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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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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