Preparation method and application of cobalt-nickel loaded silica gel type catalyst and synthesis method of allyl alcohol polyoxyethylene polyoxypropylene ether

Abstract

The invention provides a preparation method of a cobalt-nickel loaded silica gel type catalyst, which comprises the following steps: silica gel and a loading agent are mixed, the loading agent is composed of cobalt fluoride and nickel fluoride, the mass ratio of the silica gel to the loading agent is 1: 3, and the mass ratio of cobalt fluoride to nickel fluoride is 0.1-9: 1. After mixing, raising the temperature to 550-800 DEG C at the temperature raising speed of 1-5 DEG C / min, calcining, and preserving heat and calcining for at least 24 hours to obtain the catalyst. The invention also provides application of the cobalt-nickel loaded silica gel type catalyst and a synthesis method of allyl alcohol polyoxyethylene polyoxypropylene ether. The catalyst provided by the invention is beneficial to improving the reaction activity, the reaction speed and the reaction conversion rate, thereby being beneficial to improving the double bond retention rate of allyl alcohol polyoxyethylene polyoxypropylene ether and narrowing molecular distribution.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of catalysts and organic synthesis, and particularly relates to a preparation method and application of a cobalt-nickel loaded silica gel type catalyst and a synthesis method of allyl alcohol polyoxyethylene polyoxypropylene ether. BACKGROUND

[0002] The allyl alcohol polyoxyethylene polyoxypropylene ether is an allyl alcohol derivative generated by reaction of allyl alcohol, ethylene oxide and propylene oxide under the action of a catalyst. Currently, sodium hydroxide and sodium methoxide are commonly used as catalysts, but these catalysts have the problem of low catalytic activity, thereby resulting in low double bond retention rate of the polymer product. SUMMARY

[0003] In order to overcome the deficiencies of the prior art, the purpose of the present application is to provide a preparation method of a cobalt-nickel loaded silica gel type catalyst, and the prepared catalyst is beneficial to improve the reaction activity, reaction speed and reaction conversion rate.

[0004] The present application also provides the application of the cobalt-nickel loaded silica gel type catalyst and a synthesis method of the allyl alcohol polyoxyethylene polyoxypropylene ether.

[0005] To solve the above problems, the technical solution adopted by the present application is as follows:

[0006] A preparation method of a cobalt-nickel loaded silica gel type catalyst, comprising the following steps:

[0007] The silica gel is mixed with a loading agent, the loading agent is composed of cobalt fluoride and nickel fluoride, and the mass ratio of the silica gel to the loading agent is 1:3, and the mass ratio of the cobalt fluoride to the nickel fluoride is 0.1-9:1.

[0008] After mixing, the temperature is raised to 550-800 DEG C at a temperature raising speed of 1-5 DEG C / min for calcination, and the calcination is kept for at least 24 hours to obtain the catalyst.

[0009] In some possible embodiments, in the calcination step, the temperature is raised to 600-700 DEG C at a temperature raising speed of 2-4 DEG C / min for calcination, and the calcination is kept for 24-28 hours.

[0010] In some possible embodiments, in the calcination step, the temperature is raised to 650 DEG C at a temperature raising speed of 3 DEG C / min for calcination.

[0011] In some possible embodiments, before the mixing step, the preparation method further comprises:

[0012] The silica gel is ground and sieved, and a 1mm-2mm sieve is used for sieving;

[0013] After sieving, dry in an oven at 80-100℃ for 4-6 hours.

[0014] The application also provides an application of a cobalt-nickel loaded silica gel type catalyst, which is used to catalyze the synthesis of allyl alcohol polyoxyethylene polyoxypropylene ether from allyl alcohol polyoxyethylene ether, ethylene oxide and propylene oxide, so as to improve the double bond retention rate and narrow the molecular distribution.

[0015] The application also provides a synthesis method of allyl alcohol polyoxyethylene polyoxypropylene ether, which comprises the following steps:

[0016] Put the allyl alcohol polyoxyethylene ether and the cobalt-nickel loaded silica gel type catalyst into a reaction kettle, replace the air in the kettle with inert gas for multiple times, and the amount of the cobalt-nickel loaded silica gel type catalyst is 0.8‰-4‰ of the mass of the allyl alcohol polyoxyethylene ether;

[0017] Dehydrate under the condition that the vacuum degree is greater than or equal to 0.097 MPa and the temperature is 115-120℃;

[0018] After dehydration, cool down, and drop the epoxy mixture into the reaction kettle, the molar ratio of the allyl alcohol polyoxyethylene ether to the epoxy mixture is 1:2-1:50, the epoxy mixture is composed of ethylene oxide and propylene oxide, and the molar ratio of the ethylene oxide to the propylene oxide is 1:2-1:10;

[0019] After the dropping of the epoxy mixture is completed, mature the reaction at a temperature of 100-120℃ until the pressure is basically unchanged.

[0020] In some possible embodiments, the mature reaction temperature of the epoxy mixture is 110-115℃.

[0021] In some possible embodiments, the preparation of the allyl alcohol polyoxyethylene ether comprises:

[0022] Put the allyl alcohol and a strong base catalyst into a reaction kettle, and replace the air in the kettle with inert gas for multiple times;

[0023] Warm up, drop ethylene oxide into the kettle, and after the dropping of the ethylene oxide is completed, mature the reaction at a temperature of 95-115℃ until the pressure is basically unchanged, cool down, and degas to obtain the allyl alcohol polyoxyethylene ether, the molar ratio of the allyl alcohol to the ethylene oxide is 1:2-1:50, and the amount of the strong base catalyst is 1‰-3‰ of the total mass of the allyl alcohol and the ethylene oxide;

[0024] In some possible embodiments, in the step of preparing the allyl alcohol polyoxyethylene ether, the mature reaction temperature is 100-105℃.

[0025] In some possible implementation manners, the cobalt-nickel loaded silica gel type catalyst is used in an amount of 2‰-4‰ of the mass of the allyl alcohol polyoxyethylene ether.

[0026] Compared with the prior art, the application has the following beneficial effects:

[0027] In the present application, porous silica gel is selected as the catalyst carrier, and the pore structure is beneficial to improve the diffusion performance, so that the ethylene oxide and propylene oxide can better contact the loaded catalyst and the reaction substrate during the reaction, thereby accelerating the reaction speed and the reaction conversion rate. In addition, the selection of silica gel and the loading agent in a specific ratio is beneficial to ensure the combination effect of the two, thereby also being beneficial to improve the catalytic efficiency of the catalyst. Cobalt element has multiple variable valence states, which can realize the transmission of electrons through valence state change in the catalytic process, promote the reaction to proceed. The introduction of fluorine atoms can adjust the electron cloud density of the catalyst, optimize its adsorption and desorption capacity for reaction intermediates, thereby improving the catalytic activity. The nickel catalyst has the advantages of rich resources, small toxicity, high catalytic activity and the ability to widely introduce various fluorinated functional groups. Therefore, the synergistic cooperation of silica gel, fluorinated cobalt and fluorinated nickel is also beneficial to improve the reaction activity. The cooperation of the catalyst and the synthesis parameters of the present application is beneficial to improve the double bond retention rate and narrow the molecular distribution of the synthesized polymer.

[0028] The following specific embodiments further illustrate the present application. DETAILED DESCRIPTION

[0029] The technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only some of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0030] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs. The terminology used in the description of the present application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present application.

[0031] Some embodiments of the present application will be described in detail below. The following embodiments and features in the embodiments can be combined with each other without conflict.

[0032] An embodiment of the present application provides a preparation method of a cobalt-nickel loaded silica gel type catalyst, which comprises the following steps.

[0033] The silica gel is mixed with a loading agent consisting of cobalt fluoride and nickel fluoride, the mass ratio of the silica gel to the loading agent being 1:3, and the mass ratio of the cobalt fluoride to the nickel fluoride being 0.1-9:1.

[0034] After mixing, calcination is performed at a temperature rising rate of 1-5℃ / min to 550-800℃, and the calcination is maintained for at least 24 hours to obtain the catalyst.

[0035] In some embodiments, in the calcination step, the calcination is performed at a temperature rising rate of 2-4℃ / min to 600-700℃, and the calcination is maintained for 24-28 hours.

[0036] In some embodiments, in the calcination step, the calcination is performed at a temperature rising rate of 3℃ / min to 650℃, and the calcination is maintained for 24-28 hours.

[0037] The above calcination conditions are preferred to improve the tightness of the combination of the colloidal and the loading agent, and also to improve the contact specific surface area of the finished catalyst.

[0038] In some embodiments, before the mixing step, the preparation method further comprises: grinding and sieving the silica gel, and sieving is performed using a filter sieve of 1mm-2mm. After sieving, drying is performed in an oven at 80-100℃ for 4-6 hours. The steps of grinding and sieving are beneficial to homogenize the particle size of the silica gel particles, and the step of drying is beneficial to avoid water vapor interference with the loading. It can be understood that the higher the drying temperature, the lower the drying time can be selected, for example, when the drying temperature is 100℃, the drying time of 4 hours can be selected, and when the drying temperature is 80℃, the drying time of 6 hours can be selected.

[0039] Another embodiment of the present application provides an application of the cobalt-nickel loaded silica gel type catalyst, which is used to catalyze the synthesis of allyl alcohol polyoxyethylene polyoxypropylene ether from allyl alcohol polyoxyethylene ether, ethylene oxide and propylene oxide, so as to improve the double bond retention rate and narrow the molecular distribution.

[0040] Another embodiment of the present application also provides a synthesis method of allyl alcohol polyoxyethylene polyoxypropylene ether. The synthesis method comprises the following steps.

[0041] The preparation of allyl alcohol polyoxyethylene ether includes the following steps: putting allyl alcohol and a strong base catalyst into a reaction kettle, and replacing the air in the kettle with inert gas for several times. Exemplarily, the strong base catalyst can include potassium hydroxide. Exemplarily, the inert gas can be N2. After warming, drop epoxy ethane into the kettle, and then incubate the reaction at a temperature of 95-115°C until the pressure is basically unchanged. The judgment standard for the pressure being basically unchanged is that the pressure reduction in 10 min is less than or equal to 0.02 MPa. Then, after cooling and degassing, allyl alcohol polyoxyethylene ether is obtained. The molar ratio of the allyl alcohol to the epoxy ethane is 1:2-1:50, and the amount of the strong base catalyst is 1‰-3‰ of the total mass of the allyl alcohol and the epoxy ethane. The preparation conditions of the allyl alcohol polyoxyethylene ether are in the commonly used selection range in the art, and thus, in specific embodiments, the conditions of the preparation process of the allyl alcohol polyoxyethylene ether are not described in detail.

[0042] In some embodiments, in the step of preparing the allyl alcohol polyoxyethylene ether, the incubation reaction temperature is 100-105°C. The selected temperature range is conducive to making the incubation process relatively gentle, shortening the reaction time, and making the reaction more complete.

[0043] It can be understood that if the allyl alcohol polyoxyethylene ether can be obtained from other ways, the preparation process of the allyl alcohol polyoxyethylene ether can not be performed.

[0044] Put the allyl alcohol polyoxyethylene ether and the cobalt-nickel loaded silica gel type catalyst described above into a reaction kettle, replace the air in the kettle with inert gas for several times, and the amount of the cobalt-nickel loaded silica gel type catalyst is 0.8‰-4‰ of the mass of the allyl alcohol polyoxyethylene ether. Exemplarily, the inert gas can be N2. Preferably, the amount of the cobalt-nickel loaded silica gel type catalyst is 2‰-4‰ of the mass of the allyl alcohol polyoxyethylene ether, and the preferred range is conducive to ensuring that the double bond retention rate is greater than 97%.

[0045] Then, dehydrate under the condition of a vacuum degree greater than or equal to 0.097 MPa and a temperature of 115-120°C.

[0046] After dehydration, cool the reaction kettle, and then drop an epoxy mixture into the reaction kettle. The molar ratio of the allyl alcohol polyoxyethylene ether to the epoxy mixture is 1:2-1:50, and the epoxy mixture is composed of epoxy ethane and epoxy propane. The molar ratio of the epoxy ethane to the epoxy propane is 1:2-1:10.

[0047] After the dropping of the epoxy mixture is completed, incubate the reaction at a temperature of 100-120°C until the pressure is basically unchanged. The judgment standard for the pressure being basically unchanged is that the pressure reduction in 10 min is less than or equal to 0.02 MPa.

[0048] In some embodiments, the aging reaction temperature of the epoxy mixture is 110-115°C. The selection of the aging temperature facilitates a relatively gentle aging process, short reaction time and complete reaction.

[0049] For example, the number average molecular weight of the allyl alcohol polyoxyethylene polyoxypropylene ether can be 3000-5000.

[0050] In the present application, porous silica gel is selected as the catalyst carrier. The pore structure facilitates improved diffusion performance, so that ethylene oxide and propylene oxide can better contact the loaded catalyst and the reaction substrate during the reaction, thereby accelerating the reaction speed and reaction conversion rate. In addition, the use of silica gel and loading agent in a specific ratio facilitates the combination effect of the two, thereby also facilitating the improvement of the catalytic efficiency of the catalyst. Cobalt has multiple variable valence states, which can realize electron transfer through valence state change during the catalytic process, promoting the reaction. The introduction of fluorine atoms can adjust the electron cloud density of the catalyst, optimize its adsorption and desorption capacity for reaction intermediates, and thereby improve the catalytic activity. Nickel catalyst has the advantages of abundant resources, low toxicity, high catalytic activity, and the ability to widely introduce various fluorinated functional groups. Therefore, the synergistic cooperation of silica gel, fluorinated cobalt and fluorinated nickel also facilitates the improvement of reaction activity. The cooperation of the catalyst and the synthesis parameters of the present application facilitates the improvement of the double bond retention rate and the narrowing of the molecular distribution of the synthesized polymer.

[0051] The following is illustrated in detail by way of example.

[0052] Example 1

[0053] 116.0g of allyl alcohol and 2.0g of catalyst KOH were added to a 2.5L reaction kettle, the air in the kettle was replaced with N2 for several times, the temperature was raised, and 884.0g of ethylene oxide was slowly added to the kettle. After the addition of ethylene oxide was completed, the reaction was aged at a temperature of 100-105°C until the pressure did not change substantially. After cooling and degassing, the allyl alcohol polyoxyethylene ether intermediate was successfully prepared.

[0054] 1g of silica gel particles were thoroughly ground, filtered through a 1mm pore size filter screen to remove large particle materials, and then dried in a 100°C oven for 4h. The above silica gel particles were mixed with 3g of fluorinated cobalt and fluorinated nickel in a mass ratio of 1:9, and then subjected to programmed temperature calcination at a temperature increasing rate of 3°C / min to 650°C. After calcination and holding for 26h, the cobalt-nickel loaded silica gel catalyst was successfully prepared.

[0055] Take the above allyl alcohol polyoxyethylene ether 200.0 g and 0.96 g of mass ratio of 1:9 of fluorinated cobalt: nickel on silica gel type supported catalyst into the reaction kettle, replace the air in the kettle with N2 for many times, dehydrate at a vacuum degree greater than or equal to 0.097 MPa, 115℃-120℃ environment, cool down, slowly add 150 g of an epoxy mixture of ethylene oxide and 850 g of propylene oxide (need to be mixed in advance to ensure uniform mixing) to the kettle, until the epoxy mixture is added, incubate the reaction at a temperature of 110℃-115℃ until the pressure basically does not change, cool down and degas to successfully produce the allyl alcohol random polyoxyethylene polyoxypropylene ether finished product. The measured index double bond retention rate is 97.6%, and the molecular distribution is 1.10.

[0056] Example 2

[0057] Put 116.0 g of allyl alcohol and 2.0 g of catalyst KOH into a 2.5 L reaction kettle, replace the air in the kettle with N2 for many times, heat up, slowly add 884.0 g of ethylene oxide to the kettle, until the ethylene oxide is added, incubate the reaction at a temperature of 100℃-105℃ until the pressure basically does not change, cool down and degas to successfully produce the allyl alcohol polyoxyethylene ether intermediate.

[0058] Grind 1 g of silica gel particles, filter out large particle substances with a filter screen with a pore size of 1 mm, then dry in a 100℃ oven for 4 h. Mix the above silica gel particles with 3 g of mass ratio of 1:1 of cobalt fluoride, nickel fluoride, and then program the temperature to 650℃ at a heating rate of 3℃ / min, and then calcine for 26 h to successfully produce a cobalt-nickel supported silica gel catalyst.

[0059] Take the above allyl alcohol polyoxyethylene ether 150.0 g and 0.96 g of mass ratio of 1:1 of fluorinated cobalt: nickel on silica gel type supported catalyst into the reaction kettle, replace the air in the kettle with N2 for many times, dehydrate at a vacuum degree greater than or equal to 0.097 MPa, 115℃-120℃ environment, cool down, slowly add 158 g of an epoxy mixture of ethylene oxide and 892 g of propylene oxide (need to be mixed in advance to ensure uniform mixing) to the kettle, until the epoxy is added, incubate the reaction at a temperature of 110℃-115℃ until the pressure basically does not change, cool down and degas to successfully produce the allyl alcohol random polyoxyethylene polyoxypropylene ether finished product. The measured index double bond retention rate is 97.3%, and the molecular distribution is 1.09.

[0060] Example 3

[0061] Put 116.0g allyl alcohol and 2.0g catalyst KOH into a 2.5L reactor, replace the N2 in the reactor three times, heat up, slowly add 884.0g ethylene oxide to the reactor, until the ethylene oxide is added, the reaction is matured at a temperature of 100-105℃ until the pressure is basically unchanged, after cooling and degassing, the allyl alcohol polyoxyethylene ether intermediate is successfully prepared.

[0062] Grind 1g silica gel particles thoroughly, filter out large particle substances with a filter screen with a pore size of 1mm, and then dry in a 100℃ oven for 4h. Mix the above silica gel particles with 3g of cobalt fluoride and nickel fluoride with a mass ratio of 9:1, and then perform programmed temperature calcination at a temperature increase rate of 3℃ / min to 650℃, and then calcine for 26h after temperature increase, to successfully prepare a cobalt-nickel loaded silica gel type catalyst.

[0063] Take 120.0g of the above allyl alcohol polyoxyethylene ether and 0.96g of the silica gel type supported catalyst of cobalt fluoride: nickel fluoride with a mass ratio of 9:1, and put it into a reactor, replace the N2 in the reactor three times, dehydrate at a vacuum degree greater than or equal to 0.097MPa and a temperature of 115-120℃, cool down, and slowly add 162g of an epoxy mixture of ethylene oxide and 918g of propylene oxide to the reactor (mix in advance to ensure uniform mixing), until the epoxy is added, the reaction is matured at a temperature of 110-115℃ until the pressure is basically unchanged, after cooling and degassing, the allyl alcohol random polyoxyethylene polyoxypropylene ether product is successfully prepared. The measured index double bond retention rate is 96.4%, and the molecular distribution is 1.11.

[0064] Example 4

[0065] Put 116.0g allyl alcohol and 2.0g catalyst KOH into a 2.5L reactor, replace the N2 in the reactor three times, heat up, slowly add 884.0g ethylene oxide to the reactor, until the ethylene oxide is added, the reaction is matured at a temperature of 100-105℃ until the pressure is basically unchanged, after cooling and degassing, the allyl alcohol polyoxyethylene ether intermediate is successfully prepared.

[0066] Grind 1g silica gel particles thoroughly, filter out large particle substances with a filter screen with a pore size of 1mm, and then dry in a 100℃ oven for 4h. Mix the above silica gel particles with 3g of cobalt fluoride and nickel fluoride with a mass ratio of 1:9, and then perform programmed temperature calcination at a temperature increase rate of 3℃ / min to 650℃, and then calcine for 26h after temperature increase, to successfully prepare a cobalt-nickel loaded silica gel type catalyst.

[0067] Take the above allyl alcohol polyoxyethylene ether 150.0 g and 2.4 g of fluorinated cobalt: nickel fluoride silica gel type supported catalyst with a mass ratio of 1:9 into the reaction kettle, replace the air in the kettle with N2 for several times, dehydrate at a vacuum degree greater than or equal to 0.097 MPa and an environment of 115℃-120℃, cool down, slowly add 158 g of an epoxy mixture of ethylene oxide and propylene oxide (which needs to be mixed in advance to ensure uniform mixing) to the kettle, until the epoxy addition is complete, mature the reaction at a temperature of 110℃-115℃ until the pressure basically does not change, cool down and degas after the reaction to successfully produce the allyl alcohol random polyoxyethylene polyoxypropylene ether product. The measured index double bond retention rate is 97.9%, and the molecular distribution is 1.07.

[0068] Example 5

[0069] Put 116.0 g of allyl alcohol and 2.0 g of catalyst KOH into a 2.5 L reaction kettle, replace the air in the kettle with N2 for several times, heat up, slowly add 884.0 g of ethylene oxide to the kettle, until the ethylene oxide addition is complete, mature the reaction at a temperature of 100℃-105℃ until the pressure basically does not change, cool down and degas after the reaction to successfully produce the allyl alcohol polyoxyethylene ether intermediate.

[0070] Grind 1 g of silica gel particles thoroughly, filter out large particle substances with a filter screen with a pore size of 1 mm, and then dry in a 100℃ oven for 4 h. Mix the above silica gel particles with 3 g of cobalt fluoride and nickel fluoride with a mass ratio of 1:1 uniformly, and then program the temperature to 650℃ at a heating rate of 3℃ / min, and then calcine for 26 h after calcination to successfully produce a cobalt-nickel supported silica gel catalyst.

[0071] Take the above allyl alcohol polyoxyethylene ether 120.0 g and 2.4 g of fluorinated cobalt: nickel fluoride silica gel type supported catalyst with a mass ratio of 1:1 into the reaction kettle, replace the air in the kettle with N2 for several times, dehydrate at a vacuum degree greater than or equal to 0.097 MPa and an environment of 115℃-120℃, cool down, slowly add 162 g of an epoxy mixture of ethylene oxide and propylene oxide (which needs to be mixed in advance to ensure uniform mixing) to the kettle, until the epoxy addition is complete, mature the reaction at a temperature of 110℃-115℃ until the pressure basically does not change, cool down and degas after the reaction to successfully produce the allyl alcohol random polyoxyethylene polyoxypropylene ether product. The measured index double bond retention rate is 97.3%, and the molecular distribution is 1.08.

[0072] Example 6

[0073] Put 116.0g allyl alcohol and 2.0g catalyst KOH into a 2.5L reactor, replace the air in the reactor with N2several times, heat up, slowly add 884.0g ethylene oxide to the reactor, wait until the ethylene oxide is added, and then incubate the reaction at a temperature of 100-105°C until the pressure is basically unchanged, and then successfully prepare the allyl alcohol polyoxyethylene ether intermediate after cooling and degassing.

[0074] Grind 1g of silica gel particles thoroughly, filter out large particle substances with a filter screen with a pore size of 1mm, and then dry in a 100°C oven for 4h. Mix the above silica gel particles with 3g of cobalt fluoride and nickel fluoride with a mass ratio of 9:1, and then perform programmed temperature calcination with a temperature increase rate of 3°C / min to 650°C, and then successfully prepare a cobalt-nickel loaded silica gel type catalyst after calcination for 26h.

[0075] Take the above allyl alcohol polyoxyethylene ether 200.0g and 2.4g of the silica gel type supported catalyst of cobalt fluoride: nickel fluoride with a mass ratio of 9:1, and then put it into a reactor, replace the air in the reactor with N2several times, and then dehydrate at a vacuum degree greater than or equal to 0.097MPa and an environment of 115-120°C, cool down, and then slowly add 150g of an epoxy mixture of ethylene oxide and 850g of propylene oxide to the reactor (which needs to be mixed in advance to ensure uniform mixing), wait until the epoxy is added, and then incubate the reaction at a temperature of 110-115°C until the pressure is basically unchanged, and then successfully prepare the allyl alcohol random polyoxyethylene polyoxypropylene ether finished product after cooling and degassing. The measured index double bond retention rate is 98.6%, and the molecular distribution is 1.03.

[0076] Example 7

[0077] Put 116.0g allyl alcohol and 2.0g catalyst KOH into a 2.5L reactor, replace the air in the reactor with N2several times, heat up, slowly add 884.0g ethylene oxide to the reactor, wait until the ethylene oxide is added, and then incubate the reaction at a temperature of 100-105°C until the pressure is basically unchanged, and then successfully prepare the allyl alcohol polyoxyethylene ether intermediate after cooling and degassing.

[0078] Grind 1g of silica gel particles thoroughly, filter out large particle substances with a filter screen with a pore size of 1mm, and then dry in a 100°C oven for 4h. Mix the above silica gel particles with 3g of cobalt fluoride and nickel fluoride with a mass ratio of 1:9, and then perform programmed temperature calcination with a temperature increase rate of 3°C / min to 650°C, and then successfully prepare a cobalt-nickel loaded silica gel type catalyst after calcination for 26h.

[0079] Take the above allyl alcohol polyoxyethylene ether 120.0 g and 4.8 g of fluorinated cobalt: nickel fluoride of silica gel type supported catalyst with mass ratio of 1:9 into the reaction kettle, replace the air in the kettle with N2 for many times, dehydrate at a vacuum degree greater than or equal to 0.097 MPa and an environment of 115℃-120℃, cool down, slowly add 162 g of an epoxy mixture of ethylene oxide and 918 g of propylene oxide (which needs to be mixed in advance to ensure uniform mixing) to the kettle, until the epoxy addition is complete, incubate the reaction at a temperature of 110℃-115℃ until the pressure basically no longer changes, cool down and degas to successfully produce the allyl alcohol random polyoxyethylene polyoxypropylene ether finished product. The measured index double bond retention rate is 97.3%, and the molecular distribution is 1.05.

[0080] Example 8

[0081] Put 116.0 g of allyl alcohol and 2.0 g of catalyst KOH into a 2.5 L reaction kettle, replace the air in the kettle with N2 for many times, heat up, slowly add 884.0 g of ethylene oxide to the kettle, until the ethylene oxide addition is complete, incubate the reaction at a temperature of 100℃-105℃ until the pressure basically no longer changes, cool down and degas to successfully produce the allyl alcohol polyoxyethylene ether intermediate.

[0082] Grind 1 g of silica gel particles thoroughly, filter out large particle substances with a filter screen with a pore size of 1 mm, and then dry in a 100℃ oven for 4 h. Mix the above silica gel particles with 3 g of cobalt fluoride and nickel fluoride with a mass ratio of 1:1, and then perform programmed temperature calcination at a temperature increase rate of 3℃ / min to 650℃, and then calcine for 26 h to successfully produce a cobalt-nickel supported silica gel catalyst.

[0083] Take the above allyl alcohol polyoxyethylene ether 150.0 g and 4.8 g of fluorinated cobalt: nickel fluoride of silica gel type supported catalyst with mass ratio of 1:1 into the reaction kettle, replace the air in the kettle with N2 for many times, dehydrate at a vacuum degree greater than or equal to 0.097 MPa and an environment of 115℃-120℃, cool down, slowly add 158 g of an epoxy mixture of ethylene oxide and 892 g of propylene oxide (which needs to be mixed in advance to ensure uniform mixing) to the kettle, until the epoxy addition is complete, incubate the reaction at a temperature of 110℃-115℃ until the pressure basically no longer changes, cool down and degas to successfully produce the allyl alcohol random polyoxyethylene polyoxypropylene ether finished product. The measured index double bond retention rate is 97.5%, and the molecular distribution is 1.07.

[0084] Example 9

[0085] Put 116.0 g of allyl alcohol and 2.0 g of catalyst KOH into a 2.5 L reactor, replace the air in the reactor with N2 for several times, heat up, slowly add 884.0 g of ethylene oxide to the reactor, until the ethylene oxide is added, incubate the reaction at a temperature of 100-105°C until the pressure is basically unchanged, after cooling and degassing, the allyl alcohol polyoxyethylene ether intermediate is successfully prepared.

[0086] Grind 1 g of silica gel particles thoroughly, filter out large particle substances with a filter screen with a pore size of 1 mm, and then dry in a 100°C oven for 4 h. Mix the above silica gel particles with 3 g of cobalt fluoride and nickel fluoride with a mass ratio of 9:1 uniformly, and then perform programmed temperature calcination. Program the temperature to rise to 650°C at a rate of 3°C / min, and then calcine for 26 h after holding at temperature. The cobalt-nickel loaded silica gel catalyst is successfully prepared.

[0087] Take the above allyl alcohol polyoxyethylene ether 200.0 g and 4.8 g of the silica gel type supported catalyst of fluorinated cobalt: fluorinated nickel with a mass ratio of 9:1 into the reactor, replace the air in the reactor with N2 for several times, dehydrate at a vacuum degree greater than or equal to 0.097 MPa and an environment of 115-120°C, cool down, slowly add 150 g of an epoxy mixture of ethylene oxide and 850 g of propylene oxide to the reactor (mix in advance to ensure uniform mixing), until the epoxy is added, incubate the reaction at a temperature of 110-115°C until the pressure is basically unchanged, after cooling and degassing, the allyl alcohol random polyoxyethylene polyoxypropylene ether finished product is successfully prepared. The measured index double bond retention rate is 98.3%, and the molecular distribution is 1.06.

[0088] Example 10

[0089] Put 116.0 g of allyl alcohol and 2.0 g of catalyst KOH into a 2.5 L reactor, replace the air in the reactor with N2 for several times, heat up, slowly add 884.0 g of ethylene oxide to the reactor, until the ethylene oxide is added, incubate the reaction at a temperature of 100-105°C until the pressure is basically unchanged, after cooling and degassing, the allyl alcohol polyoxyethylene ether intermediate is successfully prepared.

[0090] Grind 1 g of silica gel particles thoroughly, filter out large particle substances with a filter screen with a pore size of 1 mm, and then dry in a 100°C oven for 4 h. Mix the above silica gel particles with 3 g of cobalt fluoride and nickel fluoride with a mass ratio of 9:1 uniformly, and then perform programmed temperature calcination. Program the temperature to rise to 650°C at a rate of 1°C / min, and then calcine for 26 h after holding at temperature. The cobalt-nickel loaded silica gel catalyst is successfully prepared.

[0091] Take the above allyl alcohol polyoxyethylene ether 200.0 g and 2.4 g of fluorinated cobalt: fluorinated nickel of silica gel type supported catalyst with mass ratio of 9:1 into the reaction kettle, replace the air in the kettle with N2 for many times, dehydrate at a vacuum degree greater than or equal to 0.097 MPa and an environment of 115℃-120℃, cool down, slowly add 150 g of an epoxy mixture of ethylene oxide and 850 g of propylene oxide to the kettle (need to be mixed in advance to ensure uniform mixing), until the epoxy is added, incubate the reaction at a temperature of 110℃-115℃ until the pressure basically does not change, cool down and degas to successfully produce the allyl alcohol random polyoxyethylene polyoxypropylene ether product. The measured index double bond retention rate is 98.3%, and the molecular distribution is 1.08.

[0092] Example 11

[0093] Put 116.0 g of allyl alcohol and 2.0 g of catalyst KOH into a 2.5 L reaction kettle, replace the air in the kettle with N2 for many times, heat up, slowly add 884.0 g of ethylene oxide to the kettle, until the ethylene oxide is added, incubate the reaction at a temperature of 100℃-105℃ until the pressure basically does not change, cool down and degas to successfully produce the allyl alcohol polyoxyethylene ether intermediate.

[0094] Grind 1 g of silica gel particles thoroughly, filter out large particle substances with a filter screen with a pore size of 1 mm, and then dry in a 100℃ oven for 4 h. Mix the above silica gel particles with 3 g of cobalt fluoride and nickel fluoride with a mass ratio of 9:1 uniformly, and then program the temperature to 650℃ at a heating rate of 5℃ / min, and then calcine for 26 h to successfully produce a cobalt-nickel supported silica gel catalyst.

[0095] Take the above allyl alcohol polyoxyethylene ether 200.0 g and 2.4 g of fluorinated cobalt: fluorinated nickel of silica gel type supported catalyst with mass ratio of 9:1 into the reaction kettle, replace the air in the kettle with N2 for many times, dehydrate at a vacuum degree greater than or equal to 0.097 MPa and an environment of 115℃-120℃, cool down, slowly add 150 g of an epoxy mixture of ethylene oxide and 850 g of propylene oxide to the kettle (need to be mixed in advance to ensure uniform mixing), until the epoxy is added, incubate the reaction at a temperature of 110℃-115℃ until the pressure basically does not change, cool down and degas to successfully produce the allyl alcohol random polyoxyethylene polyoxypropylene ether product. The measured index double bond retention rate is 98.3%, and the molecular distribution is 1.08.

[0096] Example 12

[0097] Put 116.0g allyl alcohol and 2.0g catalyst KOH into a 2.5L reactor, replace the air in the reactor with N2several times, heat up, slowly add 884.0g ethylene oxide to the reactor, wait until the ethylene oxide is added, and then incubate the reaction at a temperature of 100-105°C until the pressure is basically unchanged, and then successfully prepare the allyl alcohol polyoxyethylene ether intermediate after cooling and degassing.

[0098] Grind 1g of silica gel particles thoroughly, filter out large particle substances with a filter screen with a pore size of 1mm, and then dry in a 100°C oven for 4h. Mix the above silica gel particles with 3g of cobalt fluoride and nickel fluoride with a mass ratio of 9:1, and then perform programmed temperature calcination with a temperature increase rate of 3°C / min to 550°C, and then successfully prepare a cobalt-nickel loaded silica gel type catalyst after calcination for 26h.

[0099] Take the above allyl alcohol polyoxyethylene ether 200.0g and 2.4g of the silica gel type supported catalyst of mass ratio 9:1 of cobalt fluoride: nickel fluoride and put it into the reactor, replace the air in the reactor with N2several times, dehydrate at a vacuum degree greater than or equal to 0.097MPa and a temperature of 115-120°C, cool down, and then slowly add 150g of an epoxy mixture of ethylene oxide and 850g of propylene oxide to the reactor (which needs to be mixed in advance to ensure uniform mixing), wait until the epoxy is added, and then incubate the reaction at a temperature of 110-115°C until the pressure is basically unchanged, and then successfully prepare the allyl alcohol random polyoxyethylene polyoxypropylene ether product after cooling and degassing. The measured index double bond retention rate is 97.8%, and the molecular distribution is 1.10.

[0100] Example 13

[0101] Put 116.0g allyl alcohol and 2.0g catalyst KOH into a 2.5L reactor, replace the air in the reactor with N2several times, heat up, slowly add 884.0g ethylene oxide to the reactor, wait until the ethylene oxide is added, and then incubate the reaction at a temperature of 100-105°C until the pressure is basically unchanged, and then successfully prepare the allyl alcohol polyoxyethylene ether intermediate after cooling and degassing.

[0102] Grind 1g of silica gel particles thoroughly, filter out large particle substances with a filter screen with a pore size of 1mm, and then dry in a 100°C oven for 4h. Mix the above silica gel particles with 3g of cobalt fluoride and nickel fluoride with a mass ratio of 9:1, and then perform programmed temperature calcination with a temperature increase rate of 3°C / min to 800°C, and then successfully prepare a cobalt-nickel loaded silica gel type catalyst after calcination for 26h.

[0103] Take the above allyl alcohol polyoxyethylene ether 200.0 g and 2.4 g of mass ratio of 9:1 of fluorinated cobalt: nickel on silica gel type supported catalyst into the reaction kettle, replace the air in the kettle with N2 for many times, dehydrate under the environment of greater than or equal to 0.097 MPa vacuum degree, 115℃-120℃, cool down, slowly add 150 g of epoxy mixture of epoxy ethane and 850 g of epoxy propane (need to be mixed in advance to ensure uniform mixing) to the kettle, until the epoxy is added, incubate the reaction at a temperature of 110℃-115℃ until the pressure basically does not change, cool down and degas to successfully prepare the allyl alcohol random polyoxyethylene polyoxypropylene ether finished product. The measured index double bond retention rate is 97.7%, and the molecular distribution is 1.11.

[0104] The results of the above examples are shown in the following table

[0105]

[0106]

[0107] 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 other catalysts, and the molecular distribution is also lower. As the molecular weight increases, the corresponding double bond retention rate begins to decrease. At the same time, through comparative analysis of the metal content of the self-made catalyst, it can be found that when the content of fluorinated cobalt and fluorinated nickel is 9:1, the product index is the best and the application performance is the best.

[0108] Comparative Example 1

[0109] Put 116.0 g of allyl alcohol and 2.0 g of catalyst KOH into the reaction kettle, replace the air in the kettle with N2 for many times, heat up, slowly add 884.0 g of epoxy ethane to the kettle, until the epoxy ethane is added, incubate the reaction at a temperature of 100℃-105℃ until the pressure basically does not change, cool down and degas to successfully prepare the allyl alcohol polyoxyethylene ether intermediate.

[0110] Take the above allyl alcohol polyoxyethylene ether 120.0 g and 2.4 g of KOH catalyst into a 2.5 L reaction kettle, replace the air in the kettle with N2 for many times, dehydrate under the environment of greater than or equal to 0.097 MPa vacuum degree, 115℃-120℃, cool down, slowly add 162 g of epoxy mixture of epoxy ethane and 918 g of epoxy propane (need to be mixed in advance to ensure uniform mixing) to the kettle, until the epoxy is added, incubate the reaction at a temperature of 110℃-115℃ until the pressure basically does not change, cool down and degas to successfully prepare the allyl alcohol random polyoxyethylene polyoxypropylene ether finished product. The measured index double bond retention rate is 91.1%, and the molecular distribution is 1.21.

[0111] Comparative Example 2

[0112] Put 116.0g allyl alcohol and 2.0g catalyst KOH into the reaction kettle, replace the air in the kettle with N2for many times, heat up, slowly drop 884.0g ethylene oxide into the kettle, until the ethylene oxide is added, incubate the reaction at 100℃-105℃ until the pressure is basically unchanged, after cooling and degassing, the allyl alcohol polyoxyethylene ether intermediate is successfully prepared.

[0113] Put 120.0g of the above allyl alcohol polyoxyethylene ether and 2.4g of sodium methoxide catalyst into a 2.5L reaction kettle, replace the air in the kettle with N2for many times, dehydrate at a vacuum degree greater than or equal to 0.097MPa and 115℃-120℃, cool down, slowly drop 162g of an epoxy mixture of ethylene oxide and propylene oxide (need to be mixed in advance to ensure uniform mixing) into the kettle, until the epoxy is added, incubate the reaction at 110℃-115℃ until the pressure is basically unchanged, after cooling and degassing, the allyl alcohol random polyoxyethylene polyoxypropylene ether finished product is successfully prepared. The measured indicators are double bond retention rate 93.3%, molecular distribution 1.18.

[0114] Comparative Example 3

[0115] Put 116.0g allyl alcohol and 2.0g catalyst KOH into the reaction kettle, replace the air in the kettle with N2for many times, heat up, slowly drop 884.0g ethylene oxide into the kettle, until the ethylene oxide is added, incubate the reaction at 100℃-105℃ until the pressure is basically unchanged, after cooling and degassing, the allyl alcohol polyoxyethylene ether intermediate is successfully prepared.

[0116] Put 120.0g of the above allyl alcohol polyoxyethylene ether and 2.4g of sodium methoxide catalyst into a 2.5L reaction kettle, replace the air in the kettle with N2for many times, dehydrate at a vacuum degree greater than or equal to 0.097MPa and 115℃-120℃, cool down, slowly drop 162g of an epoxy mixture of ethylene oxide and propylene oxide (need to be mixed in advance to ensure uniform mixing) into the kettle, until the epoxy is added, incubate the reaction at 110℃-115℃ until the pressure is basically unchanged, after cooling and degassing, the allyl alcohol random polyoxyethylene polyoxypropylene ether finished product is successfully prepared. The measured indicators are double bond retention rate 93.3%, molecular distribution 1.18.

[0117] The results of the comparative examples are shown in the following table.

[0118]

[0119] From the data in the analysis table of the examples and comparative examples, it can be seen that the self-made cobalt-nickel loaded silica gel type catalyst of the present application has a catalytic effect obviously higher than that of the experimental methods described in the comparative examples, wherein the double bond retention rate is much higher than that of various experimental methods in the comparative examples, and the molecular distribution is also correspondingly narrower. Even the DMC catalysis in the comparative examples, which has the best catalytic effect, is much lower than the finished product index of the catalysis of the present application.

[0120] The calculation formula of the double bond retention rate is as follows, in percentage (%):

[0121]

[0122] In the formula:

[0123] IV1 is the actual iodine value, which is determined according to the provisions of GB / T 13892-2012;

[0124] IV2 is the theoretical iodine value, which is obtained from formula (2).

[0125] Theoretical iodine value:

[0126]

[0127] In the formula:

[0128] 100 is a conversion coefficient;

[0129] 254 is the molar mass of iodine, in grams per mole (g / mol);

[0130] 56110 is a conversion coefficient, in milligrams of potassium hydroxide per mole (mg / mol) in terms of potassium hydroxide (KOH);

[0131] OHV is the hydroxyl value of the sample, which is determined according to GB / T12008.3-2009.

[0132] The average molecular weight and molecular weight distribution of the polymer are determined by plastic volume exclusion chromatography, standard number: GB / T36214.1-2018.

[0133] The above embodiments are only preferred embodiments of the present application, and cannot be used to limit the scope of protection of the present application. Any non-substantial changes and substitutions made by those skilled in the art on the basis of the present application are within the scope of protection claimed by the present application.

Claims

1. A method for preparing a cobalt-nickel supported silica gel type catalyst, characterized by, The preparation method comprises the following steps: The silica gel is mixed with a loading agent, the loading agent is composed of cobalt fluoride and nickel fluoride, the mass ratio of the silica gel to the loading agent is 1:3, and the mass ratio of the cobalt fluoride to the nickel fluoride is 0.1-9:1; After mixing, the mixture is calcined at a temperature increasing rate of 1-5 ℃ / min to 550-800 ℃, and the calcination is maintained for at least 24 hours to obtain the catalyst.

2. The production method according to claim 1, wherein In the calcination step, the calcination is performed at a temperature increasing rate of 2-4 ℃ / min to 600-700 ℃, and the calcination is maintained for 24-28 hours.

3. The production method according to claim 2, wherein In the calcination step, the calcination is performed at a temperature increasing rate of 3 ℃ / min to 650 ℃.

4. The production method according to claim 1, wherein Before the mixing step, the preparation method further comprises: The silica gel is ground and sieved using a filter sieve with a size of 1 mm-2 mm. After sieving, the silica gel is dried in an oven at a temperature of 80-100 ℃ for 4-6 hours.

5. Use of a cobalt nickel on silica gel type catalyst, characterized in that, The catalyst according to any one of claims 1 to 4 is used to catalyze the synthesis of allyl alcohol polyoxyethylene polyoxypropylene ether from allyl alcohol polyoxyethylene ether, ethylene oxide and propylene oxide, so as to improve the double bond retention rate and narrow the molecular distribution.

6. A method for synthesizing an allyl polyoxyethylene polyoxypropylene ether, characterized by, The preparation method comprises the following steps: The allyl alcohol polyoxyethylene ether and the cobalt-nickel loaded silica gel type catalyst according to any one of claims 1 to 4 are placed in a reaction kettle, the air in the kettle is replaced with inert gas for multiple times, and the amount of the cobalt-nickel loaded silica gel type catalyst is 0.8‰-4‰ of the mass of the allyl alcohol polyoxyethylene ether; Dehydration is performed at a vacuum degree greater than or equal to 0.097 MPa and at an environment of 115-120 ℃; After dehydration, the temperature is lowered, and an epoxy mixture is added dropwise into the reaction kettle, the molar ratio of the allyl alcohol polyoxyethylene ether to the epoxy mixture is 1:2-1:50, the epoxy mixture is composed of ethylene oxide and propylene oxide, and the molar ratio of the ethylene oxide to the propylene oxide is 1:2-1:10; After the epoxy mixture is added dropwise, the reaction is aged at a temperature of 100-120 ℃ until the pressure is basically unchanged.

7. The method of synthesis of claim 6, wherein, The aging reaction temperature of the epoxy mixture is 110-115 ℃.

8. The method of synthesis of claim 6, wherein, The preparation of the allyl alcohol polyoxyethylene ether comprises: The allyl alcohol and a strong base catalyst are put into a reaction kettle, and the air in the kettle is replaced with inert gas for multiple times; The temperature is increased, ethylene oxide is added dropwise into the kettle, and after the addition of the ethylene oxide is completed, the reaction is aged at a temperature of 95-115 ℃ until the pressure is basically unchanged, the temperature is lowered, and the allyl alcohol polyoxyethylene ether is obtained by degassing, the molar ratio of the allyl alcohol to the ethylene oxide is 1:2-1:50, and the amount of the strong base catalyst is 1‰-3‰ of the total mass of the allyl alcohol and the ethylene oxide.

9. The method of synthesis of claim 8, wherein, In the step of preparing the allyl alcohol polyoxyethylene ether, the aging reaction temperature is 100-105 ℃.

10. The method of synthesis of claim 6, wherein, The amount of the cobalt-nickel loaded silica gel type catalyst is 2‰-4‰ of the mass of the allyl alcohol polyoxyethylene ether.

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