A kind of preparation method of polyetheramine

Abstract

The invention discloses a method for preparing a polyetheramine. The method reduces the difficulty of reaction conditions and accelerates the reaction by adopting an ionic liquid. The invention discloses a reaction device, which can reduce the occurrence of side reactions, improve the reaction conversion rate, increase the yield, and has a purification effect. Finally, a polyetheramine with mild reaction conditions, high yield and fast curing speed is synthesized, and the polyetheramine has wide application value.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer material synthesis and preparation, and particularly relates to a method for preparing polyetheramine. Background Art

[0002] Polyetheramine is a toughening curing agent for epoxy resin and the main raw material for preparing polyurethaneurea and polyurea materials. When used as a curing agent for epoxy resin, polyetheramine not only reduces the brittleness of the cured product, improves the flexibility and thermomechanical properties of the cured product, but also overcomes the shortcomings of small molecular polyamine compounds that are easy to volatilize, easy to absorb water and carbon dioxide in the air, and highly toxic. However, the curing speed of polyetheramines currently sold on the market, such as D230, is relatively slow, and it takes up to 8 to 9 hours to cure at room temperature.

[0003] At present, the preparation methods of polyetheramine mainly include catalytic reduction amination method, leaving group method, polyether nitrile alkylation method and aminobutyric acid ester method. Catalytic reduction amination method and polyether nitrile alkylation method require reaction with hydrogen under high temperature and high pressure conditions, which have high requirements on equipment and high cost; leaving group method has more side reactions, more complicated post-processing and separation, and lower product yield; aminobutyric acid ester method has poor stability because the amine group in the polyetheramine obtained by the reaction is connected to the lipid bond.

[0004] Therefore, through reasonable process design, the polyetheramine with milder synthesis reaction conditions, higher yield and faster curing speed has a wide range of application value. Summary of the invention

[0005] The object of the present invention is to provide a method for preparing polyetheramines. The present invention overcomes the defects of the traditional method of direct hydroxyl amination, such as the stringent requirements on equipment and process, and the side reactions that are easy to occur when the amine compound is connected to the polyether chain, and successfully synthesizes polyetheramines with mild reaction conditions, high yield and fast curing speed.

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

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

[0008] (1) Polyamine, ketone or aldehyde, and ionic liquid are sequentially added to the reaction system in a molar ratio of 1:1.5 to 3:0.3, and reacted at 60 to 80°C. After reacting for 5 to 7 hours, toluene is added for extraction, the liquid is separated and filtered, the aqueous phase is distilled and dried, and the ionic liquid is recovered. The organic phase is distilled under reduced pressure at a pressure of 0.02 MPa to obtain an amine compound protected by ketimine or aldimine;

[0009] (2) 0.5-1.5 mol of amine compounds protected by ketimine or aldimine are used as initiators, and after being fully mixed with a catalyst accounting for 0.3-0.4% of the mass of the amine compounds, the mixture is sprayed into mist using a sprayer under the protection of inert gas, and then added to a gaseous epoxy monomer with a molar ratio of 15-45 times, and the temperature is controlled to be 75-95°C and the initial reaction pressure is 0.2-0.3Mpa. After the addition is completed, when there are no obvious mist droplets in the reactor, 90% of the volume of the reactants is pumped into the separation reactor using a pump, and filtered using a polytetrafluoroethylene filter layer. At the same time, the vacuum pump in the separation reactor is turned on to speed up the filtration rate. After the filtration is completed, the vacuum pump is turned off, and inert gas is added to the separation reactor. The reactants that have passed through the filter membrane are continuously added to the reactor using a sprayer. After every six cycles, the extraction pump is turned on to extract the polyetheramine protected by ketimine or aldimine into the next hydrolysis reactor protected by inert gas. The reaction is terminated when the pressure in the reactor no longer changes, and the polyetheramine protected by ketimine or aldimine is obtained.

[0010] (3) adding 0.3-0.6 mol of an organic acid or an inorganic acid, 20-40 mol of deionized water, and an adsorbent accounting for 5-10% of the total mass of the acid and the deionized water to the polyetheramine of step (2), reacting at 60-150° C. for 1-3 h, removing the protecting group, performing reduced pressure distillation at a pressure of 0.02 MPa, and filtering to obtain the polyetheramine product.

[0011] The polyamine described in step (1) is a piperazine amino derivative, aliphatic amine or aromatic amine compound containing a secondary amine or a hydroxyl group and a primary amine group.

[0012] The ketones or aldehydes in step (1) are aliphatic ketones, aliphatic aldehydes and their derivatives.

[0013] The preparation method of the ionic liquid described in step (1) is to add DBU to the reaction system, slowly dropwise add an equimolar amount of isobutyric acid at a water bath temperature of 5 to 15°C, raise the water bath temperature to 35 to 40°C after the addition is completed, react for 15 to 17 hours, and after the reaction, place the product in a vacuum drying oven at 80°C and dry it for 28 to 32 hours to obtain the ionic liquid required for the reaction.

[0014] In step (2), a reaction device is designed, including a reactor, a pump, a hydrolysis reactor, a separation reactor, an atomizer, an insulation layer, a temperature monitor, a pressure monitor, a pump, a polytetrafluoroethylene filter layer, and a vacuum pump. The reactor structure is an "inverted pear" structure and is hollow inside. A pressure monitor and a temperature monitor are arranged inside the reactor. An insulation layer is arranged inside the reactor shell. The lower part of the reactor is connected to one end of the pump through a pipeline, and the other end of the pump is connected to the separation reactor through a pipeline. The separation reactor structure is a cylindrical structure and is hollow inside. A extraction pump is installed at the top of the separation kettle, a polytetrafluoroethylene filter layer is installed at the lower middle position of the separation kettle, the upper pipe of the separation kettle is close to the polytetrafluoroethylene filter layer, the separation kettle is connected with the hydrolysis kettle through the upper pipe, the liquid collection chamber is below the polytetrafluoroethylene filter layer, a vacuum pump is installed outside the liquid collection chamber, the bottom of the separation kettle is connected with the reactor through a lower pipe, the lower pipe runs through the upper part of the reactor, and an atomizer is installed at the end of the lower pipe located in the reactor.

[0015] The spray flow rate of the sprayer in step (2) is (0.15~0.25)V 反应物 / min.

[0016] The polytetrafluoroethylene filter layer described in step (2) is a polytetrafluoroethylene composite nanofiltration membrane with a membrane pore size of 1 nm.

[0017] The catalyst in step (2) is an alkali metal oxide, hydroxide, alkoxide or an alkaline earth metal oxide, hydroxide, alkoxide.

[0018] The epoxy monomer in step (2) is one of ethylene oxide and propylene oxide or a mixture of the two.

[0019] The organic acid or inorganic acid in step (3) is oxalic acid, malic acid, adipic acid, boric acid or phosphoric acid, wherein the molar ratio of the acid to the catalyst metal ion is 0.1-2.0.

[0020] The adsorbent in step (3) is diatomaceous earth, activated carbon, activated clay or silicate.

[0021] The beneficial effects of the present invention are:

[0022] (1) After isobutyric acid reacts with DBU to form an ionic liquid, the isobutyrate group in it is a strong electron-donating group that can enhance the nucleophilicity of the amine group in the polyamine, making the nucleophilic addition reaction easier to proceed, indirectly reducing the difficulty of the reaction conditions and accelerating the reaction.

[0023] (2) DBU is a strong base, while isobutyric acid is a weaker acid. Water is produced after the reaction begins. Ionic liquids are equivalent to a combination of a strong base and a weak acid. Their aqueous solution is alkaline, which has a protective effect on the imine group of the reaction product.

[0024] (3) The amine group is protected by the reaction of aldehyde group, ketone group and amine group to form imine group, which is then reduced to amine group through hydrolysis reaction after polymerization to form polyetheramine. Together with the hydroxyl group formed on the ether chain, there are three reactive groups and five active hydrogens, which can significantly accelerate the curing speed of polyetheramine and epoxy resin.

[0025] (4) After the polyamine and catalyst are evenly mixed, they are added to the gaseous epoxy monomer in the form of a spray, which can increase the gas-liquid reaction area, significantly increase the polymerization reaction rate, and shorten the polymerization reaction time.

[0026] (5) After the reaction rate is increased, the occurrence of side reactions can be reduced by lowering the temperature of the reaction system. This is because the polyetheramine reaction itself is a highly exothermic reaction. When the system temperature is high, a large amount of reaction heat cannot be transferred immediately at the beginning of the reaction. The temperature at a local location in the reaction system will be too high, resulting in an increase in side reactions. In addition, heat can be released more evenly in the form of a spray, and local overheating will not occur.

[0027] (6) While reducing the occurrence of side reactions, the average chain length of the polyetheramine is also longer than that of conventional devices, thereby improving the performance of the polyetheramine product.

[0028] (7) Filtering the reaction product can separate the target product, which has the effect of purifying the product. At the same time, the unreacted polyamine can be transferred to the reactor to continue the reaction, so as to improve the reaction conversion rate and increase the yield. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 It is a schematic diagram of the structure of the reaction device of the present invention;

[0030] In the figure: 1. Reactor; 2. Pumping; 3. Hydrolysis kettle; 4. Separation kettle; 5. Atomizer; 11. Insulation layer; 12. Epoxy-type elemental gas; 13. Reactant; 14. Temperature monitor; 15. Pressure monitor; 41. Extraction pump; 42. Polytetrafluoroethylene filter layer; 43. Vacuum pump. DETAILED DESCRIPTION

[0031] The present invention is further described below in conjunction with examples, but the embodiments of the present invention are not limited thereto.

[0032] Example 1

[0033] (1) Add 228g (1.5mol) DBU to a three-necked flask, slowly drip an equimolar amount of isobutyric acid at a water bath temperature of 10°C, raise the water bath temperature to 37°C after the addition is complete, react for 16 hours, and place the product in a vacuum drying oven at 80°C for 30 hours to obtain the ionic liquid required for the reaction. Take another three-necked flask, add 2.5mol triethylenetetramine, 6mol acetone and 0.75mol ionic liquid to the flask in sequence, and react at 70°C. After reacting for 6 hours, add toluene for extraction, separate and filter, distill and dry the aqueous phase to recover the ionic liquid, and distill the organic phase under reduced pressure at a pressure of 0.02Mpa to obtain triethylenetetramine protected by ketimine.

[0034] (2) After thoroughly mixing 2 mol of triethylenetetramine protected by ketimine and 0.3% of sodium ethoxide by mass of triethylenetetramine, use a sprayer at 0.2 V under argon protection. 反应物 / min spray flow rate is added to 50mol of gaseous propylene oxide, the reaction temperature is controlled to be 85℃ and the initial reaction pressure is 0.25Mpa. After the addition is completed, when there is no obvious mist droplets in the reactor, 90% of the volume of the reactants are pumped into the separation kettle using a pump, and filtered using a polytetrafluoroethylene composite nanofiltration membrane filter layer with a membrane pore size of 1nm. At the same time, the vacuum pump in the separation kettle is turned on to speed up the filtration rate. After the filtration is completed, the vacuum pump is turned off and argon is added to the separation kettle. Triethylenetetramine and sodium ethoxide that have passed through the polytetrafluoroethylene composite nanofiltration membrane filter layer are continuously added to the reactor using a sprayer. After each cycle of 6 times, the extraction pump is turned on to extract the polyetheramine protected by ketimine into the next inert gas protected hydrolysis kettle. When the pressure in the reactor no longer changes during the cycle, the reaction is terminated to obtain a polyetheramine protected by ketimine.

[0035] (3) Add 0.4 mol phosphoric acid, 30 mol deionized water, and activated carbon accounting for 5% of the total mass of phosphoric acid and deionized water into a hydrolysis kettle, hydrolyze at 105° C. for 2 h to remove the ketimine protecting group, perform reduced pressure distillation at 90° C. and 0.02 MPa to remove acetone in the system, and finally filter to obtain the polyetheramine product.

[0036] Example 2

[0037] (1) Add 228g (1.5mol) DBU to a three-necked flask, slowly drip an equal molar amount of isobutyric acid at a water bath temperature of 5°C, raise the water bath temperature to 40°C after the addition, react for 15h, and place the product in a vacuum drying oven at 80°C for 32h to obtain the ionic liquid required for the reaction. Take another three-necked flask, add 1.5mol tetraethylenepentamine, 4.5mol butyraldehyde and 0.45mol ionic liquid to the flask in sequence, and react at 60°C. After reacting for 7h, add toluene for extraction, separate and filter, distill and dry the aqueous phase to recover the ionic liquid, and distill the organic phase under reduced pressure at a pressure of 0.02Mpa to obtain tetraethylenepentamine protected by aldimine.

[0038] (2) After fully mixing 1 mol of tetraethylenepentamine protected by aldimine and 0.3% potassium oxide by mass of tetraethylenepentamine, use a sprayer at 0.15V under argon protection. 反应物 / min spray flow rate is added to 20mol of gaseous ethylene oxide, the reaction temperature is controlled to be 75℃ and the initial reaction pressure is 0.3Mpa. After the addition is completed, when there is no obvious mist droplet in the reactor, 90% of the volume of the reactants are pumped into the separation kettle using a pump, and filtered using a polytetrafluoroethylene composite nanofiltration membrane filter layer with a membrane pore size of 1nm. At the same time, the vacuum pump in the separation kettle is turned on to speed up the filtration rate. After the filtration is completed, the vacuum pump is turned off and argon is added to the separation kettle. Tetraethylene pentamine and potassium oxide that have passed through the polytetrafluoroethylene composite nanofiltration membrane filter layer are continuously added to the reactor using a sprayer. After each cycle of 6 times, the extraction pump is turned on to extract the polyetheramine protected by aldimine into the next hydrolysis kettle protected by inert gas. When the pressure in the reactor no longer changes, the reaction is terminated to obtain a polyetheramine protected by aldimine.

[0039] (3) Add 0.5 mol of oxalic acid, 35 mol of deionized water, and diatomaceous earth accounting for 5% of the total mass of oxalic acid and deionized water into a hydrolysis kettle, hydrolyze at 60° C. for 3 h to remove the aldimine protecting group, perform reduced pressure distillation at 90° C. and 0.02 MPa to remove butyraldehyde in the system, and finally filter to obtain the polyetheramine product.

[0040] Example 3

[0041] (1) Add 228g (1.5mol) DBU to a three-necked flask, slowly drip an equimolar amount of isobutyric acid at a water bath temperature of 15°C, raise the water bath temperature to 35°C after the addition is complete, react for 17h, and place the product in a vacuum drying oven at 80°C for 28h to obtain the ionic liquid required for the reaction. Take another three-necked flask, add 1.5mol dicyandiamide, 2.5mol methyl ethyl ketone and 0.45mol ionic liquid to the flask in sequence, and react at 80°C. After reacting for 5h, add toluene for extraction, separate and filter, distill and dry the aqueous phase to recover the ionic liquid, and distill the organic phase under reduced pressure at a pressure of 0.02Mpa to obtain dicyandiamide protected by ketimine.

[0042] (2) After thoroughly mixing 1 mol of dicyandiamide protected by ketimine and 0.4% of metallic sodium by weight of dicyandiamide, use a sprayer at 0.25V under argon protection. 反应物 / min spray flow rate is added to 20mol of gaseous ethylene oxide and 20mol of gaseous propylene oxide, the reaction temperature is controlled to be 95°C and the initial reaction pressure is 0.2Mpa. After the addition is completed, when there is no obvious mist droplet in the reactor, 90% of the volume of the reactants is pumped into the separation kettle using a pump, and filtered using a polytetrafluoroethylene composite nanofiltration membrane filter layer with a membrane pore size of 1nm. At the same time, the vacuum pump in the separation kettle is turned on to speed up the filtration rate. After the filtration is completed, the vacuum pump is turned off and argon is added to the separation kettle. The dicyandiamide and metallic sodium that have passed through the polytetrafluoroethylene composite nanofiltration membrane filter layer are continuously added to the reactor using a sprayer. After each cycle of 6 times, the extraction pump is turned on to extract the polyetheramine protected by ketimine into the next inert gas protected hydrolysis kettle. When the pressure in the reactor no longer changes, the reaction is terminated to obtain the polyetheramine protected by ketimine.

[0043] (3) Add 0.5 mol of boric acid, 25 mol of deionized water, and activated clay accounting for 10% of the total mass of boric acid and deionized water into a hydrolysis kettle, hydrolyze at 150° C. for 1 h to remove the ketimine protecting group, perform reduced pressure distillation at 90° C. and 0.02 MPa to remove methyl ethyl ketone in the system, and finally filter to obtain the polyetheramine product.

[0044] Comparative Example 1

[0045] The difference between this comparative example and Example 1 lies in step (1): taking a three-necked flask, dissolving 2.5 mol of triethylenetetramine and 6 mol of acetone in toluene, reacting at 110° C. for 8 h, separating and filtering, and distilling the organic phase under reduced pressure at 0.02 MPa to obtain ketimine-protected triethylenetetramine. The remaining steps are the same as those in Example 1.

[0046] Comparative Example 2

[0047] The difference between this comparative example and Example 1 lies in the preparation method of the ionic liquid: 228 g (1.5 mol) of DBU is added to a three-necked flask, and an equal molar amount of glacial acetic acid is slowly dripped in at a water bath temperature of 15°C. After the addition is completed, the water bath is raised to 35°C and the reaction is carried out for 17 hours. After the reaction, the product is placed in a vacuum drying oven at 80°C and dried for 28 hours to obtain the ionic liquid required for the reaction. The remaining steps are the same as in Example 1.

[0048] Comparative Example 3

[0049] The difference between this comparative example and Example 1 lies in step (2) and step (3): 2 mol of triethylenetetramine protected by ketimine and 0.3 wt% of sodium ethoxide are added to a polymerization reactor, argon is introduced for protection, 50 mol of propylene oxide is added dropwise, the reaction temperature is controlled to be 120°C and the reaction pressure is controlled to be 5 MPa, and after the addition is completed, the reaction is continued for 5 hours to obtain a polyetheramine protected by ketimine. Then, 0.4 mol of phosphoric acid, 30 mol of deionized water, and activated carbon accounting for 5% of the total mass of phosphoric acid and deionized water are added to the polymerization reactor, hydrolyzed at 105°C for 2 hours to remove the ketimine protecting group, and vacuum distilled at 90°C and 0.02 MPa to remove acetone in the system, and finally filtered to obtain the polyetheramine product, and the remaining steps are the same as those in Example 1.

[0050] Comparative Example 4

[0051] The difference between this comparative example and Example 1 is that the spray flow rate of the sprayer is 0.4V 反应物 / min.

[0052] Comparative Example 5

[0053] The difference between this comparative example and Example 1 is that the spray flow rate of the sprayer is 0.05V 反应物 / min.

[0054] The results of Examples 1, 2, and 3 of the present invention are compared with those of Comparative Examples 1, 2, 3, 4, and 5, as shown in Table 1. The corresponding meanings of the symbols in the table are as follows:

[0055] t 1 -Reaction time of polyamine and aldehyde or ketone; T 1 -Reaction temperature of polyamine with aldehyde or ketone; α 1 -polyamine conversion rate;

[0056] t 2 -Reaction time of polyamine and epoxy monomer; T 2 -Reaction temperature of polyamine and epoxy monomer; P-reaction pressure of polyamine and epoxy monomer;

[0057] α 2 -polyetheramine yield;

[0058] Table 1 Comparison of some results of the embodiments of the present invention

[0059] Implementation items <![CDATA[t 1 (h)]]> <![CDATA[T 1 (℃)]]> <![CDATA[α 1 (%)]]> <![CDATA[t 2 (h)]]> <![CDATA[T 2 (℃)]]> P(Mpa) <![CDATA[α 2 (%)]]> Example 1 6 70 96 3.5 85 0.25 95.5 Example 2 6.5 60 93 3.9 75 0.3 94.1 Example 3 6.3 80 94 3.8 95 0.2 94.4 Comparative Example 1 8 110 95 4.1 85 0.25 92.8 Comparative Example 2 7.2 70 95 4.0 85 0.25 93.0 Comparative Example 3 6 70 94 5 120 5 90.5 Comparative Example 4 6 70 95 4.2 85 0.25 93.1 Comparative Example 5 6 70 94 4.0 85 0.25 93.9

[0060] Note: For technical parameters not listed, please refer to the examples.

[0061] The performance of the polyetheramines produced in Examples 1, 2, 3, 4, and 5 of the present invention was compared with that of D230, as shown in Table 2.

[0062] Table 2 Comparison of performance results of the embodiments of the present invention

[0063] Implementation items Curing time (h) D230 8.5 Example 1 2.9 Example 2 3.3 Example 3 3.2 Comparative Example 1 3.4 Comparative Example 2 3.7 Comparative Example 3 4.2 Comparative Example 4 3.5 Comparative Example 5 3.4

[0064] Combining the data in Tables 1 and 2, it can be seen that the method of the present invention effectively reduces the difficulty of reaction conditions in the polyetheramine synthesis process by improving the solvent and the reaction device; reduces the occurrence of side reactions, thereby increasing the yield of the polyetheramine; and compared with the common D230 type polyetheramine, the curing speed is significantly improved.

Claims

1. A method for preparing a polyetheramine, The following steps are involved: (1) polyamine, ketone or aldehyde, and ionic liquid are sequentially added into the reaction system in a molar ratio of 1:1.5 to 3:0.3, reacted at a temperature of 60 to 80°C for 5 to 7 hours, and then toluene is added for extraction, the liquid is separated and filtered, the aqueous phase is distilled and dried to recover the ionic liquid, and the organic phase is distilled under reduced pressure at a pressure of 0.02 MPa to obtain an amine compound protected by ketimine or aldimine; (2) 0.5-1.5 mol of an amine compound protected by ketimine or aldimine is used as an initiator, and after being fully mixed with 0.3-0.4 wt% of a catalyst, it is sprayed into mist using a sprayer under the protection of an inert gas, and then added to a gaseous epoxy monomer with a molar ratio of 15-45 times, and the temperature is controlled to be 75-95°C and the initial reaction pressure is controlled to be 0.2-0.3 MPa. After the addition is completed, when there is no obvious mist droplet in the reactor, 90% of the volume of the reactants is pumped into a separation reactor using a pump, and filtered using a polytetrafluoroethylene filter layer. At the same time, the vacuum pump in the separation reactor is turned on. After the filtration is completed, the vacuum pump is turned off, and inert gas is added to the separation reactor; the reactants passing through the filter membrane are continuously added to the reactor using a sprayer. After each cycle of 6 times, the extraction pump is turned on to extract the polyetheramine protected by ketimine or aldimine into the next hydrolysis reactor protected by inert gas. When the pressure in the reactor no longer changes, the reaction is terminated to obtain a polyetheramine protected by ketimine or aldimine; (3) adding 0.3-0.6 mol of an organic acid or an inorganic acid, 20-40 mol of deionized water, and 5-10 wt% of an adsorbent to the polyetheramine of step (2), reacting at 60-150° C. for 1-3 h, removing the protecting group, performing reduced pressure distillation at 0.02 MPa, and filtering to obtain the polyetheramine product; The preparation method of the ionic liquid described in step (1) is as follows: DBU is added to the reaction system, and an equimolar amount of isobutyric acid is slowly dripped in at a water bath temperature of 5-15°C. After the addition is completed, the water bath is raised to 35-40°C, and the reaction is carried out for 15-17 hours. After the reaction, the product is placed in a vacuum drying oven at 80°C and dried for 28-32 hours to obtain the ionic liquid required for the reaction.

2. A method for preparing a polyetheramine according to claim 1, Features: The polyamine in step (1) is a piperazine amino derivative, aliphatic amine or aromatic amine compound containing a secondary amine or a hydroxyl group and a primary amine group; the ketone or aldehyde is aliphatic ketone, aliphatic aldehyde and its derivatives.

3. A method for preparing a polyetheramine according to claim 1, Features: The spray flow rate of the sprayer in step (2) is (0.15~0.25)V 反应物 / min.

4. A method for preparing a polyetheramine as claimed in claim 1, Features: The polytetrafluoroethylene filter layer described in step (2) is a polytetrafluoroethylene composite nanofiltration membrane with a membrane pore size of 1 nm.

5. A method for preparing a polyetheramine as claimed in claim 1, Features: The catalyst is alkali metal oxide, hydroxide, alkoxide or alkaline earth metal oxide, hydroxide, alkoxide.

6. A method for preparing a polyetheramine as claimed in claim 1, Features: The epoxy monomer in step (2) is one of ethylene oxide and propylene oxide or a mixture of the two.

7. A method for preparing a polyetheramine as claimed in claim 1, Features: The organic acid or inorganic acid in step (3) is oxalic acid, malic acid, adipic acid, boric acid or phosphoric acid, wherein the molar ratio of the acid to the catalyst metal ion is 0.1-2.

0.

8. A method for preparing a polyetheramine as claimed in claim 1, Features: The adsorbent is diatomaceous earth, activated carbon, activated clay or silicate.

9. A reaction device for the preparation method of polyetheramine as claimed in claim 1, include: A reactor (1), a pump (2), a hydrolysis reactor (3), a separation reactor (4), and an atomizer (5), characterized in that the reactor (1) is an inverted pear-shaped structure and is hollow inside, a pressure monitor (15) and a temperature monitor (14) are arranged inside the reactor (1), a heat-insulating layer (11) is arranged inside the shell of the reactor (1), the lower part of the reactor (1) is connected to one end of the pump (2) through a pipeline, and the other end of the pump (2) is connected to the separation reactor (4) through a pipeline, the separation reactor (4) is a cylindrical structure and is hollow inside, and a separation pump (15) is arranged at the top of the separation reactor (4) 41), a polytetrafluoroethylene filter layer (42) is installed in the lower middle position of the separation kettle (4), the upper pipe of the separation kettle (4) is close to the polytetrafluoroethylene filter layer (42), the separation kettle (4) is connected with the hydrolysis kettle (3) through the upper pipe, the lower part of the polytetrafluoroethylene filter layer (42) is a liquid collection chamber, the outside of the liquid collection chamber is installed with a vacuum pump (43), the bottom of the separation kettle (4) is connected with the reaction kettle (1) through a lower pipe, the lower pipe runs through the upper part of the reaction kettle (1), and an atomizer (5) is installed at the end of the lower pipe located in the reaction kettle (1).

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