CN101580488B - Preparation method and application of tridentate pyridine imine ligand - Google Patents
Preparation method and application of tridentate pyridine imine ligand Download PDFInfo
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Abstract
The present invention provides a method for synthesizing tridentate pyridine imine ligand. The method comprises the following steps of putting 2,6-pyridine-dione and aniline derivatives or naphthylamine derivatives in organic solvent, using TiCl4 as a catalyst, performing reaction for 6 to 72 hours in an inert gas atmosphere maintaining micro-positive pressure at a solvent-reflux temperature, performing rotary evaporation to remove the solvent, filtering and washing the obtained product, separating out an organic layer, reducing pressure to remove the solvent, recrystallizing a head product and obtaining the ligand of which the yield is up to over 80 percent. The catalyst prepared from the tridentate pyridine imine ligand is used for catalyzing ethylene oligomerization to prepare linear alpha-olefin. The obtained linear alpha-olefin has the selectivity more than 96 percent and has the carbon number distribution between C4 and C28, wherein the carbon number distribution between C6 and C20 is greater than 80 percent.
Description
Technical field
The present invention relates to the preparation method of trident pyridinimine ligand, in particular to the preparation method and the application of the trident pyridinimine ligand that is used for ethylene oligomerization catalyst.
Background technology
Ethylene oligomerization is one of most important reaction in the olefinic polymerization industry.By oligomerisation reaction, the small-numerator olefin of cheapness can be transformed into and have high value-added product.Ethylene oligomerization product-linear alpha-alkene (LAO) is important Organic Chemicals.LAO C for example
4-C
30Can be used as additive of the emollient component of preparation daily cleaning agent, flotation agent, emulsifying agent, refrigerator and bore liquid emollient component, softening agent, various additives, low viscosity synthetic oil, polymkeric substance and multipolymer, oil and petroleum products additive, senior alkylamines, senior organo-aluminium compound, senior alkaryl hydrocarbon polymer, high fatty alcohol and lipid acid, epoxide and thermal barrier or the like.At LAO C
20-C
30But also composite adhesives, sealing agent and coating on the basis.In recent years, along with the continuous development of polyolefin industry, the demand to alpha-olefin in the world wide increases rapidly.Wherein Jue Dabufen alpha-olefin is obtained by the ethylene oligomerization preparation.
The used catalyzer of ethylene oligomerization method mainly contains nickel system, chromium system, zirconium system and aluminium system etc., in recent years, and Brookhart group (Brookhart, M etc., J.Am.Chem.Soc., 1998,120,7143-7144; WO99/02472,1999), Gibson group (Gibson, V.C. etc., Chem.Commun., 1998,849-850; Chem.Eur.J., 2000,2221-2231) find some Fe (II) and Co (II) respectively but the oligomerisation of trident pyridinimine title complex catalyzed ethylene, not only the catalytic activity of catalyzer is very high, and the selectivity of alpha-olefin is also very high.Therefore this class title complex has very strong prospects for commercial application.And for this class Fe (II) and Co (II) composition catalyst, key is the synthetic of part.Can this class title complex obtain and cost just depends on the synthetic method of part.
Catalyzer is made with formic acid, acetate by Brookhart group and Gibson group, and catalysis pyridine diketone and anils or naphthylamine derivative condensation obtain corresponding trident pyridinimine ligand (Brookhart, M etc., J.Am.Chem.Soc., 1998,120,4049-4050; J.Am.Chem.Soc., 1998,120,7143-7144; WO99/02472,1999; Gibson, V.C. etc., Chem.Commun., 1998,849-850; Chem.Eur.J., 2000,2221-2231;-J.Am.Chem.Soc., 1999,121,8728-8740).BASF AG's report is made catalyzer with tosic acid, and catalysis pyridine diketone and anils or naphthylamine derivative condensation obtain corresponding trident pyridinimine ligand (WO01/07491 A1).
CN1322717A discloses a kind of halogenophenyl trident pyridinimine late transition metal complex, synthetic method and purposes, wherein use 2,6-pyridine diketone and halo aniline carry out the synthetic of trident pyridinimine ligand with acetate, titanium tetrachloride, formic acid or tosic acid as catalyzer in organic solvent.When this method was used for trident pyridinimine ligand synthetic, the anils of use was the halo aniline that contains the halogen electron-withdrawing group, and was used for the polymerization of ethene by the late transition metal complex that this trident pyridinimine ligand obtains, and generated polyethylene.
Undoubted, people are still in the preparation method who constantly explores and seek the new trident pyridinimine ligand that is used for ethylene oligomerization catalyst.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of novel trident pyridinimine ligand.
Another object of the present invention is to provide the application of described trident pyridinimine ligand in the preparation ethylene oligomerization catalyst.
A further object of the present invention is to provide the application of described ethylene oligomerization catalyst in the preparation ethylene oligomer.
On the one hand, the invention provides a kind of preparation method of novel trident pyridinimine ligand, described trident pyridinimine ligand has following general structure:
Wherein, R is H, C
1～4Alkyl is (as C
1～4Alkyl or C
2～4Thiazolinyl), aryl or C
1～4Alkyl is (as C
1～4Alkyl or C
2～4Thiazolinyl) aryl of Qu Daiing; R
1, R
2Phenyl or naphthyl for alkyl and/or alkoxyl group replacement is preferably C
1～4Alkyl is (as C
1～4Alkyl or C
2～4Thiazolinyl) and/or C
1～4The phenyl or naphthyl that alkoxyl group replaces; It is characterized in that making catalyzer with titanium tetrachloride in organic solvent, make 2,6-pyridine diketone and anils or naphthylamine derivative react in the inert atmosphere that keeps pressure-fired.
In the preparation method of trident pyridinimine ligand of the present invention, anils that uses or naphthylamine derivative are preferably C as the anils or the naphthylamine derivative of alkyl and/or alkoxyl group replacement
1-4Alkyl is (as C
1～4Alkyl or C
2～4Thiazolinyl) and/or C
1～4Anils or naphthylamine derivative that alkoxyl group replaces.The anils that the present invention uses or the example of naphthylamine derivative include but not limited to Ortho Toluidine, 3-monomethylaniline, 4-monomethylaniline, 2,3-xylidine, 2,4-xylidine, naphthalidine, 3-methyl isophthalic acid-naphthylamines, 4-methyl isophthalic acid-naphthylamines, 2-methyl-4-anisidine.
In the preparation method of trident pyridinimine ligand of the present invention, the organic solvent that uses is had no particular limits, can use organic solvent commonly used in the trident pyridinimine ligand preparation field, for example ether, tetrahydrofuran (THF), toluene, benzene, dimethylbenzene or methylene dichloride etc.
The preparation method of trident pyridinimine ligand of the present invention carries out in keeping the inert atmosphere of pressure-fired, preferably with pressure-controlling in the scope of 0.11～0.15MPa.Used inert gas atmosphere is the atmosphere of anaerobic, for example nitrogen, argon gas, neon etc., preferably argon gas.
In the preparation method of trident pyridinimine ligand of the present invention, use titanium tetrachloride to make catalyzer.The preferred mode that drips that adopts adds catalyzer, for example slowly drips, and more preferably rate of addition is controlled in the scope of 0.03ml/min～3ml/min.Reaction raw materials 2,6-pyridine diketone, anils or naphthylamine derivative and catalyzer three's mol ratio is 1: 2～10: 0.05～0.5.In reaction process, can add molecular sieve as water-retaining agent.
In preparation method's of the present invention specific embodiments, by 2,6-pyridine diketone and anils or naphthylamine derivative are used TiCl in organic solvent
4As catalyzer, be reflected at the maintenance pressure-fired and (in preferred 0.11～0.15MPa) the inert atmosphere, under the solvent refluxing temperature, carry out.React after 6～72 hours, rotary distillation removes and desolvates, and filters, and uses organic solvent, and filtrate is collected in preferred anhydrous diethyl ether or tetrahydrofuran (THF) washing, washes with water and tells organic layer, and removal of solvent under reduced pressure is carried out recrystallization to head product, obtains part.
On the other hand, the application of trident pyridinimine ligand in the preparation ethylene oligomerization catalyst that the invention provides by above method acquisition, it is characterized in that: under the anhydrous and oxygen-free condition, the halide reaction with described trident pyridinimine ligand and iron or cobalt obtains catalyzer.The halogenide of described iron or cobalt is preferably muriate or bromide.In the halogenide of described iron or cobalt, iron ion can be Fe (II) or Fe (III), and cobalt is Co (II).
In preferred embodiments, trident pyridinimine ligand and equimolar Iron dichloride tetrahydrate are added in the two-mouth bottle, add tetrahydrofuran (THF), induction stirring 1～24 hour is filtered, and uses the anhydrous diethyl ether repetitive scrubbing, pass through vacuum-drying again, obtain pulverous catalyzer that is used for ethylene oligomerization.
In yet another aspect, the present invention also provides the application of described ethylene oligomerization catalyst in the preparation ethylene oligomer.Ethylene oligomerization is reflected in the autoclave and carries out.Be specially under the anhydrous and oxygen-free condition, when 25～90 ℃ of ethylene pressure 0.1～30MPa, temperature of reaction, order adds organic solvent, promotor and Primary Catalysts solution, react after 10～60 minutes, be cooled to-10～10 ℃, add the methyl alcohol stopped reaction, obtain linear alpha-alkene through rectifying separation, the linear alpha-alkene selectivity that obtains thus is greater than 96%, and carbon number distribution is at C
4～C
28Between, C wherein
6～C
20Greater than 80%.In the ethylene oligomerization reaction, can use toluene, dimethylbenzene or normal heptane etc., use aikyiaiurnirsoxan beta as promotor as organic solvent.Preferably in ethylene oligomerization reaction, the mol ratio of promotor aikyiaiurnirsoxan beta and Primary Catalysts with Al/Fe (or Co) count 2000: 1～200: 1.
The advantage of technical scheme of the present invention is trident pyridinimine ligand productive rate height, can reach more than 80%; And can easily obtain highly active ethylene oligomerization catalyst by trident pyridinimine ligand.Through experiment showed, when described ethylene oligomerization catalyst is used for polymerising ethylene, not only oligomerisation is active high, and the linear alpha-alkene selectivity is greater than 96%.Trident pyridinimine ligand by the present invention's preparation has very strong prospects for commercial application.
Embodiment
Below in conjunction with embodiment the present invention is further detailed, but scope of the present invention is not limited to these embodiment.Scope of the present invention should be as the criterion with restricted portion in the appending claims.
Embodiment 1
4.94 restrain 2; 6-diacetyl pyridine and 26 milliliters of Ortho Toluidines (density 0.9984 grams per milliliter) join 250 milliliters of reactors; add 80 milliliters of anhydrous diethyl ethers; add molecular sieve in the reaction and make water-retaining agent; under argon shield, keep system pressure-fired 0.150MPa, with slowly dripping 1 milliliter of TiCl in 30 minutes
4(density 1.726 grams per milliliters), reaction is after 48 hours under the solvent refluxing temperature, and rotary evaporation removes and desolvates; filter; with anhydrous diethyl ether washing three times, collect filtrate, wash with water twice; tell organic layer; removal of solvent under reduced pressure, head product is recrystallization in ethanol, obtains product 2; 6-diacetyl pyridine two (2-aminotoluene), productive rate 82.3%.
1HNMR (CDCl
3): δ 8.38 (d, 2, H
Pyridine), 7.86 (t, 1, H
Pyridine), 7.20 (m, 4, H
Aryl), 7.00 (t, 2, H
Aryl), 6.67 (d, 2, H
Aryl), 2.32 (s, 6, N=C-CH
3), 2.10 (s, 6, aryl-CH
3).
Embodiment 2
Adopt to prepare trident pyridinimine ligand as embodiment 1 described method, different is: do not add molecular sieve in the reaction, obtain product 2,6-diacetyl pyridine two (2-aminotoluene), productive rate 82.2%.
1H NMR (CDCl
3): δ 8.42 (d, 2, H
Pyridine), 7.91 (t, 1, H
Pyridine), 7.24 (m, 4, H
Aryl), 7.07 (t, 2, H
Aryl), 6.70 (d, 2, H
Aryl), 2.36 (s, 6, N=C-CH
3), 2.14 (s, 6, aryl-CH
3).
Embodiment 3
Adopt to prepare trident pyridinimine ligand as embodiment 1 described method, different is: system pressure-fired 0.147MPa, and with slowly dripping 1 milliliter of TiCl in 30 minutes
4, obtain product 2,6-diacetyl pyridine two (2-aminotoluene), productive rate 82.1%.
Embodiment 4
Adopt to prepare trident pyridinimine ligand as embodiment 1 described method, different is: system pressure-fired 0.140MPa, and with slowly dripping 1 milliliter of TiCl in 30 minutes
4, obtain product 2,6-diacetyl pyridine two (2-aminotoluene), productive rate 81.6%.
Embodiment 5
Adopt to prepare trident pyridinimine ligand as embodiment 1 described method, different is: system pressure-fired 0.130MPa, and with slowly dripping 1 milliliter of TiCl in 30 minutes
4, obtain product 2,6-diacetyl pyridine two (2-aminotoluene), productive rate 81.2%.
Embodiment 6
Adopt to prepare trident pyridinimine ligand as embodiment 1 described method, different is: system pressure-fired 0.110MPa, and with slowly dripping 1 milliliter of TiCl in 10 minutes
4, obtain product 2,6-diacetyl pyridine two (2-aminotoluene), productive rate 80.6%.
Embodiment 7
Adopt to prepare trident pyridinimine ligand as embodiment 1 described method, different is: system pressure-fired 0.120MPa, and with 1 milliliter of TiCl of dropping in 40 seconds
4, obtain product 2,6-diacetyl pyridine two (2-aminotoluene), productive rate 80.9%.
Embodiment 8
Adopt to prepare trident pyridinimine ligand as embodiment 1 described method, different is: system pressure-fired 0.130MPa, and with 1 milliliter of TiCl of dropping in 20 seconds
4, obtain product 2,6-diacetyl pyridine two (2-aminotoluene), productive rate 81.1%.
Embodiment 9
4.94 restrain 2; 6-diacetyl pyridine and 32.5 milliliters of Ortho Toluidines (density 0.9984 grams per milliliter) join 250 milliliters of reactors; add 80 milliliters of tetrahydrofuran (THF)s; add molecular sieve in the reaction and make water-retaining agent; under nitrogen protection, keep system pressure-fired 0.150MPa, with slowly dripping 1 milliliter of TiCl in 30 minutes
4(density 1.726 grams per milliliters), reaction is after 48 hours under the solvent refluxing temperature, and rotary evaporation removes and desolvates; filter; with anhydrous diethyl ether washing three times, collect filtrate, wash with water twice; tell organic layer; removal of solvent under reduced pressure, head product is recrystallization in ethanol, obtains product 2; 6-diacetyl pyridine two (2-aminotoluene), productive rate 82.4%.
Embodiment 10
4.94 restrain 2; 6-diacetyl pyridine and 16 milliliters of Ortho Toluidines (density 0.9984 grams per milliliter) join 250 milliliters of reactors; add 80 milliliters of tetrahydrofuran (THF)s; add molecular sieve in the reaction and make water-retaining agent; under nitrogen protection, keep system pressure-fired 0.140MPa, with slowly dripping 1 milliliter of TiCl in 20 minutes
4(density 1.726 grams per milliliters), reaction is after 24 hours under the solvent refluxing temperature, and rotary evaporation removes and desolvates; filter; with anhydrous diethyl ether washing three times, collect filtrate, wash with water twice; tell organic layer; removal of solvent under reduced pressure, head product is recrystallization in ethanol, obtains product 2; 6-diacetyl pyridine two (2-aminotoluene), productive rate 81.5%.
Embodiment 11
4.94 restrain 2; 6-diacetyl pyridine and 7 milliliters of Ortho Toluidines (density 0.9984 grams per milliliter) join 250 milliliters of reactors; add 80 milliliters of tetrahydrofuran (THF)s; add molecular sieve in the reaction and make water-retaining agent; under nitrogen protection, keep system pressure-fired 0.140MPa, with slowly dripping 1 milliliter of TiCl in 20 minutes
4(density 1.726 grams per milliliters), reaction is after 24 hours under the solvent refluxing temperature, and rotary evaporation removes and desolvates; filter; with anhydrous diethyl ether washing three times, collect filtrate, wash with water twice; tell organic layer; removal of solvent under reduced pressure, head product is recrystallization in ethanol, obtains product 2; 6-diacetyl pyridine two (2-aminotoluene), productive rate 81.3%.
Embodiment 12
4.94 restrain 2; 6-diacetyl pyridine and 32.5 milliliters of Ortho Toluidines (density 0.9984 grams per milliliter) join 250 milliliters of reactors; add 80 milliliters of tetrahydrofuran (THF)s; add molecular sieve in the reaction and make water-retaining agent; under nitrogen protection, keep system pressure-fired 0.150MPa, with slowly dripping 1.6 milliliters of TiCl in 50 minutes
4(density 1.726 grams per milliliters), reaction is after 72 hours under the solvent refluxing temperature, and rotary evaporation removes and desolvates; filter; with anhydrous diethyl ether washing three times, collect filtrate, wash with water twice; tell organic layer; removal of solvent under reduced pressure, head product is recrystallization in ethanol, obtains product 2; 6-diacetyl pyridine two (2-aminotoluene), productive rate 82.4%.
Embodiment 13
4.94 restrain 2; 6-diacetyl pyridine and 32.5 milliliters of Ortho Toluidines (density 0.9984 grams per milliliter) join 250 milliliters of reactors; add 80 milliliters of tetrahydrofuran (THF)s; add molecular sieve in the reaction and make water-retaining agent; under nitrogen protection, keep system pressure-fired 0.140MPa, with slowly dripping 0.16 milliliter of TiCl in 5 minutes
4(density 1.726 grams per milliliters), reaction is after 24 hours under the solvent refluxing temperature, and rotary evaporation removes and desolvates; filter; with anhydrous diethyl ether washing three times, collect filtrate, wash with water twice; tell organic layer; removal of solvent under reduced pressure, head product is recrystallization in ethanol, obtains product 2; 6-diacetyl pyridine two (2-aminotoluene), productive rate 80.5%.
Embodiment 14
4.94 restrain 2; 6-diacetyl pyridine and 16 milliliters of Ortho Toluidines (density 0.9984 grams per milliliter) join 250 milliliters of reactors; add 80 milliliters of toluene; add molecular sieve in the reaction and make water-retaining agent; under nitrogen protection, keep system pressure-fired 0.140MPa, with slowly dripping 1.6 milliliters of TiCl in 50 minutes
4(density 1.726 grams per milliliters), reaction is after 24 hours under the solvent refluxing temperature, and rotary evaporation removes and desolvates; filter; with anhydrous diethyl ether washing three times, collect filtrate, wash with water twice; tell organic layer; removal of solvent under reduced pressure, head product is recrystallization in ethanol, obtains product 2; 6-diacetyl pyridine two (2-aminotoluene), productive rate 81.9%.
Embodiment 15
4.94 restrain 2; 6-diacetyl pyridine and 16 milliliters of Ortho Toluidines (density 0.9984 grams per milliliter) join 250 milliliters of reactors, add 80 milliliters of benzene, add molecular sieve in the reaction and make water-retaining agent; under nitrogen protection, keep system pressure-fired 0.130MPa, with slowly dripping 0.16 milliliter of TiCl in 5 minutes
4(density 1.726 grams per milliliters), reaction is after 24 hours under the solvent refluxing temperature, and rotary evaporation removes and desolvates; filter; with anhydrous diethyl ether washing three times, collect filtrate, wash with water twice; tell organic layer; removal of solvent under reduced pressure, head product is recrystallization in ethanol, obtains product 2; 6-diacetyl pyridine two (2-aminotoluene), productive rate 81.0%.
Embodiment 16
4.94 restrain 2; 6-diacetyl pyridine and 7 milliliters of Ortho Toluidines (density 0.9984 grams per milliliter) join 250 milliliters of reactors; add 80 milliliters of dimethylbenzene; add molecular sieve in the reaction and make water-retaining agent; under nitrogen protection, keep system pressure-fired 0.130MPa, with slowly dripping 1.6 milliliters of TiCl in 50 minutes
4(density 1.726 grams per milliliters), reaction is after 24 hours under the solvent refluxing temperature, and rotary evaporation removes and desolvates; filter; with anhydrous diethyl ether washing three times, collect filtrate, wash with water twice; tell organic layer; removal of solvent under reduced pressure, head product is recrystallization in ethanol, obtains product 2; 6-diacetyl pyridine two (2-aminotoluene), productive rate 81.3%.
Embodiment 17
4.94 restrain 2; 6-diacetyl pyridine and 7 milliliters of Ortho Toluidines (density 0.9984 grams per milliliter) join 250 milliliters of reactors; add 80 milliliters of methylene dichloride; add molecular sieve in the reaction and make water-retaining agent; under nitrogen protection, keep system pressure-fired 0.110MPa, with slowly dripping 0.16 milliliter of TiCl in 5 minutes
4(density 1.726 grams per milliliters), reaction is after 6 hours under the solvent refluxing temperature, and rotary evaporation removes and desolvates; filter; with anhydrous diethyl ether washing three times, collect filtrate, wash with water twice; tell organic layer; removal of solvent under reduced pressure, head product is recrystallization in ethanol, obtains product 2; 6-diacetyl pyridine two (2-aminotoluene), productive rate 80.3%.
Embodiment 18
Take by weighing 33.2g 2-methyl-4-anisidine (mass content＞99%) and be dissolved in 100 milliliters of anhydrous diethyl ethers; join in the reactor; add 4.94 grams 2 again; the 6-diacetyl pyridine; add molecular sieve in the reaction and make water-retaining agent; under argon shield, keep system pressure-fired 0.150MPa, with slowly dripping 1 milliliter of TiCl in 30 minutes
4(density 1.726 grams per milliliters), reaction was lowered the temperature after 48 hours under the solvent refluxing temperature, and rotary evaporation is removed most of solvent, obtains brown oil.Add the dehydrated alcohol of normal temperature, have yellow powder to separate out, filter.Behind the suitable calorimetric anhydrous alcohol solution of filter cake usefulness that obtains; put into-30 ℃ refrigerator; a large amount of yellow powders are separated out after 24 hours; filter; use the dehydrated alcohol repetitive scrubbing, resulting yellow powder passes through vacuum-drying again, obtains product 2; 6-diacetyl pyridine two (2-methyl-4-anisidine), productive rate 82.2%.
1H NMR (CDCl
3): δ 8.26 (d, Py-m-H), 8.02 (t, Py-p-H), 6.99 (d, H
Aryl), 6.72 (m, H
Aryl), 3.79 (s, aryl-OCH
3), 2.83 (s, N=C-CH
3), 2.34 (s, aryl-CH
3).
Comparative example 1
4.94 restrain 2,6-diacetyl pyridine and 26 milliliters of Ortho Toluidines join 250 milliliters of reactors, add 80 milliliters of anhydrous diethyl ethers, add molecular sieve in the reaction and make water-retaining agent, keep the system normal pressure under nitrogen protection, with slowly dripping 1 milliliter of TiCl in 30 minutes
4, reaction is after 48 hours under the solvent refluxing temperature, and rotary evaporation removes and desolvates; filter; with anhydrous diethyl ether washing three times, collect filtrate, wash with water twice; tell organic layer; removal of solvent under reduced pressure, head product is recrystallization in ethanol, obtains product 2; 6-diacetyl pyridine two (2-aminotoluene), productive rate 79.6%.
Comparative example 2
4.94 restrain 2,6-diacetyl pyridine and 26 milliliters of Ortho Toluidines join 250 milliliters of reactors, add 80 milliliters of anhydrous diethyl ethers, add molecular sieve in the reaction and make water-retaining agent, keep system pressure-fired 0.150MPa under nitrogen protection, 1 milliliter of TiCl of disposable adding
4, reaction is after 48 hours under the solvent refluxing temperature, and rotary evaporation removes and desolvates; filter; with anhydrous diethyl ether washing three times, collect filtrate, wash with water twice; tell organic layer; removal of solvent under reduced pressure, head product is recrystallization in ethanol, obtains product 2; 6-diacetyl pyridine two (2-aminotoluene), productive rate 79.4%.
Preparation of Catalyst embodiment 1
In 100 milliliters of twoport reaction flasks, vacuumize-after three times, the products that add 1.03 gram embodiment 1 under argon shield respectively are as part and 0.6 gram FeCl repeatedly for applying argon gas
24H
2O adds 30 milliliters of anhydrous tetrahydro furans, and stirring at room 2 hours obtains black-and-blue solid, and filter and wash three times with anhydrous tetrahydro furan, vacuum-drying, argon gas is preserved down.The final catalyst A that obtains: 2,6-(2-(CH
3) C
6H
3N=CCH
3)
2C
5H
3N}FeCl
2, structure such as figure below.Results of elemental analyses: theoretical value: C 59.00, H 4.95, and N 8.97; Measured value: C 59.21, H 4.89, and N 9.02.
Preparation of Catalyst embodiment 2
In 100 milliliters of twoport reaction flasks, vacuumize-after three times, the products that add 1.20 gram embodiment 18 under argon shield respectively are as part and 0.6 gram FeCl repeatedly for applying argon gas
24H
2O adds 30 milliliters of anhydrous tetrahydro furans, and stirring at room 2 hours obtains blackish green solid, and filter and wash three times with anhydrous tetrahydro furan, vacuum-drying, argon gas is preserved down.The final catalyst B that obtains: 2,6-((2-CH
3-4-OCH
3) C
6H
3N=CCH
3)
2C
5H
3N}FeCl
2, structure such as figure below.Results of elemental analyses: theoretical value: C 56.84, H 5.15, and N 7.95; Measured value: C 57.01, H4.96, N 8.07.
Ethylene oligomerization embodiment 1
In 300 milliliters of autoclaves, vacuumize-fill ethene repeatedly after three times, charge into ethene to 0.1MPa, the toluene that adds 50 milliliters, inject 10 milliliters by toluene: methylaluminoxane (promotor): the mol ratio of catalyst A (Primary Catalysts) is 45000: 1000: 1 the promotor and the toluene mixing solutions of Primary Catalysts, and the molar weight of the catalyst A in this mixing solutions is 1 * 10
-6Mol adds 40 milliliters of toluene again, and the ethylene pressure that increases sharply is to 1.5MPa, and 30 ℃ were reacted 30 minutes.Be cooled to 10 ℃, add the methyl alcohol stopped reaction, the rectifying separation product.Stratographic analysis, the linear alpha-alkene selectivity is 97.1%, carbon number distribution is at C
4～C
28Between, C wherein
6～C
20Be 81.2%.Experimental result is as shown in table 1.
Ethylene oligomerization embodiment 2-10
Adopt the method identical with above ethylene oligomerization embodiment 1 to carry out ethylene oligomerization, the use catalyst A has been investigated the oligomerisation reaction effect under the factors such as different catalysts concentration, oligomerisation pressure, temperature of reaction as Primary Catalysts.Experimental result is as shown in table 1.
Claims (7)
1. the preparation method of trident pyridinimine ligand, described trident pyridinimine ligand structural formula is:
Wherein, R is H, C
1～4Alkyl; R
1, R
2Be C
1～4Alkyl and/or C
1～4The phenyl or naphthyl that alkoxyl group replaces;
It is characterized in that: in organic solvent, make catalyzer with titanium tetrachloride, make 2,6-pyridine diketone and anils or naphthylamine derivative are to react in the inert atmosphere of 0.11～0.15MPa keeping reaction system pressure;
Wherein said anils or naphthylamine derivative are C
1～4Alkyl and/or C
1～4Aniline or naphthylamines that alkoxyl group replaces; And described 2,6-pyridine diketone has following structural formula:
Wherein, R is H, C
1～4Alkyl.
2. preparation method as claimed in claim 1, wherein said anils or naphthylamine derivative are selected from Ortho Toluidine, 3-monomethylaniline, 4-monomethylaniline, 23 dimethyl aniline, 2,4-xylidine, 3-methyl isophthalic acid-naphthylamines or 4-methyl isophthalic acid-naphthylamines.
3. preparation method as claimed in claim 1, wherein said 2,6-pyridine diketone, anils or naphthylamine derivative and TiCl 4 catalyst three's mol ratio is 1: 2～10: 0.05～0.5.
4. as each described preparation method among the claim 1-3, wherein the speed with 0.03ml/min～3ml/min drips titanium tetrachloride.
5. as each described preparation method among the claim 1-3, wherein said organic solvent is selected from ether, tetrahydrofuran (THF), toluene, benzene, dimethylbenzene and methylene dichloride.
6. as each described preparation method among the claim 1-3, wherein the reaction times is 6～72 hours.
7. as each described preparation method among the claim 1-3, wherein reaction is to carry out under the solvent refluxing temperature.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101117178A CN101580488B (en) | 2008-05-16 | 2008-05-16 | Preparation method and application of tridentate pyridine imine ligand |
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|---|---|---|---|
| CN2008101117178A CN101580488B (en) | 2008-05-16 | 2008-05-16 | Preparation method and application of tridentate pyridine imine ligand |
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| Publication Number | Publication Date |
|---|---|
| CN101580488A CN101580488A (en) | 2009-11-18 |
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| WO2018054362A1 (en) * | 2016-09-23 | 2018-03-29 | 中国石油化工股份有限公司 | Catalyst component for use in olefin polymerization, catalyst, and applications thereof |
| CN106632764B (en) * | 2016-10-17 | 2018-10-26 | 曲阜师范大学 | A kind of Fe-series catalyst and preparation method thereof and the application in isoprene polymerization |
| CN108530571B (en) * | 2018-04-28 | 2020-07-14 | 中国科学院青岛生物能源与过程研究所 | Iron-based alkylpyridinylimine catalyst and preparation method and application thereof |
| CN115974636A (en) * | 2022-11-23 | 2023-04-18 | 大连理工大学 | Process for preparing linear alpha-olefin by non-selective oligomerization of ethylene |
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| CN1240455A (en) * | 1996-12-17 | 2000-01-05 | 纳幕尔杜邦公司 | Polymerization of ethylene with specific iron or cobalt complexes, novel pyridinebis (imines) and novel complexes of pyridinebis (imines) with iron and cobalt |
| CN1296490A (en) * | 1998-03-31 | 2001-05-23 | 纳幕尔杜邦公司 | Preparation of transision metal imine complexes |
| CN1322717A (en) * | 2001-01-21 | 2001-11-21 | 中国科学院上海有机化学研究所 | Halophenyl pyridyl di-imine transition metal compound and its synthesis process and use |
| CN1343664A (en) * | 2001-06-29 | 2002-04-10 | 中国科学院上海有机化学研究所 | Process for synthesizing trident pyridinimine ligand |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1240455A (en) * | 1996-12-17 | 2000-01-05 | 纳幕尔杜邦公司 | Polymerization of ethylene with specific iron or cobalt complexes, novel pyridinebis (imines) and novel complexes of pyridinebis (imines) with iron and cobalt |
| CN1296490A (en) * | 1998-03-31 | 2001-05-23 | 纳幕尔杜邦公司 | Preparation of transision metal imine complexes |
| CN1322717A (en) * | 2001-01-21 | 2001-11-21 | 中国科学院上海有机化学研究所 | Halophenyl pyridyl di-imine transition metal compound and its synthesis process and use |
| CN1343664A (en) * | 2001-06-29 | 2002-04-10 | 中国科学院上海有机化学研究所 | Process for synthesizing trident pyridinimine ligand |
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