WO2022062598A1 - Supported solid super acidic catalyst, preparation method therefor and use thereof, and preparation method for ethoxylated trimethylolpropane - Google Patents

Abstract

The present invention provides a supported solid super acidic catalyst, a preparation method therefor and use thereof, and a preparation method for ethoxylated trimethylolpropane. The catalyst comprises a carrier and an active ingredient supported on the carrier, the active ingredient is a sulfide metal oxide, and the sulfide metal oxide comprises a metal oxide and a sulfate radical coordinated and adsorbed on the metal oxide; the carrier is a layered clay; and the mass of the active ingredient is 25-75% of the mass of the carrier. In the present invention, the supported solid super acidic catalyst as a catalyst, trimethylolpropane as an initiator, and ethylene oxide undergo ring-opening polymerization to prepare ethoxylated trimethylolpropane. The results show that the yield of the ethoxylated trimethylolpropane is ≥78% (up to 88.4%), the selectivity is ≥85% (up to 95%), and the catalyst is easily separated from the product, does not corrode equipment, has low environmental pollution, is easy to regenerate, and is recyclable and good in cycle stability; and after 7 cycles, the yield of the product remains at least 75%.

Description

A kind of supported solid superacid catalyst and preparation method and application thereof, preparation method of ethoxylated trimethylolpropane technical field

The invention relates to the technical field of preparation of ether compounds, in particular to a supported solid superacid catalyst, a preparation method and application thereof, and a preparation method of ethoxylated trimethylolpropane.

Background technique

Ethoxylated trimethylolpropane is an important polyether intermediate for UV curing materials, mainly used as a raw material for the synthesis of multifunctional acrylate reactive diluents. It has suitable viscosity and excellent solubility while having high activity, and can impart good flexibility to the cured film, reduce the shrinkage rate of the cured film, improve the adhesion to the substrate, and has low skin irritation. and other important features. As important intermediates for reactive diluents, these products are widely used in specialty radiation-curable coatings, inks and adhesives for mobile phone electronics, automobiles, wind power and solar cells.

Tri-functional polyether polyol is prepared by ring-opening polymerization of trimethylolpropane and epoxide under the action of catalyst. In U.S. US4382135 patent, Sinka et al. used sodium hydroxide as a catalyst to initiate ring-opening addition of ethylene oxide with trimethylolpropane to obtain ethoxylated trimethylolpropane, and this type of polymerization reaction was based on the rapid transfer of protons as The basis is that the chain growth of the polyether is completed by the continuous conversion between the alcohol and the alkoxide, so that the reaction is rapidly transferred from one chain to another chain. Because under the catalysis of strong base, the chain growth rate of EO (epoxy group) is higher than the chain initiation rate, and as a result, the polyoxyethylene branch chain length of polyether polyol is uneven, and the amount of EO contained in the molecule varies greatly, resulting in product There are not only residual raw materials and starting agents, but also homologues with different addition numbers. Therefore, in view of the problems existing in the catalytic synthesis of ethoxylated trimethylolpropane with strong base catalysts, Zhang Cheng et al. proposed a catalytic polymerization process with a double metal complex catalyst (DMC). Patents USP7723465, WO1998003571 and WO1999014258 also describe A KOH/DMC catalytic pathway for the production of multifunctional polyether polyols by semi-batch and continuous feed processes. However, DMC catalysts cannot directly use small molecules as initiators during polymerization, otherwise the initial stage of the reaction will have a long induction period, and the initiators used in the process are low molecular weight polyethers, that is, small molecules are used as initiators. The starting agent is catalyzed by KOH and epoxide is added to a certain relative molecular mass (Mn=300-1000), and then the base catalyst is removed by post-treatment to obtain the starting agent with the required relative molecular mass, which makes the process complicated and increases production. Additional time and cost for multifunctional polyether polyols. After that, Han Yong's team (Han Yong. Improved DMC Catalyst for Polyether Polyol [J]. Advances in Fine Petrochemicals, 2002(06): 22-24.) proposed to modify the DMC catalyst, and it was found that in the relative molecular When the mass is similar, the monofunctional molecule is easy to start, and the start of two or more functional molecules is still difficult. Also, when used with high functionality starting compounds, DMC catalysts tend to gradually deactivate over time before polymerization is complete. These limitations greatly reduce the utility of DMC catalysts in the production of multifunctional polyether polyols. In order to improve the deficiencies of the above methods, Chinese patent CN103476829 proposes to prepare multifunctional polyether polyols with superacid catalysts, and the protic superacids include trifluoromethanesulfonic acid (CF3SO3H), boron trifluoride (BF3), antimony pentafluoride (SbF5), fluorosulfonic acid (FSO3H), etc., all of which are at least a thousand times more acidic than sulfuric acid, and obviously achieve a higher reaction rate of the reactor material. However, such catalysts are easy to hydrolyze and corrode equipment, the removal and recovery of catalysts are difficult, the post-treatment steps are complicated, a large amount of waste acid is discharged, and the environment is polluted, which greatly limits the quality and application performance of the final product.

Therefore, there is a need to provide an efficient catalyst for synthesizing trimethylolpropane-based polyether polyols with excellent catalytic activity and selectivity, which is recyclable and environmentally friendly. Green chemistry of pollution.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a supported solid superacid catalyst, its preparation method and application, and the preparation method of ethoxylated trimethylolpropane, said supported solid superacid catalyst has high catalytic activity and is used for preparing When trimethylolpropane is ethoxylated, the yield reaches 88.4%, the selectivity reaches 95%, and it is easy to separate from the product, does not corrode equipment, is easy to regenerate, can be recycled and reused, and has good cycle stability.

In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:

The present invention provides a supported solid superacid catalyst for trimethylolpropane polyether synthesis, comprising a carrier and an active component supported on the carrier, wherein the active component is a sulfided metal oxide, and the sulfided metal oxidizes The compound includes metal oxides and sulfate groups coordinated and adsorbed on the metal oxides; the carrier is layered clay; the mass of the active component accounts for 25-75% of the mass of the carrier.

Preferably, the carrier is smectite group clay, hydrotalcite group compound, kaolinite group clay or sepiolite group clay.

Preferably, the sulfided metal oxide includes sulfided zirconia, sulfided titanium oxide or sulfided aluminum oxide.

The present invention provides the preparation method of the supported solid superacid catalyst for the synthesis of trimethylolpropane polyether according to the above technical scheme, comprising the following steps:

Mix the dispersion liquid of the carrier, the metal chloride solution and the ammonium sulfate solution, adjust the pH value to 8 to 9, carry out a precipitation reaction, and roast the obtained product to obtain a supported solid superacid catalyst for the synthesis of trimethylolpropane polyether The dosage ratio of the carrier and the metal chloride in the metal chloride solution and the ammonium sulfate in the ammonium sulfate solution is (5-15) g: (0.03-0.05) mol: (0.03-0.05) mol.

Preferably, the metal chloride in the metal chloride solution includes zirconium oxychloride, titanium tetrachloride or aluminum trichloride.

Preferably, the concentrations of the metal chloride solution and the ammonium sulfate solution are 0.1 mol/L, and the molar ratio of the metal ions in the metal chloride solution to the sulfate radicals in the ammonium sulfate solution is 1:1.

Preferably, the roasting temperature is 400-700° C., and the time is 1-4 h.

The present invention provides the supported solid superacid catalyst for the synthesis of trimethylolpropane polyether according to the above technical solution or the supported solid superacid catalyst for the synthesis of trimethylolpropane polyether prepared by the preparation method described in the above technical solution Application in the synthesis of trimethylolpropane polyether.

The invention provides a preparation method of ethoxylated trimethylolpropane, comprising the following steps:

Mixing trimethylolpropane and a supported solid superacid catalyst, feeding into ethylene oxide, and carrying out a polymerization reaction to obtain ethoxylated trimethylolpropane;

The supported solid superacid catalyst is the supported solid superacid catalyst for the synthesis of trimethylolpropane polyether described in the above technical solution or the supported solid superacid catalyst for the synthesis of trimethylolpropane polyether prepared by the preparation method described in the above technical solution. Type solid superacid catalyst.

Preferably, the mass of the supported solid superacid catalyst is 0.1-1.0% of the total mass of trimethylolpropane and ethylene oxide; the temperature of the polymerization reaction is 100-140°C.

The present invention provides a supported solid superacid catalyst for trimethylolpropane polyether synthesis, comprising a carrier and an active component supported on the carrier, wherein the active component is a sulfided metal oxide, and the sulfided metal oxidizes The compound includes metal oxides and sulfate groups coordinated and adsorbed on the metal oxides; the carrier is layered clay; the mass of the active component accounts for 25-75% of the mass of the carrier. The catalyst of the invention uses sulfided metal oxides as active components. In the sulfided metal oxides, sulfate groups are coordinated and adsorbed on the metal oxides, and the S=O double bond in SO 4 2- has a strong electron-inducing effect. , which can make the metal in the active component lack electrons, form a super acid site, provide an acidic site in the reaction, and exert a catalytic effect. The active component is supported on the sheet layer of the layered clay carrier, which can increase the catalyst ratio. The surface area, thereby improving the mass transfer and transfer rate during the catalytic reaction, makes the obtained catalyst have high catalytic activity.

The invention provides a preparation method of ethoxylated trimethylolpropane. The supported solid superacid catalyst is used as a catalyst, and trimethylolpropane is used as an initiator to undergo ring-opening polymerization with ethylene oxide to prepare ethylene oxide. Oxylated trimethylolpropane. The results show that the yield of ethoxylated trimethylolpropane is ≥ 78% (up to 88.4%), the selectivity is ≥ 85% (up to 95%), and the catalyst is easily separated from the product, without corroding equipment and polluting the environment It is small, easy to regenerate, recyclable and has good cycle stability. After 7 cycles, the product yield remains above 75%.

Description of drawings

Fig. 1 is a diagram showing the catalytic effect of the supported sulfided zirconia catalyst prepared in Example 1 after being recycled 7 times.

detailed description

The present invention provides a supported solid superacid catalyst for trimethylolpropane polyether synthesis, comprising a carrier and an active component supported on the carrier, wherein the active component is a sulfided metal oxide, and the sulfided metal oxidizes The compound includes metal oxides and sulfate groups coordinated and adsorbed on the metal oxides; the carrier is layered clay; the mass of the active component accounts for 25-75% of the mass of the carrier.

In the present invention, unless otherwise specified, the required raw material components are all commercially available commodities well known to those skilled in the art.

The supported solid superacid catalyst for the synthesis of trimethylolpropane polyether provided by the present invention comprises a carrier. In the present invention, the carrier is layered clay; the carrier is preferably smectite group clay, hydrotalcite compound, kaolinite group clay or sepiolite group clay; the specific type of the carrier in the present invention is There is no special limitation, and the above-mentioned types of carriers well known in the art can be selected. The specification of the carrier is not particularly limited in the present invention, and commercially available products well known in the art can be selected. The present invention utilizes the above types of carriers to increase the specific surface area of the catalyst, thereby improving the mass transfer and transfer rate during the catalytic reaction, and improving the efficiency and catalytic performance of the catalyst.

The supported solid superacid catalyst for the synthesis of trimethylolpropane polyether provided by the present invention comprises an active component supported on a carrier, the active component is a sulfided metal oxide, and the sulfided metal oxide includes a metal oxide and sulphate which is coordinately adsorbed on the metal oxide. In the present invention, the sulfided metal oxide preferably includes sulfided zirconia, sulfided titanium oxide or sulfided alumina.

In the present invention, the mass of the active component accounts for 25-75% of the mass of the carrier, preferably 50%.

In the supported solid superacid catalyst for the synthesis of trimethylolpropane polyether according to the present invention, sulfided metal oxide is used as the active component, and in the sulfided metal oxide, the sulfate group is coordinated and adsorbed on the metal oxide, The S=O double bond in SO 4 2- has a strong electron-inducing effect, which can make the metal in the active component lack electrons, form a super acidic site, and provide an acidic site in the reaction, so as to achieve a catalytic effect and promote The catalytic reaction proceeds.

The present invention provides the preparation method of the supported solid superacid catalyst for the synthesis of trimethylolpropane polyether according to the above technical scheme, comprising the following steps:

Mix the dispersion liquid of the carrier, the metal chloride solution and the ammonium sulfate solution, adjust the pH value to 8 to 9, carry out a precipitation reaction, and roast the obtained product to obtain a supported solid superacid catalyst for the synthesis of trimethylolpropane polyether The dosage ratio of the carrier and the metal chloride in the metal chloride solution and the ammonium sulfate in the ammonium sulfate solution is (5-15) g: (0.03-0.05) mol: (0.03-0.05) mol.

In the present invention, the dispersant used in the dispersion liquid of the carrier is preferably absolute ethanol, and the mass ratio of the carrier to the absolute ethanol is preferably 1:(10-20), more preferably 1:(12-18) , more preferably 1:(15-16). In the present invention, the preparation process of the dispersion liquid of the carrier is preferably to put the carrier into anhydrous ethanol, and stir and disperse it under ultrasonic conditions for 15-30 minutes; the present invention has no special limitations on the ultrasonic conditions and the stirring process. It is sufficient that a uniformly mixed carrier dispersion can be obtained.

In the present invention, the metal chloride in the metal chloride solution preferably includes zirconium oxychloride, titanium tetrachloride or aluminum trichloride; the concentrations of the metal chloride solution and the ammonium sulfate solution are both preferably 0.1 mol/ L, the mol ratio of the metal ion in the described metal chloride solution and the sulfate radical in the ammonium sulfate solution is preferably 1:1.

In the present invention, the dosage ratio of the carrier to the metal chloride in the metal chloride solution and the ammonium sulfate in the ammonium sulfate solution is preferably (6.5-7.5) g: (0.03-0.05) mol: (0.03-0.05) mol.

The present invention has no special limitation on the process of mixing the dispersion liquid of the carrier, the metal chloride solution and the ammonium sulfate solution, and the materials can be uniformly mixed according to a process well known in the art.

After the mixing is completed, the present invention adjusts the pH value of the obtained mixed system to 8-9, and performs a precipitation reaction. In the present invention, preferably, the mixed system is first heated to 60-70° C., and then sodium hydroxide solution or ammonia solution is added under stirring conditions to adjust the pH value to 8-9. In the present invention, the precipitation reaction is preferably carried out under the condition of water bath reflux, the temperature of the water bath reflux is preferably 60-70°C, and the time of the precipitation reaction is preferably 4-8h, more preferably 5-6h. In the present invention, the concentration of the sodium hydroxide solution or the ammonia solution is preferably 0.01 mol/L. The present invention does not have a special limitation on the stirring conditions, and the sodium hydroxide solution or the ammonia solution can be uniformly mixed according to a process well known in the art. During the precipitation reaction, metal chloride and ammonium sulfate are precipitated to form metal hydroxide.

After the precipitation reaction is completed, in the present invention, the obtained product is preferably centrifuged and washed in sequence, and then the washed precipitate is dried at 80° C., ground to 40-80 mesh, and calcined. In the present invention, the calcination temperature is preferably 400-700° C., and the time is preferably 1-4 h. During the roasting process, the metal hydroxide is converted into a metal oxide, and at the same time, it is compounded with the sulfate group, so that the sulfate group is coordinated and adsorbed on the metal oxide, and the sulfurized metal oxide is used as the active component and is supported on the carrier. catalyst.

The present invention provides the supported solid superacid catalyst for the synthesis of trimethylolpropane polyether according to the above technical solution or the supported solid superacid catalyst for the synthesis of trimethylolpropane polyether prepared by the preparation method described in the above technical solution Application in the synthesis of trimethylolpropane polyether. The method of the application is not particularly limited in the present invention, and it can be applied according to methods well known in the art.

The invention provides a preparation method of ethoxylated trimethylolpropane, comprising the following steps:

Mixing trimethylolpropane and a supported solid superacid catalyst, feeding into ethylene oxide, and carrying out a polymerization reaction to obtain ethoxylated trimethylolpropane;

The supported solid superacid catalyst is the supported solid superacid catalyst for the synthesis of trimethylolpropane polyether described in the above technical solution or the supported solid superacid catalyst for the synthesis of trimethylolpropane polyether prepared by the preparation method described in the above technical solution. Type solid superacid catalyst.

In the present invention, the mass of the supported solid superacid catalyst is preferably 0.1-1.0% of the total mass of trimethylolpropane and ethylene oxide, more preferably 0.3-0.8%, further preferably 0.5-0.6% ; The mass ratio of the trimethylolpropane and ethylene oxide is preferably 1:(1~5), more preferably 1:(2~3).

In the present invention, the process of mixing the trimethylolpropane and the supported solid superacid catalyst is preferably under normal temperature conditions, throwing trimethylolpropane into the reaction kettle, starting the stirring and heating device, and heating up to 40～ At 50°C, the trimethylolpropane was completely melted under stirring conditions, and then the supported solid superacid catalyst was added. The present invention does not have a special limitation on the process of heating and stirring conditions, and can be carried out according to a process well known in the art. The present invention does not have a special limitation on the reaction kettle, and the reaction kettle well known in the art can be used.

After the mixing is completed, the present invention preferably evacuates the reaction kettle, then feeds nitrogen to replace the air in the kettle, repeatedly uses nitrogen to replace the air three times (removes the air in the kettle), and then continues to stir and heat up for dehydration. In the present invention, the temperature of the dehydration is preferably 100-105° C., and the time is preferably 0.5-1 h, more preferably 0.6-0.8 h. The invention removes a small amount of water in trimethylolpropane and the supported solid super acid catalyst through dehydration, and reduces the by-products generated by the reaction of water and ethylene oxide.

After the dehydration is completed, the present invention preferably continues to heat up to the temperature of the polymerization reaction, and starts to feed ethylene oxide to carry out the polymerization reaction. In the present invention, the temperature of the polymerization reaction is preferably 100-140°C, more preferably 110-120°C; the time of the polymerization reaction is preferably 2-6h, more preferably 3-4h; the ethylene oxide The feed rate of alkane is preferably 180 g/h.

In the present invention, it is preferable to continuously feed ethylene oxide to carry out the polymerization reaction. When the metering point of ethylene oxide is reached, the feeding of ethylene oxide is stopped, and then the temperature in the reactor is maintained at the above-mentioned polymerization reaction temperature, and the polymerization is continued. React, until the pressure in the reaction kettle drops to negative pressure (<0MPa), stop heating (that is, stop the polymerization reaction) and introduce cooling water to cool down, degas when it is cooled to 90～100°C, and then continue to cool down to 60～80°C. °C, after filtration, ethoxylated trimethylolpropane is obtained. In the present invention, the metering point is specifically the theoretical amount of ethylene oxide required to be used when synthesizing ethoxylated trimethylolpropane. In the present invention, the temperature of the degassing is more preferably 95°C, and the time is preferably 30-45 min, more preferably 35-40 min. The present invention removes unreacted EO monomer by degassing. The present invention does not have a special limitation on the process of cooling and filtering, and it can be carried out according to the processes well known in the art.

In the present invention, after the filtration is completed, the obtained supported solid superacid catalyst is washed with distilled water, first dried at 80°C, and then calcined at 400-700°C for 1-4 hours, and can be recycled again. The present invention does not have a special limitation on the washing process and the equipment used for drying and roasting, and can be performed according to a well-known process in the art or by using a well-known equipment.

The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some, but not all, embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

Example 1

Preparation of supported sulfided zirconia catalyst: put 7.5g montmorillonite into 112.5g absolute ethanol, stir and disperse in ultrasonic for 30min, then add 300mL zirconium oxychloride octahydrate solution (0.1mol/L) to the obtained dispersion respectively. , 0.03 mol) and 300 mL of ammonium sulfate solution (0.1 mol/L, 0.03 mol), the resulting mixed system was heated to 65 ° C, and an aqueous ammonia solution (0.01 mol/L) was added under stirring to adjust the pH to 8, and at 65 ° C The water bath was refluxed for 4 hours, the obtained product was centrifuged and washed in turn, then the obtained precipitate was dried at 80 ° C, ground to 60 mesh, and then calcined at 500 ° C for 4 hours to obtain a supported solid superacid catalyst (active component sulfide oxidation The mass of zirconium accounts for 50% of the mass of the carrier), denoted as catalyst 1.

Example 2

The difference between this example and Example 1 is only that the amount of montmorillonite added is 5.0 g, other conditions are the same as those in Example 1, and the mass of the active components in the obtained supported sulfided zirconia catalyst accounts for 75% of the mass of the carrier, which is denoted as catalyst 2.

Example 3

The difference between this example and Example 1 is only that the amount of montmorillonite added is 15.0 g, and the other steps are the same as those in Example 1. The mass of the active components in the obtained supported sulfided zirconia catalyst accounts for 25% of the mass of the carrier, denoted as as catalyst 3.

Example 4

Preparation of sulfided zirconia catalyst: 112.5g of absolute ethanol was stirred and dispersed in ultrasonic for 30min, and then 300mL of zirconium oxychloride octahydrate solution (0.1mol/L, 0.03mol) and 300mL of ammonium sulfate solution (0.1 mol/L, 0.03mol), heat the obtained mixed system to 65°C, add ammonia aqueous solution (0.01mol/L) under stirring conditions to adjust the pH value to 8, reflux in a water bath at 65°C for 4h, and centrifuge the obtained product successively. After washing, the obtained precipitate was dried at 80°C, ground to 60 mesh, and then calcined at 500°C for 4 hours to obtain an unsupported solid superacid catalyst, denoted as catalyst 4.

Example 5

Preparation of supported sulfided titanium oxide catalyst: put 7.5 g of montmorillonite into 112.5 g of absolute ethanol, stir and disperse in ultrasonic for 30 min, and then add 470 mL of titanium tetrachloride solution (0.1 mol/L, 0.05 mol) and 470 mL of ammonium sulfate solution (0.1 mol/L, 0.05 mol), the resulting mixed system was heated to 65°C, and an aqueous ammonia solution (0.01mol/L) was added under stirring to adjust the pH to 8, and the mixture was heated to 65°C in a water bath. Reflux for 4 h, the obtained product was centrifuged and washed in turn, then the obtained precipitate was dried at 80 ° C, ground to 60 mesh, and then calcined at 500 ° C for 4 h to obtain a supported solid superacid catalyst (active component sulfide titanium oxide) 50% of the mass of the carrier).

Example 6

Preparation of supported sulfided zirconia catalyst: put 7.5g of hydrotalcite into 112.5g of absolute ethanol, stir and disperse in ultrasonic for 30min, and then add 300mL of zirconium oxychloride octahydrate solution (0.1mol/L, 0.03 mol) and 300 mL of ammonium sulfate solution (0.1 mol/L, 0.03 mol), the resulting mixed system was heated to 65°C, and an aqueous ammonia solution (0.01mol/L) was added under stirring to adjust the pH to 8, and the mixture was heated to 65°C in a water bath. Reflux for 4h, the obtained product was centrifuged and washed in turn, then the obtained precipitate was dried at 80°C, ground to 60 mesh, and then calcined at 500°C for 4h to obtain a supported solid superacid catalyst (active component sulfide zirconia). The mass of the carrier accounts for 50% of the mass of the carrier), denoted as catalyst 6.

Example 7

Preparation of supported sulfided zirconia catalyst: put 7.5g kaolinite into 112.5g absolute ethanol, stir and disperse in ultrasonic for 30min, and then add 300mL zirconium oxychloride octahydrate solution (0.1mol/L) to the obtained dispersion respectively. , 0.03 mol) and 300 mL of ammonium sulfate solution (0.1 mol/L, 0.03 mol), the resulting mixed system was heated to 65 ° C, and an aqueous ammonia solution (0.01 mol/L) was added under stirring to adjust the pH to 8, and at 65 ° C The water bath was refluxed for 4 hours, the obtained product was centrifuged and washed in turn, then the obtained precipitate was dried at 80 ° C, ground to 60 mesh, and then calcined at 500 ° C for 4 hours to obtain a supported solid superacid catalyst (active component sulfide oxidation The mass of zirconium accounts for 50% of the mass of the carrier), denoted as catalyst 7.

Application example 1

The catalyst 1 prepared in Example 1 is used for the synthesis of ethoxylated trimethylolpropane: under normal temperature conditions, drop into trimethylolpropane (300g) in the reactor, start stirring and heating device, and be warming up to 45 ℃ , after the trimethylolpropane is completely melted under stirring conditions, a supported solid superacid catalyst (the addition amount is 0.5% of the total mass of trihydroxypropane and ethylene oxide) is added, and after full stirring, the kettle is evacuated , and then introduce nitrogen to replace the air in the kettle, repeatedly replace the air with nitrogen three times, then continue to stir and heat up, heat up to 100 ° C, and dehydrate for 1 h; then heat up to the reaction temperature of 110 ° C, start to pass ethylene oxide, calculate the epoxy The total amount of ethane added is 900g, and the feed rate of ethylene oxide is controlled to be 180g/h, until reaching the metering point of ethylene oxide (that is, reaching 900g), stop feeding ethylene oxide, and make the reaction kettle. The temperature was kept at 110°C and the polymerization was continued until the pressure in the kettle dropped to negative pressure (the total polymerization time was 4h), the heating was stopped and cooling water was introduced to cool down. When the temperature was lowered to 90°C, degassed for 30min; At 70°C, after filtration, ethoxylated trimethylolpropane was obtained.

Application examples 2 to 4

According to the steps of Application Example 1, catalysts 2 to 4 prepared in Examples 2 to 4 were respectively used for the synthesis of ethoxylated trimethylolpropane.

Performance Testing

The catalytic performance of catalysts 1 to 4 in application examples 1 to 4 is tested, and the specific surface area adopts the BET specific surface area detection method; the content of the components in the product is determined by high performance liquid chromatography (using RID-10a from Shimadzu Corporation of Japan). High performance liquid chromatography: chromatographic column Inertsil ODS-3 (4.6×250mm5μm); mobile phase: A: methanol, B: water, A from 60% (0～15min) gradient to 85% (15～30min), flow rate 1.0 mL/min, chromatographic column temperature: 30°C, injection volume 20uL), and then test the yield and selectivity, the results are shown in Table 1.

The catalytic performance data of catalysts 1 to 4 used in the synthesis of ethoxylated trimethylolpropane in Table 1 Application Examples 1 to 4

performance		catalyst 1	catalyst 2	catalyst 3	catalyst 4
Yield/%	84	78	84	70
Selectivity/%	92	89	85	75
Specific surface area/m 2 /g	185	176	190	37

It can be seen from Table 1 that the supported sulfided zirconia catalyst has better catalytic effect, which is because clay is a typical layered two-dimensional material, and the aggregated state of the solid superacid is changed by loading the clay, which increases the specific surface area. In this way, more active sites can be exposed, which is beneficial to the catalytic reaction. . With the increase of the added amount of the carrier, the specific surface area of the catalyst increases continuously, the exposed catalytic active sites increase, the yield of ethoxylated trimethylolpropane is ≥ 78%, and the selectivity is ≥ 85%, indicating that the present invention The catalyst has high catalytic activity for the synthesis of ethoxylated trimethylolpropane.

Application example 5

The only difference between this application example and application example 1 is that the amount of epoxy added is 300 g, and other steps are the same as those of application example 1.

Application example 6

The only difference between this application example and application example 1 is that the amount of epoxy added is 1500 g, and other steps are the same as application example 1.

Application example 7

The only difference between this application example and application example 1 is that the reaction temperature is 100° C., and other steps are the same as those of application example 1.

Application example 8

The only difference between this application example and application example 1 is that the amount of the supported sulfided zirconia catalyst added is 0.1% of the total mass of trihydroxypropane and ethylene oxide, and other steps are the same as those of application example 1.

Performance Testing

1) The ethoxylated trimethylolpropane prepared in Application Examples 1 and 5 to 8 is tested for performance, wherein the theoretical relative molecular mass is measured by liquid chromatography test method; color, hydroxy value and pH are detected according to national standard method, Among them, the hydroxyl value is determined according to the provisions of the phthalic anhydride method in GB/T7383-2007, the color and luster are determined in accordance with the provisions of GB/T 9282.1-2008, and the pH is determined in accordance with the provisions of GB/T 6368-2008. The index results are shown in Table 2.

Table 2 performance index of ethoxylated trimethylolpropane prepared by application examples 1, 5-8

As can be seen from Table 2, the supported solid superacid catalyst can be used as a catalyst to prepare ethoxylated trimethylolpropane, so that the yield of ethoxylated trimethylolpropane is greater than or equal to 78% (up to 88.4%), Selectivity ≥ 85% (up to 95%), color ≤ 30, pH in the range of 6 to 7.

2) Catalyst stability test

The supported solid superacid catalyst obtained by filtering after the polymerization reaction in Application Example 1 was completed was washed with distilled water, dried at 80°C, and calcined at 500°C for 4 hours before being reused. This cycle is repeated 7 times, and its catalytic effect is shown in Figure 1.

It can be seen from Figure 1 that the supported sulfided zirconia solid acid catalyst has good repeatability in the ethoxylated trimethylolpropane polymerization reaction. When it is recycled and reused 7 times, the conversion rate of the product remains above 75%.

The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made. It should be regarded as the protection scope of the present invention.

Claims (10)

1. A supported solid superacid catalyst for trimethylolpropane polyether synthesis, comprising a carrier and an active component supported on the carrier, the active component is a sulfided metal oxide, and the sulfided metal oxide includes The metal oxide and the sulfate group coordinated and adsorbed on the metal oxide; the carrier is layered clay; the mass of the active component accounts for 25-75% of the mass of the carrier.
2. The supported solid superacid catalyst for synthesis of trimethylolpropane polyether according to claim 1, wherein the carrier is smectite clay, hydrotalcite compound, kaolinite clay or sea foam Stone Clay.
3. The supported solid superacid catalyst for trimethylolpropane polyether synthesis according to claim 1, wherein the sulfided metal oxide comprises sulfided zirconium oxide, sulfided titanium oxide or sulfided aluminum oxide.
4. The preparation method of the supported solid superacid catalyst for the synthesis of trimethylolpropane polyether according to any one of claims 1 to 3, characterized in that, comprising the following steps:

   Mix the dispersion liquid of the carrier, the metal chloride solution and the ammonium sulfate solution, adjust the pH value to 8 to 9, carry out a precipitation reaction, and roast the obtained product to obtain a supported solid superacid catalyst for the synthesis of trimethylolpropane polyether The dosage ratio of the carrier and the metal chloride in the metal chloride solution and the ammonium sulfate in the ammonium sulfate solution is (5-15) g: (0.03-0.05) mol: (0.03-0.05) mol.
5. The preparation method according to claim 4, wherein the metal chloride in the metal chloride solution comprises zirconium oxychloride, titanium tetrachloride or aluminum trichloride.
6. The preparation method according to claim 4, wherein the concentration of the metal chloride solution and the ammonium sulfate solution is 0.1 mol/L, and the metal ion in the metal chloride solution and the sulfate radical in the ammonium sulfate solution have a concentration of 0.1 mol/L. The molar ratio is 1:1.
7. The preparation method according to claim 4, wherein the roasting temperature is 400-700 DEG C, and the time is 1-4 h.
8. The supported solid superacid catalyst for the synthesis of trimethylolpropane polyether according to any one of claims 1 to 3 or the synthesis of trimethylolpropane polyether prepared by the preparation method according to any one of claims 4 to 7 Application of supported solid superacid catalyst in the synthesis of trimethylolpropane polyether.
9. A kind of preparation method of ethoxylated trimethylolpropane, is characterized in that, comprises the following steps:

   Mixing trimethylolpropane and a supported solid superacid catalyst, feeding ethylene oxide, and carrying out a polymerization reaction to obtain ethoxylated trimethylolpropane;

   The supported solid superacid catalyst is prepared by the supported solid superacid catalyst for the synthesis of trimethylolpropane polyether according to any one of claims 1 to 3 or the preparation method according to any one of claims 4 to 7. Supported solid superacid catalyst for trimethylolpropane polyether synthesis.
10. The preparation method according to claim 9, wherein the mass of the supported solid superacid catalyst is 0.1-1.0% of the total mass of trimethylolpropane and ethylene oxide; the temperature of the polymerization reaction is 100～140℃.

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