CN1168744C - Catalyst containing mono schiff base ligand and its preparation and usage for olefine polymerization - Google Patents
Catalyst containing mono schiff base ligand and its preparation and usage for olefine polymerization Download PDFInfo
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- CN1168744C CN1168744C CNB01141474XA CN01141474A CN1168744C CN 1168744 C CN1168744 C CN 1168744C CN B01141474X A CNB01141474X A CN B01141474XA CN 01141474 A CN01141474 A CN 01141474A CN 1168744 C CN1168744 C CN 1168744C
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Abstract
The present invention relates to an olefin polymerization catalyst containing a single Schiff base ligand and a single mao ligand. When single Schiff base ligand is a bidentate ligand, the structure representation formula of the single Schiff base ligand is disclosed by the formula (I) in the specification; when the single Schiff base ligand is a tridentate ligand, the structure representation formula of the single Schiff base ligand is disclosed by the formula (II) in the specification. In the formula (I) and the formula (II), R1 and R3 are respectively selected from hydrogen, or alkyl groups of C1 to C12, or alkoxy of C1 to C12, or aryl groups of C6 to C12; R2 and R2' are selected from the hydrogen, or alkyl groups of C1 to C4; M is selected from Ti, or Zr, or Hf. The catalyst is suitable for olefinic polymerization, and can obtain polymers having high molecular weight and a high copolymerization unit inserting rate.
Description
Technical field
The present invention is a kind of olefin polymerization catalysis and preparation method thereof, specifically, is a kind of transistion metal compound and preparation method who contains single schiff base ligand, comprises that also with this compound be the method that Primary Catalysts carries out alkene homopolymerization or copolymerization.
Background technology
In field of olefin polymerisation, non-luxuriant class olefin polymerization catalysis is compared with metallocene catalyst, demonstrate certain advantage in some aspects, part scope as synthetic catalyst is widened greatly, but some title complex catalysis polar monomer and alpha-olefin copolymer close, but regulation and control part substituting group catalyzed ethylene oligomerisation etc.V.C.Gibson (Angew.Chem.Int.Ed.1999.38.P428) comprehensive summing up has been discussed various non-luxuriant class catalytic systems for polymerization of olefins, and its active centre metal relates to III to the X subgroup metal.Disclose the formed late transition metal catalyst of the bidentate ligand that is used for olefinic polymerization among the CN1225645A, its part is the imines class, and central metal is selected from the metal of the 9th～11 family.
Disclose two Schiff's base [N, O] the coordinate catalytic systems for polymerization of olefins of a class among the EP0874005A first, the metallic element M in such title complex is selected from the metal of 3～11 families, and its disclosed non-bridged complex has following structural formula:
R in the formula
1Be selected from hydrogen, halogen or alkyl, this patent particularly points out, and is positioned at hydroxyl adjacent substituting group and is preferably halogen, C
3～C
20The alkyl that has side chain, if this position unsubstituted or substituting group are little alkyl such as methyl, ethyl, then its polymerization activity is lower.When the major advantage of such catalyzer is catalyzed ethylene polymerization, catalytic activity is suitable with common metallocene, and the molecular weight of polyethylene that makes is much higher with metallocene catalyst, and molecular weight distribution broad, its deficiency is that copolymerized ability is low, when being used for ethene and alpha-olefin copolymer, the molecular weight and molecular weight amplitude is big, and comonomer insertion rate is low.
An outstanding advantage of metallocene catalysis system is to have extraordinary copolymerization ability.This is to acquisition new LDPE (film grade) plastomer, even elastomerics is highly beneficial.But, the deadly defect of metallocene catalyst is that catalyzed ethylene and alpha-olefin copolymer are fashionable, along with the increase of comonomer insertion rate, polymericular weight descends very big, to such an extent as to be difficult to the polyethylene that acquisition has high molecular and high comonomer content (the high degree of branching) simultaneously.
Summary of the invention
First purpose of the present invention provides transition-metal catalyst and this Preparation of catalysts method that a class contains single schiff base ligand.
Another object of the present invention provides with above-mentioned Preparation of Catalyst high molecular and the polyolefinic method of high comonomer content.
We find, introduce single schiff base ligand and single cyclopentadienyl ligand in the transistion metal compound simultaneously, can obtain the single Schiff's base of a class/single cyclopentadienyl catalyst, this catalyzer is under polymerizing condition, be used for ethylene homo, can obtain ultra high molecular weight polyethylene, be used for ethene and alpha-olefin copolymer is fashionable, the multipolymer that obtains is when keeping higher comonomer insertion rate, also have higher molecular weight, taken into account the advantage that good copolymerization performance of metallocene catalyst and non cyclopentadienyl catalyst obtain high-molecular weight polymer.When being used for ethylene homo as preferred catalyzer of the present invention, polymkeric substance Mw reaches 3,680,000, and molecular weight distribution is 3.92, when being used for ethene and hervene copolymer, Mw still reaches 1,500,000, and the range of decrease is 59%, molecular weight distribution is 2.49, and hexene insertion rate still remains 2.78%.
Embodiment
Olefin polymerization catalysis provided by the invention has single schiff base ligand and single cyclopentadienyl ligand, when described single schiff base ligand was the bidentate coordination, its structure expression was suc as formula shown in (I), when described single schiff base ligand is tridentate ligand, its structure expression is suc as formula shown in (II)
In formula (I) and the formula (II), R
1, R
3Be selected from hydrogen, C respectively
1～C
12Alkyl, C
1～C
12Alkoxyl group or C
6～C
12Aryl, R
2And R
2' be selected from hydrogen or C
1～C
4Alkyl, M is selected from Ti, Zr or Hf.
Above-mentioned formula (I) and (II) in, R
3Be the substituting group on the cyclopentadienyl skeleton, preferred hydrogen or C
1～C
4Alkyl, more preferably methyl or ethyl.
R
1Be the substituting group on the salicylidene phenyl ring, preferred hydrogen or C
1～C
4Alkyl, as methyl, ethyl or propyl group, more preferred R
1Be hydrogen or methyl.Replacing the position and can be 3～6, preferred 3 or 5 replacements, is ortho position or the contraposition that substituting group is positioned at hydroxyl.
R in the formula (I)
2And R
2' be the substituting group on the aniline ring, preferred hydrogen or C
1～C
3Alkyl, R
2The position of substitution be 3～6, R
2And R
2' can be identical or different, when the two is identical, preferred hydrogen or C
1～C
3Alkyl, as methyl, ethyl or sec.-propyl, R
2Preferred 4 or 6 of replacement position.R
2And R
2' not simultaneously, R
2Preferred hydrogen or C
1～C
4Alkyl, as methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, R
2' preferred hydrogen or C
1～C
4Alkyl.
In the formula (II), the aniline ortho-substituent becomes oxygen key-O-, this oxygen key and aniline ring and coordination metal link, the substituent R on the aniline ring
2Preferred hydrogen or C
1～C
4Alkyl, as methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, replacing the position is 3～6, preferred 4 or 6.
M is a transition metal, preferred Ti or Zr.
Method for preparing catalyst provided by the invention comprises the steps:
(1) with the schiff base ligand compound shown in the formula (III) and alkali alkyl compound in organic medium by waiting molar ratio reaction, generate an alkali metal salt of schiff bases complex, the middle R of formula (III)
1Be selected from hydrogen, C
1～C
12Alkyl, C
1～C
12Alkoxyl group or C
6～C
12Aryl, R
2Be selected from hydrogen or C
1～C
4Alkyl, R
2" be selected from hydrogen, C
1～C
4Alkyl or C
1～C
4Alkoxyl group,
(2) in organic medium, be CpMCl with an alkali metal salt of schiff bases complex with expression formula
3The cyclopentadienyl-containing metal muriate by waiting molar ratio reaction, remove and desolvate, resistates is with organic solvent washing, filtration, with the filtrate recrystallization; Described CpMCl
3Middle M is Ti, Zr or Hf, and Cp is mono-substituted cyclopentadienyl, substituent R
3Be selected from hydrogen, C
1～C
12Alkyl, C
1～C
12Alkoxyl group or C
6～C
12Aryl.
Described (1) step is the reaction of preparation part an alkali metal salt, and suitable thermotonus is-78～25 ℃, should keep low temperature when particularly reaction begins, and to guarantee that temperature of reaction can too fastly not raise, prevents compound decomposition.Described alkali alkyl compound preferred alkyl lithium, more preferably butyllithium.During synthetic ligands salt, the mol ratio of part and alkyl metal cpd is 0.1～4: 1, preferred 0.1～24 hour of reaction times.
(2) the suitable temperature of step reaction is-78～25 ℃, preferred 0.5～24 hour of time.CpMCl during reaction
3With the mol ratio of part an alkali metal salt be 0.5～2: 1.CpMCl
3Preferred cyclopentadienyl titanous chloride of compound or methyl cyclopentadienyl titanous chloride.
Organic medium described in above-mentioned (1), (2) two steps is selected from tetrahydrofuran (THF), ether or toluene.(2) go on foot the organic solvent that is used to wash and be selected from ether, benzene, toluene, normal hexane, sherwood oil or their mixture.
The method of title complex is shown in preparation (1) step formula (III): with corresponding aniline compound in the structural formula shown in the formula (III), as aniline, 2,6-diisopropyl aniline and corresponding salicylic aldehyde compound such as press at mol ratio condensation dehydration in alcoholic solvent, be reflected under the reflux temperature and carry out, the time is to get final product in 0.1～10 hour.Reaction finishes, and reduces to room temperature, will separate out solid filtering, remove and desolvate, and promptly gets the ligand compound of formula (III).Method purification formula (III) compound of handy recrystallization, recrystallization solvent is selected from ethanol or propyl alcohol.
The preferred ligand compound of the present invention has: salicylidene aniline, salicylidene 2, the 6-xylidine, salicylidene 2, the 6-Diethyl Aniline, salicylidene 2, the 6-diisopropyl aniline, salicylidene o-isopropyl aniline, the salicylidene o-toluidine, the salicylidene cumidine, the salicylidene o-toluidine, the salicylidene ORTHO ANISIDINE, salicylidene is to the methyl ORTHO ANISIDINE, salicylidene is to methyl O-ethoxyl amine, salicylidene is to the ethyl ORTHO ANISIDINE, salicylidene is to the ethyl ORTHO ANISIDINE, 3-methyl salicylidene aniline, 3-methyl salicylidene 2, the 6-diisopropyl aniline, 3-ethyl salicylidene 2, the 6-diisopropyl aniline.
R in the ligand compound shown in the formula (III)
2" when being hydrogen or alkyl, make the catalyzer of formula (I), work as R
2" when being alkoxyl group, during as methoxy or ethoxy, make the catalyzer of formula (II).
Described (2) step CpMCl
3Compound can prepare with the following method: the sodium salt and the MCl that make cyclopentadiene and derivative thereof in the presence of ether solvent
4By etc. mol ratio react and get final product.
Catalyzer of the present invention is applicable to the homopolymerization or the copolymerization process of alpha-olefin, method is to be Primary Catalysts with catalyzer of the present invention, with the alkylaluminoxane is promotor, make alpha-olefin or alpha-olefin and comonomer at 10～110 ℃, 0.1 polymerization under the～1.0MPa, the aluminium during polymerization in the promotor is 100～1500: 1 with metal molar ratio in the Primary Catalysts.
Alpha-olefin optimal ethylene or propylene that polymerization is used, the preferred butylene of comonomer, hexene or octene.Polymerization methods can be mass polymerization, slurry polymerization or vapour phase polymerization.
Further specify the present invention below by example, but the invention is not restricted to this.
Example 1
Preparation (salicylidene 2,6-diisopropyl aniline)-(methyl cyclopentadienyl) titanium dichloride.
(1) preparation ligand compound salicylidene 2, the 6-diisopropyl aniline
In the 250ml there-necked flask; add 12.2g (0.1mol) salicylic aldehyde (China Medicine (Group) Shanghai Chemical Reagent Co.); and adding 100ml ethanol; be heated to reflux temperature; drip 30ml in half an hour and be dissolved with 17.7g (0.1mol) 2; the solution of 6-diisopropyl aniline (Chinese Shanghai reagent one factory), back flow reaction 2 hours.Be cooled to room temperature, separate out a large amount of solids.Filtration, solid 30ml ethyl alcohol recrystallization get yellow-green colour crystal 2 6g, are salicylidene 2,6-diisopropyl aniline (C
19H
23ON), productive rate 92%.
(2) preparation catalyzer
Add 1.65g (5.95mmol) salicylidene 2 in 100ml Schlenk bottle, 6-diisopropyl aniline and 30ml tetrahydrofuran (THF) are cooled to solution-70 ℃, under agitation drip 2.96ml (2.0113molL
-1, 5.95mmol) butyllithium dropwises, and rises to room temperature naturally, stirs 3 hours, gets salicylidene 2, the tetrahydrofuran solution of 6-diisopropyl aniline lithium salts.
With above-mentioned lithium salt solution, slowly be added drop-wise to 1.389g (5.95mmol) methyl cyclopentadienyl titanous chloride (MeCpTiCl in-70 ℃
3) the 30ml tetrahydrofuran solution in.Naturally rise to room temperature, stirring is spent the night.Reaction solution is drained under reduced pressure, added 5ml ether and 45ml sherwood oil, filter, filtrate was left standstill 18 hours in-20 ℃, separated out the granular crystal of 0.5g, be catalyst A: (salicylidene 2, the 6-diisopropyl aniline)-(methyl cyclopentadienyl) titanium dichloride, productive rate 18%.Molecular structural formula is as follows:
Ultimate analysis value (heavy %)
Calculated value: C 62.08, H 5.87, and N 3.02
Measured value: C 62.32, H 5.94, and N 2.89
1H NMR(CDCl
3，δ，ppm)：8.30(s，1H，CH＝N)，7.52(t，J＝7.4，1H，arom)，7.42(d，J＝7.4，1H，arom)，7.32(d，J＝7.4，1H，arom)，7.23(m，J＝7.4，3H，arom)，7.01(t，J＝7.4，1H，arom)，6.79(t，J＝2.6，2H，Cp)，6.68(t，J＝2.6，2H，Cp)，2.99(m，J＝6.8，2H，CH(CH
3)
2)，2.49(s，3H，CH
3Cp)，1.2(d，J＝6.8，12H，CH(CH
3)
2)
M.S.463(M
+)，113(CpTi
+)，65(Cp
+)
Infrared spectra score value: 1608 (s), 1552 (m), 1470 (m), 1289 (m), 1186 (w), 1123 (w), 910 (w), 862 (w), 697 (w)
Example 2
Preparation (the adjacent Oxybenzene amido of salicylidene)-(cyclopentadienyl) titanium chloride.
(1) press the method preparation of example 1, different is to replace 2 with 12.3g (0.1mol) ORTHO ANISIDINE (Chinese Shanghai reagent one factory of producer), and the 6-diisopropyl aniline reacts, and finally obtains part salicylidene ORTHO ANISIDINE 20g, productive rate 88%.
(2) preparation catalyzer
In 100ml Schlenk bottle, add 1.745g (7.68mmol) salicylidene ORTHO ANISIDINE and 30ml toluene, solution is cooled to-70 ℃, under agitation drip 3.82ml (2.0113molL
-1, 7.68mmol) butyllithium dropwises, and the bright yellow muddiness occurs, rises to room temperature naturally, stirs 3 hours, gets the toluene solution of salicylidene ORTHO ANISIDINE lithium salts.
Above-mentioned lithium salt solution is chilled to-70 ℃, drips 1.684g (7.68mmol) cyclopentadienyl titanous chloride (CpTiCl fast
3) the 40ml toluene solution in.Naturally rise to room temperature, stirred 4 hours, 80 ℃ of stirrings are spent the night, and filter, and filtrate was left standstill 18 hours in-20 ℃, separate out the granular solid of 0.995g, are catalyst B: (the adjacent oxidation aniline of salicylidene)-(cyclopentadienyl) titanium dichloride, productive rate 36%.Molecular structural formula is as follows:
Ultimate analysis value (heavy %) is
Calculated value C, 60.10; H, 3.93; N, 3.89
Measured value C, 60.41; H, 3.98; N, 3.79.
1HNMR(CDCl
3，δ，ppm)：9.17(s，1H，CH＝N)，7.76(t，J＝7，1H，arom)，7.70(d，J＝7，1H，arom)，7.63(t，J＝7.4，1H，arom)，7.31(t，J＝7.4，1H，arom)，7.24(d，J＝7，1H，arom)，7.16(t，J＝7，1H，arom)，7.05(t，J＝7，1H，arom)，6.99(t，J＝7，1H，arom)，6.20(s，5H，C
5H
5)；
Mass spectrum: 359 (M
+, 24);
INFRARED SPECTRUM: 1603 (s), 1581 (m), 1538 (m), 1463 (m), 1438 (m), 1372 (w), 1296 (s), 1146 (w), 1025 (w), 849 (m), 747 (m).
Example 3
Preparation (salicylidene is to the adjacent Oxybenzene amido of methyl)-(cyclopentadienyl) titanium dichloride.
(1) preparation ligand compound salicylidene is to the methyl ORTHO ANISIDINE.
Press the method preparation of example 1, different is with 13.7g (0.1mol) methyl ORTHO ANISIDINE (Chinese Shanghai reagent one factory) to be replaced 2, the 6-diisopropyl aniline reacts, and finally obtains the part salicylidene to methyl ORTHO ANISIDINE 21g, productive rate 87%.
(2) preparation catalyzer
In 100ml Schlenk bottle, add 2.039g (8.46mmol) salicylidene to methyl ORTHO ANISIDINE and 30ml toluene, solution is cooled to-70 ℃, under agitation drip 4.21ml (2.0113molL
-1, 8.46mmol) butyllithium dropwises, and the bright yellow muddiness occurs, rises to room temperature naturally, stirs 3 hours.Then turbid solution is chilled to-70 ℃, drips the 40ml toluene solution of 1.855g (8.46mmol) cyclopentadienyl titanous chloride fast, dropwise, rise to room temperature naturally, stirred 4 hours, keep 80 ℃ of stirrings to spend the night.With the solution sedimentation, filter, filtrate in-20 ℃ of sedimentations 18 hours, is separated out 1.2g particulate state crystal, for catalyzer C:(salicylidene to the adjacent Oxybenzene amido of methyl)-(cyclopentadienyl) titanium dichloride, productive rate 38%.Molecular structural formula is as follows:
Ultimate analysis value (heavy %) is
Calculated value: C 61.06, H 4.32, and N 3.75
Measured value: C 61.34, H 4.41, and N 3.69
1H NMR (CDCl
3, δ, ppm) analytical value: 9.16 (s, 1H, CH=N), 7.74～6.95 (m, 7H, arom), 6.19 (s, 5H, C
5H
5), 2.31 (s, 3H, CH
3)
M.S.373(M
+)
INFRARED SPECTRUM: 1603 (s), 1580 (m), 1535 (m), 1463 (s), 1435 (m), 1370 (w), 1298 (s), 1147 (w), 1025 (w), 846 (m), 746 (m)
Example 4
Preparation (the adjacent Oxybenzene amido of 5-methyl salicylidene)-(cyclopentadienyl) titanium dichloride.
(1) preparation ligand compound 5-methyl salicylidene ORTHO ANISIDINE.
Press the method preparation of example 1; different is that reactant is 13.6g (0.1mol) 5-cresotinic acid aldehyde (China Medicine (Group) Shanghai Chemical Reagent Co.) and 12.3g (0.1mol) ORTHO ANISIDINE; finally obtain part 5-methyl salicylidene ORTHO ANISIDINE 22g, productive rate 91%.
(2) preparation catalyzer
In 100ml Schlenk bottle, add 1.981g (8.22mmol) 5-methyl salicylidene ORTHO ANISIDINE and 30ml toluene, solution is cooled to-70 ℃, under agitation drip 4.09ml (2.0113molL
-1, 8.22mmol) butyllithium dropwises, and the bright yellow muddiness occurs, rises to room temperature naturally, stirs 3 hours.Then turbid solution is chilled to-70 ℃, drips the 40ml toluene solution of 1.802g (8.22mmol) cyclopentadienyl titanous chloride fast, dropwise, rise to room temperature naturally, stirred 4 hours, keep 80 ℃ of stirrings to spend the night.With the solution sedimentation, filter, filtrate in-20 ℃ of sedimentations 18 hours, is separated out 0.98g particulate state crystal, be the adjacent Oxybenzene amido of catalyzer D:(5-methyl salicylidene)-(cyclopentadienyl) titanium dichloride, productive rate 32%.Molecular structural formula is as follows:
Ultimate analysis value (heavy %) is
Calculated value: C 61.06, H 4.32, and N 3.75
Measured value: C 61.32, H 4.50, and N 3.60
1H NMR(CDCl
3，δ，ppm)：9.18(s，1H，CH＝N)，7.78～6.99(m，7H，arom)，6.20(s，5H，C
5H
5)，2.30(s，3H，CH
3)
M.S.373(M
+)
INFRARED SPECTRUM: 1605 (s), 1580 (m), 1538 (m), 1467 (s), 1435 (m), 1375 (w), 1296 (s), 1149 (w), 1025 (w), 848 (m), 748 (m)
Example 5
Preparation (the adjacent Oxybenzene amido of salicylidene)-(methyl cyclopentadienyl) titanium dichloride.
(2) preparation ligand compound salicylidene ORTHO ANISIDINE.
Press the method preparation of example 1, different is to replace 2 with 12.3g (0.1mol) ORTHO ANISIDINE (Chinese Shanghai reagent one factory), and the 6-diisopropyl aniline reacts, and finally obtains part salicylidene ORTHO ANISIDINE 20g, productive rate 88%.
(2) preparation catalyzer
In 100ml Schlenk bottle, add 1.793g (7.90mmol) salicylidene ORTHO ANISIDINE and 30ml toluene, solution is cooled to-70 ℃, under agitation drip 3.93ml (2.0113molL
-1, 7.90mmol) butyllithium dropwises, and the bright yellow muddiness occurs, rises to room temperature naturally, stirs 3 hours.Then turbid solution is chilled to-70 ℃, drips the 40ml toluene solution of 1.845g (7.90mmol) methyl cyclopentadienyl titanous chloride fast, dropwise, rise to room temperature naturally, stirred 4 hours, keep 80 ℃ of stirrings to spend the night.With the solution sedimentation, filter, filtrate in-20 ℃ of sedimentations 18 hours, is separated out 1.016g particulate state crystal, be the adjacent Oxybenzene amido of catalyzer E:(salicylidene)-(methyl cyclopentadienyl) titanium dichloride, productive rate 37%.Molecular structural formula is as follows:
Ultimate analysis value (heavy %) is
Calculated value: C 60.10, H 3.93, and N 3.89
Measured value: C 60.41, H 3.98, and N 3.79
1H NMR(CDCl
3，δ，ppm)：9.17(s，1H，CH＝N)，7.79～6.98(m，8H，arom)，6.15(t，J＝2.72Hz，2H，C
5H
4)，5.96(t，J＝2.72Hz，2H，C
5H
4)，2.33(s，3H，CH
3)
M.S.373(M
+)
INFRARED SPECTRUM: 1606 (s), 1581 (m), 1539 (m), 1466 (s), 1435 (m), 1374 (w), 1298 (s), 1149 (w), 1026 (w), 849 (m), 749 (m)
Comparative Examples 1
The catalyzer F of synthetic double schiff base ligand
The salicylidene aniline and the 30ml tetrahydrofuran (THF) that add 1.519g (7.7mmol) in 100ml Schlenk bottle are cooled to solution-70 ℃, stir to drip 3.83ml (2.0113molL down
-1, 7.7mmol) butyllithium dropwises, and rises to room temperature naturally, stirs 3 hours, makes the lithium salt solution of salicylidene aniline.
With the tetrahydrofuran solution of above-mentioned lithium salts, slowly be added drop-wise to 1.689g (7.7mmol) TiCl at-70 ℃
4The 30ml tetrahydrofuran solution in, dropwise, rise to room temperature naturally, stirring is spent the night.Drain reaction solution under the decompression, add the 150ml ether, filter, filtrate is drained, get 1.2g solid catalyzer F: two (salicylidene anilino) titanium dichloride, molecular formula C
26H
20O
2N
2TiCl
2, productive rate 61%.
1H NMR(CDCl
3，δ，ppm)8.30(s，1H，CH＝N)，7.52(t，J＝7.4，1H，arom)，7.42(d，J＝7.4，1H，arom)，7.32(d，J＝7.4，1H，arom)，7.23(m，J＝7.4，3H，arom)，7.01(t，J＝7.4，1H，arom)，6.79(t，J＝2.6，2H，Cp)，6.68(t，J＝2.6，2H，Cp)，2.99(m，J＝6.8，2H，CH(CH
3)
2)，2.49(s，3H，CH
3Cp)，1.2(d，J＝6.8，12H，CH(CH
3)
2)。
Comparative Examples 2
Preparation two (n-butyl cyclopentadienyl) zirconium dichloride
Under the ice-water bath cooling, in 100 milliliters of tetrahydrofuran (THF)s (THF) solution that contains 11.0 gram (0.09 mole) normal-butyl cyclopentadiene, slowly drip the 2.5M hexane solution of 36.7 milliliters of (0.09 mole) butyllithiums while stirring, dropwise the back and continue to stir 1 hour, obtain the white opacity solution of n-butyl cyclopentadienyl lithium.
At-78 ℃, in the n-butyl cyclopentadienyl lithium solution of above-mentioned acquisition, slowly add 10.485 gram (0.045 mole) ZrCl
4, dropwise the back stirred overnight at room temperature, get the scarlet turbid solution.Remove 90% solvent, resistates dissolves after-filtration, recrystallization with 100 milliliters of toluene, and get catalyzer G: two (n-butyl cyclopentadienyl) zirconium dichloride 12.7g, reaction yield is 70%.
Example 6～13
Below ethylene homo is carried out in reaction.
Add 100ml exsiccant toluene in the 250ml vial of replacing with nitrogen and ethene, add ethene to absorption equilibrium, system is warming up to temperature of reaction, add the toluene solution of little amount of catalyst and MAO, the mol ratio that makes metal in aluminium and the catalyzer is 1000.React after 1 hour, the ethanol solution hydrochloride with 10% stops.Filter, product is at 80 ℃, and drying is 3 hours under the vacuum, obtains polymkeric substance.Catalyst activity and polymer property see Table 1.
Example 14～20
Following example carries out the copolyreaction of ethene and hexene.
In the 250ml vial of replacing, add 100ml exsiccant toluene with nitrogen and ethene, add ethene to absorption equilibrium, system is warming up to 50 ℃, add the 5ml hexene, the toluene solution that adds little amount of catalyst and MAO then, the mol ratio that makes metal in aluminium and the catalyzer is 1000.React after 1 hour, the ethanol solution hydrochloride with 10% stops.Filter, product is at 80 ℃, and drying is 3 hours under the vacuum, obtains polymkeric substance, and catalyst activity and polymer property see Table 2, wherein polymkeric substance hexene content nucleus magnetic resonance
13C-NMR records.
By table 1 data as can be known, the ethylene homo product of catalyzer of the present invention has higher molecular weight than comparative catalyst's homopolymer, and the molecular weight distribution broad.Table 2 data show that catalyzer of the present invention is used for the ethylene copolymer reaction, than the comparative catalyst, can obtain having the copolymerized product of high molecular and high comonomer insertion rate.
Table 1
| Instance number | The catalyzer numbering | Temperature of reaction, ℃ | The catalyzer dosage, μ mol | Catalyst activity, gPE/molMh | Mw，10 4 | Mw/Mn |
| 6 | A | 30 | 29.12 | 0.644×10 4 | - | - |
| 7 | A | 50 | 29.12 | 0.996×10 4 | 368 | 3.92 |
| 8 | B | 50 | 37.2 | 1.30×10 4 | 163 | 4.77 |
| 9 | C | 50 | 30.0 | 1.50×10 4 | 170 | 4.24 |
| 10 | D | 50 | 35.0 | 1.43×10 4 | 150 | 3.95 |
| 11 | E | 50 | 28.0 | 1.43×10 4 | 175 | 4.05 |
| 12 | F | 50 | 29.32 | 0.64×10 4 | 161 | 2.85 |
| 13 | G | 50 | 10.0 | 4.1×10 5 | 11 | 2.65 |
Table 2
| Instance number | The catalyzer numbering | The catalyzer dosage, μ mol | Catalyst activity, gPE/molMh | Mw，10 4 | Mw/Mn | Hexene content in the polymkeric substance, heavy % |
| 14 | A | 29.12 | 1.66×10 4 | 150 | 2.49 | 2.78 |
| 15 | B | 37.2 | 2.1×10 4 | 41 | 4.90 | 3.10 |
| 16 | C | 30.0 | 1.5×10 4 | 50 | 4.50 | 3.50 |
| 17 | D | 35.0 | 2.3×10 4 | 38 | 4.10 | 2.90 |
| 18 | E | 28.0 | 2.5×10 4 | 52 | 4.3 | 3.60 |
| 19 | F | 36.0 | 5.81×10 4 | 34 | 2.55 | 3.27 |
| 20 | G | 3.1 | 9×10 5 | 4.75 | 3.0 | 6.80 |
*Annotate: M is titanium or zirconium in table 1, the table 2
Claims (9)
1, a kind of olefin polymerization catalysis with single Schiff's base and single cyclopentadienyl ligand, when described single schiff base ligand was the bidentate coordination, its structure expression was suc as formula shown in (I), when described single schiff base ligand is tridentate ligand, its structure expression is suc as formula shown in (II)
In formula (I) and the formula (II), R
1, R
3Be selected from hydrogen, C respectively
1～C
12Alkyl, C
1～C
12Alkoxyl group or C
6～C
12Aryl, R
2And R
2' be selected from hydrogen or C
1～C
4Alkyl, M is selected from Ti, Zr or Hf.
2, according to the described catalyzer of claim 1, it is characterized in that R
1Be selected from hydrogen or C
1～C
4Alkyl, R
2, R
2' be selected from hydrogen or C
1～C
4Alkyl, R
3Be selected from hydrogen or C
1～C
4Alkyl.
3, according to the described catalyzer of claim 1, it is characterized in that R
1Be selected from hydrogen or methyl, R
2Be selected from hydrogen, methyl, ethyl, propyl group or sec.-propyl, R
2' be selected from hydrogen, methyl, ethyl, propyl group or sec.-propyl, R
3Be selected from methyl or ethyl, M is selected from Ti.
4, the described Preparation of catalysts method of claim 1 comprises the steps:
(1) with the schiff base ligand compound shown in the formula (III) and alkali alkyl compound in organic medium by waiting molar ratio reaction, generate an alkali metal salt of schiff bases complex, the middle R of formula (III)
1Be selected from hydrogen, C
1～C
12Alkyl, C
1～C
12Alkoxyl group or C
6～C
12Aryl, R
2Be selected from hydrogen or C
1～C
4Alkyl, R
2"
Be selected from hydrogen, C
1～C
4Alkyl or C
1～C
4Alkoxyl group,
(2) in organic medium, be CpMCl with an alkali metal salt of schiff bases complex with expression formula
3The cyclopentadienyl-containing metal muriate by waiting molar ratio reaction, remove and desolvate, resistates is with organic solvent washing, filtration, with the filtrate recrystallization; Described CpMCl
3Middle M is Ti, Zr or Hf, and Cp is mono-substituted cyclopentadienyl, substituent R
3Be selected from hydrogen, C
1～C
12Alkyl, C
1～C
12Alkoxyl group or C
6～C
12Aryl.
5, in accordance with the method for claim 4, it is characterized in that (1) step temperature of reaction is-78～25 ℃, described alkali alkyl compound is a butyllithium.
6, in accordance with the method for claim 4, it is characterized in that the temperature of reaction that (2) go on foot is-78～25 ℃, CpMCl
3Compound is cyclopentadienyl titanous chloride or methyl cyclopentadienyl titanous chloride.
7, in accordance with the method for claim 4, it is characterized in that described organic medium is selected from tetrahydrofuran (THF), ether or toluene, the organic solvent that (2) step is used to wash is selected from ether, benzene, toluene, normal hexane, sherwood oil or their mixture.
8, a kind of alpha-olefin homopolymerization or copolymerization process, it is characterized in that with the described catalyzer of claim 1 be Primary Catalysts, with the alkylaluminoxane is promotor, make alpha-olefin or alpha-olefin and comonomer at 10～110 ℃, 0.1 polymerization under the～1.0MPa, the aluminium during polymerization in the promotor is 100～1500: 1 with metal molar ratio in the Primary Catalysts.
9, in accordance with the method for claim 8, it is characterized in that described alpha-olefin is selected from ethene or propylene, comonomer is selected from butylene, hexene or octene.
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