CN107552093B - Supported iridium catalyst for bisphenol F and esterification reaction and preparation method thereof - Google Patents
Supported iridium catalyst for bisphenol F and esterification reaction and preparation method thereof Download PDFInfo
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- CN107552093B CN107552093B CN201710764217.3A CN201710764217A CN107552093B CN 107552093 B CN107552093 B CN 107552093B CN 201710764217 A CN201710764217 A CN 201710764217A CN 107552093 B CN107552093 B CN 107552093B
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Abstract
The invention discloses a supported iridium catalyst for bisphenol F and esterification reaction and a preparation method thereof. The hydrotalcite carrier (layered double-hydroxyl composite hydroxide) has the characteristics of composition and structure controllability, acid-base adjustable denaturation, interaction adjustable denaturation and the like, is regarded as an excellent carrier of the nano iridium, has high thermal stability and catalytic activity, and is beneficial to catalytic synthesis of bisphenol F and esterification reaction. And the method is convenient to recycle, reduces the production cost, and is expected to become a clean process route with high competitiveness.
Description
Technical Field
The invention relates to a supported iridium catalyst for bisphenol F and esterification reaction and a preparation method thereof, and the catalyst has high thermal stability and catalytic activity, is beneficial to catalytic synthesis of bisphenol F and convenient recovery, and simultaneously shows good properties for the synthesis reaction and esterification reaction of bisphenol F.
Background
Hydrotalcite is an ionic functional clay with exchangeable interlayer ions. Due to the particularity of the layered structure of hydrotalcite, the hydrotalcite shows the special properties of ion adjustability, exchangeability, alkalinity and the like. Due to the unique structural properties of hydrotalcite, hydrotalcite becomes a supported material with great application potential, and is receiving more and more attention and application. At present, hydrotalcite materials are widely applied in the fields of catalysis, biology, environmental protection, additives, medicines, functional polymer materials and the like. By utilizing the interchangeability of anions between hydrotalcite layers and the high activity of the metal iridium complex catalyst, some metal iridium complex catalysts can be inserted between hydrotalcite layers, so that the prepared iridium-supported catalyst not only has higher catalytic activity, but also is easy to separate after the reaction is finished, thereby avoiding the influence of the iridium-supported catalyst on the product purity and simultaneously avoiding heavy metal pollution to the environment. The iridium-supported catalyst also has high thermal stability and high activity after being recycled for many times.
Bisphenol F and acetin compounds are high value-added products, and the synthesis of the bisphenol F and the acetin compounds mainly adopts strong acid or solid acid catalysts, so that the problems of high environmental pollution cost and the like exist. It also presents serious equipment corrosion problems. Therefore, finding alternative catalysts has become a hot spot for current research and development.
In order to solve the problems, the invention adopts hydrotalcite and two kinds of metal iridium compounds as the basis to prepare the composite supported benzoxazole iridium hydrotalcite catalyst for catalytic synthesis of bisphenol F and glycerol acetate, and the method is not reported at present.
Disclosure of Invention
The invention discloses a supported iridium catalyst for bisphenol F and esterification reaction and a preparation method thereof. In our studies, it was found that this composite catalyst is advantageous for the catalytic synthesis of bisphenol F and triacetin.
According to the technical scheme provided by the invention, the prepared composite supported benzoxazole iridium hydrotalcite catalyst is synthesized by the following two iridium complexes:
the invention provides a supported iridium catalyst for bisphenol F and esterification reaction and a preparation method thereof, and the specific steps and the synthetic steps are as follows:
(1) firstly, dissolving a benzoxazole ligand and iridium trichloride in a ratio of 1: 1-30: 1 in a mixed solution of ethylene glycol ethyl ether and water in a ratio of 1: 1-30: 1 by adopting a solvothermal method, stirring and heating to 25-500 ℃ under the protection of special gas, stirring for 1-48 h, and then carrying out suction filtration to obtain an iridium complex BO. BO and PEt3Mixing the raw materials in a mixed solvent of absolute ethyl alcohol and tert-butyl alcohol according to a ratio of 1: 1-1: 20, stirring for 4-12 h at room temperature, heating for 2-12 h at 50-110 ℃ by using a reaction kettle, and centrifugally drying to obtain the BOP product.
(2) BO and Hydrotalcite (HT) are mixed in a mixed solvent of deionized water, absolute ethyl alcohol and tert-butyl alcohol in a ratio of 1: 1-1: 20, stirring is carried out for 1-48 h at room temperature, heating is carried out for 1-72 h at 20-500 ℃ by using a reaction kettle, and centrifugal drying is carried out to obtain a product BO @ HT.
(3) Mixing BOP and BO @ HT in a mixed solvent of deionized water, absolute ethyl alcohol and tert-butyl alcohol according to a ratio of 1: 1-1: 30, stirring for 1-48 h at room temperature, heating for 1-72 h at 20-600 ℃ by using a reaction kettle, and centrifugally drying to obtain a product BO @ BOP @ HT.
Further, the special gas in the step (1) is performed under the protection of nitrogen, argon, etc.
Further, in the step, the temperature rise speed is 0.1-10 ℃/min.
The application of the composite supported iridium catalyst BO @ BOP @ HT bisphenol F is characterized in that: 4g of phenol and 1g of the novel composite iridium catalyst are added into 10mL of dimethylbenzene, stirred at room temperature, and then slowly added dropwise with a reaction solution of 1:1 of a mixed solution of 10% HCl and 37% formalin (4 mL) was heated to 100 ℃ and reacted for 2 hours. The obtained reaction solution was then filtered to recover the catalyst. The liquid obtained by filtration is a crude product. And recovering the solvent from the obtained crude product by rotary evaporation, recovering the residual phenol by reduced pressure distillation, and recrystallizing the residual product once by using the recovered solvent to obtain the bisphenol F.
The application of the composite supported iridium catalyst BO @ BOP @ HT in catalyzing esterification reaction of glycerol and acetic acid is characterized in that: glycerol and acetic acid are added into a reactor according to the molar ratio of 1: 2-1: 7 of alcohol acid, 30-50 mL of toluene and a composite supported iridium catalyst BO @ BOP @ HT with the mass being 0.6-5% of the total mass of reactants are added, reflux water diversion is carried out at the reaction temperature of 100-140 ℃, and stirring reaction is carried out for 2-8 hours, so as to obtain a mixture containing the acetic acid glyceride.
Drawings
FIG. 1 is a scanning electron microscope atlas of the composite supported iridium catalyst BO @ BOP @ HT prepared by the invention.
Detailed Description
The modified composite material provided by the invention can obviously improve the yield of the synthesis of the bisphenol F and the acetin, and the preparation process of the catalyst is simple and environment-friendly.
The applicant has made specific experiments on the present invention as follows. These are merely intended to be exhaustive of the invention and do not limit the scope of the invention in any way.
The first embodiment is as follows: a supported iridium catalyst for bisphenol F and esterification reaction and a preparation method thereof comprise the following process steps:
(1) firstly, dissolving a benzoxazole ligand and iridium trichloride in a ratio of 1:1 in a mixed solution of ethylene glycol ethyl ether and water in a ratio of 1:1 by adopting a solvothermal method, stirring and heating to 25-500 ℃ under the protection of special gas, stirring for 48 hours, and then carrying out suction filtration to obtain an iridium complex BO. BO and PEt3Mixing the components in a mixed solvent of absolute ethyl alcohol and tertiary butanol according to the ratio of 1:1, stirring the mixture for 4 hours at room temperature, heating the mixture for 12 hours at 110 ℃ by using a reaction kettle, and centrifugally drying the mixture to obtain a product BOP.
(2) BO and Hydrotalcite (HT) are mixed in a mixed solvent of deionized water, absolute ethyl alcohol and tertiary butanol according to a ratio of 1:20, stirred for 24 hours at room temperature, heated for 48 hours at 400 ℃ by a reaction kettle, and centrifugally dried to obtain a product BO @ HT.
(3) BOP and BO @ HT are mixed in a mixed solvent of deionized water, absolute ethyl alcohol and tertiary butyl alcohol according to the ratio of 1:30, stirred for 48 hours at room temperature, heated for 12 hours by a reaction kettle at 400 ℃, and centrifugally dried to obtain a product BO @ BOP @ HT.
Example two: a supported iridium catalyst for bisphenol F and esterification reaction and a preparation method thereof comprise the following process steps:
(1) firstly, adopting a solvothermal method to dissolve a benzoxazole ligand and iridium trichloride in a ratio of 1:2 into ethylene glycol in a ratio of 1:2Stirring and heating to 25-500 ℃ in a mixed solution of ether and water under the protection of special gas, stirring for 36 hours, and carrying out suction filtration to obtain the iridium complex BO. BO and PEt3Mixing the components in a mixed solvent of absolute ethyl alcohol and tertiary butanol according to the ratio of 1:1, stirring the mixture for 4 hours at room temperature, heating the mixture for 12 hours at 110 ℃ by using a reaction kettle, and centrifugally drying the mixture to obtain a product BOP.
(2) BO and Hydrotalcite (HT) are mixed in a mixed solvent of deionized water, absolute ethyl alcohol and tertiary butanol according to a ratio of 1:20, stirred for 24 hours at room temperature, heated for 36 hours at 300 ℃ by a reaction kettle, and centrifugally dried to obtain a product BO @ HT.
(3) BOP and BO @ HT are mixed in a mixed solvent of deionized water, absolute ethyl alcohol and tertiary butyl alcohol according to the ratio of 1:20, the mixture is stirred for 36 hours at room temperature, heated for 12 hours by a reaction kettle at the temperature of 300 ℃, and centrifugally dried to obtain a product BO @ BOP @ HT.
Example three: 4g of phenol and 1g of the novel composite iridium catalyst are added into 10mL of dimethylbenzene, stirred at room temperature, and then slowly added dropwise with a reaction solution of 1:1 of a mixed solution of 10% HCl and 37% formalin (4 mL) was heated to 100 ℃ and reacted for 2 hours. The obtained reaction solution was then filtered to recover the catalyst. The liquid obtained by filtration is a crude product. And recovering the solvent from the obtained crude product by rotary evaporation, recovering the residual phenol by reduced pressure distillation, and recrystallizing the residual product once by using the recovered solvent to obtain the bisphenol F. The yield is 86 percent
Example four: adding 0.1mol of glycerol, 0.6mol of acetic acid and 40mL of toluene into a 250mL round-bottom flask, adding 0.3g of catalyst BO @ BOP @ HT, refluxing and dividing water at the reaction temperature of 110 ℃, stirring for reaction for 2h, and performing chromatographic analysis to obtain the glycerol conversion rate of 99%, the selectivity of diacetin of 83% and the selectivity of triacetin of 14%.
Example five: the composite supported iridium catalyst BO @ BOP @ HT can be recycled:
0.1mol of glycerol, 0.6mol of acetic acid and 40mL of toluene are added into a 250mL round-bottom flask, 0.3g of recovered catalyst BO @ BOP @ HT is added, reflux and water diversion are carried out at the reaction temperature of 110 ℃, stirring is carried out for reaction for 2h, and through chromatographic analysis, the conversion rate of the glycerol is 99%, the selectivity of diacetin is 83%, and the selectivity of triacetin is 13%.
Claims (4)
1. A preparation method of a supported iridium catalyst BO @ BOP @ HT is characterized in that the catalyst is synthesized by the following two types of iridium complexes:
the specific synthesis steps of the catalyst are as follows:
(1) firstly, dissolving a benzoxazole ligand and iridium trichloride in a ratio of 1: 1-30: 1 in a mixed solution of ethylene glycol ethyl ether and water in a ratio of 1: 1-30: 1 by adopting a solvothermal method, stirring and heating to 25-500 ℃ under the protection of nitrogen or argon, stirring for 1-48 h, and performing suction filtration to obtain an iridium complex BO; BO and PEt3Mixing the mixture in a mixed solvent of absolute ethyl alcohol and tert-butyl alcohol according to a ratio of 1: 1-1: 20, stirring for 4-12 h at room temperature, heating and reacting for 2-12 h at 50-110 ℃ by using a reaction kettle, and centrifugally drying to obtain a product BOP;
(2) mixing the BO prepared in the step (1) and Hydrotalcite (HT) in a mixed solvent of deionized water, absolute ethyl alcohol and tert-butyl alcohol according to a ratio of 1: 1-1: 20, stirring at room temperature for 1-48 h, heating and reacting at 20-500 ℃ for 1-72 h by using a reaction kettle at a heating rate of 0.1-10 ℃/min, and centrifugally drying to obtain a product BO @ HT;
(3) mixing the BOP prepared in the step (1) and the BO @ HT prepared in the step (2) in a mixed solvent of deionized water, absolute ethyl alcohol and tert-butyl alcohol according to a ratio of 1: 1-1: 30, stirring at room temperature for 1-48 h, heating at 20-600 ℃ for 1-72 h by using a reaction kettle, wherein the heating rate is 0.1-10 ℃/min, and centrifugally drying to obtain the product BO @ BOP @ HT.
2. The supported iridium catalyst BO @ BOP @ HT prepared by the process of claim 1.
3. A method for synthesizing bisphenol F, which is characterized by utilizing the supported iridium catalyst in claim 2 and comprising the following steps: 4g of phenol and 1g of supported iridium catalyst are added to 10mL of xylene, stirred at room temperature, and then 4mL of a mixture of 1:1, heating a mixed solution of 10 percent HCl and 37 percent formalin to 100 ℃, and reacting for 2 hours; and then filtering the obtained reaction liquid, recovering the catalyst, taking the filtered liquid as a crude product, recovering the solvent of the obtained crude product through rotary evaporation, and recovering the residual phenol through reduced pressure distillation, and recrystallizing the residual product once by using the recovered solvent to obtain the bisphenol F.
4. The use of the supported iridium catalyst of claim 2 for catalyzing the esterification of glycerol and acetic acid by a process comprising: glycerol and acetic acid are added into a reactor according to the molar ratio of 1: 2-1: 7 of alcohol acid, 30-50 mL of toluene and a composite supported iridium catalyst BO @ BOP @ HT with the mass being 0.6-5% of the total mass of reactants are added, the reaction temperature is 100-140 ℃, water is distributed through reflux, and the mixture containing the acetic acid glyceride is obtained after stirring reaction for 2-8 hours.
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| DE10218038A1 (en) * | 2002-04-23 | 2003-11-13 | Alfred Krueger | Production of dicarboxylic acids useful in the production of polyesters or diglycidyl esters involves semi-esterification of bisphenol A with dicarboxylic anhydride(s) |
| CN102068975A (en) * | 2010-12-14 | 2011-05-25 | 西南石油大学 | Catalyst for esterification and deacidification and preparation method thereof |
| CN103706403A (en) * | 2013-12-23 | 2014-04-09 | 北京化工大学 | Application of polyacid intercalated hydrotalcite catalyst in preparing glyceryl triacetate |
| CN103922930A (en) * | 2014-05-06 | 2014-07-16 | 江苏瑞晨化学有限公司 | Method for preparing n-propyl acetate by using multi-acid intercalated hydrotalcite catalyst |
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| DE10218038A1 (en) * | 2002-04-23 | 2003-11-13 | Alfred Krueger | Production of dicarboxylic acids useful in the production of polyesters or diglycidyl esters involves semi-esterification of bisphenol A with dicarboxylic anhydride(s) |
| CN102068975A (en) * | 2010-12-14 | 2011-05-25 | 西南石油大学 | Catalyst for esterification and deacidification and preparation method thereof |
| CN103706403A (en) * | 2013-12-23 | 2014-04-09 | 北京化工大学 | Application of polyacid intercalated hydrotalcite catalyst in preparing glyceryl triacetate |
| CN103922930A (en) * | 2014-05-06 | 2014-07-16 | 江苏瑞晨化学有限公司 | Method for preparing n-propyl acetate by using multi-acid intercalated hydrotalcite catalyst |
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| 苯并噻唑铱络合物的合成及在氢转移反应中的应用;赵科研等;《第十八届全国金属有机化学学术研讨会论文摘要集》;20140819;P2-19 * |
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Effective date of registration: 20210721 Address after: 257000 Haike academy, west of HaoChun Road, Shikou Town, Dongying District, Dongying City, Shandong Province Patentee after: Shandong Yike Chemical Co.,Ltd. Address before: No. 1800 road 214122 Jiangsu Lihu Binhu District City of Wuxi Province Patentee before: Jiangnan University |