CN107903387B - Method for improving propylene oxide conversion rate in polyether polyol synthesis process - Google Patents
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- CN107903387B CN107903387B CN201711214456.8A CN201711214456A CN107903387B CN 107903387 B CN107903387 B CN 107903387B CN 201711214456 A CN201711214456 A CN 201711214456A CN 107903387 B CN107903387 B CN 107903387B
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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Abstract
The invention belongs to the technical field of polyether polyol synthesis, and particularly relates to a method for improving the conversion rate of propylene oxide in the polyether polyol synthesis process. By low temperature stage polymerization: adding an initiator into a reaction kettle, adding an amine catalyst, heating to 70-95 ℃, dropwise adding propylene oxide, and carrying out a curing reaction; medium-temperature polymerization: heating to 105-115 ℃, dropwise adding propylene oxide, and curing until the pressure in the kettle is negative pressure; high-temperature polymerization: adding micromolecular amine into a reaction kettle, heating to 120-150 ℃, dropwise adding propylene oxide, supplementing pressure with nitrogen, and carrying out curing reaction; and after curing, vacuumizing to remove unreacted propylene oxide monomers to obtain the polyether polyol. According to the invention, micromolecular amines are introduced at the later stage of the polyether polyol synthesis process, so that the reaction activity is increased while the residual PO is consumed, and the PO residue in polyether is reduced; the method has the advantages of simple process, low residual propylene oxide, high yield, high production efficiency, and good economic and environmental benefits.
Description
Technical Field
The invention belongs to the technical field of polyether polyol synthesis, and particularly relates to a method for improving the conversion rate of propylene oxide in the polyether polyol synthesis process.
Background
Polyether polyol is an important raw material in the polyurethane industry, and is widely used in the fields of household appliance heat insulation, pipeline heat insulation, sandwich boards, automotive interiors, coatings and the like. In the hard foam polyether polyol synthesis industry, there are two general production processes: the polyether is refined by KOH as a catalyst, and amine is catalyzed by dimethylamine and the like, and the amine process polyether does not need complicated post-treatment links such as metal ion removal and the like of the refining process, so that the production efficiency is greatly improved. However, the amine process polyether also generally has the problems of low conversion rate and high residual amount of intermediate propylene oxide of the synthesized polyether, the yield of the product is seriously influenced, and unreacted monomers discharged in the post-treatment monomer removal process also have certain influence on the ecological environment. Therefore, a new method for solving the problem of residual propylene oxide in polyether synthesis in the amine process is very important.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for improving the conversion rate of propylene oxide in the process of synthesizing polyether polyol. The method has simple production process, the existing reaction equipment can completely meet the requirements, no additional production auxiliary equipment is needed, the obtained final polyether polyol product has less residual propylene oxide, the material yield is high, better economic benefits are realized, and increasingly severe environmental protection requirements are met.
The method for improving the conversion rate of the propylene oxide in the process of synthesizing the polyether polyol comprises the following steps:
(1) low-temperature polymerization: adding an initiator into a reaction kettle, adding an amine catalyst, heating to 70-95 ℃, dropwise adding propylene oxide, and carrying out a curing reaction;
(2) medium-temperature polymerization: heating to 105-115 ℃, dropwise adding propylene oxide, and curing until the pressure in the kettle is negative pressure;
(3) high-temperature polymerization: adding micromolecular amine into a reaction kettle, heating to 120-150 ℃, dropwise adding propylene oxide, supplementing pressure with nitrogen, and carrying out curing reaction;
(4) and after curing, vacuumizing to remove unreacted propylene oxide monomers to obtain the polyether polyol.
Wherein:
the initiator is one or more of sucrose, sorbitol, glycerol, propylene glycol or diethylene glycol, and the mass of the initiator accounts for 29-38% of the total mass of the polyether polyol.
The amine catalyst is one of monomethylamine or dimethylamine; the adding mass of the amine catalyst accounts for 0.3-1% of the total weight of the polyether polyol.
The total mass of the propylene oxide added in the steps (1) - (3) accounts for 60-70% of the total mass of the polyether polyol.
The mass of the dropwise added epoxy propane in the step (1) accounts for 10-30% of the total mass of the epoxy propane, the curing reaction time in the step (1) is 2 hours, and the reaction pressure is-0.09-0.3 MPa.
The mass of the dropwise added propylene oxide in the step (2) accounts for 40-60% of the total mass of the propylene oxide; the curing time is 0.5 to 3 hours, and the pressure in the kettle is-0.03 to-0.09 Mpa.
The micromolecule amine is one or more of ammonia water, triethylamine, trimethylamine or triethanolamine, and the added mass accounts for 0.2-1% of the total weight of the polyether polyol.
The mass of the dropwise added propylene oxide in the step (3) accounts for 10-50% of the total mass of the propylene oxide; the pressure after nitrogen pressure supplement is 0.05-0.3 Mpa, and the curing reaction time is 0.5-5 h.
In the step (4), the process of removing unreacted propylene oxide monomer by vacuumizing is that the temperature is 105-115 ℃, the pressure is below-0.088 Mpa, and the nitrogen bubbling is kept, and the reaction time is 2-5 h.
As a preferred technical scheme, the method for improving the conversion rate of the propylene oxide in the synthesis process of the polyether polyol comprises the following steps:
(1) low-temperature polymerization: adding an initiator into a reaction kettle, replacing with nitrogen for 3-5 times, pumping in an amine catalyst in vacuum, heating to 70-95 ℃, starting to continuously dropwise add propylene oxide, dropwise adding 10-30% of the total mass of the propylene oxide at the stage, and then carrying out curing reaction.
(2) Medium-temperature polymerization: heating to 105-115 ℃, continuing to dropwise add propylene oxide, dropwise adding 40-60% of the total mass of the propylene oxide at the stage, and curing for a period of time until the pressure in the kettle is negative pressure;
(3) high-temperature polymerization: pumping the micromolecule amine substances into a reaction kettle, stirring and mixing uniformly, heating to 120-150 ℃, continuously dropwise adding the remaining 10-50% of propylene oxide, supplementing pressure with nitrogen, and curing for a period of time.
(4) And after the curing is finished, sampling to test the content of the propylene oxide in the polyether, and then vacuumizing to remove unreacted PO monomer to obtain the hard foam polyether polyol product.
The amine process for synthesizing polyether polyol is generally to add a mixture of an initiator and a catalyst (amine catalyst) into a reaction kettle, heat the mixture, continuously introduce propylene oxide into the kettle at a certain temperature, keep the pressure in the kettle at a positive pressure and ensure that the propylene oxide is subjected to continuous polymerization reaction until a certain molecular weight is reached; because the polymerization product contains unreacted propylene oxide monomer (6000-20000 ppm), if the unreacted monomer is not removed, the quality of the polyurethane foam is seriously affected, so the residual propylene oxide monomer is required to be distilled under a negative pressure state, and the polymerization product can be applied to the polyurethane foam after reaching a low content.
According to the invention, the micromolecular amines are added in the later stage of polyether polyol synthesis, so that the reaction activity is increased while the residual Propylene Oxide (PO) is consumed, thereby reducing the residual propylene oxide in polyether and improving the conversion rate.
The invention has the following beneficial effects:
(1) according to the invention, the micromolecular amine catalyst is introduced at the later stage of the polyether polyol synthesis process, so that the active groups and active sites at the later stage of the polymerization reaction are increased, and the reaction activity is increased, thereby greatly reducing the propylene oxide residue in the polyether product;
(2) the method has simple process, the existing production conditions can completely meet the requirements, and no additional production auxiliary equipment is needed;
(3) the final polyether polyol product obtained by the method has less propylene oxide residue, the material yield is obviously improved, and the method has better economic benefit;
(4) the polyether polyol obtained by the method has the advantages of simple post-treatment, less monomer removal amount and high production efficiency, and meets the increasingly severe environmental protection requirements.
Detailed Description
The present invention is further described below with reference to examples.
Comparative example 1
Adding 320g of sucrose and 175g of diethylene glycol into a 2.5L polymerization reactor, then stamping the polymerization reactor, detecting to ensure good sealing performance, performing nitrogen replacement for 5 times, vacuumizing to the vacuum degree of-0.093 MPa, weighing 11g of dimethylamine aqueous solution with the mass fraction of 40%, vacuumizing into the reaction kettle, setting the heating temperature to be 85 ℃, starting to continuously dropwise add propylene oxide at 80 ℃, keeping the temperature between 80 ℃ and +/-5 ℃, stopping adding propylene oxide when the amount of added propylene oxide is 183g, and curing for 1 h; then heating to 110 ℃, continuously dropwise adding 733g of propylene oxide, curing for 2h after dropwise adding, and performing nitrogen stamping in the curing stage; and (3) reserving a sample of the cured sample, testing the residual amount of the propylene oxide, and then vacuumizing to remove the monomer for 2 hours to obtain the prepared finished polyether polyol.
Example 1
Adding 320g of sucrose and 175g of diethylene glycol into a 2.5L polymerization reactor, then stamping the polymerization reactor, detecting to ensure good sealing performance, carrying out nitrogen replacement for 5 times, then vacuumizing to the vacuum degree of-0.093 MPa, weighing 11g of dimethylamine aqueous solution with the mass fraction of 40%, vacuumizing into the reactor, setting the heating temperature to be 85 ℃, starting to continuously dropwise add propylene oxide when the temperature is 80 ℃, keeping the temperature between 80 ℃ and +/-5 ℃, stopping adding propylene oxide and curing for 1h when the added propylene oxide amount is 183g, then heating to 110 ℃, continuously dropwise adding 458g of propylene oxide and curing for 1h, gradually reducing the pressure in the reactor to negative pressure along with the progress of curing reaction, then pumping 3g of ammonia water, keeping the reaction temperature at 130 +/-5 ℃, keeping the reaction pressure at 0.2MPa, continuously dropwise adding the rest 275g of propylene oxide, curing for 2h after dropwise adding, and (3) performing nitrogen stamping in the curing stage, reserving a cured sample, testing the residual amount of the propylene oxide, and then vacuumizing to remove the monomer for 2 hours to obtain the prepared finished polyether polyol. The performance indexes of the synthesized sucrose polyether polyol are shown in Table 1.
Example 2
Adding 320g of sucrose and 175g of diethylene glycol into a 2.5L polymerization reactor, then stamping the polymerization reactor, detecting to ensure good sealing performance, carrying out nitrogen replacement for 5 times, then vacuumizing to the vacuum degree of-0.093 MPa, weighing 11g of dimethylamine aqueous solution with the mass fraction of 40%, vacuumizing into the reactor, setting the heating temperature to be 85 ℃, starting to continuously dropwise add propylene oxide when the temperature is 80 ℃, keeping the temperature between 80 ℃ and +/-5 ℃, stopping adding propylene oxide and curing for 1h when the added propylene oxide amount is 183g, then heating to 110 ℃, continuously dropwise adding 458g of propylene oxide and curing for 1h, gradually reducing the pressure in the reactor to negative pressure along with the progress of curing reaction, then pumping 7g of ammonia water, keeping the reaction temperature at 130 +/-5 ℃, keeping the reaction pressure at 0.2MPa, continuously dropwise adding the rest 275g of propylene oxide, curing for 2h after dropwise adding, and (3) performing nitrogen stamping in the curing stage, reserving a cured sample, testing the residual amount of the propylene oxide, and then vacuumizing to remove the monomer for 2 hours to obtain the prepared finished polyether polyol. The performance indexes of the synthesized sucrose polyether polyol are shown in Table 1.
Example 3
Adding 320g of sucrose and 175g of diethylene glycol into a 2.5L polymerization reactor, then stamping the polymerization reactor, detecting to ensure good sealing performance, carrying out nitrogen replacement for 5 times, then vacuumizing to the vacuum degree of-0.093 MPa, weighing 11g of dimethylamine aqueous solution with the mass fraction of 40%, vacuumizing into the reactor, setting the heating temperature to be 85 ℃, starting to continuously dropwise add propylene oxide when the temperature is 80 ℃, keeping the temperature between 80 ℃ and +/-5 ℃, stopping adding propylene oxide and curing for 1h when the added propylene oxide amount is 183g, then heating to 110 ℃, continuously dropwise adding 458g of propylene oxide and curing for 1h, gradually reducing the pressure in the reactor to negative pressure along with the progress of curing reaction, then pumping 14g of ammonia water, keeping the reaction temperature at 130 +/-5 ℃, keeping the reaction pressure at 0.2MPa, continuously dropwise adding the rest 275g of propylene oxide, curing for 2h after dropwise adding, and (3) performing nitrogen stamping in the curing stage, reserving a cured sample, testing the residual amount of the propylene oxide, and then vacuumizing to remove the monomer for 2 hours to obtain the prepared finished polyether polyol. The performance indexes of the synthesized sucrose polyether polyol are shown in Table 1.
Example 4
Adding 320g of sucrose and 175g of diethylene glycol into a 2.5L polymerization reactor, then stamping the polymerization reactor, detecting to ensure good sealing performance, carrying out nitrogen replacement for 5 times, then vacuumizing to the vacuum degree of-0.093 MPa, weighing 11g of 40% dimethylamine aqueous solution, vacuumizing into the reactor, setting the heating temperature to 85 ℃, starting to continuously dropwise add propylene oxide at 80 ℃, keeping the temperature between 80 ℃ and plus or minus 5 ℃, stopping adding propylene oxide when the amount of added propylene oxide is 183g, curing for 1h, heating to 110 ℃, continuously dropwise adding 458g of propylene oxide, curing for 1h, gradually reducing the pressure in the reactor to negative pressure along with the progress of curing reaction, then pumping 7g of trimethylamine, keeping the reaction temperature at 130 ℃ and minus 5 ℃, keeping the reaction pressure at 0.2MPa, continuously dropwise adding the rest 275g of propylene oxide, curing for 2h after the dropwise adding, stamping with nitrogen in the curing stage, and (3) reserving a cured sample, testing the residual amount of the propylene oxide, and then vacuumizing to remove the monomer for 2 hours to obtain the prepared finished polyether polyol. The performance indexes of the synthesized sucrose polyether polyol are shown in Table 1.
Example 5
Adding 320g of sucrose and 175g of diethylene glycol into a 2.5L polymerization reactor, then stamping the polymerization reactor, detecting to ensure good sealing performance, carrying out nitrogen replacement for 5 times, then vacuumizing to the vacuum degree of-0.093 MPa, weighing 11g of 40% dimethylamine aqueous solution, vacuumizing into the reactor, setting the heating temperature to 85 ℃, starting to continuously dropwise add propylene oxide at 80 ℃, keeping the temperature between 80 ℃ and plus or minus 5 ℃, stopping adding propylene oxide when the amount of added propylene oxide is 183g, curing for 1h, heating to 110 ℃, continuously dropwise adding 458g of propylene oxide, curing for 1h, gradually reducing the pressure in the reactor to negative pressure along with the progress of curing reaction, then pumping 7g of triethylamine, keeping the reaction temperature at 130 ℃ and minus 5 ℃, keeping the reaction pressure at 0.2MPa, continuously dropwise adding the rest 275g of propylene oxide, curing for 2h after dropwise adding, carrying out nitrogen stamping in the curing stage, and (3) reserving a cured sample, testing the residual amount of the propylene oxide, and then vacuumizing to remove the monomer for 2 hours to obtain the prepared finished polyether polyol. The performance indexes of the synthesized sucrose polyether polyol are shown in Table 1.
TABLE 1 hard foam polyether polyol performance index tables obtained in examples 1-5 and comparative example 1
As can be seen from the comparative example 1 and the examples 1 to 5, the residual amount of propylene oxide in the polyether polyol is obviously lower than that of the polyether polyol prepared by the conventional method, and the reaction yield is also obviously improved; wherein, the residual amount of the propylene oxide in the methods of the examples 1 to 5 is between 200 and 350mg/kg, and the results of the examples 1 to 5 show that the change of the dosage of the small molecular amine achieves the purpose of obviously reducing the residual amount of the propylene oxide.
Claims (4)
1. A method for improving the conversion rate of propylene oxide in the process of synthesizing polyether polyol is characterized in that: the method comprises the following steps:
(1) low-temperature polymerization: adding an initiator into a reaction kettle, adding an amine catalyst, heating to 70-95 ℃, dropwise adding propylene oxide, and carrying out a curing reaction;
(2) medium-temperature polymerization: heating to 105-115 ℃, dropwise adding propylene oxide, and curing until the pressure in the kettle is negative pressure;
(3) high-temperature polymerization: adding micromolecular amine into a reaction kettle, heating to 120-150 ℃, dropwise adding propylene oxide, supplementing pressure with nitrogen, and carrying out curing reaction;
(4) after curing, vacuumizing to remove unreacted propylene oxide monomer to obtain polyether polyol;
the mass of the dropwise added propylene oxide in the step (1) accounts for 10-30% of the total mass of the propylene oxide; curing reaction time in the step (1) is 2 hours, and reaction pressure is-0.09-0.3 Mpa;
the mass of the dropwise added propylene oxide in the step (2) accounts for 40-60% of the total mass of the propylene oxide; the curing time is 0.5 to 3 hours, and the pressure in the kettle is-0.03 to-0.09 Mpa;
the mass of the dropwise added propylene oxide in the step (3) accounts for 10-50% of the total mass of the propylene oxide; after the nitrogen is used for pressure compensation, the pressure is 0.05-0.3 Mpa, and the curing reaction time is 0.5-5 h;
the amine catalyst is one of monomethylamine or dimethylamine; the added mass accounts for 0.3-1% of the total weight of the polyether polyol;
the micromolecule amine is one or more of ammonia water, triethylamine or triethanolamine, and the added mass accounts for 0.2-1% of the total mass of the polyether polyol.
2. The method of increasing the conversion of propylene oxide during the synthesis of polyether polyols according to claim 1, wherein: the initiator is one or more of sucrose, sorbitol, glycerol, propylene glycol or diethylene glycol, and accounts for 29-38% of the total mass of the polyether polyol.
3. The method of increasing the conversion of propylene oxide during the synthesis of polyether polyols according to claim 1, wherein: the total mass of the propylene oxide added in the steps (1) - (3) accounts for 60-70% of the total mass of the polyether polyol.
4. The method of increasing the conversion of propylene oxide during the synthesis of polyether polyols according to claim 1, wherein: in the step (4), the unreacted propylene oxide monomer is removed by vacuumizing, wherein the temperature is 105-115 ℃, the pressure is below-0.088 Mpa, and the nitrogen bubbling is kept, and the reaction time is 2-5 h.
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