CN102775437B - Carbon dioxide transition metal complex, preparation method and application thereof - Google Patents
Carbon dioxide transition metal complex, preparation method and application thereof Download PDFInfo
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- CN102775437B CN102775437B CN201210156114.6A CN201210156114A CN102775437B CN 102775437 B CN102775437 B CN 102775437B CN 201210156114 A CN201210156114 A CN 201210156114A CN 102775437 B CN102775437 B CN 102775437B
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Abstract
The invention relates to a carbon dioxide transition metal complex which is named as (2-(eta 5-cyclopentadienyl)-1, 1-R, phenyl-1H-imidazole-N-carbamic acid-3-3 (pentafluoro-phenyl) boron)-2 (N, N-diethylin) titanium, wherein R is hydrogen or phenyl. A preparation method of the ligand compound comprises the steps of preparing 2-(2-cyclopentyl-1, 3-or 4-diene-1-group-2, 2-R, phenyl-ethyl)-1H-imidazole, 2-(1, 1-R, phenyl)-cyclopentadienyl-1H-imidazolyl-2-(diethylin) titanium and the (2-(eta 5-cyclopentadienyl)-1, 1-R, phenyl-1H-imidazole-N-carbamic acid-3-3 (pentafluoro-phenyl) boron)-2 (N, N-diethylin) titanium. The product is taken as catalyst in vinyl polymerization reaction.
Description
Technical field
The present invention relates to a kind of carbonic acid gas transition metal complex, the invention still further relates to the preparation method and application of this compound.
Background technology
Carbonic acid gas and transition metal centre coordination are fields received much concern, it not only can realize the fixing of carbonic acid gas truly, a kind of effective way is provided for weakening Greenhouse effect, and its product carbon dioxide transition metal complex can also be utilized by organic synthesis, obtains useful organic compound or macromolecular material.At present, the research of carbonic acid gas and transition metal centre coordination mainly concentrates on the insertion reaction that carbonic acid gas and transition metal complex occur, and is inserted into the reaction of metal-hydrogen key, metal-oxygen key, metal-carbon key and metal-nitrogen key based on carbonic acid gas.Wherein, because the nitrogen source in metal-nitrogen key is more complicated, both can be unhindered amina, also can be the amine of bonding, make it receive much concern.Be inserted in the insertion reaction of metal-nitrogen key in the great amount of carbon dioxide reported, commonplace with the nitrogen studies that the nitrogen in metal-nitrogen key stems from diethylin or dimethylin.Document " Pilar G-S, Irigoyen A M, Mart í n A, et al.J Orgnomet Chem, 1995,494:C19. " reports [Cp
*ti (NR
2)
3] (Cp
*=1,2,3,4,5-pentamethylcyclopentadiene base, R=methyl or ethyl) through carbon dioxide activation, carbonic acid gas is inserted in Ti-N key, obtains compound [Cp
*ti (η
2-O
2cNR
2)
3].So far, be inserted in the insertion reaction of Ti-N key at carbonic acid gas, the title complex that the nitrogen in Ti-N key stems from imidazoles-1 nitrogen has not yet to see report.
Summary of the invention
A technical problem to be solved by this invention is that providing a kind of is inserted in the insertion reaction of Ti-N key at carbonic acid gas, and the nitrogen in Ti-N key stems from the carbonic acid gas transition metal complex of the nitrogen of imidazoles-1.
Another technical problem to be solved by this invention is the preparation method providing carbonic acid gas transition metal complex.
To be solved by this invention also have a technical problem to be as carbonic acid gas transition metal complex provides a kind of novelty teabag.
Solving the problems of the technologies described above adopted technical scheme is called after [2-(η
5-cyclopentadienyl)-1,1-R, phenyl-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron]-two (N, N dimethylamine base) titanium, the compound that represents with structure formula I:
R in formula I is hydrogen or phenyl.
The preparation method of above-mentioned carbonic acid gas transition metal complex is as follows:
1,2-(2-cyclopentyl-1,3-or 4-diene-1-base-2,2-R, phenyl-ethyl group)-1H-imidazoles is prepared
Under argon shield; (1-diethoxymethyl imidazoles-2-) lithium is added in reactor;-70 DEG C ~-40 DEG C by 6 of 0.4mmol/mL; 6-R; the tetrahydrofuran solution of phenyl fulvene joins reactor; (1-diethoxymethyl imidazoles-2-) lithium and 6,6-R, the mol ratio of phenyl fulvene is 1:1 ~ 1.2;-70 DEG C ~-40 DEG C stirring reactions 5 ~ 60 minutes; stirring at room temperature 12 hours, adds with 0.4mmol/mL 6,6-R; the isopyknic ether termination reaction of tetrahydrofuran solution of phenyl fulvene; with 0.5mmol/mL dilute hydrochloric acid adjust pH to 5, water phase separated, uses NaHCO
3the pH value to 8 of water transfer phase, dichloromethane extraction 3 times, obtains organic phase, uses anhydrous MgSO
4drying, filters, and revolve and steam except desolventizing, obtain product, use methylene dichloride recrystallization, obtain 2-(2-cyclopentyl-1,3-or 4-diene-1-base-2,2-R, phenyl-ethyl group)-1H-imidazoles, its synthetic route is as follows:
The preparation method of above-mentioned (1-diethoxymethyl imidazoles-2-) lithium is as follows:
(1) preparation of 1-diethoxymethyl imidazoles
Under argon shield, add imidazoles 13.80g, tosic acid 0.60g, triethyl orthoformate 118.60g successively in reactor, stir; be heated to 140 DEG C; react 6 hours, react complete, remove superfluous triethyl orthoformate under reduced pressure; return to room temperature; add anhydrous sodium carbonate, underpressure distillation, collect the cut of 108 ~ 110 DEG C (133Pa); obtain 1-diethoxymethyl imidazoles 21.6g, yield 64%.
(2) preparation of (1-diethoxymethyl imidazoles-2-) lithium
Under argon shield, successively 12.1g1-diethoxymethyl imidazoles, 200mL tetrahydrofuran (THF) are added in reactor, stir – 40 DEG C and the hexane solution of the n-Butyl Lithium of the 2.4mmol/mL of 4.55g is added drop-wise in reactor;-40 DEG C of stirring reaction 30min, return to room temperature, and 3Pa vacuum drains solvent; with n-hexane three times; leave standstill, abandon supernatant liquor, drying under reduced pressure; obtain (1-diethoxymethyl imidazoles-2-) lithium 5.18g, yield 76%.
Above-mentioned R is 6,6-R of hydrogen, and the preparation method of phenyl fulvene is as follows:
Under argon shield; successively 37.15g phenyl aldehyde, 70g cyclopentadiene, 300mL methyl alcohol are added in reactor; 29.16g tetramethyleneimine drops in reactor by room temperature; stirring at room temperature reacts 10 hours, revolves and steams except desolventizing, add 300mL distilled water; with acetic acid adjust pH to 7; by extracted with diethyl ether 2 times, merge and obtain organic phase, with distillation washing 3 times; obtain organic phase; revolve and steam removing ether, underpressure distillation, collect the cut of 67-69 DEG C (2.0Pa); obtain that R is hydrogen 6; 6-R, phenyl fulvene 20.3g, productive rate 32%.
Above-mentioned R is 6,6-R of phenyl, and the preparation method of phenyl fulvene is as follows:
Under argon shield; under room temperature, the 5.8g sodium Metal 99.5 be cut into small pieces is put in the reactor filling 190mL ethanol; stirring at room temperature 3 hours; add 45.6g benzophenone, heating in water bath dissolves to it, and 20g is newly steamed cyclopentadiene and is added drop-wise in reactor by 50 DEG C; 50 DEG C of stirring reactions 12 hours; suction filtration, use 20mL washing with alcohol, suction filtration obtains product; product is added in 80mL methyl alcohol and refluxes 1 hour; cooling suction filtration obtains product, uses 30mL methanol wash, vacuum-drying; obtain that R is phenyl 6; 6-R, phenyl fulvene 43.7g, productive rate 76%.
2,2-(1,1-R, phenyl)-cyclopentadienyl-1H-imidazolyl-two-(diethylin) titanium is prepared
Under argon shield, by 2-(2-cyclopentyl-1, 3-or 4-diene-1-base-2, 2-R, phenyl-ethyl group)-1H-imidazoles is added in reactor, the toluene solution of four of 0.1mmol/mL-(diethylin) titaniums is added drop-wise in reactor by 80 ~ 110 DEG C, stir, four-(diethylin) titanium and 2-(2-cyclopentyl-1, 3-or 4-diene-1-base-2, 2-R, phenyl-ethyl group) mol ratio of-1H-imidazoles is 1:1 ~ 1.2, 80 ~ 110 DEG C of stirring reactions 10 ~ 20 hours, evaporated under reduced pressure solvent, use normal hexane respectively, washed with diethylether, by product 3Pa vacuum-drying, obtain 2-(1, 1-R, phenyl)-cyclopentadienyl-1H-imidazolyl-two-(diethylin) titanium.Its chemical equation is as follows:
The preparation method of above-mentioned four-(diethylin) titaniums is as follows:
– 10 DEG C under argon shield, the diethyl ether solution of the 1.5mmol/mL diethylamine of 30.00g is dripped in the hexane solution of 2.4mmol/mL n-Butyl Lithium of 171mL, mol ratio 1:1 – 10 DEG C of stirring reactions of diethylamine and n-Butyl Lithium 30 minutes, under argon shield, room temperature is filtered, washed with diethylether, product 3Pa vacuum-drying, obtains diethylin lithium; Under argon shield; gained diethylin lithium and 100mL toluene are added in reactor successively; the toluene solution of the titanium tetrachloride of 16.2g 1mmol/mL is added drop-wise in reactor by room temperature; stirring at room temperature reacts 12 hours; concentrated, 200Pa underpressure distillation is distilled, and collects the cut of 141 ~ 143 DEG C; obtain four-(diethylin) titanium 15.10g, yield 52.92%.
1H NMR(25℃,C
6D
6):δ=1.11(t,24H,CH
3),3.57(q,16H,CH
2)。
3, [2-(η is prepared
5-cyclopentadienyl)-1,1-R, phenyl-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron]-two (N, N dimethylamine base) titanium
Under argon shield, by 2-(1, 1-R, phenyl)-cyclopentadienyl-1H-imidazolyl-two-(diethylin) titanium is added in reactor, the toluene solution of three (pentafluorophenyl group) borine of 1mmol/mL is added drop-wise in reactor by room temperature, 2-(1, 1-R, phenyl) mol ratio of-cyclopentadienyl-1H-imidazolyl-two-(diethylin) titanium and three (pentafluorophenyl group) borine is 1:1 ~ 1.2, stir 2 ~ 10 hours, pass into 0.1Mpa carbonic acid gas, room temperature continues stirring reaction 12 hours, negative pressure solvent evaporated, with n-hexane, by product 3Pa vacuum-drying, obtain [2-(η
5-cyclopentadienyl)-1,1-R, phenyl-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron]-two (N, N dimethylamine base) titanium.Its reaction equation is as follows:
Carbonic acid gas transition metal complex makes the purposes of catalyzer in ethylene polymerization, and its using method is as follows:
Under argon shield; add the toluene solution of the carbonic acid gas transition metal complex of 0.01mmol/mL to reactor, 80 DEG C pass into ethene 0.1MPa, stirring reaction 1 hour; under ice-water bath cooling; in reaction solution, add the toluene solution isopyknic 1mmol/mL hydrochloric acid termination reaction with the carbonic acid gas transition metal complex of 0.01mmol/mL, stir 15 minutes, filter; obtain product; washing with alcohol 3 ~ 5 times, dry, obtain polyethylene.
The 1-diethoxymethyl imidazoles related in the present invention, (1-diethoxymethyl imidazoles-2-) lithium, four-(diethylin) titaniums, 2-(1,1-H, phenyl)-cyclopentadienyl-1H-imidazolyl-two-(diethylin) titanium, 2-(1,1-phenylbenzene)-cyclopentadienyl-1H-imidazolyl two-(diethylin) titanium, [2-(η
5-cyclopentadienyl)-1,1-H, phenyl-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron]-two (N, N dimethylamine base) titanium or [2-(η
5-cyclopentadienyl)-1,1-phenylbenzene-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron]-two (N, N dimethylamine base) titanium all needs to be kept in glove box.The model of glove box is Super 1220/750/900, by that Company of German meter Kai Luo.
2-(2-cyclopentyl-1 is prepared in the present invention, 3-or 4-diene-1-base-2,2-R, phenyl-ethyl group) in-1H-imidazoles step 1, (1-diethoxymethyl imidazoles-2-) lithium and 6,6-R, phenyl fulvene optimum mole ratio is 1:1.1,-50 DEG C of stirring reactions 5 ~ 60 minutes, stirring at room temperature reacts 12 hours.
2-(1 is prepared in the present invention, 1-R, phenyl) in-cyclopentadienyl-1H-imidazolyl-two-(diethylin) titanium step 2, four-(diethylin) titanium and 2-(2-cyclopentyl-1,3-or 4-diene-1-base-2,2-R, phenyl-ethyl group)-1H-imidazoles optimum mole ratio is 1:1.1,90 DEG C of stirring reactions 10 ~ 20 hours.
[2-(η is prepared in the present invention
5-cyclopentadienyl)-1,1-R, phenyl-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron]-two (N, N dimethylamine base) in titanium step 3,2-(1,1-R, phenyl)-cyclopentadienyl-1H-imidazolyl-two-(diethylin) titanium and three (pentafluorophenyl group) borine optimum mole ratio is 1:1.1, stirring at room temperature 2 ~ 10 hours.
Carbonic acid gas transition metal complex provided by the invention and its preparation method and application, not only for carbonic acid gas fixedly provide a kind of effective way, this has positive environment protection significance in the difficult problem solving carbon dioxide greenhouse effect, and the carbonic acid gas transition metal complex obtained can be used as catalyst olefinic polymerization and obtains macromolecular material.
Accompanying drawing explanation
Fig. 1 is [2-(η
5-cyclopentadienyl)-1,1-H, phenyl-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron] proton nmr spectra of-two (N, N dimethylamine base) titanium.
Fig. 2 is [2-(η
5-cyclopentadienyl)-1,1-phenylbenzene-1H-imidazoles-N-amidocarbonic acid-3 three (pentafluorophenyl group) boron] proton nmr spectra of-two (N, N dimethylamine base) titanium.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in more detail, but the invention is not restricted to these embodiments.
Embodiment 1
[2-(η
5-cyclopentadienyl)-1,1-H, phenyl-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron]-two (N, N dimethylamine base) titanium, the compound that represents with structural formula (I), the R in formula (I) is hydrogen.
1,2-(2-cyclopentyl-1,3-or 4-diene-1-base-2,2-H, phenyl-ethyl group)-1H-imidazoles is prepared
Under argon shield; by 9.60g(1-diethoxymethyl imidazoles-2-) lithium is added in reactor;-55 DEG C by 6 of 16.94g 0.4mmol/mL; 6-H; the tetrahydrofuran solution of phenyl fulvene joins reactor; (1-diethoxymethyl imidazoles-2-) lithium and 6,6-H, the mol ratio of phenyl fulvene is 1: 1.1;-55 DEG C of stirring reactions 30 minutes; stirring at room temperature reacts 12 hours, adds with 0.4mmol/mL 6,6-H; the isopyknic ether termination reaction of tetrahydrofuran solution of phenyl fulvene; with 0.5mmol/mL dilute hydrochloric acid adjust pH to 5, water phase separated, uses NaHCO
3the pH value to 8 of water transfer phase, dichloromethane extraction 3 times, obtains organic phase, uses anhydrous MgSO
4drying, filters, and revolves and steams except desolventizing, obtain product, use methylene dichloride recrystallization, obtain 2-(2-cyclopentyl-1,3-or 4-diene-1-base-2,2-H, phenyl-ethyl group)-1H-imidazoles 7.75g, yield 35%.
2,2-(1,1-H, phenyl)-cyclopentadienyl-1H-imidazolyl-two-(diethylin) titanium
Under argon shield, by 6.66g 2-(2-cyclopentyl-1, 3-or 4-diene-1-base-2, 2-H, phenyl-ethyl group)-1H-imidazoles is added in reactor, the toluene solution of four of 11.10g 0.1mmol/mL-(diethylin) titaniums is added drop-wise in reactor by 95 DEG C, stir, four-(diethylin) titanium and 2-(2-cyclopentyl-1, 3-or 4-diene-1-base-2-phenylethyl) mol ratio of-1H-imidazoles is 1: 1.1, 95 DEG C of stirring reactions 15 hours, negative pressure solvent evaporated, use normal hexane respectively, washed with diethylether twice, by product 3Pa vacuum-drying, obtain 2-(1, 1-H, phenyl)-cyclopentadienyl-1H-imidazolyl-two-(diethylin) titanium 9.28g, yield 75%.
3, [2-(η is prepared
5-cyclopentadienyl)-1,1-H, phenyl-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron]-two (N, N dimethylamine base) titanium
Under argon shield, by 8.26g 2-(1, 1-H, phenyl)-cyclopentadienyl-1H-imidazolyl-two-(diethylin) titanium is added in reactor, the toluene solution of three (pentafluorophenyl group) borine of 11.26g 1mmol/mL is added drop-wise in reactor by room temperature, 2-(1, 1-H, phenyl) mol ratio of-cyclopentadienyl-1H-imidazolyl-two-(diethylin) titanium and three (pentafluorophenyl group) borine is 1: 1.1, stirring at room temperature reacts 6 hours, pass into 0.1Mpa carbonic acid gas, room temperature continues stirring reaction 12 hours, negative pressure solvent evaporated, with n-hexane, negative pressure drying, obtain [2-(η
5-cyclopentadienyl)-1,1-H, phenyl-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron]-two (N, N dimethylamine base) titanium 14.90g, yield 77%.
Prepared [2-(η
5-cyclopentadienyl)-1,1-H, phenyl-1H-imidazoles-N-amidocarbonic acid-3 three (pentafluorophenyl group) boron]-two (N, N dimethylamine base) titanium detects through nuclear magnetic resonance analyser, and detected result is shown in Fig. 1, determines that this product is target product.Its appraising datum is as follows:
1H NMR(400MHz,25℃,C
6D
6):δ=0.74,0.67(both triplet,12H,CH
3in Etgroup),3.71,3.25,3.04,3.02(both m,8H,CH
2in Et group),5.80,5.73,5.62(broadened m,4H,CH in Cp),7.28,7.16,7.06(m,5H,o,m，p-CH in PH),7.47(m,1H,CH bridged with Cp，PH).
Embodiment 2
[2-(η
5-cyclopentadienyl)-1,1-H, phenyl-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron]-two (N, N dimethylamine base) titanium, the compound that represents with structural formula (I), the R in formula (I) is hydrogen.
In preparation 2-(2-cyclopentyl-1, 3-or 4-diene-1-base-2, 2-H, phenyl-ethyl group) in-1H-imidazoles step 1, under argon shield, by 9.60g(1-diethoxymethyl imidazoles-2-) lithium is added in reactor,-70 DEG C by 6 of 15.4g 0.4mmol/mL, 6-H, the tetrahydrofuran solution of phenyl fulvene joins reactor, (1-diethoxymethyl imidazoles-2-) lithium and 6, 6-H, the mol ratio of phenyl fulvene is 1: 1,-70 DEG C of stirring reactions 60 minutes, stirring at room temperature reacts 12 hours, other step in this step is identical with embodiment 1, be prepared into 2-(2-cyclopentyl-1, 3-or 4-diene-1-base-2, 2-H, phenyl-ethyl group)-1H-imidazoles 4.88g, yield 22%.
At preparation 2-(1, 1-H, phenyl) in-cyclopentadienyl-1H-imidazolyl-two-(diethylin) titanium step 2, under argon shield, by 4.44g 2-(2-cyclopentyl-1, 3-or 4-diene-1-base-2, 2-H, phenyl-ethyl group)-1H-imidazoles is added in reactor, the toluene solution of four of 6.73g 0.1mmol/mL-(diethylin) titaniums is added drop-wise in reactor by 80 DEG C, stir, four-(diethylin) titanium and 2-(2-cyclopentyl-1, 3-or 4-diene-1-base-2, 2-H, phenyl-ethyl group) mol ratio of-1H-imidazoles is 1: 1, 80 DEG C of stirring reactions 20 hours, other step in this step is identical with embodiment 1, be prepared into 2-(1, 1-H, phenyl)-cyclopentadienyl-1H-imidazolyl-two-(diethylin) titanium 5.03g, yield 61%.
At preparation [2-(η
5-cyclopentadienyl)-1, 1-H, phenyl-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron]-two (N, N dimethylamine base) in titanium step 3, under argon shield, by 4.12g 2-(1, 1-H, phenyl) cyclopentadienyl-1H-imidazolyl-two-(diethylin) titanium is added in reactor, the toluene solution of three (pentafluorophenyl group) borine of 5.11g 1mmol/mL is added drop-wise in reactor by room temperature, 2-(1, 1-H, phenyl) mol ratio of cyclopentadienyl-1H-imidazolyl-two-(diethylin) titanium and three (pentafluorophenyl group) borine is 1: 1, stirring at room temperature reacts 10 hours, other step in this step is identical with embodiment 1, be prepared into [2-(η
5-cyclopentadienyl)-1,1-H, phenyl-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron]-two (N, N dimethylamine base) titanium 5.62g, yield 58%.
Embodiment 3
[2-(η
5-cyclopentadienyl)-1,1-H, phenyl-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron]-two (N, N dimethylamine base) titanium, the compound that represents with structural formula (I), the R in formula (I) is hydrogen.
In preparation 2-(2-cyclopentyl-1, 3-or 4-diene-1-base-2, 2-H, phenyl-ethyl group) in-1H-imidazoles step 1, under argon shield, by 9.60g(1-diethoxymethyl imidazoles-2-) lithium is added in reactor,-40 DEG C by 6 of 18.50g 0.4mmol/mL, 6-H, the tetrahydrofuran solution of phenyl fulvene joins reactor, (1-diethoxymethyl imidazoles-2-) lithium and 6, 6-H, the mol ratio of phenyl fulvene is 1: 1.2,-40 DEG C of stirring reactions 5 minutes, stirring at room temperature 12 hours, other step in this step is identical with embodiment 1, be prepared into 2-(2-cyclopentyl-1, 3-or 4-diene-1-base-2, 2-H, phenyl-ethyl group)-1H-imidazoles 5.77g, yield 26%.
At preparation 2-(1, 1-H, phenyl) in-cyclopentadienyl-1H-imidazolyl-two-(diethylin) titanium step 2, under argon shield, by 5.55g 2-(2-cyclopentyl-1, 3-or 4-diene-1-base-2, 2-H, phenyl-ethyl group)-1H-imidazoles is added in reactor, the toluene solution of four of 10.09g 0.1mmol/mL-(diethylin) titaniums is added drop-wise in reactor by 110 DEG C, stir, four-(diethylin) titanium and 2-(2-cyclopentyl-1, 3-or 4-diene-1-base-2, 2-H, phenyl-ethyl group) mol ratio of-1H-imidazoles is 1: 1.2, 110 DEG C of stirring reactions 10 hours, other step in this step is identical with embodiment 1, be prepared into 2-(1, 1-H, phenyl)-cyclopentadienyl-1H-imidazolyl-two-(diethylin) titanium 6.70g, yield 65%.
At preparation [2-(η
5-cyclopentadienyl)-1, 1-H, phenyl-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron]-two (N, N dimethylamine base) in titanium step 3, under argon shield, by 4.12g2-(1, 1-H, phenyl)-cyclopentadienyl-1H-imidazolyl-two-(diethylin) titanium is added in reactor, the toluene solution of three (pentafluorophenyl group) borine of 6.14g 1mmol/mL is added drop-wise in reactor by room temperature, 2-(1, 1-H, phenyl) mol ratio of-cyclopentadienyl-1H-imidazolyl-two-(diethylin) titanium and three (pentafluorophenyl group) borine is 1: 1.2, stirring at room temperature reacts 2 hours, other step in this step is identical with embodiment 1, be prepared into [2-(η
5-cyclopentadienyl)-1,1-H, phenyl-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron]-two (N, N dimethylamine base) titanium 6.00g, yield 62%.
Embodiment 4
[2-(η
5-cyclopentadienyl)-1,1-phenylbenzene-1H-imidazoles N-amidocarbonic acid-3-three (pentafluorophenyl group) boron]-two (N, N dimethylamine base) titanium, the compound that represents with structural formula (I), the R in formula (I) is phenyl.
In the preparation method of embodiment 1, used 6,6H, equimolar 6, the 6-phenylbenzene fulvene of phenyl fulvene are replaced, and other step is identical with corresponding embodiment.Be prepared into [2-(η
5-cyclopentadienyl)-1,1-phenylbenzene-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron]-two (N, N dimethylamine base) titanium 17.12g, yield 82%.
Prepared [2-(η
5-cyclopentadienyl)-1,1-phenylbenzene-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron]-two (N, N dimethylamine base) titanium detects through nuclear magnetic resonance analyser, and detected result is shown in Fig. 2, determines that this product is target product.Its appraising datum is as follows:
1H NMR(400MHz,25℃,C
6D
6):δ=0.70(X3 part of ABX
3spin system,12H,
3J
AX=
3J
BX=6.73Hz,CH
3)3.12,3.46(AB part of ABX3 spin system,4H+4H,
3J
AX=
3J
AB=6.71Hz,
2J
AB=14.0Hz;CH
2in CH
3CH
2),5.74(unresolved m,4H,CH inCp),7.04(m,2H,p-CH in PH),7.15(m,overlaps with C
6D
5H,4H,m-CH in PH),7.21,7.55(both d,1H+1H,
3J=1.21Hz,CH in imidazole),7.86(m,4H,o-CHin PH)
Embodiment 5
[2-(η
5-cyclopentadienyl)-1,1-phenylbenzene-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron]-two (N, N dimethylamine base) titanium, the compound that represents with structural formula (I), the R in formula (I) is phenyl.
In the preparation method of embodiment 2,3, used 6,6-H, equimolar 6, the 6-phenylbenzene fulvene of phenyl fulvene are replaced, and other step is identical with corresponding embodiment.Be prepared into [2-(η
5-cyclopentadienyl)-1,1-phenylbenzene-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron]-two (N, N dimethylamine base) titanium.
Embodiment 6
[2-(η
5-cyclopentadienyl)-1,1-H, phenyl-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron]-two (N, N dimethylamine base) titanium, the compound that represents with structural formula (I), the R in formula (I) is hydrogen.
Its using method is as follows:
Under argon shield, add [2-(the η of 0.968g 0.01mmol/mL to reactor
5-cyclopentadienyl)-1,1-H, phenyl-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron]-two (N, N dimethylamine base) toluene solution of titanium, 80 DEG C pass into ethene 0.1MPa, stirring reaction 1 hour, ice-water bath cools, and adds [2-(the η with 0.968g 0.01mmol/mL in reaction solution
5-cyclopentadienyl)-1,1-H, phenyl-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron] toluene solution isopyknic 1mmol/mL hydrochloric acid termination reaction of-two (N, N dimethylamine base) titanium, stirs 15 minutes, filter, obtain product, by washing with alcohol 3 ~ 5 times, dry, obtain polyethylene 67.56g, catalytic activity is 6.756 × 10
5g PE/ (mol TiMPah).
Embodiment 7
[2-(η
5-cyclopentadienyl)-1,1-phenylbenzene-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron]-two (N, N dimethylamine base) titanium, the compound that represents with structural formula (I), the R in formula (I) is phenyl.
In embodiment 6, [2-(η used
5-cyclopentadienyl)-1,1-H, phenyl-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron] equimolar [2-(η of-two (N, N dimethylamine base) titaniums
5-cyclopentadienyl)-1,1-phenylbenzene-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron] replacement of-two (N, N dimethylamine base) titanium, other step is identical with corresponding embodiment.Prepare polyethylene 94.37g, catalytic activity is 9.437 × 10
5g PE/ (mol TiMPah).
Claims (6)
1. a carbonic acid gas transition metal complex, is characterized in that structural formula is the compound of formula (I):
R in formula (I) is hydrogen or phenyl.
2. a preparation method for carbonic acid gas transition metal complex according to claim 1, is characterized in that it comprises the steps:
(1) 2-(2-cyclopentyl-1,3-diene-1-base-2,2-R, phenyl-ethyl group)-1H-imidazoles or 2-(2-cyclopentyl-Isosorbide-5-Nitrae-diene-1-base-2,2-R, phenyl-ethyl group)-1H-imidazoles is prepared
Under argon shield, (1-diethoxymethyl imidazoles-2-) lithium is added in reactor,-70 DEG C ~-40 DEG C by 6 of 0.4mmol/mL, 6-R, the tetrahydrofuran solution of phenyl fulvene joins reactor, (1-diethoxymethyl imidazoles-2-) lithium and 6, 6-R, the mol ratio of phenyl fulvene is 1:1 ~ 1.2,-70 DEG C ~-40 DEG C stirring reactions 5 ~ 60 minutes, stirring at room temperature reacts 12 hours, add with 0.4mmol/mL 6, 6-R, the isopyknic ether termination reaction of tetrahydrofuran solution of phenyl fulvene, with 0.5mmol/mL dilute hydrochloric acid adjust pH to 5, water phase separated, use NaHCO
3the pH value to 8 of water transfer phase, dichloromethane extraction 3 times, obtains organic phase, uses anhydrous MgSO
4drying, filters, and revolves and steams except desolventizing, obtain product, use methylene dichloride recrystallization, obtain 2-(2-cyclopentyl-1,3-diene-1-base-2,2-R, phenyl-ethyl group)-1H-imidazoles or 2-(2-cyclopentyl-Isosorbide-5-Nitrae-diene-1-base-2,2-R, phenyl-ethyl group)-1H-imidazoles,
(2) 2-(1,1-R, phenyl)-cyclopentadienyl-1H-imidazolyl-two (diethylin) titanium is prepared
Under argon shield, by 2-(2-cyclopentyl-1, 3-diene-1-base-2, 2-R, phenyl-ethyl group)-1H-imidazoles or 2-(2-cyclopentyl-1, 4-diene-1-base-2, 2-R, phenyl-ethyl group)-1H-imidazoles is added in reactor, the toluene solution of four (diethylin) titanium of 0.1mmol/mL is added drop-wise in reactor by 80 ~ 110 DEG C, stir, four (diethylin) titaniums and 2-(2-cyclopentyl-1, 3-diene-1-base-2, 2-R, phenyl-ethyl group)-1H-imidazoles or 2-(2-cyclopentyl-1, 4-diene-1-base-2, 2-R, phenyl-ethyl group) mol ratio of-1H-imidazoles is 1:1 ~ 1.2, 80 ~ 110 DEG C of stirring reactions 10 ~ 20 hours, negative pressure solvent evaporated, use normal hexane respectively, washed with diethylether, by product 3Pa vacuum-drying, obtain 2-(1, 1-R, phenyl)-cyclopentadienyl-1H-imidazolyl-two (diethylin) titanium,
(3) [2-(η is prepared
5-cyclopentadienyl)-1,1-R, phenyl-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron]-two (N, N dimethylamine base) titanium
Under argon shield, by 2-(1, 1-R, phenyl)-cyclopentadienyl-1H-imidazolyl-two (diethylin) titanium is added in reactor, the toluene solution of three (pentafluorophenyl group) borine of 1mmol/mL is added drop-wise in reactor by room temperature, 2-(1, 1-R, phenyl) mol ratio of-cyclopentadienyl-1H-imidazolyl-two (diethylin) titanium and three (pentafluorophenyl group) borine is 1:1 ~ 1.2, stirring reaction 2 ~ 10 hours, pass into 0.1Mpa carbonic acid gas, room temperature continues stirring reaction 12 hours, negative pressure solvent evaporated, with n-hexane, by product 3Pa vacuum-drying, obtain [2-(η
5-cyclopentadienyl)-1,1-R, phenyl-1H-imidazoles-N-amidocarbonic acid-3-three (pentafluorophenyl group) boron]-two (N, N dimethylamine base) titanium.
3. the preparation method of carbonic acid gas transition metal complex according to claim 2, it is characterized in that: in step (1), (1-diethoxymethyl imidazoles-2-) lithium and 6,6-R, the mol ratio of phenyl fulvene is 1:1 ~ 1.1,-50 DEG C of stirring reactions 5 ~ 60 minutes, stirring at room temperature 12 hours.
4. the preparation method of carbonic acid gas transition metal complex according to claim 2, it is characterized in that: in step (2), four (diethylin) titaniums and 2-(2-cyclopentyl-1,3-diene-1-base-2,2-R, phenyl-ethyl group)-1H-imidazoles or 2-(2-cyclopentyl-1,4-diene-1-base-2,2-R, phenyl-ethyl group) mol ratio of-1H-imidazoles is 1:1.1,90 DEG C of stirring reactions 10 ~ 20 hours.
5. the preparation method of carbonic acid gas transition metal complex according to claim 2, it is characterized in that: in step (3), 2-(1,1-R, phenyl) mol ratio of-cyclopentadienyl-1H-imidazolyl-two (diethylin) titanium and three (pentafluorophenyl group) borine is 1:1.1, stirring at room temperature 2 ~ 10 hours.
6. carbonic acid gas transition metal complex according to claim 1 in ethylene polymerization as the purposes of catalyzer.
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