CN103121987B - Method for preparing alkylene carbonate - Google Patents
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- CN103121987B CN103121987B CN201110369150.6A CN201110369150A CN103121987B CN 103121987 B CN103121987 B CN 103121987B CN 201110369150 A CN201110369150 A CN 201110369150A CN 103121987 B CN103121987 B CN 103121987B
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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, resin is easy to swell and the activity decline is rapid. With the adoption of nano-composite quaternary phosphor salt resin as a catalyst, the preparation method comprises the following steps of: (1) preparing an aqueous solution A by an assistant I; (2) preparing a solution B by a monomer, a comonomer, a nanometer material, an initiator and an assistant II; (3) mixing the solution A and liquid B, and reacting to obtain composite microspheres; (4) adding a chloromethylation reagent and zinc chloride into the composite microspheres to obtain composite chlorine spheres; and (5) adding a quaternary phosphor reagent to the composite chlorine spheres to react so as to obtain the nano-composite quaternary phosphor salt resin. The technical scheme better solves the problems, and the method can be applied to industrial production of alkylene carbonate.
Description
Technical field
The present invention relates to a kind of method for the preparation of alkylene carbonate.
Background technology
For example ethylene carbonate of alkylene carbonate and Texacar PC are a kind of Organic Chemicals with extensive use, are 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 under the effect of catalyzer, to be reacted and make with corresponding oxirane by carbonic acid gas.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 L.N.He have studied in supercritical co with Rf
3rPI (Rf～
c4F
9c
2h
4, C
6f
13c
2h
4, C
8f
17c
2h
4; RMe, Rf) be catalyzer carbonate synthesis ethyl, catalyzer can recycle, and the productive rate of ethylene carbonate reaches more than 90%, but reaction time is long, needs 24 hours.
Lanzhou chemical physics institute is by NiCl
2pPh
3as catalyzer, when promotor is Zn powder and tetra-n-butyl ammonium bromide, propylene oxide and CO 120 DEG C time
2reaction, the selectivity of products therefrom is 99% (CN1566110,2005).When using ZnCl
2as catalyzer, ionic liquid 1-methyl-3-butyl imidazole bromo salt is as promotor, and 100 DEG C of reactions 1 hour, the selectivity of product was 99% (CN1631886,2005).
The people such as Kim have studied zinc halide with 1-alkyl-3-methyl-imidazolium halides and have contained the homogeneous catalysis systems such as phosphine part for the impact of reacting (Angew.Chem.Int.Ed.39 (2000) 4096-4098, 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 can make alkylene carbonate seriously decompose by distillation.
With respect to homogeneous catalyst, heterogeneous catalyst is conducive to product and catalyzer later separation, and catalyzer is easily regenerated and can repeatedly reuse.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 declines obviously after applying mechanically.
The people such as Van Kruchten have studied the zinc halide catalyzer (CN 101511810A) being carried on ion exchange resin, but due to the expansion of ion exchange resin and the loss of catalytic activity, decline very fast to the catalytic efficiency of oxyethane and carbonic acid gas.
As can be seen here, research and develop a kind of high reactivity, highly selective and segregative catalyst system and seem very important.
Summary of the invention
Technical problem to be solved by this invention is in prior art, to have that catalyst activity is low, resin is easily swelling, and the active fast problem that declines, provides a kind of new method for the preparation of alkylene carbonate.It is high that the method has resin catalyst activity, is difficult for swellingly, is difficult for the feature of inactivation.
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 the preparation of alkylene carbonate, taking epoxy compounds and carbonic acid gas as reaction raw materials, it is 60～180 DEG C 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 obtain alkylene carbonate for 1～8 hour, wherein catalyzer used is nano combined season squama salt resin, and its preparation method comprises the following steps:
1) auxiliary agent one being made into weight percent concentration is 0.5～2% water solution A, by monomer, comonomer, nano material, initiator and auxiliary agent two wiring solution-forming B;
Wherein, described monomer is selected from least one in methyl methacrylate, butyl acrylate, vinylbenzene, alpha-methyl styrene, 4-butylstyrene or vinyl cyanide; Described comonomer is selected from least one in ethyleneglycol dimethyacrylate, diallyl benzene, divinyl phenylmethane or Vinylstyrene; Described nano material is selected from least one in multi-walled carbon nano-tubes, Single Walled Carbon Nanotube, C60 or C70 soccerballene; Described initiator is selected from least one in benzoyl peroxide, Diisopropyl azodicarboxylate, lauroyl peroxide or isopropyl benzene hydroperoxide; Described auxiliary agent one is selected from least one in polyvinyl alcohol, gelatin, starch, methylcellulose gum, wilkinite or calcium carbonate; Described auxiliary agent two is selected from least one in aliphatic hydrocarbon, polystyrene, gasoline, lipid acid or paraffin; By weight percentage, the consumption of monomer is 85～95%, and the consumption of comonomer is 2～5%, and the consumption of nano material is 0.1～3%, and the consumption of initiator is 0.1～10%; The consumption of auxiliary agent one is 150～400% of monomer consumption, and the consumption of auxiliary agent two is 50～100% of monomer consumption;
2) by solution B 60～75 DEG C of prepolymerizations 0.5～2.5 hour, then solution B is mixed with solution A, be warming up to 70～90 DEG C reaction 5～15 hours, then be warming up to 90～100 DEG C reaction 5～15 hours; After reaction finishes, through extracting, washing, filtration, be dried, sieve, obtain the complex microsphere of 0.35～0.60 millimeter of particle size range;
3) in complex microsphere, add the chloromethylation reagent that is equivalent to complex microsphere weight 200～500%, and be equivalent to the zinc chloride catalyst of complex microsphere weight 20～70%, at 30～60 DEG C, react 8～30 hours, after filtration, washing obtain compound chlorine ball, dry to constant weight; Described chloromethylation reagent is selected from least one in chloromethyl ether or Isosorbide-5-Nitrae-dichloro methyl butyl ether;
4) be equivalent to the organic solvent of complex microsphere weight 200～700%, 200～500% PR to adding in compound chlorine ball
1r
2r
3nickelous bromide with 50～200%, reacts under reflux state 8～30 hours, obtains described nano combined season squama salt resin through washing, after drying; Wherein, described organic solvent is selected from least one in cyanophenyl, toluene, tetrahydrofuran (THF), dimethyl formamide, chloroform or ethylene dichloride; PR
1r
2r
3in, R
1, R
2, R
3for methyl, ethyl, propyl group, normal-butyl, phenyl or aryl, P is phosphorus.
In technique scheme, monomer preferred version is selected from vinylbenzene, comonomer preferred version is selected from Vinylstyrene, nano material preferred version is selected from multi-walled carbon nano-tubes, initiator preferred version is selected from benzoyl peroxide, auxiliary agent one preferred version is selected from polyvinyl alcohol, and auxiliary agent two preferred versions are selected from polystyrene.The preferred version of epoxy compounds is for being selected from oxyethane or propylene oxide.
It is catalyzer that the inventive method adopts nano combined season squama salt resin, taking oxyethane and carbonic acid gas as reaction raw materials, under 120 DEG C, the condition of pressure carbon dioxide 2MPa, react 3 hours, oxyethane transformation efficiency can reach 95.3%, NSC 11801 selectivity can reach 99.0%, and the swelling capacity of resin catalyst is only 4.7% simultaneously; Catalyzer uses 6 times continuously, and activity has no obvious decline, and resin do not occur obviously swellingly, has obtained good technique effect.
Below by embodiment, the invention will be further elaborated.Be necessary to be pointed out that at this following examples, only for further illustrating of the present invention, can not be interpreted as limiting the scope of the invention.
Embodiment
[embodiment 1]
In 500 milliliters of there-necked flasks, add 58.0 grams of vinylbenzene, 0.6 gram of Vinylstyrene, 30 grams of polystyrene and 0.6 gram of benzoyl peroxide initiator, at 60 DEG C, stir 2.0 hours; Then add 2.8 grams of multi-walled carbon nano-tubes, continue to stir and within 1 hour, carry out prepolymerization.Add the 260 ml deionized water solution that are dissolved with 2.5 grams of polyvinyl alcohol.Regulate stirring velocity, be progressively warming up to 80 DEG C, react 5 hours simultaneously; Be warmed up to again 90 DEG C, react 5 hours, be finally warming up to 98 DEG C, react 6 hours.After reaction finishes, pour out supernatant liquid, with 85 DEG C of hot washes, then use cold water washing, then filter, put into 80 DEG C of oven dry of baking oven, sieve, the complex microsphere A of collection cut size within the scope of 0.35～0.60 millimeter.
The chloromethylation of complex microsphere: in the there-necked flask of 500 milliliters, add 50 grams of complex microsphere A and 250 milliliters of chloromethyl ethers, room temperature leaves standstill 4 hours, starts to stir, and adding 15 grams of zinc chloride is catalyzer, be warming up to 50 DEG C of reactions 8 hours, after chlorination finishes, be cooled to room temperature, leach chlorination mother solution, use methyl alcohol repetitive scrubbing, at 100 DEG C, dry 8 hours, obtain compound chlorine ball A.
The season squama salinization of compound chlorine ball: in 500 milliliters of there-necked flasks, add 20 grams of compound chlorine ball A, 100 milliliters of cyanophenyls, 20.0 grams of triphenylphosphines and 15 grams of nickelous bromides, stirring reaction 12 hours under reflux state, after reaction finishes, remove by filter mother liquor, use successively respectively methylene dichloride, acetone and water washing, under vacuum, dry to obtain nano combined season squama salt resin A1.
[embodiment 2]
In 500 milliliters of there-necked flasks, add the compound chlorine ball A of 20 grams of [embodiment 1] gained, 150 milliliters of cyanophenyls, 35.0 grams of dimethylphenylphosphines and 10.0 grams of nickelous bromides, stirring reaction 30 hours under reflux state, after reaction finishes, remove by filter mother liquor, use successively respectively methylene dichloride, acetone and water washing, under vacuum, dry to obtain nano combined season squama salt resin A2.
[embodiment 3]
In 500 milliliters of there-necked flasks, add the monomer mixture solution (60.0 grams of vinylbenzene, 1.7 grams of Vinylstyrenes, the 60 grams of polystyrene that contain initiator, 1.6 grams of multi-walled carbon nano-tubes and 1.0 grams of benzoyl peroxides, this solution was prior to 70 DEG C of stirring reactions 0.5 hour), start agitator, add the mixing solutions of 200 ml deionized water and 5 grams of gelatin, be warming up to 85 DEG C, react 3 hours, then be warmed up to 90 DEG C, react 9 hours, finally be warming up to 100 DEG C, react 10 hours.After reaction finishes, pour out supernatant liquid, with 85 DEG C of hot washes, then use cold water washing, then filter, put into 80 DEG C of oven dry of baking oven, sieve, the complex microsphere B of collection cut size within the scope of 0.35～0.60 millimeter.
The chloromethylation of complex microsphere: in the there-necked flask of 500 milliliters, add 50 grams of complex microsphere B and 150 milliliters of chloromethyl ethers, room temperature leaves standstill 6 hours, starts to stir, and adding 30 grams of zinc chloride is catalyzer, be warming up to 50 DEG C of reactions 24 hours, after chlorination finishes, be cooled to room temperature, leach chlorination mother solution, use methyl alcohol repetitive scrubbing, at 100 DEG C, dry 8 hours, obtain compound chlorine ball B.
The season squama salinization of compound chlorine ball: in 500 milliliters of there-necked flasks, add 20 grams of compound chlorine ball B, 150 milliliters of cyanophenyls, 30.0 grams of dimethylphenylphosphines and 12 grams of nickelous bromides, stirring reaction 24 hours under reflux state, after reaction finishes, remove by filter mother liquor, use successively respectively methylene dichloride, acetone and water washing, under vacuum, dry to obtain nano combined season squama salt resin B1.
[embodiment 4]
In 500 milliliters of there-necked flasks, add the compound chlorine ball B of 15 grams of [embodiment 3] gained, 150 milliliters of cyanophenyls, 35.0 grams of triphenylphosphines and 20.0 grams of nickelous bromides, stirring reaction 10 hours under reflux state, after reaction finishes, remove by filter mother liquor, use successively respectively methylene dichloride, acetone and water washing, under vacuum, dry to obtain nano combined season squama salt resin B2.
[embodiment 5]
Change monomer mixture solution (the 76.0 grams of alpha-methyl styrenes in [embodiment 3], 3.5 grams of Vinylstyrenes, 75 grams of gasoline, 2.4 grams of multi-walled carbon nano-tubes and 1.4 grams of benzoyl peroxides), all the other preparation conditions are identical with [embodiment 3], obtain complex microsphere C.
The chloromethylation of complex microsphere: in the there-necked flask of 500 milliliters, add 40 grams of complex microsphere C and 150 milliliters of Isosorbide-5-Nitrae-dichloro methyl butyl ethers, room temperature leaves standstill 6 hours, start to stir, adding 25 grams of zinc chloride is catalyzer, is warming up to 50 DEG C of reactions 24 hours, after chlorination finishes, is cooled to room temperature, leach chlorination mother solution, use methyl alcohol repetitive scrubbing, at 100 DEG C, dry 8 hours, obtain compound chlorine ball C.
The season squama salinization of compound chlorine ball: in 500 milliliters of there-necked flasks, add 30 grams of compound chlorine ball A, 150 milliliters of cyanophenyls, 20.0 grams of triphenylphosphines and 15 grams of nickelous bromides, stirring reaction 12 hours under reflux state, after reaction finishes, remove by filter mother liquor, use successively respectively methylene dichloride, acetone and water washing, under vacuum, dry to obtain nano combined season squama salt resin C1.
[embodiment 6]
According to the step of [embodiment 4], compound chlorine ball C is carried out to season squama salinization reaction, obtain nano combined season squama salt resin C2.
[embodiment 7]
Reaction by the nano combined season squama salt resin A1 of above-mentioned preparation for oxyethane and carbonic acid gas, condition is as follows: in 300 milliliters of autoclaves, add 10 milliliters of toluene, 40.0 grams of oxyethane, 5.0 grams of nano combined season squama salt resin A1, are filled with 1.0MPa CO
2, be warming up to 120 DEG C, then be filled with CO
2, maintain reaction pressure at 2.0MPa, react and remove by filter catalyzer after 3 hours, record oxyethane transformation efficiency C
eObe 95.3%, NSC 11801 selectivity S
eCbe 99.0%, the swelling capacity of resin catalyst is that SWELL is 4.70%.
[embodiment 8～12]
Change the nano combined season squama salt resin using, remaining reaction condition is all identical with [embodiment 7], by obtained nano combined season squama salt resin for the reaction of oxyethane and carbonic acid gas, the reaction result obtaining is in table 1.
Table 1
[embodiment 13～16]
Reaction by the nano combined season squama salt resin A1 of above-mentioned preparation for oxyethane and carbonic acid gas, condition is as follows: in 300 milliliters of autoclaves, add 10 milliliters of toluene, 40.0 grams of oxyethane, a certain amount of nano combined season squama salt resin A1, is filled with CO
2, after temperature reaction, be filled with again CO
2, maintain reaction pressure, after reaction certain hour, remove by filter catalyzer.
Table 2
[embodiment 17]
The catalyzer using in [embodiment 7] is filtered, washing, dry, then according to reactions steps and the reaction conditions of [embodiment 7], the reaction of catalytic epoxyethane and carbonic acid gas, obtains the result that catalyst recirculation is used 2 times, in table 3.By that analogy, carry out respectively cycle index and be the catalyzed reaction of 3～6 times, the results are shown in Table 3.
Table 3
Claims (8)
1. the method for the preparation of alkylene carbonate, taking epoxy compounds and carbonic acid gas as reaction raw materials, it is 60～180 DEG C 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 obtain alkylene carbonate for 1～8 hour, and wherein catalyzer used is nano combined quaternary alkylphosphonium salt resin, and its preparation method comprises the following steps:
1) auxiliary agent one being made into weight percent concentration is 0.5～2% water solution A, by monomer, comonomer, nano material, initiator and auxiliary agent two wiring solution-forming B;
Wherein, described monomer is selected from least one in methyl methacrylate, butyl acrylate, vinylbenzene, alpha-methyl styrene, 4-butylstyrene or vinyl cyanide; Described comonomer is selected from least one in ethyleneglycol dimethyacrylate, diallyl benzene, divinyl phenylmethane or Vinylstyrene; Described nano material is selected from least one in multi-walled carbon nano-tubes, Single Walled Carbon Nanotube, C60 or C70 soccerballene; Described initiator is selected from least one in benzoyl peroxide, Diisopropyl azodicarboxylate, lauroyl peroxide or isopropyl benzene hydroperoxide; Described auxiliary agent one is selected from least one in polyvinyl alcohol, gelatin, starch, methylcellulose gum, wilkinite or calcium carbonate; Described auxiliary agent two is selected from least one in polystyrene, gasoline, lipid acid or paraffin; By weight percentage, the consumption of monomer is 85～95%, and the consumption of comonomer is 2～5%, and the consumption of nano material is 0.1～3%, and the consumption of initiator is 0.1～10%; The consumption of auxiliary agent one is 150～400% of monomer consumption, and the consumption of auxiliary agent two is 50～100% of monomer consumption;
2) by solution B 60～75 DEG C of prepolymerizations 0.5～2.5 hour, then solution B is mixed with solution A, be warming up to 70～90 DEG C reaction 5～15 hours, then be warming up to 90～100 DEG C reaction 5～15 hours; After reaction finishes, through extracting, washing, filtration, be dried, sieve, obtain the complex microsphere of 0.35～0.60 millimeter of particle size range;
3) in complex microsphere, add the chloromethylation reagent that is equivalent to complex microsphere weight 200～500%, and be equivalent to the zinc chloride catalyst of complex microsphere weight 20～70%, at 30～60 DEG C, react 8～30 hours, after filtration, washing obtain compound chlorine ball, dry to constant weight; Described chloromethylation reagent is selected from least one in chloromethyl ether or Isosorbide-5-Nitrae-dichloro methyl butyl ether;
4) be equivalent to the organic solvent of complex microsphere weight 200～700%, 200～500% PR to adding in compound chlorine ball
1r
2r
3nickelous bromide with 50～200%, reacts under reflux state 8～30 hours, after washing, oven dry, obtains described nano combined quaternary alkylphosphonium salt resin; Wherein, described organic solvent is selected from least one in cyanophenyl, toluene, tetrahydrofuran (THF), dimethyl formamide, chloroform or ethylene dichloride; PR
1r
2r
3in, R
1, R
2, R
3for methyl, ethyl, propyl group, normal-butyl or aryl, P is phosphorus.
2. according to claim 1 for the preparation of the method for alkylene carbonate, it is characterized in that monomer is selected from vinylbenzene.
3. according to claim 1 for the preparation of the method fat of alkylene carbonate, it is characterized in that comonomer is selected from Vinylstyrene.
4. according to claim 1 for the preparation of the method for alkylene carbonate, it is characterized in that nano material is selected from multi-walled carbon nano-tubes.
5. according to claim 1 for the preparation of the method for alkylene carbonate, it is characterized in that initiator is selected from benzoyl peroxide.
6. according to claim 1 for the preparation of the method for alkylene carbonate, it is characterized in that auxiliary agent one is selected from polyvinyl alcohol.
7. according to claim 1 for the preparation of the method for alkylene carbonate, it is characterized in that auxiliary agent two is selected from polystyrene.
8. according to claim 1 for the preparation of the method for alkylene carbonate, it is characterized in that epoxy compounds is oxyethane or propylene oxide.
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105272858B (en) * | 2014-07-24 | 2017-09-15 | 中国石油化工股份有限公司 | The production method of dimethyl carbonate |
| CN105367541B (en) * | 2014-08-11 | 2018-06-15 | 中国科学院过程工程研究所 | The method of poly ion liquid nano-catalytic cycloaddition reaction synthesizing annular carbonate |
| CN105440007B (en) * | 2014-09-25 | 2018-04-06 | 中国石油化工股份有限公司 | The method of synthesizing ethylene carbonate |
| CN105503608B (en) * | 2014-09-25 | 2017-10-27 | 中国石油化工股份有限公司 | The method for producing ethylene carbonate |
| CN105503811B (en) * | 2014-09-25 | 2018-06-08 | 中国石油化工股份有限公司 | The method for preparing ethylene carbonate |
| CN109590029B (en) * | 2017-09-29 | 2021-11-30 | 中国石油化工股份有限公司 | Ion exchange resins and uses thereof |
| CN107903868A (en) * | 2017-12-15 | 2018-04-13 | 阜阳市龙建包装材料有限公司 | A kind of water-proof antibiotic adhesive for polyurethane |
| CN114433229B (en) * | 2020-10-20 | 2024-01-30 | 中国石油化工股份有限公司 | Catalyst for preparing alkylene carbonate, and preparation method and application thereof |
| CN114369080B (en) * | 2022-01-19 | 2024-03-29 | 凯瑞环保科技股份有限公司 | Device and method for synthesizing ethylene carbonate or propylene carbonate |
| CN114437014B (en) * | 2022-01-19 | 2024-03-19 | 凯瑞环保科技股份有限公司 | Device and method for synthesizing ethylene carbonate or propylene carbonate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1721472A (en) * | 2004-07-12 | 2006-01-18 | 中国石油化工股份有限公司 | Nano composite resin materials and method for preparing same |
| CN1752134A (en) * | 2004-09-24 | 2006-03-29 | 中国石油化工股份有限公司 | Large hole nano-composite resin material and its preparation method |
-
2011
- 2011-11-18 CN CN201110369150.6A patent/CN103121987B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1721472A (en) * | 2004-07-12 | 2006-01-18 | 中国石油化工股份有限公司 | Nano composite resin materials and method for preparing same |
| CN1752134A (en) * | 2004-09-24 | 2006-03-29 | 中国石油化工股份有限公司 | Large hole nano-composite resin material and its preparation method |
Non-Patent Citations (2)
| Title |
|---|
| Organic solvent-free process for the synthesis of propylene carbonate from supercritical carbon dioxide and propylene oxide catalyzed by insoluble ion exchange resins;Ya Du et.al.;《Green Chemistry》;20050513;第7卷;518-523 * |
| Ya Du et.al..Organic solvent-free process for the synthesis of propylene carbonate from supercritical carbon dioxide and propylene oxide catalyzed by insoluble ion exchange resins.《Green Chemistry》.2005,第7卷518-523. |
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