CN114106317B - Polyether continuous synthesis method - Google Patents
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- CN114106317B CN114106317B CN202111487696.1A CN202111487696A CN114106317B CN 114106317 B CN114106317 B CN 114106317B CN 202111487696 A CN202111487696 A CN 202111487696A CN 114106317 B CN114106317 B CN 114106317B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2663—Metal cyanide catalysts, i.e. DMC's
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2696—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the process or apparatus used
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Abstract
The invention discloses a novel technological process for continuously synthesizing polyether, and belongs to the field of polyether polyol synthesis. The invention mainly relates to a mode of adopting 4 reactors in series, epoxide is added into a first reaction kettle to pre-react with a catalyst, so that the catalyst is activated, the particle size is smaller than 1um, polyether polyol produced by the process has the characteristics of low viscosity and narrow distribution, the productivity of a device can be improved, and the product based on the process has wide application in the fields of soft foam, CASE and the like.
Description
Technical Field
The invention relates to a method for continuously synthesizing polyether, belonging to the field of polyether synthesis.
Background
Polyether polyols are an important starting material for polyurethane synthesis and are generally obtained by epoxide ring-opening polymerization. Currently, the most used catalyst systems in industry are alkali metal catalysts and bimetallic catalysts (DMC). DMC catalysts have the advantages of higher catalytic efficiency, no need for desalting treatment, and low unsaturation of the product compared with conventional alkali metal catalysts, and are therefore favored in industrial production. Especially DMC catalysts have the latch-Up effect and are therefore developed for continuous production.
The polyether polyol is produced by adopting a continuous process, the occupied area of the device is small, the product quality is stable, and the production cost is low. However, the products synthesized by the continuous process have the problems of larger viscosity and wider PDI. Taking Wanhua commercial brand F3156 as an example, the viscosity of a product synthesized by a KOH batch process is generally 480+/-10 cp@25 ℃, the PDI is about 1.05, the viscosity of a product with the same structure synthesized by other companies by adopting a continuous process is 560-700cp@25 ℃, and the PDI is about 1.25-1.40. This limits the field of application of continuous products, especially synthetic polymer polyols.
Therefore, improving the polyether continuous production process to produce low viscosity, narrow distribution products is the focus of current research.
Disclosure of Invention
The aim of the patent is to provide a polyether continuous synthesis process, by using the polymerization process, not only the synthesized product has the characteristic of low viscosity, but also the PDI distribution is narrower than that of the currently marketed continuous product, and the device productivity is improved by 10%.
In order to achieve the above purpose, the invention adopts the following technical scheme:
A method for continuously synthesizing polyether adopts a mode of connecting 4 reactors in series, wherein the first reactor is a catalyst pre-reaction kettle, the second reactor is a catalyst storage kettle, the third reactor is a product reaction kettle, and the fourth reactor is an aging reaction kettle. Wherein the first reactor is pre-reacted by adding epoxide so that the catalyst is activated and the particle size is less than 1um.
As a preferred scheme, the method for continuously synthesizing the polyether comprises the following steps of:
A. Adding DMC catalyst with certain particle size and concentration and low molecular polyether into a first reactor, introducing a certain amount of epoxide at a certain temperature for activation, and reacting to a set molecular weight, so that the particle size of the DMC catalyst is less than 1um; transferring the catalyst into a second reactor for storage, and keeping the temperature at 100-140 ℃;
B. introducing the activated catalyst solution, the small molecular alcohol and the epoxide into a third reactor according to a designed proportion, maintaining a certain temperature and pressure, and overflowing to a fourth reactor after the reaction is completed;
C. and aging in the fourth reactor at a certain temperature, and reducing the temperature to a certain temperature after aging to transfer the product into a packaging system.
Further, the first, third and fourth reactors may be stirred, jet, spray or tubular reactors, respectively, preferably all three reactors are stirred.
In step A: further, the DMC catalyst has an average particle size of 10 to 500um, preferably 10 to 100um.
Further, the low molecular polyether functionality of the dispersed DMC catalyst is consistent with the target product and has a molecular weight of 300g/mol to 1000g/mol, preferably 300 to 600g/mol.
Further, the low molecular weight polyether may be one or more of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerol, and trimethylolpropane.
Further, the DMC catalyst concentration in the low molecular polyether is 1000-20000ppm, preferably 5000-10000ppm.
Further, the catalyst activation temperature is 120-180 ℃, preferably 140-160 ℃. The molecular weight after activation is set to 600-2000g/mol, preferably 900-1200g/mol.
Further, the epoxide is one or two of ethylene oxide and propylene oxide.
Further, the epoxide is used in an amount of 1 to 3 times, preferably 1 to 1.5 times, the mass of the low molecular polyether; after the reaction, the DMC catalyst particle size was measured to be < 1um.
In step B:
further, the catalyst concentration in the third reactor is in the range of 15 to 50ppm, preferably 25 to 35ppm.
Further, the small molecular alcohol may be one or a mixture of propylene glycol, dipropylene glycol, ethylene glycol, diethylene glycol, glycerol and trimethylolpropane, and the kind of the polyhydric alcohol may be selected according to the product series. The proportions of the activated catalyst solution, the small molecule alcohol and the epoxide are designed according to the polyether polyol product prepared.
Further, the reaction temperature is 120 to 180 ℃, preferably 130 to 150 ℃.
Further, the reaction pressure is 0.05 to 1MPaG, preferably 0.4 to 0.6MPaG.
In step C:
The aging reaction temperature is 120-130 ℃, the residence time is 10-120min, the temperature is reduced to 60-80 ℃ and the product enters a packaging system.
Mature continuous polyether production technology exists in the industry, the problem that the viscosity of the product is higher than that of KOH is common, and the application range of the product is limited. Literature studies suggest that the main cause of the viscosity bias is that DMC catalysis produces very small amounts of ultra-high molecular weight polymer and entanglement results in the viscosity bias. The invention reduces the particle size of the catalyst to below 1um by increasing the pre-reaction process of the DMC catalyst, thereby reducing the ultra-high molecular weight polymer generated when the catalyst continuously becomes smaller in the reaction process, further reducing the viscosity of the product. By taking 3000 molecular weight copolymerized soft foam polyether as an example, through experimental tests, the viscosity is 500cp@25 ℃, which is lower than that of a commercial product (580cp@25 ℃), and the productivity of the device is improved by 10%.
The product prepared by the process can be applied to the fields of soft foam, CASE and the like, and particularly can be used for synthesizing low-viscosity polymer polyol.
Compared with the prior art, the invention has the outstanding characteristics and excellent effects that:
1. The key characteristics of the novel process are that the catalyst is pre-activated, the grain diameter is controlled to be less than 1um by a chemical method, and then high molecular weight byproducts are reduced, the product viscosity is low, the distribution is narrow, and the application range of the product is wider;
2. By the catalyst pre-activation process, plant throughput is improved.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
Particle size distribution
The measurement was performed by using a Markov laser particle sizer. A small amount of catalyst is taken and dispersed in tertiary butanol for 10min, tertiary butanol is taken as a dispersion medium to be measured twice, and an average value is obtained.
Apparent viscosity
The Brookfield DV-II+Pro viscometer was used with a 34# spindle. The shear viscosity torque was measured to be 50. The specific measurement method is that the rotor is placed in POP feed liquid and connected to a Brookfield DV-II+Pro viscometer, and the measurement is carried out according to the required conditions.
Molecular weight and distribution
The apparatus was Waters 1525/2414, three columns (STYRAGEL HR, HR4, HR 3) were connected in series, the mobile phase was tetrahydrofuran, and polystyrene was calibrated using Gel Permeation Chromatography (GPC).
Other projects are mainly determined by national standard method, and hydroxyl value is determined by chemical titration (GB/T12008.3-2009).
Example 1
Continuous synthesis of soft foam EO/PO polyether polyol with molecular weight of 3000g/mol
1) Pre-reacting a catalyst: 500g of a low molecular weight polyether (molecular weight 500g/mol, glycerol onset, EO/PO copolymerization) were added to the first reactor, followed by 2.5g of DMC catalyst having an average particle size of 100. Mu.m, stirred well, catalyst concentration 5000ppm, nitrogen displacement of the reactor, heating to 140℃and 50g of EO/PO (wherein EO represents 10% by weight) were added, and after a significant increase in temperature and pressure drop, EO/PO (wherein EO represents 10% by weight) was continuously introduced in a total amount of 500g. Testing the hydroxyl value of the product and the particle size of DMC catalyst in the product, transferring the product into a second kettle for storage after the product is qualified, and keeping the temperature to 120 ℃; (hydroxyl number: 168.5g/mol, reduced molecular weight 998.8g/mol, average particle size of catalyst: 745 nm).
2) The main reaction: continuously adding the activated catalyst solution, glycerin and EO/PO (wherein EO accounts for 10% wt) into a third reaction kettle according to a mass ratio of 1:3:100, maintaining the reaction temperature to be 130 ℃, and reacting at a reaction pressure of 0.4MPaG, and overflowing to a fourth reaction kettle after the reaction is completed; the experimental residence time was 2.5h.
3) Aging and discharging: the aging kettle is controlled at 125 ℃, and is cooled to 70 ℃ for discharging after staying for 10min. (hydroxyl number: 56.4mgKOH/g, viscosity 490cp@25deg.C, PDI of about 1.18).
Example 2
Continuous synthesis of polyether polyol with molecular weight of 3000g/mol
1) Pre-reacting a catalyst: 500g of low molecular weight polyether (molecular weight 500g/mol, glycerin initiation and PO polymerization) was added to the first reactor, followed by adding 2.5g of DMC catalyst having an average particle size of 200um, stirring well, catalyst concentration of 5000ppm, nitrogen substitution was performed to the reactor, heating to 150 ℃, adding 50g of PO, and continuing to introduce PO after a significant temperature increase and pressure drop was observed, the total amount being 750g. Testing the hydroxyl value of the product and the particle size of DMC catalyst in the product, transferring the product into a second kettle for storage after the product is qualified, and keeping the temperature to 100 ℃; (hydroxyl number: 135.0g/mol, reduced molecular weight 1246.7g/mol, average particle size of catalyst: 356 nm).
2) The main reaction: continuously adding the activated catalyst solution, glycerol and PO into a third reaction kettle according to the mass ratio of 1:1.75:57, maintaining the reaction temperature at 140 ℃, and the reaction pressure at 0.2MPaG, and overflowing to a fourth reaction kettle after the reaction is completed; the experimental residence time was 3.0h.
3) Aging and discharging: the aging kettle is controlled at 125 ℃, and is cooled to 70 ℃ for discharging after staying for 20 min. (hydroxyl number: 56.6mgKOH/g, viscosity 470cp@25℃, PDI of about 1.17).
Example 3
Continuous synthesis of polyether polyol for CASE with molecular weight of 2000g/mol
1) Pre-reacting a catalyst: 300g of low molecular weight polyether (molecular weight 300g/mol, propylene glycol initiation and PO polymerization) was added to the first reactor, followed by 0.3g of DMC catalyst having an average particle size of 10. Mu.m, stirred well, catalyst concentration 1000ppm, nitrogen substitution was carried out on the reactor, heating to 120℃and 30g of EO/PO (wherein EO accounts for 10% by weight) were added, and after a significant temperature increase and pressure drop, PO was continuously introduced in a total amount of 900g. Testing the hydroxyl value of the product and the particle size of DMC catalyst in the product, transferring the product into a second kettle for storage after the product is qualified, and keeping the temperature to 140 ℃; (hydroxyl number: 94.1g/mol, reduced molecular weight 1192.3g/mol, average particle size of catalyst: 145 nm).
2) The main reaction: continuously adding the activated catalyst solution, propylene glycol and PO into a third reaction kettle according to the mass ratio of 1.69:1:26.5, maintaining the reaction temperature to be 120 ℃, and reacting at the reaction pressure of 0.05MPaG, and overflowing to a fourth reaction kettle after the reaction is completed; the experimental residence time was 4h.
3) Aging and discharging: the aging kettle is controlled at 120 ℃, and is cooled to 60 ℃ for discharging after staying for 60 min. (hydroxyl number: 56.9mgKOH/g, viscosity 340cp@25℃, PDI of about 1.15).
Example 4
Continuous synthesis of polyether polyol for CASE with molecular weight of 4000g/mol
1) Pre-reacting a catalyst: 500g of low molecular weight polyether (molecular weight 500g/mol, propylene glycol initiation and PO polymerization) was added to the first reactor, followed by adding 10g of DMC catalyst having an average particle size of 500um, stirring well, catalyst concentration 20000ppm, nitrogen substitution was performed to the reactor, heating to 180 ℃, adding 50g of PO, and continuing to introduce PO after a significant temperature increase and pressure drop was observed, the total amount being 500g. Testing the hydroxyl value of the product and the particle size of DMC catalyst in the product, transferring the product to a second kettle for storage after the product is qualified, and keeping the temperature to 130 ℃; (hydroxyl number: 56.2g/mol, reduced molecular weight 1996.4g/mol, average particle size of catalyst: 805 nm).
2) The main reaction: continuously adding the activated catalyst solution, propylene glycol and PO into a third reaction kettle according to the mass ratio of 1:3:200, maintaining the reaction temperature at 180 ℃, and overflowing to a fourth reaction kettle after the reaction is completed to the full kettle under the reaction pressure of 1.0 MPaG; the experimental residence time was 7h.
3) Aging and discharging: the aging kettle is controlled at 130 ℃, and is cooled to 80 ℃ for discharging after staying for 120 min. (hydroxyl number: 28.3mgKOH/g, viscosity 840cp@25deg.C, PDI of about 1.23).
Example 5
Continuous synthesis of polyether polyol for CASE with molecular weight of 3000g/mol
1) Pre-reacting a catalyst: 400g of low molecular weight polyether (molecular weight 400g/mol, propylene glycol initiation and PO polymerization) was added to the first reactor, followed by adding 4g of DMC catalyst having an average particle size of 50um, stirring well, catalyst concentration 10000ppm, nitrogen substitution was performed to the reactor, heating to 160 ℃, adding 50g of PO, and continuing to introduce PO after a significant temperature increase and pressure drop was observed, the total amount being 800g. Testing the hydroxyl value of the product and the particle size of DMC catalyst in the product, transferring the product into a second kettle for storage after the product is qualified, and keeping the temperature to be 110 ℃; (hydroxyl number: 93.8g/mol, reduced molecular weight 1196.2g/mol, average particle size of catalyst: 521 nm).
2) The main reaction: continuously adding the activated catalyst solution, propylene glycol and PO into a third reaction kettle according to the mass ratio of 1:2.3:100, maintaining the reaction temperature at 150 ℃ and the reaction pressure at 0.6MPaG, and overflowing to a fourth reaction kettle after the reaction is completed; the experimental residence time was 5h.
3) Aging and discharging: the aging kettle is controlled at 130 ℃, and is cooled to 80 ℃ for discharging after being kept for 90 min. (hydroxyl number: 37.8mgKOH/g, viscosity 620cp@25℃, PDI of about 1.24).
Comparative example 1
Continuous synthesis of soft foam EO/PO polyether polyol with molecular weight of 3000g/mol
1) Catalyst configuration: 1000g of low molecular weight polyether (molecular weight 1000g/mol, glycerol initiation) was added to the first reactor, followed by 2.5g of DMC catalyst having an average particle size of 100. Mu.m, stirred well, at a catalyst concentration of 2500ppm;
2) The main reaction: continuously adding the catalyst solution, glycerin and EO/PO (wherein EO accounts for 10% wt) into a third reaction kettle according to a mass ratio of 1:3:100, maintaining the reaction temperature to be 130 ℃, and reacting at a reaction pressure of 0.4MPaG, and overflowing to a fourth reaction kettle after the reaction is completed; the experimental residence time was 2.7h.
3) Aging and discharging: the aging kettle is controlled at 125 ℃, and is cooled to 70 ℃ for discharging after staying for 2 hours. ( Hydroxyl number: 56.3mgKOH/g, viscosity 590cp@25deg.C, PDI of about 1.28 )
In comparison with example 1, it was found that the catalyst was not pre-reacted, 1000g/mol polyether was used directly for dispersion and then added to the main reaction, the product viscosity was higher, the PDI was higher, and the residence time was increased by 8%.
Comparative example 2
Continuous synthesis of soft foam EO/PO polyether polyol with molecular weight of 3000g/mol
1) Catalyst grinding and screening: grinding DMC catalyst by using a ball mill, sieving to obtain a catalyst with an average particle size of 150nm, adding 1000g of low molecular weight polyether (molecular weight 1000g/mol, glycerin initiation) into a first reaction kettle, and then adding 2.5g of DMC catalyst with an average particle size of 150nm, stirring uniformly, wherein the catalyst concentration is 2500ppm;
2) The main reaction: continuously adding the catalyst solution, glycerin and EO/PO (wherein EO accounts for 10% wt) into a third reaction kettle according to a mass ratio of 1:3:100, maintaining the reaction temperature to be 130 ℃, and reacting at a reaction pressure of 0.4MPaG, and overflowing to a fourth reaction kettle after the reaction is completed; the experimental residence time was 2.65h.
3) Aging and discharging: the aging kettle is controlled at 125 ℃, and is cooled to 70 ℃ for discharging after staying for 2 hours. ( Hydroxyl number: 56.5mgKOH/g, viscosity 580cp@25deg.C, PDI of about 1.25 )
In comparison with example 1, it was found that the catalyst was broken up by physical means and the main reaction was added after dispersion using 1000g/mol polyether, the product viscosity remained higher, the PDI was higher and the residence time increased by 6%.
Claims (16)
1. A method for continuously synthesizing polyether is characterized in that a mode of connecting 4 reactors in series is adopted, wherein a first reactor is a catalyst pre-reaction kettle, a second reactor is a catalyst storage kettle, a third reactor is a product reaction kettle, and a fourth reactor is an aging reaction kettle; the method comprises the following steps:
A. adding DMC catalyst with certain particle size and concentration and low molecular polyether into a first reactor, introducing a certain amount of epoxide at a certain temperature for activation, and reacting to a set molecular weight, wherein the particle size of the DMC catalyst is less than 1um, and the activation temperature of the catalyst is 120-180 ℃; transferring the catalyst into a second reactor for storage, and keeping the temperature at 100-140 ℃;
B. introducing the activated catalyst solution, the small molecular alcohol and the epoxide into a third reactor according to a designed proportion, maintaining a certain temperature and pressure, and overflowing to a fourth reactor after the reaction is completed;
C. and aging in the fourth reactor at a certain temperature, and reducing the temperature to a certain temperature after aging to transfer the product into a packaging system.
2. The method of claim 1, wherein the first, third, and fourth reactors are stirred reactors, jet reactors, spray reactors, or tubular reactors.
3. The method according to claim 2, wherein each of the three reactors uses a stirred reactor.
4. The method of claim 1, wherein in step a, the DMC catalyst has an average particle size of 10 to 500um; the DMC catalyst is present in the polyether at a concentration of from 1000 to 20000ppm.
5. The method of claim 4, wherein in step a, the DMC catalyst has an average particle size of 10 to 100um; the DMC catalyst is present in the polyether at a concentration of 5000 to 10000ppm.
6. The method of any of claims 1-5, wherein the dispersed DMC catalyst has a low molecular polyether functionality consistent with the target product and a molecular weight of 300g/mol to 1000g/mol; the low molecular weight polyether is polyether with one or more of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerol and trimethylolpropane as an initiator.
7. The method of claim 6, wherein the low molecular polyether dispersing the DMC catalyst has a molecular weight of 300 to 500g/mol.
8. The method according to any one of claims 1 to 5, wherein the set molecular weight after activation is 600-2000 g/mol.
9. The method of claim 8, wherein the catalyst activation temperature is 140-160 ℃; and/or the set molecular weight after activation is 900-1200 g/mol.
10. The method of any one of claims 1-5, wherein the epoxide is one or both of ethylene oxide and propylene oxide; in step A, the epoxide is used in an amount of 1 to 3 times the mass of the low molecular polyether.
11. The method of claim 10, wherein the epoxide is used in an amount of 1 to 1.5 times the mass of the low molecular polyether.
12. The method according to any one of claims 1-5, wherein in step B: the concentration range of the catalyst solution is 15-50ppm; the small molecular alcohol is one or more of propylene glycol, dipropylene glycol, ethylene glycol, diethylene glycol, glycerol and trimethylolpropane.
13. The method according to claim 12, wherein in step B: the catalyst solution concentration ranges from 25 to 35ppm.
14. The method according to any one of claims 1-5, wherein in step B: the reaction temperature is 120-180 ℃; the reaction pressure is 0.05-1MPaG.
15. The method according to claim 14, wherein in step B: the reaction temperature is 130-150 ℃; the reaction pressure is 0.4-0.6MPaG.
16. The method according to any one of claims 1-5, wherein in step C: the aging reaction temperature is 120-130 ℃, and the residence time is 10-120min.
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