Supported phosphazene salt catalysts, processes for their preparation and use, and processes for the preparation of high molecular weight butanol polyoxypropylene ethers

Abstract

The application belongs to the technical field of polyether polyols, and particularly relates to a supported phosphazene salt catalyst, a preparation method and application thereof, and a preparation method of high-molecular-weight butanol polyoxypropylene ether. The application provides a preparation method of a supported phosphazene salt catalyst, which comprises the following steps: mixing PZN, magnesium aluminum silicate and water, and performing hydrothermal reaction to obtain a phosphazene salt catalyst precursor; and calcining the phosphazene salt catalyst precursor to obtain the supported phosphazene salt catalyst. The supported phosphazene salt catalyst prepared by the preparation method can improve the reaction activity, reduce the requirements of the polymerization reaction on temperature and pressure, effectively reduce the content of high-molecular-weight substances and the unsaturation degree in the product when applied to the preparation of butanol polyoxypropylene ether, and has less catalyst residues in the product, no metal ion residues, no need for post-treatment and stable quality.

Description

Technical Field

[0001] This invention belongs to the field of polyether polyol technology, specifically relating to a supported phosphazene salt catalyst and its preparation method and application, and a method for preparing high molecular weight butanol polyoxypropylene ether. Background Technology

[0002] Butyl alcohol polyoxypropylene ether is an important surfactant. It is insoluble in water but readily soluble in organic solvents. It is acid and alkali resistant, non-toxic, odorless, and non-corrosive. Its industrial applications are very broad. It can be mixed with many other types of surfactants, exhibits excellent lubricity, and is an excellent lubricant. It can be widely used in various lubricating oils and has significant development value.

[0003] The butanol polyoxypropylene ether prepared using traditional strong alkaline catalysts has high unsaturation and wide distribution, and the reaction temperature and reaction time are relatively high. Especially when preparing high molecular weight butanol polyoxypropylene ethers, the catalyst is difficult to be compatible with and react with low molecular weight butanol polyethers, making it difficult for the prepared butanol polyoxypropylene ether to reach the designed molecular weight. In addition, the high content of high molecular weight substances makes it difficult to meet the kinematic viscosity requirements, which affects the performance of the product.

[0004] To address the aforementioned issues, Chinese patents CN100999577A and CN109593190A proposed using polymetallic cyanide (MMC) as a catalyst, effectively solving the problem that traditional strong alkaline catalysis is difficult to use in preparing high molecular weight butanol polyoxypropylene ether. However, high molecular weight butanol polyoxypropylene ether prepared using MMC catalysts will have MMC catalyst residues. These residual MMC catalysts will promote the generation and accumulation of volatile byproducts such as propionaldehyde, leading to product discoloration and off-odors, seriously affecting the product's storage stability and performance. Summary of the Invention

[0005] In view of this, the present invention aims to provide a supported phosphazene salt catalyst, its preparation method and application, and a method for preparing high molecular weight butanol polyoxypropylene ether. The catalyst prepared by the method provided by the present invention has excellent catalytic effect on the preparation of butanol polyoxypropylene ether.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] This invention provides a method for preparing a supported phosphazene salt catalyst, comprising the following steps:

[0008] A hydrothermal reaction was carried out by mixing a solution of phosphazene ligand P4-tert-butyl, magnesium aluminum silicate, and water to obtain a phosphazene salt catalyst precursor.

[0009] The phosphazene salt catalyst precursor was calcined to obtain the supported phosphazene salt catalyst.

[0010] Preferably, the mass ratio of the phosphazene ligand P4-tert-butyl solution to magnesium aluminum silicate is 1:5 to 15.

[0011] Preferably, the hydrothermal reaction includes a first hydrothermal reaction and a second hydrothermal reaction performed sequentially;

[0012] The temperature of the first hydrothermal reaction is 50–70°C, and the time is 2–4 hours;

[0013] The temperature of the second hydrothermal reaction is 90–120°C, and the time is 1–4 hours.

[0014] Preferably, the roasting temperature is 300-400°C and the time is 1-3 hours.

[0015] The present invention also provides a supported phosphazene salt catalyst prepared by the preparation method described above, wherein the particle size of the supported phosphazene salt catalyst is 10-20 nm.

[0016] The present invention also provides the application of the supported phosphazene salt catalyst described in the above technical solution in the preparation of butanol polyoxypropylene ether.

[0017] This invention also provides a method for preparing high molecular weight butanol polyoxypropylene ether, comprising the following steps:

[0018] Butanol, a first supported phosphazene salt catalyst and a first propylene oxide are mixed and subjected to a first polymerization reaction to obtain low molecular weight butanol polyoxypropylene ether.

[0019] The low molecular weight butanol polyoxypropylene ether, the second supported phosphazene salt catalyst, and the second propylene oxide are mixed and subjected to a second polymerization reaction to obtain the high molecular weight butanol polyoxypropylene ether.

[0020] Both the first supported phosphazene salt catalyst and the second supported phosphazene salt catalyst are the supported phosphazene salt catalysts described in the above technical solution.

[0021] Preferably, the mass ratio of butanol to the first propylene oxide is 1:4.4 to 7.1;

[0022] The mass ratio of the first supported phosphazene salt catalyst to the total mass of the butanol and the first propylene oxide is 0.02 to 0.05%.

[0023] Preferably, the mass ratio of the low molecular weight butanol polyoxypropylene ether to the second propylene oxide is 1:4 to 8;

[0024] The mass ratio of the second supported phosphazene salt catalyst to the total mass of the low molecular weight butanol polyoxypropylene ether and the second propylene oxide is 0.02 to 0.05%.

[0025] Preferably, the temperature of the first polymerization reaction is 50–80°C, the pressure is 0–0.05 MPa, and the time is 3–6 h;

[0026] The second polymerization reaction is carried out at a temperature of 50–80°C, a pressure of 0–0.05 MPa, and a time of 4–7 h.

[0027] This invention provides a method for preparing a supported phosphazene salt catalyst, comprising the following steps: mixing a phosphazene ligand P4-tert-butyl solution, magnesium aluminum silicate, and water, and carrying out a hydrothermal reaction to obtain a phosphazene salt catalyst precursor; calcining the phosphazene salt catalyst precursor to obtain the supported phosphazene salt catalyst. The supported phosphazene salt catalyst prepared by the method provided by this invention can improve reaction activity, reduce the temperature and pressure requirements of the polymerization reaction, and effectively reduce the content of high molecular weight substances and unsaturation in the product when applied to the preparation of butanol polyoxypropylene ether. The product contains little catalyst residue, no metal ion residue, requires no post-processing, and has stable quality.

[0028] The method for preparing high molecular weight butanol polyoxypropylene ether provided by this invention is a two-step process. The process is simple, and the obtained butanol polyoxypropylene ether product has stable quality, light color, and good compatibility, lubrication, thickening and low foaming properties. It can be widely used in textile, metal processing and equipment lubrication fields. Detailed Implementation

[0029] This invention provides a method for preparing a supported phosphazene salt catalyst, comprising the following steps:

[0030] A hydrothermal reaction was carried out by mixing a solution of phosphazene ligand P4-tert-butyl, magnesium aluminum silicate, and water to obtain a phosphazene salt catalyst precursor.

[0031] The phosphazene salt catalyst precursor was calcined to obtain the supported phosphazene salt catalyst.

[0032] In this invention, unless otherwise specified, all raw material components are commercially available products well known to those skilled in the art.

[0033] In this invention, a solution of phosphazene ligand P4-tert-butyl, magnesium aluminum silicate and water are mixed and subjected to a hydrothermal reaction to obtain a phosphazene salt catalyst precursor.

[0034] In this invention, the concentration of phosphazene ligand P4-tert-butyl in the phosphazene ligand P4-tert-butyl solution is preferably 0.5-1.0 mol / kg, more preferably 0.6-0.8 mol / kg, and most preferably 0.8 mol / kg; the phosphazene ligand P4-tert-butyl solution is preferably obtained from Maclean's reagent; the magnesium aluminum silicate is preferably obtained from Zhejiang Huangma Technology Co., Ltd.; the mass ratio of the phosphazene ligand P4-tert-butyl solution to magnesium aluminum silicate is preferably 1:5-15, more preferably 1:8-12, and most preferably 1:10.

[0035] In this invention, the mass ratio of the phosphazene ligand P4-tert-butyl solution to water is preferably 1:6 to 16, more preferably 1:8 to 13, and most preferably 1:11.

[0036] In this invention, the mixing method is preferably stirring; this invention does not impose any special limitations on the stirring process, and any method known to those skilled in the art can be used.

[0037] In this invention, the hydrothermal reaction preferably includes a first hydrothermal reaction and a second hydrothermal reaction performed sequentially; the temperature of the first hydrothermal reaction is preferably 50-70°C, more preferably 60-70°C, and most preferably 60°C; the time is preferably 2-4 hours, more preferably 2-3 hours, and most preferably 3 hours; the temperature of the second hydrothermal reaction is preferably 90-120°C, more preferably 100-110°C, and most preferably 100°C; the time is preferably 1-4 hours, more preferably 1-3 hours, and most preferably 2 hours.

[0038] In this invention, the hydrothermal reaction preferably includes sequential cooling, filtration, and drying; the present invention does not impose any special limitations on the cooling, filtration, and drying processes, and any methods known to those skilled in the art can be used.

[0039] After obtaining the phosphazene salt catalyst precursor, the present invention calcines the phosphazene salt catalyst precursor to obtain the supported phosphazene salt catalyst.

[0040] In this invention, the roasting temperature is preferably 300-400℃, more preferably 320-380℃, and most preferably 350℃; the roasting time is preferably 1-3h, more preferably 2-3h, and most preferably 2h.

[0041] The preparation method provided by this invention uses phosphazene ligand P4-tert-butyl solution (also known as phosphazene base P4-t-Bu solution or PZN) and magnesium aluminum silicate as raw materials to prepare a supported phosphazene salt catalyst PZN / MgAl2(SiO3)4, which can improve the reaction activity, reduce the temperature and pressure requirements of the polymerization reaction, effectively reduce the content of high molecular weight substances and unsaturation in butanol polyoxypropylene ether products, and the product has little catalyst residue, no metal ion residue, no need for post-processing and stable quality.

[0042] The present invention also provides a supported phosphazene salt catalyst prepared by the preparation method described above, wherein the particle size of the supported phosphazene salt catalyst is 10-20 nm.

[0043] In this invention, the particle size of the supported phosphazene salt catalyst is 10-20 nm, preferably 10-18 nm, and more preferably 10-15 nm.

[0044] The present invention also provides the application of the supported phosphazene salt catalyst described in the above technical solution in the preparation of butanol polyoxypropylene ether.

[0045] The present invention does not impose any special limitations on the application process, and any method known to those skilled in the art can be used.

[0046] This invention also provides a method for preparing high molecular weight butanol polyoxypropylene ether, comprising the following steps:

[0047] Butanol, a first supported phosphazene salt catalyst and a first propylene oxide are mixed and subjected to a first polymerization reaction to obtain low molecular weight butanol polyoxypropylene ether.

[0048] The low molecular weight butanol polyoxypropylene ether, the second supported phosphazene salt catalyst, and the second propylene oxide are mixed and subjected to a second polymerization reaction to obtain the high molecular weight butanol polyoxypropylene ether.

[0049] Both the first supported phosphazene salt catalyst and the second supported phosphazene salt catalyst are the supported phosphazene salt catalysts described in the above technical solution.

[0050] In this invention, the mass ratio of butanol to the first propylene oxide is preferably 1:4.4 to 7.1, more preferably 1:5 to 7.

[0051] In this invention, the mass ratio of the first supported phosphazene salt catalyst to the total mass of the butanol and the first propylene oxide is preferably 0.02 to 0.05%, more preferably 0.03 to 0.04%.

[0052] In this invention, the preferred feeding sequence of the first mixture is to first mix butanol and the first supported phosphazene salt catalyst, and then drop in the first propylene oxide; the preferred method for mixing butanol and the first supported phosphazene salt catalyst is stirring; this invention does not impose any special limitations on the stirring process, and any method known to those skilled in the art can be used; the preferred dropping time of the first propylene oxide is 2 to 5 hours, more preferably 3 to 4 hours.

[0053] In this invention, the temperature of the first polymerization reaction is preferably 50-80°C, more preferably 60-70°C; the pressure is preferably 0-0.05 MPa, more preferably 0.01-0.04 MPa, and most preferably 0.02-0.03 MPa; the time is preferably 3-6 h, more preferably 4-5 h; the first polymerization reaction is carried out under stirring conditions; this invention does not impose any special limitations on the stirring process, and any method known to those skilled in the art can be used.

[0054] In this invention, the reaction apparatus for the first polymerization reaction is preferably a high-pressure reactor; the first polymerization reaction is preferably carried out in an inert gas environment; the inert gas is preferably nitrogen; the inert gas environment is preferably provided by evacuating the reaction apparatus and then replacing the inert gas three times.

[0055] In this invention, the chemical reaction equation for the first polymerization reaction is:

[0056]

[0057] In this invention, the molecular weight of the low molecular weight butanol polyoxypropylene ether is preferably 400-600, more preferably 400-500.

[0058] In this invention, the mass ratio of the low molecular weight butanol polyoxypropylene ether to the second propylene oxide is preferably 1:4 to 8, more preferably 1:5 to 7.

[0059] In this invention, the ratio of the mass of the second supported phosphazene salt catalyst to the total mass of the low molecular weight butanol polyoxypropylene ether and the second propylene oxide is preferably 0.02 to 0.05%, more preferably 0.03 to 0.04%.

[0060] In this invention, the preferred feeding sequence for the second mixture is to first mix the low molecular weight butanol polyoxypropylene ether and the second supported phosphazene salt catalyst, and then drop in the second propylene oxide; the preferred method for mixing the low molecular weight butanol polyoxypropylene ether and the first supported phosphazene salt catalyst is stirring; this invention does not impose any special limitations on the stirring process, and any method known to those skilled in the art can be used; the preferred dropping time for the second propylene oxide is 3 to 6 hours, more preferably 4 to 5 hours.

[0061] In this invention, the temperature of the second polymerization reaction is preferably 50-80°C, more preferably 60-70°C; the pressure is preferably 0-0.05 MPa, more preferably 0.01-0.04 MPa, and most preferably 0.02-0.03 MPa; the time is preferably 3-6 h, more preferably 4-5 h; the second polymerization reaction is carried out under stirring conditions; this invention does not impose any special limitations on the stirring process, and any method known to those skilled in the art can be used.

[0062] In this invention, the reaction apparatus for the second polymerization reaction is preferably a high-pressure reactor; the second polymerization reaction is preferably carried out in an inert gas environment; the inert gas is preferably nitrogen; the inert gas environment is preferably provided by evacuating the reaction apparatus and then replacing the inert gas three times.

[0063] In this invention, the chemical reaction equation for the second polymerization reaction is:

[0064]

[0065] In this invention, the molecular weight of the high molecular weight butanol polyoxypropylene ether is preferably 3000-5000, more preferably 4000-5000.

[0066] The method for preparing high molecular weight butanol polyoxypropylene ether provided by this invention is a two-step process. The process is simple, and the obtained butanol polyoxypropylene ether product has stable quality, light color, and good compatibility, lubrication, thickening and low foaming properties. It can be widely used in textile, metal processing and equipment lubrication fields.

[0067] To further illustrate the present invention, the preparation method of high molecular weight butanol polyoxypropylene ether provided by the present invention will be described in detail below with reference to the embodiments, but these should not be construed as limiting the scope of protection of the present invention.

[0068] Example 1

[0069] 50g of 0.8mol / kg PZN, 500g of MgAl2(SiO3)4 and 550g of water were added to a four-necked flask and stirred. The mixture was heated to 70℃ and held for 3 hours, then heated to 120℃ and held for 2 hours. The mixture was then cooled to 50℃ and filtered to obtain the catalyst precursor. The precursor was dried and then calcined in a muffle furnace at 400℃ for 2 hours to obtain a supported phosphazene salt catalyst PZN / MgAl2(SiO3)4 with a particle size of 10nm.

[0070] First, 222g of butanol and 0.24g of PZN / MgAl2(SiO3)4 catalyst were added to a 2.5L high-pressure reactor. The reactor was sealed, stirred, and evacuated. Then, the gas inside the reactor was replaced with nitrogen three times. After nitrogen addition, the temperature was raised to 75-80℃, and 978g of propylene oxide was added dropwise over 4 hours. The reaction temperature was controlled at 75-80℃, and the reaction pressure at 0-0.05MPa. After the addition was complete, the mixture was allowed to mature for 1 hour, degassed, discharged, and the catalyst was removed by filtration to obtain butanol polyoxypropylene ether 400.

[0071] First, 200g of low molecular weight butanol polyoxypropylene ether 400 and 0.3g of PZN / MgAl2(SiO3)4 catalyst were added to a 2.5L high-pressure reactor. The reactor was sealed, the stirrer was turned on and a vacuum was drawn. Then, the gas in the reactor was replaced with nitrogen three times. The temperature was raised to 75-80℃, and 1300g of propylene oxide was added dropwise over 5 hours. The reaction temperature was controlled at 75-80℃ and the reaction pressure at 0-0.05MPa. After the addition was completed, the mixture was matured for 1 hour, degassed, discharged, and filtered to obtain butanol polyoxypropylene ether 3000.

[0072] Example 2

[0073] 50g of 0.8mol / kg PZN, 500g of MgAl2(SiO3)4 and 550g of water were added to a four-necked flask and stirred. The mixture was heated to 60℃ and held for 2 hours, then heated to 100℃ and held for 1 hour. The mixture was then cooled to 50℃ and filtered to obtain the catalyst precursor. The precursor was dried and then calcined in a muffle furnace at 350℃ for 2 hours to obtain a supported phosphazene salt catalyst PZN / MgAl2(SiO3)4 with a particle size of 15nm.

[0074] First, 222g of butanol and 0.45g of PZN / MgAl2(SiO3)4 catalyst were added to a 2.5L high-pressure reactor. The reactor was sealed, stirred, and evacuated. Then, the gas inside the reactor was replaced with nitrogen three times. After nitrogen addition, the temperature was raised to 60-65℃, and 1278g of propylene oxide was added dropwise over 3 hours. The reaction temperature was controlled at 75-80℃, and the reaction pressure at 0-0.05MPa. After the addition was complete, the mixture was allowed to mature for 1 hour, degassed, discharged, and the catalyst was removed by filtration to obtain 500g of butanol polyoxypropylene ether.

[0075] First, 250g of low molecular weight butanol polyoxypropylene ether 500 and 0.45g of PZN / MgAl2(SiO3)4 catalyst were added to a 2.5L high-pressure reactor. The reactor was sealed, the stirrer was turned on and a vacuum was drawn. Then, the gas inside the reactor was replaced with nitrogen three times. The temperature was raised to 60-65℃, and 1250g of propylene oxide was added dropwise over 4 hours. The reaction temperature was controlled at 60-65℃ and the reaction pressure at 0-0.05MPa. After the addition was completed, the mixture was allowed to mature for 1 hour, degassed, discharged, and filtered to obtain butanol polyoxypropylene ether 3000.

[0076] Example 3

[0077] 50g of 0.8mol / kg PZN, 500g of MgAl2(SiO3)4 and 550g of water were added to a four-necked flask and stirred. The mixture was heated to 50℃ and held for 2 hours, then heated to 90℃ and held for 1 hour. The mixture was then cooled to 50℃ and filtered to obtain the catalyst precursor. The precursor was dried and then calcined in a muffle furnace at 300℃ for 2 hours to obtain a supported phosphazene salt catalyst PZN / MgAl2(SiO3)4 with a particle size of 20nm.

[0078] First, 222g of butanol and 0.36g of PZN / MgAl2(SiO3)4 catalyst were added to a 2.5L high-pressure reactor. The reactor was sealed, stirred, and evacuated. Then, the gas inside the reactor was replaced with nitrogen three times. After nitrogen addition, the temperature was raised to 75-80℃, and 1578g of propylene oxide was added dropwise over 3 hours. The reaction temperature was controlled at 75-80℃, and the reaction pressure at 0-0.05MPa. After the addition was complete, the mixture was allowed to mature for 1 hour, degassed, discharged, and the catalyst was removed by filtration to obtain butanol polyoxypropylene ether 600.

[0079] First, 150g of low molecular weight butanol polyoxypropylene ether 600 and 0.2g of PZN / MgAl2(SiO3)4 catalyst were added to a 2.5L high-pressure reactor. The reactor was sealed, the stirrer was turned on and a vacuum was drawn. Then, the gas inside the reactor was replaced with nitrogen three times. The temperature was raised to 75-80℃, and 850g of propylene oxide was added dropwise over 4 hours. The reaction temperature was controlled at 75-80℃ and the reaction pressure at 0-0.05MPa. After the addition was completed, the mixture was allowed to mature for 1 hour, degassed, discharged, and filtered to obtain butanol polyoxypropylene ether 4000.

[0080] Example 4

[0081] 50g of 0.8mol / kg PZN, 500g of MgAl2(SiO3)4 and 550g of water were added to a four-necked flask and stirred. The mixture was heated to 70℃ and held for 3 hours, then heated to 120℃ and held for 2 hours. The mixture was then cooled to 50℃ and filtered to obtain the catalyst precursor. The precursor was dried and then calcined in a muffle furnace at 400℃ for 2 hours to obtain a supported phosphazene salt catalyst PZN / MgAl2(SiO3)4 with a particle size of 10nm.

[0082] First, 222g of butanol and 0.36g of PZN / MgAl2(SiO3)4 catalyst were added to a 2.5L high-pressure reactor. The reactor was sealed, stirred, and evacuated. Then, the gas inside the reactor was replaced with nitrogen three times. After nitrogen addition, the temperature was raised to 60-65℃, and 978g of propylene oxide was added dropwise over 4 hours. The reaction temperature was controlled at 60-65℃, and the reaction pressure at 0-0.05MPa. After the addition was complete, the mixture was allowed to mature for 1 hour, degassed, discharged, and the catalyst was removed by filtration to obtain butanol polyoxypropylene ether 400.

[0083] First, 200g of low molecular weight butanol polyoxypropylene ether 400 and 0.6g of PZN / MgAl2(SiO3)4 catalyst were added to a 2.5L high-pressure reactor. The reactor was sealed, the stirrer was turned on and a vacuum was drawn. Then, the gas inside the reactor was replaced with nitrogen three times. The temperature was raised to 60-65℃, and 1800g of propylene oxide was added dropwise over 5 hours. The reaction temperature was controlled at 60-65℃ and the reaction pressure at 0-0.05MPa. After the addition was completed, the mixture was allowed to mature for 1 hour, degassed, discharged, and filtered to obtain butanol polyoxypropylene ether 4000.

[0084] Example 5

[0085] 50g of 0.8mol / kg PZN, 500g of MgAl2(SiO3)4 and 550g of water were added to a four-necked flask and stirred. The mixture was heated to 60℃ and held for 2 hours, then heated to 100℃ and held for 1 hour. The mixture was then cooled to 50℃ and filtered to obtain the catalyst precursor. The precursor was dried and then calcined in a muffle furnace at 350℃ for 2 hours to obtain a supported phosphazene salt catalyst PZN / MgAl2(SiO3)4 with a particle size of 15nm.

[0086] First, 222g of butanol and 0.75g of PZN / MgAl2(SiO3)4 catalyst were added to a 2.5L high-pressure reactor. The reactor was sealed, stirred, and evacuated. Then, the gas inside the reactor was replaced with nitrogen three times. After nitrogen addition, the temperature was raised to 50-55℃, and 1278g of propylene oxide was added dropwise over 3 hours. The reaction temperature was controlled at 50-55℃, and the reaction pressure at 0-0.05MPa. After the addition was complete, the mixture was allowed to mature for 1 hour, degassed, discharged, and the catalyst was removed by filtration to obtain butanol polyoxypropylene ether 500.

[0087] First, add 100g of low molecular weight butanol polyoxypropylene ether 500 and 0.5g of PZN / MgAl2(SiO3)4 catalyst to a 2.5L high-pressure reactor. Seal the reactor, start stirring and evacuate. Then replace the gas in the reactor with nitrogen three times. Raise the temperature to 50-55℃ and add 900g of propylene oxide dropwise over 4 hours. Control the reaction temperature at 50-55℃ and the reaction pressure at 0-0.05MPa. After the addition is complete, mature for 1 hour, degas, discharge, and filter to obtain butanol polyoxypropylene ether 5000.

[0088] Example 6

[0089] 50g of 0.8mol / kg PZN, 500g of MgAl2(SiO3)4 and 550g of water were added to a four-necked flask and stirred. The mixture was heated to 50℃ and held for 2 hours, then heated to 90℃ and held for 1 hour. The mixture was then cooled to 50℃ and filtered to obtain the catalyst precursor. The precursor was dried and then calcined in a muffle furnace at 300℃ for 2 hours to obtain a supported phosphazene salt catalyst PZN / MgAl2(SiO3)4 with a particle size of 20nm.

[0090] First, 222g of butanol and 0.9g of PZN / MgAl2(SiO3)4 catalyst were added to a 2.5L high-pressure reactor. The reactor was sealed, stirred, and evacuated. Then, the gas inside the reactor was replaced with nitrogen three times. After nitrogen addition, the temperature was raised to 75-80℃, and 1578g of propylene oxide was added dropwise over 2 hours. The reaction temperature was controlled at 75-80℃, and the reaction pressure at 0-0.05MPa. After the addition was complete, the mixture was allowed to mature for 1 hour, degassed, discharged, and the catalyst was removed by filtration to obtain butanol polyoxypropylene ether 600.

[0091] First, 120g of low molecular weight butanol polyoxypropylene ether 600 and 0.3g of PZN / MgAl2(SiO3)4 catalyst were added to a 2.5L high-pressure reactor. The reactor was sealed, the stirrer was turned on and a vacuum was drawn. Then, the gas inside the reactor was replaced with nitrogen three times. The temperature was raised to 75-80℃, and 880g of propylene oxide was added dropwise over 3 hours. The reaction temperature was controlled at 75-80℃ and the reaction pressure at 0-0.05MPa. After the addition was completed, the mixture was allowed to mature for 1 hour, degassed, discharged, and filtered to obtain butanol polyoxypropylene ether 5000.

[0092] The process parameters for Examples 1 to 6 are shown in Table 1.

[0093] Table 1. Process parameters for Examples 1-6

[0094]

[0095]

[0096] Comparative Examples 1-6

[0097] Butanol polyoxypropylene ether was prepared according to the preparation methods of Examples 1-6, with the only difference being that the catalyst was potassium hydroxide, the amount of catalyst was adjusted to 10 times that of the examples, the reaction temperature was 120°C, and the pressure was 0-0.3 MPa. The process parameters of Comparative Examples 1-6 are shown in Table 2.

[0098] Table 2 Process parameters for Comparative Examples 1-6

[0099]

[0100] Comparative Examples 7–12

[0101] Butanol polyoxypropylene ether was prepared according to the preparation methods of Examples 1-6, with the only difference being that the catalyst was a polymetallic cyanide (MMC).

[0102] Test case

[0103] The molecular weight, kinematic viscosity, polymer content, and propylene content of the butanol polyoxypropylene ethers obtained in Examples 1-6 and Comparative Examples 1-6 were tested, and the test results are shown in Table 3.

[0104] Table 3 Performance test data of the products obtained in Examples 1-6 and Comparative Examples 1-6

[0105]

[0106]

[0107] Note: High molecular weight polyether mainly refers to high molecular weight polyether with a high content of dihydroxyl groups and a molecular weight greater than the target molecular weight.

[0108] As shown in Table 3, the actual molecular weights of the butanol polyoxypropylene ethers prepared in Comparative Examples 1-6 are lower than the designed molecular weights. Especially when the designed molecular weight exceeds 4000, the molecular weight of the butanol polyoxypropylene ether is lower than 3500, and the content of the high-molecular-weight polyether is significantly increased, with high propylene group content and high unsaturation. The butanol polyoxypropylene ethers prepared in Examples 1-6 have actual molecular weights close to the designed molecular weights, achieve the required viscosity, and have lower polymer content, lower propylene group content, and lower unsaturation.

[0109] The color, metal ion content, and aldehyde content of the butanol polyoxypropylene ethers obtained in Examples 1-6 and Comparative Examples 7-12 were tested, and the test results are shown in Table 4.

[0110] Table 4 Performance test data of the products obtained in Examples 1-6 and Comparative Examples 7-12

[0111]

[0112]

[0113] As shown in Table 4, the butanol polyoxypropylene ethers prepared in Comparative Examples 1-6 had residual metal ions and high aldehyde content, resulting in a darker color and stronger odor after a period of storage. The butanol polyoxypropylene ethers prepared in Examples 1-6 had low residual metal ions, no aldehyde content, and no odor after a period of storage, with no change in color and stable quality.

[0114] As can be seen from the above embodiments, the supported phosphazene salt catalyst prepared by the preparation method provided by the present invention can improve the reaction activity, reduce the requirements of temperature and pressure for polymerization reaction, effectively reduce the content of high molecular weight substances and unsaturation in butanol polyoxypropylene ether products, and the product has little catalyst residue, no metal ion residue, no need for post-treatment and stable quality.

[0115] The method for preparing high molecular weight butanol polyoxypropylene ether provided by this invention is a two-step process. The process is simple, and the obtained butanol polyoxypropylene ether product has stable quality, light color, and good compatibility, lubrication, thickening and low foaming properties. It can be widely used in textile, metal processing and equipment lubrication fields.

[0116] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A method for preparing high molecular weight butanol polyoxypropylene ether, characterized in that, The process includes the following steps: mixing butanol, a first supported phosphazene salt catalyst, and a first propylene oxide, and carrying out a first polymerization reaction to obtain low molecular weight butanol polyoxypropylene ether; The low molecular weight butanol polyoxypropylene ether, the second supported phosphazene salt catalyst, and the second propylene oxide are mixed and subjected to a second polymerization reaction to obtain the high molecular weight butanol polyoxypropylene ether. Both the first supported phosphazene salt catalyst and the second supported phosphazene salt catalyst are supported phosphazene salt catalysts; The mass ratio of the first supported phosphazene salt catalyst to the total mass of the butanol and the first propylene oxide is 0.02~0.05%; the mass ratio of the second supported phosphazene salt catalyst to the total mass of the low molecular weight butanol polyoxypropylene ether and the second propylene oxide is 0.02~0.05%. The preparation method of the supported phosphazene salt catalyst includes the following steps: A hydrothermal reaction was carried out by mixing a solution of phosphazene ligand P4-tert-butyl, magnesium aluminum silicate, and water to obtain a phosphazene salt catalyst precursor. The phosphazene salt catalyst precursor was calcined to obtain the supported phosphazene salt catalyst. The mass ratio of the phosphazene ligand P4-tert-butyl solution to magnesium aluminum silicate is 1:5~15; The hydrothermal reaction includes a first hydrothermal reaction and a second hydrothermal reaction performed sequentially. The temperature of the first hydrothermal reaction is 50~70℃, and the time is 2~4h; The temperature of the second hydrothermal reaction is 90~120℃, and the time is 1~4h.

2. The preparation method according to claim 1, characterized in that, The roasting temperature is 300~400℃ and the time is 1~3h.

3. The preparation method according to claim 1, characterized in that, The supported phosphazene salt catalyst has a particle size of 10~20 nm.

4. The preparation method according to claim 1, characterized in that, The mass ratio of butanol to the first propylene oxide is 1:4.4~7.

1.

5. The preparation method according to claim 1, characterized in that, The mass ratio of the low molecular weight butanol polyoxypropylene ether to the second propylene oxide is 1:4~8.

6. The preparation method according to claim 1, characterized in that, The temperature of the first polymerization reaction is 50~80℃, the pressure is 0~0.05MPa, and the time is 3~6h; The second polymerization reaction is carried out at a temperature of 50-80℃, a pressure of 0-0.05MPa, and a time of 4-7h.

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