CN103121988B - Method for preparing alkylene carbonate - Google Patents
Method for preparing alkylene carbonate Download PDFInfo
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- CN103121988B CN103121988B CN201110369156.3A CN201110369156A CN103121988B CN 103121988 B CN103121988 B CN 103121988B CN 201110369156 A CN201110369156 A CN 201110369156A CN 103121988 B CN103121988 B CN 103121988B
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- alkylene carbonate
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- -1 alkylene carbonate Chemical compound 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 5
- 239000000460 chlorine Chemical group 0.000 claims abstract description 5
- 150000002148 esters Chemical class 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920001281 polyalkylene Polymers 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims abstract description 3
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 239000011737 fluorine Substances 0.000 claims abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 13
- 235000011089 carbon dioxide Nutrition 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 6
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 abstract description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 abstract 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 abstract 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-M oxalate(1-) Chemical compound OC(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-M 0.000 abstract 1
- 239000004814 polyurethane Substances 0.000 abstract 1
- 229920002635 polyurethane Polymers 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000002608 ionic liquid Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- IPNPIHIZVLFAFP-UHFFFAOYSA-N phosphorus tribromide Chemical class BrP(Br)Br IPNPIHIZVLFAFP-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- QMLPFJXOHVKKMA-UHFFFAOYSA-N [Br].OCCN1CN(C=C1)C Chemical compound [Br].OCCN1CN(C=C1)C QMLPFJXOHVKKMA-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 229920003228 poly(4-vinyl pyridine) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
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
Technical field
The present invention relates to a kind of method of 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 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 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 separated with product, and makes product and homogeneous catalyst separation can make alkylene carbonate seriously decompose by distillation.
Ionic liquid as a kind of special quaternary ammonium salt also through being often used as the synthetic catalyzer of cyclic carbonate.The people such as Zhang Suojiang use ionic liquid 1-methyl-3-imidazole-butyl bromide as catalyzer, and under 100 ℃ and 2.0MPa, to obtain the yield of EC be 92.2% (CN1995032,2007) in reaction.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, active lower compared with metal complex catalysts, and ionic liquid is expensive, and 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 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) on load and ion exchange resin, but due to the swelling property problem of ion exchange resin self and the loss of catalytic activity, to the catalytic efficiency of oxyethane and carbonic acid gas, be only 32.9～45.4%, and along with applying mechanically the increase of number of times, the catalytic efficiency of catalyzer declines very fast.
As can be seen here, 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 in prior art, to have low, the easy inactivation of catalyst activity, and the problem of product separation difficulty provides a kind of new method of preparing alkylene carbonate.It is high that the method has catalytic activity, is difficult for inactivation, the segregative feature 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 of preparing alkylene carbonate, take epoxy compounds and carbonic acid gas as reaction raw materials, in temperature of reaction, it is 60～180 ℃, 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 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, resin matrix preferred version is selected from the multipolymer of vinylbenzene and Vinylstyrene.N preferred version is 9～136.Z preferred version is selected from phosphorus.X preferred version is selected from bromine.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 passed through resin matrix, and preferred version is after the copolymer resin matrix of vinylbenzene and Vinylstyrene is reacted with both-end base PEG, to introduce PEG segment, then by PEG terminal groups modification, prepares the resin type catalyst of oxirane and carbonic acid gas.Resin type catalyst in the inventive method is prepared reacting of ethylene carbonate for carbonic acid gas with oxyethane, product is easily separated, at 120 ℃, under the condition of 6MPa, react 5 hours, oxyethane transformation efficiency can reach 96.5%, and NSC 11801 selectivity can reach 99.0%, and catalyzer is used 5 times continuously, activity has no obvious decline, 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
The preparation of resin catalyst
[embodiment 1]
In glove box, the PEG that is 400 by 20 grams of molecular-weight average, 200 milliliters of anhydrous tetrahydro furans, 1.9 grams of potassium metals join in 500 milliliters of there-necked flasks, and 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 is 2%, charge capacity is 0.9mmol Cl/g), at 50～80 ℃, back flow reaction is 6～15 hours.Reaction finishes rear cooling, 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 obtains PS-(CH
2cH
2o)
9-H microballoon A.Wherein, Merrified resin is the body material of ion-exchange resin catalyst, is the multipolymer of vinylbenzene and Vinylstyrene, with PS, represents.
In 500 milliliters of there-necked flasks, add successively 10 grams of PS-(CH
2cH
2o)
9-H microballoon, 200 milliliters of methylene dichloride make microballoon swelling, are then cooled to 0 ℃, slowly drip 10 milliliters of phosphorus tribromides, react 4～8 hours; Then continue at room temperature to react 10～15 hours, after reaction finishes, pour out supernatant liquid, use successively tetrahydrofuran (THF), deionized water, methanol wash, vacuum-drying to constant weight obtains PS-(CH
2cH
2o)
9-Br microballoon A.
Under protection of inert gas, by 10 grams of PS-(CH
2cH
2o)
9-Br microballoon, 200 milliliters of benzene (reflux and dewater with Na), 2.5 grams of tributylphosphines join in 500 milliliters of there-necked flasks, with 65 ℃ at stirring reaction 50～100 hours, after finishing, reaction pours out supernatant liquid, use successively tetrahydrofuran (THF), deionized water, methanol wash, vacuum-drying to constant weight obtains 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 polyalkylene ester, consumption is 5 grams, and charge capacity is 2.82mmolCl/g, and all the other preparation conditions are identical with [embodiment 1], finally obtain M-(CH
2cH
2o)
9-P
+bu
3br
-microballoon B.
[embodiment 3]
In glove box, the PEG that is 2000 by 40 grams of molecular-weight average, 500 milliliters of anhydrous tetrahydro furans, 0.76 gram of potassium metal join in 1000 milliliters of there-necked flasks, and at 45 ℃, stirring and refluxing is 1～6 hour; Then add 10 grams through the Merrified of tetrahydrofuran (THF) swelling resin (100～200 orders, degree of crosslinking is 2%, charge capacity is 0.9mmol Cl/g), at 50～90 ℃, back flow reaction is 10～20 hours.Reaction finishes rear cooling, 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 obtains PS-(CH
2cH
2o)
45-H microballoon C.
In 500 milliliters of there-necked flasks, add successively 10 grams of PS-(CH
2cH
2o)
45-H microballoon, 200 milliliters of methylene dichloride make microballoon swelling, are then cooled to 0 ℃, slowly drip 10 milliliters of phosphorus tribromides, react 4～8 hours; Then continue at room temperature to react 10～15 hours, after reaction finishes, pour out supernatant liquid, use successively tetrahydrofuran (THF), deionized water, methanol wash, vacuum-drying to constant weight obtains PS-(CH
2cH
2o)
45-Br microballoon C.
Under protection of inert gas, by 10 grams of PS-(CH
2cH
2o)
45-Br microballoon, 200 milliliters of benzene (reflux and dewater with Na), 3.0 grams of triphenylphosphines join in 500 milliliters of there-necked flasks, with 65 ℃ at stirring reaction 50～100 hours, after finishing, reaction pours out supernatant liquid, use successively tetrahydrofuran (THF), deionized water, methanol wash, vacuum-drying to constant weight obtains 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], finally obtain PS-(CH
2cH
2o)
136-P
+ph
3br
-microballoon D.
The catalysis example of resin catalyst
[embodiment 5]
Reaction by the resin catalyst of above-mentioned preparation for oxyethane and carbonic acid gas, condition is as follows: under protection of inert gas, by 10 milliliters of tetrahydrofuran (THF)s, 50.0 grams of oxyethane, 5.0 grams of 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, maintain 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 obtaining is in Table 1.
Table 1
[embodiment 18]
The catalyzer using in [embodiment 5] is filtered, washing, dry, 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, in 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 (7)
1. a method of preparing alkylene carbonate, take epoxy compounds and carbonic acid gas as reaction raw materials, in temperature of reaction, it is 60～180 ℃, 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 for having following general structure:
M-PEG-Z
+R
3X
-
Wherein, M is resin matrix, is selected from multipolymer, 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 or aryl; X is fluorine, chlorine, bromine, iodine, acetate moiety, formate or oxalic acid hydrogen root.
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110369156.3A CN103121988B (en) | 2011-11-18 | 2011-11-18 | Method for preparing alkylene carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110369156.3A CN103121988B (en) | 2011-11-18 | 2011-11-18 | Method for preparing alkylene carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103121988A CN103121988A (en) | 2013-05-29 |
| CN103121988B true CN103121988B (en) | 2014-11-26 |
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| 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 |
| 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 |
Citations (2)
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| CN1796384A (en) * | 2004-12-24 | 2006-07-05 | 中国科学院兰州化学物理研究所 | Method for synthesizing cyclic carbonate from carbon dioxide and epoxy compound through reaction of cycloaddition |
| CN101511810A (en) * | 2006-08-03 | 2009-08-19 | 国际壳牌研究有限公司 | Process for the preparation of alkylene carbonate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1796384A (en) * | 2004-12-24 | 2006-07-05 | 中国科学院兰州化学物理研究所 | Method for synthesizing cyclic carbonate from carbon dioxide and epoxy compound through reaction of cycloaddition |
| CN101511810A (en) * | 2006-08-03 | 2009-08-19 | 国际壳牌研究有限公司 | Process for the preparation of alkylene carbonate |
Non-Patent Citations (6)
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| A poly(ethylene glycol)-supported quaternary ammonium salt for highly efficient and environmentally friendly chemical fixation of CO2 with epoxides under supercritical conditions;Ya Du et.al.;《Tetrahedron Letters》;20060109;第47卷;1271-1275 * |
| Efficient synthesis of dimethyl carbonate from methanol, propylene oxide and CO2 catalyzed by recyclable inorganic base/phosphonium halidefunctionalized polyethylene glycol;Jie-Sheng Tian et.al.;《Green Chemistry》;20061130;第9卷;566-571 * |
| Jie-ShengTianet.al..Efficientsynthesisofdimethylcarbonatefrommethanol propylene oxide and CO2 catalyzed by recyclable inorganic base/phosphonium halidefunctionalized polyethylene glycol.《Green Chemistry》.2006 * |
| 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..A poly(ethylene glycol)-supported quaternary ammonium salt for highly efficient and environmentally friendly chemical fixation of CO2 with epoxides under supercritical conditions.《Tetrahedron Letters》.2006,第47卷1271-1275. * |
| 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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