CN107586383B - Refining method for reducing VOC content and odor in polyether polyol - Google Patents
Refining method for reducing VOC content and odor in polyether polyol Download PDFInfo
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Abstract
The invention provides a refining method for reducing VOC content and odor in polyether polyol, and relates to the field of chemical industry. The refining method comprises the following steps: adding magnesium silicate or aluminum silicate or a mixture thereof accounting for 0.05 to 1.5 percent of the mass of the polyether polyol to be refined into the polyether polyol to be refined, heating to 95 to 115 ℃ under nitrogen atmosphere, keeping the temperature unchanged and stirring; (2) cooling to 60-90 ℃, adding water accounting for 5-10% of the mass of the polyether polyol to be refined, keeping the temperature unchanged and stirring; (3) and (3) filtering the material obtained after the treatment in the step (2), and dehydrating the filtrate to obtain the refined polyether polyol. The refining method can effectively remove potassium and sodium ions in the polyether polyol, obviously reduce the taste and VOC content of the polyether polyol under the condition of ensuring that the pH value of the polyether polyol is not too high, and especially obviously reduce the concentration of formaldehyde.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a refining method for reducing VOC content and odor in polyether polyol.
Background
Polyether polyol is an important raw material of polyurethane materials and is widely applied to various fields in life. Along with the improvement of living standard of people, the environmental protection and health are more and more concerned, and the problem of Volatile Organic Compounds (VOC) in polyurethane materials becomes the focus of public attention. Polyether polyol is used as a basic raw material of a polyurethane material, micromolecular polyol or amine is basically used as an initiator in the synthesis process, propylene oxide or ethylene oxide is catalyzed by alkali metal to carry out ring-opening polymerization to form a macromolecular polymer, and the VOC content in the polyether polyol can be increased by the introduction of the raw material, side reactions and the existence of unreacted monomers and oligomers in the polymerization process. How to remove the volatile organic compounds and reduce the odor of polyether becomes a problem which is actively concerned by polyether manufacturers at home and abroad.
In the prior art, the pH value of the refined polyether polyol is alkalescent, and the refined polyether polyol still contains high-concentration aldehyde substances, particularly formaldehyde which has great harm to human bodies, so that the VOC content is high and the taste is heavy. Because some polyether antioxidants are sensitive to pH and can develop color under the weak alkaline condition, when the pH of the polyether polyol is weak alkaline, the subsequent addition of the polyether antioxidants can increase the chroma and the taste of the polyether polyol. In addition, the filter is subjected to filtration and dehydration after water adsorption, which easily causes heavy load on the filter.
Disclosure of Invention
The invention aims to provide a refining method for reducing VOC content and odor in polyether polyol, which can effectively remove potassium and sodium ions in the polyether polyol, remarkably reduce the taste and VOC content of the polyether polyol under the condition of ensuring that the pH value of the polyether polyol is not too high, and particularly remarkably reduce the concentration of formaldehyde.
The purpose of the invention is realized by adopting the following technical scheme.
A refining method for reducing VOC content and odor in polyether polyol comprises the following steps:
(1) adding magnesium silicate or aluminum silicate or a mixture thereof accounting for 0.05 to 1.5 percent of the mass of the polyether polyol to be refined into the polyether polyol to be refined, heating to 95 to 115 ℃ under nitrogen atmosphere, keeping the temperature unchanged and stirring;
(2) cooling to 60-90 ℃, adding water accounting for 5-10% of the mass of the polyether polyol to be refined, keeping the temperature unchanged and stirring;
(3) and (3) filtering the material obtained after the treatment in the step (2), and dehydrating the filtrate to obtain the refined polyether polyol.
In the invention, the polyether polyol to be refined is obtained by carrying out polymerization reaction on polyol and oxyalkylene under the catalysis of alkali metal.
In the present invention, the alkylene oxide is propylene oxide, ethylene oxide or a mixture of the two; the polyether polyol has a functionality of 1-8 and a number average molecular weight of 400-12000.
In a preferred technical scheme, the temperature is kept constant and the stirring time in the step (1) is 0.5-2 hours.
In a preferred technical scheme, the temperature is kept constant and the stirring time in the step (2) is 1-2 hours.
In the invention, the total content of potassium ions and sodium ions in the filtered polyether polyol is less than 5 ppm.
In the present invention, the temperature during dehydration is 105-125 ℃, and the vacuum degree during dehydration is less than-0.09 MPa.
In the invention, the water content in the dehydrated polyether polyol is less than or equal to 0.1%, and the pH value is 5-7.
Through a large number of experiments, the inventor unexpectedly finds that after magnesium silicate and water are adopted for adsorption, the VOC content and the taste of polyether polyol can be obviously reduced through direct filtration, and particularly the concentration of formaldehyde is obviously reduced. In addition, the invention filters before dehydration, reduces the viscosity of polyether polyol during filtering, lightens the load of a filter, ensures that the pH value of refined polyether polyol is weakly acidic, increases the tolerance of subsequent antioxidant addition, and enables some antioxidants sensitive to pH and developing color to be added. The potassium and sodium ion concentration of the polyether polyol obtained after the refining by the method is reduced.
Detailed Description
The present invention will be described with reference to examples, but the present invention is not limited to these examples.
EXAMPLE 1 purification of crude polyether polyol a
The initiator propylene glycol and ethylene oxide are subjected to polyaddition reaction in the presence of KOH to prepare a crude product of polyether polyol a. The amount of catalyst KOH used was 0.2% of the total mass of the reactants (propylene glycol and ethylene oxide). The number average molecular weight of the polyether polyol a was 500.
1. The method for refining the polyether polyol a crude product comprises the following steps:
(1) 10g of magnesium silicate are added into a 2L stainless steel reaction kettle containing 1000g of crude polyether polyol a, stirring is started and the temperature is raised to 105 +/-5 ℃ under nitrogen atmosphere, then the temperature is kept unchanged at 105 +/-5 ℃, and stirring is carried out for 1 h.
(2) Cooling to 75 + -5 deg.C, sucking 80g of distilled water, keeping the temperature at 75 + -5 deg.C, and stirring for 1 h.
(3) And (3) performing filter pressing, after the total concentration of potassium ions and sodium ions is less than 5ppm, placing the filtrate in a reaction kettle, starting a vacuum device for vacuumizing, heating to 110 +/-5 ℃ when the vacuum degree in the reaction kettle is less than-0.09 Mpa, keeping the temperature unchanged, and dehydrating for 2 hours to obtain the finished product polyether polyol a.
2. Comparison method 1
The crude polyether polyol a was purified by the comparative method, in which steps (1) and (2) were the same as in the process of the present invention in this example, and step (3) was as follows: and (3) starting a vacuum device for vacuumizing, raising the temperature to 110 +/-5 ℃ when the vacuum degree in the reaction kettle is less than-0.09 Mpa, keeping the temperature unchanged, dehydrating for 2 hours, and then performing filter pressing to obtain a finished product polyether polyol a after the total concentration of potassium ions and sodium ions is less than 5 ppm.
3. And a second comparison method comprises the following steps:
refining the polyether polyol a crude product by a comparative method II, heating a 2L stainless steel reaction kettle containing 1000g of the polyether polyol a crude product to 70 ℃, adding 10g of pure water and 10g of magnesium silicate, stirring for 30 minutes, filtering, adding the obtained polyether polyol into the reaction kettle again, adding 10g of pure water and 10g of diatomite, stirring for 30 minutes, carrying out vacuum dehydration for 1 hour, keeping the temperature at 105 ℃, and filtering to obtain the finished product of polyether polyol a.
And (3) detecting the contents of formaldehyde, acetaldehyde, acrolein, propylene glycol allyl ether and other volatile substances in the finished product polyether polyol a obtained by the methods and the pH, moisture and potassium and sodium ion contents of the product. Wherein the contents of formaldehyde, acetaldehyde, acrolein, propylene glycol allyl ether and other volatile substances are detected by liquid chromatography. The specific test results are shown in Table 1. As can be seen from Table 1, the taste of polyether polyol a was significantly reduced, the contents of formaldehyde, acetaldehyde, acrolein, propylene glycol allyl ether and other volatile substances were significantly reduced, and the pH was weakly acidic after the purification by the method of the present invention.
TABLE 1 Performance index of the finished polyether polyol a
EXAMPLE 2 purification of crude polyether polyol b
And carrying out polyaddition reaction on the initiator glycerol and the propylene oxide in the presence of KOH to prepare a crude product of the polyether polyol b. The catalyst KOH was used in an amount of 0.25% based on the total mass of the reactants (glycerol and propylene oxide). The number average molecular weight of polyether polyol b was 3000.
1. The method for refining the crude product of polyether polyol b comprises the following steps:
(1) 9g of aluminum silicate is added into a 2L stainless steel reaction kettle containing 1000g of crude polyether polyol b, stirring is started under nitrogen atmosphere, the temperature is raised to 100 +/-5 ℃, the temperature is kept constant at 100 +/-5 ℃, and stirring is carried out for 1.5 h.
(2) The temperature in the reaction kettle is reduced to 80 ℃, 90g of distilled water is sucked in, the temperature is kept at 80 +/-5 ℃, and the mixture is stirred for 2 hours.
(3) And (3) performing filter pressing, after the total concentration of potassium ions and sodium ions is less than 5ppm, placing the filtrate in a reaction kettle, starting a vacuum device for vacuumizing, heating to 115 +/-5 ℃ when the vacuum degree in the reaction kettle is less than-0.09 Mpa, keeping the temperature at 115 +/-5 ℃ unchanged, and dehydrating for 2 hours to obtain the finished product polyether polyol b.
2. Comparison method 1
The crude polyether polyol b was purified by the comparative method, in which steps (1) and (2) were the same as in the process of the present invention in this example, and step (3) was as follows: and (3) starting a vacuum device for vacuumizing, raising the temperature to 115 +/-5 ℃ when the vacuum degree in the reaction kettle is less than-0.09 Mpa, keeping the temperature unchanged, dehydrating for 2 hours, and then performing filter pressing to obtain a finished product polyether polyol b after the total concentration of potassium ions and sodium ions is less than 5 ppm.
And a second comparison method comprises the following steps:
adopting a comparative method to refine the crude product of the polyether polyol b, heating a 2L stainless steel reaction kettle containing 1000g of the crude product of the polyether polyol a to 80 ℃, adding 20g of pure water and 20g of magnesium silicate, stirring for 30 minutes, filtering (the total concentration of potassium ions and sodium ions is less than 5ppm), adding the obtained polyether polyol into the reaction kettle again, adding 20g of pure water and 20g of diatomite, stirring for 30 minutes, carrying out vacuum dehydration for 1 hour, keeping the temperature at 105 ℃, and filtering to obtain the finished product of the polyether polyol b.
And (3) detecting the contents of formaldehyde, acetaldehyde, acrolein and propylene glycol allyl ether and other volatile substances in the finished product polyether polyol b obtained by the methods, and the pH, moisture, potassium ion content and sodium ion content of the product. Wherein the contents of formaldehyde, acetaldehyde, acrolein, propylene glycol allyl ether and other volatile substances are detected by liquid chromatography. As can be seen from Table 2, the polyether polyol b refined by the method of the present invention is odorless, significantly reduces the contents of formaldehyde, acetaldehyde, acrolein, propylene glycol allyl ether and other volatile substances, and has a weakly acidic pH.
Table 2: performance index of polyether polyol b
EXAMPLE 3 purification of crude polyether polyol c
The initiator is a mixture of glycerol and pentaerythritol. And carrying out polyaddition reaction on the initiator and a mixture of propylene oxide and ethylene oxide in the presence of KOH to prepare a crude polyether polyol c. Wherein the ethylene oxide accounts for 15 percent of the total mass of the mixture of the ethylene oxide and the propylene oxide. The catalyst KOH was used in an amount of 0.3% based on the total mass of the reactants (glycerol, pentaerythritol, propylene oxide and ethylene oxide). The polyether polyol c has a number average molecular weight of 3000 and an average functionality of 3.5.
1. The method for refining the crude product of polyether polyol c comprises the following steps:
(1) 12g of a mixture of magnesium silicate and aluminium silicate (mass ratio 4:6) are added to a 2L stainless steel reactor containing 1000g of crude polyether polyol c, stirring is started and the temperature is raised to 95 + -5 ℃ under nitrogen atmosphere, and then stirring is carried out for 1h while keeping the temperature constant at 95 + -5 ℃.
(2) The temperature in the reaction kettle is reduced to 70 ℃, 100g of distilled water is sucked in, the temperature is kept constant at 80 +/-5 ℃, and the stirring is carried out for 1 hour.
(3) And (3) filter-pressing the materials in the reaction kettle, placing the filtrate in the reaction kettle after the total concentration of potassium ions and sodium ions is less than 5ppm, starting a vacuum device to vacuumize, heating to 105 +/-5 ℃ when the vacuum degree in the reaction kettle is less than-0.09 Mpa, keeping the temperature at 105 +/-5 ℃, and dehydrating for 1.5 hours to obtain the finished product polyether polyol c.
2. Comparison method 1
The crude polyether polyol c was purified by the comparative method, in which steps (1) and (2) were the same as the process of the present invention in this example, and step (3) was as follows: and (3) starting a vacuum device for vacuumizing, heating to 105 +/-5 ℃ when the vacuum degree in the reaction kettle is less than-0.09 Mpa, keeping the temperature unchanged, dehydrating for 1.5h, and then performing pressure filtration to obtain a finished product polyether polyol c after the total concentration of potassium ions and sodium ions is less than 5 ppm.
4. And a second comparison method comprises the following steps:
refining the polyether polyol c crude product by a comparative method, heating a 2L stainless steel reaction kettle containing 1000g of the polyether polyol c crude product to 80 ℃, adding 10g of pure water and 10g of magnesium silicate, stirring for 30 minutes, filtering (the total concentration of potassium ions and sodium ions is less than 5ppm), adding the obtained polyether polyol into the reaction kettle again, adding 10g of pure water and 10g of diatomite, stirring for 30 minutes, performing vacuum dehydration for 1 hour, keeping the temperature at 105 ℃, and filtering to obtain the finished polyether polyol c.
And (3) detecting the contents of formaldehyde, acetaldehyde, acrolein and propylene glycol allyl ether and other volatile substances in the finished product polyether polyol c obtained by the methods, and the pH, moisture, potassium ion content and sodium ion content of the product. Wherein the contents of formaldehyde, acetaldehyde, acrolein, propylene glycol allyl ether and other volatile substances are detected by liquid chromatography. As can be seen from Table 3, the polyether polyol c is odorless after being refined by the method of the present invention, and the contents of formaldehyde, acetaldehyde, acrolein, propylene glycol allyl ether and other volatile substances are significantly reduced, and the pH is weakly acidic.
Table 3: performance index of finished polyether polyol c
Claims (6)
1. A refining method for reducing VOC content and odor in polyether polyol is characterized by comprising the following steps:
(1) adding magnesium silicate or aluminum silicate or a mixture thereof accounting for 0.05 to 1.5 percent of the mass of the polyether polyol to be refined into the polyether polyol to be refined, heating to 95 to 115 ℃ under nitrogen atmosphere, keeping the temperature unchanged and stirring;
(2) cooling to 60-90 ℃, adding water accounting for 5-10% of the mass of the polyether polyol to be refined, keeping the temperature unchanged and stirring;
(3) filtering the material obtained after the treatment in the step (2), and dehydrating the filtrate to obtain refined polyether polyol; the polyether polyol to be refined is obtained by the polymerization reaction of polyol and oxyalkylene under the catalysis of alkali metal;
the alkylene oxide is propylene oxide, ethylene oxide or a mixture of the two; the polyether polyol has a functionality of 1-8 and a number average molecular weight of 400-12000.
2. A purification method for reducing VOC and odor in polyether polyol according to claim 1, wherein the temperature in step (1) is kept constant and the stirring time is 0.5-2 hours.
3. A purification process for reducing VOC content and odor in polyether polyol according to claim 2, wherein the temperature in step (2) is maintained constant and the stirring is carried out for 1 to 2 hours.
4. The method of reducing VOC and odor in polyether polyols of claim 3, wherein the total potassium and sodium ion content of the filtered polyether polyol is less than 5 ppm.
5. The method as claimed in claim 4, wherein the temperature of the dehydration is 105 ℃ and 125 ℃, and the vacuum degree of the dehydration is less than-0.09 MPa.
6. The method of claim 5, wherein the dehydrated polyether polyol has a moisture content of 0.1% or less and a pH of 5 to 7.
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| CN108484896A (en) * | 2018-04-13 | 2018-09-04 | 航锦科技股份有限公司 | A kind of preparation method of low VOC high-activity high molecular weight polyether polyols |
| CN109438663A (en) * | 2018-09-25 | 2019-03-08 | 青岛世林新海绵有限公司 | The low fogging sponge of low VOC for automobile interiors and its preparation process |
| CN114763410B (en) * | 2021-01-14 | 2023-06-02 | 长华化学科技股份有限公司 | Polyethylene glycol refining method |
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| WO2008026657A1 (en) * | 2006-08-31 | 2008-03-06 | Asahi Glass Company, Limited | Method of purifying polyether compound |
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| CN102634006A (en) * | 2012-03-28 | 2012-08-15 | 浙江皇马科技股份有限公司 | Polyether amine for textile printing and dyeing auxiliary and preparation method for polyether amine |
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| CN106832249B (en) * | 2017-02-06 | 2019-05-10 | 山东一诺威新材料有限公司 | The refining methd of low smell polyether polyol with high activity |
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| EP0864598A2 (en) * | 1997-03-13 | 1998-09-16 | Basf Aktiengesellschaft | Process for treating polyetherpolyols |
| JP2005132990A (en) * | 2003-10-31 | 2005-05-26 | Asahi Glass Co Ltd | Method of producing polyethers |
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