CN103030669A - Half-metallocene compound and its application in olefin polymerization catalyst - Google Patents
Half-metallocene compound and its application in olefin polymerization catalyst Download PDFInfo
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Abstract
The invention provides a half-metallocene compound with a sulfur-containing ligand. The general formula of the compound is shown as formula I, wherein X is alkyl or hydrocarbyloxy, and Cp' is alkyl substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl. The invention also provides an olefin polymerization catalyst composed of the half-metallocene compound and alkylaluminoxane. The half-metallocene compound involved in the invention has a simple synthesis route and high yield, and is an effective olefin polymerization catalyst when methylaluminoxane serves as a cocatalyst.
Description
Technical field
The invention belongs to organic synthesis and olefinic polymerization catalysis field, be specifically related to the luxuriant transistion metal compound of a kind of list with sulfur-containing ligand, with and application in olefin polymerization catalysis.
Background technology
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 class catalyzer, all well-proportioned olefin polymers of molecular weight distribution and chemical constitution distribution both can have been obtained; Simultaneously can be by adjusting catalyst structure, so that the molecular structure of polymkeric substance and molecular weight height are controlled; In addition, by using metallocene catalyst, can also obtain the olefin polymer that traditional Z iegler-Natta catalyzer can not obtain.As now the linear low density polyethylene of suitability for industrialized production (LLDPE) be to form with metallocene catalyst catalysis, LLDPE has outstanding mechanical strength and the transparency; Other has and possesses high added value, high performance polyolefin elastomer, plastomer (POE, POP), and cyclic olefine copolymer (COC) etc. all can react under the catalysis of metallocene catalyst and forms.
The metallocene catalyst of broad sense comprises metallocene catalyst (dual metallocene catalysts) and single metallocene catalyst.And from another angle, metallocene catalyst is divided into again two kinds of bridging and non-bridgings.
Constrained geometry catalyst (CGC) has the Cp-Ti-N structure, and it is a kind of single metallocene catalyst of bridging, has very outstanding copolymerization catalyst ability; Reason is that its huge Cp-Ti-N subtended angle provides very open confession to be total to space (US5026798, Organometallics, 1995,14,789 of monomer coordination; 3132).Compare with the metallocene catalyst of non-bridging or bridging, under identical reaction conditions, the copolymerization catalyst ability of CGC catalyzer is much better than (J.Mol.Catal.A 1998,128,215).
In recent years, in the research of olefin polymerization catalysis, more and more come into one's own with the single metallocene catalyst of giving the electronics part; Because this class catalyzer and CGC catalyzer have similar structure, and easier to be more synthetic than CGC catalyzer.Bibliographical information in this class many kinds have the catalyzer of special performance.
1991, the patent US5064802 of Dow Chemical has reported the catalyst system of compound and [HNEt3]+[B (C6F5) 4]-composition shown in Chemical formula 1, at room temperature catalyzed ethylene (latm) polymerization, activity is 12.3kg-PE/mol.-Ti/hr.
Mono-metallocene Cp ' Ti (OAr) Cl with aryloxy shown in Chemical formula 2
2(Organometallics 1998,17,2152), not only showed to catalyzed ethylene (Organometallics 1998,17,2152; Macromolecules 1998,31,7588), the equal high reactivity of polymerization of vinylbenzene (Macromolecules 2004,37,5520), non-conjugated diene (Macromolecules 2004,37,1693); And to catalysis alpha-olefin (Organometallics 1998,17,2152), cycloolefin (Macromolecules 2003,36,3797; Adv.Synth.Catal.2005,347,433) etc. the copolymerization with ethene has very high activity and outstanding copolymerized ability; Can also make simultaneously the monomer that general single-site catalysts can not polymerization, participate in ethylene copolymer such as tetrahydrobenzene (J.Am.Chem.Soc.2005,127,4582), 2-Methyl-1-pentene (Macromolecules 2005,38,2053) etc.
Mono-metallocene Cp ' Ti (OAr) Cl with aryloxy
2Be used for vinyl polymerization as olefin polymerization catalysis, during as promotor, activity can reach 9290kg-PE/mol-Ti/hr take modified methylaluminoxane (MMAO), and resulting polymers has high molecular and narrow molecular weight distribution.Its polymerization activity and catalyst structure are closely related, and the substituting group on Cp ' part and the aryloxy is strong effect polymerization behavior all.If mono-metallocene Cp ' Ti (OAr) is Cl
2On a chlorine atom further replaced by aryloxy, ethylene polymerization activity also can higher (J.Organomet.Chem.1999,591,185).
And take the bridging biphenol shown in chemical formula 3 as bidentate ligand, when synthetic single cyclopentadiene titanium compound is used for catalyzed ethylene polymerization, catalytic activity lower (Organometallics 2006,25,4358).
Take the trolamine shown in chemical formula 4 as tetradentate ligands, the Monodentate compound of synthetic Ti, Zr, Hf, and be used for vinyl polymerization.Under the same reaction conditions, the catalyzed polymerization activity of titanium compound is the highest; The molecular weight of polyethylene that zirconium compounds catalysis obtains is the highest; And the catalytic activity of hafnium compound is minimum, and the molecular weight of resulting polymers is minimum (J.Organomet.Chem.2006,691,1121) also.
Use is with mono-metallocene Cp ' Ti (OAr) Cl of aryloxy
2The Copolymerization activity of catalyzed ethylene and alpha-olefin is active far above its catalyzed ethylene homopolymerization; Simultaneously, research finds, the multipolymer that generates with the single metallocene-titanium catalyst catalysis of aryloxy has alternately tendency, and the multipolymer that the CGC catalyzer obtains have the block tendency (J.Mol.Catal.A 2000,152,249; 2000,159,127; 2001,174,127; Macromolecules 2000,33, and 3187).Single metallocene catalyst with aryloxy not only shows good polymerization behavior to ethene-alpha-olefin, and some are thought that traditionally the end alkene monomer that is difficult to the participation polycoordination also shows good copolymerized ability; The for example copolymerization of ethene and 2-Methyl-1-pentene (2M1P), this 1,1-two substituted alpha-alkenes (1 of ethene, the 1-position is 2M1P after replacing with methyl and propyl group) use traditional catalyst can not participate in polycoordination, (Macromolecules 1998 to only have the minority document, 31,5145; J.Am.Chem.Soc.2003,125,10788) reported the copolymerization of ethene-iso-butylene and ethene-2M1P, in the polymerization altogether monomer need greatly excessively, and polymerization activity and the polymericular weight that obtains are all very low.With Cp ' Ti (OAr) Cl
2/ MAO is catalyst system catalyzed ethylene and 2M1P copolymerization, under medium 2M1P input concentration, can obtain common monomer content near 10% multipolymer, keeps simultaneously higher polymerization activity; But along with the content of common monomer in polymkeric substance increases, polymericular weight decline (Macromolecules 2007,40,6489).And under the same conditions, metallocene catalyst and CGC catalyzer all can not make 2M1P participate in polymerization.
The CGC catalyzer is with the representative in the single metallocene catalyst of N Atomic coordinate, because the CGC catalyzer demonstrates very superior polymerization property, the olefin polymer superior performance that obtains, this has stayed imagination space for the research of the single metallocene catalyst of N Atomic coordinate.The single metallocene catalyst of various N Atomic coordinates occurs in the literature more and more.
With alkane (virtue) oxygen base class seemingly, using the amido part is a kind of simple and effective idea and method (J.Organomet.Chem.1994,467,79 as single metallocene catalyst to the electronics part; 1995,497,17; 2000,598,179).Document shows, the mono-metallocene compound Cp ' Ti (NR shown in chemical formula 5
1R
2) Cl
2All be that effectively (Macromolecules 2003 for ethene, propylene, hexene-1, syndiotactic polymerization of phenylethylene and ethene-hexene-1 copolymerization, 36,2633), its result shows, polymerization catalyst activity and resulting polymers molecular weight and copolymerized ability and Cp ' and substituent R
1, R
2Structure closely related.
Patent US6420300B1 reported shown in chemical formula 6 with the mono-metallocene compound of imido grpup as olefin polymerization catalysis.It studies show that, take imido grpup as to the luxuriant titanium of the list of electronics part when the equal polymerization of catalyzed alkene, all show very high activity, polymericular weight is higher simultaneously, but the catalyzed copolymerization ability is all than take aryloxy ligands as the less better (J.Organomet.Chem.2004 of single cyclopentadienyl catalyst to the electronics part, 689,203; J.Mol.Catal.A2004,220,133).In addition, all right catalyzed ethylene of this class catalyzer-cycloolefin copolymerization (J.Organomet.Chem.2007,692,4675), ethene-styrene copolymerized (J.Am.Chem.Soc.2005,127,9364) etc.Patent US6355744 has reported imido grpup (N=CR
2) on carbon atom change phosphorus atom into, become new for electronics part phosphinimine base (N=PR
3), and then synthetic new single metallocene catalyst (; Organometallics 1999,18, and 1116; 2004,23,1562), shown in chemical formula 7; The activity of this class catalyst vinyl polymerization is apparently higher than metallocene catalyst.
Except with Sauerstoffatom, nitrogen-atoms and the transition-metal coordination, use in addition the two coordinations (J.Organomet.Chem.2005,690,2941) of N-P, comprise the two coordinations of N-O of Schiff alkali or the mono-metallocene compound (Chem.Commun. of polygamy position, 2005,2152; Macromolecules 2002,35, and 4871; J.Organomet.Chem.2003,665,135; Inorg.Chem.Commun.2005,8,444; Organometallics 2006,25, and 6019; 2007,26,4042) as olefin polymerization catalysis.
Can find out from existing document, about a lot of with the research of the luxuriant transition metal catalyst for olefin polymerization of list of giving the electronics part, this class catalyzer shows the characteristics different from traditional metallocene, so research and develop new part to prepare the luxuriant transition-metal catalyst of new list, remain an important problem.
Summary of the invention
The purpose of this invention is to provide the luxuriant transistion metal compound of a kind of list with sulfur-containing ligand, and the olefin polymerization catalysis that is formed by this transistion metal compound and alkylaluminoxane.The mono-metallocene compound general formula is suc as formula shown in the I among the present invention:
Among the formula I, X is alkyl or-oxyl; Cp ' replaces or unsubstituted cyclopentadienyl, indenyl or fluorenyl with alkyl.
X described in preferred the present invention is methyl, alkoxyl group or phenoxy group; More preferably described alkoxyl group is methoxyl group, isopropoxy or butoxy.
Cp ' described in preferred the present invention is cyclopentadienyl, pentamethyl-cyclopentadienyl or indenyl.
It is the catalyzer of Primary Catalysts take alkylaluminoxane as promotor that the present invention also provides more than one to state mono-metallocene compound, in the described mono-metallocene compound in Ti and the alkylaluminoxane mol ratio of Al be 1: 50 to 1: 20000.
The structure of described alkylaluminoxane can be for shown in formula II or the III:
R represents alkyl among formula II and the III, is preferably methyl, ethyl, propyl group, butyl or isobutyl-, more preferably methyl or isobutyl-; N represents the integer of 4-30, is preferably the integer of 10-30.
Preferred described alkylaluminoxane is methylaluminoxane, and in the described mono-metallocene compound in Ti and the methylaluminoxane mol ratio of Al be 1: 200 to 1: 10000.More preferably in the described mono-metallocene compound in Ti and the methylaluminoxane mol ratio of Al be 1: 500 to 1: 3000.
The present invention also provides the application of above-mentioned catalyzer in the equal polymerization of alkene or copolymerization.Preferred described alkene all is polymerized to the equal polymerization of ethene.Preferred described olefin-copolymerization is combined into the copolymerization of ethene and one or more alpha-olefins; Preferred above-mentioned alpha-olefin is propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene or 4-methyl-1-pentene.
During olefinic polymerization, described promotor and mono-metallocene compound together or respectively add polymerization reactor to be used.Polymerization temperature is-50 ℃ to 200 ℃, is preferably-20 ℃ to 150 ℃.Described promotor and mono-metallocene compound are preferably dissolved in the solvent toluene before the olefinic polymerization and during polymerization.
Concentration during described mono-metallocene compound polymerization in solvent toluene is preferably 1 * 10
-8Mol/L to 1 * 10
-2Mol/L, more preferably 1 * 10
-7Mol/L to 1 * 10
-3Mol/L.
Embodiment
The present invention is further illustrated by the following examples, but should not be construed as limitation of the invention.
Used MAO solution is the toluene solution of methylaluminoxane among the embodiment, and it is 1.67mmol that every ml soln contains MAO; Used catalyst solution is the toluene solution of mono-metallocene compound, and every ml soln comprises mono-metallocene compound 5 μ mol.
Synthesizing of embodiment 1 Primary Catalysts
Synthesizing of pentamethyl-cyclopentadienyl-penta fluoro benzene sulfenyl-dimethoxy titanium: magneton is put into 250 milliliters of dry there-necked flasks, bottle is placed the magnetic stirring apparatus of oil bath temperature control; There-necked flask vacuumized repeatedly wash three times with nitrogen afterwards.And under nitrogen atmosphere, add pentamethyl-cyclopentadienyl-trimethoxy titanium 1.8g, and toluene 50mL, penta fluoro benzene thiophenol 1.35g, the stirring at room reaction is spent the night.Obtain yellow powder 2.1g after the solvent removed in vacuo, i.e. product pentamethyl-cyclopentadienyl among the present invention-penta fluoro benzene sulfenyl-dimethoxy titanium, its molar yield is 72%.
The yellow powder that takes a morsel adds a small amount of toluene dissolving, and freezing and crystallizing obtains yellow rib shape crystal.Its characterization result is as follows, nucleus magnetic resonance:
1H-NMR (CDCl
3, 25C): δ=2.12 (15H), 3.96 (6H).The ultimate analysis calculated value is C, 48.66; H, 4.76.Experimental value is C, 48.73; H, 4.38.
The equal polymerization reaction of embodiment 2 catalyzed ethylenes
The polymerization bottle of drying vacuumized repeatedly wash three times with nitrogen afterwards, vacuumize again; Be filled with ethene under solenoid control, keeping ethylene pressure is normal pressure.The catalyzer toluene solution 1mL that under 30 ℃, adds successively toluene 17.5mL, MAO toluene solution 1.5mL and prepared by the yellow powder among the embodiment 1, the beginning timing.Behind 30 ℃ of lower polyreaction 20min, close ethene, pour reaction solution into beaker, add acidifying ethanol termination reaction, stirs that filtration obtains polymkeric substance after 6 hours, filter cake is 60 ℃ of lower vacuum-dryings 24 hours, the rear calculating catalyst activity of weighing; It the results are shown in the table 1.
The equal polymerization reaction of embodiment 3 catalyzed ethylenes
Add toluene 16mL, MAO solution 3mL in the present embodiment, all the other steps are identical with embodiment 2.
The equal polymerization reaction of embodiment 4 catalyzed ethylenes
Add toluene 13mL, MAO solution 6mL in the present embodiment, all the other steps are identical with embodiment 2.
The equal polymerization reaction of embodiment 5 catalyzed ethylenes
Add toluene 10mL, MAO solution 9mL in the present embodiment, all the other steps are identical with embodiment 2.
Table 1
Annotate: M
wBe polymer average molecular weight; M
w/ M
nBe the ratio of weight-average molecular weight and number-average molecular weight, i.e. molecular weight distribution; Aforementioned two data are gel permeation chromatography (GPC) and detect the data obtained.
By the data in the upper table as can be known, use catalyst vinyl polymerization of the present invention, catalyzer has higher catalytic activity.In addition, the mono-metallocene compound synthetic route with sulfur-containing ligand involved in the present invention is simple, and yield is higher, during as promotor, is a kind of effective olefin polymerization catalysis in methylaluminoxane.
Claims (10)
1. mono-metallocene compound, its general formula is suc as formula shown in the I:
Among the formula I, X is alkyl or-oxyl; Cp ' replaces or unsubstituted cyclopentadienyl, indenyl or fluorenyl with alkyl.
2. compound according to claim 1 is characterized in that, described X is methyl, alkoxyl group or phenoxy group.
3. compound according to claim 2 is characterized in that, described alkoxyl group is methoxyl group, isopropoxy or butoxy.
4. compound according to claim 1 is characterized in that, described Cp ' is cyclopentadienyl, pentamethyl-cyclopentadienyl or indenyl.
5. a catalyzer that contains the described mono-metallocene compound of any one among the claim 1-4 is characterized in that, also comprises promoter aluminium alkyl oxygen alkane in the described catalyzer; In the described mono-metallocene compound in Ti and the alkylaluminoxane mol ratio of Al be 1: 50 to 1: 20000.
6. catalyzer according to claim 5 is characterized in that, described alkylaluminoxane is methylaluminoxane, in the described mono-metallocene compound in Ti and the methylaluminoxane mol ratio of Al be 1: 200 to 1: 10000.
7. catalyzer according to claim 6 is characterized in that, in the described mono-metallocene compound in Ti and the methylaluminoxane mol ratio of Al be 1: 500 to 1: 3000.
8. the application of the described catalyzer of any one in the equal polymerization of alkene or copolymerization among the claim 5-7.
9. application according to claim 8 is characterized in that, described alkene all is polymerized to the equal polymerization of ethene.
10. application according to claim 8 is characterized in that, described olefin-copolymerization is combined into the copolymerization of ethene and one or more alpha-olefins.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112745365A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Metallocene-containing phenol metal complex and preparation method and application thereof |
| CN113248548A (en) * | 2021-05-19 | 2021-08-13 | 青岛科技大学 | Preparation method and application of single metallocene catalyst |
| CN113402641A (en) * | 2021-06-02 | 2021-09-17 | 北京化工大学 | Metallocene catalyst, preparation method and application |
| CN114890987A (en) * | 2022-04-13 | 2022-08-12 | 万华化学集团股份有限公司 | Thiophenol-thiophene ligand and preparation method thereof, olefin polymerization catalyst and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20060086193A (en) * | 2005-01-26 | 2006-07-31 | 주식회사 엘지화학 | Novel halophenoxy or halobenzyloxy half metallocene catalysts and method for preparing syndiotactic polystyrenes |
-
2011
- 2011-09-30 CN CN201110291489.9A patent/CN103030669B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20060086193A (en) * | 2005-01-26 | 2006-07-31 | 주식회사 엘지화학 | Novel halophenoxy or halobenzyloxy half metallocene catalysts and method for preparing syndiotactic polystyrenes |
Non-Patent Citations (3)
| Title |
|---|
| KLAPOETKE THOMAS等,: "Synthesis and spectroscopic characterization of new mono(cyclopentadienyl)titanium(IV) thiolate complexes of the type CpTi(SR)n(Cl)3-n; n = 1, 2, 3", 《ZEITSCHRIFT FUER NATURFORSCHUNG, B: CHEMICAL SCIENCES》 * |
| SEAN W. EWART等,: "Ethylene and Propylene Polymerization by a Series of Highly Electrophilic, Chiral Monocyclopentadienyltitanium Catalysts", 《ORGANOMETALLICS》 * |
| SEAN W. EWART等,: "Ethylene and propylene polymerization by cationic monocyclopentadienyl titanium catalysts containing the weakly coordinating anion [B(C6F5)4]-", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112745365A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Metallocene-containing phenol metal complex and preparation method and application thereof |
| CN112745365B (en) * | 2019-10-31 | 2023-10-10 | 中国石油化工股份有限公司 | Metallocene-containing phenol metal complex and preparation method and application thereof |
| CN113248548A (en) * | 2021-05-19 | 2021-08-13 | 青岛科技大学 | Preparation method and application of single metallocene catalyst |
| CN113402641A (en) * | 2021-06-02 | 2021-09-17 | 北京化工大学 | Metallocene catalyst, preparation method and application |
| CN114890987A (en) * | 2022-04-13 | 2022-08-12 | 万华化学集团股份有限公司 | Thiophenol-thiophene ligand and preparation method thereof, olefin polymerization catalyst and preparation method and application thereof |
| CN114890987B (en) * | 2022-04-13 | 2023-12-19 | 万华化学集团股份有限公司 | Thiophenol-thiophene ligand and preparation method thereof, olefin polymerization catalyst and preparation method and application thereof |
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