CN114181259B - Amino bisphenol tetradentate chromium (III) catalyst, preparation and application thereof - Google Patents
Amino bisphenol tetradentate chromium (III) catalyst, preparation and application thereof Download PDFInfo
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- -1 Amino bisphenol Chemical compound 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 229930185605 Bisphenol Natural products 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 6
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 title description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 32
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 27
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003446 ligand Substances 0.000 claims abstract description 20
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 14
- 239000011651 chromium Substances 0.000 claims abstract description 14
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 11
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims abstract description 10
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000007334 copolymerization reaction Methods 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 3
- 238000000034 method Methods 0.000 claims 2
- 239000002243 precursor Substances 0.000 claims 2
- 150000002989 phenols Chemical class 0.000 claims 1
- 230000001172 regenerating effect Effects 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- 239000002184 metal Substances 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 229920000515 polycarbonate Polymers 0.000 abstract description 6
- 239000004417 polycarbonate Substances 0.000 abstract description 6
- 150000004696 coordination complex Chemical class 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000012648 alternating copolymerization Methods 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract 2
- BGULNPVMQAPGLT-UHFFFAOYSA-N [Cl-].[NH4+].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [Cl-].[NH4+].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 BGULNPVMQAPGLT-UHFFFAOYSA-N 0.000 abstract 1
- SZHOPTPKIFXNFC-UHFFFAOYSA-O [N-]=[N+]=[N-].[NH4+].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [N-]=[N+]=[N-].[NH4+].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 SZHOPTPKIFXNFC-UHFFFAOYSA-O 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 239000002815 homogeneous catalyst Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 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 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QSAWJEQJMOVOJI-UHFFFAOYSA-N [Cl-].[NH4+].C1(=CC=CC=C1)[PH2](C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)[PH2](C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [Cl-].[NH4+].C1(=CC=CC=C1)[PH2](C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)[PH2](C1=CC=CC=C1)C1=CC=CC=C1 QSAWJEQJMOVOJI-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000379 polypropylene carbonate Polymers 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 235000007831 chromium(III) chloride Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
-
- 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
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses an amino bisphenol tetradentate ligand trivalent metal chromium complex catalyst, and preparation and application thereof, wherein the complex has the following structural general formula:
Description
Technical Field
The invention relates to the technical field of metal organic complex homogeneous catalysts, in particular to an amino bisphenol tetradentate ligand trivalent metal chromium complex and a catalytic copolymerization reaction of carbon dioxide and propylene oxide.
Technical Field
The rapid development of industry and the increasing social activities of human beings have caused a large amount of emission of greenhouse gases such as carbon dioxide, and the like, thereby causing the 'greenhouse effect' and acidification of seawater, and causing serious influence on the living environment of human beings and other organisms on the earth. Carbon dioxide is a nontoxic, inexpensive, renewable carbon-resource, and how to effectively utilize carbon dioxide is a current research hotspot. The copolymerization of carbon dioxide with alkylene oxide to form environmentally friendly polymeric materials has been of great interest, especially the alternating copolymerization of carbon dioxide with propylene oxide to form polypropylene carbonate. The polypropylene carbonate can be used as a completely degradable plastic, and can replace traditional plastics such as food packaging materials, disposable medical materials, foaming packaging materials, agricultural films and the like in a plurality of fields. The preparation of the environment-friendly material by taking carbon dioxide as the raw material has important significance in terms of relieving the greenhouse effect and reducing the white pollution.
The catalyst is the key for realizing the copolymerization of carbon dioxide and alkylene oxide. The Japanese scientist Inoue in 1969 has for the first time found that a mixture of ZnEt2 with water can catalyze the copolymerization of carbon dioxide with propylene oxide, after which other heterogeneous catalysts have been developed successively, such as ternary catalytic systems of rare earth metal salts, zinc carboxylate systems and double metal cyanides. These heterogeneous catalytic systems have the characteristics of simple synthesis, insensitivity to air and water, better economical efficiency, easy industrialization, etc., but have many disadvantages. Firstly, the catalyst has lower activity, longer polymerization time and more severe polymerization conditions, so that the industrialized cost is higher; secondly, because the active sites of the heterogeneous catalyst are not uniform, the molecular weight distribution of the generated polymer is wider, and the control of further processing conditions and the product performance are affected; finally, the catalytic mechanism is not yet defined, and presents great difficulty in systematically modifying catalyst activity.
Homogeneous catalysts have significant advantages in terms of product selectivity and use as a model for reaction mechanism studies due to the single active center. Thus, current reports on the copolymerization of carbon dioxide with alkylene oxides have focused mainly on homogeneous catalytic systems. Through half a century of research, various homogeneous catalytic systems have been developed, mainly including metalloporphyrins, metal Salen-like, beta-diimine zinc-like complexes and macrocyclic ligand dinuclear metal complexes, wherein the metal Salen-like is the most studied type of catalyst system due to the easy synthesis and modification of the ligand. The metal Salen system generally requires an organic base or quaternary ammonium salt as a cocatalyst to exhibit superior catalytic activity, and one reaction mechanism that is generally accepted is that Salen metal center activates alkylene oxide as a Lewis acid, the axial ligand X in the cocatalyst or Salen complex undergoes ring opening to form alkoxide, carbon dioxide is then intercalated to form an active carbonate intermediate, this active intermediate acts as an initiator to open the other activated alkylene oxide, followed by intercalation of carbon dioxide to regenerate the active carbonate intermediate, and then the polymerization process is continued. Through optimization of reaction conditions (reaction temperature and pressure), selection of a catalyst and ligand modification, the homogeneous catalytic systems can realize efficient and alternative copolymerization of carbon dioxide and cyclohexene oxide under certain reaction conditions, the alternation degree reaches 99 percent, and the molecular weight distribution of the generated polymer is narrower. However, the homogeneous catalyst has the characteristics of complex synthetic route, air sensitivity, difficult treatment and the like, and limits the industrial application thereof. Further development of catalysts for different catalytic systems is still necessary.
The amino bisphenol tetradentate ligand is an organic ligand which is easy to synthesize and modify, and the amino bisphenol tetradentate ligand is widely reported to be used for olefin polymerization by being matched with transition metal titanium, and can catalyze the ring-opening propylene glycolide polymerization by being matched with rare earth metal. Such metal complexes are related to but distinguished from metal Salen complexes in terms of steric structure and electronic effects. The nitrogen atom in the amino bisphenol tetradentate ligand is sp3 hybridized, has stronger electron donating effect, and the side chain group can be changed. Second, the amino bisphenol ligand is not planar in structure with the metal coordination. The amino bisphenol tetradentate metal complex is a high-efficiency catalyst for copolymerization of carbon dioxide and alkylene oxide, and can be used for alternately copolymerizing propylene oxide, cyclohexene oxide and carbon dioxide to generate polycarbonate.
Disclosure of Invention
The invention discloses an amino bisphenol tetradentate trivalent metal chromium complex with diethylamine as a side chain. The trivalent chromium complex is a high-efficiency catalyst for copolymerization of carbon dioxide and alkylene oxide, and can be used for alternately copolymerizing cyclohexene oxide, propylene oxide and carbon dioxide to generate polycarbonate. The prepared polycarbonate has high molecular weight and narrow distribution, and the alternation degree reaches 98 percent. The mass ratio of the catalyst to the propylene oxide amounted to 1/1000. In addition, the amino bisphenol tetradentate trivalent metal chromium complex disclosed by the invention can be regenerated through tetrahydrofuran solvent after being placed in the air for a long time for deterioration, and the regenerated catalyst activity is consistent with that of the original catalyst.
The specific technical scheme is as follows:
1. an amino bisphenol tetradentate trivalent chromium metal complex having the following structure:
Wherein R 1 is tert-butyl, tert-amyl; r2 is methyl or tert-butyl.
2. The preparation of the amino bisphenol tetradentate ligand is characterized in that: phenol, polyoxymethylene, diamine were refluxed in water overnight, and the solid was dissolved in chloroform and precipitated with methanol.
3. The preparation method of the amino bisphenol tetradentate trivalent chromium metal complex is characterized in that a ligand, tetrahydrofuran and 1.1 equivalent of sodium hydride are sequentially added into a flask under the protection of nitrogen at the temperature of minus 78 ℃ and stirred for 5min, and the mixture is stirred for 1h after naturally heating to normal temperature. The reaction solution was slowly added to a flask containing CrCl 3(THF)3 under nitrogen atmosphere, stirred for 12 hours, the solvent was removed under reduced pressure, the product was extracted with toluene, filtered through celite, and the solvent in the filtrate was removed under reduced pressure to obtain the objective product.
4. A regeneration method of an amino bisphenol tetradentate trivalent chromium complex is characterized in that: dissolving the metal complex which is placed in the air for a long time in tetrahydrofuran solvent, stirring for 30min, and removing the solvent by decompression to obtain the regenerated amino bisphenol tetradentate trivalent chromium complex.
5. An application of an amino bisphenol tetradentate trivalent chromium complex is characterized in that: the amino bisphenol tetradentate trivalent chromium complex is used as a catalyst, and bis (triphenyl phosphorane) ammonium chloride, bis (triphenyl phosphorane) ammonium azide or PPNO is used as a cocatalyst, so that the amino bisphenol tetradentate trivalent chromium complex can be used for catalyzing carbon dioxide and cyclohexene oxide to be copolymerized alternately; wherein the molar ratio of the catalyst to the epoxycyclohexane is 1: 500-1000, the mol ratio of the catalyst to the cocatalyst is 1:1, a step of; the reaction conditions during the copolymerization are the normal temperature of 60 ℃ and the carbon dioxide pressure of 40 MPa.
6. An application of an amino bisphenol tetradentate trivalent chromium complex is characterized in that: the amino bisphenol tetradentate trivalent chromium complex is used as a catalyst, and bis (triphenyl phosphorane) ammonium chloride, bis (triphenyl phosphorane) ammonium azide or PPNO is used as a cocatalyst, so that the amino bisphenol tetradentate trivalent chromium complex can be used for catalyzing copolymerization of carbon dioxide and propylene oxide; wherein the molar ratio of the catalyst to the propylene oxide is 1: 500-1000, the mol ratio of the catalyst to the cocatalyst is 1:1, a step of; the reaction conditions during the copolymerization are the normal temperature of 25 ℃ and the carbon dioxide pressure of 40 MPa.
Compared with the existing catalytic technology, the invention has the following beneficial effects:
compared with the common heterogeneous catalyst, the catalyst system provided by the invention has higher catalytic activity, and the prepared carbon dioxide-based polycarbonate has narrower molecular weight distribution.
After long-term placement in the air, the homogeneous catalyst can be regenerated through tetrahydrofuran, thereby indirectly overcoming the defects that the existing homogeneous catalyst is easy to be deactivated and difficult to preserve, and having good industrial application prospect.
Detailed Description
The invention will be further illustrated with reference to examples, but the scope of the invention is not limited to the examples.
Example 1.
Ligand 1 (3.50 g,6.67 mmol), naH (0.16 g,6.67 mmol) and tetrahydrofuran (50 mL) are sequentially added into a Schlenk flask under the nitrogen atmosphere at-78 ℃, the mixture is naturally warmed to room temperature and then reacted for 2h, the reaction solution is slowly added into the Schlenk flask containing CrCl 3(THF)3 (2.50 g,6.67 mmol) under the nitrogen atmosphere, the reaction is carried out for 12h at normal temperature, tetrahydrofuran solvent is removed by a vacuum pump after the reaction, toluene is used for extraction, diatomite is used for filtration, the solvent of filtrate is removed by a vacuum pump, pentane is used for washing, and drying is carried out to obtain the target product 4.33g(95％).Anal.Calcd.for C40H66ClCrN2O3:C,67.63;H,9.36;N, 3.94.Found:C,67.21;H,8.96;N,3.64.
Example 2.
Ligand H2[ L1] (3.50 g,6.33 mmol), naH (0.16 g,6.67 mmol) and tetrahydrofuran (50 mL) are sequentially added into a Schlenk flask under the nitrogen atmosphere of minus 78 ℃, the mixture is naturally warmed to room temperature and then reacted for 2 hours, the reaction solution is slowly added into the Schlenk flask containing CrCl3 (THF) 3 (2.50 g,6.67 mmol) under the nitrogen atmosphere, the reaction is carried out for 12 hours at normal temperature, tetrahydrofuran solvent after the reaction is removed by a vacuum pump, then toluene is used for extraction, diatomite is used for filtration, the solvent of filtrate is removed by a vacuum pump, and then pentane is used for washing and drying to obtain the target product 4.23g(94％).Anal.Calcd.for C34H54ClCrN2O3(0.3C7H8):C, 65.21;H,8.69;N,4.47.Found:C,64.91;H,8.39;N,4.27.：
Example 3.
Ligand H 2 [ L1] (3.50 g,6.33 mmol), naH (0.16 g,6.67 mmol) and tetrahydrofuran (50 mL) were sequentially added into a Schlenk flask under nitrogen atmosphere at-78deg.C, naturally warmed to room temperature and then reacted for 2 hours, the reaction solution was slowly added into a Schlenk flask containing CrCl 3 (THF) 3 (2.50 g,6.67 mmol) under nitrogen atmosphere, reacted for 12 hours at room temperature, tetrahydrofuran solvent was removed by vacuum pump after the reaction, extracted by toluene, filtered by celite, the solvent was removed by vacuum pump, washed with pentane and dried to obtain the target product 4.23g(94％).Anal.Calcd.for C42H70ClCrN2O3(0.5C7H8): C,68.31;H,9.55;N,3.79.Found:C,68.01;H,9.24;N,3.48.
Example 4.
The complex (example 1) was changed from purple to grey when exposed to air for 3 months, 1.00g of the modified complex was dissolved in 10mL of tetrahydrofuran, and after stirring for 30min under nitrogen, the tetrahydrofuran solvent was removed under reduced pressure to give 1.08g of regenerated product .Anal.Calcd.for C40H66ClCrN2O3(0.3C4H8O):C,67.63;H,9.36;N,3.94.Found:C, 67.31;H,9.01;N,3.74.
Example 5.
Vacuum drying the high-pressure reaction kettle at 80 ℃ for 24 hours in advance, cooling to room temperature, adding a catalyst, stirring a cocatalyst and alkylene oxide (cyclohexene oxide or propylene oxide) for 30 minutes, heating to a specified temperature, pressurizing to 4Mpa, reacting for 24 hours (reaction parameters are shown in tables 1-5, wherein the reaction parameters are shown in tables 1-3, carbon dioxide is copolymerized with the cyclohexene oxide, and the reaction parameters are shown in tables 4-5, carbon dioxide and propylene oxide are copolymerized), releasing carbon dioxide in the kettle, extracting solid by methylene dichloride, precipitating by methanol containing 5wt% of dilute hydrochloric acid, washing by methanol containing 5wt% of dilute hydrochloric acid for three times, and vacuum drying the obtained solid at 120 ℃ for 24 hours to obtain a white target product.
Table 1. Reaction conditions: 60 ℃,40MPa CO 2, 24 hours.
Table 2. Reaction conditions: 60 ℃,40MPa CO 2, 24 hours.
Table 3. Reaction conditions: 60 ℃,40MPa CO 2, 24 hours.
Table 4. Reaction conditions: 25 ℃,40MPa CO 2, 24h.
Table 5. Reaction conditions: 25 ℃,40MPa CO 2, 24h.
Drawings
FIG. 1 is a graph of ultraviolet visible absorption spectra.
Claims (5)
1. An amino bisphenol tetradentate trivalent chromium metal complex having the following structure:
R1 is tert-amyl; r2 is tert-butyl.
2. The method for preparing an amino bisphenol tetradentate trivalent chromium metal complex according to claim 1, comprising the following steps: ⑴ Water is used as a solvent, and substituted phenol, formaldehyde and diamine react to prepare an amino bisphenol tetradentate ligand; ⑵ Stirring the ligand and sodium hydride in tetrahydrofuran for five minutes under the condition of nitrogen and minus 78 ℃, naturally heating to normal temperature, and reacting for one hour to prepare a ligand precursor; ⑶ Stirring the ligand precursor and CrCl 3(THF)3 in tetrahydrofuran for five minutes at the temperature of minus 78 ℃ under the condition of nitrogen, naturally heating to normal temperature, stirring for 18 hours, then removing the solvent under reduced pressure, extracting toluene, filtering by diatomite, removing the solvent in the filtrate under reduced pressure, washing the solid with hexane, and carrying out suction filtration and drying to obtain the target product.
3. A method for regenerating an amino bisphenol tetradentate trivalent chromium metal complex according to claim 1, wherein the amino bisphenol tetradentate chromium complex which is long-contacted with air is dissolved in a tetrahydrofuran solvent, stirred for 0.5 hours in a nitrogen atmosphere, and the tetrahydrofuran solvent is removed by decompression, thereby obtaining the regenerated amino bisphenol tetradentate trivalent chromium metal complex according to claim 1.
4. Use of an aminobisphenol tetradentate trivalent chromium metal complex according to claim 1, characterized in that the aminobisphenol tetradentate trivalent chromium metal complex is used as a catalyst and PPNCl, PPNN3, PPNO are used as cocatalysts, which can be used for catalyzing the copolymerization of carbon dioxide and cyclohexene oxide; the molar ratio of the catalyst to the epoxycyclohexane is 1: 500-1000, the mol ratio of the catalyst to the cocatalyst is 1:1, a step of; the reaction conditions during the copolymerization are 60 ℃ and 4MPa of carbon dioxide pressure.
5. Use of an aminobisphenol tetradentate trivalent chromium metal complex according to claim 1, characterized in that the aminobisphenol tetradentate trivalent chromium metal complex is used as a catalyst and PPNCl, PPNN3, PPNO are used as cocatalysts for catalyzing the copolymerization of carbon dioxide and alkylene oxide; wherein the molar ratio of the catalyst to the propylene oxide is 1: 500-1000, the mol ratio of the catalyst to the cocatalyst is 1:1, a step of; the reaction conditions during the copolymerization are the normal temperature of 25 ℃ and the carbon dioxide pressure of 4 MPa.
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| Amine Bis(phenolate) Zirconium Complexes: Influence of Ligand Structure and Cocatalyst on Copolymerization Behavior;Sarah E. Reybuck等;Macromolecules;第38卷;2552-2558 * |
| Kaijie Ni等.Kinetic Studies of Copolymerization of Cyclohexene Oxide with CO2 by a Diamino-bis(phenolate) Chromium(III) Complex.Inorg. Chem..2018,第57卷3097−3106. * |
| Kinetic Studies of Copolymerization of Cyclohexene Oxide with CO2 by a Diamino-bis(phenolate) Chromium(III) Complex;Kaijie Ni等;Inorg. Chem.;第57卷;3097−3106 * |
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