CN109776263A - Method for olefine aldehyde condensation reaction - Google Patents

Method for olefine aldehyde condensation reaction Download PDF

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CN109776263A
CN109776263A CN201711111450.8A CN201711111450A CN109776263A CN 109776263 A CN109776263 A CN 109776263A CN 201711111450 A CN201711111450 A CN 201711111450A CN 109776263 A CN109776263 A CN 109776263A
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condensation reaction
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reaction
catalyst
poss
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俞峰萍
谢同
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The present invention relates to a kind of methods for olefine aldehyde condensation reaction.The method includes the step of under olefine aldehyde condensation reaction condition, alkene and formaldehyde and ion-exchange resin catalyst are contacted；The ion-exchange resin catalyst has following structure general formula:Wherein,For gel-type nanocomposite resin matrix；M‑For anion, it is selected from trifluoromethanesulfonic acid radical ion, hydrogen sulfate ion, phosphoric acid hydrogen radical ion, tetrafluoroborate ion or hexafluorophosphoricacid acid ions；POSS is cage-type silsesquioxane unit；

Description

Process for the ene-aldehyde condensation reaction
Technical Field
The invention relates to a method for an olefine aldehyde condensation reaction, in particular to a method for preparing 1, 3-dihydric alcohol and/or 1, 3-dioxane derivatives by the olefine aldehyde condensation reaction.
Background
The 1, 3-dihydric alcohol has the characteristics of no odor, low toxicity, good water solubility and the like, and has wide application in the aspects of fine chemical engineering, medicines, dyes and the like. The 1, 3-diol is mainly used as a synthetic monomer of polyester and polyurethane, a solvent, an antifreeze agent and the like, and is also an important medical intermediate and an organic synthetic intermediate. Especially 1, 3-propanediol, is widely used, the most important application of which is the preparation of polytrimethylene terephthalate. The polytrimethylene terephthalate is a polyester material with excellent performance, has the high performance of the polyethylene terephthalate and the easy processing performance of the polybutylene terephthalate, has good rebound resilience and pollution resistance of nylon, is easy to dye and wear-resistant, has wide application prospect in the fields of carpets, engineering plastics, clothing fabrics and the like, is a hotspot for the development of synthetic fibers internationally at present, and is predicted by experts to be one of the most main new fiber varieties in the 21 st century.
The 1, 3-diol or the 1, 3-dioxane derivative can be prepared by Prins reaction of olefin and aldehyde substances such as formaldehyde under an acid catalyst, and the 1, 3-dioxane derivative can be further hydrolyzed to obtain the 1, 3-diol.
In the 70 s of the 20 th century, the company of Imperial Japan explored the synthesis of 1, 3-propanediol from ethylene. Discovery of BF3(JP 76146405)、CuSO4-H2SO4(JP 76143605), p-toluenesulfonic acid (JP 76143606), phosphotungstic acid (JP113809), HI-BiI3(US 4338290) all act as catalysts for the Prins reaction of ethylene with formaldehyde. The first Prins reaction of ethylene and formaldehyde to form dioxane, which is acidolyzed with acetic acid to produce monoester and monoHydrolyzing the ester or continuously esterifying the ester to generate 1, 3-propylene glycol, and recovering acetic acid. However, the catalyst in the route has strong corrosivity, more side reactions and complex post-treatment process, and easily causes the problem of environmental pollution. In 2000, DuPont, Inc. in US 6111135, disclosed that ytterbium (or bismuth) trifluoroacetate was used as a catalyst, formaldehyde and ethylene were subjected to Prins reaction for 16 hours at 130 ℃ and 6.9MPa to obtain 62-66% of 1, 3-propanediol diformate, and 1, 3-propanediol was obtained after hydrolysis. The catalyst system has harsh reaction conditions and low product selectivity.
Document No. cn201110355402.x discloses a method for preparing 1, 3-diol by taking solid acidic metal oxide as a catalyst and 1, 3-dioxane or a derivative thereof as a reactant through hydrolysis reaction under the catalytic action.
Document CN201110355127.1 discloses a process for the direct preparation of 1, 3-diols from olefins. The method adopts formaldehyde, olefin and water as reaction substrates, and directly prepares the 1, 3-dihydric alcohol under the action of an acidic catalyst (comprising a molecular sieve, heteropolyacid, solid superacid and the like). Mixing formaldehyde, olefin, water and a catalyst, reacting for at least 2 hours at the temperature higher than 80 ℃, easily separating the catalyst from a reaction system after the reaction, and recycling the catalyst for multiple times, wherein the separation yield of the 1, 3-dihydric alcohol is up to 95 percent.
Document No. cn201110379819.x discloses a method for preparing 1, 3-dioxane by using a supported heteropolyacid salt as a catalyst to catalyze a condensation reaction of ethylene and formaldehyde. Under mild reaction conditions, ethylene and formaldehyde aqueous solution are used as reactants to catalytically synthesize the 1, 3-dioxane. The method has the advantages of cheap and easily-obtained raw materials, low catalyst corrosivity, high catalytic activity, easy separation from reactants and products, simple reaction process and post-treatment process and mild operation condition.
The acidic ionic liquid is used as a novel environment-friendly solvent and a high-efficiency catalyst, simultaneously has high-density reaction active sites of a traditional liquid acid catalyst and non-volatility of solid acid, and is considered to be one of the most promising green catalysts due to designability of the molecular structure and acidity of the acidic ionic liquid.
Yadav et al reported [ Bmim [ ]]Cl·AlClxApplication in olefine aldehyde condensation reaction (Eur.J.Org.chem.2003,1779-1783), the conversion rate of aldehyde in the reaction can reach 95%, but AlCl3The sensitivity of the ionic liquid to water limits the application of the ionic liquid in organic reaction.
Wang wenjuan et al reported that an imidazole type or pyrrolidone type ionic liquid was used as a catalyst to catalyze the condensation reaction of styrene and formaldehyde. With ionic liquids [ BMIM][HSO4]When the ionic liquid catalyst is used as a catalyst, the highest formaldehyde conversion rate can reach 95%, but repeated tests show that the ionic liquid catalyst has poor repeated use performance, and the formaldehyde conversion rate is reduced to 90% after 5 times of use.
Document CN201410774243.0 discloses a preparation method of a resin-supported anionic acidic ionic liquid catalyst. The strong acid cation exchange resin with sulfonic acid group is used as counter anion, and ionic compound is added to react to prepare the loaded anion type acidic ionic liquid, the catalyst can effectively catalyze Prins condensation reaction of styrene and trioxymethylene, the reaction lasts for 10 hours at 80 ℃, and the yield of 4-phenyl-1, 3-dioxane can reach 86%.
It can be seen that the catalytic activity of the supported ionic liquid catalyst depends not only on the properties of the ionic liquid itself, but also on various properties of the support, such as heat resistance, solvent resistance, porosity, etc. Therefore, it is very important to design a catalyst with high activity and excellent recycling performance.
Disclosure of Invention
The invention provides a method for an olefine aldehyde condensation reaction. The process comprises the steps of contacting an olefin and formaldehyde with an ion exchange resin catalyst under conditions for an ene-aldehyde condensation reaction; the ion exchange resin catalyst has the following structural general formula:
wherein,is a gel type nano composite resin matrix;
M-is an anion selected from the group consisting of triflate, hydrogen sulfate, hydrogen phosphate, tetrafluoroborate or hexafluorophosphate;
POSS is a cage-type silsesquioxane unit with the general formula of (-SiO)1.5)m(ii) a m is 6, 8, 10 or 12;
is an imidazolium cationic unit;
r is a connecting group between the POSS unit and the imidazole cation unit, and R is alkylene or arylene;
the gel type nano composite resin matrix is a nano gel type copolymer obtained by in-situ copolymerization of styrene monomers, comonomers and nano materials; the nano material is at least one of multi-wall carbon nano tube, single-wall carbon nano tube, C60 or C70 fullerene.
According to one aspect of the invention, the POSS units are present in the ion exchange resin in an amount of 5 to 15 wt.%.
According to one aspect of the invention, M-Is trifluoromethanesulfonate ion.
According to one aspect of the invention, the alkylene group is selected from methylene, ethylene or propylene; the arylene group is selected from phenylene, naphthylene or phenylmethyl.
According to one aspect of the invention, the styrenic monomer is selected from at least one of styrene, α -methylstyrene or 4-butylstyrene, preferably styrene.
According to one aspect of the invention, the comonomer is selected from at least one of ethylene glycol dimethacrylate, diacrylene, divinylphenylmethane or divinylbenzene, preferably divinylbenzene.
According to one aspect of the invention, the nanomaterial is preferably a multi-walled carbon nanotube.
According to one aspect of the invention, the styrene monomer is 85-95 parts, the comonomer is 2-5 parts, and the nanomaterial is 0.1-3 parts.
According to one aspect of the invention, the olefin is selected from ethylene, trimethylethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, isoprene, 1-hexene, 1-octene, styrene, α -methylstyrene or cyclohexene.
According to one aspect of the invention, the aldol condensation reaction conditions comprise: the mol ratio of the olefin to the formaldehyde is (0.1-10): 1, the dosage of the catalyst is 1-15 wt% of the total amount of the raw materials, the reaction temperature is 50-150 ℃, the reaction time is 1-24 hours, and the reaction pressure is 2.0-6.0 MPa.
In the method, the formaldehyde can be aqueous solution of formaldehyde, and the mass fraction of the aqueous solution of formaldehyde is 35-60%.
The preparation method of the ion exchange resin catalyst comprises the following steps:
a) preparing an auxiliary agent into an aqueous solution A with the weight percentage concentration of 0.5-2%, and preparing a styrene monomer, a comonomer, a nano material and an initiator into a solution B, wherein the styrene monomer is selected from at least one of styrene, α -methylstyrene or 4-butylstyrene, the comonomer is selected from at least one of ethylene glycol dimethacrylate, dipropenylbenzene, divinylphenylmethane or divinylbenzene, the nano material is selected from at least one of a multi-walled carbon nanotube, a single-walled carbon nanotube, C60 or C70 fullerene, the initiator is selected from at least one of benzoyl peroxide, azodiisobutyronitrile, lauroyl peroxide or cumene hydroperoxide, the auxiliary agent is selected from at least one of polyvinyl alcohol, gelatin, starch, methylcellulose, bentonite or calcium carbonate, the dosage of the styrene monomer is 85-95 parts by weight, the dosage of the comonomer is 2-5 parts by weight, the nano material is 0.1-3 parts by weight, the initiator is 0.1-10 parts by weight, and the dosage of the auxiliary agent is 400-150 parts by weight;
b) pre-polymerizing the solution B at 60-75 ℃ for 0.5-2.5 hours, then mixing the solution B with the solution A, heating to 70-90 ℃ for reaction for 5-15 hours, and heating to 90-100 ℃ for reaction for 5-15 hours; after the reaction is finished, extracting, washing, filtering, drying and sieving to obtain composite gel microspheres with the particle size range of 0.35-0.60 mm;
c) chloromethylating the composite gel microspheres: adding a chloromethylation reagent which is 200-500% of the weight of the composite gel microsphere and a zinc chloride catalyst which is 20-70% of the weight of the composite gel microsphere into the composite gel microsphere, reacting for 8-30 hours at 30-60 ℃, filtering and washing to obtain a composite gel chlorine ball; the chloromethylation reagent is selected from at least one of chloromethyl ether, chloroethyl ether or 1, 4-dichloromethoxybutane;
d) reacting the mixture of the composite gel chlorine spheres, imidazole and acetonitrile at 60-90 ℃ to obtain composite imidazole microspheres; in the mixture, the mol ratio of the composite gel chlorine ball to the imidazole to the acetonitrile is 1: (1-2): (30-150);
e) mixing the composite imidazole microspheres and alkyl halogenated POSS compounds according to the equimolar ratio of imidazole functional groups and halogenated functional groups, dissolving the mixture in tetrahydrofuran, filtering the mixture after the reaction is finished at 100 ℃ for 24-72 hours, and washing the mixture to obtain the composite imidazole/POSS microspheres; the alkyl halogenated POSS compound is selected from at least one of octachloromethyl POSS, octachloroethyl POSS and octachloropropyl POSS;
f) and washing the composite imidazole/POSS microspheres by using a salt solution, wherein the molar ratio of the composite imidazole/POSS microspheres to the salt solution is (1: 1) to (1: 10) (ii) a The concentration of the salt solution is 0.1-1 mol/L; and after washing, washing the product by deionized water until the pH value is 7 to obtain the ion exchange resin. The salt solution is at least one of trifluoromethanesulfonic acid (salt), bisulfate, hydrogen phosphate, tetrafluoroborate and hexafluorophosphate.
The invention has the beneficial effects that: the ion exchange resin catalyst of the present invention contains two different nanomaterials: nanocarbon materials and Polyhedral silsesquioxanes (POSS for short). Under the action of an initiator, the nano carbon material, the monomer and the comonomer are introduced into the resin matrix through in-situ polymerization, so that the glass transition temperature of the resin matrix is increased; meanwhile, due to the introduction of the nano carbon material, the swelling resistance of the resin matrix is improved. And the POSS comprises an inorganic support structure consisting of Si and O, so that the ion exchange resin is endowed with good heat resistance, and the thermal stability is obviously improved.
The preferred scheme of the invention is that chloromethylated styrene, divinyl benzene and multi-walled carbon nano-tube in-situ gel type copolymer resin matrix reacts with imidazole to obtain composite imidazole microspheres, then the imidazole groups react with alkyl halogenated POSS compounds, and finally the composite imidazole microspheres undergo ion exchange reaction with salt solution to prepare the gel type ion exchange resin containing two different nano materials. Covalent bonding of the carbon nanotubes and the polymer matrix is realized through in-situ copolymerization between the carbon nanotubes and the monomers and comonomers, and bonding between the POSS and the resin matrix is realized through chemical reaction of halogenated alkylated POSS compounds and imidazole groups.
The gel type ion exchange resin catalyst containing two different nano materials is used for the olefine aldehyde condensation reaction of olefin and formaldehyde, and has the following advantages:
(1) the catalyst has low corrosivity and high activity;
(2) the catalyst is easy to recover, has good stability and can be repeatedly used.
The invention is further illustrated by the following examples, but it is to be noted that the scope of the invention is not limited thereto, but is defined by the appended claims.
It should be particularly noted that two or more aspects (or embodiments) disclosed in the context of the present specification may be combined with each other at will, and thus form part of the original disclosure of the specification, and also fall within the scope of the present invention.
Detailed Description
[ example 1 ] preparation of ion exchange resin catalyst
47.0 g of styrene, 2.3 g of divinylbenzene and 1.6 g of benzoyl peroxide initiator are added into a 500ml three-neck flask, and stirred and reacted for 2.0 hours at the temperature of 60 ℃; then 0.6 g of multi-walled carbon nanotubes was added and stirring was continued for 1 hour for prepolymerization. A solution of 2.0 g of gelatin dissolved in 260 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the composite gel microspheres A1 with the particle size of 0.35-0.60 mm.
Chloromethylation of composite gel microspheres: adding 40 g of composite gel microsphere A1 and 250ml of chloromethyl ether into a 500ml three-neck flask, standing at room temperature for 3 hours, starting stirring, adding 10 g of zinc chloride as a catalyst, heating to 60 ℃ for reaction for 10 hours, cooling to room temperature after chloromethylation is finished, filtering out chlorinated mother liquor, repeatedly washing with methanol, and drying at 100 ℃ for 8 hours to obtain the composite gel microsphere A1.
30 g of composite gel chlorine ball A1 (chlorine content is 3.5mmol Cl/g), imidazole (105.0mmol) and 200ml of acetonitrile are added into a 500ml three-neck flask, and the mixture reacts for 24 hours at 60 ℃, is cooled to room temperature, is filtered, is washed by ethyl acetate, 0.1mol/L HCl, deionized water and methanol in sequence, and is dried for 24 hours at 60 ℃ in vacuum to obtain the composite imidazole microsphere A1.
30 g of composite imidazole microsphere A1 (imidazole group content is 3.1mmol/g), 9.8 g of octachloromethyl silsesquioxane and 300ml of tetrahydrofuran are added into a 500ml three-neck flask, and after the reaction is finished, the mixture is filtered and washed by tetrahydrofuran and deionized water in sequence at 100 ℃ for 24 hours to obtain the composite imidazole/POSS microsphere A1.
Adding 30 g of composite imidazole/POSS microspheres A1 and 500ml of deionized water solution of 0.1mol/L lithium trifluoromethanesulfonate into a 1000ml three-neck flask, and stirring at room temperature to perform an ion exchange reaction for 24 hours; then washing the catalyst by deionized water until the pH value of washing liquor is 7, and drying the catalyst in vacuum to obtain the ion exchange resin catalyst of two different nano materials, which is marked as Cat-A1, wherein the POSS unit content is 9.8 percent, and the structural formula is as follows:
[ example 2 ] preparation of ion exchange resin catalyst
A monomer mixture solution containing an initiator (60.0 g of styrene, 1.0 g of divinyl benzene, 1.6 g of multi-walled carbon nano-tube and 1.0 g of benzoyl peroxide are added into a 500ml three-neck flask, the solution is stirred and reacted for 0.5 hour at 70 ℃, a stirrer is started, a mixed solution of 200ml of deionized water and 4 g of polyvinyl alcohol is added, the temperature is increased to 85 ℃, the reaction is carried out for 3 hours, the temperature is increased to 90 ℃, the reaction is carried out for 9 hours, and finally the temperature is increased to 100 ℃, and the reaction is carried out for 10 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the composite gel microspheres B1 with the particle size of 0.35-0.60 mm.
Chloromethylation of the composite microspheres: adding 50 g of composite microsphere B1 and 200ml of chloroethyl ether into a 500ml three-neck flask, standing at room temperature for 6 hours, adding 30 g of zinc chloride serving as a catalyst, starting stirring, heating to 50 ℃ for reaction for 30 hours, cooling to room temperature after chloromethylation is finished, filtering out a chlorination mother solution, repeatedly washing with methanol, and drying at 100 ℃ for 8 hours to obtain the composite gel chlorine sphere B1.
50 g of composite gel chlorine ball B1 (the chlorine content is 4.5mmol Cl/g), imidazole (225.0mmol) and 300ml of acetonitrile are added into a 500ml three-neck flask, the mixture reacts for 16 hours at 80 ℃, the mixture is cooled to room temperature, filtered, washed by ethyl acetate, 0.1mol/L HCl, deionized water and methanol in sequence, and then dried for 24 hours at 60 ℃ in vacuum to obtain the composite imidazole microsphere B1.
50 g of composite imidazole microsphere B1 (the imidazole group content is 3.9mmol/g), 21.0 g of octachloromethyl silsesquioxane and 500ml of tetrahydrofuran are added into a 1000ml three-neck flask, and after the reaction is finished, the mixture is filtered and washed by tetrahydrofuran and deionized water in sequence at 100 ℃ for 72 hours to obtain the composite imidazole/POSS microsphere B1.
Adding 40 g of composite imidazole/POSS microspheres B1 and 400ml of deionized water solution of 1.0mol/L lithium trifluoromethanesulfonate into a 1000ml three-neck flask, and stirring at room temperature to perform an ion exchange reaction for 24 hours; then washing the catalyst by deionized water until the pH value of washing liquor is 7, and drying the catalyst in vacuum to obtain the ion exchange resin catalyst of two different nano materials, which is marked as Cat-B1, wherein the POSS unit content is 11.1 percent, and the structural formula is as follows:
[ example 3 ] preparation of ion exchange resin catalyst
A monomer mixture solution containing an initiator (42.5 g of styrene, 2.5 g of divinyl benzene, 0.1 g of multi-walled carbon nano tube and 2.0 g of benzoyl peroxide are added into a 500ml three-neck flask, the solution is stirred and reacted for 1.5 hours at 70 ℃, 200ml of a mixed solution of deionized water and 4 g of polyvinyl alcohol is added, the temperature is increased to 85 ℃, the reaction is carried out for 3 hours, the temperature is increased to 90 ℃, the reaction is carried out for 9 hours, and finally the temperature is increased to 100 ℃, and the reaction is carried out for 10 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the composite gel microspheres C1 with the particle size of 0.35-0.60 mm.
Chloromethylation of the composite microspheres: adding 20 g of composite microsphere C1 and 100 ml of 1, 4-dichloromethoxybutane into a 250ml three-neck flask, standing for 6 hours at room temperature, adding 8 g of zinc chloride as a catalyst, starting stirring, heating to 30 ℃ for reaction for 24 hours, cooling to room temperature after chloromethylation is finished, filtering out chlorinated mother liquor, repeatedly washing with methanol, and drying for 8 hours at 100 ℃ to obtain the composite gel chlorine sphere C1.
20 g of composite gel chlorine sphere C1 (chlorine content is 1.45mmol Cl/g), imidazole (34.0mmol) and 150ml of acetonitrile are added into a 250ml three-neck flask, the mixture reacts for 16 hours at 90 ℃, the mixture is cooled to room temperature and filtered, and the mixture is washed by ethyl acetate, 0.1mol/L HCl, deionized water and methanol in sequence and then dried for 24 hours at 60 ℃ in vacuum to obtain the composite imidazole microsphere C1.
20 g of composite imidazole microsphere C1 (the content of imidazole groups is 1.6mmol/g), 3.7 g of octachloroethyl silsesquioxane and 150ml of tetrahydrofuran are added into a 250ml three-neck flask, and after the reaction is finished, filtration is carried out for 72 hours at 100 ℃, and then the mixture is washed by tetrahydrofuran and deionized water in sequence to obtain the composite imidazole/POSS microsphere C1.
Adding 20 g of composite imidazole/POSS microsphere C1 and 300ml of deionized water solution of 0.5mol/L lithium trifluoromethanesulfonate into a 500ml three-neck flask, and stirring at room temperature to perform an ion exchange reaction for 24 hours; then washing the catalyst by deionized water until the pH value of washing liquor is 7, and drying the catalyst in vacuum to obtain the ion exchange resin catalyst of two different nano materials, which is marked as Cat-C1, wherein the POSS unit content is 6.1 percent, and the structural formula is as follows:
[ example 4 ] preparation of ion exchange resin catalyst
47.0 g of styrene, 2.3 g of divinylbenzene and 1.6 g of benzoyl peroxide initiator are added into a 500ml three-neck flask, and stirred and reacted for 2.0 hours at the temperature of 60 ℃; then 0.6 g of single-walled carbon nanotubes was added and stirring was continued for 1 hour for prepolymerization. A solution of 2.0 g of gelatin dissolved in 260 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the composite gel microspheres A2 with the particle size of 0.35-0.60 mm.
Chloromethylation of composite gel microspheres: adding 40 g of composite gel microsphere A2 and 250ml of chloromethyl ether into a 500ml three-neck flask, standing at room temperature for 3 hours, starting stirring, adding 10 g of zinc chloride as a catalyst, heating to 60 ℃ for reaction for 10 hours, cooling to room temperature after chloromethylation is finished, filtering out chlorinated mother liquor, repeatedly washing with methanol, and drying at 100 ℃ for 8 hours to obtain the composite gel microsphere A2.
30 g of composite gel chlorine ball A2 (chlorine content is 3.3mmol Cl/g), imidazole (99.0mmol) and 200ml of acetonitrile are added into a 500ml three-neck flask, the mixture reacts for 24 hours at 60 ℃, the mixture is cooled to room temperature and filtered, and the mixture is washed by ethyl acetate, 0.1mol/L HCl, deionized water and methanol in sequence and then dried for 24 hours at 60 ℃ in vacuum to obtain the composite imidazole microsphere A2.
30 g of composite imidazole microsphere A2 (imidazole group content is 3.0mmol/g), 9.2 g of octachloromethyl silsesquioxane and 300ml of tetrahydrofuran are added into a 500ml three-neck flask, and after the reaction is finished, the mixture is filtered and washed by tetrahydrofuran and deionized water in sequence at 100 ℃ for 24 hours to obtain the composite imidazole/POSS microsphere A2.
Adding 30 g of composite imidazole/POSS microspheres A2 and 500ml of deionized water solution of 0.1mol/L lithium trifluoromethanesulfonate into a 1000ml three-neck flask, and stirring at room temperature to perform an ion exchange reaction for 24 hours; then washing the catalyst by deionized water until the pH value of washing liquor is 7, and drying the catalyst in vacuum to obtain the ion exchange resin catalyst of two different nano materials, which is marked as Cat-A2, wherein the POSS unit content is 9.4 percent, and the structural formula is as follows:
[ example 5 ] preparation of ion exchange resin catalyst
A monomer mixture solution containing an initiator (60.0 g of styrene, 1.0 g of divinyl benzene, 1.6 g of single-walled carbon nanotube and 1.0 g of benzoyl peroxide are added into a 500ml three-neck flask, the solution is stirred and reacted for 0.5 hour at 70 ℃, a stirrer is started, a mixed solution of 200ml of deionized water and 4 g of polyvinyl alcohol is added, the temperature is increased to 85 ℃, the reaction is carried out for 3 hours, the temperature is increased to 90 ℃, the reaction is carried out for 9 hours, and finally the temperature is increased to 100 ℃, and the reaction is carried out for 10 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the composite gel microspheres B2 with the particle size of 0.35-0.60 mm.
Chloromethylation of the composite microspheres: adding 50 g of composite microsphere B2 and 200ml of chloroethyl ether into a 500ml three-neck flask, standing at room temperature for 6 hours, adding 30 g of zinc chloride serving as a catalyst, starting stirring, heating to 50 ℃ for reaction for 30 hours, cooling to room temperature after chloromethylation is finished, filtering out a chlorination mother solution, repeatedly washing with methanol, and drying at 100 ℃ for 8 hours to obtain the composite gel chlorine sphere B2.
50 g of composite gel chlorine ball B2 (the chlorine content is 4.9mmol Cl/g), imidazole (245.0mmol) and 300ml of acetonitrile are added into a 500ml three-neck flask, the mixture reacts for 16 hours at 80 ℃, the mixture is cooled to room temperature, filtered, washed by ethyl acetate, 0.1mol/L HCl, deionized water and methanol in sequence, and then dried for 24 hours at 60 ℃ in vacuum to obtain the composite imidazole microsphere B2.
50 g of composite imidazole microsphere B2 (the content of imidazole groups is 4.2mmol/g), 21.3 g of octachloromethylsilsesquioxane and 500ml of tetrahydrofuran are added into a 1000ml three-neck flask, and after the reaction is finished, the mixture is filtered and washed by tetrahydrofuran and deionized water in sequence, so that the composite imidazole/POSS microsphere B2 is obtained.
Adding 40 g of composite imidazole/POSS microspheres B2 and 400ml of deionized water solution of 1.0mol/L lithium trifluoromethanesulfonate into a 1000ml three-neck flask, and stirring at room temperature to perform an ion exchange reaction for 24 hours; then washing the catalyst by deionized water until the pH value of washing liquor is 7, and drying the catalyst in vacuum to obtain the ion exchange resin catalyst of two different nano materials, which is marked as Cat-B2, wherein the POSS unit content is 11.5 percent, and the structural formula is as follows:
[ example 6 ] preparation of ion exchange resin catalyst
A monomer mixture solution containing an initiator (42.5 g of styrene, 2.5 g of divinylbenzene, 0.1 g of single-walled carbon nanotube and 2.0 g of benzoyl peroxide are added into a 500ml three-neck flask, and the solution is stirred and reacted for 1.5 hours at 70 ℃, 200ml of a mixed solution of deionized water and 4 g of polyvinyl alcohol is added, the temperature is increased to 85 ℃, the reaction is carried out for 3 hours, then the temperature is increased to 90 ℃, the reaction is carried out for 9 hours, and finally the temperature is increased to 100 ℃, and the reaction is carried out for 10 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the composite gel microspheres C2 with the particle size of 0.35-0.60 mm.
Chloromethylation of the composite microspheres: adding 20 g of composite microsphere C2 and 100 ml of 1, 4-dichloromethoxybutane into a 250ml three-neck flask, standing for 6 hours at room temperature, adding 8 g of zinc chloride as a catalyst, starting stirring, heating to 30 ℃ for reaction for 24 hours, cooling to room temperature after chloromethylation is finished, filtering out chlorinated mother liquor, repeatedly washing with methanol, and drying for 8 hours at 100 ℃ to obtain the composite gel chlorine sphere C2.
20 g of composite gel chlorine sphere C2 (chlorine content is 1.6mmol Cl/g), imidazole (32.0mmol) and 150ml of acetonitrile are added into a 250ml three-neck flask, the mixture reacts for 16 hours at 90 ℃, the mixture is cooled to room temperature and filtered, and the mixture is washed by ethyl acetate, 0.1mol/L HCl, deionized water and methanol in sequence and then dried for 24 hours at 60 ℃ in vacuum to obtain the composite imidazole microsphere C2.
20 g of composite imidazole microsphere C2 (the content of imidazole groups is 1.5mmol/g), 3.6 g of octachloroethyl silsesquioxane and 150ml of tetrahydrofuran are added into a 250ml three-neck flask, and after the reaction is finished, filtration is carried out for 72 hours at 100 ℃, and then the mixture is washed by tetrahydrofuran and deionized water in sequence to obtain the composite imidazole/POSS microsphere C2.
Adding 20 g of composite imidazole/POSS microsphere C2 and 300ml of deionized water solution of 0.5mol/L lithium trifluoromethanesulfonate into a 500ml three-neck flask, and stirring at room temperature to perform an ion exchange reaction for 24 hours; then washing the catalyst by deionized water until the pH value of washing liquor is 7, and drying the catalyst in vacuum to obtain the ion exchange resin catalyst of two different nano materials, which is marked as Cat-C2, wherein the POSS unit content is 5.9%, and the structural formula is as follows:
comparative example 1 preparation of comparative catalyst
Preparing gel microspheres without adding nano materials: a500 mL three-necked flask was charged with 47.0 grams of styrene, 2.3 grams of divinylbenzene and 1.6 grams of benzoyl peroxide initiator. A solution of 2.0 g of gelatin dissolved in 260 ml of deionized water was added. The stirring speed was adjusted and the mixture was stirred for 2 hours. Stirring and reacting for 2.0 hours at 60 ℃, then gradually heating to 80 ℃, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the gel microspheres DZ-1 with the particle size of 0.35-0.60 mm.
Chloromethylation of gel microspheres: adding 40 g of gel microsphere DZ-1 and 250ml of chloromethyl ether into a 500ml three-neck flask, standing at room temperature for 3 hours, starting stirring, adding 10 g of zinc chloride as a catalyst, heating to 60 ℃ for reaction for 10 hours, cooling to room temperature after chloromethylation is finished, filtering out a chlorination mother solution, repeatedly washing with methanol, and drying at 100 ℃ for 8 hours to obtain the gel microsphere DZ-1.
Without the use of haloalkylated POSS compounds: 30 g of gel chlorine ball DZ-1 (the chlorine content is 3.6mmol Cl/g), N-methylimidazole (108.0mmol) and 200ml of acetonitrile are added into a 500ml three-neck flask, the mixture reacts for 24 hours at the temperature of 60 ℃, the mixture is cooled to room temperature and filtered, and then ethyl acetate, 0.1mol/L HCl, deionized water and methanol are sequentially used for washing, and then the mixture is dried for 24 hours at the temperature of 60 ℃ in vacuum to obtain the imidazole microsphere DZ-1.
Adding 30 g of imidazole microsphere DZ-1 and 500ml of deionized water solution of 0.1mol/L lithium trifluoromethanesulfonate into a 1000ml three-neck flask, and stirring at room temperature to perform an ion exchange reaction for 24 hours; followed by deionized water washing until the wash pH was 7, and drying in vacuo afforded the ion exchange resin catalyst, noted Cat-DZ-1:
comparative example 2 preparation of comparative catalyst
47.0 g of styrene, 2.3 g of divinylbenzene and 1.6 g of benzoyl peroxide initiator are added into a 500ml three-neck flask, and stirred and reacted for 2.0 hours at the temperature of 60 ℃; then 0.6 g of multi-walled carbon nanotubes was added and stirring was continued for 1 hour for prepolymerization. A solution of 2.0 g of gelatin dissolved in 260 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the composite gel microspheres DZ-2 with the particle size of 0.35-0.60 mm.
Chloromethylation of composite gel microspheres: adding 40 g of composite gel microsphere DZ-2 and 250ml of chloromethyl ether into a 500ml three-neck flask, standing for 3 hours at room temperature, starting stirring, adding 10 g of zinc chloride as a catalyst, heating to 60 ℃ for reaction for 10 hours, cooling to room temperature after chloromethylation is finished, filtering out chlorinated mother liquor, repeatedly washing with methanol, and drying for 8 hours at 100 ℃ to obtain the composite gel microsphere DZ-2.
Without the use of haloalkylated POSS compounds: 30 g of composite gel chlorine ball DZ-2 (the chlorine content is 3.5mmol Cl/g), N-methylimidazole (105.0mmol) and 200ml of acetonitrile are added into a 500ml three-neck flask, the mixture reacts for 24 hours at the temperature of 60 ℃, the mixture is cooled to room temperature and filtered, and then ethyl acetate, 0.1mol/L HCl, deionized water and methanol are sequentially used for washing, and then the mixture is dried for 24 hours at the temperature of 60 ℃ in vacuum to obtain the composite imidazole microsphere DZ-2.
Adding 30 g of compound imidazole microsphere DZ-2 and 500ml of deionized water solution of 0.1mol/L lithium trifluoromethanesulfonate into a 1000ml three-neck flask, and stirring at room temperature to perform an ion exchange reaction for 24 hours; followed by deionized water washing until the wash pH was 7, and drying in vacuo afforded the ion exchange resin catalyst, noted Cat-DZ-2:
comparative example 3 preparation of comparative catalyst
Preparing gel microspheres without adding nano materials: a500 mL three-necked flask was charged with 47.0 grams of styrene, 2.3 grams of divinylbenzene and 1.6 grams of benzoyl peroxide initiator. A solution of 2.0 g of gelatin dissolved in 260 ml of deionized water was added. The stirring speed was adjusted and the mixture was stirred for 2 hours. Stirring and reacting for 2.0 hours at 60 ℃, then gradually heating to 80 ℃, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the gel microspheres DZ-3 with the particle size of 0.35-0.60 mm.
Chloromethylation of gel microspheres: adding 40 g of gel microsphere DZ-3 and 250ml of chloromethyl ether into a 500ml three-neck flask, standing at room temperature for 3 hours, starting stirring, adding 10 g of zinc chloride as a catalyst, heating to 60 ℃ for reaction for 10 hours, cooling to room temperature after chloromethylation is finished, filtering out a chlorination mother solution, repeatedly washing with methanol, and drying at 100 ℃ for 8 hours to obtain the gel microsphere DZ-3.
30 g of gel chlorine ball DZ-3 (the chlorine content is 3.6mmol Cl/g), imidazole (108.0mmol) and 200ml of acetonitrile are added into a 500ml three-neck flask, the mixture reacts for 24 hours at the temperature of 60 ℃, the mixture is cooled to the room temperature and filtered, and then the mixture is washed by ethyl acetate, 0.1mol/L HCl, deionized water and methanol in sequence and then dried for 24 hours at the temperature of 60 ℃ in vacuum to obtain the imidazole microsphere DZ-3.
30 g of imidazole microsphere DZ-3 (the imidazole group content is 3.2mmol/g), 10.1 g of octachloromethylsilsesquioxane and 300ml of tetrahydrofuran are added into a 500ml three-neck flask, and after the reaction is finished, the mixture is filtered and washed by tetrahydrofuran and deionized water in sequence to obtain the imidazole/POSS microsphere DZ-3, wherein the temperature of the mixture is 24 hours at 100 ℃.
Adding 30 g of imidazole/POSS microsphere DZ-3 and 500ml of deionized water solution of 0.1mol/L lithium trifluoromethanesulfonate into a 1000ml three-neck flask, and stirring at room temperature to perform an ion exchange reaction for 24 hours; followed by deionized water washing until the wash pH was 7, and drying in vacuo afforded the ion exchange resin catalyst, noted Cat-DZ-3:
[ example 7 ] catalytic application
The ion exchange resin catalyst prepared [ example 1 ] was used for the ene-aldehyde condensation reaction of an olefin and formaldehyde under the following reaction conditions: adding a formaldehyde aqueous solution with the concentration of 37 percent and a catalyst Cat-A1 into a high-pressure reaction kettle, then closing the reactor, and replacing air in the reactor with inert gas. Subsequently, the mixture is mixed according to the olefine aldehyde molar ratio of 1: 1, filling propylene into a high-pressure reaction kettle, wherein the mass of the added catalyst cat-A1 is 10 percent of the total mass of the olefin/formaldehyde aqueous solution. Stirring was started and the reaction was carried out at a reaction temperature of 80 ℃ for 10 hours under a pressure of 5.0 MPa. After the reaction is finished, the reaction product is cooled to room temperature, and pressure relief sampling analysis and determination are carried out, so that the formaldehyde conversion rate is 90.5 percent, and the total selectivity of the product 1, 3-butanediol and 4-methyl-1, 3-dioxane is 92.5 percent.
[ examples 8 to 14 ] catalytic application
The reaction results obtained by carrying out the aldol condensation of propylene and formaldehyde with the resin catalyst used and the reaction temperature and time varied and the other reaction conditions were the same as in example 7 are shown in Table 1.
TABLE 1
[ example 15 ] catalytic application
The catalyst Cat-a1 used in example 7 was filtered, washed, dried, and then used to catalyze the aldol condensation reaction of propylene and formaldehyde according to the reaction procedure and reaction conditions of example 7, with the results of recycling the catalyst 2 times, as shown in table 2. And analogizing to the above, and respectively carrying out catalytic reactions with the cycle times of 3-5 times, wherein the results are shown in Table 2.
TABLE 2
Number of cycles 2 3 4 5
Conversion of formaldehyde/% 90.4 90.1 90.3 90.2
Comparative examples 4 to 6 catalytic applications
The ion exchange resin catalysts prepared [ comparative examples 1 to 3 ] were used for the ene-aldehyde condensation reaction of olefin and formaldehyde. The reaction conditions were as follows: adding a formaldehyde aqueous solution with the concentration of 37 percent and a catalyst into a high-pressure reaction kettle, then sealing the reactor, and replacing air in the reactor with inert gas. Subsequently, the mixture is mixed according to the olefine aldehyde molar ratio of 1: 1, filling propylene into a high-pressure reaction kettle, wherein the adding mass of the catalyst is 10 percent of the total mass of the olefin/formaldehyde aqueous solution. Stirring was started and the reaction was carried out at a reaction temperature of 80 ℃ for 10 hours under a pressure of 5.0 MPa. And cooling to room temperature after the reaction is finished, and carrying out pressure relief, sampling, analysis and determination.
TABLE 3
[ COMPARATIVE EXAMPLE 7 ] catalytic applications
The catalyst used in comparative examples 4 to 6 was filtered, washed, dried, and then catalyzed by the ene-aldehyde condensation reaction of propylene and formaldehyde according to the reaction procedure and reaction conditions of comparative examples 4 to 6, to obtain the result that the catalyst was recycled 2 times, as shown in table 4. And by analogy, respectively carrying out catalytic reactions with the cycle times of 3-5 times, and the results are shown in Table 4.
TABLE 4

Claims (10)

1. A process for an alkenal condensation reaction, comprising the step of contacting an olefin and formaldehyde under alkenal condensation reaction conditions with an ion exchange resin catalyst; the ion exchange resin catalyst has the following structural general formula:
wherein,is a gel type nano composite resin matrix;
M-is an anion selected from the group consisting of triflate, hydrogen sulfate, hydrogen phosphate, tetrafluoroborate or hexafluorophosphate;
POSS is a cage-type silsesquioxane unit with the general formula of (-SiO)1.5)m(ii) a m is 6, 8, 10 or 12;
is an imidazolium cationic unit;
r is a connecting group between the POSS unit and the imidazole cation unit, and R is alkylene or arylene;
the gel type nano composite resin matrix is a nano gel type copolymer obtained by in-situ copolymerization of styrene monomers, comonomers and nano materials; the nano material is at least one of multi-wall carbon nano tube, single-wall carbon nano tube, C60 or C70 fullerene.
2. The method for the aldol condensation reaction of claim 1, wherein the POSS unit is contained in the ion exchange resin catalyst in an amount of 5 to 15 wt%.
3. The process for the aldol condensation reaction of claim 1, wherein M is-Is trifluoromethanesulfonate ion.
4. The process for the alkenal condensation reaction according to claim 1, characterized in that alkylene is selected from methylene, ethylene or propylene; the arylene group is selected from phenylene, naphthylene or phenylmethyl.
5. The process for an enal condensation reaction according to claim 1, characterized in that the styrenic monomer is selected from at least one of styrene, α -methylstyrene or 4-butylstyrene;
the comonomer is selected from at least one of ethylene glycol dimethacrylate, diacrylene, divinylphenylmethane or divinylbenzene.
6. The process for the alkenal condensation reaction according to claim 5, characterized in that the styrenic monomer is selected from styrene; the comonomer is selected from divinylbenzene.
7. The method for the alkenal condensation reaction according to claim 1, characterized in that the nanomaterial is selected from multi-walled carbon nanotubes.
8. The method for the condensation reaction of olefine and aldehyde according to claim 1, wherein the amount of styrene monomer is 85-95 parts, the amount of comonomer is 2-5 parts, and the amount of nanomaterial is 0.1-3 parts.
9. The process for the aldol condensation reaction of claim 1, wherein the olefin is selected from the group consisting of ethylene, trimethylethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, isoprene, 1-hexene, 1-octene, styrene, α -methylstyrene and cyclohexene.
10. The process for an enal condensation reaction according to claim 1, characterized in that the enal condensation reaction conditions include: the mol ratio of the olefin to the formaldehyde is (0.1-10): 1, the dosage of the catalyst is 1-15 wt% of the total amount of the raw materials, the reaction temperature is 50-150 ℃, the reaction time is 1-24 hours, and the reaction pressure is 2.0-6.0 MPa.
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Application publication date: 20190521