CN101474576B - Catalytic system for synthesizing annular carbonic acid ester - Google Patents
Catalytic system for synthesizing annular carbonic acid ester Download PDFInfo
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Abstract
The invention discloses a catalytic system used for synthesizing cyclic carbonate ester. The catalytic system comprises a catalyst with structural unit shown in formula I and quaternary ammonium salt shown in a general structure of formula II, wherein n is equal to 1-4 in the general structure of formula II. The catalytic system is suitable for catalyzing the reaction system in which carbon dioxide reacts with epoxy compound to synthesize the cyclic carbonate ester, in the reaction system, all the various epoxy compounds are applicable to the method, such as propylene oxide, epoxy chloropropane, styrene oxide, 2,3-glycidyl phenyl ether or cyclohexene oxide; the reaction temperature is 30-80 DEG C; the pressure of carbon dioxide is 2-12 MPa; and reaction time is 1-24 h. Compared with the conventional method, the catalytic system has the advantages of mild reaction condition, high recovery rate and high selectivity, and reuse of the major catalyst metal-organic coordination polymer (MOF-5) by simple filtration. Therefore, the catalytic system has strong industrial application value.
Description
Technical field
The present invention relates to a kind of catalyst and catalyst system and catalyzing that is used for synthesizing annular carbonate, particularly a kind of be used for synthetic by carbon dioxide and epoxide catalyst and catalyst system and catalyzing by the cycloaddition reaction synthesizing annular carbonate.
Background technology
Carbon dioxide is topmost greenhouse gases, also is very abundant and the most cheap carbon one resource of reserves on the earth.The chemical fixation carbon dioxide both can be alleviated " greenhouse effects ", can obtain high value-added product again, meet the requirement of Green Chemistry, have very big environmental effect and economic benefit, therefore important topic (D.H.Gibson, Chem.Rev., 1996 of countries in the world common concern have been become, 96,2063; T.Sakakura etal, Chem.Rev., 2007,107,2365).Wherein, utilizing the reaction of carbon dioxide and epoxide to generate cyclic carbonate is one of important channel that successfully utilizes carbon dioxide, and this reaction equation is as follows:
Cyclic carbonate serves many purposes, the intermediate in synthesizing as organic solvent, medicine and fine chemistry industry and (J.Bayardon etal, Angew.Chem.Int.Ed., 2007,46,5971 such as electrolyte of battery; J.H.Clements, Ind.Eng.Chem.Res., 2003,42,663; S.Fukuoka etal, Green.Chem., 2003,5,497).
The catalyst of the cycloaddition reaction synthesizing annular carbonate of having reported at present that passes through carbon dioxide and epoxide mainly contains: (H.Yasuda etal such as quaternary ammonium salt or quaternary alkylphosphonium salt, alkali halide, ionic liquid, metal oxide, ion exchange resin, functionalized polymer, transient metal complex and Schiff bases catalyst, J.Catal., 2005,233,119; M.Kihare etal, J.Org.Chem., 1993,58,6198; H.Kawanami etal, Chem.Comm., 2003,896; K.Yamaguchi etal, J.Am.Chem.Soc., 1999,121,4526; Y.Du etal, Green Chem., 2005,7,518; Y.Xie etal, Angew.Chem.Int.Ed., 2007,46,7255; Y.M.Shen etal, Eur.J.Org.Chem.2004,3080; R.L.Paddock etal, J.Am.Chem.Soc.2001,123,11498; McMullen, US4314945; Harvey etal, US4841072; Deng Youquan etc., CN1343668).But above-mentioned catalyst system and catalyzing exists still that catalytic activity is not high, the synthetic difficulty of catalyst, reaction needed HTHP or the poisonous problems such as organic solvent of needs adding.Therefore, the catalyst system and catalyzing under exploitation reaction condition gentleness and the condition of no solvent remains the core of carbon dioxide Investigation on Cycloaddition Reactions.
Summary of the invention
The purpose of this invention is to provide a kind of catalyst system and catalyzing that is used for synthesizing annular carbonate.
The catalyst system and catalyzing that is used for synthesizing annular carbonate provided by the invention is made up of suc as formula the quaternary ammonium salt shown in catalyst shown in the I and the formula II general structure construction unit; In the formula II general structure, n=1-4.
(formula I)
(formula II)
Catalyst shown in the formula I construction unit is a kind of cancellated molecular sieve analog material that has, and is as follows.
In this catalyst system and catalyzing, the catalyst shown in the formula I is major catalyst (being called for short MOF-5), and quaternary ammonium salt is a co-catalyst, and this quaternary ammonium salt specifically can be TBAB, 4-propyl bromide, tetraethylammonium bromide or 4 bromide.The weight ratio of catalyst and quaternary ammonium salt is 1: 0.4-1: 2.0, preferred 1: 0.4-1: 1.7, more preferably 1: 0.8-1: 1.65.
The catalyst system and catalyzing that is used for synthesizing carbonate ester provided by the invention is applicable to the reaction system of catalysis by carbon dioxide and epoxide reaction synthesizing annular carbonate.This reaction is under the condition that catalyst system and catalyzing exists, and carbon dioxide and epoxide are reacted, and obtains cyclic carbonate.In this reaction system, various epoxides all are applicable to this method, as expoxy propane, epoxychloropropane, styrene oxide, 2,3-glycidyl phenyl ether or cyclohexene oxide; The mol ratio of epoxide and quaternary ammonium salt is 100: 0.6-100: 5.This reaction temperature is 30-80 ℃, and the pressure of carbon dioxide is 2-12MPa, and the reaction time is 1-24 hour.
Catalyst provided by the invention and catalyst system and catalyzing have advantages of high catalytic activity, mild condition, and the synthetic method of major catalyst is simple, and separates from reaction system easily; This catalyst system and catalyzing is widely applicable, can be used for carbon dioxide and multiple epoxide synthesizing annular carbonate, has stronger industrial application value.
The specific embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.
Used MOF-5 among the present invention is to be prepared according to the method that following document provides: L.Huang, et al; Microporous Mesoporous Mater.2003,58,105.
Concrete preparation method is as follows: with Zn (NO
3) 6H
2(1.21g, 4mmol), (0.32g 2mmol) is dissolved among the 40ml DMF terephthalic acid (TPA) O, and system keeps 60 ℃, adds triethylamine 1.6g under the continuous stirring, and continues to stir 4h, and the gained solid is after the DMF washing, and drying obtains MOF-5.
Embodiment 1
In 25 milliliters autoclave, add 0.1 gram MOF-5,0.161 gram TBAB and 1.16 gram expoxy propane successively, closed reactor also puts it in 50 ℃ the heating furnace, treats to charge into carbon dioxide to 6MPa after the temperature balance in reactor, and stirring reaction is after 4 hours, cooling, venting is interior mark with n-butanol, passes through gas chromatographic detection, utilize conventional internal standard method to calculate, the yield that obtains propene carbonate is 98%.
Embodiment 2
Adopt and embodiment 1 identical reaction condition and detection method, only catalyst system and catalyzing is changed into 0.1 gram MOF-5 and 0.133 gram 4-propyl bromide, the yield that obtains propene carbonate is 60%.
Embodiment 3
Adopt and embodiment 1 identical reaction condition and detection method, only catalyst system and catalyzing is changed into 0.1 gram MOF-5 and 0.12 gram TBAB, all the other are with embodiment 1, and the yield that obtains propene carbonate is 94%.
Embodiment 4
Adopt and embodiment 1 identical reaction condition and detection method, only catalyst system and catalyzing is changed into 0.1 gram MOF-5 and 0.08 gram TBAB, the yield that obtains propene carbonate is 77%.
Embodiment 5
Adopt and embodiment 1 identical reaction condition and detection method, only pressure carbon dioxide is become 2MPa, the yield that obtains propene carbonate is 98%.
Embodiment 6
Adopt and embodiment 1 identical reaction condition and detection method, only pressure carbon dioxide is become 4MPa, the yield that obtains propene carbonate is 98%.
Embodiment 7
Adopt and embodiment 1 identical reaction condition and detection method, only pressure carbon dioxide is become 8MPa, the yield that obtains propene carbonate is 78%.
Embodiment 8
Adopt and embodiment 1 identical reaction condition and detection method, only pressure carbon dioxide is become 10MPa, the yield that obtains propene carbonate is 68%.
Embodiment 9
Adopt and embodiment 1 identical reaction condition and detection method, only pressure carbon dioxide is become 12MPa, the yield that obtains propene carbonate is 57%.
Embodiment 10
Adopt and embodiment 1 identical reaction condition and detection method, only reaction temperature is become 30 ℃, the yield that obtains propene carbonate is 34%.
Embodiment 11
Adopt and embodiment 1 identical reaction condition and detection method, only reaction temperature is become 40 ℃, the yield that obtains propene carbonate is 90%.
Embodiment 12
Adopt and embodiment 1 identical reaction condition and detection method, only reaction temperature is become 60 ℃, the yield that obtains propene carbonate is 98%.
Embodiment 13
Adopt and embodiment 1 identical reaction condition and detection method, only reaction temperature is become 70 ℃, the yield that obtains propene carbonate is 98%.
Embodiment 14
Adopt and embodiment 1 identical reaction condition and detection method, only will become 1 hour the reaction time, the yield that obtains propene carbonate is 58%.
Embodiment 15
Adopt and embodiment 1 identical reaction condition and detection method, only will become 2 hours the reaction time, the yield that obtains propene carbonate is 82%.
Embodiment 16
Adopt and embodiment 1 identical reaction condition and detection method, only will become 3 hours the reaction time, the yield that obtains propene carbonate is 94%.
Embodiment 17
Adopt and embodiment 1 identical reaction condition and detection method, only will become 5 hours the reaction time, the yield that obtains propene carbonate is 98%.
Embodiment 18
Adopt and embodiment 1 identical reaction condition and detection method, only reaction substrate is become 1.85 gram epoxychloropropane, the reaction time becomes 6 hours.Weigh after the venting, system weightening finish 0.836 gram, after the catalyst separation, detecting products therefrom with the hydrogen nuclear magnetic resonance method is corresponding cyclic carbonate, yield is 95%.It is as follows that nuclear-magnetism detects data:
1H NMR (CDCl
3, 400MHz): δ (ppm): 3.75 (dd, J=3.6,12.3Hz, 1H), 3.84 (dd, J=4.9,12.3Hz, 1H), 4.42 (dd, J=5.7,8.8Hz, 1H), 4.62 (t, J=8.7Hz, 1H), 5.00-5.06 (m, 1H).
Embodiment 19
Adopt and embodiment 1 identical reaction condition and detection method, only reaction substrate is become 2.4 gram styrene oxides, the reaction time becomes 10 hours.Weigh after the venting, system weightening finish 0.854 gram, after the catalyst separation, detecting products therefrom with the hydrogen nuclear magnetic resonance method is corresponding cyclic carbonate, yield is 97%.It is as follows that nuclear-magnetism detects data:
1H NMR (CDCl
3, 400MHz): δ (ppm): 4.35 (t, J=8.2Hz, 1H), 4.80 (t, J=8.4Hz, 1H), 5.68 (t, J=8.0Hz, 1H), 7.36-7.45 (m, 5H).
Embodiment 20
Adopt and embodiment 1 identical reaction condition and detection method, only reaction substrate is become 3.0 grams 2,3-glycidyl phenyl ether.Weigh after the venting, system weightening finish 0.854 gram, after the catalyst separation, detecting products therefrom with the hydrogen nuclear magnetic resonance method is corresponding cyclic carbonate, yield is 97%.It is as follows that nuclear-magnetism detects data:
1H NMR (CDCl
3, 400MHz) δ (ppm): 4.15 (dd, J=3.6,10.5Hz, 1H), 4.24 (dd, J=4.4,10.5Hz, 1H), 4.54 (dd, J=6.0,8.5Hz, 1H), 4.62 (t, J=8.4Hz, 1H), and 5.00-5.05 (m, 1H), 6.91 (d, J=8.2Hz, 2H), 7.02 (t, J=7.4Hz, 1H), 7.31 (t, J=8.2Hz, 2H).
Embodiment 21
Adopt and embodiment 1 identical reaction condition and detection method, only reaction substrate is become 1.96 gram cyclohexene oxides, the reaction time becomes 24 hours.Weigh after the venting, system weightening finish 0.458 gram, after the catalyst separation, detecting products therefrom with the hydrogen nuclear magnetic resonance method is corresponding cyclic carbonate, yield is 52%.It is as follows that nuclear-magnetism detects data:
1H NMR (CDCl
3, 400MHz): δ (ppm): 1.42-1.48 (m, 2H), 1.58-1.64 (m, 2H), 1.88-1.91 (m, 4H), 4.68-4.71 (m, 2H).
Embodiment 22
Adopt and embodiment 1 identical reaction condition and detection method, only reaction substrate is become 1.96 gram cyclohexene oxides, reaction temperature becomes 80 ℃, and the reaction time becomes 20 hours.Weigh after the venting, system weightening finish 0.828 gram, after the catalyst separation, detecting products therefrom with the hydrogen nuclear magnetic resonance method is corresponding cyclic carbonate, yield is 94%.It is as follows that nuclear-magnetism detects data:
1H NMR (CDCl
3, 400MHz): δ (ppm): 1.42-1.48 (m, 2H), 1.58-1.64 (m, 2H), 1.88-1.91 (m, 4H), 4.68-4.71 (m, 2H).
Claims (9)
1. a catalyst system and catalyzing that is used for synthesizing annular carbonate is made up of the quaternary ammonium salt shown in catalyst MOF-5 and the formula II general structure;
(formula II)
In the described formula II general structure, n=1-4;
The weight ratio of the quaternary ammonium salt shown in described catalyst MOF-5 and the formula II general structure is 1: 0.4-1: 2.0.
2. catalyst system and catalyzing according to claim 1 is characterized in that: the weight ratio of the quaternary ammonium salt shown in described catalyst MOF-5 and the formula II general structure is 1: 0.4-1: 1.7.
3. catalyst system and catalyzing according to claim 2 is characterized in that: the weight ratio of the quaternary ammonium salt shown in described catalyst MOF-5 and the formula II general structure is 1: 0.8-1: 1.65.
4. according to the arbitrary described catalyst system and catalyzing of claim 1-3, it is characterized in that: described quaternary ammonium salt is TBAB, 4-propyl bromide, tetraethylammonium bromide or 4 bromide.
5. a method for cyclic carbonates is under the condition that catalyst system and catalyzing exists, and carbon dioxide and epoxide are reacted, and obtains described cyclic carbonate; It is characterized in that: described catalyst system and catalyzing is the described catalyst system and catalyzing of claim 1;
Described epoxide is expoxy propane, epoxychloropropane, styrene oxide, 2,3-glycidyl phenyl ether or cyclohexene oxide.
6. method according to claim 5 is characterized in that: described reaction temperature is 30-80 ℃.
7. according to claim 5 or 6 described methods, it is characterized in that: the pressure of described carbon dioxide is 2-12MPa.
8. method according to claim 5 is characterized in that: the described reaction time is 1-24 hour.
9. method according to claim 5 is characterized in that: the mol ratio of described epoxide and quaternary ammonium salt is 100: 0.6-100: 5.
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| CN101805324B (en) * | 2010-04-09 | 2013-01-23 | 兰州大学 | Cyclic carbonate compound and synthesis method thereof |
| CN102603702A (en) * | 2011-11-30 | 2012-07-25 | 黎明化工研究院 | Method for preparing end-ring carbonic acid polyester |
| CN102775377B (en) * | 2011-12-20 | 2016-01-20 | 湖南大学 | A kind of solvent-free process for catalytic synthesis of cyclic carbonate |
| CN102775378B (en) * | 2011-12-20 | 2015-10-28 | 湖南大学 | A kind of solvent-free process for catalytic synthesis of cyclic carbonate |
| US8735608B2 (en) * | 2012-02-28 | 2014-05-27 | Saudi Basic Industries Corporation | Process for preparing carbonate and diol products |
| TWI519347B (en) | 2013-10-24 | 2016-02-01 | 財團法人工業技術研究院 | Catalyst system and method for manufacturing cyclic carbonate by the same |
| CN104788309A (en) * | 2014-01-20 | 2015-07-22 | 任燕萍 | Metal organic framework, preparation method and use thereof, and carbon dioxide conversion method |
| CN104324760B (en) * | 2014-10-09 | 2017-03-01 | 济南大学 | A kind of preparation method and application of feature coordination polymer |
| CN105037317A (en) * | 2015-08-18 | 2015-11-11 | 广西大学 | Method for synthesizing propylene carbonate |
| CN109289921B (en) * | 2018-11-13 | 2021-08-10 | 北京林业大学 | Catalytic system based on phytic acid and used for synthesizing cyclic carbonate |
| CN114591284B (en) * | 2022-02-23 | 2023-09-01 | 沈阳化工大学 | Zn-MOF-based catalyst in CO 2 Process for synthesizing cyclic carbonates |
| CN115591580B (en) * | 2022-09-05 | 2023-09-12 | 华侨大学 | Multi-site catalyst for cycloaddition reaction of carbon dioxide, and preparation method and application thereof |
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