A CoFeDMC@PmPD composite catalytic material, its preparation method and application, and a method for preparing alkylphenol polyethers.

Abstract

This invention belongs to the field of alkylphenol polyether synthesis technology, specifically relating to a CoFe DMC@PmPD composite catalytic material, its preparation method and application, and a method for preparing alkylphenol polyethers. In this invention, a mixed solution of hexacyanoferric(III) salt is injected into a mixed solution of cobalt salts, followed by aging, to obtain the CoFe DMC material; the injection rate is ≥100 μL·min. ‑1 The aging time is ≥24h. The CoFe DMC material, m-phenylenediamine, a free radical initiator, and water are mixed, and a free radical polymerization reaction is carried out on the surface of the CoFe DMC material to obtain polym-phenylenediamine, thus obtaining the CoFe DMC@PmPD composite catalytic material. The CoFe DMC@PmPD composite catalytic material prepared by this invention can shorten the induction time of alkylphenol polyether preparation by more than half, which has significant guiding significance for cost reduction and efficiency improvement in the industrial production of alkylphenol polyether products.

Description

Technical Field

[0001] This invention belongs to the field of alkylphenol polyether synthesis technology, specifically relating to a CoFe DMC@PmPD composite catalytic material and its preparation method and application, and a method for preparing alkylphenol polyether. Background Technology

[0002] Bimetallic cyanide catalysts (DMCs) were first researched and developed by General Tire & Rubber Company in the 1960s. They possess an open metal-organic framework (MOF) structure, allowing transition metal ions to exist in different oxidation states while maintaining a cubic structure. This results in excellent chemical stability and wide applicability across various fields, such as catalysis, gas or ion capture, batteries, pigments, biomedical detection, imaging, therapy, and sensors. In particular, DMCs possess inherent catalytic advantages such as abundant metal active sites, high porosity, diverse structures, and tunable chemical composition, making them widely used as highly efficient catalysts for the ring-opening polymerization of epoxides to synthesize polyethers. Compared to the alkaline catalysts used in the traditional ring-opening polymerization of epoxides to synthesize polyethers, DMCs offer advantages such as lower dosage, higher catalytic activity, and no need for post-treatment. Furthermore, the resulting polyethers exhibit high molecular weight, low unsaturation, high average functionality, and narrow molecular weight distribution.

[0003] Industrially, the preparation of polyethers using DMC often employs a continuous feeding method. After introducing propylene oxide or a mixture of propylene oxide and ethylene oxide, the reaction undergoes an induction period. The induction is complete when a sudden pressure drop and temperature rise occur, after which the reaction stabilizes. However, in the synthesis of alkylphenol polyethers, the steric hindrance of the benzene ring and carbon chain in the initiator structure makes the interaction between the hydroxyl groups of alkylphenol, alkylene oxide, and DMC difficult, resulting in an excessively long induction time (greater than 4 minutes) and frequent induction failures. This is a common problem in the production of alkylphenol polyethers using DMC. An excessively long induction period leads to cumbersome production operations and prolongs the reaction cycle. Research has found that increasing the reaction temperature or the amount of DMC shortens the induction period for alkylphenol polyether synthesis. However, excessively high temperatures inevitably increase process risks and energy consumption during production. Furthermore, high catalyst levels can result in residual metal ions in the finished polyether product. These residual metal ions can cause degradation of the polyether and affect its downstream application performance. Summary of the Invention

[0004] The purpose of this invention is to provide a CoFe DMC@PmPD composite catalytic material, its preparation method and application, and a method for preparing alkylphenol polyethers. The CoFe DMC@PmPD composite catalytic material provided by this invention can significantly shorten the induction time for alkylphenol polyether synthesis, and has significant guiding significance for cost reduction and efficiency improvement in the industrial production of alkylphenol polyethers, and is suitable for widespread application.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

[0006] This invention provides a method for preparing a CoFeDMC@PmPD composite catalytic material, comprising the following steps:

[0007] A water-soluble cobalt salt, a first citrate, and water are mixed to obtain a cobalt salt mixed solution; the water-soluble cobalt salt and the first citrate are in equal molar amounts.

[0008] A mixed solution of hexacyanoferrate(III), second citrate, and water is obtained; the molar amounts of hexacyanoferrate(III) and second citrate are equal, and the molar ratio of the water-soluble cobalt salt to the hexacyanoferrate(III) is (0.1-0.5):(0.1-0.5).

[0009] The hexacyanoferrate(III) mixed solution was injected into the cobalt salt mixed solution, mixed, and then aged to obtain CoFe DMC material; the injection rate was ≥100 μL·min. -1 The aging time is ≥24 hours;

[0010] The CoFe DMC material, m-phenylenediamine, free radical initiator and water are mixed, and free radical polymerization is carried out on the surface of the CoFe DMC material to obtain polym-phenylenediamine, thus obtaining the CoFe DMC@PmPD composite catalytic material.

[0011] Preferably, in the cobalt salt mixed solution, the molar ratio of the water-soluble cobalt salt to the volume ratio of the water is (0.1-0.5) mmol: 25 mL;

[0012] In the hexacyanoferrate(III) salt mixed solution: the molar ratio of the hexacyanoferrate(III) salt to the volume ratio of the water is (0.1-0.5) mmol: 25 mL;

[0013] The injection rate is 100–1000 μL / min. -1 .

[0014] Preferably, the mass ratio of the CoFe DMC material to m-phenylenediamine is (10-100):(5-50);

[0015] The free radical initiator is ammonium persulfate, and the mass ratio of the CoFe DMC material to the free radical initiator is 1:1 to 2.

[0016] The free radical polymerization reaction is carried out under ice-water bath conditions for 5 to 8 hours.

[0017] The free radical polymerization reaction directly yields a polymerization reaction solution. After obtaining the polymerization reaction solution, the process further includes: solid-liquid separation of the polymerization reaction solution, washing and drying the obtained solid product to obtain the CoFe DMC@PmPD composite catalytic material; the drying is vacuum drying, and the vacuum drying temperature is 50-100℃.

[0018] Preferably, the aging process directly yields an aging solution. After obtaining the aging solution, the process further includes: solid-liquid separation of the aging solution, washing and drying the obtained solid product to obtain the CoFe DMC material; the drying is vacuum drying, and the vacuum drying temperature is 50-100℃.

[0019] This invention provides a CoFe DMC@PmPD composite catalytic material prepared by the preparation method described above.

[0020] This invention provides the application of the CoFe DMC@PmPD composite catalytic material described above in the preparation of alkylphenol polyethers.

[0021] This invention provides a method for preparing alkylphenol polyethers, comprising the following steps:

[0022] Alkylphenol, the CoFe DMC@PmPD composite catalyst described in the above technical solution, and olefin oxidation are mixed, and after induction and activation, a temperature-controlled reaction is carried out to obtain alkylphenol polyether.

[0023] Preferably, the alkylphenol includes one or more of propionic acid, butylphenol, pentylphenol, heptaphenol, octylphenol, nonylphenol, and decylphenol;

[0024] The oxidized olefins include propylene oxide or a mixture of ethylene oxide and propylene oxide;

[0025] When the oxidized olefin is a mixture of ethylene oxide and propylene oxide, the mass of the ethylene oxide accounts for 0 to 30% of the total mass of the mixture of ethylene oxide and propylene oxide, and is not 0.

[0026] Preferably, the number-average molecular weight of the alkylphenol polyether is 500 to 1500;

[0027] The mass of the CoFe DMC@PmPD composite catalyst accounts for 10 to 100 ppm of the total mass of the alkylphenols and olefin oxides.

[0028] Preferably, the temperature of the heat preservation reaction is 130–160°C.

[0029] This invention provides a method for preparing a CoFe DMC@PmPD composite catalytic material, comprising the following steps: mixing a water-soluble cobalt salt, a first citrate, and water to obtain a cobalt salt mixed solution; wherein the molar amounts of the water-soluble cobalt salt and the first citrate are equal; mixing hexacyanoferrate(III) salt, a second citrate, and water to obtain a hexacyanoferrate(III) salt mixed solution; wherein the molar amounts of the hexacyanoferrate(III) salt and the second citrate are equal, and the molar ratio of the water-soluble cobalt salt to the hexacyanoferrate(III) salt is (0.1–0.5):(0.1–0.5); injecting the hexacyanoferrate(III) salt mixed solution into the cobalt salt mixed solution, mixing, and aging to obtain the CoFe DMC material; wherein the injection rate is ≥100 μL·min -1 The aging time is ≥24h; the CoFe DMC material, m-phenylenediamine, free radical initiator and water are mixed, and free radical polymerization is carried out on the surface of the CoFe DMC material to obtain polym-phenylenediamine, thus obtaining the CoFe DMC@PmPD composite catalytic material. The preparation method provided by this invention selects Co 2+ and Fe 3+ By controlling the ratio of raw materials used in the preparation of CoFe DMC with two transition metal ions, the injection rate of the raw material solution during mixing, and the aging time, the particle size, morphology, and surface state of CoFe DMC can be controlled, thereby improving the catalytic activity of CoFe DMC and shortening the catalyst induction time. Finally, this invention coats the surface of CoFe DMC material with poly(m-phenylene diamine) via free radical polymerization. The surface modification of the CoFe DMC core using poly(m-phenylene diamine) (PmPD) leverages the adhesive properties of PmPD and its amino, acyl, and hydroxyl functional groups to facilitate the interaction and contact between the hydroxyl groups of alkylphenols, epoxides, and CoFe DMC, improving the catalytic activity of CoFe DMC in polyether synthesis and shortening the induction time, thus achieving cost reduction and efficiency improvement. The results of the examples show that the CoFe DMC@PmPD composite catalytic material prepared in this invention can shorten the induction time of alkylphenol polyether preparation by more than half, which has significant guiding significance for cost reduction and efficiency improvement in the industrial production of alkylphenol polyether products. Detailed Implementation

[0030] This invention provides a method for preparing a CoFeDMC@PmPD composite catalytic material, comprising the following steps:

[0031] A water-soluble cobalt salt, a first citrate, and water are mixed to obtain a cobalt salt mixed solution; the water-soluble cobalt salt and the first citrate are in equal molar amounts.

[0032] A mixed solution of hexacyanoferrate(III), second citrate, and water is obtained; the molar amounts of hexacyanoferrate(III) and second citrate are equal, and the molar ratio of the water-soluble cobalt salt to the hexacyanoferrate(III) is (0.1-0.5):(0.1-0.5).

[0033] The hexacyanoferrate(III) mixed solution was injected into the cobalt salt mixed solution, mixed, and then aged to obtain CoFe DMC material; the injection rate was ≥100 μL·min. -1 The aging time is ≥24 hours;

[0034] The CoFe DMC material, m-phenylenediamine, free radical initiator and water are mixed, and free radical polymerization is carried out on the surface of the CoFe DMC material to obtain polym-phenylenediamine, thus obtaining the CoFe DMC@PmPD composite catalytic material.

[0035] In this invention, unless otherwise specified, all raw materials / components used in the preparation are commercially available products well known to those skilled in the art.

[0036] This invention involves mixing a water-soluble cobalt salt, a first citrate, and water (hereinafter referred to as first water) to obtain a cobalt salt mixed solution; the molar amounts of the water-soluble cobalt salt and the first citrate are equal. In this invention, the water-soluble cobalt salt is preferably cobalt nitrate, specifically Co(NO3)2·6H2O. The first citrate is preferably an alkali metal citrate salt, specifically sodium citrate and / or potassium citrate. The first water is preferably deionized water. In the cobalt salt mixed solution, the volume ratio of the molar amount of the water-soluble cobalt salt to the first water is preferably (0.1–0.5) mmol:25 mL, more preferably (0.2–0.5) mmol:25 mL, specifically preferably 0.25 mmol:25 mL, 0.4 mmol:25 mL, or 0.5 mmol:25 mL. In this invention, the amount of first water should not be too small; too much first water will result in an excessively high molar concentration of the water-soluble cobalt salt, which will affect the catalytic performance of the target CoFeDMC@PmPD composite catalytic material.

[0037] This invention involves mixing hexacyanoferric(III) salt, a second citrate, and water (hereinafter referred to as second water) to obtain a mixed solution of hexacyanoferric(III) salt; the molar amounts of the hexacyanoferric(III) salt and the second citrate are equal, and the molar ratio of the water-soluble cobalt salt to the hexacyanoferric(III) salt is (0.1–0.5):(0.1–0.5). In this invention, the hexacyanoferric(III) salt is preferably K3[Fe(CN)6]. The second citrate is preferably an alkali metal citrate salt, specifically sodium citrate and / or potassium citrate. The second water is preferably deionized water. The molar ratio of the water-soluble cobalt salt to the hexacyanoferric(III) salt is preferably 1:1. In this invention, the molar ratio of hexacyanoferric(III)ate to the volume of the second water in the hexacyanoferric(III)ate mixed solution is preferably (0.1–0.5) mmol: 25 mL, more preferably (0.2–0.5) mmol: 25 mL, and specifically preferably 0.25 mmol: 25 mL, 0.4 mmol: 25 mL, or 0.5 mmol: 25 mL. In this invention, the amount of the second water must not be too small. Too little second water will result in an excessively high molar concentration of hexacyanoferric(III)ate, which will affect the catalytic performance of the target CoFeDMC@PmPD composite catalytic material.

[0038] After obtaining a mixed solution of hexacyanoferric(III)ate and a mixed solution of cobalt salt, the present invention injects the mixed solution of hexacyanoferric(III)ate into the mixed solution of cobalt salt, mixes, and then ages to obtain CoFe DMC material; the injection rate is ≥100 μL·min. -1 The aging time is ≥24 hours. In this invention, the injection is preferably performed at room temperature, specifically preferably 25°C, and the injection is preferably performed using a peristaltic pump. The injection rate is preferably 100–1000 μL / min. -1 More preferably, it is 200–1000 μL·min -1 Specifically, 300 μL·min is preferred. -1 800 μL·min -1 Or 1000 μL·min -1 The mixing is carried out under stirring conditions, and the mixing time after the injection is completed is preferably 1 to 2 hours. The aging time is preferably 24 to 30 hours, specifically 25 hours, 27 hours, or 28 hours.

[0039] In this invention, the aging process directly yields an aging solution. Preferably, the aging solution is further subjected to solid-liquid separation, and the resulting solid product is washed and dried to obtain the CoFe DMC material. The solid-liquid separation is preferably performed by centrifugation. The washing process preferably includes sequential washing with deionized water and washing with ethanol. Specifically, the deionized water washing is preferably performed by centrifugation, and the washing is preferably repeated twice. The ethanol washing is also preferably performed by centrifugation, and the washing is preferably repeated twice. The drying is vacuum drying, and the vacuum drying temperature is preferably 50–100°C, specifically 60°C, 75°C, or 90°C.

[0040] After obtaining the CoFe DMC material, this invention mixes the CoFe DMC material, m-phenylenediamine, a free radical initiator, and water (hereinafter referred to as the third water), and performs a free radical polymerization reaction on the surface of the CoFe DMC material to obtain polym-phenylenediamine, thus obtaining the CoFe DMC@PmPD composite catalytic material. In this invention, the preferred mass ratio of the CoFe DMC material to m-phenylenediamine is (10-100):(5-50), more preferably 2:1. The preferred free radical initiator is ammonium persulfate, and the preferred mass ratio of the CoFe DMC material to the free radical initiator is 1:1-2, more preferably 1:1. The preferred third water is deionized water. This invention does not have special requirements on the amount of the third water, as long as the free radical polymerization reaction proceeds smoothly. In this invention, the mixing step of the CoFe DMC material, m-phenylenediamine, free radical initiator, and third water preferably includes: ultrasonically dispersing the CoFe DMC material in the third water to obtain a CoFe DMC material dispersion; mixing the CoFe DMC material dispersion with the m-phenylenediamine and the free radical initiator. The ultrasonic dispersion is performed under ice-water bath conditions. The ultrasonic dispersion time is preferably 20-30 min. The free radical polymerization reaction is preferably performed under ice-water bath conditions, and the free radical polymerization reaction time is preferably 5-8 h; the free radical polymerization reaction is performed under stirring conditions. After the free radical polymerization reaction, a polymerization reaction solution is directly obtained. After obtaining the polymerization reaction solution, this invention preferably further includes: solid-liquid separation of the polymerization reaction solution, washing and drying the obtained solid product to obtain the CoFe DMC@PmPD composite catalyst material. The solid-liquid separation is preferably centrifugation. The washing preferably includes washing with deionized water and washing with ethanol sequentially. The specific implementation of the deionized water washing is preferably centrifugation, and the number of washings is preferably 2. The specific implementation of the ethanol washing is preferably centrifugation, and the number of washings is preferably 2. The drying process is vacuum drying, and the vacuum drying temperature is preferably 50-100℃, specifically 60℃, 80℃ or 100℃.

[0041] This invention provides a CoFe DMC@PmPD composite catalytic material prepared by the preparation method described above.

[0042] This invention provides the application of the CoFe DMC@PmPD composite catalytic material described above in the preparation of alkylphenol polyethers.

[0043] This invention provides a method for preparing alkylphenol polyethers, comprising the following steps:

[0044] Alkylphenol, the CoFe DMC@PmPD composite catalyst described in the above technical solution, and olefin oxidation are mixed, and after induction and activation, a temperature-controlled reaction is carried out to obtain alkylphenol polyether.

[0045] In this invention, the alkylphenol preferably includes one or more of propionic acid, butylphenol, pentylphenol, heptaphenol, octylphenol, nonylphenol, and decylphenol. The oxidized olefin preferably includes propylene oxide or a mixture of ethylene oxide and propylene oxide. When the oxidized olefin is a mixture of ethylene oxide and propylene oxide, the mass of the ethylene oxide preferably accounts for 0-30% of the total mass of the mixture of ethylene oxide and propylene oxide, and is not 0, more preferably 25%. The ratio of the amount of alkylphenol to the amount of oxidized olefin is based on the molecular weight of the alkylphenol polyether. The mass of the CoFe DMC@PmPD composite catalyst preferably accounts for 10-100 ppm of the mass of the alkylphenol polyether, preferably 30-10 ppm, and specifically preferably 30 ppm, 50 ppm, or 80 ppm. The number average molecular weight of the alkylphenol polyether is preferably 500-1500, and specifically preferably 800, 916, 1000, or 1200.

[0046] In this invention, before mixing the alkylphenol, the CoFe DMC@PmPD composite catalyst material described in the above technical solution, and the olefin oxide, the alkylphenol is preferably pre-dehydrated. The pre-dehydration treatment is carried out in a reaction vessel, and the preferred temperature is 115–120°C, with a vacuum degree preferably ≥-0.095 MPa. After pre-dehydration, the pre-dehydrated alkylphenol is mixed with the CoFe DMC@PmPD composite catalyst material, heated to the temperature for the heat preservation reaction, and then the olefin oxide is added, directly entering the induction activation stage. The preferred induction activation time is 1–5 minutes, specifically 1 minute 33 seconds, 3 minutes 19 seconds, 4 minutes 20 seconds, or 3 minutes 40 seconds. The preferred temperature for the heat preservation reaction is 130–160°C, more preferably 130–135°C, 140–145°C, 130–140°C, or 155–160°C. After the reaction, the product is degassed to obtain alkylphenol polyether.

[0047] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0048] Example 1

[0049] First, dissolve 0.25 mmol of Co(NO3)2·6H2O and an equimolar amount of sodium citrate in 25 mL of deionized water to obtain solution A. Then, dissolve 0.25 mmol of K3[Fe(CN)6] and an equimolar amount of sodium citrate in 25 mL of deionized water to obtain solution B.

[0050] Subsequently, in a 25°C room temperature water bath, a peristaltic pump was used to deliver 300 μL / min. -1 Solution B was added to solution A at a constant rate and mixed and stirred for 1 h, wherein the molar amounts of Co(NO3)2·6H2O and K3[Fe(CN)6] were equal, both 0.25 mmol. Afterward, the mixture was aged for 25 h. The mixture was then centrifuged, and the precipitate was washed twice with deionized water and ethanol. Finally, it was dried in a vacuum drying oven at 60 °C to obtain the CoFe DMC catalyst.

[0051] 50 mg of CoFe DMC was dispersed in 100 mL of deionized water and sonicated in ice water for 20 min. Then, 25 mg of m-phenylenediamine and 50 mg of ammonium persulfate were added. The mixture was stirred in an ice-water bath for 5 h, then centrifuged. The precipitate was washed twice with deionized water and ethanol by centrifugation, and finally dried in a vacuum drying oven at 60 °C to obtain the CoFe DMC@PmPD / A composite catalyst.

[0052] Example 2

[0053] First, dissolve 0.4 mmol of Co(NO3)2·6H2O and an equimolar amount of sodium citrate in 25 mL of deionized water to obtain solution A. Then, dissolve 0.4 mmol of K3[Fe(CN)6] and an equimolar amount of potassium citrate in 25 mL of deionized water to obtain solution B.

[0054] The reaction was then carried out in a 25°C room temperature water bath, using a peristaltic pump at a rate of 800 μL / min. -1 Solution B was added to solution A at a constant rate and mixed and stirred for 1 h. The molar amounts of Co(NO3)2·6H2O and K3[Fe(CN)6] were equal, both 0.4 mmol. After the mixture was aged for 28 h, it was then centrifuged, and the precipitate was washed twice with deionized water and ethanol. Finally, it was dried in a vacuum drying oven at 75 °C to obtain the CoFe DMC catalyst.

[0055] 80 mg of CoFe DMC was dispersed in 100 mL of deionized water and sonicated in ice water for 20 min. Then, 40 mg of m-phenylenediamine and 80 mg of ammonium persulfate were added. The mixture was stirred in an ice-water bath for 5 h, then centrifuged. The precipitate was washed twice with deionized water and ethanol, and finally dried in a vacuum drying oven at 80 °C to obtain the CoFe DMC@PmPD / B composite catalyst.

[0056] Example 3

[0057] First, dissolve 0.5 mmol of Co(NO3)2·6H2O and an equimolar amount of sodium citrate in 25 mL of deionized water to obtain solution A. Then, dissolve 0.5 mmol of K3[Fe(CN)6] and an equimolar amount of potassium citrate in 25 mL of deionized water to obtain solution B.

[0058] The reaction was then carried out in a 25°C room temperature water bath, using a peristaltic pump at a rate of 1000 μL / min. -1 Solution B was added to solution A at a constant rate and mixed and stirred for 1 h, wherein the molar amounts of Co(NO3)2·6H2O and K3[Fe(CN)6] were equal, both 0.5 mmol. Afterward, the mixture was aged for 27 h. The mixture was then centrifuged, and the precipitate was washed twice with deionized water and ethanol. Finally, it was dried in a vacuum drying oven at 90 °C to obtain the CoFe DMC catalyst.

[0059] 98 mg of CoFe DMC was dispersed in 100 mL of deionized water and sonicated in ice water for 20 min. Then, 49 mg of m-phenylenediamine and 98 mg of ammonium persulfate were added. The mixture was stirred in an ice-water bath for 5 h, then centrifuged. The precipitate was washed twice with deionized water and ethanol by centrifugation, and finally dried in a vacuum drying oven at 100 °C to obtain the CoFe DMC@PmPD / C composite catalyst.

[0060] Comparative Example 1

[0061] The preparation method is basically the same as in Example 2, except that the molar mass of Co(NO3)2·6H2O and K3[Fe(CN)6] is 1 mmol, the molar amounts of Co(NO3)2·6H2O and sodium citrate are equal in solution A, and the molar amounts of K3[Fe(CN)6] and sodium citrate are equal in solution B. The amount of deionized water used in solutions A and B is still 25 mL. The CoFe DMC@PmPD / D composite catalyst is obtained.

[0062] The preparation method is basically the same as that in Example 3, except that the peristaltic pump feed rate is 50 μL / min. -1 The CoFe DMC@PmPD / E composite catalyst was obtained.

[0063] The preparation method is basically the same as that in Example 1, except that the aging time is shortened to 5h to obtain the CoFeDMC@PmPD / F composite catalyst.

[0064] Example 4

[0065] 301g of propylphenol was added to a 2.5L polymerization reactor, heated and stirred, and dehydrated for 1.5h under conditions of 115-120℃ and a vacuum degree ≥-0.096MPa. Then, 0.162g of CoFeDMC@PmPD / A composite catalyst was added, and after heating to 135℃, 1726g of propylene oxide was continuously added. After induction and activation, the reaction was maintained at 130-135℃. After the reaction was completed, the product was degassed and discharged to obtain propylphenol polyether with a theoretical molecular weight of 916. The induction time of this reaction was 1 minute and 33 seconds.

[0066] Example 5

[0067] 233g of heptyphenol was added to a 2.5L polymerization reactor, heated and stirred, and dehydrated for 2 hours at 115–120℃ and a vacuum of ≥-0.096MPa. Then, 0.073g of CoFeDMC@PmPD / B composite catalyst was added, and the temperature was raised to 140℃ before continuously adding 1223g of propylene oxide. After induction and activation, the reaction was maintained at 140–145℃. After the reaction was completed, the product was degassed to obtain heptyphenol polyether with a theoretical molecular weight of 1200. The induction time for this reaction was 3 minutes and 19 seconds.

[0068] Example 6

[0069] 358g of octylphenol was added to a 2.5L polymerization reactor, heated and stirred, and dehydrated for 1 hour at 115–120℃ and a vacuum of ≥-0.096MPa. Then, 0.042g of CoFeDMC@PmPD / C composite catalyst was added, and the temperature was raised to 130℃ before continuously adding 1032g of propylene oxide. After induction and activation, the reaction was maintained at 130–140℃. After the reaction was completed, the product was degassed to obtain octylphenol polyether with a theoretical molecular weight of 800. The induction time for this reaction was 4 minutes and 20 seconds.

[0070] Example 7

[0071] 432g of nonylphenol was added to a 2.5L polymerization reactor, heated and stirred, and dehydrated for 1.5h under conditions of 115–120℃ and a vacuum degree ≥ -0.096MPa. Then, 0.157g of CoFeDMC@PmPD / A composite catalyst was added, and the temperature was raised to 138℃ before continuously adding a mixed olefin of 383g of ethylene oxide and 1148g of propylene oxide. After induction and activation, the reaction was maintained at 155–160℃. After the reaction was completed, the product was degassed to obtain nonylphenol polyether with a theoretical molecular weight of 1000. The induction time for this reaction was 3 minutes and 40 seconds.

[0072] Comparative Example 2

[0073] 301g of propylphenol was added to a 2.5L polymerization reactor, heated and stirred, and dehydrated for 1.5h at 115-120℃ and a vacuum of ≥-0.096MPa. Then, 0.162g of CoFe DMC catalyst (the CoFe DMC catalyst prepared in Example 1) was added, and after heating to 135℃, 1726g of propylene oxide was continuously added. After induction and activation, the reaction was maintained at 130-135℃. After the reaction was completed, the product was degassed and discharged to obtain propylphenol polyether with a theoretical molecular weight of 916. The induction time of this reaction was 4 minutes and 53 seconds.

[0074] Comparative Example 3

[0075] 233g of heptyphenol was added to a 2.5L polymerization reactor, heated and stirred, and dehydrated for 2 hours at 115–120℃ and a vacuum of ≥-0.096MPa. Then, 0.073g of CoFeDMC@PmPD / D composite catalyst was added, and the temperature was raised to 140℃ before continuously adding 1223g of propylene oxide. After induction and activation, the reaction was maintained at 140–145℃. After the reaction was completed, the product was degassed to obtain heptyphenol polyether with a theoretical molecular weight of 1200. The induction time for this reaction was 6 minutes and 46 seconds.

[0076] Comparative Example 4

[0077] 358g of octylphenol was added to a 2.5L polymerization reactor, heated and stirred, and dehydrated for 1 hour at 115–120℃ and a vacuum of ≥-0.096MPa. Then, 0.042g of CoFeDMC@PmPD / E composite catalyst was added, and the temperature was raised to 130℃ before continuously adding 1032g of propylene oxide. After induction and activation, the reaction was maintained at 130–140℃. After the reaction was completed, the product was degassed to obtain octylphenol polyether with a theoretical molecular weight of 800. The induction time for this reaction was 10 minutes and 1 second.

[0078] Comparative Example 5

[0079] 432g of nonylphenol was added to a 2.5L polymerization reactor, heated and stirred, and dehydrated for 1.5h at 115-120℃ and vacuum degree ≥-0.096MPa. Then, 0.157g of CoFe DMC@PmPD / F composite catalyst was added, and after heating to 138℃, a mixed olefin of 383g of ethylene oxide and 1148g of propylene oxide was continuously added. The reactor was then allowed to activate, but activation failed and no reaction occurred.

[0080] Comparative Example 6

[0081] 432g of nonylphenol was added to a 2.5L polymerization reactor, heated and stirred, and dehydrated for 1.5h at 115-120℃ and a vacuum of ≥-0.096MPa. Then, 0.157g of CoFe DMC catalyst (the CoFe DMC catalyst prepared in Example 1) was added, and the temperature was raised to 138℃. A mixed olefin of 383g of ethylene oxide and 1148g of propylene oxide was then continuously added. After induction and activation, the reaction was maintained at 155-160℃. After the reaction, the product was degassed and discharged to obtain nonylphenol polyether with a theoretical molecular weight of 1000. The induction time for this reaction was 9 minutes and 42 seconds.

[0082] Table 1 Summary of induction time for Examples 4-7 and Comparative Examples 2-6

[0083]

[0084]

[0085] The results in Table 1 are analyzed for Examples 4-7 and Comparative Examples 2-7:

[0086] In Example 4 and Comparative Example 2: In Example 4, the CoFe DMC@PmPD / A composite catalyst prepared in Example 1 was used to catalyze the reaction of propylphenol and propylene oxide to produce propylphenol polyether, with a reaction induction time of 1 minute and 33 seconds. In Comparative Example 2, the CoFe DMC catalyst prepared in Example 1 was used to catalyze the reaction of propylphenol and propylene oxide to produce propylphenol polyether, with a reaction induction time of 4 minutes and 53 seconds.

[0087] In Example 5 and Comparative Example 3: In Example 5, the CoFe DMC@PmPD / B composite catalyst prepared in Example 2 was used to catalyze the reaction of heptyphenol and propylene oxide to produce heptyphenol polyether, with a reaction induction time of 3 minutes and 19 seconds. In Comparative Example 3, the DMC@PmPD / D composite catalyst prepared in Comparative Example 1 was used to catalyze the reaction of heptyphenol and propylene oxide to produce heptyphenol polyether, with a reaction induction time of 6 minutes and 46 seconds.

[0088] In Example 6 and Comparative Example 4: Example 6 used the CoFe DMC@PmPD / C composite catalyst prepared in Example 3 to catalyze the reaction of octylphenol and propylene oxide to produce octylphenol polyether, with a reaction induction time of 4 minutes and 20 seconds. In Comparative Example 4, the CoFe DMC@PmPD / E composite catalyst prepared in Comparative Example 1 was used to catalyze the reaction of octylphenol and propylene oxide to produce octylphenol polyether, with a reaction induction time of 10 minutes and 1 second.

[0089] In Example 7 and Comparative Example 6: In Example 7, the CoFe DMC@PmPD / A composite catalyst prepared in Example 1 was used to catalyze the reaction of nonylphenol with a mixed olefin of ethylene oxide and propylene oxide to produce nonylphenol polyether, with a reaction induction time of 3 minutes and 40 seconds. In Comparative Example 6, the CoFe DMC catalyst prepared in Example 1 was used to catalyze the reaction of nonylphenol with a mixed olefin of ethylene oxide and propylene oxide to produce nonylphenol polyether, with a reaction induction time of 9 minutes and 42 seconds.

[0090] In Example 7 and Comparative Example 5: In Example 7, the CoFe DMC@PmPD / A composite catalyst prepared in Example 1 was used to catalyze the reaction of nonylphenol with a mixed olefin of ethylene oxide and propylene oxide to produce nonylphenol polyether, with a reaction induction time of 3 minutes and 40 seconds. In Comparative Example 5, the CoFe DMC@PmPD / F catalyst prepared in Comparative Example 1 was used to catalyze the reaction of nonylphenol with a mixed olefin of ethylene oxide and propylene oxide, but activation failed and no reaction occurred.

[0091] The comparison results between Example 4 and Comparative Example 2, and between Example 7 and Comparative Example 6, show that the induction time of alkylphenol polyether prepared by using CoFe DMC@PmPD composite catalyst is significantly shorter than that of alkylphenol polyether prepared by the original CoFe DMC catalyst.

[0092] The comparison results between Example 5 and Comparative Example 3, Example 6 and Comparative Example 4, and Example 7 and Comparative Example 5 show that the composite catalyst prepared in Comparative Example 1, after changing the operating conditions, has a generally poor effect on the induction time of alkylphenol polyether synthesis, and cannot achieve the effect of shortening the induction time, or even play a catalytic role in the reaction.

[0093] In summary, compared with alkylphenol polyethers prepared directly from CoFe DMC under the same reaction conditions, the alkylphenol polyethers prepared using the CoFe DMC@PmPD composite catalyst prepared in this invention have significantly shorter induction time (more than half the induction time). Therefore, the CoFe DMC@PmPD composite catalyst prepared in this invention has significant guiding significance for cost reduction and efficiency improvement in the industrial production of alkylphenol to alkylphenol polyethers, and is suitable for widespread use.

[0094] 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. Other embodiments can be obtained 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 a CoFeDMC@PmPD composite catalytic material, characterized in that, Includes the following steps: A water-soluble cobalt salt, a first citrate, and water are mixed to obtain a cobalt salt mixed solution; the molar amounts of the water-soluble cobalt salt and the first citrate are equal; in the cobalt salt mixed solution, the molar amount of the water-soluble cobalt salt to the volume ratio of the water is (0.1~0.5) mmol: 25 mL; A mixed solution of hexacyanoferrate(III), second citrate, and water is obtained; the molar amounts of hexacyanoferrate(III) and second citrate are equal, and the molar ratio of the water-soluble cobalt salt to the hexacyanoferrate(III) is (0.1~0.5):(0.1~0.5); in the mixed solution of hexacyanoferrate(III), the molar ratio of the hexacyanoferrate(III) to the volume of water is (0.1~0.5) mmol:25 mL; The hexacyanoferrate(III) mixed solution was injected into the cobalt salt mixed solution, mixed, and then aged to obtain CoFeDMC material; the injection rate was ≥100 μL·min. -1 The aging time is ≥24 hours; The CoFe DMC material, m-phenylenediamine, free radical initiator and water are mixed, and free radical polymerization is carried out on the surface of the CoFe DMC material to obtain polym-phenylenediamine, thus obtaining the CoFe DMC@PmPD composite catalytic material.

2. The preparation method according to claim 1, characterized in that, The injection rate is 100~1000 μL·min -1 .

3. The preparation method according to claim 1, characterized in that, The mass ratio of the CoFe DMC material to m-phenylenediamine is (10~100):(5~50). The free radical initiator is ammonium persulfate, and the mass ratio of the CoFe DMC material to the free radical initiator is 1:1~2; The free radical polymerization reaction is carried out under ice-water bath conditions for 5-8 hours. The free radical polymerization reaction directly yields a polymerization reaction solution. After obtaining the polymerization reaction solution, the process further includes: solid-liquid separation of the polymerization reaction solution, washing and drying the obtained solid product to obtain the CoFe DMC@PmPD composite catalytic material; the drying is vacuum drying, and the vacuum drying temperature is 50~100℃.

4. The preparation method according to claim 1, characterized in that, The aging process directly yields an aging solution, which further includes: solid-liquid separation of the aging solution, washing and drying the obtained solid product to obtain the CoFeDMC material; the drying is vacuum drying, and the vacuum drying temperature is 50~100℃.

5. The CoFe DMC@PmPD composite catalytic material prepared by the preparation method according to any one of claims 1 to 4.

6. The application of the CoFe DMC@PmPD composite catalytic material according to claim 5 in the preparation of alkylphenol polyethers.

7. A method for preparing an alkylphenol polyether, characterized in that, Includes the following steps: Alkylphenol, the CoFe DMC@PmPD composite catalyst material according to claim 5, and oxidized olefins are mixed, and the mixture is induced and activated before being kept at a constant temperature to obtain alkylphenol polyether.

8. The preparation method according to claim 7, characterized in that, The alkylphenols include one or more of propionic acid, butylphenol, pentylphenol, heptaphenol, octylphenol, nonylphenol, and decylphenol; The oxidized olefins include propylene oxide or a mixture of ethylene oxide and propylene oxide; When the oxidized olefin is a mixture of ethylene oxide and propylene oxide, the mass of the ethylene oxide accounts for 0 to 30% of the total mass of the mixture of ethylene oxide and propylene oxide, and is not 0.

9. The preparation method according to claim 7 or 8, characterized in that, The number-average molecular weight of the alkylphenol polyether is 500-1500; The mass of the CoFe DMC@PmPD composite catalyst accounts for 10~100 ppm of the total mass of the alkylphenol and olefin oxides.

10. The preparation method according to claim 7, characterized in that, The temperature of the heat preservation reaction is 130~160℃.

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