CN103030669B - A kind of mono-metallocene compound and the application in olefin polymerization catalysis thereof - Google Patents
A kind of mono-metallocene compound and the application in olefin polymerization catalysis thereof Download PDFInfo
- Publication number
- CN103030669B CN103030669B CN201110291489.9A CN201110291489A CN103030669B CN 103030669 B CN103030669 B CN 103030669B CN 201110291489 A CN201110291489 A CN 201110291489A CN 103030669 B CN103030669 B CN 103030669B
- Authority
- CN
- China
- Prior art keywords
- mono
- metallocene compound
- polymerization
- metallocene
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 0 C[Tl+](*)(*)Sc(c(F)c(c(F)c1F)F)c1F Chemical compound C[Tl+](*)(*)Sc(c(F)c(c(F)c1F)F)c1F 0.000 description 2
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a kind of mono-metallocene compound with sulfur-containing ligand, its general formula is such as formula shown in I, and wherein X is alkyl or-oxyl; Cp ' is for using the substituted or unsubstituted cyclopentadienyl of alkyl, indenyl or fluorenyl.The present invention also provides the olefin polymerization catalysis be made up of this mono-metallocene compound and alkylaluminoxane.Mono-metallocene compound synthetic route involved in the present invention is simple, and yield is higher; When methylaluminoxane is as promotor, it is a kind of effective olefin polymerization catalysis.
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, and its 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 kind of catalyzer, molecular weight distribution and all well-proportioned olefin polymer of chemical constitution distribution both can be obtained; Simultaneously by adjustment catalyst structure, make the molecular structure of polymkeric substance and molecular weight height controlled; In addition, by using metallocene catalyst, the not getable olefin polymer of traditional Z iegler-Natta catalyzer can also be obtained.As now the linear low density polyethylene (LLDPE) of suitability for industrialized production be form with metallocene catalyst catalysis, LLDPE has outstanding mechanical strength and the transparency; Separately have and possess high added value, high performance polyolefin elastomer, plastomer (POE, POP), cyclic olefine copolymer (COC) etc., all can react under the catalysis of metallocene catalyst and form.
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 bridging and non-bridging two kinds.
Constrained geometry catalyst (CGC) has Cp-Ti-N structure, and it is a kind of single metallocene catalyst of bridging, has very outstanding copolymerization catalyst ability; Reason is space (US5026798, Organometallics, 1995,14,789 that its huge Cp-Ti-N subtended angle provides that very open confession is total to monomer coordination; 3132).Compared 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.A1998,128,215).
In recent years, in the research of olefin polymerization catalysis, more and more come into one's own with giving the single metallocene catalyst of electron donor ligand; Because this kind of catalyzer and CGC catalyzer have similar structure, and easilier than CGC catalyzer to synthesize.During bibliographical information is this kind of, many kinds has the catalyzer of special performance.
1991, the patent US5064802 of DowChemical reports the catalyst system of compound as described in chemical formula 1 and [HNEt3]+[B (C6F5) 4]-form, at room temperature catalyzed ethylene (latm) polymerization, activity is 12.3kg-PE/mol.-Ti/hr.
Mono-metallocene Cp ' Ti (OAr) Cl with aryloxy as shown in chemical formula 2
2(Organometallics1998,17,2152), have not only showed catalyzed ethylene (Organometallics1998,17,2152; Macromolecules1998,31,7588), the high reactivity that is all polymerized of vinylbenzene (Macromolecules2004,37,5520), non-conjugated diene (Macromolecules2004,37,1693); And to catalysis alpha-olefin (Organometallics1998,17,2152), cycloolefin (Macromolecules2003,36,3797; Adv.Synth.Catal.2005,347,433) etc. with the copolymerization of ethene, there is very high activity and outstanding copolymerized ability; The monomer that simultaneously general single-site catalysts can also be made not to be polymerized, as tetrahydrobenzene (J.Am.Chem.Soc.2005,127,4582), 2-Methyl-1-pentene (Macromolecules2005,38,2053) etc. participate in ethylene copolymer.
With mono-metallocene Cp ' Ti (OAr) Cl of aryloxy
2be used for vinyl polymerization as olefin polymerization catalysis, during with modified methylaluminoxane (MMAO) for promotor, activity can reach 9290kg-PE/mol-Ti/hr, and resulting polymers has high molecular and narrow molecular weight distribution.Its polymerization activity and catalyst structure closely related, the substituting group on Cp ' part and aryloxy affects polymerization behavior all strongly.If mono-metallocene Cp ' Ti (OAr) Cl
2on a chlorine atom replaced by an aryloxy further, ethylene polymerization activity also can higher (J.Organomet.Chem.1999,591,185).
And with the bridging biphenol such as shown in chemical formula 3 for bidentate ligand, when synthesis Binary catalysts is used for catalyzed ethylene polymerization, catalytic activity lower (Organometallics2006,25,4358).
With the such as trolamine shown in chemical formula 4 for tetradentate ligands, the Monodentate compound of synthesis Ti, Zr, Hf, and for vinyl polymerization.Under 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, the molecular weight of resulting polymers also minimum (J.Organomet.Chem.2006,691,1121).
Use mono-metallocene Cp ' Ti (OAr) Cl with aryloxy
2the Copolymerization activity of catalyzed ethylene and alpha-olefin is active far above its catalyzed ethylene homopolymerization; Meanwhile, research finds, the multipolymer that the single metallocene-titanium catalyst catalysis with aryloxy generates has alternately tendency, and the multipolymer that CGC catalyzer obtains has block to be inclined to (J.Mol.Catal.A2000,152,249; 2000,159,127; 2001,174,127; Macromolecules2000,33,3187).Single metallocene catalyst with aryloxy not only shows good polymerization behavior to ethene-alpha-olefin, and also shows good copolymerized ability to the end alkene monomer that some are conventionally difficult to participate in polycoordination; The such as copolymerization of ethene and 2-Methyl-1-pentene (2M1P), this 1,1-bis-substituted alpha-alkene (1 of ethene, 1-position is 2M1P after replacing with methyl and propyl group) use traditional catalyst not participate in polycoordination, only has minority document (Macromolecules1998,31,5145; J.Am.Chem.Soc.2003,125,10788) report the copolymerization of ethene-iso-butylene and ethene-2M1P, in polymerization altogether monomer need greatly excessive, and polymerization activity and the polymericular weight that obtains 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 close to the multipolymer of 10%, keep higher polymerization activity simultaneously; But along with common monomer content in the polymer increases, polymericular weight declines (Macromolecules2007,40,6489).And under the same conditions, metallocene catalyst and CGC catalyzer all can not make 2M1P participate in polymerization.
CGC catalyzer is with the representative in the single metallocene catalyst of atom N coordination, because CGC catalyzer demonstrates very superior polymerization property, the olefin polymer superior performance obtained, this leaves imagination space to the research of the single metallocene catalyst of atom N coordination.The single metallocene catalyst of various atom N coordination occurs in the literature more and more.
With alkane (virtue) oxygen base class seemingly, use amido part to be a kind of simple and effective idea and method (J.Organomet.Chem.1994,467,79 as single metallocene catalyst to electron donor ligand; 1995,497,17; 2000,598,179).Document shows, the mono-metallocene compound Cp ' Ti (NR as shown in chemical formula 5
1r
2) Cl
2for ethene, propylene, hexene-1, syndiotactic polymerization of phenylethylene and polyethylene-hexene-1 copolymerization be all effective (Macromolecules2003,36,2633), its result shows, the active and resulting polymers molecular weight of polymerization catalyst and copolymerized ability and Cp ' and substituent R
1, R
2structure closely related.
Patent US6420300B1 reports the mono-metallocene compound with imido grpup as shown in chemical formula 6 as olefin polymerization catalysis.Its research shows, with imido grpup be to the luxuriant titanium of the list of electron donor ligand when catalyzed alkene is all polymerized, all show very high activity, polymericular weight is higher simultaneously, but catalyzed copolymerization ability is all than being to the less better (J.Organomet.Chem.2004 of single cyclopentadienyl catalyst of electron donor ligand with aryloxy ligands, 689,203; J.Mol.Catal.A2004,220,133).In addition, this kind of catalyzer can also catalyzed ethylene-cycloolefin copolymer (J.Organomet.Chem.2007,692,4675), ethylene-stryene copolymerization (J.Am.Chem.Soc.2005,127,9364) etc.Patent US6355744 reports imido grpup (-N=CR
2) on carbon atom change phosphorus atom into, become new for electron donor ligand phosphinimine base (-N=PR
3), and then synthesize new single metallocene catalyst (; Organometallics1999,18,1116; 2004,23,1562), as shown in chemical formula 7; The activity of this kind of catalyst vinyl polymerization is apparently higher than metallocene catalyst.
Except with except Sauerstoffatom, nitrogen-atoms and transition-metal coordination, also have and use the two coordination (J.Organomet.Chem.2005 of N-P, 690,2941) the two coordination of N-O of Schiff or the mono-metallocene compound (Chem.Commun. of polygamy position, is comprised, 2005,2152; Macromolecules2002,35,4871; J.Organomet.Chem.2003,665,135; Inorg.Chem.Commun.2005,8,444; Organometallics2006,25,6019; 2007,26,4042) as olefin polymerization catalysis.
As can be seen from existing document, a lot of about the research with the luxuriant transition metal catalyst for olefin polymerization of list giving electron donor ligand, this kind of catalyzer shows the feature 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 object 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 be made up of this transistion metal compound and alkylaluminoxane.In the present invention, mono-metallocene compound general formula is such as formula shown in I:
In formula I, X is alkyl or-oxyl; Cp ' is for using the substituted or unsubstituted cyclopentadienyl of alkyl, indenyl or fluorenyl.
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, pentamethylcyclopentadiene base or indenyl.
The catalyzer of the present invention also provides more than one to state mono-metallocene compound to be Primary Catalysts with alkylaluminoxane be promotor, in described mono-metallocene compound, in Ti and alkylaluminoxane, the mol ratio of Al is 1: 50 to 1: 20000.
The structure of described alkylaluminoxane can for shown in formula II or III:
In formula II and III, R represents alkyl, is preferably methyl, ethyl, propyl group, butyl or isobutyl-, is 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 described mono-metallocene compound in Ti and methylaluminoxane the mol ratio of Al be 1: 200 to 1: 10000.More preferably in described mono-metallocene compound, in Ti and methylaluminoxane, the mol ratio of Al is 1: 500 to 1: 3000.
The present invention also provides above-mentioned catalyzer to be all polymerized or application in copolymerization at alkene.Preferred described alkene is all polymerized to all polymerizations 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 and use.Polymerization temperature is-50 DEG C to 200 DEG C, is preferably-20 DEG C to 150 DEG C.Be preferably dissolved in solvent toluene with described promotor during polymerization and mono-metallocene compound before olefinic polymerization.
Concentration during described mono-metallocene compound polymerization in solvent toluene is preferably 1 × 10
-8mol/L to 1 × 10
-2mol/L, is 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.
MAO solution used in embodiment is the toluene solution of methylaluminoxane, and every ml soln is 1.67mmol containing MAO; Catalyst solution used is the toluene solution of mono-metallocene compound, and every ml soln comprises mono-metallocene compound 5 μm of ol.
The synthesis of embodiment 1 Primary Catalysts
The synthesis of pentamethylcyclopentadiene base-penta fluoro benzene sulfenyl-dimethoxy titanium: magneton is put into 250 milliliters of dry there-necked flasks, bottle is placed in the magnetic stirring apparatus of oil bath temperature control; There-necked flask is vacuumized rear nitrogen and repeatedly rinse three times.And adding pentamethylcyclopentadiene base-trimethoxy titanium 1.8g, toluene 50mL in a nitrogen atmosphere, penta fluoro benzene thiophenol 1.35g, stirring at room temperature reaction is spent the night.Obtain yellow powder 2.1g after solvent removed in vacuo, the product pentamethylcyclopentadiene base namely in 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 and dissolves, and freezing and crystallizing, obtains yellow prismatic crystal.Its characterization result is as follows, nucleus magnetic resonance:
1h-NMR (CDCl
3, 25C): δ=2.12 (15H), 3.96 (6H).Ultimate analysis calculated value is C, 48.66; H, 4.76.Experimental value is C, 48.73; H, 4.38.
The equal polyreaction of embodiment 2 catalyzed ethylene
The polymerization bottle of drying is vacuumized rear nitrogen and repeatedly rinses three times, then vacuumize; Under solenoid control, be filled with ethene, maintenance ethylene pressure is normal pressure.The catalyzer toluene solution 1mL adding toluene 17.5mL, MAO toluene solution 1.5mL successively and prepared by the yellow powder in embodiment 1 at 30 DEG C, starts timing.At 30 DEG C after polyreaction 20min, close ethene, pour reaction solution into beaker, add acidic ethanol termination reaction, to stir after 6 hours filtration and obtain polymkeric substance, filter cake vacuum-drying 24 hours at 60 DEG C, calculates catalyst activity after weighing; It the results are shown in table 1.
The equal polyreaction of embodiment 3 catalyzed ethylene
Add toluene 16mL, MAO solution 3mL in the present embodiment, all the other steps are identical with embodiment 2.
The equal polyreaction of embodiment 4 catalyzed ethylene
Add toluene 13mL, MAO solution 6mL in the present embodiment, all the other steps are identical with embodiment 2.
The equal polyreaction of embodiment 5 catalyzed ethylene
Add toluene 10mL, MAO solution 9mL in the present embodiment, all the other steps are identical with embodiment 2.
Table 1
Note: M
wfor polymer average molecular weight; M
w/ M
nfor 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.
From the data in upper table, 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, when methylaluminoxane is as promotor, is a kind of effective olefin polymerization catalysis.
Claims (1)
1. the application of the catalyzer containing mono-metallocene compound in all polymerizations of ethene, the general formula of described mono-metallocene compound is such as formula shown in I:
In formula I, X is methoxyl group; Cp ' is pentamethylcyclopentadiene base;
Described catalyzer is made up of mono-metallocene compound and promoter aluminium alkyl oxygen alkane; In described mono-metallocene compound, in Ti and alkylaluminoxane, the mol ratio of Al is 1:500 to 1:3000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110291489.9A CN103030669B (en) | 2011-09-30 | 2011-09-30 | A kind of mono-metallocene compound and the application in olefin polymerization catalysis thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110291489.9A CN103030669B (en) | 2011-09-30 | 2011-09-30 | A kind of mono-metallocene compound and the application in olefin polymerization catalysis thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103030669A CN103030669A (en) | 2013-04-10 |
| CN103030669B true CN103030669B (en) | 2016-01-20 |
Family
ID=48018108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110291489.9A Active CN103030669B (en) | 2011-09-30 | 2011-09-30 | A kind of mono-metallocene compound and the application in olefin polymerization catalysis thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103030669B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113402641B (en) * | 2021-06-02 | 2022-09-20 | 北京化工大学 | Metallocene catalyst, preparation method and application |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100782278B1 (en) * | 2005-01-26 | 2007-12-04 | 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
Non-Patent Citations (4)
| Title |
|---|
| Ethylene and Propylene Polymerization by a Series of Highly Electrophilic, Chiral Monocyclopentadienyltitanium Catalysts;Sean W. Ewart等,;《Organometallics》;19980315;第1502-1510页 * |
| Ethylene and propylene polymerization by cationic monocyclopentadienyl titanium catalysts containing the weakly coordinating anion [B(C6F5)4]-;Sean W. Ewart等,;《Journal of Organometallic Chemistry》;19990505;第106-113页 * |
| 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》.1987,第777-780页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103030669A (en) | 2013-04-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100540514C (en) | The trimerization of alkene | |
| CN106661142B (en) | Ligand compound, transistion metal compound and the carbon monoxide-olefin polymeric comprising the compound | |
| CN106488923B (en) | Ligand compound, transistion metal compound and the carbon monoxide-olefin polymeric comprising the transistion metal compound | |
| KR101050791B1 (en) | Method for preparing hybrid supported metallocene catalyst and hybrid supported metallocene catalyst prepared using the same | |
| NL2017640B1 (en) | Ligand based chromium catalyst and application in catalyzing ethylene oligomerization | |
| CN100528837C (en) | Double-core nickel series compounds, preparation method and application thereof | |
| CN103030669B (en) | A kind of mono-metallocene compound and the application in olefin polymerization catalysis thereof | |
| CN105061493A (en) | Amine bis(phenolate) tetradentate ligand fourth sub-group metal complex and application thereof | |
| CN106397259A (en) | Diimine ligand, and diimine-nickel complex and application thereof | |
| JP2018508355A (en) | Olefin oligomerization catalyst system and olefin oligomerization method using the same | |
| CN105482000A (en) | Olefin polymerization catalyst as well as preparation method and application method thereof | |
| CN105481998A (en) | Olefin polymerization catalyst as well as preparation method and application method thereof | |
| JP2017537172A (en) | Metallocene supported catalyst and method for producing polyolefin using the same | |
| CN103254329B (en) | Metal miscellaneous ligand catalyst precursor, as well as preparation and application thereof | |
| EP1958969B1 (en) | A phosphine-substituted vinyl containing metallocene catalyst, preparation process and the application of the same | |
| KR20120028269A (en) | Bi-nuclear metallocene compound and the preparation method of polyoefine using the same | |
| CN104892800A (en) | Amine bis phenolate tetradentate ligand IV subgroup metal complex with large special resistance substituent and application thereof | |
| CN107406535B (en) | Composite supported catalyst system and method for preparing polyolefin by using same | |
| CN104725540A (en) | Ethylene copolymer preparation method | |
| CN104892801A (en) | Organic porous material after-supported single cyclopentadienyl chromium catalyst and application thereof | |
| CN1132856C (en) | Catalyst for polymerizing semi-metallocene with olefin and its preparing process and application | |
| CN103030722B (en) | A kind of polymerisation process of cycloolefin | |
| CN102030843B (en) | Non-metallocene catalyst system for olefin polymerization and preparation and application thereof | |
| EP3330296A1 (en) | Method for preparing supported hybrid metallocene catalyst, and supported hybrid metallocene catalyst prepared using same | |
| CN103030721B (en) | Polymerization method for preparation of syndiotactic polystyrene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |