CN114315790B - Preparation method of cyclic carbonate - Google Patents
Preparation method of cyclic carbonate Download PDFInfo
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- CN114315790B CN114315790B CN202111483946.4A CN202111483946A CN114315790B CN 114315790 B CN114315790 B CN 114315790B CN 202111483946 A CN202111483946 A CN 202111483946A CN 114315790 B CN114315790 B CN 114315790B
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- 150000005676 cyclic carbonates Chemical class 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- 239000004417 polycarbonate Substances 0.000 claims abstract description 14
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 23
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 9
- 150000002009 diols Chemical class 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 4
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- HSNQKJVQUFYBBY-UHFFFAOYSA-N dipentyl carbonate Chemical compound CCCCCOC(=O)OCCCCC HSNQKJVQUFYBBY-UHFFFAOYSA-N 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 2
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims 1
- 229910000103 lithium hydride Inorganic materials 0.000 claims 1
- AKTIAGQCYPCKFX-SYWGCQIGSA-L magnesium;(e)-4-oxopent-2-en-2-olate Chemical compound [Mg+2].C\C([O-])=C/C(C)=O.C\C([O-])=C/C(C)=O AKTIAGQCYPCKFX-SYWGCQIGSA-L 0.000 claims 1
- PRCNQQRRDGMPKS-UHFFFAOYSA-N pentane-2,4-dione;zinc Chemical compound [Zn].CC(=O)CC(C)=O.CC(=O)CC(C)=O PRCNQQRRDGMPKS-UHFFFAOYSA-N 0.000 claims 1
- 229910000105 potassium hydride Inorganic materials 0.000 claims 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims 1
- 229910000104 sodium hydride Inorganic materials 0.000 claims 1
- 239000012312 sodium hydride Substances 0.000 claims 1
- 238000006068 polycondensation reaction Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 37
- 239000001257 hydrogen Substances 0.000 description 37
- 229910052739 hydrogen Inorganic materials 0.000 description 37
- 238000001228 spectrum Methods 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 32
- 238000005481 NMR spectroscopy Methods 0.000 description 25
- 239000004033 plastic Substances 0.000 description 16
- 229920003023 plastic Polymers 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 239000012043 crude product Substances 0.000 description 9
- 239000011261 inert gas Substances 0.000 description 9
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 7
- 238000000859 sublimation Methods 0.000 description 7
- 230000008022 sublimation Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000006392 deoxygenation reaction Methods 0.000 description 4
- 238000012691 depolymerization reaction Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- HCEPYODGJFPWOI-UHFFFAOYSA-N tridecane-1,13-diol Chemical compound OCCCCCCCCCCCCCO HCEPYODGJFPWOI-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OZCRKDNRAAKDAN-HNQUOIGGSA-N (e)-but-1-ene-1,4-diol Chemical compound OCC\C=C\O OZCRKDNRAAKDAN-HNQUOIGGSA-N 0.000 description 1
- OZCRKDNRAAKDAN-IWQZZHSRSA-N (z)-but-1-ene-1,4-diol Chemical compound OCC\C=C/O OZCRKDNRAAKDAN-IWQZZHSRSA-N 0.000 description 1
- XHJGXOOOMKCJPP-UHFFFAOYSA-N 2-[tert-butyl(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(C(C)(C)C)CCO XHJGXOOOMKCJPP-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 208000035967 Long Term Adverse Effects Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229920000426 Microplastic Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000005681 macrocyclic carbonates Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ZBPYFGWSQQFVCJ-UHFFFAOYSA-N pentadecane-1,15-diol Chemical compound OCCCCCCCCCCCCCCCO ZBPYFGWSQQFVCJ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- XLKZJJVNBQCVIX-UHFFFAOYSA-N tetradecane-1,14-diol Chemical compound OCCCCCCCCCCCCCCO XLKZJJVNBQCVIX-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of cyclic carbonate, and belongs to the technical field of organic synthesis. The method comprises the following steps: synthesis of a polycondensation polycarbonate, and selective depolymerization of the polycarbonate. Compared with the existing cyclic carbonate synthetic route, the method has the obvious advantages of low-cost and easily-obtained raw materials, wide sources, green and mild synthetic route, high atom utilization rate and the like.
Description
Technical Field
The invention belongs to the field of polymer synthesis and depolymerization, and particularly relates to a method for depolymerizing a polymer with carbonate functional groups and preparation of cyclic carbonate.
Background
The plastic is very popular in industrial and daily life applications, and the physical properties of the plastic can be adjusted according to application requirements of different scenes, so that the plastic is an excellent material. However, people enjoy the convenience brought by plastics and also cause serious damage to the surrounding environment. The main reasons are that the inherent stability of the waste plastics cannot be degraded or recycled, and the micromolecules in the waste plastics and the physically refined microplastic have long-term adverse effects on animals and plants, so that the plastic garbage in the environment becomes a non-negligible problem. Thus, degradable or recyclable polymers are expected to become a cornerstone for next generation plastic applications. On the other hand, the monomer used in the recyclable plastic can also exhibit great commercial value in other application fields (such as electrolyte preparation, fragrance formulation, etc.).
The currently reported recyclable plastics are mostly recycled by utilizing the polymerization upper limit temperature of the reaction, have higher limit on the monomer structure and have no general meaning. On the other hand, the plastic is recycled by utilizing the upper limit temperature of monomer polymerization, a large amount of solvent is also needed to participate, the environment is polluted, and the environment-friendly chemical concept is not met. The development of solvent-free, mass-producible plastic monomers, followed by polymerization and recovery, is a fundamental principle for achieving green chemistry. The specific proton transfer mechanism of the carbonate group enables the green plastic concept to be realized, and accords with the sustainable development concept.
The process for preparing cyclic carbonate monomers is mainly focused on enzymatic catalysis and depolymerization of oligomers of polymers after multi-step purification. For example, various saturated aliphatic chain polycarbonates were prepared by ring-chain dynamic equilibrium under dry toluene in 40% yield on an experimental scale of 1 gram (polym.chem., 2020,11,2166-2172) using enzyme catalysis. There is also a work of preparing oligocarbonates by pre-polycondensation followed by a depolymerization reaction. Despite the large experimental scale (> 50 g), the final cyclic carbonate yields were about 10% (J.Polym.Sci.A Polym.chem.1996,34 (12), 2399-2406, polymer1996,37 (19), 4383-4388, J.macromol.Sci., part A1997,34 (3), 417-428). The above methods have problems involving large amounts of solvents, complex multi-step reactions and purification, thereby limiting their potential for wide-ranging applications.
Disclosure of Invention
In view of the shortcomings of the existing technology, the invention aims to provide a large-scale solvent-free green depolymerization route and a preparation method of macrocyclic carbonate. The method adopts glycol as a substrate, performs polycondensation to prepare polycarbonate and performs high-selectivity depolymerization, and the obtained cyclic carbonate has high commercial application potential in the fields of plastic recovery, electrolyte and fragrance preparation.
The invention provides a two-step synthesis route of pre-polycondensation and high-selectivity depolymerization on the basis of no multi-step purification for the first time, and realizes large-scale preparation of cyclic carbonate in one reactor. The selectivity and the yield of the reaction are high. The product can be obtained in high purity by filtration or sublimation without column chromatography.
In order to expand the application of the fields of carbonate-based green plastics, electrolytes and fragrances, the invention finds and solves the problems based on practical application, and various diols are utilized to prepare cyclic carbonates with various substituents. The preparation method is proposed for the first time and applied to the synthesis of the cyclic carbonate with high added value.
The technical scheme for achieving the purpose is as follows:
a preparation method of cyclic carbonate comprises the following steps:
(1) Synthesis of polycarbonate: polycondensation of diol substrate and carbonate under the action of catalyst to produce polycarbonate; the molecular formula of the polycarbonate is shown as the formula (I):
R 1 ，R 2 is a functional group, D is a terminal group containing R 1 ，R 2 The diol of (2) is selected from the following structures:
the selected carbonate is used for preparing the polycarbonate as follows: dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dipentyl carbonate, and diphenyl carbonate.
The molar ratio of the glycol, the carbonic ester and the catalyst is 1:1.1:0.0001 to 1:1.99:0.5.
the catalysts used for preparing the polycarbonate are: liH, naH, KH, fe (acac) 3 ,Zn(acac) 2 ,Mg(acac) 2 ,Zr(acac) 4 。
The specific method for preparing the carbonic ester by polycondensation comprises the following steps: and (3) adding the carbonic ester and the diol shown in the formula II into a reactor at normal temperature, adding a catalyst, heating to 80-180 ℃ under vacuum condition, reacting for 3-6 hours, continuously heating to 180-230 ℃, and reacting for 3-5 hours to obtain the polycarbonate.
(2) Synthesis of cyclic carbonate:
the resulting polymer was subjected to high vacuum (1X 10 -4 -5×10 -1 mbar), heating to 200-285 ℃, and distilling or sublimating to obtain the corresponding cyclic carbonate.
The vacuum degree of the cyclic carbonate synthesis reaction in the step (2) is preferably 1X 10-3 to 1X 10-1mbar, the temperature is 230 to 275 ℃, and the time is more than 1 hour.
Advantageous effects
The technical scheme of the invention can at least achieve one of the following beneficial effects:
(1) The invention can efficiently synthesize the cyclic carbonate with high added value by the catalytic system, and has the characteristics of high selectivity, wide application and the like compared with the method for depolymerizing after enzyme catalysis and multi-step purification in the prior art. Has great potential for commercial application in the fields of degradable and recyclable plastics, electrolytes, and fragrance preparation.
(2) The preparation method is used for preparing the cyclic carbonate, no report exists on the preparation of the corresponding cyclic carbonate at present, and compared with the prior art, the preparation method has the advantage that the yield of the prepared cyclic carbonate is extremely high.
(3) The diol, the carbonic ester and the catalyst used in the invention are easy to obtain, have wide sources, do not need to use solvents, are beneficial to reducing the production cost, and have obvious economic benefit advantage.
In conclusion, compared with other existing catalytic systems, the catalyst has the obvious advantages of high efficiency, easiness in preparation, environment friendliness and the like.
Drawings
Embodiments of the present invention will be described in detail with reference to the accompanying drawings, in which
Fig. 1: hydrogen profile of carbonate product from example 1
Fig. 2 to 9: the hydrogen spectrograms of the carbonate products of examples 2 to 9, respectively
Detailed Description
The invention will be further illustrated by the following examples, which are intended to illustrate, but not to limit, the invention. It will be understood by those of ordinary skill in the art that these examples are not limiting of the invention in any way and that appropriate modifications and data changes may be made thereto without departing from the spirit and scope of the invention.
The nuclear magnetic resonance hydrogen spectrum involved in the examples was measured by Bruker Assend TM-400 nuclear magnetic resonance hydrogen spectrometer (Bruker), the deuterated reagent was deuterated chloroform (CDCl) 3 )。
The starting materials used in the examples below were all purchased from Alfa Aesar.
The diol structures used in the examples are as follows:
example 1:
the reaction bottle is subjected to dewatering and deoxidizing operation, and is introducedKH (9.91 mg,2.47mmol,0.05 equiv), 1, 12-dodecanediol (No. 1, 10g,49.2mmol,1.0 equiv), and diethyl carbonate (6.59 ml,54.36mmol,1.1 equiv) were added under inert gas. Under vacuum (5X 10) -1 mbar) and placing the mixture into an oil bath at 80 ℃ for reaction for 3-5 hours. After the reaction was completed, the reaction was continued under vacuum (1X 10) -1 mbar), heating to 180deg.C, reacting for 3 hr, continuously heating to 240deg.C for depolymerization reaction (3×10) when no excessive diethyl carbonate exists in the system (no residue is confirmed according to nuclear magnetic resonance hydrogen spectrum) -2 -1×10 -1 mbar). The product obtained is a colorless clear liquid, no purification step is required, the yield is 90%, and few byproducts are obtained. The hydrogen spectrum of the crude product is shown in FIG. 1, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 )。
The spectrogram data are: 1 h NMR (400 MHz, chloro form-d) delta 4.26 (t, 4H), 1.67 (m, 4H), 1.41-1.27 (m, 16H). No by-product formation was observed on the hydrogen spectrum.
Example 2:
the reaction flask was subjected to a water removal and deoxygenation operation, and NaH (55.4 mg,2.31mmol,0.05 equiv), 1, 13-tridecanediol (No. 2, 10g,46.22mmol,1.0 equiv), and dimethyl carbonate (4.70 ml,50.84mmol,1.1 equiv) were added with the inert gas introduced. Under vacuum (5X 10) -1 mbar) and placing the mixture into an oil bath at 80 ℃ for reaction for 3 to 6 hours. After the reaction was completed, the reaction was continued under vacuum (4X 10) -1 -1×10 -1 mbar), heating to 230 deg.C, reacting for 2-3 hr, continuously heating to 245-270 deg.C for depolymerization reaction (vacuum degree 1×10) when no excessive dimethyl carbonate exists in system (confirmed by hydrogen spectrum) -3 -9×10 -2 mbar). The product obtained was a colorless clear liquid, which was purified by sublimation in 85% yield. The hydrogen spectrum of the crude product is shown in FIG. 2, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: 1 H NMR(400MHz,Chloroform-d)δ4.22(t,4H),1.69(m,4H),1.41-1.27(m,18H)。
small amounts of alkene alcohol by-products of approximately 5mol% were observed on the hydrogen spectrum.
Example 3:
the reaction flask was subjected to a water removal and deoxygenation operation, and LiH (17.25 mg,2.17mmol,0.05 equiv), 1, 14-tetradecanediol (No. 3, 10g,43.40mmol,1.0 equiv), and diethyl carbonate (5.78 ml,47.74mmol,1.1 equiv) were added with the passage of inert gas. Under vacuum (2X 10) -1 -5×10 -1 mbar) and placing the mixture into an oil bath at 100 ℃ for reaction for 3-6 hours. After the reaction was completed, the reaction was continued under vacuum (4X 10) -1 -1×10 -1 mbar), heating to 230 deg.C, reacting for 4 hr, and continuing heating to 250-285 deg.C for depolymerization reaction (vacuum degree 1×10) when no excessive diethyl carbonate exists in the system (confirmed by nuclear magnetic resonance hydrogen spectrum) -4 -9×10 -2 mbar). The product obtained was a colorless clear liquid, which was purified by filtration through a silica gel column in 90% yield. The hydrogen spectrum of the crude product is shown in FIG. 3, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are:
1 H NMR(400MHz,Chloroform-d)δ4.20(t,4H),1.63(m,4H),1.27(m,20H)。
the hydrogen spectrum showed a triplet (delta 4.11 ppm) of oligocarbonate, approximately 2mol%
Example 4:
the reaction bottle is subjected to dewatering and deoxidizing operation, and Fe (acac) is added under the condition of introducing inert gas 3 (723.9 mg,2.04mmol,0.05 equiv), 1, 15-pentadecanediol (No. 4, 10g,40.91mmol,1.0 equiv), and dibutyl carbonate (8.04 ml,45mmol,1.1 equiv). Under vacuum (4X 10) -1 -1×10 -1 mbar) was placed in an oil bath at 110℃for 5 hours. After the reaction was completed, the reaction was continued under vacuum (1X 10) -1 mbar), heating to 230deg.C, reacting for 4 hr, and continuing to heat to 275deg.C to depolymerize (vacuum degree of 2×10) when no excessive diethyl carbonate exists in the system (confirmed by nuclear magnetic resonance hydrogen spectrum) -3 -9×10 -2 mbar). The product was obtained as a colorless clear liquid and purified by filtration through a silica gel column in 85% yield. The hydrogen spectrum of the crude product is shown in FIG. 4, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: 1 H NMR(400MHz,Chloroform-d)δ4.19(t,4H),1.67(m,4H),1.29(m,20H)。
the hydrogen spectrum showed a triplet (delta 4.11 ppm) of oligocarbonate of about 0.5mol%
Example 5:
the reaction bottle is subjected to dewatering and deoxidizing operation, and Zn (acac) is added under the condition of introducing inert gas 2 (1 g,4.19mmol,0.05 equiv), N-methyldiethanolamine (No. 5, 10g,83.92mmol,1.0 equiv), and diphenyl carbonate (19.77 g,92.3mmol,1.1 equiv). Under vacuum (5X 10) -1 mbar) was placed in an oil bath at 180℃for 5 hours. After the reaction was completed, the reaction was continued under vacuum (1X 10) -1 mbar), heating to 200deg.C, reacting for 3 hr, and continuing heating to 280 deg.C to depolymerize (vacuum degree 1×10) when no excessive diphenyl carbonate exists in the system (confirmed by nuclear magnetic resonance hydrogen spectrum) -4 -9×10 -2 mbar). The product obtained is white crystals, which are purified by sublimation, with a yield of 45%. The hydrogen spectrum of the crude product is shown in FIG. 5, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: 1 H NMR(400MHz,Chloroform-d)δ4.20(t,4H),2.68(t,4H),2.34(s,3H)。
no impurity formation was observed on the hydrogen spectrum.
Example 6:
the reaction bottle is subjected to dewatering and deoxidizing operation, and Mg (acac) is added under the condition of introducing inert gas 2 (800 mg,3.10mmol,0.05 equiv), N-t-butyldiethanolamine (No. 6, 10g,62.02mmol,1.0 equiv), and diethyl carbonate (8.27 ml,68.22mmol,1.1 equiv). Under vacuum (9X 10) -1 mbar) was placed in an oil bath at 120℃for 4 hours. After the reaction was completed, the reaction was continued under vacuum (2X 10) -1 mbar), heating to 180deg.C, reacting for 5 hr, and continuing heating to 250deg.C to depolymerize (vacuum degree 1×10) when no excessive diethyl carbonate exists in the system -3 -5×10 - 2 mbar). The product obtained is white crystals, and the product is purified by sublimation, with a yield of 40%. The hydrogen spectrum of the crude product is shown in FIG. 6, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are:
1 H NMR(400MHz,Chloroform-d)δ4.17(t,4H),2.79(t,4H),1.08(s,9H)。
no impurity formation was observed on the hydrogen spectrum.
Example 7:
the reaction flask was subjected to a water removal and deoxygenation operation, and KH (22.76 mg,5.67mmol,0.05 equiv), trans-1, 4-butenediol (No. 7, 10g,113mmol,1.0 equiv), and diethyl carbonate (15.13 ml,124.85mmol,1.1 equiv) were added with the passage of inert gas. Under vacuum (3-6X10) -1 mbar) was placed in an oil bath at 100℃for 4 hours. After the reaction was completed, the reaction was continued under vacuum (1X 10) -1 -7×10 -2 mbar), heating to 200deg.C, reacting for 5 hr, and continuing heating to 260deg.C to depolymerize (vacuum degree 2×10) when no excessive diethyl carbonate exists in the system (confirmed by nuclear magnetic resonance hydrogen spectrum) -3 -9×10 -2 mbar). The product obtained is white crystals, which are purified by sublimation, with a yield of 35%. The hydrogen spectrum of the crude product is shown in FIG. 7, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: 1 H NMR(400MHz,Chloroform-d)δ5.96(m,2H),4.55-4.57(d,4H)。
no impurity formation was observed on the hydrogen spectrum.
Example 8:
the reaction flask was subjected to a water removal and oxygen removal operation, and Zr (acac) 3 (2.76 g,5.67mmol,0.05 equiv.) cis-1, 4-butenediol (No. 8, 10g,113mmol,1.0 equiv.) and diethyl carbonate (15.13 ml,124.85mmol,1.1 equiv) were added with the introduction of inert gas. Under vacuum (8X 10) -1 mbar) was placed in an oil bath at 100℃for 4 hours. After the reaction was completed, the reaction was continued under vacuum (9X 10) -1 mbar), heating to 200deg.C, reacting for 5 hr, and continuing heating to 260deg.C to depolymerize (2×10deg.C) when no excessive diethyl carbonate exists in the system -3 -6×10 -2 mbar). The product obtained is white crystals, and the product is purified by sublimation, with a yield of 30%. The hydrogen spectrum of the crude product is shown in FIG. 7, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are:
1 H NMR(400MHz,Chloroform-d)δ5.88(m,2H),4.76-4.77(d,4H)。
no impurity formation was observed on the hydrogen spectrum.
Example 9:
the reaction flask was subjected to a water removal and deoxygenation operation, and KH (22.76 mg,5.67mmol,0.05 equiv), ethylene glycol (No. 9, 10g,943mmol,1.0 equiv), and diethyl carbonate (12.65 ml,103.66mmol,1.1 equiv) were added with the inert gas. Under vacuum (5X 10) -1 mbar) was placed in an oil bath at 100℃for 4 hours. After the reaction was completed, the reaction was continued under vacuum (8X 10) -1 -1×10 -1 mbar), heating to 200deg.C, reacting for 5 hr, and continuing heating to 220deg.C to depolymerize (8X10) when no excessive diethyl carbonate exists in the system -2 -1×10 -3 mbar). The product obtained was white crystals, which were purified by sublimation in 80% yield. The hydrogen spectrum of the crude product is shown in FIG. 7, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are:
1 H NMR(400MHz,Chloroform-d)δ4.32(t,8H),3.72(t,8H)。
the formation of oligomeric ethylene glycol (. Delta.4.27) was observed on the hydrogen spectrum in a yield of about 2mol%.
Claims (4)
1. A process for the preparation of a cyclic carbonate characterized by: comprises the following steps:
(1) Synthesis of polycarbonate:
adding carbonic ester and diol shown in a formula II into a reactor at normal temperature, adding a catalyst, heating to 80-180 ℃ under vacuum condition, reacting for 3-6 hours, continuously heating to 180-230 ℃, and reacting for 3-5 hours to obtain polycarbonate;
the molecular formula of the polycarbonate is shown as the formula (I):
wherein R is 1 ，R 2 Is a functional group, D is a terminal groupWherein R is contained in 1 ，R 2 The diol of formula (II) is selected from the following structures:
the carbonate is selected from the group consisting of: dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dipentyl carbonate, and diphenyl carbonate;
(2) Synthesis of Cyclic carbonate: the polycarbonate of formula (I) was subjected to vacuum of 1X 10 -4 ～5×10 -1 Heating to 200-285 deg.c in the condition of mbar, and distilling or sublimating to obtain cyclic carbonate.
2. The method of manufacturing according to claim 1, characterized in that: the vacuum degree of the synthesis of the cyclic carbonate is 1 multiplied by 10 -3 ～1×10 -1 mbar, the temperature is 230-275 ℃, and the time is more than 1 hour.
3. The method of manufacturing according to claim 1, characterized in that: the catalyst is lithium hydride, sodium hydride, potassium hydride, ferric (III) acetylacetonate, zinc (II) acetylacetonate, magnesium (II) acetylacetonate and zirconium (IV) acetylacetonate.
4. The method of manufacturing according to claim 1, characterized in that: the molar ratio of the glycol, the carbonic ester and the catalyst is 1:1.1:0.0001 to 1:1.99:0.5.
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