CN103121988A

CN103121988A - Method for preparing alkylene carbonate

Info

Publication number: CN103121988A
Application number: CN2011103691563A
Authority: CN
Inventors: 俞峰萍; 何文军
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2011-11-18
Filing date: 2011-11-18
Publication date: 2013-05-29
Anticipated expiration: 2031-11-18
Also published as: CN103121988B

Abstract

The invention relates to a method for preparing alkylene carbonate, and is mainly used for solving the problems that in the prior art, the catalyst is low in activity and easy to inactivate, and the product is hard to separate. The catalyst provided by the invention has the structural formula of M-PEG-Z<+>R3X<->, wherein M is a resin matrix selected from polyalkylene ester, copolymer of phenylethylene and divinyl benzene, polyester, polycarbonic ester, polyurethane or formaldehyde resin; PEG represents a chemical structure with the formula -(CH2CH2O)n-, and n is an integer from 1 to 150; Z is nitrogen, phosphorus or arsenic; R is methyl, ethyl, propyl, n-butyl, phenyl or aryl; and X is fluorine, chlorine, bromine, iodine, acetate, formate or hydrogen oxalate. The problems are better solved with the adoption of the technical scheme, and the method can be applied to industrial production of alkylene carbonate.

Description

The method for preparing alkylene carbonate

Technical field

The present invention relates to a kind of method for preparing alkylene carbonate.

Background technology

Alkylene carbonate for example ethylene carbonate and Texacar PC is a kind of Organic Chemicals with extensive use, is widely used as solvent and thinner in industry.Ethylene carbonate can be used as the solvent of weaving, printing, Polymer Synthesizing and electrochemistry aspect, also can be used as the raw material of makeup and medicine and the intermediate of corresponding dibasic alcohol.

Industrial alkylene carbonate is generally to react with corresponding oxirane by carbonic acid gas to make under the effect of catalyzer.Many catalyzer of having found have catalytic effect to this reaction, as transition metal complex, main group element title complex, quaternary ammonium salt, season squama salt and the catalyst system such as an alkali metal salt, ionic liquid, supercritical co.

The people such as Kim have studied zinc halide and 1-alkyl-3-methyl-imidazolium halides and have contained the homogeneous catalysis system such as phosphine part for impact (Angew.Chem.Int.Ed.39 (2000) 4096-4098 of reaction, Chem.Eur.J.9 (2003) 678-686, J.Catal.232 (2005) 80-84).After reaction, homogeneous catalyst need to carry out and the separating of product, and makes product and homogeneous catalyst separation that alkylene carbonate is seriously decomposed by distillation.

The catalyzer that ionic liquid also synthesizes through being often used as cyclic carbonate as a kind of special quaternary ammonium salt.The people such as Zhang Suojiang use ionic liquid 1-methyl-3-imidazole-butyl bromide as catalyzer, and to obtain the yield of EC be 92.2% (CN1995032,2007) in reaction under 100 ℃ and 2.0MPa.Use bidentate ionic liquid 1,2-methylimidazole monobromethane and hydroxy ion liquid 1-(2-hydroxyl-ethyl)-3-Methylimidazole bromine is during as catalyzer synthesizing annular carbonate EC, the yield that obtains EC is respectively 93% and 99.5% (CN101108843,2008; CN101130537,2008).Ionic liquid is during as catalyzer, and is active lower than metal complex catalysts, and ionic liquid is expensive, and the impurity removal difficulty is unsuitable for industrial applications.

With respect to homogeneous catalyst, heterogeneous catalyst is conducive to product and catalyzer later separation aspect, and easily regeneration and can repeatedly reusing of catalyzer.The people such as Xiao have studied P4VP or chitosan loaded zinc halide catalyst system (Appl.Catal.A 279 (2005) 125-129), but catalytic activity descends obviously after applying mechanically.

The people such as Van Kruchten have studied the zinc halide catalyzer (CN 101511810A) on load and ion exchange resin, but due to the swelling property problem of ion exchange resin self and the loss of catalytic activity, catalytic efficiency to oxyethane and carbonic acid gas is only 32.9～45.4%, and along with the increase of applying mechanically number of times, the catalytic efficiency of catalyzer descends very fast.

This shows, research and develop a kind of catalytic efficiency high, and segregative heterogeneous catalysis system seems very important.

Summary of the invention

Technical problem to be solved by this invention is to have in prior art that catalyst activity is low, easy inactivation, and the product separation hard problem provides a kind of new method for preparing alkylene carbonate.It is high that the method has catalytic activity, is difficult for inactivation, the segregative characteristics of reaction product.

For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method for preparing alkylene carbonate, take epoxy compounds and carbonic acid gas as reaction raw materials, it is 60～180 ℃ in temperature of reaction, pressure carbon dioxide is 0.1～10.0MPa, the weight ratio of catalyzer and epoxy compounds is (0.001～1): under 1 condition, raw material and catalyzer contact reacts obtained alkylene carbonate in 1～8 hour, and wherein catalyzer used is for having following general structure:

M-PEG-Z ⁺R ₃X ^-

Wherein, M is resin matrix, is selected from multipolymer, polyester, polycarbonate, urethane or the formaldehyde resin of polyalkylene ester, vinylbenzene and Vinylstyrene; PEG represents to have general formula-(CH ₂CH ₂O) _n-chemical structure, wherein n is 1～150 integer; Z is nitrogen, phosphorus or arsenic; R is methyl, ethyl, propyl group, normal-butyl, phenyl or aryl; X is fluorine, chlorine, bromine, iodine, acetate moiety, formate or oxalic acid hydrogen root.

In technique scheme, the resin matrix preferred version is selected from the multipolymer of vinylbenzene and Vinylstyrene.The n preferred version is 9～136.The Z preferred version is selected from phosphorus.The X preferred version is selected from bromine.The R preferred version is selected from normal-butyl.The preferred version of epoxy compounds is for being selected from oxyethane or propylene oxide.

The inventive method is by with resin matrix, and preferred version be will the copolymer resin matrix of vinylbenzene and Vinylstyrene and both-end base PEG reaction introducing PEG segment afterwards, then prepares the resin type catalyst of oxirane and carbonic acid gas by the PEG terminal groups modification.Resin type catalyst in the inventive method is used for the reaction that carbonic acid gas and oxyethane prepare ethylene carbonate, product is easily separated, at 120 ℃, under the condition of 6MPa, reaction is 5 hours, the oxyethane transformation efficiency can reach 96.5%, and the NSC 11801 selectivity can reach 99.0%, and catalyzer uses 5 times continuously, activity has no obvious decline, has obtained technique effect preferably.

The invention will be further elaborated below by embodiment.Be necessary to be pointed out that at this following examples only are used for further illustrating of the present invention, can not be interpreted as limiting the scope of the invention.

Embodiment

The preparation of resin catalyst

[embodiment 1]

In glove box, be that 400 PEG, 200 milliliters of anhydrous tetrahydro furans, 1.9 gram potassium metals join in 500 milliliters of there-necked flasks with 20 gram molecular-weight average, under room temperature, stirring and refluxing is 1～4 hour; Then add 25 grams through the Merrified of tetrahydrofuran (THF) swelling resin (100～200 orders, degree of crosslinking are 2%, and charge capacity is 0.9mmol Cl/g), 50～80 ℃ of lower back flow reaction 6～15 hours.Reaction is cooling after finishing, and adds methyl alcohol and unreacted potassium.Pour out subsequently supernatant liquid, use successively tetrahydrofuran (THF)-hydrochloric acid soln, deionized water, methanol wash, vacuum-drying to constant weight gets PS-(CH ₂CH ₂O) ₉-H microballoon A.Wherein, the Merrified resin is the body material of ion-exchange resin catalyst, is the multipolymer of vinylbenzene and Vinylstyrene, represents with PS.

Add successively 10 gram PS-(CH in 500 milliliters of there-necked flasks ₂CH ₂O) ₉-H microballoon, 200 milliliters of methylene dichloride make microspheres swell up, then are cooled to 0 ℃, slowly drip 10 milliliters of phosphorus tribromides, react 4～8 hours; Then continue at room temperature to react 10～15 hours, reaction pours out supernatant liquid after finishing, and uses successively tetrahydrofuran (THF), deionized water, methanol wash, and vacuum-drying to constant weight gets PS-(CH ₂CH ₂O) ₉-Br microballoon A.

Under protection of inert gas, with 10 gram PS-(CH ₂CH ₂O) ₉-Br microballoon, 200 milliliters of benzene (reflux with Na and dewater), 2.5 gram tributylphosphines join in 500 milliliters of there-necked flasks, with 65 ℃ of lower stirring reactions 50～100 hours, reaction pours out supernatant liquid after finishing, use successively tetrahydrofuran (THF), deionized water, methanol wash, vacuum-drying to constant weight gets PS-(CH ₂CH ₂O) ₉-P ⁺Bu ₃Br ^-Microballoon A, wherein Bu is normal-butyl.

[embodiment 2]

Change the resin matrix in [embodiment 1], adopt the polyalkylene ester, consumption is 5 grams, and charge capacity is 2.82mmolCl/g, and all the other preparation conditions are identical with [embodiment 1], obtain at last M-(CH ₂CH ₂O) ₉-P ⁺Bu ₃Br ^-Microballoon B.

[embodiment 3]

In glove box, be that 2000 PEG, 500 milliliters of anhydrous tetrahydro furans, 0.76 gram potassium metals join in 1000 milliliters of there-necked flasks with 40 gram molecular-weight average, 45 ℃ of lower stirring and refluxing 1～6 hour; Then add 10 grams through the Merrified of tetrahydrofuran (THF) swelling resin (100～200 orders, degree of crosslinking are 2%, and charge capacity is 0.9mmol Cl/g), 50～90 ℃ of lower back flow reaction 10～20 hours.Reaction is cooling after finishing, and adds methyl alcohol and unreacted potassium.Pour out subsequently supernatant liquid, use successively tetrahydrofuran (THF)-hydrochloric acid soln, deionized water, methanol wash, vacuum-drying to constant weight gets PS-(CH ₂CH ₂O) ₄₅-H microballoon C.

Add successively 10 gram PS-(CH in 500 milliliters of there-necked flasks ₂CH ₂O) ₄₅-H microballoon, 200 milliliters of methylene dichloride make microspheres swell up, then are cooled to 0 ℃, slowly drip 10 milliliters of phosphorus tribromides, react 4～8 hours; Then continue at room temperature to react 10～15 hours, reaction pours out supernatant liquid after finishing, and uses successively tetrahydrofuran (THF), deionized water, methanol wash, and vacuum-drying to constant weight gets PS-(CH ₂CH ₂O) ₄₅-Br microballoon C.

Under protection of inert gas, with 10 gram PS-(CH ₂CH ₂O) ₄₅-Br microballoon, 200 milliliters of benzene (reflux with Na and dewater), 3.0 gram triphenylphosphines join in 500 milliliters of there-necked flasks, with 65 ℃ of lower stirring reactions 50～100 hours, reaction pours out supernatant liquid after finishing, use successively tetrahydrofuran (THF), deionized water, methanol wash, vacuum-drying to constant weight gets PS-(CH ₂CH ₂O) ₄₅-P ⁺Ph ₃Br ^-Microballoon C, wherein Ph is phenyl.

[embodiment 4]

Change the PEG (molecular-weight average is 6000, and consumption is 120 grams) in [embodiment 3], all the other preparation conditions are identical with [embodiment 3], obtain at last PS-(CH ₂CH ₂O) ₁₃₆-P ⁺Ph ₃Br ^-Microballoon D.

The catalysis example of resin catalyst

[embodiment 5]

The resin catalyst of above-mentioned preparation is used for the reaction of oxyethane and carbonic acid gas, condition is as follows: under protection of inert gas, with 10 milliliters of tetrahydrofuran (THF)s, 50.0 gram oxyethane, 5.0 gram PS-(CH ₂CH ₂O) ₉-P ⁺Bu ₃Br ^-Microballoon A adds in 300 milliliters of autoclaves, is filled with 1.0MPa CO ₂, be warming up to 120 ℃, then be filled with CO ₂, keep reaction pressure at 2.0MPa, react and remove by filter catalyzer after 5 hours, record oxyethane transformation efficiency C _EOBe 95.5%, NSC 11801 selectivity S _ECBe 99.0%.

[embodiment 6～17]

Change the resin catalyst and the consumption thereof that use, and the temperature and pressure of reaction, all identical with [embodiment 5] catalyzed reaction of carrying out oxyethane and carbonic acid gas of remaining reaction condition, the reaction result that obtains sees Table 1.

Table 1

[embodiment 18]

The catalyzer that uses in [embodiment 5] is filtered, washing, drying, then according to reactions steps and the reaction conditions of [embodiment 5], the reaction of catalytic epoxyethane and carbonic acid gas obtains catalyst recirculation and uses the result of 2 times, sees Table 2.By that analogy, carry out respectively cycle index and be the catalyzed reaction of 3～5 times, the results are shown in Table 2.

Table 2

Claims

1. method for preparing alkylene carbonate, take epoxy compounds and carbonic acid gas as reaction raw materials, it is 60～180 ℃ in temperature of reaction, pressure carbon dioxide is 0.1～10.0MPa, the weight ratio of catalyzer and epoxy compounds is (0.001～1): under 1 condition, raw material and catalyzer contact reacts obtained alkylene carbonate in 1～8 hour, and wherein catalyzer used is for having following general structure:

M-PEG-Z ⁺R ₃X ^-

2. prepare according to claim 1 the method for alkylene carbonate, it is characterized in that resin matrix is the multipolymer of vinylbenzene and Vinylstyrene.

3. prepare according to claim 1 the method for alkylene carbonate, it is characterized in that n=9～136.

4. prepare according to claim 1 the method for alkylene carbonate, it is characterized in that Z is phosphorus.

5. prepare according to claim 1 the method for alkylene carbonate, it is characterized in that X is bromine.

6. prepare according to claim 1 the method for alkylene carbonate, it is characterized in that R is normal-butyl.

7. prepare according to claim 1 the method for alkylene carbonate, it is characterized in that epoxy compounds is oxyethane or propylene oxide.