CN1277848C - Preparing method and application of schiff base coordinate zirconium complex ethylene oligomerization catalyst - Google Patents
Preparing method and application of schiff base coordinate zirconium complex ethylene oligomerization catalyst Download PDFInfo
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- CN1277848C CN1277848C CN 03159271 CN03159271A CN1277848C CN 1277848 C CN1277848 C CN 1277848C CN 03159271 CN03159271 CN 03159271 CN 03159271 A CN03159271 A CN 03159271A CN 1277848 C CN1277848 C CN 1277848C
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- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 52
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000005977 Ethylene Substances 0.000 title claims abstract description 30
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title abstract description 4
- 239000002262 Schiff base Substances 0.000 title abstract 3
- 150000004753 Schiff bases Chemical class 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 26
- 150000001336 alkenes Chemical class 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 96
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 88
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 50
- 229910052757 nitrogen Inorganic materials 0.000 claims description 39
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 24
- 229910007926 ZrCl Inorganic materials 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 150000002466 imines Chemical class 0.000 claims description 6
- 239000006210 lotion Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004711 α-olefin Substances 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 238000002386 leaching Methods 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- -1 alkyl aluminum compound Chemical class 0.000 abstract description 3
- 125000002252 acyl group Chemical group 0.000 abstract description 2
- 229910007932 ZrCl4 Inorganic materials 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 239000003446 ligand Substances 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 42
- 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 19
- HXFYGSOGECBSOY-UHFFFAOYSA-N 2-[[2-[(2-hydroxyphenyl)methylideneamino]phenyl]iminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NC1=CC=CC=C1N=CC1=CC=CC=C1O HXFYGSOGECBSOY-UHFFFAOYSA-N 0.000 description 15
- 238000005303 weighing Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 238000009826 distribution Methods 0.000 description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FZHSPPYCNDYIKD-UHFFFAOYSA-N 5-methoxysalicylaldehyde Natural products COC1=CC=C(O)C(C=O)=C1 FZHSPPYCNDYIKD-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a simple synthesizing method and an application of Schiff base coordinate Zr complex, a catalyst for ethylene oligomerization. The Zr complex is synthesized by the reaction of various non-substituted and substituted Schiff base ligands with ZrCl4. A system compounded from the zirconium complex of a catalyst precursor and an alkyl aluminum compound can effectively catalyze ethylene oligomerization reaction, and C4-C16 alkene is produced. The selectivity of low-carbon alkene (C4-C10) is larger than 85%, the selectivity of neutral line alpha-alkene is larger than 90%, and the catalytic activity can reach order of magnitude of 10<5> (g oligomer / mol Zr. h [-1]. atm [1]). The catalyst precursor is stable in the air, and has certain tolerance to acyl, hydroxy group and a small amount of water.
Description
Technical field the present invention relates to class west Buddhist alkali and integrates synthetic method and the application of coordinate zirconium complex as the ethylene oligomerization catalyst precursor.
The 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-olefin is important Organic Chemicals.For example, C
4～C
8Linear alpha-olefin has demand widely as comonomer in polymerization industry, and market demand sustainable growth in recent years; C
10～C
18Alpha-olefin then is widely used in produces washing composition, softening agent, lubricant and tensio-active agent etc.Because there is heavy demand as basic chemical raw materials in the low-carbon (LC) linear alpha-alkene in olefinic polymerization, meticulous various fields such as synthetic, chemist is constantly being sought the more optimization approaches of production of linear alpha-olefins.The chemist not only improves industrialized existing catalyst system, and constantly new catalyst system is carried out exploratory development, expectation development of new high reactivity, highly selective olefin oligomerization catalyst.
Research for ethylene oligomerization catalyst mainly concentrates on Ti, Zr, Cr and Ni complex compound (Chem.Rev.1991,91,613～648 for many years; Catal.Today 1992,14, and 1～124).In recent years, people such as Brookhart and Gibson gathers for western Buddhist alkali coordination Fe, Co, Ni and Pd complex catalysis ethene height and the research of oligomerisation is reported, make luxuriant back complex compound, the synthetic and Catalytic Performance of especially various western Buddhist alkali chelating coordination transition metal complexes becomes the new focus in homogeneous catalysis field.Up to now, have only the research report of several examples, utilize the document or the patent of this class titanium, zirconium complex catalyzed alkene oligomerisation reaction not to appear in the newspapers as yet about Salen type or class Salen type titanium, the high poly-reaction of zirconium complex catalyzed ethylene.Nineteen ninety, the people such as Floriani of Lausanne, SUI university synthetic and measured be not with on the salicylic aldehyde phenyl ring substituent Salen type zirconium complex 1 and Salphen type zirconium complex 2 (J.Chem.Soc., Dalton Trans.1990,1335-1344).The at first synthetic and separation zirconium complex ZrCl of this method
42THF is initiator and N with it then, N '-1,2-C
2H
4-(o-N=CHC
6H
4ONa)
2Or N, N '-1,2-C
6H
4-(o-N=CHC
6H
4ONa)
2Reaction adopts two step synthesis methods to prepare zirconium complex 1 and 2.1997, people such as the Repo of Univ Helsinki Finland reported Salen type zirconium complex 1 have been loaded to SiO
2On, be the high poly-reaction of promotor catalyzed ethylene (Macromolecules 1997,30,171～175) with methylaluminoxane MAO, generate superpolymer M
w=8.8～105.4 * 10
4Calendar year 2001, people such as Qian Yanlong have reported and have utilized Zr (O
iPr)
4HO
iPr and mphenylenediamine deutero-two (salicylic alidehyde imine) reaction obtain zirconium complex 3 (Inorg.Chem.Commun.2001,4,392～394), and it is combined formation catalyst system catalyzed ethylene with MAO high poly-, generates the high product that gathers.
Summary of the invention the invention provides class west Buddhist alkali coordination zirconium Zr complex compound catalyst precursor LZrCl
2Or LZrCl
2Sol.Wherein L represents part, and Sol represents solvent: tetrahydrofuran THF, acetone Me
2CO, methyl alcohol MeOH, water H
2The simple synthesis of O and catalyst precursor and application.The L part has following general structure:
In the formula: X=-CH
2CH
2-or 1,2-C
6H
4-
R=-CH
3,-t-C
4H
9,-OCH
3,-OC
2H
5,-Cl or-Br
Work as X=-CH
2CH
2-, L part and ZrCl
2During coordination:
R=-H can obtain Salen type zirconium complex 1
R=-CH
3, can obtain Salen type zirconium complex 4
R=-t-C
4H
9, can obtain Salen type zirconium complex 5
R=-OCH
3, can obtain Salen type zirconium complex 6
R=-OC
2H
5, can obtain Salen type zirconium complex 7
R=-Cl can obtain Salen type zirconium complex 8
R=-Br can obtain Salen type zirconium complex 9
Work as X=-1,2-C
6H
4-, L part and ZrCl
2During coordination:
R=-H can obtain Salphen type zirconium complex 2
R=-CH
3, can obtain Salphen type zirconium complex 10
R=-t-C
4H
9, can obtain Salphen type zirconium complex 11
R=-OCH
3, can obtain Salphen type zirconium complex 12
R=-OC
2H
5, can obtain Salphen type zirconium complex 13
R=-Cl can obtain Salphen type zirconium complex 14
R=-Br can obtain Salphen type zirconium complex 15
The present invention has synthesized first on 12 salicylic aldehyde phenyl ring and has had R substituting group :-CH
3,-t-C
4H
9,-OCH
3,-OC
2H
5,-Cl or-Salen type and the Salphen type zirconium complex 4～15 of Br and have the different solvents molecule, tetrahydrofuran THF, acetone Me
2CO, methyl alcohol MeOH and water H
2O coordinate zirconium complex.
The present invention simplifies and improves the synthetic method of Salen type and Salphen type zirconium complex, promptly with the ZrCl of cheapness
4Be initiator, by part sodium salt Na
2L and ZrCl
4Direct reaction obtains LZrCl
2Or LZrCl
2THF.Its characteristics: (1) does not separate the sodium salt Na of part and NaH reaction generation
2L, original position is used for next step reaction; (2) synthetic in advance and separate ZrCl
4The 2THF complex compound directly adds ZrCl at low temperatures and adopt in batches
4, to avoid ZrCl
4Produce the ill effect that very exothermic is brought during with the tetrahydrofuran THF solvent action.
The simple synthesis of zirconium complex catalyst precursor is as follows:
(1) catalyst precursor LZrCl
2THF's is synthetic
Under nitrogen protection, with H
2L part N, N '-ethylene or phenylene-two (5-R substituting group salicylic alidehyde imine) add in the exsiccant reaction flask, add tetrahydrofuran (THF) and make it dissolving.Magnetic stirs down, and the NaH of content 60% is added in the reaction flask in batches, emits a large amount of hydrogen, and being stirred to does not have bubble substantially and emit.After heating reflux reaction 0.5-1 hour, be cooled to room temperature.Then under ℃ stirring of low temperature-25～-30, with ZrCl
4Under nitrogen protection, slowly add in the reaction solution in batches.H
2L, NaH and ZrCl
4Mol ratio be preferably 1: 2: 1.Reinforced finishing continues low temperature and stirred 10 minutes, makes reaction solution rise to room temperature gradually subsequently, stirs 1 hour, refluxes then 0.5 hour.The reaction rear suspension liquid filters, and filter cake washs for several times with tetrahydrofuran (THF), and washing lotion is incorporated in the filtrate.Filtrate concentrates, cooling, separates out yellow solid, and press filtration, vacuum-drying obtain Salen type or Salphen type zirconium complex catalyst precursor LZrCl
2THF is at N
2But protection is the room temperature long-term storage down.
(2) catalyst precursor LZrCl
2Synthetic
With the above synthetic LZrCl that obtains
2THF is dissolved in the toluene, and nitrogen protection refluxed 1.5～2 hours down, can slough the coordination tetrahydrofuran (THF) and does not destroy the structure of complex compound, thereby obtain catalyst precursor LZrCl
2
(3) catalyst precursor LZrCl
2Sol's is synthetic, Sol=Me
2CO, MeOH or H
2O
With LZrCl
2Or LZrCl
2THF is at Me
2The separable complex compound LZrCl that obtains of recrystallization among CO or the MeOH
2OCMe
2And LZrCl
2MeOH.
With LZrCl
2Or LZrCl
2Add the water of equivalent in the toluene solution of THF, stir after 5 minutes, filtrate concentrating separated out yellow crystals, separates, and vacuum-drying obtains LZrCl
2H
2O.
The present invention is used for ethylene oligomerization with Salen type zirconium complex first, and promotor is R
2AlCl, R=Me or Et; Primary Catalysts concentration is 3～16mmol/L; The Al/Zr mol ratio is 100～000: 1; Ethylene pressure is 1.0～4.0MPa; Temperature of reaction is 100～180 ℃.Optimizing under the reaction conditions, generate C
4-C
16The selectivity of alkene is greater than 99%, low-carbon alkene C
4-C
10Selectivity greater than 85%, wherein the selectivity of linear alpha-alkene is greater than 90%, catalytic activity can reach 10
5G oligopolymer/mol Zrh
-1Atm
-1The order of magnitude.
In sum, the present invention and former study report difference are: (1) is simplified the synthetic method of Salen type and Salphen type zirconium complex and is improved, direct ZrCl with cheapness
4Be initiator, do not separate intermediate, adopt reaction in the same reactor; (2) synthesized first on the salicylic aldehyde phenyl ring and had substituent R=Me, t-C
4H
9, OMe, OEt, the Salen type of Cl or Br and Salphen type zirconium complex 4～15, and have different solvents molecule Me
2CO, MeOH or H
2O coordinate Salen type and Salphen type zirconium complex; (3) first with Salen type zirconium complex and R
2The AlCl combination, R=Me or Et obtain the ethylene oligomerization catalysis system of new catalytic excellent property.Various N
2O
2Four tooth coordination Salen types and Salphen zirconium complex have many superiority as catalyst precursor; for example easily synthetic; have certain tolerance for organo-functional groups such as less water and acyl groups, can connect space coordination environment and cloud density that multiple auxiliary group R comes the modulation central metal on the part.This catalyst system generates low-carbon alkene to ethylene oligomerization and has very high catalytic activity and selectivity.
Below provide zirconium complex LZrCl
2And LZrCl
29 examples of THF catalyzed ethylene oligomerisation.
Embodiment 1
(1) Preparation of catalysts
Under nitrogen protection, with the N of 1.24g, 4.61mmol, N '-ethylene-two (salicylic alidehyde imine) adds in the exsiccant reaction flask, adds the 70mL tetrahydrofuran (THF) and makes it dissolving.Magnetic stirs down, and with content 60%, the NaH of 0.37g, 9.23mmol adds in the reaction solution in batches, releasing hydrogen gas, and being stirred to does not have bubble substantially and emits.Behind the heating reflux reaction 1 hour, be cooled to room temperature.Then under ℃ stirring of low temperature-25～-30, with the ZrCl of 1.07g, 4.61mmol
4Under nitrogen protection, slowly add in the reaction solution in batches.Reinforced finishing continues low temperature and stirred 10 minutes, makes reaction solution rise to room temperature gradually subsequently, stirs 1 hour, refluxes then 0.5 hour.The reaction rear suspension liquid filters, and filter cake washs for several times with tetrahydrofuran (THF), and washing lotion is incorporated in the filtrate.Filtrate concentrates, places refrigerator and cooled and but spends the night, and separates out yellow solid, and press filtration, vacuum-drying obtain 0.92g catalyst precursor L
1ZrCl
2THF, L
1=[1,2-C
2H
4(N=CHC
6H
4-2-O
-)
2], at N
2Protection is room temperature preservation down.
(2) ethylene oligomerization
Ethylene oligomerization is reflected in the 100ml autoclave that has induction stirring and carries out.At first the exsiccant autoclave is found time nitrogen replacement three times.Under nitrogen protection, take by weighing 0.01mmol Primary Catalysts 1THF and add in the Schlenk bottle, add 15mL toluene, inject 1.0mL Et with the exsiccant syringe
2The toluene solution of AlCl, Al/Zr mol ratio are 1: 100, and stirred for several minute treats that solid dissolves fully, with the exsiccant syringe catalyst solution is added in the autoclave, and the Schlenk bottle is used 10mL and 5mL toluene washing bottle wall at twice again, and solution adds in the reactor.Weighing autoclave weight.Autoclave inserted in 150 ℃ the oil bath, magnetic stirs fast, feeds the ethene of constant voltage 1.4MPa.React after 30 minutes, stop heating, close the ethene valve, autoclave is chilled to 0～5 ℃, opens the autoclave vent valve, makes unreacted ethene discharge the autoclave of weighing once more.Open autoclave, do not have high poly-solid in the still.Add 0.5mLNaOH/EtOH saturated solution cancellation reaction, and accurately add the 0.6mL normal heptane as interior mark, after stirring, filter, the reaction clear liquid adopts GC and GC/MS methods analyst to measure.Products distribution is C
4～C
10Account for 89.1%, wherein C
4Account for 10.1%, C
6Account for 35.9%, C
8Account for 31.0, C
10Account for 12.1%, the selectivity of linear alpha-alkene is 91.5%.The activity of calculating catalyst system according to autoclave weight difference before and after the reaction is 6.80 * 10
5G oligopolymer/molZrh
-1Atm
-1
Embodiment 2
(1) Preparation of catalysts
With embodiment 1.
(2) ethylene oligomerization
Under nitrogen protection, take by weighing 0.01mmol Primary Catalysts 1THF and add in the Schlenk bottle, add 15mL toluene, inject 3.0mL Et with the exsiccant syringe
2The toluene solution of AlCl, Al/Zr mol ratio are 1: 300,, stirred for several minute treats that solid dissolves fully, with the exsiccant syringe catalyst solution is added in the autoclave, and the Schlenk bottle is used 10mL and 5mL toluene washing bottle wall at twice again, and solution adds in the reactor.Operate subsequently with embodiment 1.Products distribution is C
4～C
10Account for 86.3%, wherein the selectivity of linear alpha-alkene is 91.0%.The activity of calculating catalyst system according to autoclave weight difference before and after the reaction is 7.48 * 10
5G oligopolymer/mol Zrh
-1Atm
-1
Embodiment 3
(1) Preparation of catalysts
With embodiment 1.
(2) ethylene oligomerization
Under nitrogen protection, take by weighing 0.01mmol Primary Catalysts 1THF and add in the Schlenk bottle, add 15mL toluene, inject 3.0mL Et with the exsiccant syringe
2The toluene solution of AlCl, Al/Zr mol ratio are 1: 300,, stirred for several minute treats that solid dissolves fully, with the exsiccant syringe catalyst solution is added in the autoclave, and the Schlenk bottle is used 10mL and 5mL toluene washing bottle wall at twice again, and solution adds in the reactor.Weighing autoclave weight.Autoclave inserted in 150 ℃ the oil bath, magnetic stirs fast, feeds the ethene of constant voltage 1.8MPa.Next operate with embodiment 1.Products distribution is C
4～C
10Account for 89.3%, wherein the selectivity of linear alpha-alkene is 94.9%.The activity of calculating catalyst system according to autoclave weight difference before and after the reaction is 7.67 * 10
5G oligopolymer/mol Zrh
-1Atm
-1
Embodiment 4
(1) Preparation of catalysts
With embodiment 1.
(2) ethylene oligomerization
Under nitrogen protection, take by weighing 0.01mmol Primary Catalysts 1THF and add in the Schlenk bottle, add 15mL toluene, inject 1.0mL Et with the exsiccant syringe
2The toluene solution of AlCl, Al/Zr mol ratio are 1: 100,, stirred for several minute treats that solid dissolves fully, with the exsiccant syringe catalyst solution is added in the autoclave, and the Schlenk bottle is used 10mL and 5mL toluene washing bottle wall at twice again, and solution adds in the reactor.Weighing autoclave weight.Autoclave inserted in 135 ℃ the oil bath, magnetic stirs fast, feeds the ethene of constant voltage 1.4MPa.Next operate with embodiment 1.Products distribution is C
4～C
10Account for 94.5%, wherein the selectivity of linear alpha-alkene is 97.7%.The activity of calculating catalyst system according to autoclave weight difference before and after the reaction is 3.27 * 10
5G oligopolymer/mol Zrh
-1Atm
-1
Embodiment 5
(1) Preparation of catalysts
Under nitrogen protection, with the N of 1.46g, 4.61mmol, N '-1,2-phenylene-two (salicylic alidehyde imine) add in the exsiccant reaction flask, add the 70mL tetrahydrofuran (THF) and make it dissolving.Magnetic stirs down, is that 60% NaH adds in the reaction solution in batches with 0.37g, 9.23mmol content, releasing hydrogen gas, and being stirred to does not have bubble substantially and emits.Behind the heating reflux reaction 1 hour, be cooled to room temperature.Then under low temperature-25～30 ℃ stirring, with the ZrCl of 1.07g, 4.61mmol
4Under nitrogen protection, slowly add in the reaction solution in batches.Reinforced finishing continues low temperature and stirred 10 minutes, makes reaction solution rise to room temperature gradually subsequently, stirs 1 hour, refluxes then 1 hour.The reaction rear suspension liquid filters, and filter cake washs for several times with tetrahydrofuran (THF), and washing lotion is incorporated in the filtrate.Filtrate draining obtains the tawny solid.Add 30mL toluene and make the orange solids dissolving, refluxed 2 hours under nitrogen protection, mother liquor concentrates, and places refrigerator and cooled and but spends the night, and separates out yellow solid, and press filtration, pentane washing, vacuum-drying obtain the catalyst precursor L that 1.65g sloughs the coordination tetrahydrofuran (THF)
2ZrCl
2, L
2=[1,2-C
6H
4(N=CHC
6H
4-2-O
-)
2], at N
2Protection is room temperature preservation down.
(2) ethylene oligomerization
Under nitrogen protection, take by weighing 0.05mmol Primary Catalysts 2 and add in the Schlenk bottle, add 15mL toluene, inject 5.0mL Et with the exsiccant syringe
2The toluene solution of AlCl, Al/Zr mol ratio are 1: 100, and stirred for several minute treats that solid dissolves fully, with the exsiccant syringe catalyst solution is added in the autoclave, and the Schlenk bottle is used 10mL and 5mL toluene washing bottle wall at twice again, and solution adds in the reactor.Other operation and reaction conditions are with embodiment 1.Products distribution is C
4～C
10Account for 89.8%, wherein the selectivity of linear alpha-alkene is 87.5%.The activity of calculating catalyst system according to autoclave weight difference before and after the reaction is 2.46 * 10
5G oligopolymer/mol Zrh
-1Atm
-1
Embodiment 6
(1) Preparation of catalysts
Under nitrogen protection, with the N of 1.64g, 5.0mmol, N '-ethylene-two (5-methoxysalicyl aldehyde imines) adds in the exsiccant reaction flask, adds the 80mL tetrahydrofuran (THF).Magnetic stirs down, is that 60% NaH adds in the reaction solution in batches with 0.42g, 10.5mmol content, releasing hydrogen gas, and being stirred to does not have bubble substantially and emits.Behind the heating reflux reaction 0.5 hour, be cooled to room temperature.Then under low temperature-25～30 ℃ stirring, with the ZrCl of 1.17g, 5.02mmol
4Under nitrogen protection, slowly add in the reaction solution in batches.Reinforced finishing continues low temperature and stirred 10 minutes, makes reaction solution rise to room temperature gradually subsequently, stirs 1 hour, refluxes then 0.5 hour.The reaction rear suspension liquid filters, and filter cake washs for several times with tetrahydrofuran (THF), and washing lotion is incorporated in the filtrate.The filtrate vacuum concentration adds the 2mL normal hexane and separates out yellow solid to 2mL.Press filtration, pentane washing, vacuum-drying obtain 1.82g catalyst precursor L
6ZrCl
2THF, L
6=[1,2-C
2H
4(N=CHC
6H
3-5-OCH
3-2-O
-)
2], at N
2Protection is room temperature preservation down.
(2) ethylene oligomerization
Under nitrogen protection, take by weighing 0.01mmol Primary Catalysts 6THF and add in the Schlenk bottle, add 15mL toluene, inject 3.0mL Et with the exsiccant syringe
2The toluene solution of AlCl, Al/Zr mol ratio are 1: 300, and stirred for several minute treats that solid dissolves fully, with the exsiccant syringe catalyst solution is added in the autoclave, and the Schlenk bottle is used 10mL and 5mL toluene washing bottle wall at twice again, and solution adds in the reactor.Other operation and reaction conditions are with embodiment 1.Products distribution is C
4～C
10Account for 86.2%, wherein the selectivity of linear alpha-alkene is 91.5%.The activity of calculating catalyst system according to autoclave weight difference before and after the reaction is 6.94 * 10
5G oligopolymer/mol Zrh
-1Atm
-1
Embodiment 7
(1) Preparation of catalysts
Under nitrogen protection, will get N, N '-ethylene-two (5-chloro-salicylic aldehyde imines) adds in the exsiccant reaction flask, adds the 90mL tetrahydrofuran (THF).Magnetic stirs down, is that 60% NaH adds in the reaction solution in batches with 0.42g, 10.5mmol content, releasing hydrogen gas, and being stirred to does not have bubble substantially and emits.Behind the heating reflux reaction 1 hour, be cooled to room temperature.Then under ℃ stirring of low temperature-25～-30, with the ZrCl of 1.17g, 5.02mmol
4Under nitrogen protection, slowly add in the reaction solution in batches.Reinforced finishing continues low temperature and stirred 10 minutes, makes reaction solution rise to room temperature gradually subsequently, stirs 1 hour, refluxes then 0.5 hour.The reaction rear suspension liquid filters, and filter cake washs for several times with tetrahydrofuran (THF), and washing lotion is incorporated in the filtrate.The filtrate vacuum concentration adds the 2mL normal hexane and separates out yellow solid to 5mL.Press filtration, pentane washing, vacuum-drying obtain 1.91g catalyst precursor L
8ZrCl
2THF, L
8=[1,2-C
2H
4(N=CHC
6H
3-5-Cl-2-O
-)
2], at N
2Protection is room temperature preservation down.
(2) ethylene oligomerization
Under nitrogen protection, take by weighing 0.01mmol Primary Catalysts 8THF and add in the Schlenk bottle, add 15mL toluene, inject 3.0mL Et with the exsiccant syringe
2The toluene solution of AlCl, Al/Zr mol ratio are 1: 300, and stirred for several minute treats that solid dissolves fully, with the exsiccant syringe catalyst solution is added in the autoclave, and the Schlenk bottle is used 10mL and 5mL toluene washing bottle wall at twice again, and solution adds in the reactor.Other operation and reaction conditions are with embodiment 1.Products distribution is C
4～C
10Account for 86.7%, wherein the selectivity of linear alpha-alkene is 88.7%.The activity of calculating catalyst system according to autoclave weight difference before and after the reaction is 4.96 * 10
5G oligopolymer/mol Zrh
-1Atm
-1
Embodiment 8
(1) Preparation of catalysts
With embodiment 6.
(2) ethylene oligomerization
Under nitrogen protection, take by weighing 0.01mmol Primary Catalysts 6THF and add in the Schlenk bottle, add 15mL toluene, inject 10.0mL Et with the exsiccant syringe
2The toluene solution of AlCl, the Al/Zr mol ratio is 1: 1000, and a stirred for several minute suspended solids dissolves fully, with the exsiccant syringe catalyst solution is added in the autoclave, the Schlenk bottle is used 10mL and 5mL toluene washing bottle wall at twice again, and solution adds in the reactor.Other operation and reaction conditions are with embodiment 1.Products distribution is C
4～C
10Account for 88.3%, wherein the selectivity of linear alpha-alkene is 83.3%.The activity of calculating catalyst system according to autoclave weight difference before and after the reaction is 8.97 * 10
5G oligopolymer/mol Zrh
-1Atm
-1
Embodiment 9
(3) Preparation of catalysts
With embodiment 6.
(4) ethylene oligomerization
Under nitrogen protection, take by weighing 0.01mmol Primary Catalysts 6THF and add in the Schlenk bottle, add 15mL toluene, inject 5.0mL Me with the exsiccant syringe
2The toluene solution of AlCl, Al/Zr mol ratio are 1: 500, stir the low suspension solid and dissolve rapidly, with the exsiccant syringe catalyst solution are added in the autoclave, and the Schlenk bottle is used 10mL and 5mL toluene washing bottle wall at twice again, and solution adds in the reactor.Other operation and reaction conditions are with embodiment 1.Products distribution is C
4～C
10Account for 97.2%, wherein the selectivity of linear alpha-alkene is 99.3%.The activity of calculating catalyst system according to autoclave weight difference before and after the reaction is 3.77 * 10
5G oligopolymer/mol Zrh
-1Atm
-1
Claims (6)
1, a kind of zirconium tetrachloride ZrCl that directly uses
4With part N, N '-1,2-C
2H
4-(o-N=CH-5-R-C
6H
3ONa)
2Or N, N '-1,2-C
6H
4-(o-N=CH-5-R-C
6H
3ONa)
2Have the substituent zirconium complex catalyst precursor of R on the salicylic aldehyde phenyl ring of prepared in reaction, it is characterized in that zirconium complex catalyst precursor general formula is LZrCl
2Or LZrCl
2Sol, wherein:
X=-CH
2CH
2-or 1,2-C
6H
4-
R=-CH
3,-t-C
4H
9,-OCH
3,-OC
2H
5,-Cl-or Br;
Sol=tetrahydrofuran (THF), acetone, methyl alcohol or water.
2, a kind of preparation method according to the described zirconium complex catalyst precursor of claim 1 is characterized in that under nitrogen protection, with H
2L part N, N '-1,2-ethylidene-two (5-R substituting group salicylic alidehyde imine) or N, N '-1,2-phenylene-two (5-R substituting group salicylic alidehyde imine) is put into the dry reaction bottle, adds tetrahydrofuran (THF) and makes it dissolving, and magnetic stirs down, with content is that 60% NaH adds in batches, is stirred to no hydrogen and emits; Heating reflux reaction 0.5-1.0 hour, be chilled to room temperature, then under-25～-30 ℃ of stirrings with ZrCl
4Under nitrogen protection, slowly be added in the reaction solution in batches, make part: NaH: ZrCl
4Mol ratio be 1: 2: 1; Reinforced finishing, continuation was stirred 10 minutes at-25～-30 ℃, be warming up to room temperature gradually, stirred 1 hour, refluxed 0.5 hour, filter, use the tetrahydrofuran (THF) washing leaching cake, washing lotion is incorporated in the filtrate, through concentrating, cool off, separate out yellow solid, press filtration, vacuum-drying, makes zirconium complex catalyst precursor LZrCl
2Tetrahydrofuran (THF); It is dissolved in the toluene, under the nitrogen protection backflow 1.5-2.0 hour, obtains zirconium complex catalyst precursor LZrCl
2
3, according to the preparation method of the described zirconium complex catalyst precursor of claim 2, it is characterized in that LZrCl
2Or LZrCl
2Tetrahydrofuran (THF) is recrystallization, separation in acetone, obtains zirconium complex LZrCl
2OC (CH
3)
2
4, according to the preparation method of the described zirconium complex catalyst precursor of claim 2, it is characterized in that LZrCl
2Or LZrCl
2Tetrahydrofuran (THF) is recrystallization, separation in methyl alcohol, obtains zirconium complex LZrCl
2CH
3OH.
5, according to the preparation method of the described zirconium complex catalyst precursor of claim 2, it is characterized in that LZrCl
2Or LZrCl
2In the toluene solution of tetrahydrofuran (THF), add the water of equivalent, stirred 5 minutes, solution concentration is separated out yellow crystal, separates, and vacuum-drying obtains LZrCl
2H
2O.
6, according to the purposes of the described zirconium complex catalyst precursor of claim 1 in ethylene oligomerization, it is characterized in that making Primary Catalysts with the zirconium complex catalyst precursor, its concentration is 3-16mmol/L, and promotor is R
2AlCl, R are methyl or ethyl, and the Al/Zr mol ratio is 100-1000: 1, and ethylene pressure is 1.0-4.0MPa, and temperature of reaction is 100-180 ℃, and ethylene oligomerization generates C
4-C
16The selectivity of alkene is greater than 99%, alkene C
4-C
10Selectivity greater than 85%, wherein the selectivity of linear alpha olefin is greater than 90%, catalyst activity reaches 10
5G oligopolymer/molZrh
-1.-atm
-1The order of magnitude.
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| JPWO2006057229A1 (en) * | 2004-11-26 | 2008-06-05 | 三井化学株式会社 | Method for producing low molecular weight olefin polymer containing double bond at one end |
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