CN106866612A - A kind of method that cyclic carbonate is directly prepared by alkene - Google Patents
A kind of method that cyclic carbonate is directly prepared by alkene Download PDFInfo
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- CN106866612A CN106866612A CN201510920949.8A CN201510920949A CN106866612A CN 106866612 A CN106866612 A CN 106866612A CN 201510920949 A CN201510920949 A CN 201510920949A CN 106866612 A CN106866612 A CN 106866612A
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- alkene
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- oxidant
- alkali
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
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Abstract
The invention provides a kind of method that cyclic carbonate is directly prepared by alkene, its technical scheme is：The mixed solvent that alkene, oxidant, bromating agent, alkali, water and organic solvent are constituted is added in reactor, is passed through carbon dioxide (CO2), 60~140 DEG C of reaction temperature, 2~10h of reaction time obtains product circular carbonic ester.The present invention prepares cyclic carbonate, process is simple, mild condition, environmental protection, with certain prospects for commercial application by one kettle way.
Description
Technical field
The present invention relates to cyclic carbonate, the method that specifically a kind of alkene directly prepares cyclic carbonate.
Background technology
Cyclic carbonate is the organic solvent and important fine-chemical intermediate of a class excellent performance, its application
Widely, can be used as the electrolyte of high-energy-density battery and electric capacity, be additionally operable to polycarbonate synthesis, heat hard
The property changed resin, synthesis thermal recording material etc..The preparation of the cyclic carbonate of open report at present is used mostly
It is the method for epoxides and CO2 cycloaddition reactions, its preparation cost is higher, toxicity is larger.Little
The method that document report directly prepares cyclic carbonate from cheap and toxicity less alkene, though
So there is a problem of more, but once succeed in developing, before there is very big economic worth and wide market
Scape.
Document：Sun J M,Fujita S,Bhanage B M,Arai M.Direct oxidative
carboxylation of styrene to styrene carbonate in the presence of ionic
liquids[J].Catalysis Communications,2004,5:83 report and are with TBHP
Oxidant, TBAB is catalyst, is passed through CO2, and one-step method is directly synthesized styrene by styrene
Cyclic carbonate.
Document：Sun J M,Fujita S,Zhao F Y,Hasegawa M,Arai M.A direct
synthesis of styrene carbonate from styrene with the
Au/SiO2–ZnBr2/Bu4NBr catalyst system[J].Journal of
Catalysis,2005,230:398 report by styrene, organic hydroperoxide, CO2 be raw material,
Au/SiO2, zinc bromide, TBAB are catalyst system and catalyzing, and one-step method is directly synthesized styrene ring-type carbon
Acid esters.
Document：Eghbali N,Li C J.Conversion of carbon dioxide and olefins into
cyclic carbonates in water[J].Green Chemistry,2007,9:213 report with H2O2
It is oxidant, TBAB is epoxidation catalyst, and the carbon -7- alkene of 1,8- diazabicylo [5.4.0] 11 is to urge altogether
Agent, is passed through CO2, the method that various alkene can be directly synthesized corresponding cyclic carbonate.
The content of the invention
A kind of method that cyclic carbonate is directly prepared by alkene, by alkene, oxidant, bromating agent, alkali,
The mixed solvent of water and organic solvent composition is added in reactor, is passed through carbon dioxide (CO2), reaction temperature
60~140 DEG C of degree, 2~10h of reaction time obtains product circular carbonic ester.
Described alkene is
Wherein R1, R2 are respectively hydrogen, straight chained alkyl (CnH2n+1, n=1-10), cyclic alkyl (CnH2n-1,
N=5-8), aryl.
Oxidant can be aqueous hydrogen peroxide solution or the hydrogen peroxide, the tert-butyl alcohol peroxide that are dissolved in organic solvent
Change hydrogen (TBHP) or isopropyl benzene hydroperoxide (CHP).Bromating agent is that bromating agent is N- bromosuccinic acids
Acid imide (NBS), tetraethylammonium bromide, TBAB (TBAB), cetyl trimethyl bromine
Change ammonium, KBr, at least one of sodium bromide.Alkali is the hydroxide of alkali metal hydroxide, alkaline-earth metal
Thing, the carbonate of alkali metal, the carbonate of alkaline-earth metal, the bicarbonate of alkali metal, the carbon of alkaline-earth metal
Sour hydrogen salt, pyridine, bipyridyl, triethylamine, carbon -7- alkene (DBU) of 1,8- diazabicylos 11 are at least
It is a kind of.Alkali can before the reaction be added and can also added after the reaction.Organic solvent be chloroform, dichloroethanes,
Carbon tetrachloride, benzene,toluene,xylene, heavy aromatics, acetonitrile, butyl acetate, dioxane, dimethyl
At least one in formamide, tributyl phosphate, tetrabutyl urea, methyl alcohol, ethanol, acetone or ethyl acetate.
The mass ratio of mixed solvent reclaimed water and organic solvent is 1：0.1~1：10, water or water and organic solvent group
Into the quality of mixed solvent be 1~50 times of alkene quality.The mol ratio of alkene and oxidant is 1：0.3~1：
2.The mol ratio of oxidant and bromating agent is 1：0.01~1：0.5.The mol ratio of alkene and alkali is 1：0.5~1：
5。
Specific embodiment
Below by embodiment further instruction is given to the present invention：
Embodiment 1：
1.0g aqueous hydrogen peroxide solutions (mass concentration 50%) are sequentially added in stainless steel cauldron,
6.0g dioxane, 0.2g styrene, 0.05g NBS, 0.6g DBU, closed reactor is filled with 10g
CO2 (3.0Mpa), reactor is put into 70 DEG C of waters bath with thermostatic control and heats 4h.Reaction terminates to react
Kettle is cooled to less than 15 DEG C, is slowly deflated to normal pressure.Liquid phase is by gas chromatographic analysis, styrene ring-type
Carbonic ester is 60% to the yield of oxidant (hydrogen peroxide and NBS).
Embodiment 2：
1.5g tert-butyl alcohol hydrogenperoxide steam generator (mass concentrations are sequentially added in stainless steel cauldron
70%), 6.0g acetonitriles, 0.3g styrene, 0.05g TBAB, 0.2g NaHCO3 closed reactors,
10g CO2 (3.0Mpa) are filled with, reactor are put into 120 DEG C of oil baths and are heated 4h.Reaction terminate by
Reactor is cooled to less than 15 DEG C, is slowly deflated to normal pressure.Liquid phase is by gas chromatographic analysis, styrene
Cyclic carbonate is 73% to the yield of oxidant (tert-butyl alcohol hydrogen peroxide).
Embodiment 3：
2.0g aqueous hydrogen peroxide solutions (mass concentration 50%) are sequentially added in stainless steel cauldron,
8.0g methyl alcohol, 0.3g styrene, 0.05g TBAB, 0.2g KHCO3, closed reactor is filled with 10g
CO2 (3.0Mpa), reactor is put into 100 DEG C of oil baths and heats 6h.Reaction terminates that reactor is cold
But to less than 15 DEG C, slowly it is deflated to normal pressure.Liquid phase is by gas chromatographic analysis, styrene cyclic carbonate
Ester is 65% to the yield of oxidant (hydrogen peroxide).
Embodiment 4：
0.5 tert-butyl alcohol hydrogenperoxide steam generator (mass concentration 70%) is sequentially added in stainless steel cauldron,
6.0g dioxane, 0.3g cyclohexene, 0.05g NBS, 0.8g DBU, closed reactor is filled with 5g
CO2 (2.0Mpa), reactor is put into 70 DEG C of waters bath with thermostatic control and heats 4h.Reaction terminates to react
Kettle is cooled to less than 15 DEG C, is slowly deflated to normal pressure.Liquid phase is by gas chromatographic analysis, cyclohexene ring-type
Carbonic ester is 56% to the yield of oxidant (tert-butyl alcohol hydrogen peroxide and NBS).
Embodiment 5：
2.0g aqueous hydrogen peroxide solutions (mass concentration 50%) are sequentially added in stainless steel cauldron,
6.0g dichloroethanes, 0.05g KBr, 0.8g DBU, closed reactor is filled with 0.3g ethene, then fill
Enter 15g CO2 (3.5Mpa), reactor is put into 140 DEG C of oil baths and heats 4h.Reaction terminates will be anti-
Answer kettle to be cooled to less than 15 DEG C, be slowly deflated to normal pressure.Liquid phase is by gas chromatographic analysis, ethylene carbonate
Ester is 45% to the yield of oxidant (hydrogen peroxide).
Claims (10)
1. a kind of method that cyclic carbonate is directly prepared by alkene, by alkene, oxidant, bromating agent,
The mixed solvent of alkali, water or water and organic solvent composition is added in reactor, is passed through carbon dioxide
(CO2), 60~140 DEG C of reaction temperature, 2~10h of reaction time obtains product circular carbonic ester.
2. method according to claim 1, it is characterised in that：Described alkene is
Wherein R1, R2 are respectively hydrogen, straight chained alkyl (CnH2n+1, n=1-10), cyclic alkyl
(CnH2n-1, n=5-8), aryl.
3. method according to claim 1, it is characterised in that：Oxidant can be that hydrogen peroxide is water-soluble
Liquid or the hydrogen peroxide being dissolved in organic solvent, tert-butyl alcohol hydrogen peroxide (TBHP) or isopropylbenzene peroxide
Change one or two or more kinds in hydrogen (CHP).
4. method according to claim 1, it is characterised in that：Bromating agent is sub- N- bromosuccinic acids acyl
Amine (NBS), tetraethylammonium bromide, TBAB (TBAB), cetyl trimethyl bromination
Ammonium, KBr, at least one of sodium bromide.
5. method according to claim 1, it is characterised in that：Alkali is alkali metal hydroxide, alkaline earth
The hydroxide of metal, the carbonate of alkali metal, the carbonate of alkaline-earth metal, the bicarbonate of alkali metal,
The bicarbonate of alkaline-earth metal, pyridine, bipyridyl, triethylamine, the carbon -7- alkene of 1,8- diazabicylos 11
(DBU) at least one.
6. method according to claim 1, it is characterised in that：Organic solvent be chloroform, dichloroethanes,
Carbon tetrachloride, benzene,toluene,xylene, heavy aromatics, acetonitrile, butyl acetate, dioxane, diformazan
In base formamide, tributyl phosphate, tetrabutyl urea, methyl alcohol, ethanol, acetone or ethyl acetate at least
It is a kind of.
7. according to the method for claim 1 or 6, it is characterised in that：Mixed solvent reclaimed water and organic molten
The mass ratio of agent is 1: 0.1~1: 10.
8. method according to claim 1, it is characterised in that：It is mixed that water or water and organic solvent are constituted
The quality of bonding solvent is 1~50 times of alkene quality.
9. according to the method for claim 1,2,3,4 or 5, it is characterised in that：Alkene and oxidant
Mol ratio be 1: 0.3~1: 2；The mol ratio of oxidant and bromating agent is 1: 0.01~1: 0.5；Alkene
The mol ratio of hydrocarbon and alkali is 1: 0.5~1: 5.
10. method according to claim 1, it is characterised in that：The mol ratio of alkene and CO2 is 1:
2~1: 20.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114585632A (en) * | 2019-09-30 | 2022-06-03 | Ptt全球化学股份有限公司 | Catalyst composition for the manufacture of cyclic carbonates from CO2 and olefins |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724315A (en) * | 2012-10-12 | 2014-04-16 | 中国科学院大连化学物理研究所 | Method used for synthesizing cyclic carbonate in enhanced microreactor system |
| CN103752344A (en) * | 2013-12-29 | 2014-04-30 | 哈尔滨工业大学 | Simple and high-activity catalyst for cyclic carbonate synthesized from CO2 and epoxide and method for synthesizing cyclic carbonate |
| CN103788055A (en) * | 2012-10-31 | 2014-05-14 | 中国科学院大连化学物理研究所 | Method for direct preparation of cyclic carbonate from alkene |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724315A (en) * | 2012-10-12 | 2014-04-16 | 中国科学院大连化学物理研究所 | Method used for synthesizing cyclic carbonate in enhanced microreactor system |
| CN103788055A (en) * | 2012-10-31 | 2014-05-14 | 中国科学院大连化学物理研究所 | Method for direct preparation of cyclic carbonate from alkene |
| CN103752344A (en) * | 2013-12-29 | 2014-04-30 | 哈尔滨工业大学 | Simple and high-activity catalyst for cyclic carbonate synthesized from CO2 and epoxide and method for synthesizing cyclic carbonate |
Non-Patent Citations (2)
| Title |
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| 孙建敏，等人: "溴化四丁铵催化苯乙烯一步合成苯乙烯环状碳酸酯", 《高等学校化学学报》 * |
| 王芳霄: "含钴介孔分子筛Co-MCM-41耦合溴化四丁基铵协同催化苯乙烯直接氧化碳酰化制备苯乙烯环状碳酸酯", 《应用化学》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114585632A (en) * | 2019-09-30 | 2022-06-03 | Ptt全球化学股份有限公司 | Catalyst composition for the manufacture of cyclic carbonates from CO2 and olefins |
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Application publication date: 20170620 |