CN109046452B - Immobilized heteropolyacid catalyst and preparation method and application thereof - Google Patents

Immobilized heteropolyacid catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN109046452B
CN109046452B CN201810527823.8A CN201810527823A CN109046452B CN 109046452 B CN109046452 B CN 109046452B CN 201810527823 A CN201810527823 A CN 201810527823A CN 109046452 B CN109046452 B CN 109046452B
Authority
CN
China
Prior art keywords
catalyst
carbon
reaction
integer
long
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810527823.8A
Other languages
Chinese (zh)
Other versions
CN109046452A (en
Inventor
张志炳
杨国强
刘甲
刘颖
张锋
李磊
周政
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing University
Original Assignee
Nanjing University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing University filed Critical Nanjing University
Priority to CN201810527823.8A priority Critical patent/CN109046452B/en
Publication of CN109046452A publication Critical patent/CN109046452A/en
Application granted granted Critical
Publication of CN109046452B publication Critical patent/CN109046452B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B01J2231/72—Epoxidation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses an immobilized heteropoly acid catalyst and a preparation method and application thereof. The catalyst comprises a quaternized resin and a phosphoheteropoly acid anion, the quaternized resin comprising
Figure DDA0001676441880000011
The structural unit of (1), wherein,
Figure DDA0001676441880000012
is a high molecular polymer carrier, R2Is C2～3R is C13～20Long carbon chain alkyl of (C)3～6X is an integer of 1 to 5, y is an integer of 400 to 1000, and j is an integer of 0 to 5. The catalyst has the characteristics of high nitrogen content, high load of the heteropoly acid anions containing phosphorus, adjustable catalytic activity and selectivity through the carbon chain length of the quaternary ammonium salt cations and the molar ratio of phosphorus to heteroatoms, convenient recovery of the catalyst, stable reusability and the like. The catalyst solves the problems that the phase transfer catalyst is difficult to recycle, the process is complex and the like, can replace metal salt and the phase transfer catalyst to a certain extent, and can adapt to different olefin reactants due to adjustable catalytic activity and selectivity.

Description

Immobilized heteropolyacid catalyst and preparation method and application thereof
Technical Field
The invention belongs to the field of catalysts, and particularly relates to an immobilized heteropoly acid catalyst and a preparation method and application thereof.
Background
The epoxide of olefin is an important intermediate in organic synthesis, pharmacy and perfume industry, and the demand of epoxide is rapidly increased at home and abroad in recent years, and the supply and demand of epoxide are short. In industry, epoxides other than ethylene oxide are mostly prepared by a halohydrin method or a hydrogen peroxide catalytic epoxidation method. The halohydrin method has high epoxide selectivity, but has many reaction steps, high material consumption and energy consumption, and serious pollution due to the generation of a large amount of high-salt wastewater. The hydrogen peroxide catalytic epoxidation method has the advantages of one-step synthesis, environmental friendliness, economy, no environmental pollution and the like, but needs a catalyst with high activity, high reaction selectivity and high stability. The reaction control phase transfer catalysts reported in patents CN101337191, CN101564697, CN206304715U, CN103880783A, etc. are used for catalyzing hydrogen peroxide epoxidation of olefins, and have high olefin conversion rate, high hydrogen peroxide utilization rate and high epoxide selectivity, but such catalysts with phase transfer function are difficult to keep stable in practical industrial application, catalytic activity and selectivity will gradually decrease, and the catalysts are easy to block pipelines, and no mature industrial devices are in operation so far.
Patent CN 101485990a discloses an immobilized heteropoly acid catalyst, which can be used for synthesizing epoxy resin, and the heteropoly acid is immobilized on quaternary ammonium salt resin to realize phase transfer catalysis. However, the quaternary ammonium salt resin adopted by the method has limited active sites and does not regulate and control the activity of the catalyst, so that the catalyst has limited catalytic capability and limited application.
Disclosure of Invention
Aiming at the problems, the invention provides the immobilized heteropoly acid catalyst which has high loading capacity, high catalytic activity, good stability, wide application range, easy recovery and suitability for industrial production by increasing active sites and regulating and controlling the hydrophilicity and lipophilicity of the surface of the catalyst.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an immobilized heteropolyacid catalyst comprising a quaternized resin and an anion, the anion being a phosphoheteropoly acid anion, the quaternized resin comprising the following structural units:
Figure BDA0001676441870000021
wherein the content of the first and second substances,
Figure BDA0001676441870000022
is a high molecular polymer carrier, R2Is C2～3R is a long-carbon chain alkyl group or a short-carbon chain alkyl group, the long-carbon chain alkyl group is C13～20The short-chain C-alkanyl radical is C3～6X is an integer of 1 to 5, y is an integer of 400 to 1000, and j is an integer of 0 to 5. The combination of carbon chains with different lengths ensures that the cation part of the quaternary ammonium salt has different hydrophilicity/lipophilicity, thereby being suitable for reactants with different properties.
Preferably, the high molecular polymer carrier is
Figure BDA0001676441870000023
Preferably, the high molecular polymer carrier is methyl polystyrene. That is, j is preferably 1.
Preferably, said R is2Is C2Alkyl group of (1).
Preferably, the long carbon chain alkyl is C16～18Linear or branched alkyl.
Preferably, the anion is a phosphotungstic heteropoly acid anion or a phosphomolybdic heteropoly acid anion.
Preferably, the molar ratio of phosphorus to tungsten or phosphorus to molybdenum in the anion is 1: 2-4. Different molar ratios of phosphorus to tungsten/molybdenum will have different heteropolyacid structures and thus catalysts of different catalytic activity and epoxidation selectivity can be obtained.
Preferably, the molar ratio of phosphorus to tungsten or phosphorus to molybdenum in the anion is 1: 2.
The second purpose of the invention is to provide a preparation method of the solid supported heteropoly acid catalyst, which comprises the following steps:
(1) will be provided withThe structural unit is
Figure BDA0001676441870000031
The high molecular polymer is dispersed in an organic solvent to swell, and then structural units are added
Figure BDA0001676441870000032
The reaction of the polymer (A) to obtain a grafted high molecular polymer containing a structural unit shown as a formula II, wherein X is halogen and R is halogen2Is C2～3X is an integer of 1 to 5, y is an integer of 400 to 1000, and j is an integer of 0 to 5;
formula II:
Figure BDA0001676441870000033
(2) swelling the grafted high molecular polymer prepared in the step (1) in an organic alcohol solvent, adding long-carbon-chain halogenated alkane, stirring at 100-150 ℃ for reaction, adding short-carbon-chain halogenated alkane, stirring at 30-80 ℃, preferably 50-60 ℃ for reaction, and obtaining the quaternary ammonium salt resin comprising the structural unit shown in the formula III-Ca, wherein R is long-carbon-chain alkyl or short-carbon-chain alkyl, and the long carbon chain is C13～20The long carbon chain halogenated alkane is C13～20The short carbon chain is C3～6The short carbon chain halogenated alkane is C3～6The halogenated alkane of (a);
formula III-Ca:
Figure BDA0001676441870000034
(3) and (3) adding the quaternary ammonium salt resin prepared in the step (2) into a phosphorus-containing heteropoly acid solution for ion exchange to obtain the immobilized heteropoly acid catalyst.
Preferably, the high molecular weight polymer in the step (1) has a structural unit of
Figure BDA0001676441870000041
Namely, the high molecular weight polymer is preferably substituted polystyrene.
Preferably, in the structural unit of the high molecular weight polymer described in the step (1), j is preferably 1. Namely, the high molecular weight polymer is preferably halogenated methyl polystyrene.
Preferably, the high molecular polymer in the step (1) is chloromethyl polystyrene. That is, X in the high molecular weight polymer structure is preferably Cl.
Preferably, the organic solvent in step (1) is N, N-dimethylformamide.
In the step (1), the structural unit is
Figure BDA0001676441870000042
The polymer (b) is preferably polyethyleneimine, accordingly, R2Is C2H4。
Preferably, the structural unit is
Figure BDA0001676441870000043
The relative molecular mass of the polymer is 600-70000, and the structural unit is
Figure BDA0001676441870000044
The relative molecular mass of the polymer (D) is 6000-10000.
Preferably, the structural unit in the step (1) is
Figure BDA0001676441870000045
The addition amount of the polymer (b) is 1-50 wt%, preferably 5-30 wt% of the high molecular polymer carrier.
Preferably, the reaction temperature in the step (1) is 10-50 ℃, and more preferably, the reaction temperature is 25 ℃.
Preferably, the reaction time of the step (1) is 1-24 h, and more preferably, the reaction time is 2-10 h.
Preferably, the swelling time in the step (1) is 1-10 h, and more preferably, the swelling time is 3-5 h.
Preferably, step (1) further comprises the steps of filtering and washing the grafted high molecular polymer.
Preferably, the organic alcohol solvent in the step (2) is one or more of ethanol, n-propanol, isopropanol, isobutanol and n-butanol; isopropyl alcohol is preferred.
Preferably, the reaction of adding the long carbon chain halogenated alkane in the step (2) is carried out at a temperature of 105-120 ℃.
Preferably, the reaction of adding the long-carbon-chain halogenated alkane or the reaction of adding the short-carbon-chain halogenated alkane in the step (2) lasts for 1-10 h, and more preferably, the reaction time lasts for 5 h.
Preferably, the step (2) further comprises the steps of filtering and washing the quaternary ammonium salt resin.
Preferably, the molar ratio of the long-carbon-chain halogenated alkane to the short-carbon-chain halogenated alkane in the step (2) is 0.1-2: 1, and more preferably 0.5-1.5: 1.
Preferably, the heteropoly acid containing phosphorus in the step (3) is heteropoly tungstophosphoric acid or heteropoly molybdophosphoric acid. Phosphotungstic heteropoly acids are preferred.
Preferably, the phosphotungstic heteropoly acid or phosphomolybdic heteropoly acid is prepared by the following steps (can also be prepared by the prior art or directly purchased):
(3-1) adding hydrochloric acid into a sodium tungstate or sodium molybdate solution, and stirring to obtain a colloidal solid;
(3-2) adding hydrogen peroxide into the colloidal solid obtained in the step (3-1) until the colloidal solid disappears to obtain peroxytungstic acid or peroxymolybdic acid;
(3-3) adding phosphoric acid or a phosphate solution into the peroxytungstic acid or peroxymolybdic acid obtained in the step (3-2) to enable the molar ratio of phosphorus to tungsten or molybdenum to be 1: 2-4, and stirring to obtain the phosphotungstic heteropoly acid or phosphomolybdic heteropoly acid.
Preferably, the molar ratio of the sodium tungstate or the sodium molybdate to the hydrochloric acid in the step (3-1) is 1: 2-5. The preferred molar ratio is 1: 2.
Preferably, step (3-3) employs phosphate.
Preferably, disodium hydrogen phosphate is used in step (3-3).
The process for preparing the supported heteropolyacid catalyst is shown as the following formula:
Figure BDA0001676441870000061
Figure BDA0001676441870000062
wherein, CmH2m+1Y (m ═ 13 to 20) represents the above-mentioned long-carbon-chain halogenated alkane, CmH2m+1Y (m is 3-6) represents the short-carbon-chain halogenated alkane, Y represents halogen, Y represents-Represents a halogen anion.
The formula III-Ca is a cationic moiety of formula III. The anionic portion of formula II is not shown in the reaction scheme.
Under the optimal condition, the catalyst is prepared by the following steps:
(1) dispersing chloromethyl polystyrene (marked as PS-Cl) in N, N-dimethylformamide to swell for 1-10 h, then adding polyethyleneimine with the relative molecular mass of 600-70000, wherein the addition amount is 5-30 wt% of the high-molecular polymer carrier, and stirring at 10-50 ℃ to react for 1-24 h to obtain a grafted high-molecular polymer shown as a formula II-2;
(2) placing the grafted high molecular polymer prepared in the step (1) into isopropanol for swelling, and then adding C13～20The chloralkane is stirred and reacted for 5 hours at the temperature of 100-150 ℃, and then C is added3～6Stirring the chloralkane at 30-80 ℃ for reaction to obtain quaternary ammonium salt resin shown as a formula III-2, wherein R is C13～20Straight or branched alkyl or C3～6Alkyl groups of (a); said C is13～20With said C3～6The mole ratio of the chloralkane is 0.1-2: 1;
(3) adding the quaternary ammonium salt resin prepared in the step (2) into a phosphotungstic heteropoly acid solution for ion exchange to obtain the immobilized heteropoly acid catalyst, wherein the phosphotungstic heteropoly acid is prepared by the following method:
(3-1) adding hydrochloric acid into a sodium tungstate solution, wherein the molar ratio of sodium tungstate to hydrochloric acid is 1:2, and stirring to obtain a colloidal solid;
(3-2) adding 30 wt% of hydrogen peroxide to the colloidal solid obtained in the step (3-1) until the colloidal solid disappears to obtain peroxytungstic acid;
and (3-3) adding a disodium hydrogen phosphate solution into the peroxytungstic acid obtained in the step (3-2) to enable the molar ratio of phosphorus to tungsten to be 1: 2-4, and stirring to obtain the phosphotungstic heteropoly acid.
The reaction process under the optimal conditions comprises the following steps:
Figure BDA0001676441870000071
the third purpose of the invention is to provide the application of the solid-supported catalyst in olefin epoxidation reaction.
The application comprises the following steps:
and adding the catalyst into the olefin solution, and slowly dropwise adding hydrogen peroxide at 20-70 ℃ to react to obtain an olefin epoxidation product.
Preferably, the solvent of the olefin solution is ethanol, acetonitrile, dioxane, chloroform or dichloromethane, preferably ethanol or acetonitrile.
Preferably, the addition amount of the catalyst is as follows: 5-30% of the mass of the olefin.
Preferably, the olefin is cyclohexene, butene, styrene or cyclopentene.
Preferably, the volume ratio of the solvent to the olefin in the olefin solution is 1: 0.5-5.
Preferably, the addition amount of the hydrogen peroxide is as follows: active ingredient H2O2The molar ratio of the olefin to the olefin is 1: 1-10.
Preferably, the concentration of the hydrogen peroxide is 20-50 wt%.
Preferably, the reaction time is 1-8 h.
Preferably, the reaction temperature is 30-60 ℃.
The catalyst of the present invention may be used after completion of the reaction by filtration or centrifugation.
The invention has the beneficial effects that:
the catalyst of the invention can be conveniently separated and recovered for recycling in the reaction because the catalyst is not dissolved in a reaction medium and completely shows the characteristic of a heterogeneous catalyst in the reaction process, and the recovered catalysis and reaction effect can reach the level of the original catalyst.
The catalyst has high olefin conversion rate and good epoxide selectivity, is easy to separate and recover, can meet the requirements of technical economy, and is a novel catalyst suitable for industrial scale application.
The catalyst is used for olefin epoxidation reaction, and has the characteristics of controllable reaction, high catalyst activity, stability and easy recovery, and can be used for a fixed bed.
The catalyst of the invention has adjustable catalytic activity and epoxidation reaction selectivity based on different carbon numbers of R, thereby being capable of adapting to various olefins and different reaction degree requirements.
The catalyst has high nitrogen content and high load of the heteropoly phosphoric acid anion, and the catalytic activity and selectivity can be regulated and controlled by the carbon chain length of the quaternary ammonium salt cation and the molar ratio of phosphorus to heteroatom.
The specific implementation mode is as follows:
example 1:
(1) 200mL of N, N-dimethylformamide solvent was added to a 250mL three-necked round-bottomed flask, and 40g of chloromethyl polystyrene (hereinafter referred to as PS-Cl) having a chlorine content of 10 wt% and a particle diameter of 0.8 to 1.0mm was added to the flask and soaked and swollen for 3 hours. And adding 5.0g of polyethyleneimine with the relative molecular mass of 600 into the flask, stirring at 25 ℃ for reaction for 6 hours, filtering to remove N, N-dimethylformamide, leaching the resin with ethanol, and drying in an oven at 70 ℃ to obtain the compound of the formula II-2 with enriched surface amino groups. Wherein x is an integer of 1 to 5, and y is an integer of 400 to 1000.
(2) Swelling the compound of the formula II-2 with 100mL of isopropanol solution for 3h, adding 0.1mol of 1-chlorooctadecane, stirring and reacting for 6h at the temperature of 120 ℃ under the reflux condition, cooling the temperature to 60 ℃, adding 0.25mol of 1-chloropropane, continuously stirring and reacting for 5h, cooling to room temperature, filtering out resin, leaching with ethanol, and drying in a 70 ℃ oven to obtain the compound of the formula III-2 with the surface quaternized.
(3) In a 50mL beaker, Na was added2WO440mmol and 40mL deionized water are fully stirred and dissolved to obtain clear and transparent sodium tungstate aqueous solution. Dropwise adding a hydrochloric acid solution containing 80mmol of hydrochloric acid into the sodium tungstate aqueous solution to generate a large amount of light yellow precipitates, and standing for 20min after the hydrochloric acid is dropwise added to obtain a tungstic acid suspension. And (3) dropwise adding 30 wt% of hydrogen peroxide into the continuously stirred tungstic acid suspension until the precipitate disappears to obtain a clear and transparent peroxytungstic acid solution.
In a 50mL beaker, 20mmol Na was added2HPO4·12H2O and 20mL of deionized water, and fully stirring to dissolve. Adding the solution into the peroxytungstic acid solution, and fully stirring for 10 minutes to obtain the phosphotungstic acid solution. Wherein P/W is 1: 2.
And (3) mixing the compound of the formula III-2 prepared in the step (2) with a phosphotungstic heteropoly acid solution, stirring for 3 hours at normal temperature, filtering out resin, leaching with deionized water, and drying in a drying box at 80 ℃ to obtain the immobilized catalyst, wherein the immobilized catalyst is marked as PS-PW-A.
Example 2:
chloromethyl polystyrene with 23 wt% of chlorine content and polyethyleneimine with the relative molecular mass of 70000 are used as raw materials, phosphotungstic heteropoly acid is prepared according to the prior art and has the P/W ratio of 1:2, and the rest of the synthesis steps and conditions are the same as those in example 1. The prepared immobilized catalyst is marked as PS-PW-B.
Example 3:
chloromethyl polystyrene chloride with a chlorine content of 17 wt% and polyethyleneimine with a relative molecular mass of 5000 were used as raw materials, phosphotungstic heteropoly acid was purchased with a P/W ratio of 1:2, and the remaining synthesis steps and conditions were the same as in example 1. The prepared immobilized catalyst is marked as PS-PW-C.
Example 4:
the synthesis procedure and conditions were the same as in example 1, except that chlorohexadecane was used instead of chlorooctadecane. The prepared immobilized catalyst is marked as PS-PW-D.
Example 5:
the synthesis procedure and conditions were the same as in example 1, except that chlorohexane was used instead of chloropropane. The prepared immobilized catalyst is marked as PS-PW-E.
Example 6:
the synthesis procedure and conditions were the same as in example 1, except that 20mmol of Na was used2HPO4·12H2O is replaced by 13mmol of NaH2PO4·2H2O, and the resulting phosphotungstate catalyst P/W is 1:3, and the resulting catalyst is designated PS-PW-F.
Example 7
The synthesis procedure and conditions were the same as in example 1, except that 20mmol of Na was used2HPO4·12H2O is replaced by 10mmol H3PO4The phosphorus tungstate catalyst obtained was 1: 4P/W, and the catalyst obtained was designated as PS-PW-G.
Example 8
(1) 200mL of N, N-dimethylformamide solvent was added to a 250mL three-necked round-bottomed flask, 40g of brominated polystyrene was added thereto, and the mixture was soaked and swollen for 4 hours. Then 0.4g of polypropyleneimine with the relative molecular mass of 10000 is added into the flask, and the mixture is stirred and reacts for 24 hours at the temperature of 10 ℃ to obtain the grafted high molecular polymer.
(2) Swelling the grafted high molecular polymer obtained in the step (1) for 3h by using 100mL of n-butyl alcohol solution, adding 0.1mol of 1-bromotridecane, stirring and reacting for 5h under the reflux condition at 105 ℃, reducing the temperature to 50 ℃, adding 1mol of 1-bromobutane, continuing stirring and reacting for 1h, cooling, filtering out resin, leaching by using ethanol, and drying to obtain quaternary ammonium salt resin.
(3) To the solution containing 40mmol of Na2MoO4And adding a solution containing 120mmol of hydrochloric acid dropwise into the sodium molybdate aqueous solution to obtain a molybdic acid suspension. And (3) dropwise adding 30 wt% of hydrogen peroxide into the continuously stirred molybdic acid suspension until the precipitate disappears to obtain a clear and transparent peroxymolybdic acid solution.
20mL of Na with a concentration of 1mol/L2HPO4Adding the solution into the above-mentioned peroxomolybdic acid solutionThe solution was sufficiently stirred for 10 minutes to obtain a phosphomolybdic heteropoly acid solution having a P/Mo ratio of 1: 2.
And (3) mixing the quaternary ammonium salt resin prepared in the step (2) with a phosphomolybdic heteropoly acid solution, stirring for 3 hours at normal temperature, filtering out the resin, washing with deionized water, and drying to obtain the immobilized catalyst.
Example 9
(1) 200mL of N, N-dimethylformamide solvent is added into a 250mL three-neck round-bottom flask, 40g of fluorinated polyethylstyrene is added, and the mixture is soaked and swelled for 1 h. And adding 2g of polypropylene imine with the relative molecular mass of 6000 into the flask, and stirring at 35 ℃ for reaction for 2 hours to obtain the grafted high molecular polymer.
(2) Swelling the grafted high molecular polymer obtained in the step (1) for 5h by using 100mL of ethanol solution, adding 0.5mol of 1-bromoeicosane, stirring and reacting for 10h under the condition of 100 ℃ backflow, reducing the temperature to 80 ℃, adding 1mol of 1-bromopentane, continuing stirring and reacting for 10h, cooling, filtering out resin, leaching by using ethanol, and drying to obtain quaternary ammonium salt resin.
(3) To the solution containing 40mmol of Na2MoO4160mmol of hydrochloric acid solution is dropped into the sodium molybdate aqueous solution to obtain molybdic acid suspension. And (3) dropwise adding 30 wt% of hydrogen peroxide into the continuously stirred molybdic acid suspension until the precipitate disappears to obtain a clear and transparent peroxymolybdic acid solution.
20mL of Na with a concentration of 1mol/L2HPO4The solution was added to the above-mentioned peroxymolybdic acid solution and sufficiently stirred for 10 minutes to obtain a phosphomolybdic heteropolyacid solution in which P/Mo is 1: 2.
And (3) mixing the quaternary ammonium salt resin prepared in the step (2) with a phosphomolybdic heteropoly acid solution, stirring for 3 hours at normal temperature, filtering out the resin, washing with deionized water, and drying to obtain the immobilized catalyst.
Example 10
(1) 200mL of N, N-dimethylformamide solvent was added to a 250mL three-necked round-bottomed flask, 40g of chlorinated polypropylene styrene was added thereto, and the mixture was soaked and swollen for 5 hours. Then 12g of polyethyleneimine with a relative molecular mass of 30000 was added to the flask, and the mixture was stirred at 50 ℃ for 10 hours to react, thereby obtaining a graft polymer.
(2) Swelling the grafted high molecular polymer obtained in the step (1) for 3h by using 100mL of n-propanol solution, adding 1mol of 1-chlorohexadecane, stirring and reacting for 1h under the reflux condition at the temperature of 110 ℃, reducing the temperature to 70 ℃, adding 1mol of 1-chlorohexane, continuing stirring and reacting for 3h, cooling, filtering out the resin, leaching by using ethanol, and drying to obtain the quaternary ammonium salt resin.
(3) To the solution containing 40mmol of Na2MoO4And dropwise adding a solution containing 200mmol of hydrochloric acid into the sodium tungstate aqueous solution to obtain a tungstic acid suspension. And (3) dropwise adding 30 wt% of hydrogen peroxide into the continuously stirred tungstic acid suspension until the precipitate disappears to obtain a clear and transparent peroxytungstic acid solution.
20mL of Na with a concentration of 1mol/L2HPO4The solution was added to the above peroxytungstic acid solution and stirred well for 10 minutes to give a phosphotungstic acid solution with P/W of 1: 2.
And (3) mixing the quaternary ammonium salt resin prepared in the step (2) with a phosphotungstic heteropoly acid solution, stirring for 3 hours at normal temperature, filtering out the resin, washing with deionized water, and drying to obtain the immobilized catalyst.
Example 11
(1) 200mL of N, N-dimethylformamide solvent was added to a 250mL three-necked round-bottomed flask, 40g of chlorinated polybutylstyrene was added, and the flask was soaked and swollen for 10 hours. Then 20g of polyethyleneimine with the relative molecular mass of 1000 was added to the flask, and the mixture was stirred at 25 ℃ for 2 hours to react, thereby obtaining a graft polymer.
(2) Swelling the grafted high molecular polymer obtained in the step (1) for 3h by using 100mL of isobutanol solution, adding 1.5mol of 1-chlorohexadecane, stirring and reacting for 2h under the condition of refluxing at 135 ℃, reducing the temperature to 30 ℃, adding 1mol of 1-chloropropane, continuing stirring and reacting for 9h, cooling, filtering out the resin, leaching by using ethanol, and drying to obtain the quaternary ammonium salt resin.
(3) To the solution containing 40mmol of Na2MoO4Dropwise adding solution containing 40mmol of hydrochloric acid into the sodium tungstate aqueous solution to obtain tungstic acid suspension. And (3) dropwise adding 30 wt% of hydrogen peroxide into the continuously stirred tungstic acid suspension until the precipitate disappears to obtain a clear and transparent peroxytungstic acid solution.
20mL of the solution is added to a solution with a concentration of1mol/L of Na2HPO4The solution was added to the above peroxytungstic acid solution and stirred well for 10 minutes to give a phosphotungstic acid solution with P/W of 1: 2.
And (3) mixing the quaternary ammonium salt resin prepared in the step (2) with a phosphotungstic heteropoly acid solution, stirring for 3 hours at normal temperature, filtering out the resin, washing with deionized water, and drying to obtain the immobilized catalyst.
Example 12
(1) 200mL of N, N-dimethylformamide solvent was added to a 250mL three-necked round-bottomed flask, 40g of chlorinated polypentylstyrene was added, and the flask was soaked and swollen for 10 hours. And adding 16g of polyethyleneimine with the relative molecular mass of 4000 into the flask, and stirring at 10 ℃ for reacting for 18 hours to obtain the grafted high polymer.
(2) Swelling the grafted high molecular polymer obtained in the step (1) for 3h by using 100mL of isopropanol solution, adding 2mol of 1-chlorohexadecane, stirring and reacting for 2h under the reflux condition of 150 ℃, reducing the temperature to 40 ℃, adding 1mol of 1-chloropropane, continuously stirring and reacting for 7h, cooling, filtering out resin, leaching by using ethanol, and drying to obtain quaternary ammonium salt resin.
(3) To the solution containing 40mmol of Na2MoO4And dropwise adding a solution containing 80mmol of hydrochloric acid into the sodium tungstate aqueous solution to obtain a tungstic acid suspension. And (3) dropwise adding 30 wt% of hydrogen peroxide into the continuously stirred tungstic acid suspension until the precipitate disappears to obtain a clear and transparent peroxytungstic acid solution.
20mL of Na with a concentration of 1mol/L2HPO4The solution was added to the above peroxytungstic acid solution and stirred well for 10 minutes to give a phosphotungstic acid solution with P/W of 1: 2.
And (3) mixing the quaternary ammonium salt resin prepared in the step (2) with a phosphotungstic heteropoly acid solution, stirring for 3 hours at normal temperature, filtering out the resin, washing with deionized water, and drying to obtain the immobilized catalyst. The prepared catalyst has the structural unit as follows:
Figure BDA0001676441870000131
wherein R is C16 alkyl or C3 alkyl, x is 1-5, and y is 400-1000.
EXAMPLE 13 epoxidation of cyclohexene
30ml of acetonitrile was added as a solvent to a 250ml tank reactor, then 8.2g (0.1mol) of cyclohexene and 2.46g (30% by mass relative to the cyclohexene) of the catalyst PS-PW-B synthesized in example 2 were added, and at 35 ℃ and 1atm, 600r/min, stirring was carried out to start the reaction and 11.4g of 30 wt% hydrogen peroxide (active ingredient H) was slowly added dropwise thereto2O2The mol ratio of cyclohexene to the reaction is 1:1), and the reaction is stirred for 8 hours. After the reaction was completed, the conversion of cyclohexene was 92% and the selectivity of cyclohexene oxide was 98%. The catalyst was recovered from the reaction system by filtration and dried in vacuo. The recovered catalyst was recycled 6 times with the above reaction conditions, and the reaction results are shown in table 1.
Table 1: PS-PW-B catalyst testing
Number of catalyst cycles Cyclohexene conversion (%) Cyclohexanoxide Selectivity (%) H2O2Conversion ratio of (1%)
Fresh PS-PW-B 92 98 98
1 93 98 99
2 92 98 98
3 92 97 97
4 92 97 98
5 92 97 97
6 91 97 97
Example 14
Changing the concentration of the solvent and hydrogen peroxide in the reaction system and the effective component H2O2The molar ratio to cyclohexene, catalyst, reaction temperature and time, and other conditions were the same as in [ example 13 ], and the results of the cyclohexene epoxidation reaction are shown in Table 2.
Table 2: epoxidation of cyclohexene under different conditions
Figure BDA0001676441870000141
Example 15
0.1mol of butene, styrene and cyclopentene were used as raw materials, reaction temperature was changed, and the remaining reaction conditions were the same as in example 13, and the reaction results are shown in Table 3.
Table 3: epoxidation of different olefins
Figure BDA0001676441870000142
Example 16 comparison of the Supported catalyst of the invention with the catalyst described in patent CN 101485990A
The conditions were the same as in example 13 except that the kind of the catalyst used in the reaction system was changed, and the results of the epoxidation reaction of cyclohexene are shown in Table 4.
Table 4: comparison of catalytic Activity of different catalysts in cyclohexene epoxidation System
Figure BDA0001676441870000151
It is demonstrated by the foregoing examples that the oxidation supported catalyst of the present invention can selectively perform olefin epoxidation reactions in a suitable reaction medium under the conditions provided by the present invention. The immobilized catalyst has high nitrogen content, high load of the heteropoly phosphoric acid anion, catalytic activity and selectivity which can be regulated and controlled by the carbon chain length of the quaternary ammonium salt cation and the molar ratio of phosphorus to the heteroatom, mild reaction conditions, and easy separation, recovery and recycling of the catalyst after reaction. Can meet the requirement of technical economy, and is a novel catalyst suitable for large-scale industrial application.

Claims (16)

1. An immobilized heteropolyacid catalyst, comprising a quaternized resin and an anion, wherein the anion is a phosphoheteropoly acid anion, and the quaternized resin comprises the following structural units:
Figure DEST_PATH_IMAGE002
wherein, in the step (A),
Figure DEST_PATH_IMAGE004
is a high molecular polymer carrier which is
Figure DEST_PATH_IMAGE006
，R2Is C2~3R is a long-carbon chain alkyl group or a short-carbon chain alkyl group, the long-carbon chain alkyl group is C13~20The short-chain C-alkanyl radical is C3~6X is an integer of 1-5, y is an integer of 400-1000, and j is an integer of 0-5;
the anion is a phosphotungstic heteropoly acid anion or a phosphomolybdic heteropoly acid anion.
2. The supported heteropolyacid catalyst according to claim 1, wherein the long-carbon chain alkyl group is C16~18Linear or branched alkyl.
3. The immobilized heteropolyacid catalyst according to claim 1, wherein the molar ratio of phosphorus to tungsten or phosphorus to molybdenum in the anion is 1:2 to 4.
4. The immobilized heteropolyacid catalyst of claim 3, wherein the molar ratio of phosphorus to tungsten or phosphorus to molybdenum in the anion is 1: 2.
5. A process for the preparation of the supported heteropolyacid catalyst according to any one of claims 1 to 4, which comprises the steps of:
(1) the structural unit is
Figure DEST_PATH_IMAGE008
The high molecular polymer is dispersed in an organic solvent to swell, and then structural units are added
Figure DEST_PATH_IMAGE010
To obtain a graft comprising structural units of the formula IIBranched high molecular polymer, wherein X is halogen, R2Is C2~3X is an integer of 1 to 5, y is an integer of 400 to 1000, and j is an integer of 0 to 5;
formula II:
Figure DEST_PATH_IMAGE012
；
(2) swelling the grafted high molecular polymer prepared in the step (1) in an organic alcohol solvent, adding long-carbon-chain halogenated alkane, stirring at 100-150 ℃ for reaction, adding short-carbon-chain halogenated alkane, stirring at 30-80 ℃ for reaction to obtain the quaternary ammonium salt resin comprising the structural unit shown in the formula III-Ca, wherein R is long-carbon-chain alkyl or short-carbon-chain alkyl, and the long carbon chain is C13~20The long carbon chain halogenated alkane is C13~20The short carbon chain is C3~6The short carbon chain halogenated alkane is C3~6The halogenated alkane of (a);
formula III-Ca:
Figure DEST_PATH_IMAGE014
；
(3) and (3) adding the quaternary ammonium salt resin prepared in the step (2) into a phosphorus-containing heteropoly acid solution for ion exchange to obtain the immobilized heteropoly acid catalyst.
6. The process according to claim 5, wherein the structural unit in the step (1) is
Figure DEST_PATH_IMAGE016
The polymer of (a) is polyethyleneimine.
7. The process according to claim 5, wherein the structural unit in the step (1) is
Figure DEST_PATH_IMAGE017
The polymer of (a) is added in an amount of the high molecular polymer carrier1~50%wt。
8. The method according to claim 7, wherein the structural unit in the step (1) is
Figure DEST_PATH_IMAGE018
The addition amount of the polymer is 5-30 wt% of the high molecular polymer carrier.
9. The method according to claim 5, wherein the reaction in step (1) is carried out at a temperature of 10 to 50 ℃.
10. The method according to claim 9, wherein the reaction in step (1) is carried out at a temperature of 25 ℃.
11. The preparation method according to claim 5, wherein the organic alcohol solvent in step (2) is one or more of ethanol, n-propanol, isopropanol, isobutanol, and n-butanol.
12. The method according to claim 11, wherein the organic alcohol solvent in step (2) is isopropanol.
13. The method according to claim 5, wherein the molar ratio of the long-carbon-chain halogenated alkane to the short-carbon-chain halogenated alkane in the step (2) is 0.1-2: 1.
14. The method according to claim 13, wherein the molar ratio of the long-carbon-chain halogenated alkane to the short-carbon-chain halogenated alkane in the step (2) is 0.5-1.5: 1.
15. Use of the supported heteropolyacid catalyst according to any one of claims 1 to 4 in an olefin epoxidation reaction, comprising the steps of:
and adding the catalyst into the olefin solution, and slowly dropwise adding hydrogen peroxide at 20-70 ℃ to react to obtain an olefin epoxidation product.
16. Use according to claim 15, wherein the olefin is cyclohexene, butene, styrene or cyclopentene.
CN201810527823.8A 2018-05-29 2018-05-29 Immobilized heteropolyacid catalyst and preparation method and application thereof Active CN109046452B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810527823.8A CN109046452B (en) 2018-05-29 2018-05-29 Immobilized heteropolyacid catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810527823.8A CN109046452B (en) 2018-05-29 2018-05-29 Immobilized heteropolyacid catalyst and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN109046452A CN109046452A (en) 2018-12-21
CN109046452B true CN109046452B (en) 2022-02-08

Family

ID=64819714

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810527823.8A Active CN109046452B (en) 2018-05-29 2018-05-29 Immobilized heteropolyacid catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN109046452B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110563884B (en) * 2019-04-10 2021-06-29 江苏扬农化工集团有限公司 Preparation method of supported heteropolyacid catalyst
CN111068781A (en) * 2020-01-02 2020-04-28 江苏扬农化工集团有限公司 Preparation of heteropolyacid catalyst and application of heteropolyacid catalyst in chloropropene epoxidation
CN111841644B (en) * 2020-08-27 2022-10-28 郑州大学 Metal-organic complex immobilized phosphotungstic acid catalyst for synthesizing epoxy cyclohexane
CN115739179B (en) * 2022-11-01 2024-04-09 南京大学 Composite high-molecular catalyst and preparation method and application thereof

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1301592A (en) * 1999-12-24 2001-07-04 中国科学院感光化学研究所 Method for preparing 12-tungstophosphoric acid
CN1526707A (en) * 2003-03-03 2004-09-08 中国科学院大连化学物理研究所 Homogeneous catalyst recovering process
CN101485990A (en) * 2009-03-10 2009-07-22 睿鹰制药（苏州）有限公司 Solid supported heteropoly acid catalyst and preparation method thereof
JP2010155805A (en) * 2008-12-26 2010-07-15 Showa Denko Kk Method for producing epoxy compound
CN101910248A (en) * 2008-01-07 2010-12-08 三井化学株式会社 Novel polymer particle and use thereof
CN102439017A (en) * 2009-05-28 2012-05-02 施里特马克控股公司 Method for the manufacture of aminopolyalkylene phosphonic acids
CN103193589A (en) * 2013-03-15 2013-07-10 湘潭大学 Method for preparing epoxy compound, cyclohexanol and cyclohexanone by co-oxidation synthesis
CN103880779A (en) * 2012-12-20 2014-06-25 中国科学院大连化学物理研究所 Method utilizing quaternary ammonium heteropolyate to catalyze alkene epoxidation
CN104998689A (en) * 2015-06-29 2015-10-28 湖北大学 Anion resin-carried peroxyphosphotungstic acid, its preparation method and use, and epoxycycloparaffin synthesis method

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1301592A (en) * 1999-12-24 2001-07-04 中国科学院感光化学研究所 Method for preparing 12-tungstophosphoric acid
CN1526707A (en) * 2003-03-03 2004-09-08 中国科学院大连化学物理研究所 Homogeneous catalyst recovering process
CN101910248A (en) * 2008-01-07 2010-12-08 三井化学株式会社 Novel polymer particle and use thereof
JP2010155805A (en) * 2008-12-26 2010-07-15 Showa Denko Kk Method for producing epoxy compound
CN101485990A (en) * 2009-03-10 2009-07-22 睿鹰制药（苏州）有限公司 Solid supported heteropoly acid catalyst and preparation method thereof
CN102439017A (en) * 2009-05-28 2012-05-02 施里特马克控股公司 Method for the manufacture of aminopolyalkylene phosphonic acids
CN103880779A (en) * 2012-12-20 2014-06-25 中国科学院大连化学物理研究所 Method utilizing quaternary ammonium heteropolyate to catalyze alkene epoxidation
CN103193589A (en) * 2013-03-15 2013-07-10 湘潭大学 Method for preparing epoxy compound, cyclohexanol and cyclohexanone by co-oxidation synthesis
CN104998689A (en) * 2015-06-29 2015-10-28 湖北大学 Anion resin-carried peroxyphosphotungstic acid, its preparation method and use, and epoxycycloparaffin synthesis method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
环氧化SBS制备及其改性环氧树脂性能的研究;余谋发;《中国优秀硕士学位论文全文数据库工程科技I辑》;20091215;第46-47页第2.2、2.2.1.3节和第49页第2.2.2.2节 *

Also Published As

Publication number Publication date
CN109046452A (en) 2018-12-21

Similar Documents

Publication Publication Date Title
CN109046452B (en) Immobilized heteropolyacid catalyst and preparation method and application thereof
Chen et al. Conversion of fructose into 5-hydroxymethylfurfural catalyzed by recyclable sulfonic acid-functionalized metal–organic frameworks
CA2236126C (en) Process for producing alkylene glycol
CN101485990B (en) Solid supported heteropoly acid catalyst and preparation method thereof
CN109776480A (en) A kind of preparation method for the catalyst of synthesizing annular carbonate, preparation method and cyclic carbonate
Wang et al. Optimization of fructose dehydration to 5-hydroxymethylfurfural catalyzed by SO 3 H-bearing lignin-derived ordered mesoporous carbon
Niakan et al. Sulfonic acid functionalized dendrimer-grafted cellulose as a solid acid catalyst for the high-yield and green production of 5-hydroxymethylfurfural
CN101717327A (en) Method for producing propylene glycol mono-methyl ether with energy conservation
CN110252394B (en) Catalyst for preparing propylene oxide by propylene oxidation, preparation and application thereof
CN103008007B (en) Resin-type solid base catalyst for synthesis of propylene glycol ether and preparation method and application thereof
CN108465487B (en) Polyion liquid-based heteropolyacid catalyst for olefin epoxidation reaction, preparation method and application thereof
CN109647497B (en) Catalyst for preparing dimethyl carbonate from epoxide, methanol and carbon dioxide, preparation method and application thereof
CN111790438A (en) Catalyst for cycloaddition reaction of ethylene oxide and carbon dioxide and preparation method and application thereof
CN101564697B (en) Reaction control phase transfer catalyst and application thereof in epoxidation reaction
CN105618138A (en) Immobilized tungstophosphoric heteropoly acid catalyst and use thereof
CN109225227A (en) A kind of order mesoporous C catalyst and preparation method thereof being used to prepare hexahydrophthalic anhydride
CN112939924B (en) Process for producing cyclic carbonate
CN110090662B (en) Preparation method and catalytic application of sulfonic group covalent modified vacancy polyacid composite material
CN110857273B (en) Method for preparing carbonic ester from oxalate
CN112570025A (en) Barbituric acid modified polymetallic oxygen cluster hybrid and preparation method thereof
CN112844473A (en) Alumina-supported polyion liquid catalyst and preparation method and application thereof
CN111203272A (en) Water-resistant sulfonic heteropoly acid salt catalyst and synthesis and application thereof
KR100869445B1 (en) Production method of dimethoxymethane using heteropolyacid catalyst immobilized on mesoporous carbon
CN116253887B (en) POSS-based organic porous polymer for catalyzing cycloaddition reaction of epoxide and carbon dioxide
US5798412A (en) Alkylene glycol production using carbon catalysts

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant