CN115197410A - Preparation method of cyclic carbonate - Google Patents
Preparation method of cyclic carbonate Download PDFInfo
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- CN115197410A CN115197410A CN202210932693.2A CN202210932693A CN115197410A CN 115197410 A CN115197410 A CN 115197410A CN 202210932693 A CN202210932693 A CN 202210932693A CN 115197410 A CN115197410 A CN 115197410A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 150000005676 cyclic carbonates Chemical class 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 20
- 239000004417 polycarbonate Substances 0.000 claims abstract description 20
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims description 12
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims 1
- 125000004430 oxygen atom Chemical group O* 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000010790 dilution Methods 0.000 abstract description 2
- 239000012895 dilution Substances 0.000 abstract description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 20
- 229910052739 hydrogen Inorganic materials 0.000 description 20
- 239000001257 hydrogen Substances 0.000 description 20
- 238000001228 spectrum Methods 0.000 description 15
- 238000005481 NMR spectroscopy Methods 0.000 description 13
- 239000004033 plastic Substances 0.000 description 13
- 229920003023 plastic Polymers 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000011261 inert gas Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 238000010791 quenching Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- -1 woods Substances 0.000 description 11
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 208000035967 Long Term Adverse Effects Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229920005565 cyclic polymer Polymers 0.000 description 1
- 238000013501 data transformation Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000002009 diols Chemical group 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/02—Aliphatic polycarbonates
- C08G64/0208—Aliphatic polycarbonates saturated
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a preparation method of cyclic polycarbonate, belonging to the technical field of organic synthesis. The preparation of the cyclic polycarbonate is realized by a high-selectivity ring-opening polymerization method by adopting cyclic carbonate as a substrate. Compared with the prior art for preparing the cyclic polycarbonate in the high-dilution environment, the method has the characteristics of economy, rapidness, high molecular weight, controllable reaction and the like.
Description
Technical Field
The invention belongs to the field of polymer synthesis, and particularly relates to a cyclic polymer with carbonate functional groups.
Background
Plastics have wide application in daily life, are excellent materials, and replace stones, woods, glass and the like. However, the conventional plastic has high thermal stability and cannot be degraded in natural environment. Small molecules such as plasticizers in waste plastics, and physically refined micro-plastics have long-term adverse effects on the environment and animals and plants, so that the plastic wastes in the environment become a non-negligible problem. Therefore, redesigning the plastic structure so that it is degradable or recyclable is an important way to address the plastic crisis.
Most of the currently reported recyclable plastics utilize the upper limit temperature of polymerization reaction for recycling, have higher requirements on monomer structures, and have no general significance. In addition, the upper limit temperature of monomer polymerization is utilized to recover the plastic, a large amount of solvent is needed to participate, the environment is polluted, the concept of green chemistry and sustainable development is not met, and the guiding idea of a 'double-carbon' strategy is violated. Therefore, the main goal of realizing green chemistry is to study the solvent-free, large-scale preparable plastic monomers, and then to carry out polymerization and recovery. The carbonate group having a proton transfer mechanism enables the above-mentioned concept of green plastics, and conforms to the concept of sustainable development.
The preparation method of cyclic polycarbonates is mainly prepared by end group back-biting in a highly diluted environment, requires the use of large amounts of solvents, and the selectivity of the product is not controllable (Reactive & Functional Polymers,2012, 868-877); or by carbene-catalyzed ring-opening polymerization, but the variety of substrates is limited to small cyclic carbonate monomers containing nitrogen atoms in part (ACS Macro Lett.2016, 1162-1166). Reports of cyclic polycarbonates having long carbon chains have not been realized.
Disclosure of Invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a process for the preparation of large scale, solvent free, green cyclic polycarbonates. The preparation of the cyclic polycarbonate is realized by adopting cyclic carbonate as a substrate through a high-selectivity ring-opening polymerization method, and the cyclic polycarbonate has high commercial application potential in the fields of plasticizers, lubricating oil and the like.
The invention firstly proposes the preparation of the cyclic polycarbonate by a ring-opening polymerization mode. The selectivity and the yield of the reaction are high. The product can be obtained with high purity by filtration or precipitation without column chromatography.
In order to expand the application of carbonate-based green plastics, plasticizers, material matrixes and lubricating oil, the invention finds and solves the problems on the basis of practical application, and realizes the cyclic polycarbonate by ring-opening polymerization of cyclic carbonate. The preparation method is firstly proposed and applied to the synthesis of the cyclic polycarbonate with high added value.
The technical scheme for realizing the purpose is as follows:
a preparation method of cyclic carbonate shown as a formula (I) is disclosed, wherein a monomer shown as a formula (II) or a formula (III) is subjected to ring-opening polymerization under the catalysis of carbene shown as a formula (IV) to generate cyclic polycarbonate shown as the formula (I), and the reaction general formula is as follows:
wherein R is methylene, oxygen atom, nitrogen atom, alkyl substituted nitrogen atom with 1-4 carbon atoms, sulfur atom, selenium atom; x is the length of a carbon chain, and x is a natural number of 1-15; y is a natural number greater than 1 and less than 1 ten thousand.
Preferably, R is methylene, oxygen and X is 1 to 13, y =1 to 8000.
Preferably, the monomer represented by formula (II) is selected from the following structures:
preferably, the monomer represented by formula (iii) is selected from the following structures:
preferably, the catalyst is a carbene catalyst, and the structure is as follows:
preferably, the molar ratio of the monomer shown in the formula (II) or the formula (III) to the carbene shown in the formula (IV) is 10:1 to 1000:1
Preferably, the reaction takes place at 0-65 ℃ for 1-24 hours.
Advantageous effects
(1) The invention can efficiently synthesize the cyclic polycarbonate with high added value through the catalytic system, and has the characteristics of high selectivity, wide application and the like compared with the prior art which utilizes a high solvent system for dilution. Has great commercial application potential in the fields of degradable and recyclable plastics, lubricating oil, drug delivery and the like.
(2) The preparation method is used for preparing the cyclic polycarbonate, no corresponding preparation report of the cyclic polycarbonate is available at present, and compared with the known technology, the yield of the cyclic polycarbonate obtained by the invention is extremely high.
(3) The carbene, the cyclic carbonate 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 advantages.
Compared with other existing catalytic systems, the catalyst has the obvious advantages of high efficiency, easiness in preparation, environmental 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: example 1 Hydrogen Spectrum of Cyclic polycarbonate product
FIGS. 2 to 8: hydrogen spectra of the carbonate products of examples 2 to 8, respectively
FIG. 9: carbon spectrum of cyclic polycarbonate product in example 1
FIGS. 10 to 15: carbon spectra of the cyclic polycarbonate products of examples 2-7
Detailed Description
The invention is further illustrated by the following examples, which are intended to be illustrative and not limiting. It will be understood by those of ordinary skill in the art that these examples are not intended to limit the present invention in any way and that suitable modifications and data transformations may be made without departing from the spirit and scope of the present invention.
The hydrogen nuclear magnetic resonance spectra referred to in the examples were determined using a hydrogen nuclear magnetic resonance spectrometer model Bruker Ascend TM-400 from Bruker, inc. (Bruker), the deuterated reagent being deuterated chloroform (CDCl) 3 )。
The feedstocks used in the following examples were all purchased from Alfa Aesar.
The diol structures used in the examples are as follows:
example 1:
the reaction flask was subjected to water removal and oxygen removal, and methylcarbene (9.6 mg,0.1mmol, 0.1equiv), structure 1 (130mg, 0.5mmol,1.0 equiv), and 0.5 ml of tetrahydrofuran were added under an inert gas atmosphere, and reacted for 5 hours. After the reaction is finished, carbon disulfide CS is used 2 Quench, yield 95%. The hydrogen spectrum of the product is shown in figure 1, (hydrogen nuclear magnetic resonance spectrum, 400Hz, CDCl) 3 ). The spectrogram data are as follows: 1 H NMR(400MHz,Chloroform-d)δ4.13(t,4H),1.71(m,4H),1.47(m,6H)。
example 2:
the reaction flask was subjected to water removal and oxygen removal, and methylcarbin (9.6 mg,0.1mmol, 0.1equiv), structure 2 (1440mg, 0.5mmol, 1.0equiv), and 0.5 ml of tetrahydrofuran were added under an inert gas atmosphere, and reacted for 5 hours. After the reaction is finished, carbon disulfide CS is used 2 Quench, 96% yield. The hydrogen spectrum of the product is shown in figure 1, (hydrogen nuclear magnetic resonance spectrum, 400Hz, CDCl) 3 ). The spectrogram data is as follows: 1 H NMR(400MHz,Chloroform-d)δ4.12(t,4H),1.68(m,4H),1.41(m,8H)。。
example 3:
the reaction flask was subjected to water removal and oxygen removal, and ethyl carbene (12.4 mg,0.1mmol, 0.1equiv), structure 3 (15800mg, 0.5mmol,1.0 equiv), and 0.5 ml of tetrahydrofuran were added under an inert gas atmosphere, and reacted for 5 hours. After the reaction is finished, carbon disulfide CS is used 2 Quench, 95% yield. The hydrogen spectrum of the product is shown in FIG. 1, (hydrogen spectrum of nuclear magnetic resonance, 400Hz, CDCl) 3 ). The spectrogram data is as follows: 1 H NMR(400MHz,Chloroform-d)δ4.13(t,4H),1.68(m,4H),1.38(m,10H)。
example 4:
the reaction flask was subjected to water removal and oxygen removal, and ethyl carbene (12.4 mg,0.1mmol, 0.1equiv), structure 4 (93mg, 0.5mmol, 1.0equiv), and 0.5 ml of tetrahydrofuran were added under an inert gas atmosphere, and reacted for 1 hour. After the reaction is finished, carbon disulfide CS is used 2 Quench, 95% yield. The hydrogen spectrum of the product is shown in figure 1, (hydrogen nuclear magnetic resonance spectrum, 400Hz, CDCl) 3 ). The spectrogram data is as follows: 1 H NMR(400MHz,Chloroform-d)δ4.11(t,4H),1.66(m,4H),1.30(m,14H)。
example 5:
the reaction flask was subjected to water removal and oxygen removal, and ethyl carbene (12.4 mg,0.1mmol, 0.1equiv), structure 5 (100mg, 0.5mmol,1.0 equiv), and 0.5 ml of tetrahydrofuran were added under an inert gas feed, and reacted for 10 hours. After the reaction is finished, carbon disulfide CS is used 2 Quench and yield 97%. The hydrogen spectrum of the product is shown in FIG. 1, (hydrogen spectrum of nuclear magnetic resonance, 400Hz, CDCl) 3 ). The spectrogram data is as follows: 1 H NMR(400MHz,Chloroform-d)δ4.11(t,4H),1.65(m,4H),1.28(m,16H)。
example 6:
the reaction flask was subjected to water and oxygen removal, and ethyl carbene (12.4 mg,0.1mmol, 0.1equiv), structure 6 (112mg, 0.5mmol,1.0 equiv), and 0.5 ml of tetrahydrofuran were added under an inert gas atmosphere at a temperature of 65 ℃ for 5 hours. After the reaction is finished, carbon disulfide CS is used 2 Quenching, yield 96%. The hydrogen spectrum of the product is shown in figure 1, (hydrogen nuclear magnetic resonance spectrum, 400Hz, CDCl) 3 ). The spectrogram data is as follows: 1 H NMR(400MHz,Chloroform-d)δ4.11(t,4H),1.66(m,4H),1.27(m,18H)。
example 7:
the reaction flask was subjected to water removal and oxygen removal, and ethyl carbene (12.4 mg,0.1mmol, 0.1equiv), structure 7 (132mg, 0.5mmol,1.0 equiv), and 0.5 ml of dichloroethane were added under an inert gas atmosphere, and reacted for 6 hours. After the reaction is finished, carbon disulfide CS is used 2 Quench, yield 92%. The hydrogen spectrum of the product is shown in FIG. 1, (hydrogen spectrum of nuclear magnetic resonance, 400Hz, CDCl) 3 ). The spectrogram data are as follows: 1 H NMR(400MHz,Chloroform-d)δ4.28(t,4H),3.72(m,4H)。
example 8:
the reaction flask was subjected to water and oxygen removal, and ethyl carbene (12.4 mg,0.1mmol, 0.1equiv), structure 8 (88mg, 0.5mmol,1.0 equiv), and 0.5 ml of dichloromethane were added under an inert gas atmosphere, and reacted for 2 hours. After the reaction is finished, carbon disulfide CS is used 2 Quench, 98% yield. The hydrogen spectrum of the product is shown in figure 1,(hydrogen nuclear magnetic resonance, 400Hz, CDCl 3 ). The spectrogram data is as follows: 1 H NMR(400MHz,Chloroform-d)δ4.27(t,4H),3.71(t,4H),3.65(s,4H)。
example 9:
the reaction flask was subjected to water removal and oxygen removal, and isopropyl carbene (15.2 mg,0.1mmol, 0.1equiv), structure 9 (114mg, 0.5mmol,1.0 equiv), and 0.5 ml of dichloromethane were added under an inert gas atmosphere, and reacted for 2 hours. After the reaction is finished, carbon disulfide CS is used 2 Quench, yield 95%.
Example 10:
the reaction flask was subjected to water removal and oxygen removal, and isopropyl carbene (15.2mg, 0.1mmol, 0.1equiv), structure 10 (172mg, 0.5mmol,1.0 equiv), and 0.5 ml of dichloromethane were added under an inert gas atmosphere, and reacted for 2 hours. After the reaction is finished, carbon disulfide CS is used 2 Quench, yield 90%.
Example 11:
the reaction flask was subjected to water removal and oxygen removal, and isopropyl carbene (15.2 mg,0.1mmol, 0.1equiv), structure 11 (110mg, 0.5mmol,1.0 equiv), and 0.5 ml of dichloromethane were added under an inert gas atmosphere, and reacted for 2 hours. After the reaction is finished, carbon disulfide CS is used 2 Quench, yield 95%.
Claims (7)
1. A preparation method of cyclic carbonate shown as a formula (I) is characterized in that a monomer shown as a formula (II) or a formula (III) is subjected to ring-opening polymerization under the catalysis of carbene shown as a formula (IV) to generate cyclic polycarbonate shown as the formula (I), and the reaction general formula is as follows:
wherein R is methylene, oxygen atom, nitrogen atom, alkyl substituted nitrogen atom with 1-4 carbon atoms, sulfur atom, selenium atom; x is the length of a carbon chain, and x is a natural number of 1-15; y is a natural number greater than 1 and less than 1 ten thousand.
2. The production method according to claim 1, wherein R is a methylene group, an oxygen atom, and X is 1 to 13,y =1 to 8000.
3. The method of claim 1, wherein the monomer of formula (ii) is selected from the following structures:
4. the method according to claim 1, wherein the monomer represented by formula (iii) is selected from the following structures:
5. the method of claim 1, wherein: the catalyst is a carbene catalyst and has the following structure:
6. the method of claim 1, wherein: the molar ratio of the monomer shown in the formula (II) or the formula (III) to the carbene shown in the formula (IV) is 10:1 to 1000: 1.
7. The method of claim 1, wherein: the reaction takes place at 0-65 ℃ for 1-24 hours.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1738847A (en) * | 2003-01-21 | 2006-02-22 | 拜尔材料科学股份公司 | Cyclic polycarbonates and copolycarbonates, their preparation and use |
| JP2009108138A (en) * | 2007-10-26 | 2009-05-21 | Mitsubishi Chemicals Corp | Production method of polycarbonate resin |
| CN112316978A (en) * | 2020-11-12 | 2021-02-05 | 大连理工大学 | Organic catalyst for synthesizing cyclic carbonate, preparation method and catalytic reaction method thereof |
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- 2022-08-04 CN CN202210932693.2A patent/CN115197410A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1738847A (en) * | 2003-01-21 | 2006-02-22 | 拜尔材料科学股份公司 | Cyclic polycarbonates and copolycarbonates, their preparation and use |
| JP2009108138A (en) * | 2007-10-26 | 2009-05-21 | Mitsubishi Chemicals Corp | Production method of polycarbonate resin |
| CN112316978A (en) * | 2020-11-12 | 2021-02-05 | 大连理工大学 | Organic catalyst for synthesizing cyclic carbonate, preparation method and catalytic reaction method thereof |
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