阅读说明：本技术 一种聚醚多元醇的精制方法及其产物与应用 (Refining method of polyether polyol, product and application thereof ) 是由 朱建海 胡丽云 杨正勇 夏军 陈颂义 于 2020-06-09 设计创作，主要内容包括：本发明公开了一种聚醚多元醇的精制方法及其产物与应用,所述精制方法包括：采用吸附剂对聚醚多元醇进行吸附处理,其中,将所述吸附剂分至少两批加入聚醚多元醇中进行至少两次吸附处理,在每次加吸附剂之前先向所述聚醚多元醇中加水,每次吸附处理后进行脱水和过滤。本发明的精制工序未使用磷酸进行中和,避免了磷酸的投入,导致大量磷酸盐的生成使聚醚变浑浊,而是采用酸性吸附剂,直接进行吸附,使磷腈类催化剂控制在10ppm左右(去除率达到90％以上)；本发明所述方法主要应用在磷腈作催化剂的聚醚合成体系,其工艺简单,用时少,能有效去除聚醚多元醇中的磷腈催化剂,改善产品的pH值,并最大程度的降低了聚醚的氨类气味。(The invention discloses a refining method of polyether polyol, a product and application thereof, wherein the refining method comprises the following steps: and (2) adsorbing polyether polyol by adopting an adsorbent, wherein the adsorbent is added into the polyether polyol in at least two batches for at least two times of adsorption treatment, water is added into the polyether polyol before the adsorbent is added for each time, and dehydration and filtration are performed after each adsorption treatment. According to the invention, phosphoric acid is not used for neutralization in the refining process, so that the phenomenon that a large amount of phosphate is generated to enable polyether to become turbid due to the input of phosphoric acid is avoided, and an acidic adsorbent is directly used for adsorption, so that the content of the phosphazene catalyst is controlled to be about 10ppm (the removal rate is more than 90%); the method is mainly applied to a polyether synthesis system with phosphazene as a catalyst, has simple process and less time consumption, can effectively remove the phosphazene catalyst in polyether polyol, improves the pH value of a product, and reduces the ammonia odor of polyether to the maximum extent.)

1. A method for refining polyether polyol, comprising: and (2) adsorbing polyether polyol by adopting an adsorbent, wherein the adsorbent is added into the polyether polyol in at least two batches for at least two times of adsorption treatment, water is added into the polyether polyol before the adsorbent is added for each time, and dehydration and filtration are performed after each adsorption treatment.

2. The purification process according to claim 1, wherein the water is added in an amount of 0.5 to 10 parts by weight, preferably 1 to 8 parts by weight, more preferably 3 to 6 parts by weight, per 100 parts by weight of the polyether polyol.

3. Refining process according to claim 1, characterized in that the adsorbent is selected from solid acid adsorbents, preferably from aluminosilicates or from mixtures of aluminosilicates with other silicates, more preferably from aluminosilicates or from mixtures of aluminosilicates with magnesium aluminosilicates.

4. The refining method according to claim 1, wherein the adsorbent has a particle size of 50 to 200 μm and a specific surface area of 100m or more²/g。

5. The purification process according to claim 1, wherein the adsorbent is added in an amount of 0.2 to 5 parts by weight, preferably 0.5 to 3 parts by weight, more preferably 0.5 to 2 parts by weight per 100 parts by weight of the polyether polyol.

6. Refining process according to claim 1, characterized in that the moisture content in the polyether polyol is controlled to be 0.5% or less, preferably 0.1% or less, after each dehydration.

7. The refining method according to any one of claims 1 to 6, wherein the refining method adopts two times of adsorption treatment, and comprises the following steps:

step 1, adding water into a polyether polyol crude product to be treated to obtain a system I, adding an adsorbent into the system I, stirring, and then dehydrating and filtering to obtain a polyether polyol intermediate product;

and 2, adding water into the polyether polyol intermediate product to obtain a second system, adding an adsorbent into the second system, stirring, dehydrating and filtering to obtain a polyether polyol finished product.

8. The refining method according to claim 7, wherein in step 1 and step 2, both the first system and the second system are subjected to stirring treatment: stirring for 0.5-5 h at 30-120 ℃, preferably stirring for 1-3 h at 40-90 ℃.

9. The purification process according to claim 7, wherein the stirring treatment after the addition of the adsorbent in step 1 and step 2 is carried out as follows: the reaction is carried out at 60-120 ℃ for 0.5-5 h, preferably at 80-100 ℃ for 1-3 h.

10. The refining method according to claim 7, wherein in step 1 and step 2, the dehydration is performed as follows: vacuum dehydration is carried out at 60-130 ℃, preferably at 100-120 ℃.

11. The refining method according to claim 7,

in step 1, the moisture content in both the crude polyether polyol product and the polyether polyol intermediate product is less than or equal to 0.5 percent, preferably less than or equal to 0.1 percent; and/or

The moisture content in the finished polyether polyol obtained in the step 2 is less than or equal to 0.1 percent, preferably less than or equal to 0.05 percent.

12. The polyether polyol obtained by the purification process according to any one of claims 1 to 11, wherein the content of the phosphazene catalyst is 15ppm or less, particularly 12ppm or less.

13. Use of the purification method of any one of claims 1 to 11 in a polyether synthesis system using a phosphazene compound as a catalyst.

Technical Field

The invention relates to the purification of polyether polyol, in particular to the purification of polyether polyol synthesized by a phosphazene catalyst.

Background

The polyether polyol is a bulk chemical raw material and is widely applied. The industrial synthesis of polyether polyols generally employs both basic and bimetallic catalysts. KOH is the most common basic catalyst, the reaction conditions are mild, the reaction is easy to control, and the catalyst cost is low, but chain transfer reaction is easy to occur in the catalytic process, so that a series of defects of low relative molecular mass, wide distribution, high unsaturation degree and the like of a product are caused, the performance index of the product is influenced, and the application of the product is limited. The polyether produced by the bimetallic catalyst does not have the problems, the catalyst activity is high, the prepared product has the characteristics of high relative molecular mass, narrow distribution, low unsaturation degree and the like, but the bimetallic catalyst cannot use a small molecular compound (such as propylene glycol, glycerol and the like) as an initiator, and the produced polyether contains a metal component, so that the application range of the polyether polyol is influenced.

The phosphazene compound is a novel polyether synthesis catalyst with great development potential and popularization value. Compared with KOH catalyst widely used in industry, the catalyst has the advantages of high polymerization activity of epoxy monomer, low unsaturation degree of polyether product and the like; compared with high-activity bimetallic catalysts, the catalyst has the advantages of using small molecular compounds as initiators, directly capping EO, and the like. In addition, the phosphazene catalyst is characterized in that the molecular structure of the phosphazene catalyst does not contain metal elements, so that polyether prepared by the phosphazene catalyst is colorless and has higher purity, and a polyurethane product produced by the polyether is not easy to color and has excellent physical properties, so that the development and gradual large-scale application of the phosphazene catalyst are of great significance to the production and application of polyether polyol. However, phosphazene catalysts are generally alkaline, and if they are present in polyether products, they seriously affect the storage stability and the use performance, and the polyether has certain ammonia odor, which is harmful to human body, so that they must be removed.

Chinese patent CN105237759A discloses a polyether polyol for a high-tensile elastomer and a preparation method thereof, wherein the polyether polyol is prepared from the following raw materials in parts by weight: 50-100 parts of salicyl alcohol, 2-20 parts of catalyst and 4000 parts of propylene oxide; the preparation method comprises the following steps: putting salicyl alcohol and a catalyst into a reaction kettle, replacing the salicyl alcohol and the catalyst with nitrogen, heating to 85 ℃, adding propylene oxide for polymerization reaction, curing to obtain a crude product after the reaction is finished, and then washing, neutralizing, adsorbing, drying and filtering to obtain the polyether polyol. The polyether polyol for the high-tensile elastomer is prepared by adopting the salicyl alcohol as an initiator and performing ring-opening polymerization with the propylene oxide under the action of the composite catalyst of the alkali metal catalyst, the double metal cyanide complex catalyst and the phosphazene catalyst, and can obviously improve the tensile property of the elastomer when used for preparing the elastomer; the preparation method is scientific, reasonable, simple and feasible.

Chinese patent CN110577637A relates to the technical field of polyether polyol, in particular to a low-odor refining method of phosphazene catalytic system polyether polyol. The low-odor refining method of the phosphazene catalytic system polyether polyol comprises the following steps: (1) putting the crude polyether glycol into a refining reaction kettle, adding water and stirring; (2) adding a neutralizing agent for neutralization, and then adding an adsorbent for adsorption; (3) dehydrating under negative pressure, and adding ion exchange resin for adsorption exchange; (4) adding an antioxidant, and filtering to obtain the refined polyether polyol. The method for refining the polyether polyol with the phosphazene catalytic system is simple and efficient, can be used for producing by using common neutralization-adsorption equipment without equipment transformation, can effectively reduce the odor of the polyether polyol, can remove the residual catalyst in the polyether polyol to the maximum extent, and has less volatile organic compounds and low odor of the refined polyether polyol.

Chinese patent CN108059717A discloses a refining method of low-odor polyether polyol and application thereof. The refining method comprises the following steps: 1) adding water and a compound antioxidant to the crude polyether polyol; 2) neutralizing with neutralizer, and adding adsorbent for adsorption; 3) dehydrating under negative pressure, and filtering to obtain refined polyether polyol; the crude polyether polyol is polyether polyol synthesized by using alkali metal catalysis, and the compound antioxidant comprises antioxidant 1010 and antioxidant DPDP. The refining method of the invention can effectively reduce the odor of polyether and remove the alkali metal catalyst to the maximum extent.

The purification of polyether polyols by alkali metal catalysts disclosed in the prior art generally requires neutralization with an organic or inorganic acid and then adsorption with an adsorbent. However, if the method is directly adopted for purifying the polyether polyol synthesized by the phosphazene catalyst, the system is turbid, the content of the catalyst remaining in the polyether is high, and the ammonia smell of the system is strong.

Disclosure of Invention

In order to overcome the problems in the prior art, the invention provides a method for refining polyether polyol, which is mainly applied to a polyether synthesis system taking a phosphazene compound as a catalyst, has simple process and less time consumption, can effectively remove the phosphazene catalyst in the polyether polyol, improve the pH value of a product, and furthest reduce the ammonia odor of the polyether.

An object of the present invention is to provide a method for purifying polyether polyol, comprising: and (2) carrying out adsorption treatment on the polyether polyol by using an adsorbent, wherein the adsorbent is added into the polyether polyol in at least two batches for at least two times (for example, twice), water is added into the polyether polyol before each time of adding the adsorbent, and dehydration and filtration are carried out after each time of adsorption treatment.

In a preferred embodiment, water is added in an amount of 0.5 to 10 parts by weight, preferably 1 to 8 parts by weight, and more preferably 3 to 6 parts by weight per 100 parts by weight of the polyether polyol.

The purpose of adding water is to promote the polyether polyol to emulsify, release the phosphazene catalyst in the polyether polyol, and then adsorb the released phosphazene catalyst through an adsorbent to achieve the purpose of removing. Although the removal of the phosphazene catalyst can be promoted by emulsification, the emulsification degree is too high, polyether is easy to be vacuumized away together with water in the dehydration process, the water is not completely removed, and the polyether still in an emulsified state can be hung on a filter screen in the filtering process, so that the product yield is reduced. Therefore, it is crucial how to achieve high removal of phosphazene catalyst at low emulsification levels (i.e., as little water as possible).

Based on the above, in order to achieve high removal efficiency of the phosphazene catalyst at a low emulsification degree as much as possible, the adsorbent is used for adsorbing the polyether polyol for multiple times, that is, a small amount of water is used each time to ensure a low emulsification degree, and multiple emulsification and adsorption processes are performed simultaneously. According to the thought, the inventor carries out a large number of experiments and finds that under the technical scheme of the invention, the removal effect of the phosphazene catalyst is greatly improved, and the energy loss of polyether polyol in the refining process is greatly reduced.

In a preferred embodiment, the adsorbent is selected from solid acid adsorbents, preferably from aluminosilicates or from mixtures of aluminosilicates with other silicates.

In a further preferred embodiment, the adsorbent is selected from aluminium silicate or from a mixture of aluminium silicate and magnesium aluminium silicate.

Among them, the inventors have found through a lot of experiments that magnesium silicate, which is frequently used in the prior art, is far less effective in removing magnesium silicate than aluminum silicate and magnesium aluminum silicate.

In a preferred embodiment, the adsorbent has a particle size of 50 to 200 μm (preferably 50 to 150 μm) and a specific surface area of 100m or more²/g。

In a preferred embodiment, the adsorbent is added in an amount of 0.2 to 5 parts by weight, preferably 0.5 to 3 parts by weight, and more preferably 0.5 to 2 parts by weight per one part by weight based on 100 parts by weight of the polyether polyol.

In the present invention, the amount of adsorbent added per adsorption treatment is significantly lower than that of the prior art, but the effect is still very excellent, even better than that disclosed in the prior art.

In a preferred embodiment, the moisture content in the polyether polyol is controlled to be 0.5% or less, preferably 0.1% or less, after each dehydration.

The inventors have found through extensive experimental studies that the water content of the crude polyether polyol and the polyether polyol intermediate product needs to be strictly controlled and cannot be higher than 0.5%, because if the water content is higher than 0.5%, the polyether polyol is still in an emulsified state, and the emulsified polyether polyol is hung on a filter screen during the filtration process, which finally causes product loss and reduces the yield, so that the invention also can be seen in that the emulsification degree of the polyether polyol is strictly controlled.

In a preferred embodiment, the refining process employs two adsorption treatments, including the steps of:

step 1, adding water into a polyether polyol crude product to be treated to obtain a system I, adding an adsorbent into the system I, stirring, and then dehydrating and filtering to obtain a polyether polyol intermediate product;

and 2, adding water into the polyether polyol intermediate product to obtain a second system, adding an adsorbent into the second system, stirring, dehydrating and filtering to obtain a polyether polyol finished product.

In a preferred embodiment, in the first system of step 1, the water is added in an amount of 0.5 to 10 parts by weight, preferably 1 to 8 parts by weight, and more preferably 3 to 6 parts by weight, based on 100 parts by weight of the crude polyether polyol.

In a preferred embodiment, in the second system in step 2, the water is added in an amount of 0.5 to 10 parts by weight, preferably 1 to 8 parts by weight, and more preferably 3 to 6 parts by weight, based on 100 parts by weight of the polyether polyol intermediate.

In a preferred embodiment, in step 1 and step 2, the first system and the second system are both subjected to stirring treatment, which is performed as follows: stirring for 0.5-5 h at 30-120 ℃, preferably stirring for 1-3 h at 40-90 ℃.

The system I and the system II are stirred before the adsorbent is added, so that the emulsification of the system can be promoted, the optimal emulsification effect can be achieved under the condition of low water consumption, and the phosphazene catalyst is released as far as possible.

In a preferred embodiment, in step 1 and step 2, the adsorbent is selected from solid acid adsorbents, preferably from aluminosilicates or from mixtures of aluminosilicates with other silicates.

In a further preferred embodiment, in step 1 and step 2, the adsorbent is selected from aluminium silicate or from a mixture of aluminium silicate and magnesium aluminium silicate.

In a preferred embodiment, the adsorbent has a particle size of 50 to 200 μm (preferably 50 to 150 μm) and a specific surface area of 100m or more²/g。

In a preferred embodiment, in step 1, the adsorbent is used in an amount of 0.2 to 5 parts by weight, preferably 0.5 to 3 parts by weight, and more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the crude polyether polyol.

In a preferred embodiment, in step 2, the adsorbent is used in an amount of 0.2 to 5 parts by weight, preferably 0.5 to 3 parts by weight, and more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the polyether polyol intermediate.

In a preferred embodiment, in step 1 and step 2, the stirring treatment after the addition of the adsorbent is carried out as follows: the reaction is carried out at 60-120 ℃ for 0.5-5 h, preferably at 80-100 ℃ for 1-3 h.

Wherein the adsorption effect of the adsorbent can be promoted under high-temperature stirring.

In a preferred embodiment, in step 1 and step 2, the dehydration is carried out as follows: vacuum dehydration is carried out at 60-130 ℃, preferably at 100-120 ℃.

In a preferred embodiment, in step 1, the moisture content in both the crude polyether polyol and the intermediate polyether polyol is 0.5% or less, preferably 0.1% or less.

The inventors have found through extensive experimental studies that the water content of the crude polyether polyol and the polyether polyol intermediate product needs to be strictly controlled and cannot be higher than 0.5%, because if the water content is higher than 0.5%, the polyether polyol is still in an emulsified state, and the emulsified polyether polyol is hung on a filter screen during the filtration process, which finally causes product loss and reduces the yield, so that the invention also can be seen in that the emulsification degree of the polyether polyol is strictly controlled.

In a preferred embodiment, the moisture content in the finished polyether polyol obtained in step 2 is less than or equal to 0.1%, preferably less than or equal to 0.05%.

In the invention, the removal rate of the phosphazene catalyst reaches more than 90 percent through two adsorption processes.

Another object of the present invention is to provide a polyether polyol obtained by the purification method according to the first object of the present invention, wherein the content of the phosphazene catalyst is 15ppm or less, particularly 12ppm or less.

The third purpose of the invention is to provide the application of the refining method in a polyether synthesis system using a phosphazene compound as a catalyst, and particularly to the refining of polyether polyol in a phosphazene catalyst system.

Compared with the prior art, the invention has the following beneficial effects:

(1) according to the invention, phosphoric acid is not used for neutralization in the refining process, so that the phenomenon that a large amount of phosphate is generated to enable polyether to become turbid due to the input of phosphoric acid is avoided, and an acidic adsorbent is used for direct adsorption;

(2) the invention adopts a multi-step (such as two-step) adsorption method to control the phosphazene catalyst to be about 10ppm (the removal rate reaches more than 90 percent);

(3) the invention strictly controls the emulsification degree of the polyether polyol in the refining process, and reduces the loss of the polyether polyol, namely, the removal rate of the phosphazene catalyst is improved, and the loss of the polyether polyol is reduced;

(4) the method is mainly applied to a polyether synthesis system with phosphazene as a catalyst, has simple process and less time consumption, can effectively remove the phosphazene catalyst in polyether polyol, improves the pH value of a product, and reduces the ammonia odor of polyether to the maximum extent.

Detailed Description

While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.

The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.

In the examples and comparative examples, the aluminum silicate had a particle size of 80um and a specific surface area of 700m²The particle diameter of the magnesium aluminum silicate is 60nm, and the specific surface area is 500m²The particle diameter of the magnesium silicate is 70nm, and the specific surface area is 600m²/g。

The measurement method provided by the invention can be a conventional method in the field, and the specific methods are respectively as follows:

measurement of the phosphazene content. The P element was measured by an ICP instrument.

[ example 1 ]

Adding 1000g of phosphazene polyether polyol crude product to be refined into a 2L three-neck flask, adding 50g of pure water, heating to 85 ℃, stirring for 1 hour, then adding 10g of acidic aluminum silicate adsorbent, heating to 90 ℃, stirring for 2 hours, heating to 100 ℃, dehydrating, filtering after the moisture is qualified (less than or equal to 0.5%), obtaining polyether polyol intermediate product, and measuring the content of P element, wherein the content of P element is shown in Table 1.

Putting the polyether polyol intermediate product into a 2L three-neck flask again, adding 40g of pure water, heating to 85 ℃, stirring for 1 hour, adding 10g of acidic aluminum silicate adsorbent, heating to 90 ℃, stirring for 2 hours, heating to 100 ℃, dehydrating, filtering after the moisture is qualified to obtain a polyether polyol finished product, and measuring the content of the P element, wherein the content of the P element is shown in Table 1.

[ example 2 ]

Adding 1000g of phosphazene polyether polyol to be refined into a 2L three-neck flask, adding 50g of pure water, heating to 85 ℃, stirring for 1 hour, then adding 5g of acidic aluminum silicate and 5g of acidic magnesium aluminum silicate adsorbent, heating to 90 ℃, stirring for 2 hours, heating to 100 ℃, dehydrating, filtering after the moisture is qualified (less than or equal to 0.5%), obtaining a polyether polyol intermediate product, and measuring the content of P element, wherein the content of P element is shown in Table 1.

Putting the polyether polyol intermediate product into a 2L three-neck flask again, adding 40g of pure water, heating to 85 ℃, stirring for 1 hour, adding 5g of acidic aluminum silicate and 5g of acidic aluminum magnesium silicate adsorbent, heating to 90 ℃, stirring for 2 hours, heating to 100 ℃, dehydrating, filtering after the moisture is qualified to obtain a polyether polyol finished product, and measuring the content of the P element, wherein the content of the P element is shown in Table 1.

[ example 3 ]

1000g of phosphazene polyether polyol to be refined is added into a 2L three-neck flask, 50g of pure water is added, the temperature is raised to 85 ℃, the mixture is stirred for 1 hour, 10g of acidic aluminum silicate adsorbent is added, the temperature is raised to 90 ℃, the mixture is stirred for 4 hours, then the mixture is dehydrated after being heated to 100 ℃, and after the moisture is qualified (less than or equal to 0.5 percent), the intermediate product of polyether polyol is obtained by filtration, and the content of P element is measured, and the content is shown in Table 1.

Putting the polyether polyol intermediate product into a 2L three-neck flask again, adding 40g of pure water, heating to 85 ℃, stirring for 1 hour, adding 5g of acidic aluminum silicate and 5g of acidic aluminum magnesium silicate adsorbent, heating to 90 ℃, stirring for 4 hours, heating to 100 ℃, dehydrating, filtering after the moisture is qualified to obtain a polyether polyol finished product, and measuring the content of the P element, wherein the content of the P element is shown in Table 1.

[ example 4 ]

Adding 1000g of phosphazene polyether polyol crude product to be refined into a 2L three-neck flask, adding 80g of pure water, heating to 90 ℃, stirring for 1 hour, then adding 15g of acidic aluminum silicate adsorbent, heating to 120 ℃, stirring for 1 hour, dehydrating at 120 ℃, and filtering after the moisture is qualified (less than or equal to 0.5%) to obtain a polyether polyol intermediate product.

And putting the polyether polyol intermediate product into a 2L three-neck flask again, adding 20g of pure water, heating to 90 ℃, stirring for 1 hour, adding 5g of acidic aluminum silicate adsorbent, heating to 120 ℃, stirring for 1 hour, dehydrating at 120 ℃, and filtering after the water content is qualified to obtain a polyether polyol finished product.

[ example 5 ]

Adding 1000g of phosphazene polyether polyol crude product to be refined into a 2L three-neck flask, adding 30g of pure water, heating to 40 ℃, stirring for 3 hours, then adding 5g of acidic aluminum silicate adsorbent, heating to 60 ℃, stirring for 5 hours, heating to 90 ℃, dehydrating, and filtering after the moisture is qualified (less than or equal to 0.5%) to obtain a polyether polyol intermediate product.

And putting the polyether polyol intermediate product into a 2L three-neck flask again, adding 20g of pure water, heating to 40 ℃, stirring for 3 hours, adding 5g of acidic aluminum silicate adsorbent, heating to 60 ℃, stirring for 5 hours, heating to 90 ℃, dehydrating, and filtering after the water content is qualified to obtain a polyether polyol finished product.

[ example 6 ]

Adding 1000g of phosphazene polyether polyol crude product to be refined into a 2L three-neck flask, adding 60g of pure water, heating to 100 ℃, stirring for 0.5 hour, then adding 15g of acidic aluminum magnesium silicate adsorbent, heating to 110 ℃, stirring for 1.5 hours, heating to 120 ℃, dehydrating, and filtering after the water content is qualified (less than or equal to 0.5%) to obtain a polyether polyol intermediate product.

And putting the polyether polyol intermediate product into a 2L three-neck flask again, adding 10g of pure water, heating to 100 ℃, stirring for 0.5 hour, adding 15g of acidic aluminum silicate adsorbent, heating to 110 ℃, stirring for 1.5 hours, heating to 120 ℃, dehydrating, and filtering after the water content is qualified to obtain a polyether polyol finished product.

[ example 7 ]

Adding 1000g of phosphazene polyether polyol crude product to be refined into a 2L three-neck flask, adding 10g of pure water, heating to 30 ℃, stirring for 5 hours, then adding 12g of acidic aluminum silicate adsorbent, heating to 70 ℃, stirring for 2.5 hours, heating to 100 ℃, dehydrating, and filtering to obtain a polyether polyol intermediate product after the moisture is qualified (less than or equal to 0.5%).

And putting the polyether polyol intermediate product into a 2L three-neck flask again, adding 70g of pure water, heating to 30 ℃, stirring for 5 hours, adding 8g of acidic aluminum silicate adsorbent, heating to 70 ℃, stirring for 2.5 hours, heating to 100 ℃, dehydrating, and filtering after the water content is qualified to obtain a polyether polyol finished product.

Comparative example 1

Adding 1000g of phosphazene polyether polyol to be refined into a 2L three-neck flask, adding 50g of pure water, heating to 85 ℃, stirring for 1 hour, then adding 20g of acidic aluminum silicate adsorbent, heating to 90 ℃, stirring for 4 hours, heating to 100 ℃, dehydrating, filtering after the moisture is qualified to obtain a polyether polyol finished product, and measuring the content of the P element, wherein the content of the P element is shown in Table 1.

Comparative example 2

Adding 1000g of phosphazene polyether polyol to be refined into a 2L three-neck flask, adding 90g of pure water, heating to 85 ℃, stirring for 1 hour, then adding 20g of acidic aluminum silicate adsorbent, heating to 90 ℃, stirring for 4 hours, heating to 100 ℃, dehydrating, filtering after the moisture is qualified to obtain a polyether polyol finished product, and measuring the content of the P element, wherein the content of the P element is shown in Table 1.

Comparative example 3

Adding 1000g of phosphazene polyether polyol to be refined into a 2L three-neck flask, adding 50g of pure water, heating to 85 ℃, stirring for 1 hour, adding 5g of phosphoric acid with the content of 50%, stirring for 1 hour, then adding 20g of acidic aluminum silicate adsorbent, heating to 90 ℃, stirring for 4 hours, heating to 100 ℃, dehydrating, filtering after the moisture is qualified to obtain a polyether polyol finished product, and measuring the content of P element, wherein the content of P element is shown in Table 1.

Comparative example 4

1000g of phosphazene polyether polyol to be refined is added into a 2L three-neck flask, 50g of pure water is added, the temperature is raised to 85 ℃, the mixture is stirred for 1 hour, 10g of magnesium silicate adsorbent is added, the temperature is raised to 90 ℃, the mixture is stirred for 2 hours, the temperature is raised to 100 ℃, then dehydration is carried out, the mixture is filtered after the moisture is qualified (less than or equal to 0.5%), a polyether polyol intermediate product is obtained, and the content of the P element is measured, wherein the content of the P element is shown in Table 1.

Putting the polyether polyol intermediate product into a 2L three-neck flask again, adding 40g of pure water, heating to 85 ℃, stirring for 1 hour, adding 10g of magnesium silicate adsorbent, heating to 90 ℃, stirring for 2 hours, heating to 100 ℃, dehydrating, filtering after the moisture is qualified to obtain a polyether polyol finished product, and measuring the content of the P element, wherein the content of the P element is shown in Table 1.

Comparative example 5

1000g of phosphazene polyether polyol to be refined is added into a 2L three-neck flask, 50g of pure water is added, the temperature is raised to 85 ℃, the mixture is stirred for 1 hour, 10g of magnesium silicate adsorbent is added, the temperature is raised to 90 ℃, the mixture is stirred for 2 hours, the temperature is raised to 100 ℃, then dehydration is carried out, the mixture is filtered after the moisture is qualified (less than or equal to 0.5%), a polyether polyol intermediate product is obtained, and the content of the P element is measured, wherein the content of the P element is shown in Table 1.

Putting the polyether polyol intermediate product into a 2L three-neck flask again, adding 40g of pure water, heating to 85 ℃, stirring for 1 hour, adding 10g of aluminum silicate adsorbent, heating to 90 ℃, stirring for 2 hours, heating to 100 ℃, dehydrating, filtering after the moisture is qualified to obtain a polyether polyol finished product, and measuring the content of the P element, wherein the content of the P element is shown in Table 1.

Table 1:

as can be seen from Table 1, the phosphorus content in the product obtained in the example of the invention is below 12ppm, and the removal rate of the catalyst reaches more than 90%, specifically:

(1) comparative example 1 and comparative example 1: in example 1, the adsorbent was added twice to perform adsorption treatment twice, and in comparative example 1, the adsorbent was added once to perform adsorption treatment once, and the total amount of the adsorbents used was the same. It can be seen from the results in table 1 that, under the premise of using the same amount of adsorbent, the catalyst removal effect of example 1 is significantly better than that of comparative example 1, the removal rate is improved by 20.6%, and an unexpected effect is achieved.

According to the experience of the ordinary technicians in the chemical field, the post-treatment effect can be theoretically improved (but not necessarily) by carrying out the post-treatment for a small number of times, but is generally 1-5% higher, but the inventor has surprisingly found through experiments that the catalyst removal rate can be improved by 20.6% in the invention by adding the adsorbent in two times in batches, which is far beyond the original expectation.

(2) Comparative example 1 and comparative example 2: in example 1, the adsorbent was added twice to perform adsorption treatment, and in comparative example 1, the adsorbent was added once to perform adsorption treatment, and the total amount of the adsorbents was the same, and the total amount of water added was also the same. As can be seen from Table 1, the removal rate of example 1 is significantly higher than that of comparative example 2, and in the comparative example 2, the polyether polyol emulsification degree is too high due to the fact that the addition amount of the equivalent polyether polyol-based water is 2 times (the total amount is the same) of the addition amount of water of example 1 each time, the subsequent dehydration time is longer, and the polyether polyol is easily pulled away by vacuum in the dehydration process, so that the yield is reduced.

(3) Comparative example 1 and comparative example 3: example 1 was performed 2 times with adsorption treatment and comparative example 3 was performed using prior art protocol, first with acid neutralization followed by adsorption. As can be seen from the data in table 1, the effect of example 1 is significantly better than that of comparative example 3.

(4) Comparing example 1 with comparative example 4, example 1 using an aluminum silicate adsorbent and comparative example 4 using a magnesium silicate adsorbent, it can be seen from the data in table 1 that the effect of example 1 is significantly higher than that of comparative example 4, which is not suggested in the prior art, and thus, the present invention optimizes the selection of the adsorbents.

(5) Comparing example 1 with comparative example 5, example 1 using aluminum silicate for both steps, and comparative example 5 using magnesium silicate first and then aluminum silicate, it can be seen from the data in table 1 that the effect of example 1 is significantly higher than that of comparative example 5.

Table 2:

	yield of finished product
		Example 1	98.24％
Comparative example 1	98.45％
		Comparative example 2	96.34％

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.