, the peak is 3371cm^-1The antisymmetric stretching vibration absorption peak of the amino group is detected, and the introduction of the amino group into the terminal phenol polyether is proved. The presence of these characteristic absorption peaks indicates that the polyetheramine product was synthesized. And the intensity and the position of other infrared absorption peaks are not obviously changed, which shows that amino only has chemical reaction with benzene ring, and other structures in polyether are well retained.

Example 2

1) Adding 400 g of polyether (average molecular weight is 400), 2-methyl-1, 4-benzenediquinone (317 g) and ethyl sulfonic acid (2.2 g) into a reaction bottle; controlling the temperature of the reaction solution at 100 ℃ and reacting for 7 hours;

2) after the reaction is finished, cooling to 80 ℃, adding water, heating steam for distillation to remove redundant benzoquinone, and then cooling to room temperature; concentrating the residual reaction solution under reduced pressure to obtain a product, namely the terminal phenol polyether;

3) adding the terminal phenol polyether into a reaction kettle, and adding 1200 water to obtain a solution; 170 g of formaldehyde (37%) and N-ethyl-1, 6-hexanediamine (262.6 g) were added; controlling the temperature of the kettle at 70 ℃, and continuing to react for 6 hours;

4) after the reaction is finished, the reaction product is decompressed and concentrated to obtain the product, namely the terminal phenol amine polyether amine.

Example 3

1) 800 g of polyether (average molecular weight of 800), 2-methyl-1, 4-benzenediquinone (366 g) and trifluoromethanesulfonic acid (3.0 g) were added to a reaction flask; controlling the temperature of the reaction solution at 90 ℃ and reacting for 6 hours;

2) after the reaction is finished, cooling to 70 ℃, adding water, heating steam for distillation to remove redundant benzoquinone, and then cooling to room temperature; concentrating the residual reaction solution under reduced pressure to obtain a product, namely the polyether with the terminal phenol group;

3) adding the terminal phenol polyether into a reaction kettle, and adding 2400 g of ethanol to obtain a solution; trioxymethylene (63 g) and ethylenediamine (121 g) were added; controlling the temperature of the kettle at 60 ℃, and continuing to react for 4 hours;

4) after the reaction is finished, the reaction product is decompressed and concentrated to obtain the product, namely the terminal phenol amine polyether amine.

Example 4

1) 1000 g of polyether (average molecular weight 1000), 2-methyl-1, 4-benzenediquinone (317 g) and trifluoromethanesulfonic acid (3.6 g) were added to a reaction flask; controlling the temperature of the reaction solution at 100 ℃ and reacting for 5 hours;

2) after the reaction is finished, cooling to 80 ℃, adding water, heating steam for distillation to remove redundant benzoquinone, and then cooling to room temperature; concentrating the residual reaction solution under reduced pressure to obtain a product, namely the terminal phenol polyether;

3) adding the terminal phenol polyether into a reaction kettle, and adding 4000 g of methanol to obtain a solution; trioxymethylene (63 g) and N-methyl-1, 6-hexanediamine (237.8 g) were added; controlling the kettle temperature at 90 ℃, and continuing to react for 10 hours;

4) after the reaction is finished, the reaction product is decompressed and concentrated to obtain the product, namely the terminal phenol amine polyether amine.

Example 5

1) 1000 g of polyether (average molecular weight 1000), 1, 4-benzenediquinone (281 g) and trifluoromethanesulfonic acid (3 g) were added to a reaction flask; controlling the temperature of the reaction solution at 80 ℃ and reacting for 7 hours;

2) after the reaction is finished, cooling to 60 ℃, adding water, heating steam for distillation to remove redundant benzoquinone, cooling to room temperature, and removing a water layer by layering; and (3) concentrating the residual reaction solution under reduced pressure to obtain a product, namely the polyether with the terminal phenol group.

3) Adding the terminal phenol polyether into a reaction kettle, and adding 2000 g of methanol to obtain a solution; paraformaldehyde (63 g) and N-ethyl-1, 2-ethylenediamine (177.8 g) were added; controlling the temperature of the kettle at 60 ℃, and continuing to react for 10 hours;

4) after the reaction is finished, the reaction product is decompressed and concentrated to obtain the product, namely the terminal phenol amino polyether amine.

Example 6

1) Adding 1800 g of polyether (with an average molecular weight of 1800), 1, 4-benzenediquinone (324 g) and p-toluenesulfonic acid monohydrate (7.6 g) into a reaction bottle; controlling the temperature of the reaction solution at 120 ℃ and reacting for 9 hours;

2) after the reaction is finished, cooling to 60 ℃, adding water, heating steam for distillation to remove redundant benzoquinone, cooling to room temperature, and removing a water layer by layering; and (3) concentrating the residual reaction solution under reduced pressure to obtain a product, namely the terminated phenol polyether.

3) Adding the terminal phenol polyether into a reaction kettle, and adding 3600 g of toluene to obtain a solution; trioxymethylene (72 g) and N-phenyl-1, 2-ethylenediamine (285.6 g) were added; controlling the kettle temperature at 110 ℃, and continuing to react for 16 hours;

4) after the reaction is finished, the reaction product is decompressed and concentrated to obtain the product, namely the terminal phenol amino polyether amine.

Example 7

1) 2000 g of polyether (average molecular weight 2000), 2-methyl-1, 4-benzenediquinone (317 g) and trifluoromethanesulfonic acid (3.6 g) were added to a reaction flask; controlling the temperature of the reaction solution at 110 ℃, and reacting for 10 hours;

2) after the reaction is finished, cooling to 70 ℃, adding water, heating steam for distillation to remove redundant benzoquinone, cooling to room temperature, and removing a water layer by layering; and (3) concentrating the residual reaction solution under reduced pressure to obtain a product, namely the terminated phenol polyether.

3) Adding the terminal phenol polyether into a reaction kettle, and adding 4000 g of a xylene solvent to obtain a solution; 194.6 g of aqueous formaldehyde (37%) and 1, 4-butanediamine (184.8 g) were added; controlling the temperature of the kettle at 100 ℃, and continuing to react for 2 hours;

4) after the reaction is finished, the reaction product is decompressed and concentrated to obtain the product, namely the terminal phenol amino polyether amine.

Example 8

With the polyetheramine prepared in example 4 as a detergent, refer to GB19592-2004 "motor gasoline detergent" and GB/T19230.6-2003 part 6: the method and specifications specified in the engine bench test method (M111 method) in which gasoline detergents have an influence on the generation tendency of gasoline engine intake valves were tested. Different concentrations of polyetheramine detergents were added to E1093# ethanol gasoline to explore their effect on intake valve deposits. The results are as follows:

TABLE 1 Effect of different concentrations of polyetheramine detergent on intake valve deposits

As can be seen in FIG. 3, the valve faces and the valve stems of the intake valves of the automobile without detergent are obviously deposited when the automobile runs to 9968 km; the polyether amine gasoline detergent sample prepared by the invention is added into fuel (600mg/kg), and after cleaning, an air inlet valve is detected by an endoscope, and as can be seen from figure 4, deposits on the valve surface and the valve rod of the automobile air inlet valve are thoroughly cleaned.

The foregoing embodiments have described the general principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the present invention, and that various changes and modifications may be made without departing from the scope of the principles of the present invention, and the invention is intended to be covered by the appended claims.