CN112708125A - Preparation method of sorbitol-based polyether polyol - Google Patents
Preparation method of sorbitol-based polyether polyol Download PDFInfo
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- CN112708125A CN112708125A CN201911026161.7A CN201911026161A CN112708125A CN 112708125 A CN112708125 A CN 112708125A CN 201911026161 A CN201911026161 A CN 201911026161A CN 112708125 A CN112708125 A CN 112708125A
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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
- C08G65/2648—Alkali metals or compounds thereof
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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 relates to a preparation method of sorbitol-based polyether polyol, which mainly solves the problems of high hydroxyl value, low viscosity and dark color of a product in the existing method using liquid sorbitol as an initiator, and comprises the following steps: s1, carrying out polymerization reaction on the liquid sorbitol, the catalyst and a part of epoxide, and dehydrating the obtained product to obtain a first intermediate product with the water content less than or equal to 2 wt%; s2, carrying out polymerization reaction on the first intermediate product and the rest epoxide to obtain crude sorbitol polyether polyol; s3, refining the crude sorbitol-based polyether polyol to obtain a sorbitol-based polyether polyol finished product; wherein, in step S1, the temperature of the polymerization reaction is 60-110 ℃, and the temperature of the dehydration treatment is 70-100 ℃. The method has the advantages of high economic value, accurate feeding amount, stable preparation process and stable product quality, and can be used in the field of polyurethane foam.
Description
Technical Field
The invention belongs to the technical field of preparation of polyether polyol, and particularly relates to a preparation method of sorbitol-based polyether polyol, and more particularly relates to a method for preparing sorbitol-based polyether polyol by taking liquid sorbitol as an initiator.
Background
In the general polyether polyol category, polyether prepared by polymerizing ethylene glycol, propylene glycol, glycerin, hexanetriol, pentaerythritol, xylitol and sucrose as initiators with epoxides has been reported, and these polyether products can be used for soft, semi-soft and rigid foams for various purposes.
Sorbitol is used as a high-functionality initiator, foam plastic prepared by taking sorbitol polyether as a raw material is superior to products taking glycerol polyether, xylitol polyether and sucrose polyether as bases in the aspects of aging performance, dimensional stability, mechanical performance, softening temperature, oil resistance and the like, and can be used as heat insulation, sound insulation, moisture prevention and structural materials, particularly, the high-molecular high-functionality sorbitol polyether can effectively improve the fineness of foam pores, improve the dimensional stability of the foam and improve the openness of the foam.
At present, solid sorbitol is generally used as an initiator in the production process of sorbitol-based polyether polyol, but the viscosity of the sorbitol-based polyether polyol is higher after the sorbitol-based polyether polyol and an alkali metal catalyst are heated and dissolved, so that a certain amount of solvent or regulator is required to be added in the actual production process to reduce the viscosity of the sorbitol-based polyether polyol. In addition, sorbitol sold in the market at present is generally divided into solid sorbitol (with the content of 98%) and liquid sorbitol (with the content of 70%), and the price of the solid sorbitol is 2.5-3 times that of the liquid sorbitol, so that the raw material cost of the existing sorbitol-based polyether polyol production process is high. In addition, in the feeding stage of the production process of the sorbitol-based polyether polyol, after the vacuum is pulled in the kettle, solid sorbitol is sucked into the reaction kettle manually through a pipe, the method is easy to block a pipeline, the labor force is large, the field environment is dirty, the problems of inaccurate measurement and the like exist in the actual input amount, and the product index is easy to deviate. Because the sorbitol-based polyether polyol prepared by taking liquid sorbitol as an initiator has the problems of unstable product quality control and unstable preparation process due to high hydroxyl value, low viscosity and dark color, most manufacturers cannot prepare the sorbitol-based polyether polyol by using the liquid sorbitol capable of reducing the production cost at present.
As the market demand of sorbitol-based polyether polyol is large, liquid sorbitol with relatively lower cost is used as an initiator, which undoubtedly has higher economic value. Therefore, there is a problem that research and development of a method for preparing sorbitol-based polyether polyol using liquid sorbitol as an initiator are urgently needed.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of sorbitol-based polyether polyol aiming at the defects of the prior art. The method avoids the problems of unstable product quality control and unstable preparation process caused by high hydroxyl value, low viscosity and dark color of the product in the existing preparation process taking liquid sorbitol as an initiator, and realizes the advantages of no need of adding a solvent or a regulator in the preparation process, accurate feeding amount, stable preparation process and stable product quality while ensuring low cost.
In order to solve the technical problems, the invention provides a preparation method of sorbitol-based polyether polyol, which comprises the following steps:
s1, carrying out polymerization reaction on the liquid sorbitol, the catalyst and a part of epoxide, and dehydrating the obtained product to obtain a first intermediate product with the water content less than or equal to 2 wt%;
s2, carrying out polymerization reaction on the first intermediate product and the rest epoxide to obtain crude sorbitol polyether polyol;
s3, refining the crude sorbitol-based polyether polyol to obtain a sorbitol-based polyether polyol finished product;
wherein, in step S1, the temperature of the polymerization reaction is 60-110 ℃, and the temperature of the dehydration treatment is 70-100 ℃.
In the above technical solution, in step S1, the temperature of the polymerization reaction is 70 to 90 ℃, and the temperature of the dehydration treatment is 80 to 100 ℃.
In the above technical solution, in step S2, the temperature of the polymerization reaction is 90-140 ℃, preferably 110-130 ℃.
In the above technical solution, in step S1, the water content of the first intermediate product is less than or equal to 1 wt%.
In the technical scheme, the step S1 is carried out in a reaction kettle; preferably, the dehydration treatment employs nitrogen bubbling for dehydration. Preferably, a distributor is arranged at the bottom of the reaction kettle and is used for increasing the contact area of the materials and the nitrogen and shortening the time of dehydration treatment; more preferably, the time of the dehydration treatment is 3 to 7 hours.
In the above technical scheme, the catalyst is an alkali metal catalyst. The catalyst is used in an amount of 0.2 wt% to 1.0 wt%, preferably 0.2 wt% to 0.5 wt%, based on the total weight of the liquid sorbitol and all epoxides. More preferably, the catalyst comprises one or more of sodium hydroxide, potassium hydroxide, sodium alkoxide and potassium alkoxide. Further preferably, the catalyst comprises sodium hydroxide and/or potassium hydroxide.
In the above technical solution, the amount of the epoxide in step S1 is 10 wt% to 50 wt%, preferably 20 wt% to 40 wt%, based on the total weight of the liquid sorbitol and all epoxides; more preferably, the epoxide is selected from propylene oxide and/or ethylene oxide.
In the above technical solution, in step S1, the sorbitol content (purity) in the liquid sorbitol is not less than 70 wt%.
In the above technical solution, in step S3, the number average molecular weight of the finished sorbitol-based polyether polyol is 300-15000. The number average molecular weight of the finished sorbitol-based polyether polyol is controlled such that its viscosity is suitable for the application.
In the above technical solution, in step S3, the refining process includes emulsification, neutralization, adsorption, dehydration, and filtration.
In the present invention, the method of the neutralization treatment comprises subjecting the crude sorbitol-based polyether polyol to a neutralization reaction with an acidic substance to a pH of 4.5 to 6.0. Preferably, the acidic substance comprises oxalic acid and/or phosphoric acid and the like.
In the present invention, the adsorption treatment method comprises contacting the neutralized crude sorbitol-based polyether polyol with an adsorbent. Preferably, the adsorbent comprises one or more of magnesium silicate, aluminum silicate and magnesium aluminum silicate. The adsorbent is used in an amount of 0.1 wt% to 0.5 wt%, preferably 0.2 wt% to 0.5 wt%, based on the total weight of the liquid sorbitol and all epoxides.
In the invention, a two-stage polymerization method is adopted for preparing the sorbitol-based polyether polyol. Since liquid sorbitol contains a large amount of moisture, the first stage polymerization (polymerization of liquid sorbitol with a portion of epoxide) is controlled to be performed at a lower reaction temperature in the present invention to suppress side reactions of the large amount of moisture in liquid sorbitol with epoxide. Meanwhile, the invention also controls the dehydration treatment of the product obtained by the first-stage polymerization at a relatively low temperature, and arranges a distribution pipe in the reaction kettle for nitrogen bubbling dehydration so as to increase the contact area of the material and the nitrogen and reduce the dehydration time, thereby avoiding deepening the color of the product due to long-time high-temperature vacuum dehydration. In addition, the present invention controls the water content of the dehydrated first intermediate product to avoid side reactions of the epoxide with water in the first intermediate product during the second stage of polymerization.
In the present invention, liquid sorbitol can be placed in the reservoir. When the device is needed to be used, the liquid sorbitol is pumped into the reaction kettle through the pump, the input amount is controlled through the flow meter, the labor force is reduced, the on-site clean environment is kept, and meanwhile, the input amount is accurate and controllable.
Compared with the prior art, the invention has the following beneficial effects:
compared with the existing method using solid sorbitol as an initiator, the preparation method of the sorbitol-based polyether polyol provided by the invention has the advantages of no need of adding a solvent or a regulator, accurate feeding amount, stable preparation process, stable product quality and low cost, and simultaneously solves the problems of unstable product quality control and unstable preparation process caused by high hydroxyl value, low viscosity and deep color of the product in the existing method using liquid sorbitol as an initiator, so that the preparation method has higher economic value and can be used in the field of polyurethane foam.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the scope of the invention.
The measurement method provided by the invention can be a conventional method in the field, and the specific methods are respectively as follows:
(1) measurement method of hydroxyl value: acylation of phthalic anhydride.
(2) Viscosity measurement method. Rotational viscometer method.
(3) The method for measuring the water content comprises the following steps: karl fischer process.
(4) Method for measuring acid value: neutralization titration.
(5) The measuring method of the potassium ion content comprises the following steps: and a flame photometer.
(6) The color number GD measuring method comprises the following steps: a colorimetric method.
Examples
Example 1
520g of liquid sorbitol (purity 70 wt%) and 6g of potassium hydroxide (amount of 0.39 wt% based on the total weight of liquid sorbitol and all epoxides) were added to a 2L stainless steel reactor (equipped with a sparger at the bottom of the reactor), nitrogen substitution was carried out, and after the oxygen content in the reactor was measured to be less than 150ppm, the temperature was raised, 460g of the first stage propylene oxide (30.3 wt% based on the total weight of liquid sorbitol and all epoxides) was added dropwise in steps at 85 c, after the addition, reacting for 3 hours under internal pressure at the reaction temperature, then heating to 90 ℃, carrying out bubbling dehydration for 5 hours by adopting nitrogen, sampling and analyzing the water content to be 0.85 wt%, continuing heating to 115 ℃, dropwise adding 540g of second-stage propylene oxide, after the dropwise adding is finished, and carrying out internal pressure reaction for 3 hours at the reaction temperature, vacuumizing to remove unreacted monomers, cooling and discharging to obtain the crude sorbitol-based polyether polyol.
Putting the crude sorbitol-based polyether polyol into a refining kettle, adding 75g of pure water, stirring and emulsifying, heating to 90 ℃, adding 18g of phosphoric acid with the purity of 50 wt% after 1 hour for neutralization reaction, adding 4g of magnesium aluminum silicate (based on the total weight of liquid sorbitol and all epoxides, the amount is 0.26 wt%) after 1 hour, adsorbing, dehydrating and filtering to obtain a sorbitol-based polyether polyol finished product. The obtained sorbitol-based polyether polyol finished product was subjected to a performance test, and specific test results are shown in table 1.
Example 2
A2L stainless steel reactor (equipped with a distributor at the bottom) was charged with 510g of liquid sorbitol (purity 70 wt%) and 5g of potassium hydroxide (amount of 0.33 wt% based on the total weight of liquid sorbitol and all epoxides) and nitrogen substitution was carried out, after the oxygen content in the reactor was measured to be less than 150ppm, the temperature was raised, 410g of the first stage propylene oxide (26.9 wt.%, based on the total weight of liquid sorbitol and all epoxides) were added dropwise in steps at 85 c, after the addition, reacting for 3 hours under internal pressure at the reaction temperature, then heating to 90 ℃, carrying out bubbling dehydration for 5 hours by adopting nitrogen, sampling and analyzing the water content to be 0.85 wt%, continuing heating to 115 ℃, dropwise adding 605g of second-stage propylene oxide, after the dropwise adding is finished, and carrying out internal pressure reaction for 3 hours at the reaction temperature, vacuumizing to remove unreacted monomers, cooling and discharging to obtain the crude sorbitol-based polyether polyol.
Putting the crude sorbitol-based polyether polyol into a refining kettle, adding 75g of pure water, stirring and emulsifying, heating to 90 ℃, adding 18g of phosphoric acid with the purity of 50 wt% after 1 hour for neutralization reaction, adding 4g of magnesium aluminum silicate (based on the total weight of liquid sorbitol and all epoxides, the amount is 0.26 wt%) after 1 hour, adsorbing, dehydrating and filtering to obtain a sorbitol-based polyether polyol finished product. The obtained sorbitol-based polyether polyol finished product was subjected to a performance test, and specific test results are shown in table 1.
Example 3
A2L stainless steel reactor (equipped with a distributor at the bottom) was charged with 520g of liquid sorbitol (purity 70 wt%) and 6g of potassium hydroxide (used in an amount of 0.39 wt% based on the total weight of liquid sorbitol and all epoxides) and nitrogen substitution was carried out, after the oxygen content in the reactor was measured to be less than 150ppm, the temperature was raised, 460g of the first stage propylene oxide (30.3 wt% based on the total weight of liquid sorbitol and all epoxides) was added dropwise in steps at 85 c, after the addition, reacting for 3 hours under internal pressure at the reaction temperature, then heating to 90 ℃, carrying out bubbling dehydration for 4 hours by adopting nitrogen, sampling and analyzing the water content to be 1.5 wt%, continuing heating to 115 ℃, dropwise adding 540g of second-stage propylene oxide, after the dropwise adding is finished, and carrying out internal pressure reaction for 3 hours at the reaction temperature, vacuumizing to remove unreacted monomers, cooling and discharging to obtain the crude sorbitol-based polyether polyol.
Putting the crude sorbitol-based polyether polyol into a refining kettle, adding 75g of pure water, stirring and emulsifying, heating to 90 ℃, adding 18g of phosphoric acid with the purity of 50 wt% after 1 hour for neutralization reaction, adding 4g of magnesium aluminum silicate (based on the total weight of liquid sorbitol and all epoxides, the amount is 0.26 wt%) after 1 hour, adsorbing, dehydrating and filtering to obtain a sorbitol-based polyether polyol finished product. The obtained sorbitol-based polyether polyol finished product was subjected to a performance test, and specific test results are shown in table 1.
Example 4
520g of liquid sorbitol (purity 70 wt%) and 6g of potassium hydroxide (amount of 0.39 wt% based on the total weight of liquid sorbitol and all epoxides) were added to a 2L stainless steel reactor (equipped with a sparger at the bottom of the reactor), nitrogen substitution was carried out, and after the oxygen content in the reactor was measured to be less than 150ppm, the temperature was raised, 460g of the first stage propylene oxide (30.3 wt% based on the total weight of liquid sorbitol and all epoxides) were gradually added dropwise at 70 c, after completion of the addition, reacting for 3 hours under internal pressure at the reaction temperature, then heating to 90 ℃, carrying out bubbling dehydration for 5 hours by adopting nitrogen, sampling and analyzing the water content to be 0.85 wt%, continuing heating to 115 ℃, dropwise adding 540g of second-stage propylene oxide, after the dropwise adding is finished, and carrying out internal pressure reaction for 3 hours at the reaction temperature, vacuumizing to remove unreacted monomers, cooling and discharging to obtain the crude sorbitol-based polyether polyol.
Putting the crude sorbitol-based polyether polyol into a refining kettle, adding 75g of pure water, stirring and emulsifying, heating to 90 ℃, adding 18g of phosphoric acid with the purity of 50 wt% after 1 hour for neutralization reaction, adding 4g of magnesium aluminum silicate (based on the total weight of liquid sorbitol and all epoxides, the amount is 0.26 wt%) after 1 hour, adsorbing, dehydrating and filtering to obtain a sorbitol-based polyether polyol finished product. The obtained sorbitol-based polyether polyol finished product was subjected to a performance test, and specific test results are shown in table 1.
Example 5
520g of liquid sorbitol (purity 70 wt%) and 6g of potassium hydroxide (amount of 0.39 wt% based on the total weight of liquid sorbitol and all epoxides) were added to a 2L stainless steel reactor (equipped with a sparger at the bottom of the reactor), nitrogen substitution was carried out, and after the oxygen content in the reactor was measured to be less than 150ppm, the temperature was raised, 460g of the first stage propylene oxide (30.3 wt% based on the total weight of liquid sorbitol and all epoxides) was added dropwise in steps at 85 c, after the addition, reacting for 3 hours under internal pressure at the reaction temperature, then heating to 80 ℃, carrying out bubbling dehydration for 7 hours by adopting nitrogen, sampling and analyzing the water content to be 0.85 wt%, continuing heating to 115 ℃, dropwise adding 540g of second-stage propylene oxide, after the dropwise adding is finished, and carrying out internal pressure reaction for 3 hours at the reaction temperature, vacuumizing to remove unreacted monomers, cooling and discharging to obtain the crude sorbitol-based polyether polyol.
Putting the crude sorbitol-based polyether polyol into a refining kettle, adding 75g of pure water, stirring and emulsifying, heating to 90 ℃, adding 18g of phosphoric acid with the purity of 50 wt% after 1 hour for neutralization reaction, adding 4g of magnesium aluminum silicate (based on the total weight of liquid sorbitol and all epoxides, the amount is 0.26 wt%) after 1 hour, adsorbing, dehydrating and filtering to obtain a sorbitol-based polyether polyol finished product. The obtained sorbitol-based polyether polyol finished product was subjected to a performance test, and specific test results are shown in table 1.
Example 6
520g of liquid sorbitol (purity 70 wt%) and 6g of potassium hydroxide (amount of 0.39 wt% based on the total weight of liquid sorbitol and all epoxides) were added to a 2L stainless steel reactor (equipped with a sparger at the bottom of the reactor), nitrogen substitution was carried out, and after the oxygen content in the reactor was measured to be less than 150ppm, the temperature was raised, 460g of the first stage propylene oxide (30.3 wt% based on the total weight of liquid sorbitol and all epoxides) was added dropwise in steps at 85 c, after the addition, reacting for 3 hours under internal pressure at the reaction temperature, then heating to 90 ℃, carrying out bubbling dehydration for 5 hours by adopting nitrogen, sampling and analyzing the water content to be 0.85 wt%, continuing heating to 100 ℃, dropwise adding 540g of second-stage propylene oxide, after the dropwise adding is finished, and carrying out internal pressure reaction for 3 hours at the reaction temperature, vacuumizing to remove unreacted monomers, cooling and discharging to obtain the crude sorbitol-based polyether polyol.
Putting the crude sorbitol-based polyether polyol into a refining kettle, adding 75g of pure water, stirring and emulsifying, heating to 90 ℃, adding 18g of phosphoric acid with the purity of 50 wt% after 1 hour for neutralization reaction, adding 4g of magnesium aluminum silicate (based on the total weight of liquid sorbitol and all epoxides, the amount is 0.26 wt%) after 1 hour, adsorbing, dehydrating and filtering to obtain a sorbitol-based polyether polyol finished product. The obtained sorbitol-based polyether polyol finished product was subjected to a performance test, and specific test results are shown in table 1.
Comparative example 1
Adding 360g of solid sorbitol, 8.5g of pure water and 6g of potassium hydroxide (the dosage is 0.44 wt% based on the total weight of the solid sorbitol and all epoxides) into a 2L stainless steel reaction kettle, carrying out nitrogen replacement, heating to 110 ℃ after the oxygen content in the kettle is measured to be less than 150ppm, dissolving for 4 hours, continuing heating to 115 ℃, gradually dropwise adding 1000g of propylene oxide, carrying out internal pressure reaction for 3 hours at the reaction temperature after dropwise adding, vacuumizing to remove unreacted monomers, cooling and discharging to obtain the crude sorbitol-based polyether polyol.
Putting the crude sorbitol-based polyether polyol into a refining kettle, adding 75g of pure water, stirring and emulsifying, heating to 90 ℃, adding 18g of phosphoric acid with the purity of 50 wt% after 1 hour for neutralization reaction, adding 4g of magnesium aluminum silicate (based on the total weight of solid sorbitol and all epoxides, the amount is 0.29 wt%) after 1 hour, adsorbing, dehydrating and filtering to obtain a sorbitol-based polyether polyol finished product. The obtained sorbitol-based polyether polyol finished product was subjected to a performance test, and specific test results are shown in table 1.
Comparative example 2
520g of liquid sorbitol (purity 70 wt%) and 6g of potassium hydroxide (amount of 0.39 wt% based on the total weight of liquid sorbitol and all epoxides) were added to a 2L stainless steel reactor (equipped with a sparger at the bottom of the reactor), nitrogen substitution was carried out, and after the oxygen content in the reactor was measured to be less than 150ppm, the temperature was raised, 460g of the first stage propylene oxide (30.3 wt% based on the total weight of the liquid sorbitol and all epoxides) was added dropwise in steps at 115 deg.C, after the addition, reacting for 3 hours under internal pressure at the reaction temperature, then heating to 90 ℃, carrying out bubbling dehydration for 5 hours by adopting nitrogen, sampling and analyzing the water content to be 0.60 wt%, continuing heating to 115 ℃, dropwise adding 540g of second-stage propylene oxide, after the dropwise adding is finished, and carrying out internal pressure reaction for 3 hours at the reaction temperature, vacuumizing to remove unreacted monomers, cooling and discharging to obtain the crude sorbitol-based polyether polyol.
Putting the crude sorbitol-based polyether polyol into a refining kettle, adding 75g of pure water, stirring and emulsifying, heating to 90 ℃, adding 18g of phosphoric acid with the purity of 50 wt% after 1 hour for neutralization reaction, adding 4g of magnesium aluminum silicate (based on the total weight of the liquid sorbitol and all epoxides, the amount is 0.26 wt%) after 1 hour, adsorbing, dehydrating and filtering to obtain a sorbitol-based polyether polyol finished product. The obtained sorbitol-based polyether polyol finished product was subjected to a performance test, and specific test results are shown in table 1.
Comparative example 3
520g of liquid sorbitol (purity 70 wt%) and 6g of potassium hydroxide (amount of 0.39 wt% based on the total weight of liquid sorbitol and all epoxides) were added to a 2L stainless steel reactor (equipped with a sparger at the bottom of the reactor), nitrogen substitution was carried out, and after the oxygen content in the reactor was measured to be less than 150ppm, the temperature was raised, 460g of the first stage propylene oxide (30.3 wt% based on the total weight of liquid sorbitol and all epoxides) was added dropwise in steps at 85 c, after the addition, reacting for 3 hours under internal pressure at the reaction temperature, then heating to 110 ℃, carrying out bubbling dehydration for 5 hours by adopting nitrogen, sampling and analyzing the water content to be 0.55%, continuing heating to 115 ℃, dropwise adding 540g of second-stage propylene oxide, after the dropwise adding is finished, and carrying out internal pressure reaction for 3 hours at the reaction temperature, vacuumizing to remove unreacted monomers, cooling and discharging to obtain the crude sorbitol-based polyether polyol.
Putting the crude sorbitol-based polyether polyol into a refining kettle, adding 75g of pure water, stirring and emulsifying, heating to 90 ℃, adding 18g of phosphoric acid with the purity of 50 wt% after 1 hour for neutralization reaction, adding 4g of magnesium aluminum silicate (based on the total weight of liquid sorbitol and all epoxides, the amount is 0.26 wt%) after 1 hour, adsorbing, dehydrating and filtering to obtain a sorbitol-based polyether polyol finished product. The obtained sorbitol-based polyether polyol finished product was subjected to a performance test, and specific test results are shown in table 1.
Comparative example 4
520g of liquid sorbitol (purity 70 wt%) and 6g of potassium hydroxide (amount of 0.39 wt% based on the total weight of liquid sorbitol and all epoxides) were added to a 2L stainless steel reactor (equipped with a sparger at the bottom of the reactor), nitrogen substitution was carried out, and after the oxygen content in the reactor was measured to be less than 150ppm, the temperature was raised, 460g of the first stage propylene oxide (30.3 wt% based on the total weight of liquid sorbitol and all epoxides) was added dropwise in steps at 85 c, after the addition, reacting for 3 hours under internal pressure at the reaction temperature, then heating to 90 ℃, carrying out bubbling dehydration for 3 hours by adopting nitrogen, sampling and analyzing the water content to be 2.5 wt%, continuing heating to 115 ℃, dropwise adding 540g of second-stage propylene oxide, after the dropwise adding is finished, and carrying out internal pressure reaction for 3 hours at the reaction temperature, vacuumizing to remove unreacted monomers, cooling and discharging to obtain the crude sorbitol-based polyether polyol.
Putting the crude sorbitol-based polyether polyol into a refining kettle, adding 75g of pure water, stirring and emulsifying, heating to 90 ℃, adding 18g of phosphoric acid with the purity of 50 wt% after 1 hour for neutralization reaction, adding 4g of magnesium aluminum silicate (based on the total weight of liquid sorbitol and all epoxides, the amount is 0.26 wt%) after 1 hour, adsorbing, dehydrating and filtering to obtain a sorbitol-based polyether polyol finished product. The obtained sorbitol-based polyether polyol finished product was subjected to a performance test, and specific test results are shown in table 1.
TABLE 1 Performance test results for sorbitol-based polyether polyols
As can be seen from the comparison of the above examples 1 to 6 with comparative example 1, the present invention can also produce a sorbitol-based polyether polyol product of stable quality using liquid sorbitol as a raw material. As can be seen from the comparison between the above examples 1-6 and the comparative examples 2-4, the sorbitol-based polyether polyol product obtained by the preparation method of sorbitol-based polyether polyol provided by the invention has good performance indexes (such as hydroxyl value, viscosity, color and the like) and higher economic value.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A method for preparing sorbitol-based polyether polyol, comprising the steps of:
s1, carrying out polymerization reaction on the liquid sorbitol, the catalyst and a part of epoxide, and dehydrating the obtained product to obtain a first intermediate product with the water content less than or equal to 2 wt%;
s2, carrying out polymerization reaction on the first intermediate product and the rest epoxide to obtain crude sorbitol polyether polyol;
s3, refining the crude sorbitol-based polyether polyol to obtain a sorbitol-based polyether polyol finished product;
wherein, in step S1, the temperature of the polymerization reaction is 60-110 ℃, and the temperature of the dehydration treatment is 70-100 ℃.
2. The method according to claim 1, wherein in step S1, the polymerization reaction temperature is 70 to 90 ℃ and the dehydration treatment temperature is 80 to 100 ℃.
3. The preparation method according to claim 1 or 2, characterized in that, in step S2, the temperature of the polymerization reaction is 90-140 ℃, preferably 110-130 ℃.
4. The method according to any one of claims 1 to 3, wherein the first intermediate product has a water content of 1 wt% or less.
5. The production method according to any one of claims 1 to 4, wherein step S1 is performed in a reaction tank; preferably, the dehydration treatment adopts nitrogen bubbling for dehydration; the bottom of the reaction kettle is provided with a distributor for increasing the contact area of the materials and the nitrogen and shortening the time of dehydration treatment; preferably, the time of the dehydration treatment is 3 to 7 hours.
6. The production method according to any one of claims 1 to 5, wherein the catalyst is an alkali metal-based catalyst; the catalyst is used in an amount of 0.2 wt% to 1.0 wt%, preferably 0.2 wt% to 0.5 wt%, based on the total weight of the liquid sorbitol and all epoxides; more preferably, the catalyst comprises one or more of sodium hydroxide, potassium hydroxide, sodium alkoxide and potassium alkoxide.
7. The method according to any one of claims 1 to 6, wherein the epoxide is used in an amount of 10 wt% to 50 wt%, preferably 20 wt% to 40 wt%, based on the total weight of the liquid sorbitol and all epoxides in step S1; more preferably, the epoxide is selected from propylene oxide and/or ethylene oxide.
8. The method according to any one of claims 1 to 7, wherein in step S1, the sorbitol content in the liquid sorbitol is 70 wt% or more.
9. The method as set forth in any one of claims 1 to 8, wherein in step S3, the number average molecular weight of the finished sorbitol-based polyether polyol is 300-15000.
10. The production method according to any one of claims 1 to 9, wherein in step S3, the refining treatment includes emulsification, neutralization, adsorption, dehydration, and filtration.
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| CN102702505A (en) * | 2012-06-27 | 2012-10-03 | 淄博德信联邦化学工业有限公司 | High-temperature-resistant polyether polyol and preparation method thereof |
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