CN101328264B - Process for producing polycarbonate using ion liquid supported catalysts - Google Patents
Process for producing polycarbonate using ion liquid supported catalysts Download PDFInfo
- Publication number
- CN101328264B CN101328264B CN2008100630034A CN200810063003A CN101328264B CN 101328264 B CN101328264 B CN 101328264B CN 2008100630034 A CN2008100630034 A CN 2008100630034A CN 200810063003 A CN200810063003 A CN 200810063003A CN 101328264 B CN101328264 B CN 101328264B
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- CN
- China
- Prior art keywords
- polycarbonate
- ion liquid
- liquid supported
- salen metal
- metal catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 24
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 23
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 10
- 239000007788 liquid Substances 0.000 title claims description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 29
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000004593 Epoxy Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 11
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 150000002500 ions Chemical class 0.000 claims description 21
- 235000011089 carbon dioxide Nutrition 0.000 claims description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims description 5
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000007334 copolymerization reaction Methods 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002608 ionic liquid Substances 0.000 abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000004032 porphyrins Chemical class 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- -1 Zinc carboxylate Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical group C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a method for preparing polycarbonate by a Salen metal catalyst supported by an ionic liquid. Carbon dioxide and an epoxy compound are taken as raw materials, Salen metal supported by the ionic liquid is taken as a catalyst, and a copolymerization reaction is performed at a carbon dioxide pressure of between 0.1 and 5.5MPa and a reaction temperature of between 20 and 150 DEG C to prepare the polycarbonate. The catalyst used by the method has good thermal stability to the temperature of air and water, simple operation and higher catalytic activity. The prepared polycarbonate has the characteristics of higher molecular weight, narrow molecular weight distribution and so on.
Description
Technical field
The present invention relates to a kind of is catalyzer with ion liquid supported Salen metal, by the method for carbonic acid gas and epoxy compounds copolymerization polycarbonate.
Background technology
Carbonic acid gas and epoxy compounds copolymerization generate degradable polycarbonate material, are one of the research focuses in environment-friendly material field.Research report to the catalyst system of carbonic acid gas and epoxy compounds copolymerization mainly comprises: zinc ethyl-auxiliary agent catalyzer (J.Polym.Sci.Part B:Polym.Let., 1969,7,287-292), though the development of many proton compounds of ZnEt2-catalyst system early, but system is very responsive to water and air, and is difficult in actually operating.Zinc carboxylate (J.Polym.Sci.:Polym.Chem., 1999,37 (12): 1863-1876) be another kind of can catalysis CO2 and the catalyst system of epoxy compounds copolymerization, its catalytic efficiency is better than the ZnEt2 system, also comparatively stable to water and air, it is simple relatively to operate, but its catalytic efficiency is still lower, is difficult to realize industrial applications.Be subjected to the inspiration of chlorophyll structure, (Makromol.Chem. such as Inoue in 1978,1978,179 (5): 1377-1381) find that α, β, γ, δ-tetraphenyl methoxyl group porphyrin aluminium (TPP) AlX are a kind of brand-new catalyzer of CO2 and propylene oxide copolymerization.Have monodispersed characteristics by porphyrin aluminium system synthetic polycarbonate, but the content of carbonic acid ester bond is lower in the multipolymer.The preparation process complexity of porphyrin aluminium system, polymerization time is long, and (12～40d), the content of carbonic acid ester bond is lower in the multipolymer, and molecular weight is not high yet.Afterwards the research of this system was only limited to the exploration of catalytic mechanism, but the highly selective that the high-order stopband of porphyrin aluminium comes has good use for reference of planning to the development with rear catalyst.(CN 85104956) such as an aromatic plant metioned in ancient books in Shen utilize ternary RE metal catalyst Y (P204) 3-Al (i-Bu) 3-glycerine to realize the copolyreaction of CO2 and epoxy compounds.This catalyzer obtains the high-molecular weight polycarbonate, but the molecular weight distribution broad of polycarbonate.Salen metal catalyst (Acc.Chem.Res., 2004,37,836-844; J.Am.Chem.Soc., 2005,127,14026-14038) to the water and air temperature, catalytic efficiency is higher, and the polycarbonate molecular weight narrowly distributing for preparing is a kind of catalyzer that the industrial applications prospect is relatively arranged.At present, the main problem of traditional Salen metal catalyst is that the polycarbonate molecular weight that obtains of catalysis is low, and catalytic efficiency remains further to be improved, and some reaction time is also longer.Therefore, development of new high-level efficiency, Salen metal catalyst easy to operate, cheap and easy to get are the research directions of present carbon dioxide copolymerization catalyzer.
Summary of the invention
The purpose of this invention is to provide a kind of novel method for preparing polycarbonate, use ion liquid supported Salen metal composite to be catalyzer, by carbonic acid gas and epoxy compounds copolymerization polycarbonate.
Method with ion liquid supported Salen Preparation of Catalyst polycarbonate provided by the invention, with carbonic acid gas and epoxy compounds is raw material, with ion liquid supported Salen metal is catalyzer, at pressure carbon dioxide is 0.1～5.5MPa, temperature is under 20 ℃～150 ℃ temperature of reaction, and copolyreaction generates polycarbonate.
The structural formula of ion liquid supported Salen metal catalyst used in the present invention is as follows:
In the formula: R
1, R
2, R
3, R
4, R
5Be H, Me, Et, Pr or Bu; Metal ions M is Co
3+Or Cr
3+, negatively charged ion Y
-Be BF
4 -, PF
6 -, Cl
-, Br
-, F
-, NO
3 -Or CH
3COO
-
The mol ratio of epoxy compounds and ion liquid supported Salen metal catalyst can be in the variation range of a broad, usually between 10000: 1 to 100: 1, and preferably between 5000: 1 to 1000: 1 among the present invention.
Temperature of reaction of the present invention is between 20 ℃～150 ℃, and preferably between 50 ℃～100 ℃.
Pressure carbon dioxide is controlled at 0.1～5.5Mpa in of the present invention, and preferably between 3～4MPa.
Compare with traditional method, the used catalyzer of the present invention is very novel, and this ion liquid supported Salen catalyzer has following characteristic: 1) good thermostability is all very stable to water and air; 2) in water, has solvability preferably; 3) high catalytic activity (TOF＞1000); 4) polycarbonate for preparing has higher molecular weight (＞2 ten thousand); 5) the polycarbonate molecular weight narrowly distributing (between 1.1～1.3) for preparing.
Embodiment
Following enforcement will more comprehensively be described the present invention.
Embodiment 1
In the 200ml autoclave, add 80g cyclohexene oxide (CHO), ion liquid supported SalenCrCl catalyzer and the 1.5g promotor (Methylimidazole) of 0.5g.The logical nitrogen replacement in airtight back 2-3 time is rapidly heated and charges into CO
2To pressure be 2.5MPa.After reaction for some time (5h), fast cooling, relief pressure.Place 60 ℃ in vacuum dry down the multipolymer that obtains, the molecular weight of polymkeric substance and the employing Water150-C gel permeation chromatograph that distributes are measured, and tetrahydrofuran (THF) is a solvent, and massfraction is about 5 ‰, 35 ℃, flow velocity 0.8ml/mim, and 12 kinds of polystyrene standards are demarcated.Reaction polycarbonate selectivity is 98%, and TOF is 1020, and polymericular weight is 31200, and molecular weight distribution is 1.15.
Embodiment 2-5
Be similar to embodiment 1, polymeric reaction temperature is 60 ℃, and pressure carbon dioxide is to carry out under the condition of 3.5MPa, and the reaction times is 5h; Change the ratio of ion liquid supported catalysts and cyclohexene oxide, get following result (table one) after reaction finishes:
Table one ion liquid supported catalysts consumption is to the influence of CHO catalytic effect
Embodiment 6
Add 50g (1mol) propylene oxide (PO), ion liquid supported SalenCoCl catalyzer and the 1.5g promotor (Methylimidazole) of 0.5g.The logical nitrogen replacement in airtight back 2-3 time is rapidly heated and charges into CO
2To pressure 4MPa.After reaction for some time (5h), fast cooling, relief pressure.Place 60 ℃ in vacuum dry down the multipolymer that obtains.Reaction polycarbonate selectivity is 97%, and TOF is 1300, and polymericular weight is 31300, and molecular weight distribution is 1.15.
Embodiment 7-10
Be similar to embodiment 6, polymeric reaction temperature is 80 ℃, and pressure carbon dioxide is to carry out under the condition of 4MPa, and the reaction times is 5h; Change the ratio of ion liquid supported catalysts and propylene oxide, get following result (table two) after reaction finishes:
Table two ion liquid supported catalysts consumption is to the influence of PO catalytic effect
Claims (2)
1. method for preparing polycarbonate with ion liquid supported Salen metal catalyst, it is characterized in that with carbonic acid gas and epoxy compounds be raw material, with ion liquid supported Salen metal is that catalyzer carries out copolyreaction and prepares polycarbonate, the mol ratio of described epoxy compounds and ion liquid supported Salen metal catalyst is between 10000: 1 to 100: 1, pressure carbon dioxide is 3～4MPa, and temperature of reaction is 50 ℃～100 ℃; The structural formula of described ion liquid supported Salen metal catalyst is as follows:
In the formula: R
1, R
2, R
3, R
4, R
5Be H, Me, Et, Pr or Bu; Metal ions M is Co
3+Or Cr
3+, negatively charged ion Y
-Be BF
4 -, PF
6 -, Cl
-, Br
-, F
-, NO
3 -Or CH
3COO
-
2. the ion liquid supported Salen metal catalyst of usefulness according to claim 1 prepares the method for polycarbonate, it is characterized in that the epoxy compounds with carbonic acid gas generation copolyreaction is cyclohexene oxide, propylene oxide or oxyethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100630034A CN101328264B (en) | 2008-07-10 | 2008-07-10 | Process for producing polycarbonate using ion liquid supported catalysts |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100630034A CN101328264B (en) | 2008-07-10 | 2008-07-10 | Process for producing polycarbonate using ion liquid supported catalysts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101328264A CN101328264A (en) | 2008-12-24 |
| CN101328264B true CN101328264B (en) | 2010-12-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100630034A Expired - Fee Related CN101328264B (en) | 2008-07-10 | 2008-07-10 | Process for producing polycarbonate using ion liquid supported catalysts |
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| Country | Link |
|---|---|
| CN (1) | CN101328264B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9598603B2 (en) * | 2011-11-23 | 2017-03-21 | Sk Innovation Co., Ltd. | Resin composition for high barrier paper-coating |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103395769B (en) * | 2013-07-31 | 2015-09-30 | 浙江大学 | A kind of porous carbon preparation method for material based on ion thermal process |
| CN103936976B (en) * | 2014-04-25 | 2015-09-30 | 新疆康润洁环保科技有限公司 | A kind of ionic liquid is as the method for catalyst preparing polycarbonate |
| CN105949451B (en) * | 2016-07-14 | 2017-10-20 | 中国科学院过程工程研究所 | A kind of method of alkali ionic liquid catalyzed preparation of poly carbonic ester |
| CN116410455B (en) * | 2023-03-03 | 2023-11-14 | 天津工业大学 | Method for preparing polyester by copolymerization of carbon dioxide and epoxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1257885A (en) * | 1998-12-24 | 2000-06-28 | 中国科学院长春应用化学研究所 | Process for preparing high-molecular aliphatic polycarbonate |
| CN1343198A (en) * | 1999-03-08 | 2002-04-03 | 西巴特殊化学品控股有限公司 | Manganese complexes of salen ligands and the use thereof |
| CN1463272A (en) * | 2001-06-27 | 2003-12-24 | 尔艾斯特公司 | Chiral salen catalyst and methods for prepn. of chirol compounds from racemic epoxides by using new catalyst |
-
2008
- 2008-07-10 CN CN2008100630034A patent/CN101328264B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1257885A (en) * | 1998-12-24 | 2000-06-28 | 中国科学院长春应用化学研究所 | Process for preparing high-molecular aliphatic polycarbonate |
| CN1343198A (en) * | 1999-03-08 | 2002-04-03 | 西巴特殊化学品控股有限公司 | Manganese complexes of salen ligands and the use thereof |
| CN1463272A (en) * | 2001-06-27 | 2003-12-24 | 尔艾斯特公司 | Chiral salen catalyst and methods for prepn. of chirol compounds from racemic epoxides by using new catalyst |
Non-Patent Citations (2)
| Title |
|---|
| JP特开平7-145157A 1995.06.06 |
| Y.Peng et al..Ionic Liquid-Grafted Mn(III)-Shiff Based Complex:A Highly Efficient and Recyclable Catalyst for the Epoxidation of Chalcones.《SYNLETT》.2005,(第14期),2147-2150. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9598603B2 (en) * | 2011-11-23 | 2017-03-21 | Sk Innovation Co., Ltd. | Resin composition for high barrier paper-coating |
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| Publication number | Publication date |
|---|---|
| CN101328264A (en) | 2008-12-24 |
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Granted publication date: 20101215 Termination date: 20120710 |