CN102807580B - Transition metal compound containing bidentate ligand and application thereof in olefin polymerization - Google Patents
Transition metal compound containing bidentate ligand and application thereof in olefin polymerization Download PDFInfo
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- CN102807580B CN102807580B CN201110148495.9A CN201110148495A CN102807580B CN 102807580 B CN102807580 B CN 102807580B CN 201110148495 A CN201110148495 A CN 201110148495A CN 102807580 B CN102807580 B CN 102807580B
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 47
- 239000003446 ligand Substances 0.000 title claims abstract description 10
- 150000001336 alkenes Chemical class 0.000 title abstract description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract description 9
- 150000003623 transition metal compounds Chemical class 0.000 title abstract description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000010936 titanium Substances 0.000 claims abstract description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 229910052735 hafnium Chemical group 0.000 claims abstract description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 17
- 150000002736 metal compounds Chemical class 0.000 claims description 14
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 10
- 238000007334 copolymerization reaction Methods 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 9
- 230000037048 polymerization activity Effects 0.000 abstract description 9
- 239000005977 Ethylene Substances 0.000 abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000012968 metallocene catalyst Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002899 organoaluminium compounds Chemical class 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- 125000005574 norbornylene group Chemical group 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003755 zirconium compounds Chemical class 0.000 description 2
- YKZUNWLMLRCVCW-UHFFFAOYSA-N 4-[2-(4-bicyclo[2.2.1]hept-2-enyl)ethyl]bicyclo[2.2.1]hept-2-ene Chemical compound C1CC(C2)C=CC21CCC1(C=C2)CC2CC1 YKZUNWLMLRCVCW-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 101100310622 Mus musculus Soga1 gene Proteins 0.000 description 1
- 229920000034 Plastomer Polymers 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a transition metal compound containing a bidentate ligand, which is shown in a general formula (I), wherein M is titanium, zirconium or hafnium; and X is halogen atom or alkyl containing 1-30 carbon atoms or alkoxyl containing 1-30 carbon atoms. The invention further relates to an olefin polymerization catalysis system formed by the transition metal compound and an organo-aluminum compound. When the polymeric system is used for catalyzing ethylene polymerization, higher polymerization activity can be obtained.
Description
Technical field
The invention belongs to organic synthesis, catalysis and field of olefin polymerisation, relate to a kind of transistion metal compound of the bidentate ligand with ad hoc structure, and with the catalyst system of olefinic polymerization of this transistion metal compound and organo-aluminium compound composition.
Technical background
The metallocene catalyst of for olefines polymerization is the study hotspot of Organometallic Chemistry, catalysis, polymer chemistry and materialogy in nearly decades always.Because use this kind of catalyzer, can obtain molecular weight distribution and all well-proportioned olefin polymer of chemical constitution distribution, simultaneously the molecular structure of polymkeric substance and molecular weight can be controlled by adjustment catalyst structure height.Pass through metallocene catalyst, the not getable olefin polymer of traditional Z iegler-Natta catalyzer can be obtained, as industrialized linear low density polyethylene (LLDPE), there is excellent mechanical strength and the transparency, there is high added value, high performance polyolefin elastomer, plastomer (POE, POP), cyclic olefine copolymer (COC) etc.
In recent years, the research of non-metallocene catalyst slowly became one of focus of research institution and Ge great chemical company.This is because, when metallocene catalyst is applied to olefinic polymerization, need to use a large amount of expensive methylaluminoxane (MAO), meanwhile, metallocene catalyst is very responsive to the impurity in system and raw material, and, although relative to traditional Z iegler-Natta system, metallocene can copolymerization monomer scope greatly expand, but for large steric hindrance with containing heteroatomic monomer, the activity that metallocene shows and copolymerized ability are also bad.By the research to metallocene catalyst, investigator to Organometallic Chemistry, catalysis, polymer chemistry and materialogy and between relation had considerable understanding, this makes to research and develop novel non-metallocene catalyst becomes possibility.By research and development, wish that new catalyst has more efficient, wide spectrum copolymerization performance, looser working conditions and cheaper use cost.
In the design studies of novel non-metallocene catalyst, the IVB transistion metal compound with bidentate ligand (having the part of two haptos) receives publicity especially.1998, Gibson reported compound as structure 1 and 2 (see figure), and ethylene polymerization activity is about 10
5-10
6g-PE/mol-cat hr bar, polymer average molecular weight can reach 10
5, but molecular weight distribution wider (Chem.Commun., 1998,313).McConville reports the compound as structure 3, at room temperature, can realize the living polymerization (J.Am.Chem.Soc.1996,118,10008) of alpha-olefin.The Soga catalyzer of this structure carries out propylene polymerization, can obtain fusing point close to the isotatic polypropylene (Macromol.Rapid Commun.1998,19,597) of 130 DEG C.There is the zirconium compounds (structure 4) of the asymmetric diamines coordination of bibliographical information, 10 are only had to the activity of vinyl polymerization
4g-PE/mol-cat hr bar (J.Mol.Catal.A:Chem.2002,182-183,411).Arnold report take ferrocene as the zirconium compounds (structure 5) of the diamines coordination of bridging, ethylene polymerization activity is 10
5g-PE/mol-cat hr atm (Organometallics2003,22,567; Inorg.Chim.Acta, 2003,345,216).The compound of bibliographical information structure 6 is used as ethylene rolymerization catalyst, obtains being not more than 10
4the polymerization activity (Inorg.Chim.Acta, 2003,345,81) of g-PE/mol-cat hr atm.The compound of structure 7 is used as ethylene rolymerization catalyst, obtains 10
4the activity (Inorg.Chem.2003,42,6592) of g-PE/mol-cat hr.
The compound 8 of the nitrogen oxygen coordination of Raush report, catalyzed ethylene polymerization activity can reach 10
6g-PE/mol-cat hr (J.Organomet.Chem.2001,625,95).The compound 9 of another nitrogen oxygen coordination, be used separately as the catalyzer of vinyl polymerization, norbornene polymerization and ethylene-norbornene copolymerization, vinyl polymerization, the activity of norbornene polymerization is all 10
4the level of g-Polymer/mol-cat hr, copolymerization activity is very low (states in document, but do not provide concrete data), catalyzer is very strong to the copolymerized ability of norbornylene, the most high-content of the norbornylene of polymkeric substance reaches 43mol%, and glass transition temperature of polymer is (Polymer, 2006 up to 114 DEG C, 47,8289).
1991, there is bibliographical information Ti (OEt)
4with C
6h
11cH (OH) CH (OH) C
6h
11reaction can obtain the dimer compound (Angew.Chem.Int.Ed.1991,30,1668) of titanium.Nineteen ninety-five, the bibliographical information compound of structure 10, take MAO as promotor, ethylene polymerization activity can reach 10
6the level of g-PE/mol-cat hr, but molecular weight distribution very wide (J.Am.Chem.Soc.1995,117,3008).2007, bibliographical information with the compound of structure 10 and 11 for catalyzer, the research (J.Appl.Polym.Sci.2007,104,1531) of the vinyl polymerization carried out.1997, Okuda reported with the compound of structure 12 for catalyzer, carries out ethylene-stryene copolymerization, and catalyzer is very strong to cinnamic copolymerized ability, but polymerization activity not high (Organometallics 1997,16,4240).
Patent documentation WO 92/12162 discloses the IVB group transition metal compound of the phenodiazine coordination of bridging or non-bridging, and use this compound as catalyzer, carry out olefinic polymerization, the isotatic polypropylene of the polyolefine of high molecular, particularly high molecular can be obtained.CN98802644 discloses a kind of method preparing two replacement terminal olefine multipolymer, and as shown at 13, catalyzer has good copolymerizable to iso-butylene to used catalyst structure, and molecular weight distribution is about 2, but polymerization activity and polymericular weight are not high.
As can be seen from document, research about the olefin polymerization catalysis with bidentate ligand is a lot, this kind of catalyzer has showed the feature different from traditional metallocene, but it is not high still to there is polymerization activity, polymericular weight is not high, molecular weight distribution is wider, and the problem such as comonomer used is wide in range not.So research and develop new part, to prepare new transition-metal catalyst, thus obtain better polymerization effect, remain an important problem.
Summary of the invention
The object of this invention is to provide a kind of transistion metal compound of the bidentate ligand with ad hoc structure, and using this transistion metal compound as the application of the olefinic polymerization of catalyzer.
Be used as the transistion metal compound of olefin polymerization catalysis in the present invention, there is following general formula:
In formula: X is anion ligand, comprise halogen atom or alkyl, alkoxyl group, aryloxy containing 1-30 carbon atom, wherein preferred chlorine atom, isopropoxy and phenoxy group;
M is titanium, zirconium or hafnium, wherein preferred titanium, zirconium, more preferred titanium.
The invention provides a kind of catalyst system of olefinic polymerization, comprise described transistion metal compound and the organo-aluminium compound being referred to as promotor above.
Organo-aluminium compound as promotor is alkyl aikyiaiurnirsoxan beta, and its structure may be:
Wherein R represents alkyl, is preferably methyl, ethyl, propyl group, butyl, is preferably methyl or isobutyl-the most.N represents the integer of 4-30, is preferably the integer of 10-30.
Described alkyl aikyiaiurnirsoxan beta is 50: 1 to 20000: 1 with the molar ratio of the transistion metal compound being used as olefin polymerization catalysis, and preferable range is 200: 1 to 10000: 1.
During polymerization, cocatalyst component together or respectively adds polymerization reactor with the transistion metal compound being used as olefin polymerization catalysis and uses.
The concentration of transistion metal compound when being polymerized as olefin polymerization catalysis is 1x10
-8mol/L is to 1x10
-3mol/L, is preferably 1x10
-7mol/L is to 1x10
-5mol/L.
Polymerization temperature is-50 DEG C to 200 DEG C, is preferably-20 DEG C to 150 DEG C.
Catalytic systems for polymerization of olefins provided by the present invention can be used for homopolymerization and the copolymerization of alkene, be particularly suitable for the homopolymerization of ethene and the copolymerization of ethene and other terminal olefines, wherein, terminal olefine is the one in propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 4-methyl-1-pentene.
Embodiment
The present invention is further illustrated by the following examples, but should not be construed as limitation of the invention.
MAO solution used in embodiment is the toluene solution of methylaluminoxane; Catalyst solution is the toluene solution of 5 μm of ol/mL.
The synthesis of embodiment 1 norbornylene-dimethoxy-diisopropoxy titanium
250 milliliters of there-necked flasks of abundant oven dry put into stirring magneton, are placed in oil bath, vacuumize, nitrogen wash, three times repeatedly.Add tetraisopropoxy titanium 10 milliliters under nitrogen atmosphere, add norbornylene dimethanol 1.65 grams, start and stir, room temperature reaction 12 hours.Be evacuated down to 7000Pa, oil bath 130 DEG C, stirring reaction 12 hours.Naturally rise to room temperature, add the hexane of 10mL through anhydrous and oxygen-free process, fully stir, freezing and crystallizing, obtain white powder.H
1-NMR(25℃in CDCl
3)，δ5.6(2H)，3.3-3.6(6H)，1.6-2.3(6H)，1.2(12H)。
Embodiment 2 with norbornylene-dimethoxy-diisopropoxy titanium for catalyst vinyl polymerization
The polymerization bottle of abundant oven dry, vacuumizes, nitrogen wash, three times repeatedly.Vacuumize, solenoid control, be filled with ethene, under design temperature, add 27.5 milliliters of toluene, 1.5 milliliters of MAO solution, 1 milliliter of catalyst solution successively, start timing.After polymerization setting-up time, close ethene, pour reaction solution into beaker, add acidic ethanol, stir more than 6 hours, filter and obtain polymkeric substance, vacuum-drying 24 hours, calculated activity of weighing.The results are shown in table 1.
Embodiment 3 with norbornylene-dimethoxy-diisopropoxy titanium for catalyst vinyl polymerization
The polymerization bottle of abundant oven dry, vacuumizes, nitrogen wash, three times repeatedly.Vacuumize, solenoid control, be filled with ethene, under design temperature, add 26 milliliters of toluene, 3 milliliters of MAO solution, 1 milliliter of catalyst solution successively, start timing.After polymerization setting-up time, close ethene, pour reaction solution into beaker, add acidic ethanol, stir more than 6 hours, filter and obtain polymkeric substance, vacuum-drying 24 hours, calculated activity of weighing.The results are shown in table 1.
Embodiment 4 with norbornylene-dimethoxy-diisopropoxy titanium for catalyst vinyl polymerization
The polymerization bottle of abundant oven dry, vacuumizes, nitrogen wash, three times repeatedly.Vacuumize, solenoid control, be filled with ethene, under design temperature, add 23 milliliters of toluene, 6 milliliters of MAO solution, 1 milliliter of catalyst solution successively, start timing.After polymerization setting-up time, close ethene, pour reaction solution into beaker, add acidic ethanol, stir more than 6 hours, filter and obtain polymkeric substance, vacuum-drying 24 hours, calculated activity of weighing.The results are shown in table 1.
Embodiment 5 with norbornylene-dimethoxy-diisopropoxy titanium for catalyst vinyl polymerization
The polymerization bottle of abundant oven dry, vacuumizes, nitrogen wash, three times repeatedly.Vacuumize, solenoid control, be filled with ethene, under design temperature, add 20 milliliters of toluene, 9 milliliters of MAO solution, 1 milliliter of catalyst solution successively, start timing.After polymerization setting-up time, close ethene, pour reaction solution into beaker, add acidic ethanol, stir more than 6 hours, filter and obtain polymkeric substance, vacuum-drying 24 hours, calculated activity of weighing.The results are shown in table 1.
Table 1 vinyl polymerization
a
A, polymerizing condition: catalyzer, 5 μm of ol, polymerization temperature 25 DEG C, polymerization time 20 minutes, normal pressure ethene
B, polymer average molecular weight and molecular weight distribution, GPC data.
Claims (11)
1. the transistion metal compound containing bidentate ligand of being stated by logical formula I, is characterized in that:
In formula, M is titanium, zirconium or hafnium;
X is halogen atom or the alkyl containing 1-30 carbon atom or contains the-oxyl of 1-30 carbon atom.
2. compound according to claim 1, is characterized in that, in formula, M is titanium.
3. compound according to claim 1, is characterized in that, in formula, X is alkyl.
4. compound according to claim 1, is characterized in that, described X is alkoxyl group.
5. compound according to claim 1, is characterized in that, described X is isopropoxy.
6. compound according to claim 1, is characterized in that, described X is phenoxy group.
7. compound according to claim 1, is characterized in that, described X is chlorine atom.
8. for a catalyzer for olefinic polymerization, it is characterized in that, comprise the reaction product of following component:
(1) transistion metal compound containing bidentate ligand that one of claim 1-7 is described;
(2) one or more alkylaluminoxanes;
The mol ratio of the transistion metal compound described in component (1) and component (2) alkylaluminoxane is 1:200 to 1:10000.
9. the catalyzer for olefinic polymerization according to claim 8, is characterized in that, described alkylaluminoxane is methylaluminoxane.
10. the application of the catalyzer for olefinic polymerization in olefinic polyreaction that one of claim 8-9 is described.
The application of catalyzer in olefinic polyreaction of 11. olefinic polymerizations according to claim 10, wherein said olefinic polyreaction be all polymerizations of ethene or ethene and one or more contain the copolymerization of the alpha-olefin of 2-100 carbon atom.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992012162A1 (en) * | 1990-12-27 | 1992-07-23 | Exxon Chemical Patents Inc. | An amido transition metal compound and a catalyst system for the production of isotactic polypropylene |
| CN1974611A (en) * | 2006-11-20 | 2007-06-06 | 华东理工大学 | Prepn and application of catalytic nucleating agent for polyolefin |
-
2011
- 2011-06-03 CN CN201110148495.9A patent/CN102807580B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992012162A1 (en) * | 1990-12-27 | 1992-07-23 | Exxon Chemical Patents Inc. | An amido transition metal compound and a catalyst system for the production of isotactic polypropylene |
| CN1974611A (en) * | 2006-11-20 | 2007-06-06 | 华东理工大学 | Prepn and application of catalytic nucleating agent for polyolefin |
Non-Patent Citations (4)
| Title |
|---|
| 《Enantio- and Diastereoselective Titanium-TADDOLate Catalyzed Addition of Diethyl and bis(3-Buten-1-yl) Zinc to Aldehydes A Full Account with Preparative Details》;Dieter Seebach等;《Tetrahedron》;ELSEVIER;19940411;第50卷(第15期);第4363-4384页 * |
| 《On the Mechanisms of Enantioselective Reactions Using α,α,α,α-Tetraaryl-l,3-dioxolane-4,5-dimethanol(TADDOL)-Derived Titanates: Differences between C2- and C1-Symmetrical TADDOLs-Facts, Implications and Generalizations》;Dieter Seebach等;《HELVETICA CHIMICA ACTA》;Wiley;19921111;第75卷(第7期);第2171-2209页 * |
| 《Preparation and Structural Analysis of Several New α,α,α,α-Tetraaryl-l,3-dioxolane-4,5-dimethanols(TADDOLs) and TADDOL Analogs, Their Evaluation as Titanium Ligands …… Benzaldehyde, and Refinement of the Mechanistic Hypothesis》;Yoshio N. Ito等;《HELVETICA CHIMICA ACTA》;Wiley;19941014;第77卷(第8期);第2071-2110页 * |
| 《第ⅣB 族非茂金属烯烃聚合催化剂研究进展》;殷喜丰等;《化工进展》;CNKI;20091005;第28卷(第10期);第1750-1755页 * |
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