Synthesis method and application of polyether amine

Abstract

The invention discloses a synthesis method of polyether amine, and belongs to the technical field of organic polymer synthesis. The preparation method specifically comprises the following steps: adding diamine and a catalyst into a reaction kettle, heating to 150-180 DEG C, then introducing epoxypropane, reacting for 3-6 hours, introducing ethylene oxide into the reaction kettle after the reaction is finished, stirring and reacting for 3-6 hours at 150-180 DEG C, continuously introducing epoxypropane into the reaction kettle after the reaction is finished, stirring and reacting for 8-10 hours at 150-180 DEG C, cooling a reaction product to room temperature, and then purifying to obtain the diamine. Compared with the prior art, the method has the advantages that the operation is simple, the total reaction time is short, in the synthesized polyether amine, the structural molar ratio of EO to PO is 1PO-4EO-3PO, the average molecular weight of the polyether amine is 4000-4400, and the obtained polyether amine has excellent water solubility and low foam property. The synthesized polyether amine is particularly suitable for being applied to water-based cleaning agents and water-based cutting fluid.

Description

Technical Field

[0001] The invention belongs to the technical field of organic polymer synthesis, and specifically relates to a synthesis method and application of a polyetheramine. Background Art

[0002] In the field of polymer chemistry, polyetheramines are highly functional polymer materials that are widely used in many industries due to their unique physical and chemical properties. Polyetheramines have attracted widespread attention because they have a very special molecular structure. In this structure, PO (propylene oxide) and EO (ethylene oxide) are arranged alternately to form a triblock copolymer. This special arrangement gives the material unique physical and chemical properties, especially in cutting fluids and cleaning agents, and can be used as lubricants and cleaning functional additives.

[0003] At present, polyethers or polyetheramines are often used as lubricants and cleaning agents in fully synthetic cutting fluids. However, the polyetheramines currently on the market are basically EO-PO block structures with low molecular weight, high amine value, and poor water solubility. They have no obvious cleaning effect in fully synthetic water-based cutting fluids or cleaning agents, so their applications are limited.

[0004] Alcohol polyether is a polyether product with ethylene oxide and propylene oxide added to ethylene glycol or propylene glycol as the starting group. It is mostly used in cleaning agents as a cleaning surface active and as a lubricant in machining grinding fluids. It has the characteristics of good biological stability and clean and transparent diluted liquid. However, it has poor cleaning and dispersing ability in aqueous cleaning agent products and insufficient lubricity in aqueous cutting fluids. Summary of the invention

[0005] The purpose of the invention is to overcome the problems that the existing alcohol polyether products which are added with ethylene oxide and propylene oxide and take ethylene glycol or propylene glycol as starting groups have poor cleaning and dispersing ability in aqueous cleaning agent products and insufficient lubricity in aqueous cutting fluids, and to provide a method for synthesizing polyetheramines. The synthesized polyetheramines can disperse oil stains and metal dust during cleaning, improve the cleaning ability of aqueous cleaning agents, improve lubricity in aqueous cutting fluids, and quickly clean and remove metal chips.

[0006] To achieve the above object, the present invention adopts the following technical solution:

[0007] A method for synthesizing a polyetheramine comprises the following steps:

[0008] (1) Add diamine and catalyst into a reaction kettle, raise the temperature to 150-180°C, then introduce propylene oxide and react for 3-6 hours;

[0009] (2) After the reaction in step (1) is completed, ethylene oxide is introduced into the reaction kettle and stirred at 150-180° C. for 3-6 hours;

[0010] (3) After the reaction in step (2) is completed, propylene oxide is continuously introduced into the reaction kettle, and the reaction is stirred at 150-180° C. for 8-10 hours to obtain a reaction product, which is then cooled to room temperature and purified to obtain a polyetheramine.

[0011] Furthermore, in step (1), the diamine is selected from one or a combination of two or more of ethylenediamine, 1,3-propylenediamine or 1,4-butylenediamine in any proportion.

[0012] Furthermore, in step (1), the catalyst is a potassium hydroxide aqueous solution with a mass concentration of 48%-50%.

[0013] Furthermore, the weight ratio of the ethylene oxide, the total amount of propylene oxide in steps (1) and (3), and the catalyst is 440:580:(1-2), and the weight ratio of the propylene oxide in steps (1) and (3) is 1:3.

[0014] Furthermore, in step (3), the purification method is: washing the reaction product with deionized water and then distilling and dehydrating it.

[0015] The polyetheramine synthesized by the above method is used in the preparation of water-based cleaning agents.

[0016] The polyetheramine synthesized by the above method is used in the preparation of water-based cutting fluid.

[0017] Compared with the prior art, the present invention has the following beneficial effects:

[0018] 1) The present invention provides a method for synthesizing a polyetheramine, which is simple to operate and has a short total reaction time. In the synthesized polyetheramine, the molar ratio of EO (M44) to PO (M58) is: 1PO-4EO-3PO, and the average molecular weight of the polyetheramine is 4000-4400. The triblock polyetheramine obtained has excellent water solubility and low foaming properties, and is PO-initialized and terminated.

[0019] 2) The polyetheramine synthesized in the present invention is particularly suitable for use in aqueous cleaning agents. It can disperse oil stains and metal ash during the cleaning process and improve the cleaning ability of the cleaning agent.

[0020] 3) The polyetheramine synthesized in the present invention is also suitable for being added to aqueous cutting fluids, which can improve lubricity and quickly clean and remove metal chips. DETAILED DESCRIPTION

[0021] The technical solution of the present invention is clearly and completely described below in conjunction with specific embodiments.

[0022] Example 1

[0023] A method for synthesizing a polyetheramine comprises the following steps:

[0024] (1) Add 60.1 g of ethylenediamine and 5 g of a 48% potassium hydroxide solution into a 10 L reactor, heat to 150° C., then introduce 580 g of propylene oxide, and stir to react for 4 h;

[0025] (2) After the reaction in step (1) was completed, 1760 g of ethylene oxide was introduced into the reactor and stirred at 150° C. for 4 h;

[0026] (3) After the reaction in step (2) is completed, 1740 g of propylene oxide is continuously introduced into the reactor, and the reaction is stirred at 150° C. for 8 h to obtain a reaction product. The reaction product is cooled to room temperature, then washed with deionized water to remove unreacted diamine and catalyst, and finally distilled and dehydrated to obtain a polyetheramine with a yield of more than 98%.

[0027] Example 2

[0028] A method for synthesizing a polyetheramine comprises the following steps:

[0029] (1) Add 74.1 g of 1,3-propylenediamine and 6 g of a 48% potassium hydroxide solution into a 10 L reactor, heat to 150° C., then introduce 580 g of propylene oxide, and stir to react for 4 h;

[0030] (2) After the reaction in step (1) was completed, 1760 g of ethylene oxide was introduced into the reactor and stirred at 150° C. for 4 h;

[0031] (3) After the reaction in step (2) is completed, 1740 g of propylene oxide is continuously introduced into the reactor, and the reaction is stirred at 150° C. for 8 h to obtain a reaction product. The reaction product is cooled to room temperature, then washed with deionized water to remove unreacted diamine and catalyst, and finally distilled and dehydrated to obtain a polyetheramine with a yield of more than 98%.

[0032] Example 3

[0033] A method for synthesizing a polyetheramine comprises the following steps:

[0034] (1) Add 88.1 g of 1,4-butanediamine and 7 g of a 50% potassium hydroxide solution into a 10 L reactor, heat to 150° C., then introduce 580 g of propylene oxide, and stir to react for 4 h;

[0035] (2) After the reaction in step (1) was completed, 1760 g of ethylene oxide was introduced into the reactor and stirred at 150° C. for 4 h;

[0036] (3) After the reaction in step (2) is completed, 1740 g of propylene oxide is continuously introduced into the reactor, and the reaction is stirred at 150° C. for 8 h to obtain a reaction product. The reaction product is cooled to room temperature, then washed with deionized water to remove unreacted diamine and catalyst, and finally distilled and dehydrated to obtain a polyetheramine with a yield of more than 98%.

[0037] Performance Testing:

[0038] 1. The amine value and molecular weight of the polyetheramines synthesized in Examples 1-3 were tested, wherein the amine value was determined according to the method in the national standard GB / T7378-2012, and the molecular weight was determined and calculated according to the method in the national standard GB / T12008.3-2009 for hydroxyl value.

[0039] The test results are shown in Table 1:

[0040] Table 1

[0041] Polyetheramine Example 1 Example 2 Example 3 Molecular weight (Mw) 4141 4154 4168 Amine value mgKOH / g 27 26 26

[0042] It can be seen from the test results in Table 1 that the molecular weight of the polyetheramines obtained in Examples 1-3 of the present invention is in the range of 4000-4400, and the structure (amine value) is also within the design range, which meets the design requirements.

[0043] 2. The polyetheramines synthesized in Examples 1-3 were mixed with sodium hydroxide, isomeric decanol polyoxyethylene (10) ether, and water according to the mass percentages in the cleaning agent formula in Table 2 to prepare three cleaning agents, and then the cleaning ability of the cleaning agents was tested according to the method in the national standard GB / T35759-2017, and the cleaning agent without adding polyetheramine was used as a control cleaning agent for test comparison.

[0044] The test results of the cleaning ability of the cleaning agent are shown in Table 2:

[0045] Table 2

[0046]

[0047] It can be seen from the test results in Table 2 that adding the polyetheramine synthesized in the embodiment of the present invention to the cleaning agent formula can greatly improve the cleaning power of the cleaning agent.

[0048] 3. The polyetheramines synthesized in Examples 1-3 were mixed with rust inhibitors, alcohol amines, and water according to the mass percentages in the cutting fluid formula in Table 3 to obtain three cutting fluids. The lubrication properties of the cutting fluids were tested according to the method in the national standard GB / T3142-2019, and the cutting fluid with added ethylene glycol block polyether L64 (Dow Chemical) was used as the control cutting fluid for testing and comparison.

[0049] The lubrication performance test data of cutting fluid is shown in Table 3:

[0050] Table 3

[0051]

[0052] It can be seen from the test results in Table 3 that the addition of polyetheramine effectively increases the maximum no-seizure load pb value of cutting, thereby improving the lubrication performance of the cutting fluid, which has a significant effect on reducing friction during machining.

[0053] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for synthesizing a polyetheramine, characterized in that: The steps include: (1) Add diamine and catalyst into a reaction kettle, raise the temperature to 150-180°C, then introduce propylene oxide and react for 3-6 hours; (2) After the reaction in step (1) is completed, ethylene oxide is introduced into the reaction kettle and stirred at 150-180° C. for 3-6 hours; (3) After the reaction in step (2) is completed, propylene oxide is continuously introduced into the reaction kettle, and the reaction is stirred at 150-180° C. for 8-10 hours to obtain a reaction product, which is then cooled to room temperature and purified to obtain a polyetheramine.

2. The method for synthesizing polyetheramine according to claim 1, characterized in that: In step (1), the diamine is selected from one or a combination of two or more of ethylenediamine, 1,3-propylenediamine or 1,4-butylenediamine in any proportion.

3. The method for synthesizing polyetheramine according to claim 1, characterized in that: In step (1), the catalyst is a potassium hydroxide aqueous solution with a mass concentration of 48%-50%.

4. The method for synthesizing polyetheramine according to claim 1, characterized in that: The weight ratio of the ethylene oxide, the total amount of propylene oxide in steps (1) and (3), and the catalyst is 440:580:(1-2), and the weight ratio of the propylene oxide in steps (1) and (3) is 1:

3.

5. The method for synthesizing the polyetheramine according to claim 1, 2, 3 or 4, characterized in that: In step (3), the purification method is: washing the reaction product with deionized water and then distilling and dehydrating it.

6. Use of the polyetheramine synthesized by the method according to any one of claims 1 to 5 in the preparation of an aqueous cleaning agent.

7. Use of the polyetheramine synthesized by the method according to any one of claims 1 to 5 in the preparation of cutting fluid.

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