A supported solid base catalyst, its preparation method and application

Abstract

The present application relates to a kind of supported solid base catalyst, including carrier and active component supported on carrier, the carrier is one of SiO2, ZrO2, attapulgite or Al2O3;The active component is alkali metal and / or alkaline earth metal hydroxide.The present application a kind of supported solid base catalyst has higher catalytic activity, excellent stability;With the supported solid base catalyst prepared glycerol polyoxyethylene polyoxypropylene ether can reach higher molecular weight, and molecular weight distribution is narrow, low unsaturation, higher primary hydroxyl content;The supported solid base catalyst is easy to separate from product, can be recycled after regeneration, and no more three wastes are generated.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ether compound preparation, in particular to a supported solid base catalyst, a preparation method and application thereof. BACKGROUND

[0002] Glycerol polyether is a glycerol derivative synthesized from glycerol and propylene oxide (EO) or a mixture of ethylene oxide (EO) and propylene oxide (PO) under the action of a catalyst. It is generally a colorless to light yellow liquid at room temperature, slightly soluble in water, and easily soluble in solvents such as methanol and ethanol. Glycerol polyether has three active hydroxyl groups, which can react with polyisocyanate to form hard foam polyurethane thermal insulation materials, and can also be used in soft foam polyurethane materials and polyurethane elastomers. It can be used as an adhesive when reacted with isocyanate-containing silane coupling agents. Glycerol polyether fatty acid esters synthesized by reacting glycerol polyether with fatty acids can be used as defoamers. With the rapid development of the polyurethane industry in recent decades, the use of glycerol polyether has also been increasing. Scholars at home and abroad are constantly expanding the synthesis methods and application fields of glycerol polyether.

[0003] The current industrial glycerol polyether catalytic process can be divided into two categories according to the catalytic mechanism: alkali metal compound anion catalysis and double metal cyanide complex (DMC) catalysis. Patent CN200710070149 uses alkali metal compound anion catalysis to synthesize glycerol polyether, which uses solid sodium methoxide, potassium methoxide methanol solution, KOH or NaOH, etc. Alkali metal compounds (preferably KOH) as catalysts to synthesize glycerol block polyether with a molecular weight of 300-6000, and add phosphoric acid, diatomite, polyether adsorbent, etc. to refine the product. The glycerol block polyether obtained by this process has low metal ion content and low electrical conductivity, and is a homogeneous catalyst system represented by strong alkali metal KOH which is still widely used in industry. However, this method has the following disadvantages: it is not suitable for synthesizing polyether with a molecular weight of more than 6000, the molecular weight distribution is wide, the viscosity is relatively high, and after the polymerization reaction is completed, the catalyst must be separated from the polyether product, otherwise it will cause unnecessary side reactions in the downstream product, and the polyether refining process is relatively complex, generally including neutralization, adsorption, dehydration and pressure filtration steps, the production cycle is long, and it is difficult to avoid the generation of three wastes.

[0004] The DMC catalyst is generally prepared by reacting water-soluble metal cyanide complex and other metal compounds and combining with organic ligands. A typical double metal cyanide catalyst is, for example, Zn3[Co(CN)6]2·xZnCl2·yH2O·z complexing agents. Patent CN100999574 discloses a method for synthesizing glycerol polyether with DMC catalyst. The prepared glycerol polyether has the characteristics of high reactivity, low unsaturation and short reaction period, and the molecular weight of the prepared glycerol polyether can reach 25000, and the unsaturation is below 0.03. Although this catalyst improves the anionic and cationic polymerization and can synthesize high molecular weight polyether with low unsaturation, it cannot use small molecule initiators, the polymerization selectivity of the head-to-tail of the polyether molecule is low, and it cannot be capped with ethylene oxide; in addition, the polyol containing DMC catalyst residue is relatively unstable during storage, which may bring odor to the polyol and cause undesirable side reactions in the production of polyurethane.

[0005] Therefore, it is necessary to provide a solid base catalyst with high activity and good stability and its application in the preparation method of glycerol polyoxyethylene polyoxypropylene ether. SUMMARY

[0006] Therefore, it is necessary to provide a solid base catalyst with high activity and good stability and its application in the preparation method of glycerol polyoxyethylene polyoxypropylene ether.

[0007] To achieve the above object, the present application provides the following technical solutions.

[0008] In a first aspect, the present application provides a supported solid base catalyst, which comprises a carrier and an active component supported on the carrier, wherein the carrier is one of SiO2, ZrO2, attapulgite or Al2O3; and the active component is alkali metal and / or alkaline earth metal hydroxide.

[0009] Further, the mass of the active component accounts for 1% to 10% of the mass of the carrier.

[0010] Further, the alkaline earth metal hydroxide is one of NaOH, KOH and CsOH.

[0011] In a second aspect, the present application provides a preparation method of the supported solid base catalyst, which comprises the following steps.

[0012] An active component aqueous solution is prepared, and the concentration of the active component aqueous solution is 5%-15%; the pre-prepared carrier powder is dissolved in anhydrous ethanol, and then the active component aqueous solution is added, and the mixture is stirred vigorously at 60-80℃ for 6-8h, and then the intermittent ultrasonic assisted impregnation is performed twice to obtain the supported solid base catalyst.

[0013] Further, the preparation method of the pre-prepared carrier powder is as follows:

[0014] After the carrier powder is dried at 80-100℃, it is placed in a muffle furnace to be calcined, obtaining a pre-prepared carrier powder.

[0015] In a third aspect, the present application provides a preparation method of glycerol polyoxyethylene polyoxypropylene ether, comprising the following steps:

[0016] ① Glycerol and the supported solid base catalyst are added into a high-pressure reaction kettle, and the reaction kettle is replaced with nitrogen and heated;

[0017] ② After the temperature is raised to 100-120℃, the water in the reaction system is removed, and the time is 0.5-1.5h;

[0018] ③ After dehydration, the temperature in the kettle is maintained at 70-130℃, and the reaction kettle is purged with ethylene oxide and propylene oxide to perform a polymerization reaction, and after the reaction is completed, the low-boiling substances are removed;

[0019] ④ The temperature is lowered to 40-70℃, and the glycerol polyoxyethylene polyoxypropylene ether product is obtained by filtration.

[0020] Further, the mass ratio of the ethylene oxide to the propylene oxide is 1:1-10; and the total mass of the ethylene oxide and the propylene oxide to the mass of glycerol is 5-100:1.

[0021] Further, the mass of the supported solid base catalyst is 1-3% of the total mass of glycerol, ethylene oxide and propylene oxide.

[0022] Further, the polymerization reaction in step ③ is performed for 2-6h.

[0023] Further, in step ①, the reaction kettle is vacuumed by a vacuum pump, and then purged with nitrogen to replace the air in the kettle.

[0024] The present application has the following advantages and beneficial effects:

[0025] The supported solid base catalyst has high catalytic activity and excellent stability; the glycerol polyoxyethylene polyoxypropylene ether prepared by using the supported solid base catalyst has a high molecular weight, a narrow molecular weight distribution, a low unsaturation degree and a high primary hydroxyl content; the supported solid base catalyst is easy to separate from the product, can be recycled after regeneration, and does not generate much waste. DETAILED DESCRIPTION

[0026] The application provides a supported solid base catalyst, which comprises a carrier and an active component supported on the carrier, the carrier is one of SiO2, ZrO2, attapulgite (ATP) or Al2O3, and the active component is alkali metal and / or alkaline earth metal hydroxide.

[0027] In some specific embodiments of the application, the carrier is Al2O3, because the surface of aluminum oxide has abundant acid-base active sites, so that the use of aluminum oxide as the carrier can increase the specific surface area of the catalyst, thereby improving the mass transfer and transfer rate during the catalytic reaction.

[0028] The active component is one of alkaline earth metal hydroxides NaOH, KOH and CsOH, and in some specific embodiments of the application, the alkaline earth metal hydroxide is CsOH. Because the strength and quantity of the basic sites on the surface of the catalyst are the key to affect the catalytic activity, the catalytic activity of the catalyst increases with the increase of the alkali metal property of the loaded alkali metal hydroxide. In the synthesis of glycerol polyoxyethylene polyoxypropylene ether, the CsOH / Al2O3 catalyst shows the most excellent catalytic activity.

[0029] Preferably, the mass of the active component accounts for 1-10% of the mass of the carrier. With the increase of the mass of the active component, the activity of the supported solid base catalyst also increases, but decreases when the proportion exceeds 10%, and there is an optimal value for the loading amount of the active component.

[0030] The application further provides a preparation method of the supported solid base catalyst, which comprises the following steps:

[0031] After drying the commercially available carrier powder, the powder is placed in a muffle furnace for calcination to obtain a pre-prepared carrier powder.

[0032] The active component is added into anhydrous ethanol to prepare an active component aqueous solution, and the concentration of the active component aqueous solution is 5%-15%.

[0033] The pre-prepared carrier powder is dissolved in anhydrous ethanol, and the active component aqueous solution is added, and then the mixture is stirred vigorously at 60-80℃ for 6-8h to ensure that the carrier and the active component are in full contact. Intermittent ultrasonic assisted impregnation is performed by using an ultrasonic cleaner, and the ultrasonic time is 20min and the frequency is 50hz. After each impregnation, the mixture is filtered, and then placed in a 120℃ electric vacuum drying box for drying for 12h to form a porous honeycomb solid. Then, the mixture is vacuum calcined at 600℃ for 3h to convert it into an insoluble solid, and then the next impregnation is performed. The impregnation is performed twice to obtain the supported solid base catalyst. In the application, ethanol is volatile, so that the active component can be better supported on the surface of the carrier during the impregnation. Meanwhile, the use of ultrasonic assisted impregnation can make the active component better adhere to the carrier.

[0034] The application also provides a preparation method of the supported solid base catalyst for glycerol polyoxyethylene polyoxypropylene ether, comprising the following steps:

[0035] ① Glycerol and the supported solid base catalyst are added into a high-pressure reaction kettle, and the reaction kettle is replaced with nitrogen and heated;

[0036] ② After the temperature is increased to 100-120°C, the water in the reaction system is removed by a vacuum pump for 0.5-1.5 h; the water in the system is removed to reduce the generation of unnecessary by-products by the reaction of water with ethylene oxide or propylene oxide.

[0037] ③ After dehydration, the temperature in the kettle is maintained at 70-130°C, a certain amount of ethylene oxide and propylene oxide is continuously introduced into the reaction kettle for polymerization, and after the reaction is completed, the low-boiling substances are removed, and the low-boiling substances removed are unreacted ethylene oxide and propylene oxide and other small molecular substances generated by the reaction.

[0038] ④ The temperature is reduced to 40-70°C, and filtration is performed to obtain glycerol polyoxyethylene polyoxypropylene ether.

[0039] Preferably, the mass ratio of the ethylene oxide to the propylene oxide is 1:1-10; and the total mass of the ethylene oxide and the propylene oxide to the mass of glycerol is 5-100:1.

[0040] Preferably, the mass of the supported solid base catalyst is 1-3% of the total mass of glycerol, ethylene oxide and propylene oxide.

[0041] Preferably, the polymerization reaction in step ③ is performed for 2-6 h.

[0042] Preferably, the way of replacing the high-pressure reaction kettle with nitrogen in step ① is to repeatedly replace the air in the kettle three times by repeatedly vacuumizing the reaction kettle by a vacuum pump and introducing nitrogen.

[0043] In the preparation method of glycerol polyoxyethylene polyoxypropylene ether, after filtration, the supported solid base catalyst is washed with distilled water, vacuum dried at 80°C, and then calcined at 400-700°C for 1-4 h, and can be recycled again. The application does not have special limitations on the washing process and the equipment used for drying and calcining, and can be performed according to the processes or equipment well known in the art.

[0044] The technical solutions in the present application will be clearly and completely described below in combination with the embodiments in the present application. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all the other embodiments obtained by those skilled in the art without creative effort belong to the scope of the present application.

[0045] In the present application, the required raw material components are all commercially available goods well known to those skilled in the art, unless otherwise specified.

[0046] Example 1

[0047] Preparation of supported solid base catalyst CsOH / Al2O3:

[0048] 20 g of CsOH was weighed and added to anhydrous ethanol to prepare an active component aqueous solution, and the concentration of the active component aqueous solution was 10%.

[0049] Commercially available Al2O3 powder was dried at 80℃ for 2 h and then placed in a muffle furnace and calcined at 600℃ for 4 h to obtain 200 g of pre-prepared alumina powder. The pre-prepared alumina powder had a high proportion of γ-Al2O3, which has strong adsorption and catalytic activity. The pre-prepared alumina powder was added to 1000 mL of anhydrous ethanol, and then the above active component aqueous solution was added. The mixture was stirred vigorously at 70℃ for 6 h to ensure that the Al2O3 and CsOH were in sufficient contact. An ultrasonic cleaner was used for intermittent ultrasonic assisted impregnation, with an ultrasonic frequency of 50 hz and an ultrasonic time of 20 min. After each impregnation, the mixture was filtered and placed in a 120℃ electric vacuum drying oven for drying for 12 h to form a porous honeycomb-shaped solid. The solid was then calcined at 600℃ for 3 h in a vacuum to convert it into an insoluble solid, and then subjected to the next impregnation. The impregnation was repeated twice to obtain a supported solid base catalyst CsOH / Al2O3, in which the mass of the active component CsOH accounted for 10% of the mass of the carrier, and the catalyst was denoted as catalyst 1.

[0050] Example 2

[0051] The difference between this example and Example 1 is that 6 g of CsOH was weighed and added to anhydrous ethanol to prepare an active component aqueous solution, and the concentration of the active component aqueous solution was 10%. The other conditions were the same as in Example 1. The supported solid base catalyst CsOH / Al2O3 obtained in this example had an active component whose mass accounted for 3% of the mass of the carrier, and the catalyst was denoted as catalyst 2.

[0052] Example 3

[0053] The difference between this example and Example 1 is that 14 g of CsOH is weighed and added to anhydrous ethanol to prepare an active component aqueous solution, the concentration of the active component aqueous solution is 10%, and other conditions are the same as in Example 1. The obtained supported solid base catalyst CsOH / Al2O3 has a mass of active component that accounts for 7% of the mass of the carrier, and is recorded as catalyst 3.

[0054] Example 4

[0055] Preparation of supported solid base catalyst NaOH / SiO2:

[0056] 20 g of NaOH is weighed and added to anhydrous ethanol to prepare an active component aqueous solution, and the concentration of the active component aqueous solution is 5%.

[0057] Commercially available SiO2 powder is dried at 100°C for 2 h and then placed in a muffle furnace and calcined at 600°C for 4 h to obtain 200 g of pre-prepared SiO2 powder; the pre-prepared SiO2 powder is added to 1000 mL of anhydrous ethanol, and then the above-mentioned active component aqueous solution is added, and the mixture is stirred vigorously at 60°C for 7 h to ensure that the SiO2 and NaOH are in sufficient contact. Intermittent ultrasonic assisted impregnation is performed using an ultrasonic cleaner, with ultrasonic treatment for 20 min and a frequency of 50 hz. After each impregnation, filtration is performed, and the product is placed in a 120°C electric vacuum drying oven and dried for 12 h to form a porous honeycomb-shaped solid. The product is then calcined at 600°C for 3 h in a vacuum to convert it into an insoluble solid, and the next impregnation is performed. The impregnation is performed twice to obtain a supported solid base catalyst NaOH / SiO2, in which the mass of the active component NaOH accounts for 10% of the mass of the carrier, and is recorded as catalyst 4.

[0058] Example 5

[0059] Preparation of supported solid base catalyst Na / ZrO2:

[0060] 20 g of Na is weighed and added to anhydrous ethanol to prepare an active component aqueous solution, and the concentration of the active component aqueous solution is 15%.

[0061] The commercially available ZrO2 powder is dried at 90°C for 2h and then placed in a muffle furnace and calcined at 600°C for 4h to obtain 200g of pre-prepared ZrO2 powder; the pre-prepared ZrO2 powder is added to 1000ml of anhydrous ethanol, and then the above active component aqueous solution is added, and the mixture is stirred vigorously at 80°C for 8h to ensure that the ZrO2 and Na are in sufficient contact; intermittent ultrasonic assisted impregnation is performed using an ultrasonic cleaner for 20min at a frequency of 50hz. After each impregnation, the mixture is filtered and placed in a 120°C electric vacuum drying oven for 12h to form a porous honeycomb solid, which is then calcined at 600°C for 3h to convert it into an insoluble solid before the next impregnation; the impregnation is performed twice to obtain a supported solid base catalyst Na / ZrO2, wherein the mass of Na in the active component accounts for 10% of the mass of the carrier, and the catalyst is denoted as catalyst 5.

[0062] Example 6

[0063] Preparation of a supported solid base catalyst NaNO3 / ZrO2:

[0064] 10g of a mixture of Na and KOH is weighed and added to anhydrous ethanol to prepare an active component aqueous solution, and the concentration of the active component aqueous solution is 10%.

[0065] The commercially available ZrO2 powder is dried at 80°C for 2h and then placed in a muffle furnace and calcined at 600°C for 4h to obtain 200g of pre-prepared ZrO2 powder; the pre-prepared ZrO2 powder is added to 1000ml of anhydrous ethanol, and then the above active component aqueous solution is added, and the mixture is stirred vigorously at 70°C for 6h to ensure that the ZrO2 and NaNO3 are in sufficient contact; intermittent ultrasonic assisted impregnation is performed using an ultrasonic cleaner for 20min at a frequency of 50hz. After each impregnation, the mixture is filtered and placed in a 120°C electric vacuum drying oven for 12h to form a porous honeycomb solid, which is then calcined at 600°C for 3h to convert it into an insoluble solid before the next impregnation; the impregnation is performed twice to obtain a supported solid base catalyst Na / NaNO3, wherein the mass of NaNO3 in the active component accounts for 10% of the mass of the carrier, and the catalyst is denoted as catalyst 6.

[0066] Example 7

[0067] Preparation of a supported solid base catalyst (a mixture of Na and KOH) / Al2O3:

[0068] 10g of a mixture of Na and KOH is weighed and added to anhydrous ethanol to prepare an active component aqueous solution, and the concentration of the active component aqueous solution is 10%.

[0069] The commercially available Al2O3 powder was dried at 80°C for 2h and then placed in a muffle furnace and calcined at 600°C for 4h to obtain 200g of pre-prepared Al2O3 powder; the pre-prepared Al2O3 powder was added to 1000ml of anhydrous ethanol, and then the above active component aqueous solution was added, and the mixture was stirred vigorously at 70°C for 6h to ensure that the Al2O3 was in full contact with Na and KOH; intermittent ultrasonic assisted impregnation was performed using an ultrasonic cleaner for 20min at a frequency of 50hz. After each impregnation, the mixture was filtered and placed in a 120°C electric vacuum drying oven for drying for 12h to form a porous honeycomb solid, which was then calcined at 600°C for 3h to convert it into an insoluble solid before the next impregnation; the impregnation was performed twice to obtain a supported solid base catalyst Na and KOH mixture / Al2O3, wherein the mass of the active component accounted for 10% of the mass of the carrier, and the catalyst was denoted as catalyst 7.

[0070] Example 8

[0071] Preparation of a supported solid base catalyst Na / attapulgite (ATP):

[0072] 20g of NaOH was weighed and added to anhydrous ethanol to prepare an active component aqueous solution, and the concentration of the active component aqueous solution was 10%.

[0073] The commercially available ATP powder was dried at 80°C for 2h and then placed in a muffle furnace and calcined at 600°C for 4h to obtain 200g of ATP powder; the obtained ATP powder was added to 1000ml of anhydrous ethanol, and then the above active component aqueous solution was added, and the mixture was stirred vigorously at 70°C for 6h to ensure that the ATP was in full contact with Na; intermittent ultrasonic assisted impregnation was performed using an ultrasonic cleaner for 20min at a frequency of 50hz. After each impregnation, the mixture was filtered and placed in a 120°C electric vacuum drying oven for drying for 12h to form a porous honeycomb solid, which was then calcined at 600°C for 3h to convert it into an insoluble solid before the next impregnation; the impregnation was performed twice to obtain a supported solid base catalyst Na / ATP, wherein the mass of the active component Na accounted for 10% of the mass of the carrier, and the catalyst was denoted as catalyst 8.

[0074] Catalyst comparative example 1

[0075] The carrier of this comparative example was a mixture of SiO2, ZrO2 and Al2O3, and the SiO2, ZrO2 and Al2O3 were mixed according to a mass ratio of 1:1:1.

[0076] 20g of NaOH was weighed and added to anhydrous ethanol to prepare an active component aqueous solution, and the concentration of the active component aqueous solution was 10%.

[0077] The SiO2, ZrO2 and Al2O3 powders were mixed with 67 g of each in 1000 ml of anhydrous ethanol, and then the active component aqueous solution was added. The mixture was stirred at 70°C for 6 h to ensure that the SiO2, ZrO2 and Al2O3 were in full contact with the CsOH. The impregnation was assisted by intermittent ultrasonic treatment using an ultrasonic cleaner for 20 min at a frequency of 50 Hz. After each impregnation, the mixture was filtered and dried in an electric vacuum drying oven at 120°C for 12 h. The next impregnation was carried out after the mixture was converted into an insoluble solid by calcination at 600°C for 3 h. The impregnation was repeated twice to obtain the supported solid base catalyst (NaOH / SiO2.ZrO2.Al2O3), which was designated as catalyst 9.

[0078] Catalyst Comparative Example 2

[0079] The difference between this comparative example and Example 1 is that:

[0080] The difference between this example and Example 1 is that 30 g of CsOH was weighed into anhydrous ethanol to prepare the active component aqueous solution, and the concentration of the active component aqueous solution was 10%. The other conditions were the same as in Example 1. The supported solid base catalyst CsOH / Al2O3 obtained had an active component mass that accounted for 15% of the mass of the carrier, and was designated as catalyst 10.

[0081] Catalyst Comparative Example 3

[0082] The difference between this comparative example and Example 1 is that the impregnation was assisted by intermittent ultrasonic treatment using an ultrasonic cleaner once. The other conditions were the same as in Example 1. The supported solid base catalyst CsOH / Al2O3 obtained was designated as catalyst 11.

[0083] The supported solid base catalyst prepared was applied to the preparation of glycerol polyoxyethylene polyoxypropylene ether, as follows:

[0084] Application Example 1

[0085] S1: 23 g of glycerol and 41.2 g of the catalyst 1 prepared in Example 1 were added to a high-pressure reaction kettle. The reaction kettle was evacuated to -0.098 MPa using a vacuum pump, and then nitrogen was introduced into the reaction kettle. This was repeated three times, and then the reaction kettle was heated.

[0086] S2: The temperature was increased to 110°C, and the water in the reaction system was removed using a vacuum pump for 1 h.

[0087] S3: The temperature was maintained at 100°C, and 295 g of ethylene oxide and 1182 g of propylene oxide were continuously introduced into the reaction kettle to carry out the polymerization reaction. The reaction time was 4 h. When the pressure in the reaction kettle no longer decreased, the low-boiling substances in the reaction kettle were removed using a vacuum pump.

[0088] S4: After the removal is completed, the temperature of the reaction kettle is reduced to 50°C, and filtration is performed, to obtain the glycerol polyoxyethylene polyoxypropylene ether product.

[0089] Application Example 2

[0090] S1: 23 g of glycerol and 25 g of the catalyst 2 prepared in Example 2 are added to a high-pressure reaction kettle, the reaction kettle is vacuumed to -0.098 MPa by using a vacuum pump, and then nitrogen is introduced, and the replacement is repeated for 3 times, and then heating is performed;

[0091] S2: The temperature is increased to 120°C, and the water in the reaction system is removed by using a vacuum pump, and the time is 1 h;

[0092] S3: The temperature is maintained at 130°C, and 738 g of ethylene oxide and 738 g of propylene oxide are continuously introduced into the reaction kettle, and the polymerization reaction is performed, and the reaction time is 6 h, and when the pressure in the reaction kettle no longer decreases, the low-boiling substances in the reaction kettle are removed by using a vacuum pump;

[0093] S4: After the removal is completed, the temperature of the reaction kettle is reduced to 70°C, and filtration is performed, to obtain the glycerol polyoxyethylene polyoxypropylene ether product.

[0094] Application Example 3

[0095] S1: 23 g of glycerol and 107 g of the catalyst 3 prepared in Example 3 are added to a high-pressure reaction kettle, the reaction kettle is vacuumed to -0.098 MPa by using a vacuum pump, and then nitrogen is introduced, and the replacement is repeated for 3 times, and then heating is performed;

[0096] S2: The temperature is increased to 100°C, and the water in the reaction system is removed by using a vacuum pump, and the time is 1 h;

[0097] S3: The temperature is maintained at 70°C, and 148 g of ethylene oxide and 1329 g of propylene oxide are continuously introduced into the reaction kettle, and the polymerization reaction is performed, and the reaction time is 2 h, and when the pressure in the reaction kettle no longer decreases, the low-boiling substances in the reaction kettle are removed by using a vacuum pump;

[0098] S4: After the removal is completed, the temperature of the reaction kettle is reduced to 40°C, and filtration is performed, to obtain the glycerol polyoxyethylene polyoxypropylene ether product.

[0099] Application Example 4

[0100] According to the procedure of Application Example 1, the catalyst 4 prepared in Example 4 is applied to the preparation of glycerol polyoxyethylene polyoxypropylene ether, and the rest is the same as Application Example 1.

[0101] Application Example 5

[0102] According to the procedure of Application Example 1, the catalyst 5 prepared in Example 5 is applied to the preparation of glycerol polyoxyethylene polyoxypropylene ether, and the rest is the same as Application Example 1.

[0103] Example 6

[0104] Example 6 was used for the preparation of glycerol polyoxyethylene polyoxypropylene ether according to the procedure of Example 1, with the exception that the remaining conditions were as in Example 1.

[0105] Example 7

[0106] Example 7 was used for the preparation of glycerol polyoxyethylene polyoxypropylene ether according to the procedure of Example 1, with the exception that the remaining conditions were as in Example 1.

[0107] Example 8

[0108] Example 8 was used for the preparation of glycerol polyoxyethylene polyoxypropylene ether according to the procedure of Example 1, with the exception that the remaining conditions were as in Example 1.

[0109] Example 9

[0110] This example differs from Example 1 only in that 7 g of catalyst 1 prepared in Example 1 was used, with the exception that the remaining conditions were as in Example 1.

[0111] Example 10

[0112] This example differs from Example 1 only in that 0.75 g of catalyst 1 prepared in Example 1 was used, with the exception that the remaining conditions were as in Example 1.

[0113] Example 11

[0114] Example 1, with the exception that catalyst 9 prepared in Catalyst Comparative Example 1 was used for the preparation of glycerol polyoxyethylene polyoxypropylene ether.

[0115] Example 12

[0116] Example 1, with the exception that catalyst 10 prepared in Catalyst Comparative Example 2 was used for the preparation of glycerol polyoxyethylene polyoxypropylene ether.

[0117] Example 13

[0118] Example 1, with the exception that catalyst 11 prepared in Catalyst Comparative Example 3 was used for the preparation of glycerol polyoxyethylene polyoxypropylene ether.

[0119] Catalyst Comparative Example 1

[0120] Glycerol polyoxyethylene polyoxypropylene ether was synthesized using KOH, which is currently used in industry, as a catalyst, according to the following procedure:

[0121] S1: Put 23 g of glycerol, 3.45 g of KOH into a high-pressure reaction kettle, use a vacuum pump to vacuum the reaction kettle to-0.098 Mpa, then introduce nitrogen, replace 3 times repeatedly, and then heat;

[0122] S2: Increase the temperature to 110°C, remove the water in the reaction system with a vacuum pump, time 1 h;

[0123] S3: Maintain the temperature at 100°C, start continuously introducing ethylene oxide 295 g and propylene oxide 1182 g into the reaction kettle, carry out polymerization reaction, reaction time 4 h, when the pressure in the reaction kettle no longer decreases, remove the low-boiling substances in the reaction kettle with a vacuum pump;

[0124] S4: When the temperature of the crude product drops below 50°C, transfer the crude product into a post-treatment kettle for post-treatment, add deionized water 105 g and polyether adsorbent magnesium silicate 25.5 g, stir thoroughly for 30 min, then increase the temperature of the polyether crude product to about 80°C, slowly remove the water in the system with a vacuum pump, when the system pressure drops to-0.098 Mpa, increase the temperature to 120°C and keep for h, then decrease the temperature, filter to obtain glycerol polyoxyethylene polyoxypropylene ether.

[0125] Application Comparative Example 2

[0126] Prepare glycerol polyoxyethylene polyoxypropylene ether with DMC catalyst, the steps are as follows:

[0127] S1: Put refined glycerol polyoxyethylene polyoxypropylene ether ether 600 oligomer 150 g into a high-pressure reaction kettle, use a vacuum pump to vacuum the reaction kettle to-0.098 Mpa, then introduce nitrogen, replace 3 times repeatedly, and then heat;

[0128] S2: Increase the temperature to 110°C, remove the water in the reaction system with a vacuum pump, time 1 h;

[0129] S3: After dehydration, decrease the temperature of the reaction kettle to below 80°C, add DMC catalyst 0.3 g into the reaction kettle, replace nitrogen, and increase the temperature to 145°C;

[0130] S4: When the temperature rises, quickly introduce a mixture of ethylene oxide and propylene oxide into the reaction kettle, when the pressure in the kettle is 0.25 Mpa, stop adding the mixture of ethylene oxide and propylene oxide when the pressure in the reaction kettle rapidly decreases, react for a certain time to complete the activation reaction;

[0131] S5: When the pressure in the reactor is not decreasing, continue to pass the remaining amount of the mixture of ethylene oxide and propylene oxide to the metering point, wherein the total amount of ethylene oxide is 338 g and the total amount of propylene oxide is 1012 g. After the addition is completed, the reaction is continued for a certain period of time until the pressure is not decreasing. The low boiling point substances in the reactor are removed by a vacuum pump. The temperature is lowered to 50°C and the product is discharged, thereby obtaining the glycerol polyoxyethylene polyoxypropylene ether product.

[0132] Comparative Example 3

[0133] The glycerol polyoxyethylene polyoxypropylene ether is prepared by using the supported potassium fluoride / attapulgite solid catalyst (KF / ATP). The steps are as follows:

[0134] 23 g of glycerol and 41.2 g of attapulgite solid catalyst are added to a high-pressure reactor. The reactor is vacuumed to -0.098 Mpa by a vacuum pump and then nitrogen is introduced. The process is repeated for three times and then the reactor is heated.

[0135] S2: The temperature is increased to 120°C and the water in the reaction system is removed by a vacuum pump for 1 h.

[0136] S3: The temperature is maintained at 100°C. The polymerization reaction is started by continuously passing 295 g of ethylene oxide and 1182 g of propylene oxide into the reactor. The reaction time is 4 h. When the pressure in the reactor is not decreasing, the low boiling point substances in the reactor are removed by a vacuum pump.

[0137] S4: After the removal is completed, the temperature in the reactor is lowered to 50°C. The product is filtered, thereby obtaining the glycerol polyoxyethylene polyoxypropylene ether product.

[0138] Comparative Example 4

[0139] The difference between this comparative example and Example 1 is that the amount of catalyst 1 added is 10 g. The rest is the same as Example 1.

[0140] The solid supported catalyst prepared in Example 1 was characterized: wide-angle 10-70° X-ray diffraction of the sample was tested by an Empyrean type X-ray diffractometer (XPD) under the conditions of Cu Ka target, tube current of 40 Ma, tube voltage of 40 Kv, diffraction slit of 0.25°, and scanning speed of 10° / min. The results showed that the loading of alkaline earth metal oxides did not change the crystal structure of the carrier Al2O3, and CsOH may exist in an amorphous form or a better dispersed state on the surface of the Al2O3 carrier. NH3-TPD and CO2-TPD characterization was performed by a ChemBET Pulsar TPR / TPD type chemisorption instrument. The carrier gas was helium, and the detector was TCD. First, the sample was processed by tabletting 40-60 mesh and placed in a quartz tube, then pre-treated by heating to 500°C at a temperature rising rate of 10°C / min for half an hour in a helium atmosphere, then the temperature was reduced to 100°C and kept, and NH3 and CO2 were adsorbed for half an hour respectively, then purged with helium for one hour, and after the baseline was stable, the desorption was started in a helium atmosphere at a temperature rising rate of 10°C / min, and the NH3 and CO2 desorption curves of the sample were obtained. The results showed that as the loading amount of CsOH increased, the number of basic sites on the surface of the supported catalyst gradually increased, and when the loading amount increased to a certain value, the number of basic sites tended to be constant, which may be due to the fact that the pores of the carrier were filled.

[0141] The glycerol polyoxyethylene polyoxypropylene ether prepared by the supported solid catalyst was characterized: the molecular weight Mp and the molecular weight distribution coefficient of the product were measured by high performance liquid chromatography (GPC) test method, and then the catalytic performance of the supported catalyst was tested; the hydroxyl value, unsaturation, and primary hydroxyl content were detected according to the national standard method, wherein the hydroxyl value was determined according to the phthalic anhydride method specified in GB / T7383-2007, the unsaturation was tested according to GB / T12008.6-2010, and the primary hydroxyl content was measured by acylating the glycerol polyether crude product with trifluoroacetic anhydride, and then quantitatively measuring the product trifluoroacetate according to the different chemical shifts. The test results are shown in Table 1 below.

[0142] Table 1

[0143]

[0144]

[0145] The stability of the catalyst was tested: the supported solid base catalyst obtained by filtering after the polymerization reaction in Example 1 was dried in an electric vacuum drying oven at 80°C, then calcined at 500°C for 3h, and then regenerated and applied to the preparation of the glycerol polyoxyethylene polyoxypropylene ether again, which was repeated for 5 times, and the molecular weight and conversion rate were tested. The test results are shown in Table 2 below.

[0146] Table 2

[0147]

[0148] From Table 1, it can be seen that with the increase of the loading amount of the active component, the catalytic performance of the supported solid base catalyst is continuously improved; when the mass of the active component accounts for 10% of the mass of the carrier, the catalytic performance reaches the highest value, but when it exceeds 10%, the catalytic performance decreases instead. In the synthesis of glycerol polyether with high molecular weight, compared with other existing processes, the product has small molecular weight distribution coefficient, low unsaturation, high primary hydroxyl content and high conversion rate, which indicates that the supported solid base catalyst has high catalytic activity and good selectivity; from Table 2, it can be seen that after the regeneration of the supported solid base catalyst, the conversion rate does not obviously decrease after being repeatedly used for five times, which indicates that the prepared supported solid base catalyst has excellent stability.

[0149] The above-mentioned examples only express several embodiments of the present application, and the description is relatively specific and detailed, but it should not be understood as the limitation of the patent scope of the present application. It should be pointed out that for ordinary skilled persons in the art, several modifications and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application should be subject to the appended claims.

Claims

1. A supported solid base catalyst, characterized in that: It includes a support and an active component loaded on the support, wherein the support is Al2O3; the active component is CsOH; and the mass of the active component accounts for 1% to 10% of the mass of the support. The preparation method of the supported solid base catalyst includes the following steps: Prepare an aqueous solution of the active component, with a concentration of 5%-15%. The pre-supported powder was dissolved in anhydrous ethanol, and then an aqueous solution of the active component was added. The mixture was stirred vigorously at 60-80°C for 6-8 hours, and intermittently ultrasonically assisted impregnation was performed twice. After each impregnation, the mixture was dried at 120°C to form a porous honeycomb solid, and then calcined under vacuum at 600°C for 3 hours to obtain a supported solid base catalyst. The ultrasonic frequency was 50 Hz and the duration was 20 min.

2. The supported solid base catalyst according to claim 1, characterized in that, The preparation method of the pre-fabricated carrier powder is as follows: The carrier powder is dried at 80-100℃ and then calcined in a muffle furnace to obtain the pre-prepared carrier powder.

3. A method for preparing glycerol polyoxyethylene polyoxypropylene ether, characterized in that, Includes the following steps: ① Add glycerol and the supported solid base catalyst as described in claim 1 or 2 into a high-pressure reactor, replace the reactor with nitrogen gas, and then raise the temperature; ②After the temperature rises to 100-120℃, remove the water from the reaction system over a period of 0.5-1.5 hours; ③ After dehydration, maintain the temperature inside the reactor at 70-130℃, introduce ethylene oxide and propylene oxide into the reactor to carry out the polymerization reaction, and remove the low-boiling substances after the reaction is completed. ④ Reduce the temperature to 40-70℃, filter, and you will get the finished product of glycerol polyoxyethylene polyoxypropylene ether.

4. The method for preparing glycerol polyoxyethylene polyoxypropylene ether according to claim 3, characterized in that: The mass ratio of ethylene oxide to propylene oxide is 1:1 to 10; the mass ratio of the total mass of ethylene oxide and propylene oxide to the mass of glycerol is 5 to 100:

1.

5. The method for preparing glycerol polyoxyethylene polyoxypropylene ether according to claim 4, characterized in that, The mass of the supported solid base catalyst is 1-3% of the total mass of glycerol, ethylene oxide, and propylene oxide.

6. The method for preparing glycerol polyoxyethylene polyoxypropylene ether according to claim 3, characterized in that, The polymerization reaction in step ③ takes 2 to 6 hours.

7. The method for preparing glycerol polyoxyethylene polyoxypropylene ether according to claim 3, characterized in that: In step ①, the high-pressure reactor is replaced with nitrogen by using a vacuum pump to evacuate the reactor and then introducing nitrogen to replace the air inside the reactor.

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