Supported catalyst and method for preparing allyl alcohol block polyether using the same

Abstract

The application belongs to the technical field of polyether preparation, and discloses a supported catalyst and a method for preparing allyl alcohol block polyether by using the same. The supported catalyst comprises silica gel and zinc and nickel supported on the silica gel; the mass ratio of zinc to nickel is (2-8):(2-8). The supported catalyst provided by the application can be used to prepare allyl alcohol block polyether with high double bond retention rate and low allyl content; the cost of the catalyst is low, the preparation method is simple, the stability is high, and the catalyst is convenient to recycle and use. The preparation method for the allyl alcohol block polyether provided by the application is simple in process, does not need complicated post-treatment, and is low in process cost.

Description

Technical Field

[0001] This invention belongs to the field of polyether preparation technology, specifically relating to a supported catalyst and a method for preparing allyl alcohol block polyethers using the catalyst. Background Technology

[0002] Allyl alcohol block polyoxyethylene polyoxypropylene ether is mainly used in the grafting modification of silicone oil. Allyl alcohol polyether is synthesized into polyether-modified polysiloxane under the action of a catalyst. The siloxane backbone in the polyether-modified polysiloxane acts as a hydrophobic group, giving the product excellent stability, anti-aging, electrical insulation, and flexibility, while the hydrophilic polyether segments give the product good surface activity.

[0003] There is considerable research on allyl alcohol block polyethers. For example, patent CN1974630A discloses a method for preparing medium-to-high molecular weight allyl alcohol polyether unit alcohols. Using monofunctional allyl polyether unit alcohols with double bonds (300-1000 molecular weight) as initiators and bimetallic cyanide (DMC) as catalysts, allyl alcohol polyethers with molecular weights of 2000-5000 can be synthesized at temperatures of 100-160℃. The advantage of this method is its ability to synthesize high molecular weight polyethers. However, a drawback is that the synthesized polyethers contain residual metal ions, which affect the catalytic activity of chloroplatinic acid when reacting with hydrogen-containing silicone oil, leading to deactivation of the chloroplatinic acid catalytic activity. This necessitates increasing the catalyst dosage. Furthermore, when the synthesized polyether-modified silicone oil is used as a foam leveler in polyurethane flexible foaming, the foam opening is uneven, affecting product quality.

[0004] Patent CN117326919A provides a method for preparing ultra-low molecular weight capped polyethers suitable for textile auxiliaries. The method includes the following steps: reacting allyl alcohol with epoxides in the presence of sodium hydride catalyst to obtain a basic polyether; reacting the basic polyether with an alkylating capping agent in the presence of an alkaline catalyst to obtain crude allyl alcohol alkyl-capped polyether polyol; and refining the crude allyl alcohol alkyl-capped polyether polyol by washing with water, neutralizing with acid, adsorption, drying, and filtration to obtain the final product. This preparation method can produce ultra-low molecular weight capped polyethers in high yield. Polyethers, during the preparation process, allow metal ions to be easily removed, resulting in products containing metal ions. Low content. But this process... The process is complex and cumbersome, requires post-processing, and has high costs. Therefore, finding a method for preparing allyl alcohol block polyethers with high double bond retention, high product quality, and a simple process route has become the focus of current research. Summary of the Invention

[0005] The present invention aims to at least solve one of the technical problems existing in the prior art. To this end, the present invention proposes a supported catalyst and a method for preparing allyl alcohol block polyethers using the catalyst. The supported catalyst provided by the present invention can prepare high-quality allyl alcohol block polyethers with high double bond retention and low allyl content; the preparation of allyl alcohol block polyethers using the catalyst simplifies the process and reduces costs.

[0006] This invention provides a supported catalyst.

[0007] Specifically, a supported catalyst includes silica gel and zinc and nickel supported on the silica gel; the mass ratio of zinc to nickel is (2-8):(2-8).

[0008] Preferably, the mass ratio of zinc to nickel is 2:(2-8).

[0009] Preferably, the mass of the silicone is 20%-100% of the total mass of the zinc and the nickel; more preferably, the mass of the silicone is 20%-80% of the total mass of the zinc and the nickel; even more preferably, the mass of the silicone is 20%-50% of the total mass of the zinc and the nickel.

[0010] The present invention also provides a method for preparing the above-mentioned supported catalyst.

[0011] Specifically, the preparation method of the above-mentioned supported catalyst includes the following steps:

[0012] A supported catalyst was prepared by mixing silica gel with zinc and nickel and then calcining it at a higher temperature.

[0013] Preferably, the calcination process involves heating to 450-650°C at a heating rate of 1-4°C / min and holding at that temperature for 8-18 hours; more preferably, the calcination process involves heating to 500-650°C at a heating rate of 2-4°C / min and holding at that temperature for 10-15 hours; and even more preferably, the calcination process involves heating to 550-650°C at a heating rate of 2.5-3.5°C / min and holding at that temperature for 10-12 hours.

[0014] Preferably, the silica gel further includes a pretreatment process before being mixed with the zinc and nickel. The pretreatment process involves grinding the silica gel, sieving it, and then drying it for later use. The sieving process uses a filter screen with a pore size of 1mm-2mm.

[0015] Preferably, the drying process involves drying in an oven at 80-100°C for 4-6 hours.

[0016] The present invention also provides a method for preparing allyl alcohol block polyether.

[0017] Specifically, a method for preparing an allyl alcohol block polyether includes the following steps:

[0018] Using allyl alcohol as a raw material, an addition reaction is carried out with ethylene oxide under the action of a strong base catalyst to obtain an allyl alcohol polyoxyethylene ether intermediate; then, under the action of the above-mentioned supported catalyst, a secondary addition reaction is carried out with propylene oxide to obtain an allyl alcohol block polyether (allyl alcohol block polyoxyethylene polyoxypropylene ether).

[0019] Preferably, the molar ratio of allyl alcohol to ethylene oxide is 1:(2-50).

[0020] Preferably, the temperature of the first addition reaction is 100℃-105℃, the time of the first addition reaction is 2-5 hours, and the reaction continues until the pressure basically no longer changes (the criterion is that the pressure decrease is no more than 0.02 MPa in 10 minutes).

[0021] Preferably, the strong base catalyst is one or a mixture of KOH, NaOH, KOCH3, and NaOCH3.

[0022] Preferably, the mass of the strong base catalyst is 1‰-3‰ of the mass of the allyl alcohol polyoxyethylene ether intermediate.

[0023] Preferably, the mass of the supported catalyst is 0.3‰-6‰ of the mass of the allyl alcohol block polyether. More preferably, the mass of the supported catalyst is 0.5‰-5‰ of the mass of the allyl alcohol block polyether; more preferably, the mass of the supported catalyst is 1.0‰-2.5‰ of the mass of the allyl alcohol block polyether.

[0024] Preferably, the molar ratio of allyl alcohol to propylene oxide is 1:(2-50).

[0025] Preferably, the temperature of the secondary addition reaction is 100℃-105℃.

[0026] More specifically, a method for preparing an allyl alcohol block polyether includes the following steps:

[0027] Allyl alcohol and a strong base catalyst are added to a reaction vessel. After replacing the N2 in the vessel, the temperature is raised to 100℃-105℃, and ethylene oxide is slowly added dropwise. After the ethylene oxide is added, the reaction is matured at 100℃-105℃ for 2-5 hours until the pressure basically stops changing (the criterion is that the pressure decrease is no more than 0.02 MPa in 10 minutes). After cooling and degassing, allyl alcohol polyoxyethylene ether intermediate is obtained.

[0028] The allyl alcohol polyoxyethylene ether intermediate and the supported catalyst were added to a reactor to replace the N2 in the reactor. After dehydration for 1 hour under a vacuum of ≥0.097 MPa and at 115℃-120℃, the temperature was lowered, and propylene oxide was slowly added dropwise to the reactor. After the propylene oxide was added, the reaction was matured at 100℃-105℃ for 2-5 hours until the pressure basically stopped changing (the criterion for judgment is that the pressure drop is not greater than 0.02 MPa in 10 minutes). After cooling and degassing, allyl alcohol block polyoxyethylene polyoxypropylene ether (allyl alcohol block polyether) was obtained.

[0029] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0030] (1) This invention provides a supported catalyst comprising silica gel and zinc and nickel supported on the silica gel. Zinc and nickel are firmly bonded to the silica gel without the risk of peeling. This catalyst combines the excellent thermal stability of zinc with the strong corrosion resistance and chemical stability of nickel; moreover, the supported carrier is porous, has a large specific surface area, and adjustable pore size, allowing for greater contact area between the epoxide and the reaction substrate during the reaction, thereby accelerating the reaction process. Simultaneously, zinc ions exhibit strong selectivity during the reaction, undergoing only the ring-opening reaction of the epoxide, thus significantly reducing the occurrence of epoxide isomerization. Therefore, the propylene group content is extremely low. Furthermore, by controlling the zinc-nickel ratio, the catalyst effectively protects the double bonds from breaking during the reaction, allowing them to participate in the reaction, resulting in a high double bond retention rate in the synthesized allyl alcohol block polyoxyethylene polyoxypropylene ether, leading to excellent product quality.

[0031] (2) The supported catalyst provided by the present invention can prepare high-quality allyl alcohol block polyether with high double bond retention rate and low allyl content; and it is low in cost, simple in preparation method, strong in stability, and easy to recycle and use.

[0032] (3) The preparation method of allyl alcohol block polyether provided by the present invention is simple, requires no complicated post-processing, and has low process cost. Detailed Implementation

[0033] To enable those skilled in the art to more clearly understand the technical solutions described in this invention, the following embodiments are provided for illustration. It should be noted that the following embodiments do not constitute a limitation on the scope of protection claimed by this invention.

[0034] Unless otherwise specified, the raw materials, reagents or apparatus used in the following examples and comparative examples are available from conventional commercial sources or can be obtained by existing known methods.

[0035] 1. In the following examples and comparative examples, the double bond retention rate is calculated using the following formula, expressed as a percentage (%):

[0036]

[0037] In the formula:

[0038] IV1—Actual iodine value, determined according to GB / T13892-2020;

[0039] IV2—theoretical iodine value, obtained from equation (2).

[0040] Theoretical iodine value:

[0041]

[0042] In the formula:

[0043] 100 – Conversion factor;

[0044] 254 — the molar mass of iodine, expressed in grams per mole (g / mol);

[0045] 56110 — Conversion factor, in units of potassium hydroxide (KOH), expressed as milligrams of potassium hydroxide per mole (mg / mol);

[0046] OHV—The hydroxyl value of the sample, determined by GB / T12008.3-2009.

[0047] 2. The method for determining the propylene content is as follows:

[0048] 2.1 Preprocessing

[0049] Weigh 5-7g of sample, add 50ml of methanol to each of the two conical flasks containing the sample and the blank conical flask, stir well to completely dissolve the sample, and accurately measure 20ml of solution into each conical flask using a pipette, and shake well.

[0050] 2.2 Titration

[0051] The sample was rapidly titrated with a 0.1 mol / L sodium thiosulfate standard solution. At the beginning of the titration, the sodium thiosulfate standard solution was added dropwise in a linear manner. When the color turned light yellow, the sodium thiosulfate standard solution was added dropwise. The reaction endpoint was reached when the yellow color disappeared within 15 seconds. The volume of the sodium thiosulfate standard solution was recorded.

[0052] 2.3 Result Calculation

[0053] W = (Vo - V1) × C × 4.1 ÷ 2m;

[0054] W --- The numerical value of propylene content, in percentage (%);

[0055] V0 --- The volume of sodium thiosulfate standard solution consumed in the blank, in milliliters (mL);

[0056] V1---The volume of sodium thiosulfate standard solution consumed by the sample, in milliliters (mL);

[0057] C --- The concentration of sodium thiosulfate standard solution, expressed in moles per liter (mol / L);

[0058] m --- Sample weight, in grams (g).

[0059] Example 1

[0060] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel; wherein the mass ratio of zinc to nickel is 20:80, and the total mass of zinc and nickel is 3 times the mass of silica gel.

[0061] The preparation method of the supported catalyst is as follows:

[0062] After thoroughly grinding the silica gel particles, large particles were filtered out using a 1mm pore size filter sieve, and then dried in an oven at 100℃ for 4 hours. Next, 1g of the dried silica gel particles were mixed evenly with 3g of a zinc-nickel metal mixture (zinc to nickel mass ratio of 20:80), and then subjected to programmed temperature calcination. The temperature was increased to 600℃ at a rate of 30℃ / 10min, and then calcined and held at that temperature for 12 hours, successfully preparing a zinc-nickel supported silica gel catalyst.

[0063] A method for preparing an allyl alcohol block polyether includes the following steps:

[0064] 116.0g of allyl alcohol and 1.6g of catalyst KOH were added to a 2.5L reactor. After replacing the N2 in the reactor three times, the temperature was raised and 1484.0g of ethylene oxide was slowly added dropwise to the reactor. After the ethylene oxide was added, the reaction was matured at 100℃-105℃ for 3 hours until the pressure basically stopped changing. After cooling and degassing, allyl alcohol polyoxyethylene ether intermediate was successfully obtained.

[0065] 427.0 g of the above-mentioned allyl alcohol polyoxyethylene ether and 0.8 g of the supported catalyst prepared in Example 1 were added to a 2.5 L reactor. The N2 in the reactor was replaced three times. After dehydration for 40 min under a vacuum of ≥0.097 MPa and at 115℃-120℃, the temperature was lowered, and 1173.0 g of propylene oxide was slowly added dropwise. After the propylene oxide was added completely, the reaction was matured at 100℃-105℃ for 3 hours until the pressure essentially stopped changing. After cooling and degassing, the allyl alcohol block polyoxyethylene polyoxypropylene ether product was successfully obtained. The measured double bond retention rate was 97.6%, and the propylene group content was 0.018%.

[0066] Example 2

[0067] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel;

[0068] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel; wherein the mass ratio of zinc to nickel is 50:50, and the total mass of zinc and nickel is 3 times the mass of silica gel.

[0069] The preparation method of the supported catalyst is as follows:

[0070] After thoroughly grinding the silica gel particles, large particles were filtered out using a 1mm pore size filter sieve, and then dried in an oven at 100℃ for 4 hours. Then, 1g of the dried silica gel particles were mixed evenly with 3g of a zinc-nickel metal mixture (zinc:nickel mass ratio 50:50), and subjected to programmed temperature calcination. The temperature was increased to 600℃ at a rate of 30℃ / 10min, and then calcined and held at that temperature for 12 hours, successfully yielding a zinc-nickel supported silica gel catalyst.

[0071] A method for preparing an allyl alcohol block polyether includes the following steps:

[0072] 116.0g of allyl alcohol and 1.6g of KOH catalyst were added to a 2.5L reactor. The N2 in the reactor was replaced three times. The temperature was raised, and 1484.0g of ethylene oxide was slowly added dropwise to the reactor. After the ethylene oxide was added, the reaction was matured at 100℃-105℃ for 3 hours until the pressure basically stopped changing. After cooling and degassing, the allyl alcohol polyoxyethylene ether intermediate was successfully obtained.

[0073] 320.0 g of the above-mentioned allyl alcohol polyoxyethylene ether and 0.8 g of the supported catalyst prepared in Example 2 were added to a 2.5 L reactor. The N2 in the reactor was replaced three times. After dehydration for 40 min under a vacuum of ≥0.097 MPa and at 115℃-120℃, the temperature was lowered, and 1280.0 g of propylene oxide was slowly added dropwise. After the propylene oxide was added completely, the reaction was matured at 100℃-105℃ for 3 hours until the pressure essentially stopped changing. After cooling and degassing, the allyl alcohol block polyoxyethylene polyoxypropylene ether product was successfully obtained. The measured double bond retention rate was 97.3%, and the propylene group content was 0.023%.

[0074] Example 3

[0075] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel;

[0076] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel; wherein the mass ratio of zinc to nickel is 80:20, and the total mass of zinc and nickel is 3 times the mass of silica gel.

[0077] The preparation method of the supported catalyst is as follows:

[0078] After thoroughly grinding the silica gel particles, large particles were filtered out using a 1mm pore size filter sieve, and then dried in an oven at 100℃ for 4 hours. Then, 1g of the dried silica gel particles were mixed evenly with 3g of a zinc-nickel metal mixture (zinc to nickel mass ratio of 80:20), and subjected to programmed temperature calcination. The temperature was increased to 600℃ at a rate of 30℃ / 10min, and then calcined and held at that temperature for 12 hours, successfully obtaining a zinc-nickel supported silica gel catalyst.

[0079] A method for preparing an allyl alcohol block polyether includes the following steps:

[0080] 116.0g of allyl alcohol and 1.6g of KOH catalyst were added to a 2.5L reactor. The N2 in the reactor was replaced three times. The temperature was raised, and 1484.0g of ethylene oxide was slowly added dropwise to the reactor. After the ethylene oxide was added, the reaction was matured at 100℃-105℃ for 3 hours until the pressure basically stopped changing. After cooling and degassing, the allyl alcohol polyoxyethylene ether intermediate was successfully obtained.

[0081] 256.0 g of the above-mentioned allyl alcohol polyoxyethylene ether and 0.8 g of the supported catalyst prepared in Example 3 were added to a 2.5 L reactor. The N2 in the reactor was replaced three times. After dehydration for 40 min under a vacuum of ≥0.097 MPa and at 115℃-120℃, the temperature was lowered, and 1344.0 g of propylene oxide was slowly added dropwise. After the propylene oxide was added completely, the reaction was matured at 100℃-105℃ for 3 hours until the pressure essentially stopped changing. After cooling and degassing, the allyl alcohol block polyoxyethylene polyoxypropylene ether product was successfully obtained. The measured double bond retention rate was 96.4%, and the propylene group content was 0.047%.

[0082] Example 4

[0083] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel;

[0084] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel; wherein the mass ratio of zinc to nickel is 20:80, and the total mass of zinc and nickel is 3 times the mass of silica gel.

[0085] The preparation method of the supported catalyst is as follows:

[0086] After thoroughly grinding the silica gel particles, large particles were filtered out using a 1mm pore size filter sieve, and then dried in an oven at 100℃ for 4 hours. Then, 1g of the dried silica gel particles were mixed evenly with 3g of a zinc-nickel metal mixture (zinc to nickel mass ratio of 20:80), and subjected to programmed temperature calcination. The temperature was increased to 600℃ at a rate of 30℃ / 10min, and then calcined and held at that temperature for 12 hours, successfully yielding a zinc-nickel supported silica gel catalyst.

[0087] A method for preparing an allyl alcohol block polyether includes the following steps:

[0088] 116.0g of allyl alcohol and 1.6g of KOH catalyst were added to a 2.5L reactor. The N2 in the reactor was replaced three times. The temperature was raised, and 1484.0g of ethylene oxide was slowly added dropwise to the reactor. After the ethylene oxide was added, the reaction was matured at 100℃-105℃ for 3 hours until the pressure basically stopped changing. After cooling and degassing, the allyl alcohol polyoxyethylene ether intermediate was successfully obtained.

[0089] 256.0 g of the above-mentioned allyl alcohol polyoxyethylene ether and 0.8 g of the supported catalyst prepared in Example 4 were added to a 2.5 L reactor. The N2 in the reactor was replaced three times. After dehydration for 40 min under a vacuum of ≥0.097 MPa and at 115℃-120℃, the temperature was lowered, and 1344.0 g of propylene oxide was slowly added dropwise. After the propylene oxide was added completely, the reaction was matured at 100℃-105℃ for 3 hours until the pressure essentially stopped changing. After cooling and degassing, the allyl alcohol block polyoxyethylene polyoxypropylene ether product was successfully obtained. The measured double bond retention rate was 96.8%, and the propylene group content was 0.027%.

[0090] Example 5

[0091] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel;

[0092] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel; wherein the mass ratio of zinc to nickel is 20:80, and the total mass of zinc and nickel is 3 times the mass of silica gel.

[0093] The preparation method of the supported catalyst is as follows:

[0094] After thoroughly grinding the silica gel particles, large particles were filtered out using a 1mm pore size filter sieve, and then dried in an oven at 100℃ for 4 hours. Then, 1g of the dried silica gel particles were mixed evenly with 3g of a zinc-nickel metal mixture (zinc to nickel mass ratio of 20:80), and subjected to programmed temperature calcination. The temperature was increased to 600℃ at a rate of 30℃ / 10min, and then calcined and held at that temperature for 12 hours, successfully yielding a zinc-nickel supported silica gel catalyst.

[0095] A method for preparing an allyl alcohol block polyether includes the following steps:

[0096] 116.0g of allyl alcohol and 1.6g of KOH catalyst were added to a 2.5L reactor. The N2 in the reactor was replaced three times. The temperature was raised, and 1484.0g of ethylene oxide was slowly added dropwise to the reactor. After the ethylene oxide was added, the reaction was matured at 100℃-105℃ for 3 hours until the pressure basically stopped changing. After cooling and degassing, the allyl alcohol polyoxyethylene ether intermediate was successfully obtained.

[0097] 320.0 g of the above-mentioned allyl alcohol polyoxyethylene ether and 3.2 g of the supported catalyst prepared in Example 5 were added to a 2.5 L reactor. The N2 in the reactor was replaced three times. After dehydration for 40 min under a vacuum of ≥0.097 MPa and at 115℃-120℃, the temperature was lowered, and 1280.0 g of propylene oxide was slowly added dropwise. After the propylene oxide was added completely, the reaction was matured at 100℃-105℃ for 3 hours until the pressure essentially stopped changing. After cooling and degassing, the allyl alcohol block polyoxyethylene polyoxypropylene ether product was successfully obtained. The measured double bond retention rate was 98.2%, and the propylene group content was 0.014%.

[0098] Example 6

[0099] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel;

[0100] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel; wherein the mass ratio of zinc to nickel is 50:50, and the total mass of zinc and nickel is 3 times the mass of silica gel.

[0101] The preparation method of the supported catalyst is as follows:

[0102] After thoroughly grinding the silica gel particles, large particles were filtered out using a 1mm pore size filter sieve, and then dried in an oven at 100℃ for 4 hours. Then, 1g of the dried silica gel particles were mixed evenly with 3g of a zinc-nickel metal mixture (zinc:nickel mass ratio 50:50), and subjected to programmed temperature calcination. The temperature was increased to 600℃ at a rate of 30℃ / 10min, and then calcined and held at that temperature for 12 hours, successfully yielding a zinc-nickel supported silica gel catalyst.

[0103] A method for preparing an allyl alcohol block polyether includes the following steps:

[0104] 116.0g of allyl alcohol and 1.6g of KOH catalyst were added to a 2.5L reactor. The N2 in the reactor was replaced three times. The temperature was raised, and 1484.0g of ethylene oxide was slowly added dropwise to the reactor. After the ethylene oxide was added, the reaction was matured at 100℃-105℃ for 3 hours until the pressure basically stopped changing. After cooling and degassing, the allyl alcohol polyoxyethylene ether intermediate was successfully obtained.

[0105] 256.0 g of the above-mentioned allyl alcohol polyoxyethylene ether and 3.2 g of the supported catalyst prepared in Example 6 were added to a 2.5 L reactor. The N2 in the reactor was replaced three times. After dehydration for 40 min under a vacuum of ≥0.097 MPa and at 115℃-120℃, the temperature was lowered, and 1344.0 g of propylene oxide was slowly added dropwise. After the propylene oxide was added completely, the reaction was matured at 100℃-105℃ for 3 hours until the pressure essentially stopped changing. After cooling and degassing, the allyl alcohol block polyoxyethylene polyoxypropylene ether product was successfully obtained. The measured double bond retention rate was 96.7%, and the propylene group content was 0.030%.

[0106] Example 7

[0107] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel;

[0108] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel; wherein the mass ratio of zinc to nickel is 80:20, and the total mass of zinc and nickel is 3 times the mass of silica gel.

[0109] The preparation method of the supported catalyst is as follows:

[0110] After thoroughly grinding the silica gel particles, large particles were filtered out using a 1mm pore size filter sieve, and then dried in an oven at 100℃ for 4 hours. Then, 1g of the dried silica gel particles were mixed evenly with 3g of a zinc-nickel metal mixture (zinc to nickel mass ratio of 80:20), and subjected to programmed temperature calcination. The temperature was increased to 600℃ at a rate of 30℃ / 10min, and then calcined and held at that temperature for 12 hours, successfully obtaining a zinc-nickel supported silica gel catalyst.

[0111] A method for preparing an allyl alcohol block polyether includes the following steps:

[0112] 116.0g of allyl alcohol and 1.6g of KOH catalyst were added to a 2.5L reactor. The N2 in the reactor was replaced three times. The temperature was raised, and 1484.0g of ethylene oxide was slowly added dropwise to the reactor. After the ethylene oxide was added, the reaction was matured at 100℃-105℃ for 3 hours until the pressure basically stopped changing. After cooling and degassing, the allyl alcohol polyoxyethylene ether intermediate was successfully obtained.

[0113] 427.0 g of the above-mentioned allyl alcohol polyoxyethylene ether and 3.2 g of the supported catalyst prepared in Example 7 were added to a 2.5 L reactor. The N2 in the reactor was replaced three times. After dehydration for 40 min under a vacuum of ≥0.097 MPa and at 115℃-120℃, the temperature was lowered, and 1173.0 g of propylene oxide was slowly added dropwise. After the propylene oxide was added completely, the reaction was matured at 100℃-105℃ for 3 hours until the pressure essentially stopped changing. After cooling and degassing, the allyl alcohol block polyoxyethylene polyoxypropylene ether product was successfully obtained. The measured double bond retention rate was 97.4%, and the propylene group content was 0.025%.

[0114] Example 8

[0115] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel;

[0116] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel; wherein the mass ratio of zinc to nickel is 20:80, and the total mass of zinc and nickel is 3 times the mass of silica gel.

[0117] The preparation method of the supported catalyst is as follows:

[0118] After thoroughly grinding the silica gel particles, large particles were filtered out using a 1mm pore size filter sieve, and then dried in an oven at 100℃ for 4 hours. Then, 1g of the dried silica gel particles were mixed evenly with 3g of a zinc-nickel metal mixture (zinc to nickel mass ratio of 20:80), and subjected to programmed temperature calcination. The temperature was increased to 600℃ at a rate of 30℃ / 10min, and then calcined and held at that temperature for 12 hours, successfully yielding a zinc-nickel supported silica gel catalyst.

[0119] A method for preparing an allyl alcohol block polyether includes the following steps:

[0120] 116.0g of allyl alcohol and 1.6g of KOH catalyst were added to a 2.5L reactor. The N2 in the reactor was replaced three times. The temperature was raised, and 1484.0g of ethylene oxide was slowly added dropwise to the reactor. After the ethylene oxide was added, the reaction was matured at 100℃-105℃ for 3 hours until the pressure basically stopped changing. After cooling and degassing, the allyl alcohol polyoxyethylene ether intermediate was successfully obtained.

[0121] 256.0 g of the above-mentioned allyl alcohol polyoxyethylene ether and 3.2 g of the supported catalyst prepared in Example 8 were added to a 2.5 L reactor. The N2 in the reactor was replaced three times. After dehydration for 40 min under a vacuum of ≥0.097 MPa and at 115℃-120℃, the temperature was lowered, and 1344.0 g of propylene oxide was slowly added dropwise. After the propylene oxide was added completely, the reaction was matured at 100℃-105℃ for 3 hours until the pressure essentially stopped changing. After cooling and degassing, the allyl alcohol block polyoxyethylene polyoxypropylene ether product was successfully obtained. The measured double bond retention rate was 97.6%, and the propylene group content was 0.015%.

[0122] Example 9

[0123] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel;

[0124] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel; wherein the mass ratio of zinc to nickel is 20:80, and the total mass of zinc and nickel is 3 times the mass of silica gel.

[0125] The preparation method of the supported catalyst is as follows:

[0126] After thoroughly grinding the silica gel particles, large particles were filtered out using a 1mm pore size filter sieve, and then dried in an oven at 100℃ for 4 hours. Then, 1g of the dried silica gel particles were mixed evenly with 3g of a zinc-nickel metal mixture (zinc to nickel mass ratio of 20:80), and subjected to programmed temperature calcination. The temperature was increased to 600℃ at a rate of 30℃ / 10min, and then calcined and held at that temperature for 12 hours, successfully yielding a zinc-nickel supported silica gel catalyst.

[0127] A method for preparing an allyl alcohol block polyether includes the following steps:

[0128] 116.0g of allyl alcohol and 1.6g of KOH catalyst were added to a 2.5L reactor. The N2 in the reactor was replaced three times. The temperature was raised, and 1484.0g of ethylene oxide was slowly added dropwise to the reactor. After the ethylene oxide was added, the reaction was matured at 100℃-105℃ for 3 hours until the pressure basically stopped changing. After cooling and degassing, the allyl alcohol polyoxyethylene ether intermediate was successfully obtained.

[0129] 256.0 g of the above-mentioned allyl alcohol polyoxyethylene ether and 8.0 g of the supported catalyst prepared in Example 9 were added to a 2.5 L reactor. The N2 in the reactor was replaced three times. After dehydration for 40 min under a vacuum of ≥0.097 MPa and at 115℃-120℃, the temperature was lowered, and 1344.0 g of propylene oxide was slowly added dropwise. After the propylene oxide was added completely, the reaction was matured at 100℃-105℃ for 3 hours until the pressure essentially stopped changing. After cooling and degassing, the allyl alcohol block polyoxyethylene polyoxypropylene ether product was successfully obtained. The measured double bond retention rate was 97.1%, and the propylene group content was 0.028%.

[0130] Example 10

[0131] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel;

[0132] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel; wherein the mass ratio of zinc to nickel is 50:50, and the total mass of zinc and nickel is 3 times the mass of silica gel.

[0133] The preparation method of the supported catalyst is as follows:

[0134] After thoroughly grinding the silica gel particles, large particles were filtered out using a 1mm pore size filter sieve, and then dried in an oven at 100℃ for 4 hours. Then, 1g of the dried silica gel particles were mixed evenly with 3g of a zinc-nickel metal mixture (zinc:nickel mass ratio 50:50), and subjected to programmed temperature calcination. The temperature was increased to 600℃ at a rate of 30℃ / 10min, and then calcined and held at that temperature for 12 hours, successfully yielding a zinc-nickel supported silica gel catalyst.

[0135] A method for preparing an allyl alcohol block polyether includes the following steps:

[0136] 116.0g of allyl alcohol and 1.6g of KOH catalyst were added to a 2.5L reactor. The N2 in the reactor was replaced three times. The temperature was raised, and 1484.0g of ethylene oxide was slowly added dropwise to the reactor. After the ethylene oxide was added, the reaction was matured at 100℃-105℃ for 3 hours until the pressure basically stopped changing. After cooling and degassing, the allyl alcohol polyoxyethylene ether intermediate was successfully obtained.

[0137] 427.0 g of the above-mentioned allyl alcohol polyoxyethylene ether and 8.0 g of the supported catalyst prepared in Example 10 were added to a 2.5 L reactor. The N2 in the reactor was replaced three times. After dehydration for 40 min under a vacuum of ≥0.097 MPa and at 115℃-120℃, the temperature was lowered, and 1173.0 g of propylene oxide was slowly added dropwise. After the propylene oxide was added completely, the reaction was matured at 100℃-105℃ for 3 hours until the pressure essentially stopped changing. After cooling and degassing, the allyl alcohol block polyoxyethylene polyoxypropylene ether product was successfully obtained. The measured double bond retention rate was 97.5%, and the propylene group content was 0.013%.

[0138] Example 11

[0139] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel;

[0140] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel; wherein the mass ratio of zinc to nickel is 80:20, and the total mass of zinc and nickel is 3 times the mass of silica gel.

[0141] The preparation method of the supported catalyst is as follows:

[0142] After thoroughly grinding the silica gel particles, large particles were filtered out using a 1mm pore size filter sieve, and then dried in an oven at 100℃ for 4 hours. Then, 1g of the dried silica gel particles were mixed evenly with 3g of a zinc-nickel metal mixture (zinc to nickel mass ratio of 80:20), and subjected to programmed temperature calcination. The temperature was increased to 600℃ at a rate of 30℃ / 10min, and then calcined and held at that temperature for 12 hours, successfully obtaining a zinc-nickel supported silica gel catalyst.

[0143] A method for preparing an allyl alcohol block polyether includes the following steps:

[0144] 116.0g of allyl alcohol and 1.6g of KOH catalyst were added to a 2.5L reactor. The N2 in the reactor was replaced three times. The temperature was raised, and 1484.0g of ethylene oxide was slowly added dropwise to the reactor. After the ethylene oxide was added, the reaction was matured at 100℃-105℃ for 3 hours until the pressure basically stopped changing. After cooling and degassing, the allyl alcohol polyoxyethylene ether intermediate was successfully obtained.

[0145] 320.0 g of the above-mentioned allyl alcohol polyoxyethylene ether and 8.0 g of the supported catalyst prepared in Example 11 were added to a 2.5 L reactor. The N2 in the reactor was replaced three times. After dehydration for 40 min under a vacuum of ≥0.097 MPa and at 115℃-120℃, the temperature was lowered, and 1280.0 g of propylene oxide was slowly added dropwise. After the propylene oxide was added completely, the reaction was matured at 100℃-105℃ for 3 hours until the pressure essentially stopped changing. After cooling and degassing, the allyl alcohol block polyoxyethylene polyoxypropylene ether product was successfully obtained. The measured double bond retention rate was 97.2%, and the propylene group content was 0.021%.

[0146] Example 12

[0147] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel;

[0148] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel; wherein the mass ratio of zinc to nickel is 20:80, and the total mass of zinc and nickel is 3 times the mass of silica gel.

[0149] The preparation method of the supported catalyst is as follows:

[0150] After thoroughly grinding the silica gel particles, large particles were filtered out using a 1mm pore size filter sieve, and then dried in an oven at 100℃ for 4 hours. Then, 1g of the dried silica gel particles were mixed evenly with 3g of a zinc-nickel metal mixture (zinc to nickel mass ratio of 20:80), and subjected to programmed temperature calcination. The temperature was increased to 600℃ at a rate of 30℃ / 10min, and then calcined and held at that temperature for 12 hours, successfully yielding a zinc-nickel supported silica gel catalyst.

[0151] A method for preparing an allyl alcohol block polyether includes the following steps:

[0152] 116.0g of allyl alcohol and 1.6g of KOH catalyst were added to a 2.5L reactor. The N2 in the reactor was replaced three times. The temperature was raised, and 1484.0g of ethylene oxide was slowly added dropwise to the reactor. After the ethylene oxide was added, the reaction was matured at 100℃-105℃ for 3 hours until the pressure basically stopped changing. After cooling and degassing, the allyl alcohol polyoxyethylene ether intermediate was successfully obtained.

[0153] 256.0 g of the above-mentioned allyl alcohol polyoxyethylene ether and 8.0 g of the supported catalyst prepared in Example 12 were added to a 2.5 L reactor. The N2 in the reactor was replaced three times. After dehydration for 40 min under a vacuum of ≥0.097 MPa and at 115℃-120℃, the temperature was lowered, and 1344.0 g of propylene oxide was slowly added dropwise. After the propylene oxide was added completely, the reaction was matured at 100℃-105℃ for 3 hours until the pressure essentially stopped changing. After cooling and degassing, the allyl alcohol block polyoxyethylene polyoxypropylene ether product was successfully obtained. The measured double bond retention rate was 97.4%, and the propylene group content was 0.020%.

[0154] Table 1. Allyl alcohol block polyether properties in the examples

[0155]

[0156] Analysis of the data in the table shows that when the catalyst content is 2%, the double bond retention rate is higher than that of catalysts with other contents, while the propylene group content is also lower. As the molecular weight increases, the double bond retention rate begins to decrease. Furthermore, comparative analysis of the metal content in supported catalysts reveals that a zinc to nickel ratio of 2:8 results in the best product performance and application characteristics.

[0157] Comparative Example 1

[0158] A method for preparing an allyl alcohol block polyether includes the following steps:

[0159] 116.0g of allyl alcohol and 1.6g of KOH catalyst were added to a 2.5L reactor. The N2 in the reactor was replaced three times. The temperature was raised, and 1484.0g of ethylene oxide was slowly added dropwise to the reactor. After the ethylene oxide was added, the reaction was matured at 100℃-105℃ for 3 hours until the pressure basically stopped changing. After cooling and degassing, the allyl alcohol polyoxyethylene ether intermediate was successfully obtained.

[0160] 256.0 g of the above-mentioned allyl alcohol polyoxyethylene ether and 3.2 g of KOH catalyst were added to a 2.5 L reactor. The N2 in the reactor was replaced three times. After dehydration for 40 min under a vacuum of ≥0.097 MPa and at 115℃-120℃, the temperature was lowered, and 1344.0 g of propylene oxide was slowly added dropwise. After the propylene oxide was added completely, the reaction was matured at 100℃-105℃ for 3 hours until the pressure essentially stopped changing. After cooling and degassing, the allyl alcohol block polyoxyethylene polyoxypropylene ether product was successfully obtained. The measured double bond retention rate was 80.2%, and the propylene group content was 0.30%.

[0161] Comparative Example 2

[0162] A method for preparing an allyl alcohol block polyether includes the following steps:

[0163] 116.0g of allyl alcohol and 1.6g of KOH catalyst were added to a 2.5L reactor. The N2 in the reactor was replaced three times. The temperature was raised, and 1484.0g of ethylene oxide was slowly added dropwise to the reactor. After the ethylene oxide was added, the reaction was matured at 100℃-105℃ for 3 hours until the pressure basically stopped changing. After cooling and degassing, the allyl alcohol polyoxyethylene ether intermediate was successfully obtained.

[0164] 256.0 g of the above-mentioned allyl alcohol polyoxyethylene ether was added to a 2.5 L reactor. The nitrogen in the reactor was replaced three times. After dehydration for 40 min under a vacuum of ≥0.097 MPa and at 115℃-120℃, the temperature was lowered to 80℃. Then, 3.2 g of DMC catalyst was added to the reactor, and the nitrogen in the reactor was replaced three times. The temperature was then raised, and 1344.0 g of propylene oxide was slowly added dropwise. After the propylene oxide was added completely, the reaction was matured at 100℃-105℃ for 3 hours until the pressure essentially stopped changing. After cooling and degassing, the allyl alcohol block polyoxyethylene polyoxypropylene ether product was successfully obtained. The measured double bond retention rate was 92.0%, and the propylene group content was 0.10%.

[0165] Comparative Example 3

[0166] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel;

[0167] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel; wherein the mass ratio of zinc to nickel is 5:95, and the total mass of zinc and nickel is 3 times the mass of silica gel.

[0168] The preparation method of the supported catalyst is as follows:

[0169] After thoroughly grinding the silica gel particles, large particles were filtered out using a 1mm pore size filter sieve, and then dried in an oven at 100℃ for 4 hours. Then, 1g of the dried silica gel particles were mixed evenly with 3g of a zinc-nickel metal mixture (zinc to nickel mass ratio of 0.5:95), and subjected to programmed temperature calcination. The temperature was increased to 600℃ at a rate of 30℃ / 10min, and then calcined and held at that temperature for 12 hours, successfully obtaining a zinc-nickel supported silica gel catalyst.

[0170] A method for preparing an allyl alcohol block polyether includes the following steps:

[0171] 116.0g of allyl alcohol and 1.6g of KOH catalyst were added to a 2.5L reactor. The N2 in the reactor was replaced three times. The temperature was raised, and 1484.0g of ethylene oxide was slowly added dropwise to the reactor. After the ethylene oxide was added, the reaction was matured at 100℃-105℃ for 3 hours until the pressure basically stopped changing. After cooling and degassing, the allyl alcohol polyoxyethylene ether intermediate was successfully obtained.

[0172] 256.0 g of the above-mentioned allyl alcohol polyoxyethylene ether and 3.2 g of the supported catalyst prepared in Comparative Example 3 were added to a 2.5 L reactor. The N2 in the reactor was replaced three times. After dehydration for 40 min under a vacuum of ≥0.097 MPa and at 115℃-120℃, the temperature was lowered, and 1344.0 g of propylene oxide was slowly added dropwise. After the propylene oxide was added completely, the reaction was matured at 100℃-105℃ for 3 hours until the pressure essentially stopped changing. After cooling and degassing, the allyl alcohol block polyoxyethylene polyoxypropylene ether product was successfully obtained. The measured double bond retention rate was 94.3%, and the propylene group content was 0.030%.

[0173] Comparative Example 4

[0174] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel;

[0175] A supported catalyst includes silica gel and zinc and nickel supported on the silica gel; wherein the mass ratio of zinc to nickel is 95:5, and the total mass of zinc and nickel is 3 times the mass of silica gel.

[0176] The preparation method of the supported catalyst is as follows:

[0177] After thoroughly grinding the silica gel particles, large particles were filtered out using a 1mm pore size filter sieve, and then dried in an oven at 100℃ for 4 hours. Then, 1g of the dried silica gel particles were mixed evenly with 3g of a zinc-nickel metal mixture (zinc to nickel mass ratio of 95:05), and subjected to programmed temperature calcination. The mixture was heated to 600℃ at a rate of 30℃ / 10min, and then calcined and held at that temperature for 12 hours, successfully obtaining a zinc-nickel supported silica gel catalyst.

[0178] A method for preparing an allyl alcohol block polyether includes the following steps:

[0179] 116.0g of allyl alcohol and 1.6g of KOH catalyst were added to a 2.5L reactor. The N2 in the reactor was replaced three times. The temperature was raised, and 1484.0g of ethylene oxide was slowly added dropwise to the reactor. After the ethylene oxide was added, the reaction was matured at 100℃-105℃ for 3 hours until the pressure basically stopped changing. After cooling and degassing, the allyl alcohol polyoxyethylene ether intermediate was successfully obtained.

[0180] 256.0 g of the allyl alcohol polyoxyethylene ether and 3.2 g of the supported catalyst prepared in Comparative Example 4 were added to a 2.5 L reactor. The N2 in the reactor was replaced three times. After dehydration at a vacuum degree ≥0.097 MPa and 115℃-120℃ for 40 min, the reactor was cooled, and 1344.0 g of propylene oxide was slowly added dropwise. After the propylene oxide was added completely, the reaction was matured at 100℃-105℃ for 3 hours until the pressure essentially stopped changing. After cooling and degassing, the allyl alcohol block polyoxyethylene polyoxypropylene ether product was successfully obtained. The measured double bond retention rate was 93.1%, and the propylene group content was 0.033%.

[0181] Table 2 Comparative allyl alcohol block polyether properties

[0182]

[0183] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. A process for the preparation of an allyl alcohol blocked polyether, characterized in that, The method comprises the following steps: The allyl alcohol is used as a raw material, and a first addition reaction is carried out with ethylene oxide under the action of a strong base catalyst to obtain an allyl alcohol polyoxyethylene ether intermediate; then a second addition reaction is carried out with propylene oxide under the action of a supported catalyst to obtain an allyl alcohol block polyether; The supported catalyst comprises silica gel and zinc and nickel supported on the silica gel; the mass ratio of the zinc to the nickel is (2-8):(2-8); and the mass of the silica gel is 20%-100% of the total mass of the zinc and the nickel.

2. The production method according to claim 1, characterized by, The mass ratio of the zinc to the nickel is 2:(2-8).

3. The production method according to claim 1 or 2, characterized by, The mass of the silica gel is 20%-80% of the total mass of the zinc and the nickel.

4. The production method according to claim 3, characterized by, The supported catalyst is prepared by mixing the silica gel with the zinc and the nickel and then performing temperature rising calcination.

5. The preparation method according to claim 4, characterized in that, The temperature rising calcination process is to rise the temperature to 450-650 DEG C at a temperature rising speed of 1-4 DEG C / min, and then to keep the temperature for 8-18 h.

6. The production method according to claim 5, wherein The temperature rising calcination process is to rise the temperature to 500-650 DEG C at a temperature rising speed of 2-4 DEG C / min, and then to keep the temperature for 10-15 h.

7. The preparation method according to claim 1, characterized in that, The molar ratio of the allyl alcohol to the ethylene oxide is 1:(2-50).

8. The production method according to claim 7, characterized by, The mass of the strong base catalyst is 1‰-3‰ of the mass of the allyl alcohol polyoxyethylene ether intermediate.

9. The method of claim 1, wherein, The mass of the supported catalyst is 0.3‰-6‰ of the mass of the allyl alcohol block polyether.

10. The method of claim 9, wherein, The molar ratio of the allyl alcohol to the propylene oxide is 1:(2-50).

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