CN1189246C - High activity catalyzer utilized to synthesize cyclic carbonate - Google Patents
High activity catalyzer utilized to synthesize cyclic carbonate Download PDFInfo
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- CN1189246C CN1189246C CNB021446407A CN02144640A CN1189246C CN 1189246 C CN1189246 C CN 1189246C CN B021446407 A CNB021446407 A CN B021446407A CN 02144640 A CN02144640 A CN 02144640A CN 1189246 C CN1189246 C CN 1189246C
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- promotor
- catalyst
- annular carbonate
- synthesizing annular
- schiff base
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Links
- 150000005676 cyclic carbonates Chemical class 0.000 title abstract description 7
- 230000000694 effects Effects 0.000 title abstract 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 16
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 14
- 239000004593 Epoxy Substances 0.000 claims abstract description 12
- 239000002262 Schiff base Substances 0.000 claims abstract description 12
- 150000003839 salts Chemical group 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 18
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 235000011089 carbon dioxide Nutrition 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 9
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 7
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 5
- 150000003863 ammonium salts Chemical group 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- IKWKJIWDLVYZIY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;bromide Chemical group [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 IKWKJIWDLVYZIY-UHFFFAOYSA-M 0.000 claims description 2
- MFIUDWFSVDFDDY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 MFIUDWFSVDFDDY-UHFFFAOYSA-M 0.000 claims description 2
- RQNCKGZETNCAMA-UHFFFAOYSA-M butyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 RQNCKGZETNCAMA-UHFFFAOYSA-M 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- JNMIXMFEVJHFNY-UHFFFAOYSA-M methyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 JNMIXMFEVJHFNY-UHFFFAOYSA-M 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 2
- GKXDJYKZFZVASJ-UHFFFAOYSA-M tetrapropylazanium;iodide Chemical compound [I-].CCC[N+](CCC)(CCC)CCC GKXDJYKZFZVASJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 abstract description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 238000006352 cycloaddition reaction Methods 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000004417 polycarbonate Substances 0.000 abstract description 3
- 229920000515 polycarbonate Polymers 0.000 abstract description 3
- 229920000570 polyether Polymers 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 2
- 150000001450 anions Chemical group 0.000 abstract 2
- 239000004721 Polyphenylene oxide Substances 0.000 abstract 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 239000007809 chemical reaction catalyst Substances 0.000 abstract 1
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 13
- 230000009466 transformation Effects 0.000 description 10
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical class CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- -1 arsine halide salt Chemical class 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- PONXTPCRRASWKW-UHFFFAOYSA-N 1,2-diphenylethane-1,2-diamine Chemical compound C=1C=CC=CC=1C(N)C(N)C1=CC=CC=C1 PONXTPCRRASWKW-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- IVMXIWBXHLIKBO-UHFFFAOYSA-N C(O)(O)=O.ClC=CC Chemical class C(O)(O)=O.ClC=CC IVMXIWBXHLIKBO-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- NKAAEMMYHLFEFN-UHFFFAOYSA-M monosodium tartrate Chemical compound [Na+].OC(=O)C(O)C(O)C([O-])=O NKAAEMMYHLFEFN-UHFFFAOYSA-M 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- REPWBKQJAMXHFL-UHFFFAOYSA-N phenylphosphane;hydrobromide Chemical class [Br-].[PH3+]C1=CC=CC=C1 REPWBKQJAMXHFL-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention provides a catalyst with high activity for synthesizing cyclic carbonate, and relates to a cycloaddition reaction catalyst, particularly to a catalyst with high activity for epoxyalkane and carbon dioxide to react and synthesize cyclic carbonate. Main catalyst is quadridentate Schiff base aluminum complex (R1) (R2) SalenMX, wherein M is metal ion; R1 and R2 are groups of H, alkyl groups and alkoxy groups with 1 to 6 carbon atoms, Cl, Br, NO2, etc; R3 and R4 are-(CH2) 4-, H, CH3, Ph and-(CH) 4-; X is anion. A cocatalyst is salt with a chemical formula of R<1>R<2>3XX<1>, wherein R<1> and R<2> are hydrocarbyl; X is an element of the fifth main group; X<1> is univalent anion. The molar ratio of the cocatalyst to the quadridentate Schiff base aluminum complex of the main catalyst is 0.2: 1 to 5: 1. The bi-component catalyst can catalyze an epoxy compound and the carbon dioxide to react with high efficiency to synthesize cyclic carbonate under the moderate condition, and have no by-products of polycarbonate, polyether, etc.
Description
Technical field
The present invention relates to the cycloaddition reaction catalyzer, particularly a kind of be used for epoxy alkane by with the high activated catalyst of carbon dioxide reaction synthesizing annular carbonate.
Background technology
In US 43 14945, McMullen has described with tetraalkyl quaternary ammonium salt catalysis epoxy alkane and carbon dioxide reaction synthesizing annular carbonate.
Sachs and Harvey have described in US 4786741 and US 4841072 respectively and be used for catalysis carbonic acid gas and oxyethane cycloaddition reaction De quaternary alkylphosphonium salt catalyzer under 2.5-20MPa pressure.In US 4931571, Weinstein described with season the arsine halide salt be catalyzer catalysis carbonic acid gas and reacting ethylene oxide synthesizing ethylene carbonate in 90-200 ℃ of scope.
Kisch (Chem.Ber., 1986,119,1090-1094; 1990,123,277-283) reported the dual-function catalyst of forming by ZnCl2 and high density quaternary ammonium salt Huo quaternary alkylphosphonium salt.
In CN 1343668, Deng You has described entirely and has used by nitrogen-containing heterocycle compound halogenated alkyl pyridine or halogenation 1, the ionic liquid that is liquid state under the room temperature that 3-dialkylimidazolium and non-metallic halide constitute is a catalyzer, alkali metal halide or Tetrabutyl amonium bromide are as the promotor of reaction, is 1.5-4.5MPa at 100-140 ℃ with the carbonic acid gas original pressure, catalyst levels is under the 0.2-2.5mol% condition of epoxy compounds amount, through reaction in 4-8 hour epoxy compounds is transformed into corresponding cyclic carbonate.
Utilize the catalyzer of foregoing description, often need be in the presence of high temperature, high pressure and high concentration catalyst catalysis epoxy alkane and the synthetic corresponding cyclic carbonate of carbon dioxide reaction effectively.
Generate in the process of cyclic carbonate at epoxy alkane and carbon dioxide reaction, often be attended by the generation of by products such as polycarbonate and polyethers simultaneously, especially under low temperature, low pressure condition.
Summary of the invention
Purpose of the present invention just provides a kind of high activated catalyst that is used for synthesizing annular carbonate that cycloaddition reaction is had high reactivity, highly selective under gentle conditions such as low temperature, low pressure.
Technical solution of the present invention is that the high activated catalyst that is used for synthesizing annular carbonate is made up of Primary Catalysts and promotor.Primary Catalysts is tetradentate schiff base metal complexes (R
1) (R
2) SalenMX, its structural formula is:
Wherein, M is Al (III) or Cr (III).
R
1, R
2Be-H, 1-6 carbon alkyl, alkoxyl group ,-Cl ,-Br or-NO
2Group; R
3, R
4For-(CH
2)
4-, H, CH
3Or Ph ,-(CH)
4-; X is Cl
-, Br
-, I
-, CH
3O
-, CH
3CH
2O
-, NO
3 -, CH
3COO
-, ClO
4 -, BF
4 -Or BPh
4 -Negative ion.
Promotor is that chemical formula is R
1R
2 3NX
1Quaternary ammonium salt or chemical formula be R
1R
2 3PX
1The De quaternary alkylphosphonium salt, R in the formula
1, R
2Be alkyl, X
1Be the monovalence negative ion.
The mol ratio of promotor and Primary Catalysts tetradentate schiff base metal complexes is 0.2: 1 to 5: 1.
Promotor is that chemical formula is R
1R
2 3NX
1Quaternary ammonium salt, R in the formula
1Be 1-16 carbon alkyl, R
2Be 1-6 carbon alkyl, X
1Be Cl
-, Br
-, I
-, NO
3 -, CH
3COO
-, ClO
4 -, BF
4 -Or BPh
4 -Negative ion.
Promotor is that chemical formula is R
1R
2 3PX
1The De quaternary alkylphosphonium salt, R in the formula
1Be 1-16 carbon alkyl, R
2Be 1-6 carbon alkyl or phenyl, X
1Be Cl
-, Br
-, I
-, NO
3 -, CH
3COO
-, ClO
4 -, BF
4 -Or BPh
4 -Negative ion.
The mol ratio of promotor and Primary Catalysts tetradentate schiff base metal complexes is 0.2: 1 to 5: 1.
In the Primary Catalysts, be to react the tetradentate schiff base part that obtains by salicylic aldehyde homologue and diamine compounds with metallic ion coordination.
The contained substituting group of salicylic aldehyde homologue be the tertiary butyl ,-OCH
3,-Cl ,-Br or-NO
2Group.
Diamine compounds is a quadrol, 1,2-propylene diamine, O-Phenylene Diamine, cyclohexanediamine or 1,2-diphenyl ethylene diamine.
The metal ion that forms title complex with the tetradentate schiff base part is Al (III) or Cr (III).
Axial ligand X is Cl
-, Br
-, I
-, CH
3O
-, CH
3CH
2O
-, NO
3 -, CH
3COO
-, ClO
4 -, BF
4 -Or BPh
4 -Negative ion.
These metal complexess are easy to synthesize, and yield is very high, synthesize and can consult (S.J.Dzugan, V.L.Goedken, Inorg.Chem.1986,25,2858 and D.A.Atwood, J.A.Jegier, D.Rutherford, Inorg.Chem.1996,35,63, and L.E.Martinez, E.N.Jacobsen, et al., J.Am.Chem.Soc., document such as 1995,117,5897).
Quaternary ammonium salt is the tetraalkyl ammonium halide.
The tetraalkyl ammonium halide is Tetrabutyl amonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, tetrapropyl ammonium iodide, tetraethylammonium bromide, etamon chloride.
Quaternary alkylphosphonium salt is the tetraalkyl phosphonium halide.
The tetraalkyl phosphonium halide is butyl triphenyl phosphonium bromide, butyl triphenyl phosphonium iodide, butyl triphenyl phosphonium chloride, ethyl triphenyl phosphonium bromide, methyl triphenyl phosphonium iodide.
The mol ratio of promotor and tetradentate schiff base metal complexes is 0.2: 1 to 5: 1.
In carbonic acid gas and the reaction of epoxy alkane synthesizing annular carbonate, temperature is 15-120 ℃, feed the carbonic acid gas constant voltage and be controlled at 0.1-6MPa, the mol ratio of tetradentate schiff base metal complexes and epoxy alkane is 1: 200 to 1: 10000, and the mol ratio of promotor and tetradentate schiff base metal complexes is 0.2: 1 to 5: 1.
Embodiment
The present invention is further illustrated below in conjunction with embodiment,
Embodiment 1
In effective volume is to add in the following order under envrionment temperature in the stainless steel autoclave of 200ml: 0.5 * 10
-3The mole tetrabutylammonium iodide, 0.5 * 10
-3Mole SalenAlCl (R
1=R
2=R
3=R
4=H), under carbon-dioxide protecting, add 0.25 mole of propylene oxide then with syringe.
Temperature is controlled at 25 ℃, in autoclave, adds carbonic acid gas simultaneously so that keep the 0.7MPa constant pressure.
Reaction stopped logical carbonic acid gas after 10 hours under magnetic stirs, and slowly bled off unreacted carbonic acid gas and epoxy alkane in the autoclave.
Underpressure distillation go out 24.4 the gram propylene carbonates, its purity is higher than 99.5%, residue through FTIR and
1H,
13C-NMR analyzes and does not see by products such as polycarbonate and polyethers.Loss when considering distillation, the transformation efficiency of propylene oxide should be higher than 98%.
Embodiment 2
With embodiment 1 in the same equipment that uses, under the same conditions, just replace propylene oxide with oxyethane.After 7 hours, obtain 21 gram NSC 11801 25 ℃ of reactions, the transformation efficiency of oxyethane is higher than 95%.
Embodiment 3
With embodiment 1 in the same equipment that uses, under the same conditions, just replace tetrabutylammonium iodide with normal-butyl three phenyl phosphonium bromides.After 12 hours, obtain 25.2 gram propylene carbonates 25 ℃ of reactions, the transformation efficiency of propylene oxide is 99%.
Embodiment 4
With embodiment 1 in the same equipment that uses, under the same conditions, just with (t-Bu) SalenAlCl (R
1=t-Bu, R
2=R
3=R
4=H) replace SalenAlCl (R
1=R
2=R
3=R
4=H).After 11 hours, obtain 25 gram propylene carbonates 25 ℃ of reactions, the transformation efficiency of propylene oxide is 98%.
Embodiment 5
In effective volume is to add in the following order under envrionment temperature in the stainless steel autoclave of 200ml: 0.5 * 10
-3The mole tetra-n-butyl ammonium bromide, 0.5 * 10
-3Mole SalenAlCl (R
1=R
2=R
3=R
4=H), under carbon-dioxide protecting, add 0.25 mole of propylene oxide then with syringe.
At this moment temperature is raised to 45 ℃, in autoclave, adds carbonic acid gas simultaneously so that keep the 0.8MPa constant pressure.Reaction obtained 25.3 gram propylene carbonates after 6 hours under magnetic stirs, and the transformation efficiency of propylene oxide is 99%.
Embodiment 6
In effective volume is to add in the following order under envrionment temperature in the stainless steel autoclave of 200ml: 0.25 * 10
-3The mole tetrabutylammonium iodide, 0.25 * 10
-3Mole SalenAlCl (R
1=R
2=R
3=R
4=H), under carbon-dioxide protecting, add 0.25 mole of propylene oxide then with syringe.
At this moment oil bath temperature is raised to 110 ℃, in autoclave, adds carbonic acid gas simultaneously so that keep the 2.0MPa constant pressure.Reaction obtained 25.2 gram propylene carbonates after 1 hour under magnetic stirs, and the transformation efficiency of propylene oxide is 98%.
Embodiment 7
With embodiment 6 in the same equipment that uses, under the same conditions, just replace propylene oxide with epoxy chloropropane.Reaction obtained 33 gram carbonic acid propenyl chloride esters after 3 hours under 110 ℃ and 2.0MPa carbonic acid gas constant pressure, and the transformation efficiency of epoxy chloropropane is 97%.
Embodiment 8
With embodiment 6 in the same equipment that uses, under the same conditions, just with (t-Bu)
2SalenCrCl (R
1=R
2=t-Bu, R
3=R
4=H) replace SalenAlCl.After 1 hour, obtain 24.6 gram propylene carbonates 110 ℃ of reactions, the transformation efficiency of propylene oxide is 96%.
Embodiment 9
With embodiment 6 in the same equipment that uses, under the same conditions, just with (t-Bu)
2SalenCrCl (R
1=R
2=t-Bu, R
3And R
4For-(CH
2)
4-) replacement SalenAlCl.After 1 hour, obtain 25.3 gram propylene carbonates 110 ℃ of reactions, the transformation efficiency of propylene oxide is 99%.
Embodiment 10
With embodiment 6 in the same equipment that uses, under the same conditions, just with (t-Bu)
2SalenCrCl (R
1=R
2=t-Bu, R
3=R
4=Ph) replace SalenAlCl.After 1 hour, obtain 25 gram propylene carbonates 110 ℃ of reactions, the transformation efficiency of propylene oxide is 98%.
Claims (7)
1. be used for the high activated catalyst of synthesizing annular carbonate, it is characterized in that, form by Primary Catalysts and promotor,
Primary Catalysts is tetradentate schiff base metal complexes (R
1) (R
2) SalenMX, its structural formula is:
Wherein, M is Al (III) or Cr (III),
R
1, R
2Be-H, 1-6 carbon alkyl, alkoxyl group ,-Cl ,-Br or-NO
2Group; R
3, R
4For-(CH
2)
4-,-H ,-CH
3Or-Ph ,-(CH)
4-; X is Cl
-, Br
-, I
-, CH
3O
-, CH
3CH
2O
-, NO
3 -, CH
3COO
-, ClO
4 -, BF
4 -Or BPh
4 -Negative ion,
Promotor is that chemical formula is R
1R
2 3NX
1Quaternary ammonium salt or chemical formula be R
1R
2 3PX
1The De quaternary alkylphosphonium salt, R in the formula
1, R
2Be alkyl, X
1Be the monovalence negative ion,
The mol ratio of promotor and Primary Catalysts tetradentate schiff base metal complexes is 0.2: 1 to 5: 1.
2. the high activated catalyst that is used for synthesizing annular carbonate according to claim 1 is characterized in that, promotor is that chemical formula is R
1R
2 3NX
1Quaternary ammonium salt, R in the formula
1Be 1-16 carbon alkyl, R
2Be 1-6 carbon alkyl, X
1Be Cl
-, Br
-, I
-, NO
3 -, CH
3COO
-, ClO
4 -, BF
4 -Or BPh
4 -Negative ion.
3. the high activated catalyst that is used for synthesizing annular carbonate according to claim 1 is characterized in that, promotor is that chemical formula is R
1R
2 3PX
1The De quaternary alkylphosphonium salt, R in the formula
1Be 1-16 carbon alkyl, R
2Be 1-6 carbon alkyl or phenyl, X
1Be Cl
-, Br
-, I
-, NO
3 -, CH
3COO
-, ClO
4 -, BF
4 -Or BPh
4 -Negative ion.
4. the high activated catalyst that is used for synthesizing annular carbonate according to claim 1 is characterized in that its axial ligand is CH
3O
-Or CH
3CH
2O
-
5. the high activated catalyst that is used for synthesizing annular carbonate according to claim 1 and 2, it is characterized in that the promotor quaternary ammonium salt is Tetrabutyl amonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, tetrapropyl ammonium iodide, tetraethylammonium bromide or etamon chloride.
6. according to claim 1 or the 3 described high activated catalysts that are used for synthesizing annular carbonate, it is characterized in that the promotor quaternary alkylphosphonium salt is butyl triphenyl phosphonium bromide, butyl triphenyl phosphonium iodide, butyl triphenyl phosphonium chloride, ethyl triphenyl phosphonium bromide or methyl triphenyl phosphonium iodide.
7. the application of high activated catalyst as claimed in claim 1 in synthesizing annular carbonate, it is characterized in that, in carbonic acid gas and the reaction of epoxy alkane synthesizing annular carbonate, temperature is 15-120 ℃, feed the carbonic acid gas constant voltage and be controlled at 0.1-6MPa, the mol ratio of tetradentate schiff base metal complexes and epoxy alkane is 1: 200 to 1: 10000, and the mol ratio of promotor and tetradentate schiff base metal complexes is 0.2: 1 to 5: 1.
Priority Applications (1)
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|---|---|---|---|
| CNB021446407A CN1189246C (en) | 2002-11-26 | 2002-11-26 | High activity catalyzer utilized to synthesize cyclic carbonate |
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|---|---|---|---|
| CNB021446407A CN1189246C (en) | 2002-11-26 | 2002-11-26 | High activity catalyzer utilized to synthesize cyclic carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1415416A CN1415416A (en) | 2003-05-07 |
| CN1189246C true CN1189246C (en) | 2005-02-16 |
Family
ID=4750619
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|---|---|---|---|
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| TWI601571B (en) * | 2016-12-07 | 2017-10-11 | 財團法人工業技術研究院 | Catalyst and method for synthesizing cyclic carbonate by the same |
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| JP7480154B2 (en) * | 2018-09-18 | 2024-05-09 | ピーティーティー・エクスプロレイション・アンド プロダクション・パブリック・カンパニー・リミテッド | CATALYST SYSTEM FOR PRODUCING CYCLIC CARBONATES AND RELATED METHODS - Patent application |
| CN109675634A (en) * | 2019-01-02 | 2019-04-26 | 昆明理工大学 | The preparation method and application of heterogeneous Schiff base catalyst |
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| CN110643024B (en) * | 2019-09-06 | 2022-06-28 | 杭州师范大学 | Organic metal catalyst for preparing poly (p-dioxanone) |
| EP4021913A4 (en) * | 2019-09-30 | 2023-11-22 | PTT Global Chemical Public Company Limited | Catalyst composition for cyclic carbonate production from co2 and epoxides |
| CN113278004B (en) * | 2020-10-23 | 2022-05-27 | 源创核新(北京)新材料科技有限公司 | Preparation method of aliphatic cyclic polycarbonate |
| CN113416147A (en) * | 2021-06-28 | 2021-09-21 | 上海应用技术大学 | Schiff base-metal organic complex and preparation method and application thereof |
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2002
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI601571B (en) * | 2016-12-07 | 2017-10-11 | 財團法人工業技術研究院 | Catalyst and method for synthesizing cyclic carbonate by the same |
| US9839906B1 (en) | 2016-12-07 | 2017-12-12 | Industrial Technology Research Institute | Catalyst and method for synthesizing cyclic carbonate by the same |
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