WO2022052067A1 - 金属有机骨架材料mil-125及其制备方法和应用 - Google Patents

金属有机骨架材料mil-125及其制备方法和应用 Download PDF

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WO2022052067A1
WO2022052067A1 PCT/CN2020/114895 CN2020114895W WO2022052067A1 WO 2022052067 A1 WO2022052067 A1 WO 2022052067A1 CN 2020114895 W CN2020114895 W CN 2020114895W WO 2022052067 A1 WO2022052067 A1 WO 2022052067A1
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framework material
organic framework
metal
material mil
preparation
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French (fr)
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邢嘉成
杨丽平
袁丹华
徐云鹏
刘中民
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中国科学院大连化学物理研究所
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Priority to PCT/CN2020/114895 priority Critical patent/WO2022052067A1/zh
Priority to US18/025,660 priority patent/US20230338935A1/en
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Definitions

  • the present application relates to a metal-organic framework material MIL-125, a preparation method and application thereof, and belongs to the field of material preparation.
  • Metal-organic framework material MIL-125 is a typical titanium-containing metal-organic framework material. It is the first titanium-doped carboxylic acid complex with crystal structure and pore structure. It is widely used in photocatalytic oxidation, adsorption and separation. .
  • metal organic framework material MIL-125 Since the titanium source is easily hydrolyzed, it is difficult to control its hydrolysis rate during synthesis. Therefore, in the current synthesis methods, it is necessary to strictly remove water during the synthesis process, and most of the operations need to be carried out in a glove box, which seriously affects the application of metal-organic framework material MIL-125 and its industrial scale-up process.
  • the metal-organic framework material MIL-125 is a typical microporous material with more catalytic active centers and good catalytic oxidation performance.
  • the catalytic oxidation It has important applications in the reaction system of hexene.
  • the purpose of the present application is to provide a titanium-containing metal organic framework material MIL-125, which has a large number of microporous structures, a large external specific surface area, and has higher catalytic activity in oxidation.
  • a metal organic framework material MIL-125 is provided, the metal organic framework material MIL-125 is a cake-shaped crystal block; the external specific surface area is 160-220 m 2 /g.
  • the mass content of particles with a particle size of 1.6-1.8 microns is 85-95%.
  • the external specific surface area of the metal-organic framework material MIL-125 provided in this application is as high as 236 m 3 /g, which is much larger than the external specific surface area of the traditional metal-organic framework material MIL-125 (the external specific surface area is 91-98 m 3 /g). ), which has the advantages of reducing the mass transfer resistance and increasing the reaction diffusion path, which is conducive to the diffusion of reaction raw materials and products, and improves the reaction conversion rate.
  • the metal-organic framework material MIL-125 in the present application has regular morphology and uniform size, while the traditional metal-organic framework material MIL-125 is fragmented, with extremely uneven particle size distribution and irregular morphology.
  • the metal-organic framework material MIL-125 contains micropores with a specific surface area of 1000-1500 m 2 /g.
  • the metal organic framework material MIL-125 contains micropores with a specific surface area of 1200-1300 m 2 /g.
  • the microporous metal organic framework material MIL-125 has a larger micropore area.
  • the particle size of the metal organic framework material MIL-125 is 1.6-1.8 microns.
  • a method for preparing the above metal-organic framework material MIL-125 is provided, and the metal-organic framework material MIL-125 is prepared by using a titanium ester polymer as a titanium source.
  • the titanium ester polymer in the present application is formed by connecting a titanium source to the same polymer.
  • the method includes: crystallizing a mixture containing a titanium ester polymer, an organic ligand and an organic solvent to obtain the metal-organic framework material MIL-125;
  • the organic ligand is terephthalic acid; and the crystallization is solvothermal crystallization.
  • a titanium source that is insoluble in water and not hydrolyzed that is, titanium ester polymers are insoluble in water and not hydrolyzed, so in the process of synthesizing the metal organic framework material MIL-125, it is not Strict removal of water is required, and there will be no precipitation of titanium dioxide, which enables mass production of metal-organic framework material MIL-125, which is suitable for industrial applications.
  • the preparation method of the metal organic framework material MIL-125 in this application includes:
  • step b) carrying out vacuum distillation after the reaction in step a), the vacuum degree of the control system is 0.01 ⁇ 5KPa, the reaction temperature is between 170 ⁇ 230°C, and the reaction time is between 0.5 ⁇ 5 hours, to obtain the titanium ester polymer;
  • step b) mixing the titanium ester polymer obtained in step b) with terephthalic acid and an organic solvent, and stirring at a temperature not higher than 120° C. for 0-100 hours to obtain a gel mixture;
  • step d) The gel mixture obtained in step c) is heated to 100-200° C. under airtight conditions, and crystallized under autogenous pressure for 0-30 days to obtain the microporous metal organic framework material MIL-125.
  • the crystallization is carried out dynamically or statically.
  • the solid product is separated, washed to neutrality, and dried to obtain the metal organic framework material MIL-125.
  • the titanate polymer is obtained by transesterification of raw materials containing titanate and polyol.
  • the transesterification is performed under stirring conditions.
  • reaction conditions for the transesterification are: in an inert atmosphere, the reaction is carried out at 80-180° C. for 2-10 hours.
  • the upper limit of the reaction temperature of the transesterification is selected from 85°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 175°C or 180°C;
  • the lower limit is selected from 80°C, 85°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C or 175°C.
  • the upper limit of the reaction time of the transesterification is selected from 2.5 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 9.5 hours or 10 hours; the lower limit is selected from 2 hours, 2.5 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours or 9.5 hours.
  • the reaction conditions for the transesterification are: nitrogen protection, the reaction temperature is between 80 and 180°C, and the reaction time is between 2 and 10 hours.
  • reaction conditions of the transesterification are: in an inert atmosphere, the reaction is carried out at 100-160° C. for 2-10 hours.
  • reaction conditions of the transesterification are: in an inert atmosphere, the reaction is carried out at 100-160° C. for 4-8 hours.
  • reaction conditions for the transesterification are as follows: under nitrogen protection, the reaction temperature is between 100 and 160° C., and the reaction time is between 4 and 8 hours.
  • the inactive atmosphere includes at least one of nitrogen gas and inert gas.
  • the conversion of the transesterification is between 60% and 80%.
  • the conversion of the transesterification is not greater than 90%.
  • the transesterification further includes distillation under reduced pressure.
  • the conditions of the vacuum distillation are: under the condition that the vacuum degree is 0.01-5KPa, the reaction is performed at 170-230°C for 0.5-5 hours.
  • the degree of vacuum is 0.05-3Kpa.
  • the upper limit of the temperature of the vacuum distillation is selected from 175°C, 180°C, 190°C, 200°C, 210°C, 220°C, 225°C or 230°C; the lower limit is selected from 170°C, 175°C, 180°C, 190°C, 200°C, 210°C, 220°C or 225°C.
  • the time upper limit of the vacuum distillation is selected from 0.8 hours, 1 hour, 2 hours, 3 hours, 4 hours, 4.5 hours or 5 hours; the lower limit is selected from 0.5 hours, 0.8 hours, 1 hour, 2 hours, 3 hours, 4 hours or 4.5 hours.
  • the upper limit of the vacuum degree of the vacuum distillation is selected from 0.02Kpa, 0.03Kpa, 0.05Kpa, 0.08Kpa, 0.1Kpa, 0.5Kpa, 1Kpa, 1.5Kpa, 2Kpa, 2.5Kpa, 3Kpa, 3.5Kpa, 4Kpa, 4.5Kpa or 5Kpa; the lower limit is selected from 0.01KPa, 0.02Kpa, 0.03Kpa, 0.05Kpa, 0.08Kpa, 0.1Kpa, 0.5Kpa, 1Kpa, 1.5Kpa, 2Kpa, 2.5Kpa, 3Kpa, 3.5Kpa, 4Kpa or 4.5Kpa.
  • the molar ratio of the titanate and polyol satisfies:
  • Titanate: polyol (0.5 to 5) x: 4
  • x is the number of moles of hydroxyl groups contained in each mole of the polyol
  • the moles of the above substances are calculated based on the moles of the substances themselves.
  • the molar ratio of the titanate and polyol satisfies:
  • Titanate: polyol (0.8 to 1.2) x: 4
  • x is the number of moles of hydroxyl groups contained in each mole of the polyol
  • the moles of the above substances are calculated based on the moles of the substances themselves.
  • the upper limit of the molar ratio of the titanate to polyol is selected from 0.85x:4, 0.9x:4, 0.95x:4, 1.0x:4, 1.15x:4 or 1.2x:4; the lower limit is selected from From 0.8x:4, 0.85x:4, 0.9x:4, 0.95x:4, 1.0x:4 or 1.15x:4; wherein x is the number of moles of hydroxyl groups contained in each mole of the polyol.
  • the titanate is selected from at least one of the compounds with the chemical formula shown in formula II:
  • R 5 , R 6 , R 7 and R 8 are independently selected from one of C 1 -C 10 alkyl groups.
  • R 5 , R 6 , R 7 , and R 8 in formula II are independently selected from one of C 1 -C 4 alkyl groups.
  • the titanate includes at least one of tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetrahexyl titanate, and tetraisooctyl titanate.
  • the titanate is one or more of tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetrahexyl titanate, tetraisooctyl titanate, and the like.
  • the polyols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4- Butanediol, 1,6-hexanediol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 800, 1,4-cyclohexanediol, 1,4-cyclohexanediol At least one of hexanedimethanol, terephthalic alcohol, glycerol, trimethylolpropane, pentaerythritol, xylitol, and sorbitol.
  • the number of hydroxyl groups contained in the polyol is greater than or equal to 2; including ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3- Propylene glycol, 1,4-butanediol, 1,6-hexanediol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 800, 1,4-cyclohexanediol , 1,4-cyclohexanedimethanol, terephthalimethanol, glycerol, trimethylolpropane, pentaerythritol, xylitol, sorbitol, etc., or a mixture of any of them.
  • 2 including ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3- Propylene glycol, 1,4-butanediol, 1,6
  • the titanium ester polymer includes at least one of a titanium polyethylene glycol ester polymer, a titanium glycol ester polymer, and a titanium terephthalate polymer.
  • the crystallization conditions are: under airtight conditions, the temperature is 100-200° C., and the crystallization under autogenous pressure does not exceed 30 days.
  • the upper limit of the crystallization temperature is selected from 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C or 200°C; the lower limit is selected from 100°C, 110°C °C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C or 190°C.
  • the upper time limit of the crystallization is selected from 1 hour, 5 hours, 10 hours, 15 hours, 20 hours, 1 day, 2 days, 5 days, 10 days, 12 days, 15 days, 20 days, 25 days days, 28 days or 30 days; the lower limit is selected from 0.5 hours, 1 hour, 5 hours, 10 hours, 15 hours, 20 hours, 1 day, 2 days, 5 days, 10 days, 12 days, 15 days, 20 days, 25 days or 28 days.
  • the crystallization conditions are: under airtight conditions, the temperature is 120-180° C., and the crystallization is performed under autogenous pressure for 1-15 days.
  • the molar ratio of the titanium ester polymer and the organic ligand is (0.5-2):1;
  • the number of moles of the titanium ester polymer is calculated by the titanium content in the titanium ester polymer
  • the titanium content in the titanium ester polymer is measured in moles of TiO 2 .
  • the upper limit of the molar ratio of the titanium ester polymer to terephthalic acid is selected from 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.82, 0.84, 0.86, 0.88, 0.92, 0.94, 0.96, 0.98, 1.2, 1.5, 1.6, 1.8, 1.9 or 2.0; lower limit selected from 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.82, 0.84, 0.86, 0.88, 0.92, 0.94, 0.96, 0.98, 1.2, 1.5, 1.6 , 1.8, 1.9.
  • the number of moles of the titanium ester polymer is calculated as the sum of the titanium content in the titanium ester polymer; the content of titanium in the titanium ester polymer is calculated as the number of moles of TiO 2 .
  • the organic solvent is selected from at least one of N,N-dimethylformamide and methanol.
  • the organic solvent includes N,N-dimethylformamide and methanol; the volume ratio of N,N-dimethylformamide and methanol is (6-15):1.
  • the upper limit of the volume ratio of the N,N-dimethylformamide to methanol is selected from 6.2, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.5, 11.0, 12.0, 13.0, 14.0 or 15.0 ; the lower limit is selected from 6.0, 6.2, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.5, 11.0, 12.0, 13.0, 14.0.
  • the titanium ester polymer is prepared by transesterification of titanate and polyol.
  • the preparation method of the metal organic framework material MIL-125 includes:
  • step b' connecting the device after step a') reaction with a water pump or an oil pump to carry out underpressure distillation to make the transesterification more complete, the vacuum degree of the control system is 0.01 ⁇ 5KPa, the reaction temperature is between 170 ⁇ 230°C, and the reaction time Between 0.5 and 5 hours, the conversion rate of the transesterification reaction is greater than 90%, and the titanium ester polymer is obtained;
  • step b' mixing the titanium ester polymer obtained in step b') with terephthalic acid, an organic solvent, etc., and stirring at a temperature not higher than 120° C. for 0-100 hours to obtain a gel mixture;
  • step d' put the gel mixture obtained in step c') into the autoclave, seal it, heat it up to 100-200°C, and crystallize under autogenous pressure for 0-30 days;
  • the preparation method of the titanium ester polymer includes:
  • the control system vacuum degree is at 0.01 ⁇ 5KPa
  • the reaction temperature is between 170 ⁇ 230 °C
  • the reaction time is between In 0.5 to 5 hours
  • the conversion rate of the transesterification reaction is greater than 90%
  • the titanium ester polymer is obtained.
  • the synthesis process of the titanium-containing microporous metal-organic framework material MIL-125 of the present invention is divided into two steps: the first step is to mix the titanium ester and the polyol to carry out the transesterification reaction, and the generated alcohol is distilled out to obtain the titanium ester polymer In the second step, the titanium ester polymer, terephthalic acid, organic solvent, etc. are solvothermally crystallized in the reactor to obtain the titanium-containing microporous metal-organic framework material MIL-125. In this method, the titanium source is connected to the same polymer to form a titanium ester polymer, which can prevent the precipitation of TiO 2 .
  • the synthesis process is simple, and the steps of operating in a glove box and solvent removal in the traditional synthesis process are not required.
  • the synthesized metal-organic framework material MIL-125 has a large number of microporous structures, therefore, the metal-organic framework material MIL-125 obtained by this method has higher catalytic activity in oxidation.
  • the titanium-containing microporous metal-organic framework material MIL-125 prepared according to any one of the above-mentioned methods is used for the selective oxidation reaction of organic substances containing H 2 O 2 and tert-butyl hydroperoxide.
  • a method for preparing epoxycyclohexane comprising: mixing a raw material containing compound A and cyclohexene in the presence of a metal organic framework material MIL-125, reaction, the epoxy cyclohexane can be obtained;
  • the compound A is selected from at least one of hydrogen peroxide and tert-butyl hydroperoxide;
  • the metal-organic framework material MIL-125 is selected from any one of the above-mentioned metal-organic framework material MIL-125 and the metal-organic framework material MIL-125 prepared according to the above method.
  • the mass ratio of compound A, cyclohexene and metal organic framework material MIL-125 is 0.3-1.0:0.3-1.2:0.05-0.1.
  • the reaction conditions are as follows: the reaction temperature is 35-80° C.; and the reaction time is 2-8 h.
  • the method includes: reacting a mixture containing a metal-organic framework material MIL-125, a solvent, cyclohexene, and compound A to obtain the epoxycyclohexane.
  • the concentration of the compound A is 30% to 55%.
  • the solvent is selected from at least one of methanol and N,N-dimethylformamide.
  • reaction is carried out in a water bath.
  • C 1 -C 10 , C 1 -C 4 and the like all refer to the number of carbon atoms contained in the group.
  • alkyl is a group formed by the loss of any hydrogen atom on the molecule of an alkane compound.
  • the external specific surface area refers to the specific surface area of the porous material obtained by the t-Plot method in the measurement of physical adsorption, that is, the total BET area of the material minus its micropore specific surface area.
  • the metal-organic framework material MIL-125 provided by the present application has a regular morphology, is a regular round cake, and has a uniform size. It has a large number of microporous structures and a large external specific surface area, which effectively reduces the mass transfer resistance and is beneficial to the reaction process Diffusion of products and reactants, with higher catalytic activity in oxidation.
  • the titanium source in the preparation method is connected to the same polymer to form a titanium ester polymer, which is not hydrolyzed and insoluble in water, which can prevent the precipitation of TiO 2 , and the synthesis process is simple and does not require operation and solvent in a glove box in the traditional synthesis process. step of removing water.
  • FIG. 1 is an XRD pattern of the product synthesized according to Example 1 of the present invention.
  • SEM scanning electron microscope
  • Example 3 is a physical adsorption isotherm (BET) diagram of the product synthesized according to Example 1 of the present invention.
  • Example 4 is a laser particle size distribution diagram of a product synthesized according to Example 1 of the present invention.
  • the SEM morphology analysis of the product adopts a Hitachi SU8020 scanning electron microscope.
  • the physical adsorption and pore distribution analysis of the product adopts the ASAP2020 automatic physical instrument of Mike Company.
  • the particle size distribution analysis of the product adopts the ParticleTrack G600B particle size analyzer of METTLER TOLEDO.
  • the transformation efficiency of transesterification is calculated by the following method:
  • n determines that the number of groups participating in the transesterification reaction is n, and the total number of moles of titanates in the reaction raw materials is m, then the conversion rate of the transesterification reaction is: n/4m.
  • the method for preparing the metal-organic framework material MIL-125 is as follows:
  • step b) connecting the device after step a) with a water pump or an oil pump to carry out vacuum distillation to make the transesterification more complete, the vacuum degree of the control system is at 0.01 ⁇ 5KPa, the reaction temperature is between 170 ⁇ 230 °C, and the reaction time is between In 0.5 to 5 hours, the conversion rate of the transesterification reaction is greater than 90%, and the titanium ester polymer is obtained.
  • step b) Mix the titanium ester polymer obtained in step b) with terephthalic acid, organic solvent, etc., and keep stirring at a temperature not higher than 120° C. or stand still for 0-100 hours to obtain a gel mixture:
  • step d) put the gel mixture obtained in step c) into the autoclave, seal it, heat up to 100-200°C, and crystallize under autogenous pressure for 0-30 days;
  • the titanate in the described step a) is one or more of tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetrahexyl titanate, tetraisooctyl titanate, etc. ;
  • the general formula of the polyol in the step a) is R-(OH) x , where x ⁇ 2; including ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol , 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol One of alcohol 800, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, terephthalic alcohol, glycerol, trimethylolpropane, pentaerythritol, xylitol, sorbitol, etc. or any mixture of several.
  • titanate and polyol have the following molar ratio:
  • the reaction in the step a) is carried out under nitrogen protection, the reaction temperature is between 80 and 180°C, and the reaction time is between 2 and 10 hours.
  • the conversion rate of the transesterification reaction in the step a) is between 65% and 80%.
  • the step b) is carried out under reduced pressure distillation, and the vacuum degree of the control system is 0.05-3KPa.
  • the reaction temperature is between 170 and 230° C.
  • the reaction time is between 0.5 and 5 hours.
  • the conversion rate of the transesterification reaction in the step b) is greater than 90%.
  • the titanium ester polymer and terephthalic acid have the following molar ratios:
  • the number of moles of the titanium ester polymer is calculated by the titanium content in the titanium ester polymer
  • the titanium content in the titanium ester polymer is measured in moles of TiO 2 ;
  • the organic solvent described in the step c) is dimethylformamide and methanol, and its volume ratio satisfies:
  • the stirring process in the step c) can be omitted or performed, and the stirring temperature is 20-100° C. and the stirring time is 1-50 hours.
  • the temperature for crystallization in the step d) is 120-180° C.
  • the crystallization time is 1-15 days.
  • the crystallization process in the step d) is carried out statically or dynamically.
  • the metal-organic framework material MIL-125 obtained in the step e) has a microporous structure with narrow pore size distribution and less non-framework titanium.
  • the specific batching process is as follows: add 5g of tetraethyl titanate and 10g of polyethylene glycol 200 into a three-necked flask and mix evenly, carry out a transesterification reaction under stirring, connect a distillation device, pass nitrogen protection, heat up to 175 ° C, and react Time 5 hours, the conversion rate of the transesterification reaction is 75%, connect the water pump to carry out vacuum distillation to make the transesterification reaction more complete, control the vacuum degree of the system at 3KPa, the reaction temperature is 200 °C, the reaction time is 1 hour, the transesterification reaction The conversion rate was 92%, and the titanium polyethylene glycol ester polymer was obtained.
  • the specific batching process is as follows: add 5g of tetraethyl titanate and 3.13g of ethylene glycol into a three-necked flask and mix evenly, carry out a transesterification reaction under stirring, connect a distillation device, pass nitrogen protection, heat up to 100 ° C, and the reaction time After 5 hours, the conversion rate of the transesterification reaction was 70%. Connect the water pump to carry out vacuum distillation to make the transesterification reaction more complete. The ratio is 90%, and the titanium glycol ester polymer is obtained.
  • the specific batching process is as follows: add 5g of tetrabutyl titanate and 11.35g of terephthalic alcohol into a three-necked flask and mix evenly, carry out a transesterification reaction under stirring, connect a distillation device, pass nitrogen protection, heat up to 160 ° C, and react Time 5 hours, the conversion rate of the transesterification reaction is 80%, connect the water pump to carry out vacuum distillation to make the transesterification reaction more complete, control the vacuum degree of the system at 3KPa, the reaction temperature is 230 °C, the reaction time is 1 hour, the transesterification reaction is 1 hour. The conversion rate was 95%, and the titanium terephthalate polymer was obtained.
  • the crystallization described in Examples 1 to 3 is static crystallization.
  • the metal-organic framework material MIL-125 was prepared by the same method as in Example 1, and the difference between the specific preparation conditions and Example 1 is shown in Table 1 and Table 2.
  • Example 4 The crystallization involved in Example 4 is dynamic crystallization, and the crystallization conditions are: a rotary oven is used, the crystallization temperature and crystallization time are shown in Table 2, and the rotation speed of the rotary oven is 35 rpm.
  • the specific batching process is as follows: add 5g of tetraethyl titanate and 10g of polyethylene glycol 200 into a three-necked flask and mix evenly, carry out a transesterification reaction under stirring, connect a distillation device, pass nitrogen protection, heat up to 175 ° C, and react Time 5 hours, the conversion rate of the transesterification reaction is 75%, connect the water pump to carry out vacuum distillation to make the transesterification reaction more complete, control the vacuum degree of the system at 3KPa, the reaction temperature is 200 °C, the reaction time is 1 hour, the transesterification reaction The conversion rate was 92%, and the titanium polyethylene glycol ester polymer was obtained.
  • titanium ester polymer obtained in this patent is resistant to hydrolysis and is insoluble in water
  • 5g of the obtained titanium polyethylene glycol ester polymer was mixed with 5g of terephthalic acid, 18ml of dimethylformamide, 2ml of methanol, 0.5 g water was stirred at room temperature for 2 hours and then transferred to a stainless steel autoclave.
  • the autoclave was sealed and put into an oven that has been raised to a constant temperature of 120°C, and crystallized under autogenous pressure for 2 days.
  • the solid product was centrifuged, washed with deionized water until neutral, and dried in air at 110°C to obtain a microporous metal-organic framework material MIL-125, marked as A8.
  • the crystallization is static crystallization.
  • Samples A1 to A8 in Examples 1 to 5 were subjected to XRD phase structure analysis, with Example 1 as a typical representative, Figure 1 is the XRD pattern of the sample A1 prepared in Example 1, as can be seen from the figure It can be seen that the sample A1 is a microporous metal organic framework material MIL-125.
  • the XRD pattern of the microporous metal organic framework material MIL-125 synthesized by this patent has clear peaks and The peak shape is sharp, there is no tailing, and the baseline is flat, indicating that the microporous metal-organic framework material MIL-125 synthesized by this patent has a regular structure, no impurity crystals, and no amorphous products are formed.
  • test results of other samples are only slightly different from the pattern of sample A1 in Example 1 in the intensity of the diffraction peaks, which are all microporous metal-organic framework materials MIL-125.
  • Samples A1 to A8 in Examples 1 to 5 were analyzed by SEM, with Example 1 as a typical representative.
  • Figure 2 is the SEM spectrum of the sample A1 prepared in Example 1, and its scanning electron microscope spectrum can be seen , the synthesized products have regular morphology, all are round cakes, and their size distribution is uniform, and no other miscellaneous crystals and amorphous products are formed.
  • test results of other samples are similar to the test results of sample 1 in Example 1.
  • the sample is a typical I-type adsorption isotherm and has a typical microporous structure.
  • test results of other samples are similar to the test results of sample A1 in Example 1, and all the samples have a specific surface area of 1000-1500 square meters per gram.
  • the external specific surface area of the samples was calculated by the t-Plot method, and the external specific surface areas of the samples A1 to A6 prepared in Examples 1 to 4 were 160 to 214 square meters per gram.
  • test results of other samples are similar to the test results of sample A1 in Example 1, and the samples all have an external specific surface area of 160-220 square meters per gram.
  • Example 1 The samples A1 to A8 of Examples 1 to 5 were subjected to laser particle size analysis, with Example 1 as a typical representative.
  • Figure 4 is the particle size distribution diagram of the sample A1 prepared in Example 1. It can be seen from the figure that the synthesized The particle size distribution of the sample is relatively concentrated and uniform, and the particle size is between 1 and 2 microns.
  • test results of other samples are similar to the test results of sample 1 in Example 1.
  • the particle size distribution of the sample is relatively concentrated and uniform, and the particle size is between 1 and 2 microns.
  • Embodiment 11 Determination of oxidation reaction performance
  • a typical representative is sample A1, and the specific steps include:
  • sample A1 (as a catalyst), add 10ml of acetonitrile, 0.36g of cyclohexene, 0.5g of hydrogen peroxide (30% mass fraction) in a round-bottomed flask, under the condition of heating in a water bath at 60 degrees Celsius, condense and reflux for 4 hours .
  • the reaction results of sample A1 are: the conversion rate of cyclohexene is 38%, the selectivity of epoxidation products in the product is 78.5%, the conversion rate of hydrogen peroxide is 73.2%, and the selectivity of oxidant to epoxidation products is 72.2%.
  • the conversion rate of cyclohexene is 26%, and the epoxidation product selectivity in the product is only 25%.

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Abstract

本申请公开了一种金属有机骨架材料MIL-125及其制备方法和应用，所述金属有机骨架材料MIL-125为圆饼状的晶块；外比表面积为160～220m 2/g。本申请提供的金属有机骨架材料MIL-125，具有大量的微孔结构、外比表面积大，在氧化上具有更高的催化活性。

Description

金属有机骨架材料MIL-125及其制备方法和应用 技术领域
本申请涉及一种金属有机骨架材料MIL-125及其制备方法和应用，属于材料制备领域。
背景技术
金属有机骨架材料MIL-125是一种典型的含钛金属有机骨架材料，是第一个具有晶体结构和孔结构的钛掺杂羧酸配合物，被广泛的应用于光催化氧化，吸附分离中。
目前合成金属有机骨架材料MIL-125上存在较大的困难，由于钛源极易水解，在合成中很难控制其水解速率。因此目前合成的方法中，都需要在合成过程中严格除水，大部分的操作需要在手套箱中进行，这严重的影响了金属有机骨架材料MIL-125的应用和其工业化放大过程。
与此同时，金属有机骨架材料MIL-125是典型的微孔材料，同时具有较多的催化活性中心，具有良好的催化氧化性能，在采用叔丁基过氧化氢或者双氧水为氧化剂，催化氧化环己烯的反应体系中，具有重要应用。
发明内容
本申请的目的在于提供一种含钛金属有机骨架材料MIL-125，具有大量的微孔结构、外比表面积大，在氧化上具有更高的催化活性。
根据本申请的第方面，提供了一种金属有机骨架材料MIL-125，所述金属有机骨架材料MIL-125为圆饼状的晶块；外比表面积为160～220m 2/g。
可选地，所述金属有机骨架材料MIL-125中，粒径为1.6～1.8微米的粒子的质量含量为85～95％。
具体地，本申请中提供的金属有机骨架材料MIL-125外比表面积高达236m 3/g，远大于传统的金属有机骨架材料MIL-125的外比表 面积(外比表面积为91～98m 3/g)，具有降低传质阻力和增加反应扩散路径，利于反应原料和产物的扩散，提高反应转化率的优势。
具体地，本申请中的金属有机骨架材料MIL-125形貌规整，大小均一，而传统的金属有机骨架材料MIL-125为碎片状，粒度分布极不均一，形貌不规则。
可选地，所述金属有机骨架材料MIL-125中含有比表面积为1000-1500m 2/g的微孔。
可选地，所述金属有机骨架材料MIL-125中含有比表面积为1200-1300m 2/g的微孔。
可选地，所述微孔金属有机骨架材料MIL-125具有较大的微孔面积。
可选地，所述金属有机骨架材料MIL-125的粒径为1.6～1.8微米。
根据本申请的第二方面，提供了一种上述金属有机骨架材料MIL-125的制备方法，以钛酯类聚合物为钛源，制备得到所述金属有机骨架材料MIL-125。
具体地，本申请中的钛酯类聚合物由钛源连接在同一种聚合物上形成。
可选地，所述方法包括：将含有钛酯类聚合物、有机配体和有机溶剂的混合物，晶化，即可得到所述金属有机骨架材料MIL-125；
所述有机配体为对苯二甲酸；所述晶化为溶剂热晶化。
具体地，本申请中，提供了一种不溶于水且不水解的钛源，即钛酯类聚合物不溶于水，且不水解，因此在合成金属有机骨架材料MIL-125的过程中，不需要严格除水，也不会有二氧化钛的沉淀生成，这就可以实现金属有机骨架材料MIL-125的大量生产，适用于工业应用。
可选地，本申请中金属有机骨架材料MIL-125的制备方法包括：
a)将钛酸酯与多元醇混合均匀，搅拌状态下进行酯交换反应，通氮气保护，反应温度介于80～180℃，反应时间介于2～10小时；
b)将步骤a)反应后进行减压蒸馏，控制体系真空度在0.01～5KPa，反应温度介于170～230℃，反应时间介于0.5～5小时，即得钛酯类聚合物；
c)将步骤b)得到的钛酯类聚合物与对苯二甲酸、有机溶剂混合，并保持在不高于120℃的温度下搅拌0～100小时，得到凝胶混合物；
d)将步骤c)所得的凝胶混合物在密闭条件下，升温到100～200℃，在自生压力下晶化0～30天，即得微孔金属有机骨架材料MIL-125。
可选地，所述晶化在动态或静态下进行。可选地，晶化完成后，将固体产物分离，洗涤至中性，干燥，得到金属有机骨架材料MIL-125。
可选地，所述钛酯类聚合物由含有钛酸酯和多元醇的原料进行酯交换反应获得。
可选地，所述酯交换在搅拌条件下进行。
可选地，所述酯交换的反应条件为：在非活性气氛下，80～180℃反应2～10小时。
可选地，所述酯交换的反应温度上限选自85℃、90℃、100℃、110℃、120℃、130℃、140℃、150℃、160℃、170℃、175℃或180℃；下限选自80℃、85℃、90℃、100℃、110℃、120℃、130℃、140℃、150℃、160℃、170℃或175℃。
可选地，所述酯交换的反应时间上限选自2.5小时、3小时、4小时、5小时、6小时、7小时、8小时、9小时、9.5小时或10小时；下限选自2小时、2.5小时、3小时、4小时、5小时、6小时、7小时、8小时、9小时或9.5小时。
可选地，所述酯交换的反应条件为：通氮气保护，反应温度介于80～180℃，反应时间介于2～10小时。
可选地，所述酯交换的反应条件为：在非活性气氛下，100～160℃反应2～10小时。
可选地，所述酯交换的反应条件为：在非活性气氛下，100～160℃反应4～8小时。
可选地，所述酯交换的反应条件为：氮气保护条件下进行，反应温度介于100～160℃，反应时间介于4～8小时。
可选地，所述非活性气氛包括氮气、惰性气体中的至少一种。
可选地，所述酯交换的转化率介于60％～80％。
可选地，所述酯交换的转化率不大于90％。
可选地，所述酯交换还包括减压蒸馏。
可选地，所述减压蒸馏的条件为：在真空度为0.01～5KPa的条件下，170～230℃反应0.5～5小时。
可选地，所述真空度为0.05～3Kpa。
可选地，所述减压蒸馏的温度上限选自175℃、180℃、190℃、200℃、210℃、220℃、225℃或230℃；下限选自170℃、175℃、180℃、190℃、200℃、210℃、220℃或225℃。
可选地，所述减压蒸馏的时间上限选自0.8小时、1小时、2小时、3小时、4小时、4.5小时或5小时；下限选自0.5小时、0.8小时、1小时、2小时、3小时、4小时或4.5小时。
可选地，所述减压蒸馏的真空度上限选自0.02Kpa、0.03Kpa、0.05Kpa、0.08Kpa、0.1Kpa、0.5Kpa、1Kpa、1.5Kpa、2Kpa、2.5Kpa、3Kpa、3.5Kpa、4Kpa、4.5Kpa或5Kpa；下限选自0.01KPa、0.02Kpa、0.03Kpa、0.05Kpa、0.08Kpa、0.1Kpa、0.5Kpa、1Kpa、1.5Kpa、2Kpa、2.5Kpa、3Kpa、3.5Kpa、4Kpa或4.5Kpa。
可选地，所述钛酸酯和多元醇的摩尔比满足：
钛酸酯：多元醇＝(0.5～5)x：4
其中，x为每摩尔所述多元醇中含有的羟基摩尔数；
上述各物质的摩尔数均为物质本身的摩尔数计算。
可选地，所述钛酸酯和多元醇的摩尔比满足：
钛酸酯：多元醇＝(0.8～1.2)x：4
其中，x为每摩尔所述多元醇中含有的羟基摩尔数；
上述各物质的摩尔数均为物质本身的摩尔数计算。
可选地，所述钛酸酯与多元醇的摩尔比上限选自0.85x:4、0.9x:4、0.95x:4、1.0x:4、1.15x:4或1.2x:4；下限选自0.8x:4、0.85x:4、 0.9x:4、0.95x:4、1.0x:4或1.15x:4；其中，x为每摩尔所述多元醇中含有的羟基摩尔数。
可选地，所述钛酸酯选自具有式II所示化学式的化合物中的至少一种：
Figure PCTCN2020114895-appb-000001
其中，R 5，R 6，R 7，R 8独立地选自C 1～C 10的烷基中的一种。
可选地，式II中所述R 5，R 6，R 7，R 8独立地选自C 1～C 4的烷基中的一种。
可选地，所述钛酸酯包括钛酸四乙酯、钛酸四异丙酯、钛酸四丁酯、钛酸四己酯、钛酸四异辛酯中的至少一种。
可选地，所述钛酸酯为钛酸四乙酯、钛酸四异丙酯、钛酸四丁酯、钛酸四己酯、钛酸四异辛酯等中的一种或几种。
可选地，所述多元醇包括乙二醇、一缩二乙二醇、二缩三乙二醇、三缩四乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、聚乙二醇200、聚乙二醇400、聚乙二醇600、聚乙二醇800、1,4-环己二醇、1,4-环己烷二甲醇、对苯二甲醇、丙三醇、三羟甲基丙烷、季戊四醇、木糖醇、山梨醇中的至少一种。
可选地，多元醇中含有的羟基数≥2；包括乙二醇、一缩二乙二醇、二缩三乙二醇、三缩四乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、聚乙二醇200、聚乙二醇400、聚乙二醇600、聚乙二醇800、1,4-环己二醇、1,4-环己烷二甲醇、对苯二甲醇、丙三醇、三羟甲基丙烷、季戊四醇、木糖醇、山梨醇等中的一种或任意几种的混合物。
可选地，所述钛酯类聚合物包括钛聚乙二醇酯聚合物、钛乙二醇酯聚合物、钛对苯二甲醇酯聚合物中的至少一种。
可选地，所述晶化的条件为：密闭条件下，温度为100～200℃，在自生压力下晶化不超过30天。
可选地，所述晶化的温度上限选自110℃、120℃、130℃、140℃、150℃、160℃、170℃、180℃、190℃或200℃；下限选自100℃、110℃、120℃、130℃、140℃、150℃、160℃、170℃、180℃或190℃。
可选地，所述晶化的时间上限选自1小时、5小时、10小时、15小时、20小时、1天、2天、5天、10天、12天、15天、20天、25天、28天或30天；下限选自0.5小时、1小时、5小时、10小时、15小时、20小时、1天、2天、5天、10天、12天、15天、20天、25天或28天。
优选地，所述晶化的条件为：密闭条件下，温度为120～180℃，在自生压力下晶化1～15天。
可选地，所述钛酯类聚合物和有机配体的摩尔比为(0.5～2):1；
其中，所述钛酯类聚合物的摩尔数以钛酯类聚合物中的钛含量计算；
所述钛酯类聚合物中的钛含量按TiO 2的摩尔数计。
可选地，所述钛酯类聚合物与对苯二甲酸的摩尔比上限选自0.55、0.6、0.65、0.7、0.75、0.8、0.82、0.84、0.86、0.88、0.92、0.94、0.96、0.98、1.2、1.5、1.6、1.8、1.9或2.0；下限选自0.5、0.55、0.6、0.65、0.7、0.75、0.8、0.82、0.84、0.86、0.88、0.92、0.94、0.96、0.98、1.2、1.5、1.6、1.8、1.9。其中，所述钛酯类聚合物的摩尔数以钛酯类聚合物中的钛含量之和计算；所述钛酯类聚合物中的钛含量按TiO 2的摩尔数计。
可选地，所述有机溶剂选自N,N-二甲基甲酰胺、甲醇中的至少一种。
可选地，所述有机溶剂包括N,N-二甲基甲酰胺和甲醇；N,N-二甲基甲酰胺和甲醇的体积比为(6～15)：1。
可选地，所述N,N-二甲基甲酰胺与甲醇的体积比上限选自6.2、6.5、7.0、7.5、8.0、8.5、9.0、9.5、10.5、11.0、12.0、13.0、14.0或15.0；下限选自6.0、6.2、6.5、7.0、7.5、8.0、8.5、9.0、9.5、10.5、 11.0、12.0、13.0、14.0。
可选地，所述钛酯类聚合物由钛酸酯和多元醇发生酯交换反应制备得到。
作为其中一种具体的实施方式，所述金属有机骨架材料MIL-125的制备方法包括：
a')将钛酸酯与多元醇加入三口烧瓶中混合均匀，搅拌状态下进行酯交换反应，接上蒸馏装置，通氮气保护，反应温度介于80～180℃，反应时间介于2～10小时，酯交换反应的转化率介于60％～80％；
b')将步骤a')反应后的装置接上水泵或油泵进行减压蒸馏使酯交换反应进行的更完全，控制体系真空度在0.01～5KPa，反应温度介于170～230℃，反应时间介于0.5～5小时，酯交换反应的转化率大于90％，即得钛酯类聚合物；
c')将步骤b')得到的钛酯类聚合物与对苯二甲酸、有机溶剂等混合，并保持在不高于120℃的温度下搅拌0～100小时，得到凝胶混合物；
d')将步骤c')所得的凝胶混合物装入高压合成釜，密闭，升温到100～200℃，在自生压力下晶化0～30天；
e')待晶化完全后，将固体产物分离，用去离子水洗涤至中性，干燥后即得所述金属有机骨架材料MIL-125。
作为其中一种具体的实施方式，所述钛酯类聚合物的制备方法包括：
1)将钛酸酯与多元醇加入三口烧瓶中混合均匀，搅拌状态下进行酯交换反应，接上蒸馏装置，通氮气保护，反应温度介于80～180℃，反应时间介于2～10小时，酯交换反应的转化率介于60％～80％；
2)将步骤1)反应后的装置接上水泵或油泵进行减压蒸馏使酯交换反应进行的更完全，控制体系真空度在0.01～5KPa，反应温度介于170～230℃，反应时间介于0.5～5小时，酯交换反应的转化率大于90％，即得钛酯类聚合物。
本发明的含钛微孔金属有机骨架材料MIL-125合成过程分为两步：第一步是将钛酯与多元醇混合进行酯交换反应，将生成的醇蒸出，得到钛酯类聚合物；第二步将钛酯类聚合物、对苯二甲酸、有机溶剂等在反应釜中溶剂热晶化，得到含钛微孔金属有机骨架材料MIL-125。该方法中钛源连接在同一种聚合物上形成钛酯类聚合物，可以防止TiO 2的沉淀，合成过程简单，无需传统合成过程中在手套箱中操作和溶剂除水的步骤，与此同时，合成的金属有机骨架材料MIL-125具有大量微孔结构，因此，此法得到的金属有机骨架材料MIL-125在氧化上具有更高的催化活性。
可选地，根据上述任一项所述的方法制备得到的含钛微孔金属有机骨架材料MIL-125用于含有H 2O 2和叔丁基过氧化氢的有机物的选择性氧化反应。
根据本申请的第三方面，还提供了一种环氧环己烷的制备方法，所述方法包括：将含有化合物A和环己烯的原料，在金属有机骨架材料MIL-125的存在下，反应，即可得到所述环氧环己烷；
所述化合物A选自过氧化氢、叔丁基过氧化氢中的至少一种；
所述金属有机骨架材料MIL-125选自上述金属有机骨架材料MIL-125、根据上述方法制备得到的金属有机骨架材料MIL-125中的任一种。
可选地，所述化合物A、环己烯和金属有机骨架材料MIL-125的质量比为0.3～1.0:0.3～1.2:0.05～0.1。
可选地，所述反应的条件为：反应温度为35～80℃；反应时间为2～8h。
可选地，所述方法包括：将含有金属有机骨架材料MIL-125、溶剂、环己烯、化合物A的混合物，反应，即可得到所述环氧环己烷。
可选地，所述化合物A的浓度为30％～55％。
可选地，所述溶剂选自甲醇，N,N-二甲基甲酰胺中的至少一种。
可选地，所述反应在水浴下进行。
本申请中，“C 1～C 10、C 1～C 4”等均指基团中所包含的碳原子数。
本申请中，“烷基”是由烷烃化合物分子上失去任意一个氢原子所 形成的基团。
本申请中，外比表面积指的是在物理吸附的测量中通过t-Plot方法得到的多孔物质的比表面积，即材料的BET总面积减去其微孔比表面积。
本申请能产生的有益效果包括：
本申请提供的金属有机骨架材料MIL-125形貌规整，为规则的圆饼状，且大小均一，具有大量的微孔结构、外比表面积大，有效的降低传质阻力，有利于反应过程中产物和反应物的扩散，在氧化上具有更高的催化活性。制备方法中的钛源连接在同一种聚合物上形成钛酯类聚合物，不水解且不溶于水，可防止TiO 2的沉淀，合成过程简单，无需传统合成过程中在手套箱中操作和溶剂除水的步骤。
附图说明
图1是根据本发明实施例1合成的产物的XRD图。
图2是根据本发明实施例1合成的产物的扫描电镜(SEM)图。
图3是根据本发明实施例1合成的产物的物理吸附等温线(BET)图。
图4是根据本发明实施例1合成的产物的激光粒度分布图。
具体实施方式
下面结合实施例详述本申请，但本申请并不局限于这些实施例。
如无特别说明，本申请的实施例中的原料均通过商业途径购买。
在本申请的实施例中，产物的X射线粉末衍射物相分析(XRD)采用荷兰帕纳科(PANalytical)公司的X’Pert PRO X射线衍射仪，Cu靶，Kα辐射源(λ＝0.15418nm)，电压40KV，电流40mA。
在本申请的实施例中，产物的SEM形貌分析采用Hitachi的SU8020扫描电子显微镜。
在本申请的实施例中，产物的物理吸附及孔分布分析采用麦克公司的ASAP2020全自动物理仪。
在本申请的实施例中，产物的粒度分布分析采用梅特勒-托利多公司的ParticleTrack G600B粒度分析仪。
本申请的实施例中，酯交换反应的转化率通过以下方法计算：
根据反应过程中馏出的副产品醇类的摩尔数n，确定参与酯交换反应中参与反应的基团数为n，反应原料中钛酸酯的摩尔数总和为m，则酯交换反应的转化率为：n/4m。
根据本申请的一种实施方式，用于制备金属有机骨架材料MIL-125的方法如下：
a)将钛酸酯与多元醇加入三口烧瓶中混合均匀，搅拌状态下进行酯交换反应，接上蒸馏装置，通氮气保护，反应温度介于80～180℃，反应时间介于2～10小时，酯交换反应的转化率介于60％～80％。
b)将步骤a)反应后的装置接上水泵或油泵进行减压蒸馏使酯交换反应进行的更完全，控制体系真空度在0.01～5KPa，反应温度介于170～230℃，反应时间介于0.5～5小时，酯交换反应的转化率大于90％，即得钛酯类聚合物。
c)将步骤b)得到的钛酯类聚合物与对苯二甲酸、有机溶剂等混合，并保持在不高于120℃的温度下搅拌或静止0～100小时，得到凝胶混合物：
d)将步骤c)所得的凝胶混合物装入高压合成釜，密闭，升温到100～200℃，在自生压力下晶化0～30天；
e)待晶化完全后，将固体产物分离，用去离子水洗涤至中性，干燥后，即得所述微孔金属有机骨架材料MIL-125；
所述步骤a)中的钛酸酯为钛酸四乙酯、钛酸四异丙酯、钛酸四丁酯、钛酸四己酯、钛酸四异辛酯等中的一种或几种；
所述步骤a)中的多元醇的通式为R-(OH) x，其中x≥2；包括乙二醇、一缩二乙二醇、二缩三乙二醇、三缩四乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、聚乙二醇200、聚乙二醇400、聚乙二醇600、聚乙二醇800、1,4-环己二醇、1,4-环己烷二甲醇、对 苯二甲醇、丙三醇、三羟甲基丙烷、季戊四醇、木糖醇、山梨醇等中的一种或任意几种的混合物。
优选的，所述步骤a)中钛酸酯与多元醇具有如下摩尔配比：
Ti(OR) 4/R-(OH) x＝(0.8～1.2)x/4
优选的，所述步骤a)中反应是在氮气保护条件下进行，反应温度介于80～180℃，反应时间介于2～10小时。
优选的，所述步骤a)中酯交换反应的转化率介于65％～80％。
优选的，所述步骤b)是在减压蒸馏条件下进行，控制体系真空度在0.05～3KPa。
优选的，所述步骤b)中反应温度介于170～230℃，反应时间介于0.5～5小时。
优选的，所述步骤b)中酯交换反应的转化率大于90％。
优选的，所述步骤c)中钛酯类聚合物、对苯二甲酸具有如下摩尔配比：
钛酯类聚合物：对苯二甲酸＝(0.5～2)：1；
所述钛酯类聚合物的摩尔数以钛酯类聚合物中的钛含量计算；
所述钛酯类聚合物中的钛含量按TiO 2的摩尔数计；
优选的，所述步骤c)所述的有机溶剂为二甲基甲酰胺和甲醇，其体积比满足：
二甲基甲酰胺：甲醇＝(6～15):1；
优选的，所述步骤c)中的搅拌过程可省略，也可进行，搅拌温度为20～100℃，时间为1～50小时。
优选的，所述步骤d)中进行晶化的温度为120～180℃，晶化时间为1～15天。
优选的，所述步骤d)中的晶化过程在静态或动态下进行。
优选的，所述步骤e)中得到的金属有机骨架材料MIL-125具有孔径分布较窄的微孔结构和较少的非骨架钛。
实施例1
具体的配料过程如下：将5g钛酸四乙酯与10g聚乙二醇200加 入三口烧瓶中混合均匀，搅拌状态下进行酯交换反应，接上蒸馏装置，通氮气保护，升温至175℃，反应时间5小时，酯交换反应的转化率75％，接上水泵进行减压蒸馏使酯交换反应进行的更完全，控制体系真空度在3KPa，反应温度200℃，反应时间1小时，酯交换反应的转化率为92％，即得钛聚乙二醇酯聚合物。将得到的钛聚乙二醇酯聚合物5g与5g对苯二甲酸，18ml二甲基甲酰胺，2ml甲醇，在室温搅拌2小时，再转移到不锈钢高压合成釜中。将高压合成釜密闭并放入已升至恒温120℃的烘箱中，在自生压力下晶化2天。晶化结束后，将固体产物离心分离，用去离子水洗涤至中性，在110℃空气中烘干后，得微孔金属有机骨架材料MIL-125，标记为A1。
实施例2
具体的配料过程如下：将5g钛酸四乙酯与3.13g乙二醇加入三口烧瓶中混合均匀，搅拌状态下进行酯交换反应，接上蒸馏装置，通氮气保护，升温至100℃，反应时间5小时，酯交换反应的转化率70％，接上水泵进行减压蒸馏使酯交换反应进行的更完全，控制体系真空度在3KPa，反应温度170℃，反应时间1小时，酯交换反应的转化率为90％，即得钛乙二醇酯聚合物。将得到的钛乙二醇酯聚合物3g与2g对苯二甲酸，9ml二甲基甲酰胺，1.2ml甲醇，在室温搅拌2小时，再转移到不锈钢高压合成釜中。将高压合成釜密闭并放入已升至恒温150℃的烘箱中，在自生压力下晶化15天。晶化结束后，将固体产物离心分离，用去离子水洗涤至中性，在110℃空气中烘干后，得金属有机骨架材料MIL-125，标记为A2。
实施例3
具体的配料过程如下：将5g钛酸四丁酯与11.35g对苯二甲醇加入三口烧瓶中混合均匀，搅拌状态下进行酯交换反应，接上蒸馏装置，通氮气保护，升温至160℃，反应时间5小时，酯交换反应的转化率80％，接上水泵进行减压蒸馏使酯交换反应进行的更完全，控制体系真空度在3KPa，反应温度230℃，反应时间1小时，酯交换反应的转化率为95％，即得钛对苯二甲醇酯聚合物。将得到的钛对苯二甲醇 酯聚合物4g与6.2g对苯二甲酸，20ml二甲基甲酰胺，2.3ml甲醇，在室温搅拌2小时，再转移到不锈钢高压合成釜中。将高压合成釜密闭并放入已升至恒温170℃的烘箱中，在自生压力下晶化1天。晶化结束后，将固体产物离心分离，用去离子水洗涤至中性，在110℃空气中烘干后，得金属有机骨架材料MIL-125，标记为A3。
实施例1至实施例3中所述晶化为静态晶化。
实施例4
采用与实施例1相同的方法制备金属有机骨架材料MIL-125，具体制备条件与实施例1的区别参见表1和表2。
表1
Figure PCTCN2020114895-appb-000002
表2合成金属有机骨架材料MIL-125的条件
Figure PCTCN2020114895-appb-000003
实施例4中涉及的晶化为动态晶化，晶化条件为：采用旋转烘箱，晶化温度和晶化时间如表2所示，旋转烘箱的转速为35rpm。
实施例5
具体的配料过程如下：将5g钛酸四乙酯与10g聚乙二醇200加入三口烧瓶中混合均匀，搅拌状态下进行酯交换反应，接上蒸馏装置，通氮气保护，升温至175℃，反应时间5小时，酯交换反应的转化率75％，接上水泵进行减压蒸馏使酯交换反应进行的更完全，控制体系真空度在3KPa，反应温度200℃，反应时间1小时，酯交换反应的转化率为92％，即得钛聚乙二醇酯聚合物。为验证本专利中得到的钛酯类聚合物耐水解，且不溶于水，将得到的钛聚乙二醇酯聚合物5g与5g对苯二甲酸，18ml二甲基甲酰胺，2ml甲醇，0.5g水在室温搅拌2小时，再转移到不锈钢高压合成釜中。将高压合成釜密闭并放入已升至恒温120℃的烘箱中，在自生压力下晶化2天。晶化结束后，将固体产物离心分离，用去离子水洗涤至中性，在110℃空气中烘干后，得微孔金属有机骨架材料MIL-125，标记为A8。所述晶化为静态晶化。
实施例6物相结构分析
对实施例1至实施例5中的样品A1～A8进行XRD物相结构分析，以实施例1为典型代表，图1为实施例1中制备得到的样品A1的XRD图谱，从图中可以看出，样品A1为微孔金属有机骨架材料MIL-125,相比于现有技术合成的产品的XRD图谱，采用本专利合成的微孔金属有机骨架材料MIL-125的XRD图谱，出峰清晰且峰形尖锐，无拖尾情况，基线平整，说明采用本专利合成的微孔金属有机骨架材料MIL-125结构规整，无杂晶，且没有无定形产物生成。
其他样品的测试结果与实施例1中样品A1的图谱仅仅是衍射峰的强度略有差异，均为微孔金属有机骨架材料MIL-125。
实施例7形貌测试
对实施例1至实施例5中的样品A1～A8进行SEM相貌分析，以实施例1为典型代表，图2为实施例1中制备得到的样品A1的SEM图谱，其扫描电镜图谱可以看出，合成的产品形貌规整，均为圆饼状，且其大小分布均匀，无其他杂晶和无定形产物生成。
实施例8低温氮气物理吸附分析
对实施例1至实施例5的样品A1～A8进行低温氮气物理吸附分析，以实施例1为典型代表，图3为实施例1中制备得到的样品A1的物理吸附等温线，由图可见，是典型的I型等温吸附线，是典型微孔结构。
其他样品的测试结果与实施例1中样品1的测试结果类似，样品是典型的I型等温吸附线，是典型微孔结构。
实施例9孔分布分析
对实施例1至实施例5的样品A1～A8进行物理吸附以及孔分布分析，表3为实施例1至实施例4中制备得到的样品A1～A6的物理吸附及孔分布结果，样品具有1200～1350平方米每克的比表面积，微孔孔径为0.37～0.48纳米。
表3样品的比表面积及孔分布
样品 BET比表面积/m 2g- 1 t-Plot外比表面积/m 2g- 1 孔分布/nm
A1 1350 167 0.40
A2 1268 170 0.37
A3 1212 181 0.40
A4 1304 165 0.41
A5 1312 214 0.45
A6 1289 200 0.48
其他样品的测试结果与实施例1中样品A1的测试结果类似，样品中均具有1000～1500平方米每克的比表面积。
通过t-Plot方法计算出样品的外比表面积，实施例1至实施例4中制备得到的样品A1～A6的外比表面积为160～214平方米每克。
其他样品的测试结果与实施例1中样品A1的测试结果类似，样品中均具有160～220平方米每克的外比表面积。
实施例10粒度分布分析
对实施例1至实施例5的样品A1～A8进行激光粒度分析，以实施例1为典型代表，图4为实施例1中制备得到的样品A1的粒度分 布图，由图可见，合成出的样品的粒度分布较为集中均匀，粒径在1～2微米之间。
其他样品的测试结果与实施例1中样品1的测试结果类似，样品是粒度分布较为集中均匀，粒径在1～2微米之间。
实施例11氧化反应性能测定
以双氧水作为氧化剂，测定氧化环己烯反应性能。
典型代表如样品A1，具体步骤包括：
取0.1g样品A1(作为催化剂)，加入10ml乙腈，0.36g环己烯，0.5g双氧水(30％质量分数)于圆底烧瓶中，在60摄氏度水浴加热的条件下，冷凝回流，反应4小时。
样品A1反应结果为：环己烯转化率为38％，产物中环氧化产物选择性78.5％，双氧水转化率为73.2％，氧化剂对环氧化产物的选择性72.2％。对比现有技术中环己烯转化率为26％，产物中环氧化产物选择性仅为25％。
样品A2～A8按上述步骤进行性能测定，所得反应结果与样品A1类似。
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。

Claims (16)

  1. 一种金属有机骨架材料MIL-125，其特征在于，所述金属有机骨架材料MIL-125为圆饼状的晶块；外比表面积为160～220m 2/g。
  2. 根据权利要求1所述的金属有机骨架材料MIL-125，其特征在于，所述金属有机骨架材料MIL-125中，粒径为1.6～1.8微米的粒子的质量含量为85～95％。
  3. 根据权利要求1所述的金属有机骨架材料MIL-125，其特征在于，所述金属有机骨架材料MIL-125中含有比表面积为1000-1500m 2/g的微孔。
  4. 根据权利要求3所述的金属有机骨架材料MIL-125，其特征在于，所述微孔的孔径为0.35～0.50nm。
  5. 权利要求1至4任一项所述的金属有机骨架材料MIL-125的制备方法，其特征在于，以钛酯类聚合物为钛源，制备得到所述金属有机骨架材料MIL-125。
  6. 根据权利要求5所述的制备方法，其特征在于，所述方法包括：将含有钛酯类聚合物、有机配体和有机溶剂的混合物，晶化，即可得到所述金属有机骨架材料MIL-125；
    所述有机配体为对苯二甲酸；所述晶化为溶剂热晶化。
  7. 根据权利要求6所述的制备方法，其特征在于，所述晶化的条件为：密闭条件下，温度为100～200℃，在自生压力下晶化不超过30天。
  8. 根据权利要求6所述的制备方法，其特征在于，所述晶化的 条件为：密闭条件下，温度为120～180℃，在自生压力下晶化1～15天。
  9. 根据权利要求6所述的制备方法，其特征在于，所述钛酯类聚合物和有机配体的摩尔比为(0.5～2):1；
    其中，所述钛酯类聚合物的摩尔数以钛酯类聚合物中的钛含量计算；
    所述钛酯类聚合物中的钛含量按TiO 2的摩尔数计。
  10. 根据权利要求6所述的制备方法，其特征在于，所述有机溶剂选自N,N-二甲基甲酰胺、甲醇中的至少一种。
  11. 根据权利要求10所述的制备方法，其特征在于，所述有机溶剂包括N,N-二甲基甲酰胺和甲醇；N,N-二甲基甲酰胺和甲醇的体积比为(6～15)：1。
  12. 根据权利要求6所述的制备方法，其特征在于，所述钛酯类聚合物由钛酸酯和多元醇发生酯交换反应制备得到。
  13. 根据权利要求12所述的制备方法，其特征在于，所述钛酸酯选自具有如式II所示化学式的化合物中的至少一种：
    Figure PCTCN2020114895-appb-100001
    其中，R 5，R 6，R 7，R 8独立地选自C 1～C 10的烷基中的一种；
    所述多元醇包括乙二醇、一缩二乙二醇、二缩三乙二醇、三缩四乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、聚乙二 醇200、聚乙二醇400、聚乙二醇600、聚乙二醇800、1,4-环己二醇、1,4-环己烷二甲醇、对苯二甲醇、丙三醇、三羟甲基丙烷、季戊四醇、木糖醇、山梨醇中的至少一种。
  14. 一种环氧环己烷的制备方法，其特征在于，所述方法包括：将含有化合物A和环己烯的原料，在金属有机骨架材料MIL-125的存在下，反应，即可得到所述环氧环己烷；
    所述化合物A选自过氧化氢、叔丁基过氧化氢中的至少一种；
    所述金属有机骨架材料MIL-125选自权利要求1至4任一项所述的金属有机骨架材料MIL-125、根据权利要求5至13任一项所述方法制备得到的金属有机骨架材料MIL-125中的任一种。
  15. 根据权利要求14所述的制备方法，其特征在于，所述化合物A、环己烯和金属有机骨架材料MIL-125的质量比为0.3～1.0:0.3～1.2:0.05～0.1。
  16. 根据权利要求14所述的制备方法，其特征在于，所述反应的条件为：反应温度为35～80℃；反应时间为2～8h。
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