PREPARATION METHOD OF POROUS OXIDE
20230331578 · 2023-10-19
Assignee
Inventors
Cpc classification
C01F7/30
CHEMISTRY; METALLURGY
International classification
Abstract
A preparation method of a porous oxide is provided, which includes: preparing the porous oxide with a polyester polyol as a raw material. The porous oxide prepared by the preparation method in the present application has characteristics such as uniform and adjustable pore sizes and controllable distribution of mesopores, micropores, and macropores.
Claims
1. A preparation method of a porous oxide, comprising: preparing the porous oxide with a polyester polyol as a raw material.
2. The preparation method according to claim 1, comprising: in an atmosphere comprising a gas A, roasting the raw material comprising the polyester polyol to obtain the porous oxide, wherein the gas A is at least one selected from the group consisting of an air, a nitrogen, an inert gas, and an oxygen.
3. The preparation method according to claim 2, wherein the roasting is conducted at 350° C. to 900° C. for 1.5 h to 25 h.
4. The preparation method according to claim 1, comprising: subjecting a raw material comprising an oxygen-containing acid ester and a polyol to a transesterification reaction to obtain the polyester polyol.
5. The preparation method according to claim 4, wherein the oxygen-containing acid ester is at least one selected from the group consisting of a compound with a chemical formula shown in formula I and a compound with a chemical formula shown in formula II:
M(OR.sup.1).sub.n.sup.1 formula I
O═P(OR.sup.2).sub.n.sup.2 formula II wherein M is a metallic element or a non-metallic element excluding P; R.sup.1 and R.sup.2 each are independently at least one selected from the group consisting of C.sub.1-C.sub.8 alkyl groups; and n.sup.1 is 2 to 8 and n.sup.2 is 2 to 8.
6. The preparation method according to claim 5, wherein M is at least one selected from the group consisting of B, Si, Ge, Al, Ti, Fe, Sn, V, Ga, Zr, Cr, Sb, and W.
7. The preparation method according to claim 4, wherein there are no less than two hydroxyl groups in the polyol.
8. The preparation method according to claim 4, wherein the polyol comprises at least one selected from the group consisting of ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG), tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, polyethylene glycol (PEG) 200, PEG 400, PEG 600, PEG 800, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol (1,4-CHDM), 1,4-benzenedimethanol, glycerol, trimethylolpropane, pentaerythritol, xylitol, and sorbitol.
9. The preparation method according to claim 4, wherein the transesterification reaction is conducted for 2 h to 10 h at 80° C. to 180° C. under a stirring in an inert atmosphere.
10. A porous oxide, wherein the porous oxide is prepared by the preparation method according to claim 1.
11. The porous oxide according to claim 10, wherein the porous oxide has a pore size of 0.4 nm to 80 nm and a specific surface area (SSA) of 150 m.sup.2/g to 1,500 m.sup.2/g.
12. The porous oxide according to claim 10, wherein the porous oxide comprises a micropore with a pore size of 0.4 nm to 2.0 nm.
13. The porous oxide according to claim 10, wherein the porous oxide comprises a mesopore with a pore size of 2.0 nm to 50 nm.
14. The porous oxide according to claim 10, wherein the porous oxide comprises a macropore with a pore size of 50 nm to 80 nm.
15. The porous oxide according to claim 10, wherein the preparation method of the porous oxide comprises: in an atmosphere comprising a gas A, roasting the raw material comprising the polyester polyol to obtain the porous oxide, wherein the gas A is at least one selected from the group consisting of an air, a nitrogen, an inert gas, and an oxygen.
16. The porous oxide according to claim 15, wherein the roasting in the preparation method of the porous oxide is conducted at 350° C. to 900° C. for 1.5 h to 25 h.
17. The porous oxide according to claim 10, wherein the preparation method of the porous oxide comprises: subjecting a raw material comprising an oxygen-containing acid ester and a polyol to a transesterification reaction to obtain the polyester polyol.
18. The porous oxide according to claim 17, wherein the oxygen-containing acid ester is at least one selected from the group consisting of a compound with a chemical formula shown in formula I and a compound with a chemical formula shown in formula II:
M(OR.sup.1).sub.n.sup.1 formula I
O═P(OR.sup.2).sub.n.sup.2 formula II wherein M is a metallic element or a non-metallic element excluding P; R.sup.1 and R.sup.2 each are independently at least one selected from the group consisting of C.sub.1-C.sub.8 alkyl groups; and n.sup.1 is 2 to 8 and n.sup.2 is 2 to 8.
19. The preparation method according to claim 18, wherein M is at least one selected from the group consisting of B, Si, Ge, Al, Ti, Fe, Sn, V, Ga, Zr, Cr, Sb, and W.
20. The preparation method according to claim 17, wherein there are no less than two hydroxyl groups in the polyol.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF THE EMBODIMENTS
[0087] The present application will be described in detail below with reference to examples, but the present application is not limited to these examples.
[0088] Unless otherwise specified, the raw materials in the examples of the present application are all purchased from commercial sources.
[0089] Analysis methods in the examples of the present application are as follows:
[0090] TGA is conducted using a TGA analyzer with a model of TAQ-600 produced by TA Instruments, where a flow rate of nitrogen is 100 mL/min, and a temperature is raised at a heating rate of 10° C./min to 700° C.
[0091] In an embodiment of the present application, the physical adsorption and pore distribution of a product are analyzed by the ASAP2020 automatic physical instrument of Micromeritics.
[0092] In an embodiment of the present application, a TEM image of a product is acquired by Thermo Fisher Themis™ ETEM.
[0093] In an embodiment of the present application, a conversion rate of the transesterification reaction is calculated in the following way:
[0094] According to a mole number n of alcohol distilled during the reaction, a number of groups participating in the transesterification reaction is determined to be n, and a total mole number of the ester in the reaction raw material is m, such that the conversion rate of the transesterification reaction is: n/xm, where x depends on a number of alkoxy groups in the esters that are attached to a central atom.
[0095] According to an embodiment of the present application, a preparation method of the porous oxide, a polyester polyol polymer, and a preparation method of the polyester polyol polymer are provided, and the preparation method of the porous oxide polymer includes the following steps:
[0096] a) An oxygen-containing acid ester, a polyol, and a transesterification catalyst are thoroughly mixed in a three-necked flask, the three-necked flask is connected to a distillation device, nitrogen is introduced for protection, and a resulting mixture is subjected to a transesterification reaction for 2 h to 10 h at 80° C. to 180° C. under stirring, where a conversion rate of the transesterification reaction is 60% to 80%.
[0097] b) The device obtained after the reaction in step a) is connected to a water pump or oil pump, and a resulting reaction system is subjected to vacuum distillation for 0.5 h to 5 h at a vacuum degree of 0.01 KPa to 5 KPa and a temperature of 170° C. to 230° C. to make the transesterification reaction more complete, where a conversion rate of the transesterification reaction is greater than 90%.
[0098] Optionally, the oxygen-containing acid ester in step a) has a general formula of M(OR).sub.n, where M is selected from the group consisting of B, Si, Ge, Al, Ti, Fe, Sn, V, Ga, Zr, Cr, Sb, and W and R is an alkyl group with 1 to 8 carbon atoms; and the oxygen-containing acid ester includes any one or a mixture of two or more selected from the group consisting of trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, tri-n-hexyl borate, triisooctyl borate, trioctyl borate, TMOS, TEOS, TPOS, TBOS, ethyl orthogermanate, TEP, TPP, TBP, tri-n-pentyl phosphate, THP, aluminum triethoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum tert-butoxide, tetraethyl titanate, TIPT, tetrabutyl titanate, tetrahexyl titanate, tetraisooctyl titanate, tetrabutyl ferrite, tetrabutyl stannate, butyl orthovanadate, gallium ethoxide, tetra-n-propyl zirconate, tetrabutyl zirconate, tert-butyl chromate, ethyl antimonite, butyl antimonite, tungsten ethoxide, and tungsten isopropoxide.
[0099] Optionally, the polyol in step a) has a general formula of R—(OH).sub.x, where x≥2; and the polyol includes any one or a mixture of two or more selected from the group consisting of EG, DEG, TEG, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, PEG 200, PEG 400, PEG 600, PEG 800, 1,4-cyclohexanediol, 1,4-CHDM, 1,4-benzenedimethanol, glycerol, trimethylolpropane, pentaerythritol, xylitol, and sorbitol.
[0100] Optionally, a molar ratio of the oxygen-containing acid ester to the polyol in step a) is:
M(OR).sub.n/R—(OH).sub.x=(0.8−1.2)x/n.
[0101] Optionally, the transesterification catalyst used in step a) is a basic catalyst including alcohol-soluble bases (such as NaOH, KOH, NaOCH.sub.3, and organic bases) and a variety of solid base catalysts; or an acidic catalyst including alcohol-soluble acids (such as sulfuric acid and sulfonic acid), a variety of solid acid catalysts, alkoxyaluminum, phenoxyaluminum, tetrabutyl stannate, alkoxytitanium, alkoxyzirconium, ethyl antimonite, and butyl antimonite. The transesterification catalyst is used at an amount of 0.1 wt % to 5 wt % of an amount of the oxygen-containing acid ester.
[0102] Optionally, the reaction in step a) is conducted for 2 h to 10 h at 80° C. to 180° C. under nitrogen protection.
[0103] Optionally, a conversion rate of the transesterification reaction in step a) is 60% to 80%.
[0104] Optionally, the step b) is conducted under vacuum distillation at a vacuum degree of 0.01 KPa to 5 KPa.
[0105] Optionally, the reaction in step b) is conducted at 170° C. to 230° C. for 0.5 h to 5 h.
[0106] Optionally, a conversion rate of the transesterification reaction in step b) is greater than 90%.
[0107] c) A product obtained after the reaction in step b) is roasted at 350° C. to 900° C. for 1.5 h to 20 h in an atmosphere that is one or a mixture of two or more selected from the group consisting of air, oxygen, and nitrogen.
Example 1
[0108] 10 g of 1,3-propanediol, 6.84 g of TEOS, and 5 g of TMOS were added to a three-necked flask, a distillation device was connected, and 0.12 g of concentrated sulfuric acid (mass fraction: 98%) was added dropwise as a catalyst under stirring; a temperature was raised to 100° C. under nitrogen protection to allow a reaction for 6 h, where a large amount of methanol and ethanol were distilled out and a conversion rate of the transesterification reaction was 75%; then a vacuum device was connected, and vacuum distillation was conducted to allow a reaction for 1 h at a vacuum degree of 1 KPa and a temperature of 170° C.; the reaction was stopped, a resulting reaction system was naturally cooled to room temperature, and a sample was taken out, where a conversion rate of the transesterification reaction was 93%; and the sample was roasted at 550° C. for 8 h in an air atmosphere to obtain a silicon porous oxide.
Example 2
[0109] 5 g of EG and 8.7 g of aluminum triethoxide were added to a three-necked flask, where the aluminum triethoxide served as both an oxygen-containing acid ester and a transesterification catalyst; a distillation device was connected, and a temperature was raised to 175° C. under nitrogen protection to allow a reaction for 5 h, where a large amount of ethanol was distilled out and a conversion rate of the transesterification reaction was 73%; then a vacuum device was connected, and vacuum distillation was conducted to allow a reaction for 1 h at a vacuum degree of 0.1 KPa and a temperature of 210° C.; the reaction was stopped, a resulting reaction system was naturally cooled to room temperature, and a sample was taken out, where a conversion rate of the transesterification reaction was 92%; and the sample was roasted at 750° C. for 4 h in an oxygen atmosphere to obtain an aluminum porous oxide.
Example 3
[0110] 10 g of 1,4-benzenedimethanol, 5.07 g of tripropyl borate, and 4 g of tetrapropyl titanate were added to a three-necked flask, where the tetrabutyl titanate served as both an oxygen-containing acid ester and a transesterification catalyst; a distillation device was connected, and a temperature was raised to 180° C. under stirring and nitrogen protection to allow a reaction for 6 h, where a large amount of propanol was distilled out and a conversion rate of the transesterification reaction was 75%; then a vacuum device was connected, and vacuum distillation was conducted to allow a reaction for 1 h at a vacuum degree of 1 KPa and a temperature of 230° C.; the reaction was stopped, a resulting reaction system was naturally cooled to room temperature, and a sample was taken out, where a conversion rate of the transesterification reaction was 93%; and the sample was roasted at 450° C. for 25 h in a mixed atmosphere of nitrogen and air to obtain a boron-titanium porous oxide.
Example 4
[0111] Specific materials and reaction conditions involved were shown in Table 1 below, and other operations in a synthesis process were the same as in Example 1.
TABLE-US-00001 TABLE 1 Composition and ratio of raw materials and crystallization conditions in each of Examples 4 to 13 Transesterification Oxygen- Vacuum distillation Example containing Reaction Reaction Vacuum Reaction Reaction No. acid ester Polyol Catalyst temperature time degree temperature time 4 Tetrahexyl DEG, 0.2 mol NaOH, 0.03 g 80° C. 10 h 5 KPa 180° C. 2 h titanate, 0.1 mol 5 TEP, 0.2 mol PEG 200, 0.3 mol Na.sub.2CO.sub.3, 0.1 g 100° C. 5 h 2 KPa 200° C. 0.5 h 6 Tetrabutyl Trimethylolpropane, Sulfonic 150° C. 2 h 0.01 KPa 175° C. 5 h stannate, 0.15 mol 0.2 mol acid, 0.06 g 7 Tungsten Xylitol, 0.1 mol Tetrabutyl The same The same The same The same The same ethoxide, 0.2 mol stannate, 0.02 g as in as in as in as in as in Example 1 Example 1 Example 1 Example 1 Example 1 8 Tetrabutyl 1,4- Ethyl The same The same The same The same The same ferrite, 0.1 mol Butanediol, 0.2 mol antimonite, as in as in as in as in as in 0.04 g Example 1 Example 1 Example 1 Example 1 Example 1 9 Butyl Glycerol, 0.2 mol Butyl The same The same The same The same The same orthovanadate, antimonite, as in as in as in as in as in 0.1 mol 0.02 g Example 1 Example 1 Example 1 Example 1 Example 1 10 Gallium Pentaerythritol, The same The same The same The same The same The same ethoxide, 0.3 mol as in as in as in as in as in as in 0.4 mol Example 1 Example 1 Example 1 Example 1 Example 1 Example 1 11 Tetra-n-propyl Cyclohexanediol, The same The same The same The same The same The same zirconate, 0.4 mol as in as in as in as in as in as in 0.2 mol Example 1 Example 1 Example 1 Example 1 Example 1 Example 1 12 Tert-butyl The same The same The same The same The same The same The same chromate, 0.1 mol as in as in as in as in as in as in as in Example 1, Example 1 Example 1 Example 1 Example 1 Example 1 Example 1 0.1 mol 13 Ethyl The same The same The same The same The same The same The same antimonite, as in as in as in as in as in as in as in 0.4 mol Example 1, Example 1 Example 1 Example 1 Example 1 Example 1 Example 1 0.3 mol
TABLE-US-00002 TABLE 2 Roasting conditions in Examples 4 to 13 Roasting treatment Example Roasting No. Atmosphere Roasting time temperature 4 Nitrogen 1.5 h 380° C. 5 Oxygen 2.5 h 400° C. 6 Air 3 h 500° C. 7 Air and oxygen 7.5 h 550° C. 8 Air and nitrogen 8 h 600° C. 9 Nitrogen and oxygen 10 h 650° C. 10 Air, nitrogen, 9 h 750° C. and oxygen 11 Nitrogen 14 h 850° C. 12 Air 16 h 900° C. 13 Oxygen 20 h The same as in Example 1
Example 5 TGA
[0112] The polyester polyols prepared in Examples 1 to 13 each were subjected to TGA, with Examples 1 and 2 as typical representatives.
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[0114] Test results of the polyester polyols in other examples are similar to those described above, and initial decomposition temperatures of the polyester polyols are higher than 300° C.
Example 6 Physical Adsorption Analysis
[0115] The porous oxides prepared in Examples 1 to 13 each were subjected to physical adsorption characterization, with Examples 1 and 2 as typical representatives. BET curves of Examples 1 and 2 are shown in
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TABLE-US-00003 TABLE 3 SSA and pore size information for Examples 1 to 13 Nitrogen physical adsorption information Example BET SSA Micropore area External SSA Pore size No. m.sup.2/g m.sup.2/g m.sup.2/g nm 1 425 336 89 0.55 2 708 197 511 4.0 3 859 636 223 0.42 7 908 180 728 18 8 1202 814 388 1.8 9 1008 280 728 25 10 1378 509 869 4.5 11 1480 483 997 32 12 678 58 620 60 13 226 72 154 72
Example 7 TEM Analysis
[0117] The porous oxides prepared in Examples 1 to 13 each were subjected to TEM characterization, with Examples 1 and 2 as typical representatives. TEM images of Examples 1 and 2 are shown in
[0118] The above examples are merely few examples of the present application, and do not limit the present application in any form. Although the present application is disclosed as above with preferred examples, the present application is not limited thereto. Some changes or modifications made by any technical personnel familiar with the profession using the technical content disclosed above without departing from the scope of the technical solutions of the present application are equivalent to equivalent implementation cases and fall within the scope of the technical solutions.