WO2020024923A1 - 纳米笼限域催化剂、制备方法及应用 - Google Patents

纳米笼限域催化剂、制备方法及应用 Download PDF

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WO2020024923A1
WO2020024923A1 PCT/CN2019/098304 CN2019098304W WO2020024923A1 WO 2020024923 A1 WO2020024923 A1 WO 2020024923A1 CN 2019098304 W CN2019098304 W CN 2019098304W WO 2020024923 A1 WO2020024923 A1 WO 2020024923A1
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catalyst
salen1
substituted
iii
nanocage
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PCT/CN2019/098304
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English (en)
French (fr)
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陶桂菊
杨为民
何文军
俞峰萍
金少青
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中国石油化工股份有限公司
中国石油化工股份有限公司上海石油化工研究院
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Priority claimed from CN201810854835.1A external-priority patent/CN110773232B/zh
Priority claimed from CN201811251045.0A external-priority patent/CN111097528B/zh
Priority claimed from CN201811251064.3A external-priority patent/CN111097529B/zh
Priority to CA3107987A priority Critical patent/CA3107987A1/en
Priority to KR1020217006072A priority patent/KR20210038653A/ko
Priority to JP2021505279A priority patent/JP7432580B2/ja
Application filed by 中国石油化工股份有限公司, 中国石油化工股份有限公司上海石油化工研究院 filed Critical 中国石油化工股份有限公司
Priority to US17/265,178 priority patent/US20210299644A1/en
Priority to BR112021001734-8A priority patent/BR112021001734A2/pt
Priority to SG11202101016QA priority patent/SG11202101016QA/en
Priority to EP19844935.7A priority patent/EP3831478A4/en
Priority to MX2021001265A priority patent/MX2021001265A/es
Publication of WO2020024923A1 publication Critical patent/WO2020024923A1/zh

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    • C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
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Definitions

  • the invention relates to a nanocage limited-area catalyst, a preparation method and an application thereof.
  • Ethylene glycol is an important organic chemical raw material and intermediate. It is mainly used in the production of polyester fibers, bottle resins, films, engineering plastics, antifreeze and coolants. It is also widely used in the production of plasticizers, desiccants, Raw materials such as lubricants have a wide range of uses (Guangdong Chemical Industry, 2011, 38: 242). As of 2015, the global annual demand for ethylene glycol reached more than 28 million tons (http://www.shell.com/business-customers/chemicals/factsheets-speeches-and-articles/factsheets/mono-ethylene-glycol. html). At present, ethylene glycol is mainly produced by direct hydration of ethylene oxide in the industry.
  • the technology requires a reaction at 190-200 ° C, greater than 1.9 MPa, and a molar ratio of water to ethylene oxide (water ratio for short) of 22-25: 1. Under the conditions, this makes the water content in the product as high as 85 wt.% Or more.
  • the invention aims to provide a catalyst with high activity, low water ratio and short reaction time, which has high activity for alkane oxide hydration to produce diol and does not require activation, and has good recycling performance, and a preparation method thereof to solve the existing problems.
  • the catalyst for the hydration of alkylene oxide to diol has the problems of high water ratio required and good circulation of the activated side.
  • the catalyst provided by the present invention has high activity for diols produced by hydration of alkylene oxide under high and low water ratios and short reaction times, and has good recyclability without activation; the preparation method provided by the present invention is simple It is feasible, which can provide reference for the synthesis of other nanocage confined catalysts.
  • the present invention provides a nanocage confined catalyst, and the catalyst expression is:
  • NC is a material with a nanocage structure
  • M (Salen1) X of the subexpression (I-1) and M '(Salen2) of the subexpression (I-2) are the active centers, respectively; each occurrence of M is independent Ground is selected from Co ions, Fe ions, Ga ions, Al ions, Cr ions and mixtures thereof; each occurrence of M ′ is independently selected from Cu ions, Ni ions and mixtures thereof; m is 0-100; n is 0- 100, provided that at least one of m and n is not 0; each occurrence of Salen1 and Salen2 is a Shiff base derivative independently; X is an axial anion selected from substituted or unsubstituted acetate, substituted or unsubstituted the tosylate, a substituted or unsubstituted benzoate, halogen anion (e.g. F -, Cl -, Br - , I -), SbF 6 -, PF
  • each occurrence of M is independently selected from Fe3 + , Ga3 + , Al3 + , Cr3 +, and mixtures thereof.
  • each occurrence of M ' is independently selected from Cu2 + , Ni2 +, and mixtures thereof.
  • m and n are integers used to represent the number of active center species in the sub-expressions (I-1) and (I-2) of the catalyst.
  • the catalyst may be NC-2 [M (Salen1) X] -1 [M '(Salen2)], which means that the catalyst consists of 2 different formulas (I-1)
  • the active center is combined with one active center in formula (I-2), for example, NC-1 [Fe (Salen1) OAc] -1 [Ga (Salen1) OTs] -1 [Cu (Salen2)], which represents [ Fe (Salen1) OAc], [Ga (Salen1) OTs], and [Cu (Salen2)] are used together in three active centers.
  • the catalyst may be NC-1 [Ga (Salen1) SbF 6 ] -1 [Al (Salen1) Cl] -0 [Cu (Salen2)], which means [Ga (Salen1) SbF 6 ] is used with [Al (Salen1) Cl]; correspondingly, the catalyst can be uniformly expressed as NC- [Ga (Salen1) SbF 6 ]-[Al (Salen1) Cl].
  • the proportion of the amount of use between the active sites of the neutron expressions (I-1) and (I-2) in the catalyst of formula (I) is not particularly limited.
  • the molar ratio between the active centers of the sub-expressions (I-1) and (I-2) is 0.001-1000, such as 0.01-100, or 0.1-10, or 0.5-5.
  • m is 0-20, preferably 0-10, and also preferably 0-5, such as 0-2.
  • n is 0-10, preferably 0-5, and still more preferably 0-3, such as 0-1.
  • m is 0-2 and n is 0-1. In a preferred embodiment, m is 2, n is 0-1, and each M (Salen1) X is the same or different. In a preferred embodiment, m is 2, n is 0, and each M (Salen1) X is the same or different.
  • M (Salen1) X in each (I-1) is independently the same or different.
  • M ′ (Salen2) in each (I-2) is independently the same or different.
  • m is 1 and n is 0, M is not of Co, X is not halogen; and m is 2, wherein the at least one X is SbF 6 -, and preferably, the other X is F - , Cl -, Br - or I -.
  • the NC is a mesoporous silica nanoparticle having a nanocage structure or an organic hybrid mesoporous silica nanoparticle having a nanocage structure.
  • the NC includes SBA-6, SBA-16, FDU-1, FDU-12, KIT-5, AMS-8, and the like.
  • the Shiff base derivative is N, N′-disalicylidene-1,2-cyclohexanediamine or substituted N, N′-disalicylidene- 1,2-cyclohexanediamine, such as (1R, 2R) -N, N'-disalicylidene-1,2-cyclohexanediamine or substituted (1R, 2R) -N, N'- Disalicylidene-1,2-cyclohexanediamine.
  • the catalyst may have the following expression (I-3) or (I-4):
  • M (Salen1) X and M '(Salen2) are active centers, respectively, and M and M' are metal ions.
  • M includes Fe 3+ , Ga 3+ , Al 3+ , Cr 3+ , and M 'includes Cu 2+ , Ni 2+ , and X are axial anions, and Salen1 and Salen2 have the same definition as Salen1 and Salen2 described in the first aspect, that is, Shiff base derivatives.
  • X includes acetate, benzenesulfonate, benzoate, substituted acetate, substituted benzenesulfonate, and substituted benzoate.
  • the catalyst may have the following expression (II-2):
  • M (Salen1) SbF 6 --M (Salen1) X is the active center, M is a metal ion, Salen1 is a Shiff base derivative, X is an axial anion, and X is a halogen anion.
  • M includes Co 3+ , Fe 3+ , Ga 3+ , Al 3+ , and Cr 3+ .
  • halogen anion is F -, Cl -, Br - , I -.
  • the catalyst may have the following expression (III):
  • M (Salen1) X is the active center
  • M is a metal ion
  • M includes Co 3+ , Fe 3+ , Ga 3+ , Al 3+ , Cr 3+
  • Salen is a Shiff base derivative
  • X is an axial anion
  • X is PF 6 -, BF 4 -.
  • Salen1 has the same definition as Salen1 or Salen2 described in the first aspect.
  • the catalyst may have the following expression (II-3):
  • M is a metal ion
  • NC and Salen1 each independently have the same definition as in the aforementioned first aspect and one embodiment of the first to third exemplary variants
  • X is a halogen anion
  • M includes Co 3+ , Fe 3+ , Ga 3+ , Al 3+ , and Cr 3+ .
  • halogen anion is F -, Cl -, Br - , I -.
  • the catalyst may have the following expression (II-4):
  • M is a metal ion
  • NC and Salen1 each independently have the same definition as in the aforementioned first aspect and one embodiment of the first to fourth exemplary variants
  • X is a halogen anion
  • M includes Co 3+ , Fe 3+ , Ga 3+ , Al 3+ , and Cr 3+ .
  • halogen anion is F -, Cl -, Br - , I -.
  • the nanocage confined catalyst according to the present invention may have formula (III-1) or (III-2):
  • NC and Salen1 each independently have the same definition as in the aforementioned first aspect and one embodiment of each exemplified variation.
  • the active centers NC, M, Salen1, Salen2, X, m, and n, etc. have The definition of the first aspect has the same meaning.
  • the second aspect of the present invention also provides a method for preparing a nanocage-limited catalyst, including the following steps:
  • the active center M (Salen1) X or M '(Salen2) and the nanocage material NC are added to a solvent and stirred; the solvent is removed; and the nanocage confined catalyst is obtained by encapsulation.
  • M, M ', Salen1, or Salen2, X, and NC each independently have the same definition as in the aforementioned first aspect and one embodiment of each exemplified variation.
  • the preparation method according to the second aspect of the present invention can be used to prepare the nanocage confined catalyst of the first aspect of the present invention and its exemplary variants.
  • the solvent includes at least one of dichloromethane, ethanol, and methanol.
  • the temperature for stirring and removing the solvent is -96 ° C to 61 ° C. More preferably, it is 20-50 ° C. In an exemplary embodiment, the stirring time is ⁇ 30 min. In an exemplary embodiment, removing the solvent is specifically volatile the solvent with open stirring.
  • the packaging is performed by adding a packaging reagent.
  • the encapsulation of the active center is achieved by using a pre-hydrolyzed ortho-silicate or a pre-hydrolyzed ortho-silicate or a silane coupling agent.
  • the application conditions are water ratio ⁇ 2: 1, reaction time is 10min ⁇ 24h, the yield of ethylene glycol or propylene glycol obtained by first catalyzing the hydration reaction of ethylene oxide or propylene oxide is ⁇ 91%, preferably ⁇ 93%; Yield of ethylene glycol or propylene glycol obtained by direct recycling once after activation regeneration is ⁇ 75%, preferably ⁇ 90%; yield of ethylene glycol or propylene glycol obtained by direct recycling without activation regeneration is ⁇ 64%. It is preferably ⁇ 83%, and more preferably ⁇ 84%.
  • the catalyst of the present invention comprises a matrix material containing a nanocage structure and an active center M (Salen1) X or M '(Salen2) confined in the nanocage, wherein M is Co 3+ , Fe 3+ , Ga 3+ , Al 3+ , Cr 3+ , M 'is Cu 2+ , Ni 2+ , Salen1 and Salen2 are Shiff base derivatives, X is an axial anion, and the catalyst has high and low water ratios and short reactions. Under the time, they have high activity to diols produced by hydration of alkylene oxides, and do not need to be activated to have good recyclability, good stability, and achieved unexpected technical effects.
  • the method provided by the present invention is simple and feasible, and can provide reference for the synthesis of other nanocage confined catalysts.
  • FIG. 1 is a TEM photograph of the catalyst prepared in Example I-1.
  • FIG. 2 is a TEM photograph of the catalyst prepared in Example II-1.
  • FIG. 3 is a TEM photograph of the catalyst prepared in Example III-1.
  • range is given in the form of lower and upper limits, such as one or more lower limits and one or more upper limits.
  • a given range can be defined by selecting a lower limit and an upper limit, and the selected lower and upper limits define the boundaries of the given range. All ranges defined in this way are inclusive and combinable, that is, any lower limit can be combined with any upper limit to form a range.
  • the ranges of 60-110 and 80-120 are listed for specific parameters, and it is understood that the ranges of 60-120 and 80-110 are also expected.
  • the lower limits listed are 1 and 2 and the upper limits listed are 3, 4, and 5, the following ranges are all predictable: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5.
  • the numerical range "a-b” represents a shortened representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the value range "0-5" indicates that all real numbers between "0-5" have been listed in this document, and "0-5" is only an abbreviated representation of the combination of these values.
  • the method includes steps (a) and (b), meaning that the method may include steps (a) and (b) performed sequentially, and may also include steps (b) and (a) performed sequentially.
  • the method can also include step (c), meaning that step (c) can be added to the method in any order, for example, the method can include steps (a), (b), and (c), also It can include steps (a), (c), and (b), and it can also include steps (c), (a), and (b).
  • reaction temperature is 10-100 ° C
  • specific reaction temperature described in the examples is 20 ° C. It can be considered that the range of 10-20 ° C has been specifically disclosed herein, or 20 -100 ° C range, and this range can be combined with other features of other parts of the description to form a new technical solution.
  • a nanocage confined catalyst characterized in that the catalyst expression is: NC- [M (Salen) X] or NC- [M '(Salen)], and NC is a material having a nanocage structure; M (Salen) X and M '(Salen) are active centers, M and M' are metal ions, M includes Fe 3+ , Ga 3+ , Al 3+ , Cr 3+ , and M 'includes Cu 2+ and Ni 2 + , Salen is a Shiff base derivative, and X is an axial anion.
  • NC is a mesoporous silica nanoparticle having a nanocage structure or an organic hybrid mesoporous silica nanoparticle having a nanocage structure.
  • a method for preparing a nanocage confined catalyst comprising the following steps:
  • the active center M (Salen) X or M '(Salen) and the nanocage material NC are added to a solvent, stirred; the solvent is removed; and the nanocage confined catalyst is obtained by encapsulation.
  • the preparation method according to the exemplary embodiment 1.6 wherein the M includes Fe 3+ , Ga 3+ , Al 3+ , Cr 3+ , and M ′ includes Cu 2+ and Ni 2+ ; Salen is Shiff base derivatives, X is an axial anion, and X includes acetate, benzenesulfonate, benzoate, substituted acetate, substituted benzenesulfonate, and substituted benzoate.
  • a high-performance nanocage confined catalyst characterized in that the catalyst expression is: NC- [M (Salen) SbF 6 . M (Salen) X], NC is a material with a nanocage structure; M (Salen) SbF 6 . M (Salen) X is the active center, M is a metal ion, Salen is a Shiff base derivative, X is an axial anion, and X is a halogen anion.
  • the NC is a mesoporous silica nanoparticle having a nanocage structure or an organic hybrid mesoporous silica nanoparticle having a nanocage structure
  • the NC includes SBA-6, SBA-16, FDU-1, FDU-12, KIT-5, AMS-8.
  • halogen anion is F -, Cl -, Br - , I -.
  • a method for preparing a nanocage confined catalyst including the following steps:
  • the active centers M (Salen) SbF 6 , M (Salen) X, and nanocage material NC are added to a solvent, stirred; the solvent is removed; and the nanocage confined catalyst is obtained by encapsulation.
  • a catalyst for the production of diols from the hydration of alkylene oxides characterized in that the catalyst is a nanocage confined catalyst with the expression: NC- [M (Salen) X], M (Salen) X confined
  • NC is a material with a nanocage structure
  • M (Salen) X active center M is a metal ion
  • M includes Co 3+ , Fe 3+ , Ga 3+ , Al 3+ , Cr 3+
  • Salen is Shiff bases derivative
  • X is PF 6 -, BF 4 -.
  • NC is a mesoporous silica nanoparticle having a nanocage structure or an organic hybrid mesoporous silica nanoparticle having a nanocage structure.
  • a method for preparing an alkylene oxide hydration catalyst for diol comprising the following steps:
  • the active center M (Salen) X and the nanocage material NC are dispersed in a solvent and stirred; the solvent is removed; and a packaging reagent is added for encapsulation to obtain a nanocage confined catalyst.
  • Example I-7 The catalyst that was used once in Example I-7 was recovered without regeneration. The catalytic performance was examined under the same catalytic conditions as in Example I-7. The results are shown in Table I-1.
  • Example I-8 The catalyst used in Example I-8 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples I-7 and I-8. The results are shown in Table I-1.
  • Example I-10 The catalyst once used in Example I-10 was recovered without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Example I-10. The results are shown in Table I-1.
  • Example I-11 The catalyst used in Example I-11 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples I-10 and 11. The results are shown in Table I-1.
  • Example I-13 The catalyst used in Example I-13 was recovered without regeneration. The catalytic performance was examined under the same catalytic conditions as in Example I-13. The results are shown in Table I-1.
  • Example I-14 The catalyst used in Example I-14 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples I-13 and 14. The results are shown in Table I-1.
  • Example I-16 The catalyst once used in Example I-16 was recovered without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Example I-16. The results are shown in Table I-2.
  • Example I-17 The catalyst used in Example I-17 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples I-16 and 17. The results are shown in Table I-2.
  • Example I-19 The catalyst used in Example I-19 was recovered and regenerated without activation. The catalytic performance was examined under the same catalytic conditions as in Example I-19. The results are shown in Table I-2.
  • Example I-20 The catalyst used in Example I-20 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples I-19 and 20. The results are shown in Table I-2.
  • Example I-22 The catalyst used in Example I-22 was recovered and regenerated without activation. The catalytic performance was examined under the same catalytic conditions as in Example I-22. The results are shown in Table I-2.
  • Example I-23 The catalyst used in Example I-23 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples I-22 and 23. The results are shown in Table I-2.
  • Example I-25 The catalyst once used in Example I-25 was recovered without regeneration. The catalytic performance was examined under the same catalytic conditions as in Example I-25. The results are shown in Table I-3.
  • Example I-26 The catalyst used in Example I-26 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples I-25 and 26. The results are shown in Table I-3.
  • Example I-28 The catalyst used in Example I-28 was recovered without regeneration and activation. The catalytic performance was examined under the same catalytic conditions as in Example I-28. The results are shown in Table I-3.
  • Example I-29 The catalyst used in Example I-29 was recovered twice without regeneration. Under the same catalytic conditions as in Examples I-28 and 29, the catalytic performance was examined. The results are shown in Table I-3.
  • Example I-31 The catalyst once used in Example I-31 was recovered and regenerated without activation. The catalytic performance was examined under the same catalytic conditions as in Example I-31. The results are shown in Table I-3.
  • Example I-32 The catalyst used in Example I-32 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples I-31 and 32. The results are shown in Table I-3.
  • Example I-34 The catalyst used in Example I-34 was recovered and regenerated without activation. The catalytic performance was examined under the same catalytic conditions as in Example I-34. The results are shown in Table I-4.
  • Example I-35 The catalyst used in Example I-35 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples I-34 and 35. The results are shown in Table I-4.
  • Example I-37 The catalyst once used in Example I-37 was recovered without regeneration and activation. The catalytic performance was examined under the same catalytic conditions as in Example I-37. The results are shown in Table I-4.
  • Example I-38 The catalyst used in Example I-38 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples I-37 and 38. The results are shown in Table I-4.
  • Example I-40 The catalyst once used in Example I-40 was recovered without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Example I-40. The results are shown in Table I-4.
  • Example I-41 The catalyst used in Example I-41 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples I-40 and 41. The results are shown in Table I-4.
  • Comparative Example I-2 The catalyst used in Comparative Example I-2 was recovered and regenerated without activation. The catalytic performance was examined under the same catalytic conditions as Comparative Example I-2. The results are shown in Table I-5.
  • Example II-5 The catalyst used in Example II-5 was recovered without regeneration and activation. The catalytic performance was examined under the same catalytic conditions as in Example II-5. The results are shown in Table II-1.
  • Example II-6 The catalyst used in Example II-6 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples II-5 and 6. The results are shown in Table II-1.
  • Example II-8 The catalyst used in Example II-8 was recovered without regeneration. The catalytic performance was examined under the same catalytic conditions as in Example II-8. The results are shown in Table II-1.
  • Example II-8 The catalyst used in Example II-8 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples II-8 and 9. The results are shown in Table II-1.
  • Example II-11 The catalyst once used in Example II-11 was recovered and was regenerated without activation. The catalytic performance was examined under the same catalytic conditions as in Example II-11. The results are shown in Table II-2.
  • Example II-12 The catalyst used in Example II-12 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples II-11 and 12. The results are shown in Table II-2.
  • Example II-14 The catalyst that was used once in Example II-14 was recovered without regeneration. The catalytic performance was examined under the same catalytic conditions as in Example II-14. The results are shown in Table II-2.
  • Example II-15 The catalyst used in Example II-15 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as those in Examples II-14 and 15. The results are shown in Table II-2.
  • Example II-17 The catalyst once used in Example II-17 was recovered without regeneration and activation. The catalytic performance was examined under the same catalytic conditions as in Example II-17. The results are shown in Table II-3.
  • Example II-18 The catalyst used in Example II-18 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples II-17 and 18. The results are shown in Table II-3.
  • Example II-20 The catalyst once used in Example II-20 was recovered without regeneration and activation. The catalytic performance was examined under the same catalytic conditions as in Example II-20. The results are shown in Table II-3.
  • Example II-21 The catalyst used in Example II-21 was recovered twice without regeneration. Under the same catalytic conditions as those in Examples II-21 and 22, the catalytic performance was examined. The results are shown in Table II-3.
  • Example II-23 The catalyst once used in Example II-23 was recovered without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Example II-23. The results are shown in Table II-4.
  • Example II-24 The catalyst used in Example II-24 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples II-23 and 24. The results are shown in Table II-4.
  • Example II-26 The catalyst once used in Example II-26 was recovered without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Example II-26. The results are shown in Table II-4.
  • Example II-27 The catalyst used in Example II-27 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples II-26 and 27. The results are shown in Table II-4.

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Abstract

一种纳米笼限域催化剂、制备方法及其用途，所述催化剂表达式为：NC-m[M(Salen1)X]-n[M'(Salen2)]，其中：NC为具有纳米笼结构的材料，M(Salen1)X和M'(Salen2)分别为活性中心；每次出现的M独立地选自Co离子，Fe离子，Ga离子，Al离子，Cr离子及其混合；每次出现的M'独立地选自Cu离子，Ni离子及其混合；m为0-100；n为0-100，条件是m和n中至少一个不为0；每次出现的Salen1和Salen2各自独立地为Shiff碱类衍生物；X为轴阴离子，选自取代或未取代的醋酸根、取代或未取代的苯磺酸根、取代或未取代的苯甲酸根，F -，Cl -，Br -，I -，SbF 6 -，PF 6 -，BF 4 -及其混合。

Description

纳米笼限域催化剂、制备方法及应用 技术领域
本发明涉及一种纳米笼限域催化剂、制备方法及其应用。
背景技术
乙二醇是一种重要的有机化工原料及中间体，主要用于生产聚酯纤维、瓶用树脂、薄膜、工程塑料、防冻剂和冷却剂，还大量用作生产增塑剂、干燥剂、润滑剂等多种化工产品的原料，用途非常广泛(广东化工，2011，38：242)。截至2015年，乙二醇的全球年需求量高达2800万吨以上(http://www.shell.com/business-customers/chemicals/factsheets-speeches-and-articles/factsheets/mono-ethylene-glycol.html)。目前工业上主要通过环氧乙烷直接水合法生产乙二醇。为了降低副产物如二甘醇和三甘醇的含量，该技术要求反应在190–200℃、大于1.9MPa以及水和环氧乙烷进料摩尔比(简称水比)为22-25:1的条件下进行，这使得产物中水的含量高达85wt.％以上。除去如此大量的水，需要使用多效蒸发系统并消耗大量的蒸汽(如，当水比为20:1时，生产1吨乙二醇要消耗5.5吨蒸汽)，最终导致乙二醇的整个生产过程能耗大、设备复杂、流程长、生产成本高(工业催化，2002，10：3；石油化工，2010，39：562；化工中间体，2009：59)。因此，发展低水比的环氧乙烷催化水合技术有望实现节能降耗，其核心是催化剂的研制。
迄今为止，多种催化剂被开发出来，如阴/阳离子交换树脂(CN102372815B；Journal of Applied Polymer Science，2010，115：2946；RSC Advances，2015，5：2550)、负载型金属氧化物(CN100413579C；Journal of Catalysis，2006，241:173)、Sn沸石(CN104437607B；ACS Catalysis，2016，6：2955)等。然而这些催化剂仍需要较高的水比(≥8:1)或者长的反应时间(≥24h)方具有良好的催化性能。最近一项突破性进展，为大化所开发的纳米笼催化剂FDU-12-[Co(Salen)X](X＝OAc -/OTs -)(CN201110070058.X；Angewandte Chemie International Edition，2012，51：11517；Journal of Catalysis，2016，338：184),其可在水比为2:1的条件下，获得98％ 以上的乙二醇收率。然而FDU-12-[Co(Salen)X](X＝OAc -/OTs -)稳定性差，需要活化，方具有良好的循环使用性，这严重限制了其工业化应用。因此，本领域迫切需要开发出在低水比和短反应时间下对环氧烷烃水合制二醇具有高的活性和不需活化即具有良好的循环使用性的催化剂。
发明内容
本发明旨在提供一种高、低水比和短反应时间下均对环氧烷烃水合制二醇具有高活性和不需活化即具有良好循环使用性的催化剂及其制备方法，以解决现有技术中环氧烷烃水合制二醇的催化剂存在所需水比高以及需活化方具有良好循环性的问题。本发明提供的催化剂，在高、低水比和短反应时间下，均对环氧烷烃水合制二醇具有高活性，并且不需活化便具有良好循环使用性；本发明提供的制备方法，简单可行，可为其他纳米笼限域催化剂的合成提供借鉴。
第一方面，本发明提供一种纳米笼限域催化剂，所述的催化剂表达式为：
NC-m[M(Salen1)X]-n[M'(Salen2)]，(I)
其中，NC为具有纳米笼结构的材料，子表达式(I-1)的M(Salen1)X和子表达式(I-2)的M'(Salen2)分别为活性中心；每次出现的M独立地选自Co离子，Fe离子，Ga离子，Al离子，Cr离子及其混合；每次出现的M'独立地选自Cu离子，Ni离子及其混合；m为0-100；n为0-100，条件是m和n中至少一个不为0；每次出现的Salen1和Salen2各自独立地为Shiff碱类衍生物；X为轴阴离子，选自取代或未取代的醋酸根、取代或未取代的苯磺酸根、取代或未取代的苯甲酸根，卤素阴离子(如F -，Cl -，Br -，I -)，SbF 6 -，PF 6 -，BF 4 -及其混合。
在一个实施方案中，每次出现的M独立地选自Fe 3+，Ga 3+，Al 3+，Cr 3+及其混合。
在一个实施方案中，每次出现的M'独立地选自Cu 2+，Ni 2+及其混合。
根据本发明，m和n是整数，用来表示催化剂的子表达式(I-1)和(I-2)中活性中心种类的数量。例如，在一个实施方案中，所述催化剂可以为NC-2[M(Salen1)X]-1[M'(Salen2)]，其表示该催化剂由2种不同的式 (I-1)中的活性中心和1种式(I-2)中的活性中心组合形成，例如为NC-1[Fe(Salen1)OAc]-1[Ga(Salen1)OTs]-1[Cu(Salen2)]，表示[Fe(Salen1)OAc]、[Ga(Salen1)OTs]和[Cu(Salen2)]这3种结构的活性中心一起使用。再如，在一个实施方案中，所述催化剂可以为NC-1[Ga(Salen1)SbF 6]-1[Al(Salen1)Cl]-0[Cu(Salen2)]，表示[Ga(Salen1)SbF 6]和[Al(Salen1)Cl]一起使用；相应地，该催化剂可以统一表示为NC-[Ga(Salen1)SbF 6]-[Al(Salen1)Cl]。
根据本发明，式(I)催化剂中子表达式(I-1)和(I-2)的活性中心之间的用量比例没有特别限制。在一个实施方案中，子表达式(I-1)和(I-2)的活性中心之间的摩尔比为0.001-1000，例如0.01-100，或者0.1-10，或0.5-5。
在一个实施方案中，m为0-20，优选0-10，还优选0-5，例如0-2。
在一个实施方案中，n为0-10，优选0-5，还优选0-3，例如0-1。
在一个实施方案中，m为0-2，n为0-1。在一个优选实施方案中，m为2，n为0-1，每个M(Salen1)X相同或不同。在一个优选实施方案中，m为2，n为0，每个M(Salen1)X相同或不同。
在前述实施方案中，当m为2或更大时，每个(I-1)中M(Salen1)X独立地相同或不同。
在前述实施方案中，当n为2或更大时，每个(I-2)中M'(Salen2)独立地相同或不同。
在一个实施方案中，m为1，且n为0，M不为Co，X不为卤素；以及m为2时，其中至少一个X为SbF 6 -，以及优选地，另一个X为F -，Cl -，Br -或I -。
在一个实施方案中，优选地，所述NC为具有纳米笼结构的介孔二氧化硅纳米颗粒或者具有纳米笼结构的有机杂化的介孔二氧化硅纳米颗粒。
在一个实施方案中，优选地，所述NC包括SBA-6，SBA-16，FDU-1，FDU-12，KIT-5，AMS-8等。
在一个实施方案中，优选地，所述Shiff碱类衍生物为N,N′-二亚水杨基-1,2-环己二胺或取代的N,N′-二亚水杨基-1,2-环己二胺，例如为(1R,2R)-N,N′-二亚水杨基-1,2-环己二胺或取代的(1R,2R)-N,N′-二亚水杨基-1,2-环己二胺。
在本发明第一方面所述纳米笼限域催化剂的第一例示变体中，所述的催化剂可以具有如下表达式(I-3)或(I-4)：
NC-[M(Salen1)X](I-3)，或者
NC-[M'(Salen2)](I-4)；
其中，M(Salen1)X和M'(Salen2)分别为活性中心，M和M'为金属离子，M包括Fe 3+，Ga 3+，Al 3+，Cr 3+，M'包括Cu 2+，Ni 2+，X为轴阴离子，Salen1和Salen2具有与第一方面所述的Salen1和Salen2相同的定义，即为Shiff碱类衍生物。
上述第一例示变体的一个实施方案中，优选地，X包括醋酸根、苯磺酸根、苯甲酸根、取代的醋酸根、取代的苯磺酸根、取代的苯甲酸根。
在本发明第一方面所述纳米笼限域催化剂的第二例示变体中，所述的催化剂可以具有如下表达式(II-2)：
NC-[M(Salen1)SbF 6-M(Salen1)X](II-2)；
M(Salen1)SbF 6--M(Salen1)X为活性中心，M为金属离子，Salen1为Shiff碱类衍生物，X为轴阴离子，X为卤素阴离子。
上述第二例示变体的一个实施方案中，优选地，M包括Co 3+，Fe 3+，Ga 3+，Al 3+，Cr 3+。
上述第二例示变体的一个实施方案中，优选地，所述卤素阴离子为F -，Cl -，Br -，I -。
在本发明第一方面所述纳米笼限域催化剂的第三例示变体中，所述的催化剂可以具有如下表达式(III)：
NC-[M(Salen1)X](III)
其中，M(Salen1)X为活性中心，M为金属离子，M包括Co 3+，Fe 3+，Ga 3+，Al 3+，Cr 3+，Salen为Shiff碱类衍生物，X为轴阴离子，X为PF 6 -，BF 4 -。
上述第三例示变体的一个实施方案中，Salen1具有与第一方面所述的Salen1或Salen2相同的定义。
在本发明第一方面所述纳米笼限域催化剂的第四例示变体中，所述的催化剂可以具有如下表达式(II-3)：
NC-[Co(Salen1)SbF 6-M(Salen1)X](II-3)，
式(II-3)中，M为金属离子，NC、Salen1各自独立地具有与前述第 一方面以及第一至第三例示变体的一个实施方案中相同的定义，X为卤素阴离子。
上述第四例示变体的一个实施方案中，优选地，M包括Co 3+，Fe 3+，Ga 3+，Al 3+，Cr 3+。
上述第四例示变体的一个实施方案中，优选地，所述卤素阴离子为F -，Cl -，Br -，I -。
在本发明第一方面所述纳米笼限域催化剂的第五例示变体中，所述的催化剂可以具有如下表达式(II-4)：
NC-[M(Salen1)SbF 6-Co(Salen1)X](II-4)，
式(II-4)中，M为金属离子，NC、Salen1各自独立地具有与前述第一方面以及第一至第四例示变体的一个实施方案中相同的定义，X为卤素阴离子。
上述第五例示变体的一个实施方案中，优选地，M包括Co 3+，Fe 3+，Ga 3+，Al 3+，Cr 3+。
上述第五例示变体的一个实施方案中，优选地，所述卤素阴离子为F -，Cl -，Br -，I -。
在本发明第一方面所述纳米笼限域催化剂的第六例示变体中，本发明所述纳米笼限域催化剂可以具有式(III-1)或(III-2)：
NC-[Co(Salen1)PF 6](III-1)或
NC-[Co(Salen1)BF 4](III-2)，
其中，NC、Salen1各自独立地具有与前述第一方面以及各例示变体的一个实施方案中相同的定义。
以上所述本发明第一方面的各个例示变体中，在各个例示变体中没有专门指明的情况下，涉及的活性中心、NC、M、Salen1、Salen2、X、m、和n等具有与第一方面的定义相同的含义。
本发明第二方面还提供了一种纳米笼限域催化剂的制备方法，包括以下步骤：
将活性中心M(Salen1)X或M'(Salen2)、纳米笼材料NC加入溶剂中，搅拌；移除溶剂；封装，得纳米笼限域催化剂。
其中，M、M'、Salen1或Salen2、X和NC各自独立地具有与前述第一方面以及各例示变体的一个实施方案中相同的定义。
在一个实施方案中，本发明所述第二方面的制备方法可用于制备 本发明第一方面及其各例示变体的纳米笼限域催化剂。
上述技术方案中，优选地，所述的溶剂包括二氯甲烷、乙醇和甲醇中的至少一种。
上述技术方案中，优选地，所述搅拌和移除溶剂温度为-96℃～61℃。较为优选地，20-50℃。在一个例示的实施方案中，所述搅拌时间≥30min。在一个例示的实施方案中，移除溶剂具体为敞口搅拌下将所述溶剂挥发。
上述技术方案中，优选地，所述封装为加封装试剂进行封装。在一个实施方案中，具体为，采用预水解的正硅酸甲酯或者预水解的正硅酸乙酯或者硅烷偶联剂实现活性中心的封装。
本发明第三方面还提供一种上述催化剂或采用上述制备方法制得的催化剂在环氧烷烃水合制二醇反应中的应用。
应用条件为水比≥2:1，反应时间为10min～24h，首次催化环氧乙烷或者环氧丙烷的水合反应得到的乙二醇或者丙二醇的产率≥91％，优选≥93％；不经过活化再生直接循环使用1次得到的乙二醇或者丙二醇的产率≥75％，优选≥90％；不经过活化再生直接循环使用2次得到的乙二醇或者丙二醇的产率≥64％，优选≥83％，还优选≥84％。
本发明催化剂，包括含纳米笼结构的基体材料，和限域于所述纳米笼中的活性中心M(Salen1)X或M'(Salen2)，其中，M为Co 3+，Fe 3+，Ga 3+，Al 3+，Cr 3+，M'为Cu 2+，Ni 2+，Salen1和Salen2为Shiff碱类衍生物，X为轴阴离子，所述催化剂，在高、低水比和短反应时间下均对环氧烷烃水合制二醇具有高活性，并且不需活化即具有良好的循环使用性，稳定性好，取得了意料不到的技术效果。本发明提供的方法，简单可行，为其他纳米笼限域催化剂的合成提供借鉴。
附图说明
图1是实施例I-1中制得的催化剂的TEM照片。
图2是实施例II-1中制得的催化剂的TEM照片。
图3是实施例III-1中制得的催化剂的TEM照片。
具体实施方式
下面对本发明的具体实施方式进行详细说明，但是需要指出的是，本发明的保护范围并不受这些具体实施方式的限制，而是由附录的权利要求书来确定。
本说明书提到的所有出版物、专利申请、专利和其它参考文献全都引于此供参考。除非另有定义，本说明书所用的所有技术和科学术语都具有本发明所属领域内一般技术人员常理解的相同意思。在有冲突的情况下，包括定义在内，以本说明书为准。
本说明书提到的各种范围均包括它们的端点在内，除非另有明确说明。此外，当对量、浓度或其它值或参数给出范围、一个或多个优选范围或很多优选上限值与优选下限值时，应把它理解为具体公开了由任意对任意范围上限值或优选值与任意范围下限值或优选值所形成的所有范围，不论是否一一公开了这些数值对。
在没有明确指明的情况下，本说明书内所提到的所有百分数、份数、比率等都是以重量为基准的，除非以重量为基准时不符合本领域技术人员的常规认识。
本文所公开的“范围”以下限和上限的形式，例如一个或多个下限与一个或多个上限的形式给出。给定范围可通过选择一个下限和一个上限来进行限定，选定的下限和上限限定了给定范围的边界。所有以这种方式限定的范围是包含和可组合的，即任何下限可与任何上限组合形成一个范围。例如，针对特定参数列出了60-110和80-120的范围，理解为60-120和80-110的范围也是可预料到的。此外，如果列出的下限为1和2而列出的上限为3，4和5，则下面的范围都是可预料到的：1-3、1-4、1-5、2-3、2-4和2-5。
在本文中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本文中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。
在本文中，除非有其他说明，组合物的各组分的含量范围以及其优选范围之间可以相互组合形成新的技术方案。
在本文中，除非有其他说明，所有组合物中各组分的百分含量之和为100％。
在本文中，除非有其他说明，本文所提到的所有实施方式以及优 选实施方式可以相互组合形成新的技术方案。
在本文中，除非有其他说明，本文所提到的所有技术特征以及优选特征可以相互组合形成新的技术方案。
在本文中，除非有其他说明，本文所提到的所有步骤可以顺序进行，也可以随机进行，但是优选是顺序进行的。例如，所述方法包括步骤(a)和(b)，表示所述方法可包括顺序进行的步骤(a)和(b)，也可以包括顺序进行的步骤(b)和(a)。例如，提到所述方法还可包括步骤(c)，表示步骤(c)可以任意顺序加入到所述方法，例如，所述方法可以包括步骤(a)、(b)和(c)，也可包括步骤(a)、(c)和(b)，也可以包括步骤(c)、(a)和(b)等。
在本文中，除非有其他说明，术语“包括”、“包含”、“含有”、“具有”和类似措词表示开放式，但是也应当理解为同时明确公开了封闭式的情形。例如，“包括”表示还可以包含没有列出的其他要素，但是也同时明确公开了仅包括所列出的要素的情形。此外，如本文所用，将“包含/包括”解释为明确说明存在提及的所述特征、整数、步骤或组分，但是不排除一种或多种其它特征、整数、步骤、组分或其组的存在或添加。另外，术语“包含”旨在包括由术语“基本上由…组成”和“由…组成”涵盖的实施方式。相似地，术语“基本上由…组成”旨在包括由术语“由…组成”涵盖的实施方式。
在本文中，除非有其他说明，实施例中记载的具体步骤、具体数值以及具体物质可与说明书其它部分的其他特征结合。例如，说明书发明内容或具体实施方式部分提到反应的温度为10-100℃，而实施例记载的具体反应温度为20℃，那么可以认为本文已经具体公开了10-20℃的范围，或者20-100℃的范围，且该范围可以与说明书其它部分的其他特征结合起来形成新的技术方案。
根据本发明，例如提供了以下的例示实施方式：
1.1.一种纳米笼限域催化剂，其特征在于，所述催化剂表达式为：NC-[M(Salen)X]或者NC-[M'(Salen)]，NC为具有纳米笼结构的材料；M(Salen)X和M'(Salen)为活性中心，M和M'为金属离子，M包括Fe 3+，Ga 3+，Al 3+，Cr 3+，M'包括Cu 2+，Ni 2+，Salen为Shiff碱类衍生物，X为轴阴离子。
1.2、根据例示实施方式1.1所述的催化剂，其特征在于，所述X 包括醋酸根、苯磺酸根、苯甲酸根、取代的醋酸根、取代的苯磺酸根、取代的苯甲酸根。
1.3、根据例示实施方式1.1所述的催化剂，其特征在于，所述NC为具有纳米笼结构的介孔二氧化硅纳米颗粒或者具有纳米笼结构的有机杂化的介孔二氧化硅纳米颗粒。
1.4、根据例示实施方式1.1所述的催化剂，其特征在于，所述NC包括SBA-6，SBA-16，FDU-1，FDU-12，KIT-5，AMS-8。
1.5、根据例示实施方式1.1所述的催化剂，其特征在于，所述Shiff碱类衍生物为N,N′-二亚水杨基-1,2-环己二胺或取代的N,N′-二亚水杨基-1,2-环己二胺。
1.6、一种纳米笼限域催化剂的制备方法，包括以下步骤：
将活性中心M(Salen)X或M'(Salen)、纳米笼材料NC加入溶剂中，搅拌；移除溶剂；封装，得纳米笼限域催化剂。
1.7、根据例示实施方式1.6所述的制备方法，其特征在于，所述M包括Fe 3+，Ga 3+，Al 3+，Cr 3+，M'包括Cu 2+，Ni 2+；Salen为Shiff碱类衍生物，X为轴阴离子，所述X包括醋酸根、苯磺酸根、苯甲酸根、取代的醋酸根、取代的苯磺酸根、取代的苯甲酸根。
1.8、根据例示实施方式1.6所述的制备方法，其特征在于，所述的溶剂包括二氯甲烷、乙醇、和甲醇中的至少一种。
1.9、根据例示实施方式1.6所述的制备方法，其特征在于，所述搅拌和移除溶剂温度为-96℃～61℃。
1.10、例示实施方式1.1-1.5任一所述催化剂或采用例示实施方式1.6-1.9任一所述制备方法制得的催化剂在环氧烷烃水合制二醇反应中的应用。
2.1.一种高性能纳米笼限域催化剂，其特征在于，所述催化剂表达式为：NC-[M(Salen)SbF 6﹒M(Salen)X]，NC为具有纳米笼结构的材料；M(Salen)SbF 6﹒M(Salen)X为活性中心，M为金属离子，Salen为Shiff碱类衍生物，X为轴阴离子，X为卤素阴离子。
2.2、根据例示实施方式2.1所述的催化剂，其特征在于，所述M独立地包括Co 3+，Fe 3+，Ga 3+，Al 3+，Cr 3+。
2.3、根据例示实施方式2.1所述的催化剂，其特征在于，所述NC为具有纳米笼结构的介孔二氧化硅纳米颗粒或者具有纳米笼结构的有 机杂化的介孔二氧化硅纳米颗粒，优选地，所述NC包括SBA-6，SBA-16，FDU-1，FDU-12，KIT-5，AMS-8。
2.4、根据例示实施方式2.1所述的催化剂，其特征在于，所述Shiff碱类衍生物为N,N′-二亚水杨基-1,2-环己二胺或取代的N,N′-二亚水杨基-1,2-环己二胺。
2.5、根据例示实施方式2.1所述的催化剂，其特征在于，所述卤素阴离子为F -，Cl -，Br -，I -。
2.6、一种纳米笼限域催化剂的制备方法，包括以下步骤：
将活性中心M(Salen)SbF 6、M(Salen)X、纳米笼材料NC加入溶剂中，搅拌；移除溶剂；封装，得纳米笼限域催化剂。
2.7、根据例示实施方式2.6所述的制备方法，其特征在于，所述的溶剂包括二氯甲烷、乙醇和甲醇的至少一种。
2.8、根据例示实施方式2.6所述的制备方法，其特征在于，所述搅拌和移除溶剂温度为-96℃～61℃。
2.9、根据例示实施方式2.6所述的制备方法，其特征在于，所述M为金属离子，M包括Co 3+，Fe 3+，Ga 3+，Al 3+，Cr 3+，Salen为Shiff碱类衍生物，X为轴阴离子，X为卤素阴离子。
2.10、例示实施方式2.1-2.5任一所述催化剂或采用例示实施方式2.6-2.9任一所述制备方法制得的催化剂在环氧烷烃水合制二醇反应中的应用。
3.1.一种环氧烷烃水合制二醇催化剂，其特征在于，所述催化剂是一种纳米笼限域催化剂，表达式为：NC-[M(Salen)X]，M(Salen)X限域于NC中，NC为具有纳米笼结构的材料；M(Salen)X活性中心，M为金属离子，M包括Co 3+，Fe 3+，Ga 3+，Al 3+，Cr 3+，Salen为Shiff碱类衍生物，X为轴阴离子，X为PF 6 -，BF 4 -。
3.2、根据例示实施方式3.1所述的催化剂，其特征在于，所述NC为具有纳米笼结构的介孔二氧化硅纳米颗粒或者具有纳米笼结构的有机杂化的介孔二氧化硅纳米颗粒。
3.3、根据例示实施方式3.1所述的催化剂，其特征在于，所述NC包括SBA-6，SBA-16，FDU-1，FDU-12，KIT-5，AMS-8。
3.4、根据例示实施方式3.1所述的催化剂，其特征在于，所述Shiff碱类衍生物为N,N′-二亚水杨基-1,2-环己二胺或取代的N,N′-二亚水 杨基-1,2-环己二胺。
3.5、一种环氧烷烃水合制二醇催化剂的制备方法，包括以下步骤：
将活性中心M(Salen)X、纳米笼材料NC分散到溶剂中，搅拌；移除溶剂；加封装试剂进行封装，得纳米笼限域催化剂。
3.6、根据例示实施方式3.5所述的制备方法，其特征在于，所述的溶剂包括二氯甲烷、乙醇和甲醇的至少一种。
3.7、根据例示实施方式3.5所述的制备方法，其特征在于，所述搅拌和移除溶剂温度为-96℃～61℃。
3.8、根据例示实施方式3.5所述的制备方法，其特征在于，所述M为金属离子，M包括Co 3+，Fe 3+，Ga 3+，Al 3+，Cr 3+，Salen为Shiff碱类衍生物，X为轴阴离子，X包括PF 6 -，BF 4 -。
3.9、根据例示实施方式3.5所述的制备方法，其特征在于，所述移除溶剂具体为，敞口搅拌使溶剂挥发。
3.10、例示实施方式3.1-3.4任一所述催化剂或采用例示实施方式3.5-3.9任一所述制备方法制得的催化剂在环氧烷烃水合制二醇反应中的应用。
实施例I-1
称取0.50g的F127，0.6g的均三甲苯和2.5g的KCl于16℃下溶解到30mL 2M HCl水溶液中，搅拌2h；加入2.08g的TEOS，继续在16℃下搅拌24h后置于100℃烘箱中水热24h。取出洗涤干燥后，于550℃煅烧6h得纳米笼基体材料FDU-12。称取0.2g的对甲基苯磺酸单水合物和0.490g的Fe(N,N′-二亚水杨基-1,2-环己二胺)，溶解于20mL二氯甲烷中，室温敞口搅拌12h，将溶剂旋去，用正己烷充分洗涤干燥后得活性中心Fe(N,N′-二亚水杨基-1,2-环己二胺)OTs。称取1.0g的FDU-12，置于4mL含100mg Fe(N,N′-二亚水杨基-1,2-环己二胺)OTs的二氯甲烷溶液中，20℃密封搅拌2h后，20℃敞口搅拌至溶剂挥发干。加入预水解的正硅酸甲酯，搅拌40min后，加入乙醇，离心分离，充分洗涤，干燥得催化剂I-A。
实施例I-2
称取1.0g的SBA-6，置于4mL含300mg Ga(N,N′-双(3,5-二叔丁基亚水杨基)-1,2-环乙二胺)OAc的乙醇和二氯甲烷混合溶液中，20 ℃密封搅拌3h后，40℃敞口搅拌至溶剂挥发干。加入预水解的正硅酸乙酯，搅拌60min后，加入乙醇，离心分离，充分洗涤，干燥得催化剂I-B。
实施例I-3
称取1.0g的SBA-16，置于6mL含400mg Al(N,N′-二亚水杨基-1,2-环乙二胺)OAc的甲醇溶液中，20℃密封搅拌4h后，30℃敞口搅拌至溶剂挥发干。加入预水解的正硅酸乙酯，搅拌60min后，加入乙醇，离心分离，充分洗涤，干燥得催化剂I-C。
实施例I-4
称取1.0g的FDU-1，置于6mL含500mg Cr(N,N′-双(3-二叔丁基亚水杨基)-1,2-环己二胺)OAc的甲醇和乙醇混合溶液中，30℃密封搅拌4h后，40℃敞口搅拌至溶剂挥发干。加入2mL甲苯，2mg对甲苯磺酸和20mmol三甲氧基丙基硅烷回流过夜，离心分离，充分洗涤，干燥得催化剂I-D。
实施例I-5
称取1.0g的KIT-5，置于8mL含600mg Cu(N,N′-双(3-叔丁基亚水杨基)-1,2-环乙二胺)的乙醇溶液中，30℃密封搅拌3h后，50℃敞口搅拌至溶剂挥发干。加入2mL甲苯，2mg对甲苯磺酸和20mmol三甲氧基丙基硅烷回流过夜，离心分离，充分洗涤，干燥得催化剂I-E。
实施例I-6
称取1.0g的AMS-8，置于10mL含700mg Ni(N,N′-双(5-叔丁基亚水杨基)-1,2-环己二胺)的乙醇溶液中，30℃密封搅拌3h后，50℃敞口搅拌至溶剂挥发干。加入2mL甲苯，2mg对甲苯磺酸和20mmol三甲氧基丙基硅烷回流过夜，离心分离，充分洗涤，干燥得催化剂I-F。
对比例I-1
称取1.0g的SBA-16，置于6mL含400mg Co(N,N′-二亚水杨基-1,2-环己二胺)OTs的甲醇溶液中，20℃密封搅拌4h后，30℃敞口搅拌至溶剂挥发干。加入预水解的正硅酸乙酯，搅拌60min后，加入乙醇，离心分离，充分洗涤，干燥得催化剂I-G。
实施例I-7
称取1.32g的环氧乙烷，在温度为20℃、压力为1.0MPa、水比为2:1、催化剂和环氧乙烷物质的量比为1:1000以及反应时间为7h 条件下，考察催化剂I-A的性能，结果见表I-1。
实施例I-8
回收实施例I-7中用过一次的催化剂，不经活化再生，在与实施例I-7相同的催化条件下，考察其催化性能，结果见表I-1。
实施例I-9
回收实施例I-8中用过两次的催化剂，不经活化再生，在与实施例I-7和I-8相同的催化条件下，考察其催化性能，结果见表I-1。
实施例I-10
称取1.32g的环氧乙烷，在温度为20℃、压力为1.0MPa、水比为2:1、催化剂和环氧乙烷物质的量比为1:1000以及反应时间为7h条件下，考察催化剂I-B的性能，结果见表I-1。
实施例I-11
回收实施例I-10中用过一次的催化剂，不经活化再生，在与实施例I-10相同的催化条件下，考察其催化性能，结果见表I-1。
实施例I-12
回收实施例I-11中用过两次的催化剂，不经活化再生，在与实施例I-10和11相同的催化条件下，考察其催化性能，结果见表I-1。
实施例I-13
称取1.32g的环氧乙烷，在温度为20℃、压力为1.0MPa、水比为2:1、催化剂和环氧乙烷物质的量比为1:1000以及反应时间为7h条件下，考察催化剂I-C的性能，结果见表I-1。
实施例I-14
回收实施例I-13中用过一次的催化剂，不经活化再生，在与实施例I-13相同的催化条件下，考察其催化性能，结果见表I-1。
实施例I-15
回收实施例I-14中用过两次的催化剂，不经活化再生，在与实施例I-13和14相同的催化条件下，考察其催化性能，结果见表I-1。
表I-1催化剂I-A、I-B、I-C的循环使用性
催化剂 首次乙二醇产率(％) 循环1次乙二醇产率(％) 循环2次乙二醇产率(％)
I-A 94 79 69
I-B 94 78 68
I-C 92 76 66
实施例I-16
称取1.32g的环氧乙烷，在温度为40℃、压力为1.0MPa、水比为6:1、催化剂和环氧乙烷物质的量比为1:500以及反应时间为4h条件下，考察催化剂I-D的性能，结果见表I-2。
实施例I-17
回收实施例I-16中用过一次的催化剂，不经活化再生，在与实施例I-16相同的催化条件下，考察其催化性能，结果见表I-2。
实施例I-18
回收实施例I-17中用过两次的催化剂，不经活化再生，在与实施例I-16和17相同的催化条件下，考察其催化性能，结果见表I-2。
实施例I-19
称取1.32g的环氧乙烷，在温度为40℃、压力为1.0MPa、水比为6:1、催化剂和环氧乙烷物质的量比为1:500以及反应时间为4h条件下，考察催化剂I-E的性能，结果见表I-2。
实施例I-20
回收实施例I-19中用过一次的催化剂，不经活化再生，在与实施例I-19相同的催化条件下，考察其催化性能，结果见表I-2。
实施例I-21
回收实施例I-20中用过两次的催化剂，不经活化再生，在与实施例I-19和20相同的催化条件下，考察其催化性能，结果见表I-2。
实施例I-22
称取1.32g的环氧乙烷，在温度为40℃、压力为1.0MPa、水比为6:1、催化剂和环氧乙烷物质的量比为1:500以及反应时间为4h条件下，考察催化剂I-F的性能，结果见表I-2。
实施例I-23
回收实施例I-22中用过一次的催化剂，不经活化再生，在与实施例I-22相同的催化条件下，考察其催化性能，结果见表I-2。
实施例I-24
回收实施例I-23中用过两次的催化剂，不经活化再生，在与实施例I-22和23相同的催化条件下，考察其催化性能，结果见表I-2。
表I-2催化剂I-D、I-E、I-F的循环使用性
催化剂 首次乙二醇产率(％) 循环1次乙二醇产率(％) 循环2次乙二醇产率(％)
I-D 94 79 68
I-E 92 77 67
I-F 93 78 68
实施例I-25
称取1.74g的环氧丙烷，在温度为40℃、压力为1.0MPa、水比为2:1、催化剂和环氧丙烷物质的量比为1：1000以及反应时间为7h条件下，考察催化剂I-D的性能，结果见表I-3。
实施例I-26
回收实施例I-25中用过一次的催化剂，不经活化再生，在与实施例I-25相同的催化条件下，考察其催化性能，结果见表I-3。
实施例I-27
回收实施例I-26中用过两次的催化剂，不经活化再生，在与实施例I-25和26相同的催化条件下，考察其催化性能，结果见表I-3。
实施例I-28
称取1.74g的环氧丙烷，在温度为40℃、压力为1.0MPa、水比为2:1、催化剂和环氧丙烷物质的量比为1：1000以及反应时间为7h条件下，考察催化剂I-E的性能，结果见表I-3。
实施例I-29
回收实施例I-28中用过一次的催化剂，不经活化再生，在与实施例I-28相同的催化条件下，考察其催化性能，结果见表I-3。
实施例I-30
回收实施例I-29中用过两次的催化剂，不经活化再生，在与实施例I-28和29相同的催化条件下，考察其催化性能，结果见表I-3。
实施例I-31
称取1.74g的环氧丙烷，在温度为40℃、压力为1.0MPa、水比为2:1、催化剂和环氧丙烷物质的量比为1：1000以及反应时间为7h条件下，考察催化剂I-F的性能，结果见表I-3。
实施例I-32
回收实施例I-31中用过一次的催化剂，不经活化再生，在与实施 例I-31相同的催化条件下，考察其催化性能，结果见表I-3。
实施例I-33
回收实施例I-32中用过两次的催化剂，不经活化再生，在与实施例I-31和32相同的催化条件下，考察其催化性能，结果见表I-3。
表I-3催化剂I-D、I-E、I-F的循环使用性
催化剂 首次丙二醇产率(％) 循环1次丙二醇产率(％) 循环2次丙二醇产率(％)
I-D 93 78 67
I-E 91 75 64
I-F 92 77 66
实施例I-34
称取1.74g的环氧丙烷，在温度为40℃、压力为1.0MPa、水比为8:1、催化剂和环氧丙烷物质的量比为1：500以及反应时间为4h条件下，考察催化剂I-A的性能，结果见表I-4。
实施例I-35
回收实施例I-34中用过一次的催化剂，不经活化再生，在与实施例I-34相同的催化条件下，考察其催化性能，结果见表I-4。
实施例I-36
回收实施例I-35中用过两次的催化剂，不经活化再生，在与实施例I-34和35相同的催化条件下，考察其催化性能，结果见表I-4。
实施例I-37
称取1.74g的环氧丙烷，在温度为40℃、压力为1.0MPa、水比为8:1、催化剂和环氧丙烷物质的量比为1：500以及反应时间为4h条件下，考察催化剂I-B的性能，结果见表I-4。
实施例I-38
回收实施例I-37中用过一次的催化剂，不经活化再生，在与实施例I-37相同的催化条件下，考察其催化性能，结果见表I-4。
实施例I-39
回收实施例I-38中用过两次的催化剂，不经活化再生，在与实施例I-37和38相同的催化条件下，考察其催化性能，结果见表I-4。
实施例I-40
称取1.74g的环氧丙烷，在温度为40℃、压力为1.0MPa、水比为8:1、催化剂和环氧丙烷物质的量比为1：500以及反应时间为4h条件下，考察催化剂I-C的性能，结果见表I-4。
实施例I-41
回收实施例I-40中用过一次的催化剂，不经活化再生，在与实施例I-40相同的催化条件下，考察其催化性能，结果见表I-4。
实施例I-42
回收实施例I-41中用过两次的催化剂，不经活化再生，在与实施例I-40和41相同的催化条件下，考察其催化性能，结果见表I-4。
表I-4催化剂I-A、I-B、I-C的循环使用性
催化剂 首次丙二醇产率(％) 循环1次丙二醇产率(％) 循环2次丙二醇产率(％)
I-A 93 77 68
I-B 93 76 67
I-C 92 76 66
对比例I-2
称取1.32g的环氧乙烷，在温度为20℃、压力为1.0MPa、水比为2:1、催化剂和环氧乙烷物质的量比为1:1000以及反应时间为7h条件下，考察催化剂I-G的性能，结果见表I-5。
对比例I-3
回收对比例I-2中用过一次的催化剂，不经活化再生，在与对比例I-2相同的催化条件下，考察其催化性能，结果见表I-5。
表I-5催化剂I-G的循环使用性
催化剂I- 首次乙二醇产率(％) 循环1次乙二醇产率(％)
G 96 44
实施例II-1
称取0.50g的F127，0.6g的均三甲苯和2.5g的KCl于16℃下溶解到30mL 2M HCl水溶液中，搅拌2h；加入2.08g的TEOS，继续在16℃下搅拌24h后置于100℃烘箱中水热24h。取出洗涤干燥 后，于550℃煅烧6h得纳米笼基体材料FDU-12。称取0.344g的六氟锑酸银和0.492g的Co(N,N′-二亚水杨基-1,2-环己二胺)，溶解于40mL二氯甲烷中，室温避光敞口搅拌12h，用硅藻土进行多次抽滤，收集滤液旋干得活性中心Co(N,N′-二亚水杨基-1,2-环己二胺)SbF 6。1.0g的Co(N,N′-二亚水杨基-1,2-环乙二胺)OTs溶解到40ml的二氯甲烷,再置于分液漏斗中用40ml的饱和氯化钠洗涤三次,硫酸钠干燥，去除溶剂后将得到的固体悬浮于戊烷中，过滤，得活性中心Co(N,N′-二亚水杨基-1,2-环乙二胺)Cl。称取1.0g的FDU-12，置于4mL含40mg Co(N,N′-二亚水杨基-1,2-环己二胺)SbF 6和60mg Co(N,N′-二亚水杨基-1,2-环乙二胺)Cl的二氯甲烷溶液中，20℃密封搅拌2h后，20℃敞口搅拌至溶剂挥发干。加入预水解的正硅酸甲酯，搅拌40min后，加入乙醇，离心分离，充分洗涤，干燥得催化剂II-A。
实施例II-2
称取1.0g的SBA-6，置于4mL含100mg Co(N,N′-双(3,5-二叔丁基亚水杨基)-1,2-环乙二胺)SbF 6和200mg Fe(N,N′-二亚水杨基-1,2-环己二胺)F的乙醇和二氯甲烷混合溶液中，20℃密封搅拌3h后，40℃敞口搅拌至溶剂挥发干。加入预水解的正硅酸乙酯，搅拌60min后，加入乙醇，离心分离，充分洗涤，干燥得催化剂II-B。
实施例II-3
称取1.0g的SBA-16，置于6mL含300mg Ga(N,N′-二亚水杨基-1,2-环乙二胺)SbF 6和100mg Al(N,N′-双(3-叔丁基亚水杨基)-1,2-环乙二胺)Br的甲醇溶液中，20℃密封搅拌4h后，30℃敞口搅拌至溶剂挥发干。加入预水解的正硅酸乙酯，搅拌60min后，加入乙醇，离心分离，充分洗涤，干燥得催化剂II-C。
实施例II-4
称取1.0g的FDU-1，置于8mL含300mg Fe(N,N′-二亚水杨基-1,2-环乙二胺)SbF 6和200mg Cr(N,N′-双(5-叔丁基亚水杨基)-1,2-环乙二胺)I的甲醇和乙醇混合溶液中，30℃密封搅拌4h后，40℃敞口搅拌至溶剂挥发干。加入2mL甲苯，2mg对甲苯磺酸和20mmol三甲氧基丙基硅烷回流过夜，离心分离，充分洗涤，干燥得催化剂II-D。
对比例II-1
称取1.0g的FDU-12，置于4mL含100mg Co(N,N′-二亚水杨 基-1,2-环己二胺)SbF 6的二氯甲烷溶液中，20℃密封搅拌2h后，20℃敞口搅拌至溶剂挥发干。加入预水解的正硅酸甲酯，搅拌40min后，加入乙醇，离心分离，充分洗涤，干燥得催化剂II-E。对比例II-2
称取1.0g的FDU-12，置于4mL含100mg Co(N,N′-二亚水杨基-1,2-环乙二胺)Cl的二氯甲烷溶液中，20℃密封搅拌2h后，20℃敞口搅拌至溶剂挥发干。加入预水解的正硅酸甲酯，搅拌40min后，加入乙醇，离心分离，充分洗涤，干燥得催化剂II-F。
实施例II-5
称取1.32g的环氧乙烷，在温度为20℃、压力为1.0MPa、水比为2:1、催化剂和环氧乙烷物质的量比为1:1000以及反应时间为7h条件下，考察催化剂II-A的性能，结果见表II-1。
实施例II-6
回收实施例II-5中用过一次的催化剂，不经活化再生，在与实施例II-5相同的催化条件下，考察其催化性能，结果见表II-1。
实施例II-7
回收实施例II-6中用过两次的催化剂，不经活化再生，在与实施例II-5和6相同的催化条件下，考察其催化性能，结果见表II-1。
实施例II-8
称取1.32g的环氧乙烷，在温度为20℃、压力为1.0MPa、水比为2:1、催化剂和环氧乙烷物质的量比为1:1000以及反应时间为7h条件下，考察催化剂II-B的性能，结果见表II-1。
实施例II-9
回收实施例II-8中用过一次的催化剂，不经活化再生，在与实施例II-8相同的催化条件下，考察其催化性能，结果见表II-1。
实施例II-10
回收实施例II-8中用过两次的催化剂，不经活化再生，在与实施例II-8和9相同的催化条件下，考察其催化性能，结果见表II-1。
表II-1催化剂II-A、II-B的循环使用性
催化剂 首次乙二醇产率(％) 循环1次乙二醇产率(％) 循环2次乙二醇产率(％)
II-A 95 90 84
II-B 93 88 81
实施例II-11
称取1.32g的环氧乙烷，在温度为40℃、压力为1.0MPa、水比为6:1、催化剂和环氧乙烷物质的量比为1:500以及反应时间为4h条件下，考察催化剂II-C的性能，结果见表II-2。
实施例II-12
回收实施例II-11中用过一次的催化剂，不经活化再生，在与实施例II-11相同的催化条件下，考察其催化性能，结果见表II-2。
实施例II-13
回收实施例II-12中用过两次的催化剂，不经活化再生，在与实施例II-11和12相同的催化条件下，考察其催化性能，结果见表II-2。
实施例II-14
称取1.32g的环氧乙烷，在温度为40℃、压力为1.0MPa、水比为6:1、催化剂和环氧乙烷物质的量比为1:500以及反应时间为4h条件下，考察催化剂II-D的性能，结果见表II-2。
实施例II-15
回收实施例II-14中用过一次的催化剂，不经活化再生，在与实施例II-14相同的催化条件下，考察其催化性能，结果见表II-2。
实施例II-16
回收实施例II-15中用过两次的催化剂，不经活化再生，在与实施例II-14和15相同的催化条件下，考察其催化性能，结果见表II-2。
表II-2催化剂II-C、II-D的循环使用性
催化剂 首次乙二醇产率(％) 循环1次乙二醇产率(％) 循环2次乙二醇产率(％)
II-C 94 89 83
II-D 93 87 80
实施例II-17
称取1.74g的环氧丙烷，在温度为40℃、压力为1.0MPa、水比为2:1、催化剂和环氧丙烷物质的量比为1：1000以及反应时间为7h条件下，考察催化剂II-C的性能，结果见表II-3。
实施例II-18
回收实施例II-17中用过一次的催化剂，不经活化再生，在与实施例II-17相同的催化条件下，考察其催化性能，结果见表II-3。
实施例II-19
回收实施例II-18中用过两次的催化剂，不经活化再生，在与实施例II-17和18相同的催化条件下，考察其催化性能，结果见表II-3。
实施例II-20
称取1.74g的环氧丙烷，在温度为40℃、压力为1.0MPa、水比为2:1、催化剂和环氧丙烷物质的量比为1：1000以及反应时间为7h条件下，考察催化剂II-D的性能，结果见表II-3。
实施例II-21
回收实施例II-20中用过一次的催化剂，不经活化再生，在与实施例II-20相同的催化条件下，考察其催化性能，结果见表II-3。
实施例II-22
回收实施例II-21中用过两次的催化剂，不经活化再生，在与实施例II-21和22相同的催化条件下，考察其催化性能，结果见表II-3。
表II-3催化剂II-C、II-D的循环使用性
催化剂 首次丙二醇产率(％) 循环1次丙二醇产率(％) 循环2次丙二醇产率(％)
II-C 92 87 81
II-D 91 85 79
实施例II-23
称取1.74g的环氧丙烷，在温度为40℃、压力为1.0MPa、水比为8:1、催化剂和环氧丙烷物质的量比为1：500以及反应时间为4h条件下，考察催化剂II-A的性能，结果见表II-4。
实施例II-24
回收实施例II-23中用过一次的催化剂，不经活化再生，在与实施例II-23相同的催化条件下，考察其催化性能，结果见表II-4。
实施例II-25
回收实施例II-24中用过两次的催化剂，不经活化再生，在与实施例II-23和24相同的催化条件下，考察其催化性能，结果见表II-4。
实施例II-26
称取1.74g的环氧丙烷，在温度为40℃、压力为1.0MPa、水比为8:1、催化剂和环氧丙烷物质的量比为1：500以及反应时间为4h条件下，考察催化剂II-B的性能，结果见表II-4。
实施例II-27
回收实施例II-26中用过一次的催化剂，不经活化再生，在与实施例II-26相同的催化条件下，考察其催化性能，结果见表II-4。
实施例II-28
回收实施例II-27中用过两次的催化剂，不经活化再生，在与实施例II-26和27相同的催化条件下，考察其催化性能，结果见表II-4。
表II-4催化剂II-A、II-B的循环使用性
催化剂 首次丙二醇产率(％) 循环1次丙二醇产率(％) 循环2次丙二醇产率(％)
II-A 94 89 83
II-B 93 87 81
对比例II-3
称取1.32g的环氧乙烷，在温度为20℃、压力为1.0MPa、水比为2:1、催化剂和环氧乙烷物质的量比为1:1000以及反应时间为7h条件下，考察催化剂II-E的性能，结果见表II-5。
对比例II-4
称取1.32g的环氧乙烷，在温度为20℃、压力为1.0MPa、水比为2:1、催化剂和环氧乙烷物质的量比为1:1000以及反应时间为7h条件下，考察催化剂II-F的性能，结果见表II-5。
表II-5催化剂II-E、II-F的性能
催化剂 首次乙二醇产率(％)
II-E 12
II-F 63
实施例III-1
称取0.50g的F127，0.6g的均三甲苯和2.5g的KCl于16℃下溶解到30mL 2M HCl水溶液中，搅拌2h；加入2.08g的TEOS，继续在16℃下搅拌24h后置于100℃烘箱中水热24h。取出洗涤干燥后，于550℃煅烧6h得纳米笼基体材料FDU-12。称取0.331g的二茂铁六氟磷酸和0.492g的Co(N,N′-二亚水杨基-1,2-环己二胺)，溶解于15mL二氯甲烷和15mL乙腈的混合溶液中，室温敞口搅拌12h，将溶剂旋去，用正己烷充分洗涤干燥后得活性中心Co(N,N′-二亚水杨基-1,2-环己二胺)PF 6。称取1.0g的FDU-12，置于6mL含100mg Co(N,N′-二亚水杨基-1,2-环己二胺)PF 6的二氯甲烷溶液中，20℃密封搅拌2h后，20℃敞口搅拌至溶剂挥发干。加入预水解的正硅酸甲酯，搅拌40min后，加入乙醇，离心分离，充分洗涤，干燥得催化剂III-A。
实施例III-2
称取1.0g的SBA-6，置于6mL含100mg Fe(N,N′-双(3,5-二叔丁基亚水杨基)-1,2-环乙二胺)PF 6的二氯甲烷溶液中，20℃密封搅拌2h后，20℃敞口搅拌至溶剂挥发干。加入预水解的正硅酸甲酯，搅拌40min后，加入乙醇，离心分离，充分洗涤，干燥得催化剂III-B。
实施例III-3
称取1.0g的SBA-16，置于6mL含100mg Ga(N,N′-二亚水杨基-1,2-环乙二胺)PF 6的二氯甲烷溶液中，20℃密封搅拌2h后，20℃敞口搅拌至溶剂挥发干。加入预水解的正硅酸甲酯，搅拌40min后，加入乙醇，离心分离，充分洗涤，干燥得催化剂III-C。
实施例III-4
称取1.0g的FDU-1，置于6mL含100mg Al(N,N′-双(3-叔丁基亚水杨基)-1,2-环乙二胺)PF 6的二氯甲烷溶液中，20℃密封搅拌2h后，20℃敞口搅拌至溶剂挥发干。加入预水解的正硅酸甲酯，搅拌40min后，加入乙醇，离心分离，充分洗涤，干燥得催化剂III-D。
实施例III-5
称取1.0g的KIT-5，置于6mL含100mg Cr(N,N′-双(5-叔丁基亚水杨基)-1,2-环己二胺)PF 6的二氯甲烷溶液中，20℃密封搅拌2h后， 20℃敞口搅拌至溶剂挥发干。加入预水解的正硅酸甲酯，搅拌40min后，加入乙醇，离心分离，充分洗涤，干燥得催化剂III-E。
实施例III-6
称取1.0g的SBA-16，置于6mL含100mg Co(N,N′-二亚水杨基-1,2-环己二胺)BF 4的二氯甲烷溶液中，20℃密封搅拌2h后，20℃敞口搅拌至溶剂挥发干。加入预水解的正硅酸甲酯，搅拌40min后，加入乙醇，离心分离，充分洗涤，干燥得催化剂III-F。
对比例III-1
称取1.0g的SBA-16，置于6mL含100mg Co(N,N′-二亚水杨基-1,2-环己二胺)OTs的二氯甲烷溶液中，20℃密封搅拌2h后，20℃敞口搅拌至溶剂挥发干。加入预水解的正硅酸甲酯，搅拌40min后，加入乙醇，离心分离，充分洗涤，干燥得催化剂III-G。
实施例III-7～15
称取1.32g的环氧乙烷，在温度为20℃、压力为1.0MPa、水比为2:1、催化剂和环氧乙烷物质的量比为1:1000以及反应时间为7h条件下，考察催化剂III-A、III-B、III-C的性能。再将用过的催化剂III-A、III-B、III-C离心回收，不经过活化再生直接在相同条件下用于下次催化反应(如此循环两次)，结果见表III-1。
表III-1催化剂III-A、III-B、III-C的循环使用性
催化剂 首次乙二醇产率(％) 循环1次乙二醇产率(％) 循环2次乙二醇产率(％)
III-A ≥97 ≥94 ≥89
III-B ≥96 ≥93 ≥88
III-C ≥96 ≥93 ≥87
实施例III-16～24
称取1.32g的环氧乙烷，在温度为40℃、压力为1.0MPa、水比为6:1、催化剂和环氧乙烷物质的量比为1:500以及反应时间为4h条件下，考察催化剂III-D、III-E、III-F的性能。再将用过的催化剂III-D、III-E、III-F离心回收，不经过活化再生直接在相同条件下用于下次催化反应(如此循环两次)，结果见表III-2。
表III-2催化剂III-D、III-E、III-F的循环使用性
催化剂 首次乙二醇产率(％) 循环1次乙二醇产率(％) 循环2次乙二醇产率(％)
III-D ≥95 ≥92 ≥85
III-E ≥94 ≥91 ≥84
III-F ≥95 ≥92 ≥86
实施例III-25～33
称取1.74g的环氧丙烷，在温度为40℃、压力为1.0MPa、水比为2:1、催化剂和环氧丙烷物质的量比为1：1000以及反应时间为7h条件下，考察催化剂III-D、III-E、III-F的性能。再将用过的催化剂III-D、III-E、III-F离心回收，不经过活化再生直接在相同条件下用于下次催化反应(如此循环两次)，结果见表III-3。
表III-3催化剂III-D、III-E、III-F的循环使用性
催化剂 首次丙二醇产率(％) 循环1次丙二醇产率(％) 循环2次丙二醇产率(％)
III-D ≥94 ≥91 ≥83
III-E ≥93 ≥90 ≥83
III-F ≥94 ≥90 ≥84
实施例III-34-42
称取1.74g的环氧丙烷，在温度为60℃、压力为1.0MPa、水比为8:1、催化剂和环氧丙烷物质的量比为1：500以及反应时间为4h条件下，考察催化剂III-A、III-B、III-C的性能。再将用过的催化剂III-A、III-B、III-C离心回收，不经过活化再生直接在相同条件下用于下次催化反应(如此循环两次)，结果见表III-4。
表III-4催化剂III-A、III-B、III-C的循环使用性
催化剂 首次丙二醇产率(％) 循环1次丙二醇产率(％) 循环2次丙二醇产率(％)
III-A ≥96 ≥93 ≥88
III-B ≥95 ≥92 ≥86
III-C ≥95 ≥93 ≥87
对比例III-2-3
称取1.32g的环氧乙烷，在温度为20℃、压力为1.0MPa、水比为2:1、催化剂和环氧乙烷物质的量比为1:1000以及反应时间为7h条件下，考察活性中心Co(N,N′-二亚水杨基-1,2-环己二胺)PF 6和Co(N,N′-二亚水杨基-1,2-环己二胺)OTs作为均相催化剂的性能，结果见表III-5。
表III-5活性中心Co(N,N′-二亚水杨基-1,2-环己二胺)PF 6和Co(N,N′-二亚水杨基-1,2-环己二胺)OTs作为均相催化剂的性能
催化剂 乙二醇产率(％)
Co(N,N′-二亚水杨基-1,2-环己二胺)PF 6 ≥85
Co(N,N′-二亚水杨基-1,2-环己二胺)OTs ≥92
对比例III-4
称取1.32g的环氧乙烷，在温度为20℃、压力为1.0MPa、水比为2:1、催化剂和环氧乙烷物质的量比为1:1000以及反应时间为7h条件下，考察催化剂III-G的性能。再将用过的催化剂III-G离心回收，不经过活化再生直接在相同条件下用于下次催化反应，结果见表III-6。
表III-6催化剂III-G的循环使用性
催化剂 首次乙二醇产率(％) 循环1次乙二醇产率(％)
III-G ≥97 ≥45

Claims (20)

  1. 一种纳米笼限域催化剂，其特征在于，所述催化剂具有式(I-1)和/或(I-2)的活性中心：
    M(Salen1)X  (I-1)
    M'(Salen2)  (I-2)
    从而使得该催化剂具有式(I)：
    NC-m[M(Salen1)X]-n[M'(Salen2)]   (I)
    其中：
    NC为具有纳米笼结构的材料，
    每次出现的M独立地选自Co离子，Fe离子，Ga离子，Al离子，Cr离子及其混合；每次出现的M'独立地选自Cu离子，Ni离子及其混合；
    m为0-100的整数，n为0-100的整数；条件是m和n中至少一个不为0；
    每次出现的Salen1和Salen2各自独立地为Shiff碱类衍生物；
    X为轴阴离子，每次出现的X独立地选自取代或未取代的醋酸根、取代或未取代的苯磺酸根、取代或未取代的苯甲酸根，F -，Cl -，Br -，I -，SbF 6 -，PF 6 -，BF 4 -及其混合；条件是：
    (1)X为取代或未取代的醋酸根、取代或未取代的苯磺酸根、或取代或未取代的苯甲酸根时，M不为Co离子，或者
    (2)X为F -，Cl -，Br -，或I -时，m不小于2，且至少一个式(I-1)中的X为SbF 6 -。
  2. 根据权利要求1所述的催化剂，其特征在于，每个式(I-1)中出现的M独立地选自Co 3+，Fe 3+，Ga 3+，Al 3+，Cr 3+及其混合，和/或每个式(I-2)中出现的M'独立地选自Cu 2+，Ni 2+及其混合。
  3. 根据权利要求1所述的催化剂，其特征在于，m为0-20，优选0-10，还优选0-5，例如0-2。
  4. 根据权利要求1所述的催化剂，其特征在于，n为0-10，优选0-5，还优选0-3，例如0-1。
  5. 根据权利要求1所述的催化剂，其特征在于，m为0-2，n为0-1。
  6. 根据权利要求1所述的催化剂，其特征在于，m为1，且n为0， X选自取代或未取代的醋酸根、取代或未取代的苯磺酸根、取代或未取代的苯甲酸根，SbF 6 -，PF 6 -和BF 4 -。
  7. 根据权利要求1所述的催化剂，其特征在于，m为2，n为0-1，每个式(I-1)的M(Salen1)X不同以形成式(II)的催化剂：
    NC-[M(Salen1)X]-[M(Salen1)X]-n[M'(Salen2)]   (II)；
    优选地，m为2，n为0，每个M(Salen1)X不同以形成式(II-1)的催化剂
    NC-[M(Salen1)X]-[M(Salen1)X]    (II-1)，
    式(II)或(II-1)中，每个M不同且独立地选自Co 3+，Fe 3+，Ga 3+，Al 3+，Cr 3+，每个Salen1相同或不同。
  8. 根据权利要求7所述的催化剂，其特征在于其中一个X为SbF 6 -，另一个X为F -，Cl -，Br -或I -。
  9. 根据权利要求1所述的催化剂，其特征在于，m为2或更大，每个式(I-1)的M(Salen1)X不同。
  10. 根据权利要求1所述的催化剂，其特征在于，n为2或更大，每个式(I-2)的M'(Salen2)不同。
  11. 根据权利要求1所述的催化剂，其特征在于，所述NC为具有纳米笼结构的介孔二氧化硅纳米颗粒或者具有纳米笼结构的有机杂化的介孔二氧化硅纳米颗粒。
  12. 根据权利要求1所述的催化剂，其特征在于，所述NC选自SBA-6，SBA-16，FDU-1，FDU-12，KIT-5和AMS-8。
  13. 根据权利要求1所述的催化剂，其特征在于，所述Shiff碱类衍生物为N,N′-二亚水杨基-1,2-环己二胺或取代的N,N′-二亚水杨基-1,2-环己二胺。
  14. 一种纳米笼限域催化剂，其特征在于，所述催化剂具有式(II-3)：
    NC-[Co(Salen1)SbF 6-M(Salen1)X]     (II-3)，
    其中，NC、Salen1各自独立地如前述权利要求任一项中所定义；X选自F -，Cl -，Br -，和I -；且M选自Co 3+，Fe 3+，Ga 3+，Al 3+和Cr 3+。
  15. 一种纳米笼限域催化剂，其特征在于，所述催化剂具有式(II-4)：
    NC-[M(Salen1)SbF 6-Co(Salen1)X]    (II-4)，
    其中，NC、Salen1各自独立地如前述权利要求任一项中所定义；X选自F -，Cl -，Br -，和I -；且M选自Co 3+，Fe 3+，Ga 3+，Al 3+和Cr 3+。
  16. 一种纳米笼限域催化剂，其特征在于，所述催化剂具有式(III-1)或(III-2)：
    NC-[Co(Salen1)PF 6]   (III-1)，或
    NC-[Co(Salen1)BF 4]    (III-2)，
    其中，NC、Salen1各自独立地如前述权利要求任一项中所定义。
  17. 一种纳米笼限域催化剂的制备方法，包括以下步骤：
    将活性中心M(Salen1)X或M'(Salen2)、纳米笼材料NC加入溶剂中，搅拌；移除溶剂；封装，得纳米笼限域催化剂。
  18. 根据权利要求17所述的制备方法，其特征在于，所述M包括Fe 3+，Ga 3+，Al 3+，Cr 3+，M'包括Cu 2+，Ni 2+；Salen1和Salen2为Shiff碱类衍生物，X为轴阴离子，所述X包括醋酸根、苯磺酸根、苯甲酸根、取代的醋酸根、取代的苯磺酸根、取代的苯甲酸根，F -，Cl -，Br -，I -，SbF 6 -，PF 6 -，BF 4 -。
  19. 根据权利要求17所述的制备方法，其特征在于，所述的溶剂包括二氯甲烷、乙醇、和甲醇中的至少一种。
  20. 权利要求1-16任一所述催化剂或采用权利要求17-20任一所述制备方法制得的催化剂在环氧烷烃水合制二醇反应中的用途。
PCT/CN2019/098304 2018-07-31 2019-07-30 纳米笼限域催化剂、制备方法及应用 WO2020024923A1 (zh)

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