CN1125088C - Transition metal catalyst containing acacyclopentadiene in its ligand and its preparing process and application - Google Patents
Transition metal catalyst containing acacyclopentadiene in its ligand and its preparing process and application Download PDFInfo
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Abstract
The present invention relates to an olefin polymerization catalyst which has the general expression formula disclosed in the specification, wherein L is a ligand group comprising an azacyclopentadiene skeleton or diazacyclopentadiene skeleton, 2 nitrogen atoms in the diazacyclopentadiene skeleton are arranged in meta positions or adjacent positions, and the azacyclopentadiene skeleton can have 1 to 4 substituents; Cp is a ligand group comprising a cyclopentadiene skeleton; M is titanium or zirconium; X and Y are respectively selected from halogen and C1 to C24 alkyl, alkoxy, siloxy or alkaryl. The catalyst together with an alkylaluminoxane cocatalyst is used for the homopolymerization or the copolymerization of alpha-olefin, such as the homopolymerization or the copolymerization of ethylene or styrene.
Description
The present invention relates to a kind of polyolefin catalyst and preparation method thereof and application, specifically, be a kind of be the olefine polymerizing semi-metallocene catalyst and preparation method thereof and application of class cyclopentadienyl ligand with the pyrrole derivative.
In recent years, metallocene catalyst is used for olefinic polymerization production polyolefine technology and is widely known by the people, and wherein the part of metallocene catalyst is cyclopentadiene and derivative, and metal is a transition metal.It is found that the transistion metal compound of heteroatomic big parts such as containing aerobic, nitrogen, sulphur now, have than the higher polymerization activity of metallocene.USP5,539,124 promptly disclose a kind of transition metal compound catalizer that contains pyrrole ring, and general formula is: (L) m (Cp) qM (Y) n (B) p.L in the formula is the condensed ring part that contains pyrrole ring, or the mixture of part, and Cp is the cyclopentadienyl that cyclopentadienyl or alkyl replace, and B is a Lewis alkali, and Y is hydrogen, C
1～C
20Alkoxyl group, C
1～C
20Siloxy or the mixture of the two, M is Ti, Zr or their mixture, wherein m is 2～4, that is to say that the number of ligand L is at least 2, n is 0～1, p is 0～2, q is 0～1, m+n+q=4, and m+q=3 or 4.This catalyzer can be used for catalysis in olefine polymerization, and as the polymerization of ethene, but catalytic activity is lower, is equivalent to every gram catalyzer approximately and per hour produces 1.5 kilograms of polyethylene.
CN1151993A discloses a kind of novel metal cyclopentadienyl catalyst of vinyl polymerization, this catalyzer is a ligand transition metal with the pyrryl or derivatives thereof, when vinyl polymerization, be promotor with the sesquialter aluminium triethyl, and be promotor without aikyiaiurnirsoxan beta, show advantages of high catalytic activity, the gained molecular weight of polyethylene is low, narrow molecular weight distribution.For example, be the polymerization Primary Catalysts with the dipyrryl titanium dichloride, 50 ℃ of temperature of reaction, ethylene pressure 0.04MPa, under the 7 hours reaction times situation, polymerization activity is 3.4 * 10
5Gram polyethylene/mole titanium, molecular weight distribution is 1.47.
The purpose of this invention is to provide the transition metal compound catalizer that contains pyrrole in a kind of part, this catalyzer has advantages of high catalytic activity.
Another object of the present invention provides above-mentioned Preparation of catalysts method.
A further object of the present invention provides the application of above-mentioned catalyzer in the polyene polymerization.
Olefin polymerization catalysis of the present invention has following general expression:
L is the ligand groups that contains pyrrole skeleton or imidazole skeleton in the formula, two nitrogen-atoms in the described imidazole skeleton be between position or ortho position arrange, 1～4 substituent R is arranged on the five-membered ring of pyrrole skeleton or imidazole skeleton
1, two adjacent substituting groups can be connected with each other and form the above condensed ring of binary on its skeleton, but and also nitrogen atom on the condensed ring that forms with pyrrole; Cp is the ligand groups that contains cyclopentadienyl skeleton, and 1～5 substituent R is arranged on the cyclopentadienyl skeleton
2, two adjacent substituting groups on the described skeleton can be connected with each other and form the above condensed ring of binary; Described R
1And R
2Be selected from hydrogen, C respectively
1～C
18Alkyl or perfluoroalkyl, C
6～C
24Aralkyl or alkaryl, M is selected from IVB family metal, X and Y are selected from halogen, C respectively
1～C
24Alkyl, alkoxyl group, silylation or alkaryl.
Preferred titanium of described M or zirconium, preferred halogen of X and Y or benzyl.
R
1And R
2Preferred hydrogen, C
1～C
6Alkyl, C
1～C
6Perfluoroalkyl, C
6～C
24Aralkyl or alkaryl.
Described ligand L is selected from the part that contains the pyrrole skeleton, and 1～4 substituting group is arranged on the pyrrole five-ring skeleton, and two adjacent substituting groups can be connected with each other and form condensed ring with the pyrrole skeleton, and also can contain nitrogen-atoms on the condensed ring that forms with pyrrole.Such part has pyrryl, indyl, carbazyl, 7-azaindolyl, or contains the above-mentioned group of single replacement or multi-substituent, and described substituting group is C
1～C
6Alkyl or perfluoroalkyl.Ligand L is also optional from the part that contains the imidazole skeleton, so-called imidazole is meant that the carbon atom on the cyclopentadienyl skeleton is replaced formed group by two nitrogen-atoms, 1～3 substituting group can be arranged on the five-ring of imidazole, and adjacent substituting group can be connected with each other and imidazole forms condensed ring, such part has imidazolyl, pyrazolyl, benzimidazolyl-, indazolyl, or containing single the replacement or the above-mentioned group of multi-substituent, described substituting group is C
1～C
6Alkyl or perfluoroalkyl.
The preferred cyclopentadienyl of described Cp, indenyl, fluorenyl, or single the replacement or polysubstituted above-mentioned group, substituting group is C
1～C
8Alkyl or perfluoroalkyl.
Catalyzer provided by the invention comparatively preferably has: (pyrryl) (cyclopentadienyl) titanium dichloride, (indyl) (cyclopentadienyl) titanium dichloride, (carbazyl) (cyclopentadienyl) titanium dichloride, (7-azaindolyl) (cyclopentadienyl) titanium dichloride, (imidazolyl) (cyclopentadienyl) titanium dichloride, (benzimidazolyl-) (cyclopentadienyl) titanium dichloride, (indazolyl) (cyclopentadienyl) titanium dichloride, (pyrazolyl) (cyclopentadienyl) titanium dichloride; (pyrryl) (pentamethyl--cyclopentadienyl) titanium dichloride, (indyl) (pentamethyl--cyclopentadienyl) titanium dichloride, (carbazyl) (pentamethyl-ring-pentadienyl) titanium dichloride, (7-azaindolyl) (pentamethyl--cyclopentadienyl) titanium dichloride, (imidazolyl) (pentamethyl--cyclopentadienyl) titanium dichloride, (benzimidazolyl-) (pentamethyl--cyclopentadienyl) titanium dichloride, (indazolyl) (pentamethyl--cyclopentadienyl) titanium dichloride, (pyrazolyl) (pentamethyl--cyclopentadienyl) titanium dichloride; (pyrryl) (tertiary butyl-cyclopentadienyl) titanium dichloride, (indyl) (tertiary butyl-cyclopentadienyl) titanium dichloride, (carbazyl) (tertiary butyl-cyclopentadienyl) titanium dichloride, (7-azaindolyl) (tertiary butyl-cyclopentadienyl) titanium dichloride, (imidazolyl) (tertiary butyl-cyclopentadienyl) titanium dichloride, (benzimidazolyl-) (tertiary butyl-cyclopentadienyl) titanium dichloride, (indazolyl) (tertiary butyl-cyclopentadienyl) titanium dichloride, (pyrazolyl) (tertiary butyl-cyclopentadienyl) titanium dichloride; (pyrryl) (indenyl) titanium dichloride, (indyl) (indenyl) titanium dichloride, (carbazyl) (indenyl) titanium dichloride, (7-azaindolyl) (indenyl) titanium dichloride, (imidazolyl) (indenyl) titanium dichloride, (benzimidazolyl-) (indenyl) titanium dichloride, (indazolyl) (indenyl) titanium dichloride, (pyrazolyl) (indenyl) titanium dichloride; (pyrryl) (fluorenyl) titanium dichloride, (indyl) (fluorenyl) titanium dichloride, (carbazyl) (fluorenyl) titanium dichloride, (7-azaindolyl) (fluorenyl) titanium dichloride, (imidazolyl) (fluorenyl) titanium dichloride, (benzimidazolyl-) (fluorenyl) titanium dichloride, (indazolyl) (fluorenyl) titanium dichloride, (pyrazolyl) (fluorenyl) titanium dichloride.
Catalyzer of the present invention can be prepared by several different methods, generate part salt as the ligand compound that will contain pyrrole and strongly alkaline compound reaction, and then be that halogenide, alkylide, alkoxy compound, siloxy compound, the alkyl aryl compound of the transition metal of part reacts and make catalyzer this part salt and cyclopentadiene or derivatives thereof; Or it is opposite, earlier cyclopentadiene ligand compound and strongly alkaline compound reaction are generated cyclopentadiene part salt, and then be that halogenide, alkylide, alkoxy compound, siloxy compound, the alkyl aryl compound of the transition metal of part reacts and make catalyzer this salt and pyrrole or derivatives thereof.The present invention also can be directly made by halogenide, alkylide, alkoxy compound, siloxy compound, the alkyl aryl compound of cyclopentadiene ligand compound or derivatives thereof and the ligand compound reaction that contains pyrrole, but this reaction is preferably under the existence of tertiary amine and carries out.
First kind of preparation method of catalyzer of the present invention comprises the steps:
(1) in ether solvent, the strongly alkaline compound of equimolar amount is fully contacted with ligand compound HL, remove then and desolvate, obtain the salt of ligand compound,
(2) in organic solvent, making the salt and the general formula of the above-mentioned ligand compound of equimolar amount is CpMX
2The compound of Y fully contacts, and removes solid matter, the solvent in the gained liquid is removed promptly got catalyzer.
The same catalyzer of symbol definition in the compound expression formula of using in the described method.The temperature of (1) step reaction is-80～100 ℃ in preparation process, is preferably-20～80 ℃, and the amount of ether solvent should be 10～20 times of ligand compound HL weight.Reaction times is preferably 0.5～48 hour, preferred 2～24 hours.
The temperature of (2) step reaction is preferably-80～150 ℃, and preferred-20～80 ℃, the reaction times is 0.5～96 hour, preferred 2～48 hours.The amount of organic solvent is preferably 10～20 times of reactant gross weight during reaction.
Second kind of preparation method of catalyzer of the present invention may further comprise the steps:
(1) in ether solvent, make the strongly alkaline compound and the abundant contact reacts of Cyclopeutadiene type ligand compound of equimolar amount, remove desolvate the salt of Cyclopeutadiene type ligand compound,
(2) in organic solvent, make LMX
3Mol ratio such as press with the salt of Cyclopeutadiene type ligand compound and under agitation condition, fully stir contact reacts, remove solid matter, the solvent in the gained liquid is removed promptly got catalyzer.
The used same catalyzer of compound general formula symbol definition in the aforesaid method.The temperature of (1) step reaction preferably is controlled at-80～100 ℃, preferred-20～80 ℃.Reaction times is 0.5～48 hour, preferred 1～24 hour.The amount of ether solvent should be 10～20 times of ligand compound weight.
The temperature of (2) step reaction is preferably-80～150 ℃, and preferred-20～80 ℃, the reaction times is 0.5～96 hour, preferred 1～48 hour.The amount of organic solvent is preferably 10～20 times of reactant gross weight during reaction.
The transistion metal compound LMX that contains the azepine cyclopentadienyl ligand in the aforesaid method
3Make by following method,, preferred-20～50 ℃, the transistion metal compound MX of mol ratio such as in the exsiccant organic solvent, add at-80～100 ℃
4With the ligand compound HL that contains the pyrrole skeleton, after stirring, adding is reacted with the trialkylamine of HL equimolar amount again, then filtrate is concentrated, and removes insoluble solids, the solvent of gained solution is removed promptly got LMX again
3The same catalyzer of symbol definition in the compound used therefor general formula wherein.
Preparation LMX
3Trialkylamine described in the process can be triethylamine, tripropyl amine etc., and preferred triethylamine adds trialkylamine and can shorten the reaction times, and the general reaction times is 0.5～96 hour in this preparation process, preferred 0.5～48 hour.
Described LMX
3Also can be prepared by following method: the ligand compound HL and the strongly alkaline compound that will contain the pyrrole skeleton earlier react in ether solvent in equimolar ratio, and temperature is-80～100 ℃ during reaction, preferred-20～80 ℃, obtain L part salt.In organic solvent, make L part salt and transistion metal compound MX then
4Pressed equimolar quantitative response 0.5～48 hour, temperature of reaction is-80～100 ℃, preferred-20～80 ℃, remove by filter insolubles after the reaction, and filtrate is concentrated, the collection solids gets final product.
Strongly alkaline compound described in the aforesaid method is selected from alkyl magnesium bromide, basic metal, alkali-metal alkylide or hydride.Described basic metal preferred lithium, sodium or potassium, alkyl preferable methyl, ethyl or butyl in the alkylide, as butyllithium, the preferred C of the alkyl in the alkyl halide magnesium
1～C
8Alkyl or aralkyl, as methyl-magnesium-bromide, butyl magnesium bromide, benzyl magnesium bromide.Preferred ether of described ether solvent or tetrahydrofuran (THF).
The third preparation method of catalyzer of the present invention comprises: in organic solvent, making general formula is CpMX
2The compound of Y fully contacts with mol ratios such as ligand compound HL press, and then the trialkylamine of adding and HL equimolar amount, fully stirs the mixture, and removes solid matter, the solvent in the gained liquid is removed obtained catalyzer.
In the third preparation method of catalyzer, suitable temperature of reaction is-80～150 ℃, is preferably-50～80 ℃.Reaction times is 0.5～96 hour, is preferably 1～48 hour.The amount of organic solvent generally is controlled to be 10～20 times of total reactant during reaction.
The used preferred ether of organic solvent, methylene dichloride, trichloromethane or toluene among the described preparation method.
The preferred pyrroles of ligand compound HL, indoles, carbazole, 7-azaindole, imidazoles, pyrazoles, benzoglyoxaline, the indazole of mentioning in the aforesaid method or contain single the replacement or the derivative of the above-claimed cpd of multi-substituent, described substituting group is C
1～C
6Alkyl or perfluoroalkyl.
The preferred cyclopentadiene of described Cyclopeutadiene type ligand compound, indenes, fluorenes, or have single the replacement or the derivative of the above-claimed cpd of multi-substituent, described substituting group is C
1～C
8Alkyl, as pentamethyl-cyclopentadiene, tertiary butyl cyclopentadiene, normal-butyl cyclopentadiene, ethyl cyclopentadiene, propyl group cyclopentadiene, 1-methyl, 3-propyl group cyclopentadiene etc.
Catalyzer provided by the invention is applicable to the homopolymerization or the copolyreaction of 'alpha '-olefin monomers, need use aikyiaiurnirsoxan beta, aluminum alkyls, alkyl aluminum halide or their mixture to be promotor during polymerization.During reaction in the promotor in aluminium and the Primary Catalysts mol ratio of transition metal be 10～10000, be preferably 50～5000, more preferably 50～3000.
As the aikyiaiurnirsoxan beta of promotor can be linear or the cyclic polymkeric substance, and preferred aikyiaiurnirsoxan beta is methylaluminoxane, ethyl aikyiaiurnirsoxan beta or isobutyl aluminium alkoxide; The preferred trimethyl aluminium of aluminum alkyls, triethyl aluminum or triisobutyl aluminium, preferred aluminium diethyl monochloride of alkyl aluminum halide or sesquialter aluminium diethyl monochloride.Highly preferred promotor is a methylaluminoxane.
Be used for the preferred C of polymeric 'alpha '-olefin monomers
2～C
14Alkene is as ethene, propylene, vinylbenzene or the mixture of the two arbitrarily between them.Polyolefin products such as polyethylene or polystyrene be can produce with catalyzer of the present invention, ethene and other alpha-olefin also can be produced, as the copolymerized product of propylene, butylene, hexene.Polymerizing condition is 0～150 ℃, 0.01～10.0MPa, and comparatively preferred condition is 10～90 ℃, 0.1～5.0MPa.
Polymerization technique can adopt solution polymerization, and as slurry polymerization, the solvent during polymerization can be selected organic solvents such as alkane, aromatic hydrocarbons or halogenated alkane for use.Also available catalyzer of the present invention adopts the gas phase bulk technique to produce olefin polymer.
Transition metal compound catalizer provided by the invention is a kind of half luxuriant type catalyzer, contain 1～2 nitrogen-atoms in this catalyzer with in the part of transition-metal coordination, can regard the ligand groups that forms by the carbon atom on the nitrogen-atoms substituted-cyclopentadienyl or derivatives thereof skeleton as.Catalyzer provided by the invention is used for olefinic polymerization and has higher activity, and can polymerization under lower temperature, and resulting polymers has higher molecular weight and narrower molecular weight distribution.
Below by example in detail the present invention, but the present invention is not limited to this.
The operation of preparation catalyzer all uses the Schlenk instrument to carry out under the high pure nitrogen protection in the example.In example, on behalf of pyrryl, Id, Pr represent indyl, Mz to represent imidazolyl, Ai to represent 7-azaindolyl, Iz to represent indazolyl, Bi benzimidazolyl-, Cp to represent cyclopentadienyl, Ind to represent indenyl, Flu to represent fluorenyl.
Example 1
This examples preparation (pyrryl) (cyclopentadienyl) titanium dichloride [(Pr) (Cp) TiCl
2].
(1) preparation pyrroles's sodium salt (Pr) Na
Get 2 mmole sodium hydrides (connection chemical reagent factory in Beijing), under nitrogen protection, wash once vacuum-drying with a small amount of exsiccant sherwood oil.Add 10 milliliters of tetrahydrofuran (THF)s, stir, be cooled to 0 ℃.Splash into 2 mmole pyrroles (Switzerland, Fluka company) and 5 milliliters of solution that tetrahydrofuran (THF)s form.Stirred 4 hours under the room temperature, decompression evaporation down obtains pyrroles's sodium salt (Pr) Na except that desolvating.
(2) preparation catalyzer
Add 10 milliliters of methylene dichloride in above-mentioned (Pr) Na that obtains, stirring makes evenly, splashes into 2 mmole CpTiCl
3(Sweden, ACR S company produces) and the yellow solution that 10 milliliters of methylene dichloride form, mixture becomes yellow-green colour, and 40 ℃ were refluxed 48 hours down.Filter, concentrated filtrate refilters to about 5 milliliters, and solid is washed twice with 10 milliliters of hexanes, obtains 0.36 gram catalyst A [(Pr) (Cp) TiCl
2], productive rate is 72 heavy %.
Results of elemental analyses is: C 44.00 heavy %, and N 6.15 heavy %, H 4.11 heavy %,
Titanium 19.15 heavy %.
Example 2
This examples preparation (indyl) (cyclopentadienyl) titanium dichloride [(Id) (Cp) TiCl
2].
The method of pressing example 1 prepares indoles sodium salt (Id) Na, refabrication catalyzer earlier.Different is that the pyrroles that (1) goes on foot replaces solvents tetrahydrofurane substituted ether, room temperature reaction 6 hours with indoles (Britain, The British Drug Houses LTD. produces).(2) reaction times in step was 24 hours, got 0.36 gram catalyst B [(Id) (Cp) TiCl
2], ultimate yield is 60 heavy %.
Results of elemental analyses is: C 53.04 heavy %, and N 4.98 heavy %, H 4.12 heavy %,
Titanium 14.88 heavy %.
Example 3
This examples preparation (imidazolyl) (cyclopentadienyl) titanium dichloride [(Mz) (Cp) TiCl
2].
The method of pressing example 1 prepares imidazoles sodium salt (Mz) Na, refabrication catalyzer earlier.Different is that the pyrroles that (1) goes on foot replaces room temperature reaction 2 hours with imidazoles (Sweden, ACR S company produces).(2) step was 12 hours in the reaction times, 0.38 gram catalyzer C[(Mz) (Cp) TiCl
2], ultimate yield is 75 heavy %.
Results of elemental analyses is: C 38.17 heavy %, and N 10.84 heavy %, H 2.90 heavy %,
Titanium 19.08 heavy %.
Example 4
This examples preparation (7-azaindolyl) (cyclopentadienyl) titanium dichloride [(Ai) (Cp) TiCl
2].
Get 10 milliliters of new methylene dichloride that steam in 100 milliliters of there-necked flasks, add the 7-azaindole (Sweden, ACR S company produces) of 1 mmole and the triethylamine (the sharp fine chemicals of Peking blue company limited) of 1 mmole, stir.Drip 1 mmole CpTiCl after being cooled to 0 ℃
3With the solution that 10 milliliters of methylene dichloride form, reaction is 48 hours under the room temperature.Filter, concentrated filtrate refilters to about 5 milliliters, and the gained solid obtains 0.23 and restrains catalyzer D[(Ai with 10 milliliters of hexane wash twice) (Cp) TiCl
2], productive rate is 77 heavy %.
Results of elemental analyses is: C 47.26 heavy %, and N 9.37 heavy %, H 3.23 heavy %,
Titanium 15.21 heavy %.
Example 5
This examples preparation (indazolyl) (cyclopentadienyl) titanium dichloride [(Iz) (Cp) TiCl
2].
Get 20 milliliters of new methylene dichloride that steam and be put in 100 milliliters of there-necked flasks, add the indazole (Sweden, ACR S company produces) of 1 mmole and the CpTiCl of 1 mmole
3, stir and make dissolving.Drip 1 mmole triethylamine after being cooled to 0 ℃, reaction is 48 hours under the room temperature.Filter, concentrated filtrate refilters to about 5 milliliters, and the gained solid makes 0.24 and restrains catalyzer E[(Iz with 10 milliliters of hexane wash twice) (Cp) TiCl
2], productive rate is 80 heavy %.
Results of elemental analyses is: C 48.88 heavy %, and N 9.78 heavy %, H 4.25 heavy %,
Titanium 15.72 heavy %.
Example 6
Method according to example 5 prepares catalyzer F (benzimidazolyl-) (cyclopentadienyl) titanium dichloride [(Bi) (Cp) TiCl
2].The benzoglyoxaline (Sweden, ACR S company produces) that different is with 2 mmoles replaces indazole, in addition, and triethylamine and CpTiCl
3Add-on be 2 mmoles, at last 0.43 gram catalyzer F, productive rate is 72.2 heavy %.
Results of elemental analyses is: C 46.85 heavy %, and N 8.37 heavy %, H 4.19 heavy %,
Titanium 16.03 heavy %.
Example 7
This examples preparation (pyrryl) (indenyl) titanium dichloride [(Pr) (Ind) TiCl
2].
Method by example 1 is prepared, and different is with 2 mmole indenyl titanous chloride (Ind) TiCl when (2) goes on foot reaction
3(Sweden, ACR S company produces) replaced C pTiCl
3Make 0.39 gram catalyzer G[(Pr) (Ind) TiCl
2].Productive rate is 65.0 heavy %.
Results of elemental analyses is: C 523.6 heavy %, and N 4.87 heavy %, H 4.03 heavy %,
Titanium 14.97 heavy %.
Example 8
This examples preparation (pyrryl) (fluorenyl) titanium dichloride [(Pr) (Flu) TiCl
2].
Method by example 1 is prepared, and different is with 2 mmole fluorenyl titanous chloride (Flu) TiCl when (2) goes on foot reaction
3(Sweden, ACR S company produces) replaced C pTiCl
3Make 0.44 gram catalyzer H[(Pr) (Flu) TiCl
2].Productive rate is 63.0 heavy %.
Results of elemental analyses is: C 57.64 heavy %, and N 4.34 heavy %, H 4.10 heavy %,
Titanium 13.14 heavy %.
Example 9
This examples preparation (pyrryl) (indenyl) zirconium dichloride [(Pr) (Ind) ZrCl
2].
(1) preparation (pyrryl) tri-chlorination zirconium (Pr) ZrCl
3
Under condition of ice bath, to being dissolved with 2 mmole ZrCl
420 milliliters of tetrahydrofuran solutions in add 2 mmole pyrroles, after stirring, splash into 2 mmole triethylamines again.Reacted 36 hours down at 25 ℃, filter, filtrate is concentrated, refilter, the gained solid is under reduced pressure drained, and washes twice with 10 milliliters of hexanes, gets (Pr) ZrCl
3
(2) preparation indenyl sodium
The NaH that adds 2 mmoles in new dry 10 milliliters of tetrahydrofuran (THF)s crossing slowly splashes into the indenes of equimolar amount under the condition of ice bath, room temperature reaction is after 6 hours, and the solvent of taking out in the dereaction thing gets indenyl sodium [Na (Ind)].
(3) preparation catalyzer
Get (Pr) ZrCl of 2 mmoles
3Be dissolved in 20 milliliters of exsiccant methylene dichloride, stir under the condition of ice bath, and slowly add the Na (Ind) of 2 mmoles, return to room temperature gradually, reacted 12 hours.Filter, the filtrate solvent is drained, the gained solid carries out recrystallization with 40 milliliters of hexanes, 0.40 restrain catalyzer K[(Pr) (Ind) ZrCl
2], productive rate is 58 heavy %.
Results of elemental analyses is: C 46.03 heavy %, and N 4.78 heavy %, H 3.97 heavy %,
Zirconium 25.67 heavy %.
Example 10～18
Following example carries out polyreaction, the preparation polyethylene.
The toluene solution concentration of used methylaluminoxane (MAO) is 10 heavy % in the example, is produced by U.S. Albemarle company, and its total add-on reaches 7.5 * 10 with the content of MAO during polymerization
-3Mole is as the criterion.
250 milliliters of reaction flasks that agitator is housed are replaced twice with nitrogen replacement three times, pure ethylene, feed ethylene gas, under agitation add earlier the toluene solution of 50 milliliters of exsiccant toluene and MAO, and then the toluene solution that adds catalyzer and MAO is made into liquid, catalyst levels is 1.0 * 10
-5Mole, Al/M is 500: 1 in the system.Stop after 0.5 hour stirring 30 ℃ of following isothermal reactions, use excess ethyl alcohol earlier then, use the small amount of hydrochloric acid termination reaction again.Reactant was continued to stir in excess ethyl alcohol 1 hour, filters, and use ethanol, water, washing with alcohol successively, 60 ℃ of following vacuum-drying 4 hours, polymkeric substance.Each embodiment polyreaction catalyst system therefor and polymer property see Table 1.Polymkeric substance weight-average molecular weight Mw and molecular weight distribution M
w/ M
nIs solvent gel chromatography (waters150C chromatographic instrument) at 135 ℃ with the orthodichlorobenzene.
Example 19
Present embodiment carries out the styrene polymerization reaction, the preparation syndiotactic polystyrene.
Underpressure distillation again after SILVER REAGENT vinylbenzene dewatered with hydrolith, the lucifuge cryopreservation.Polyreaction is carried out under nitrogen protection.150 milliliters of reaction flasks are placed 30 ℃ of oil baths, add 20 milliliters of toluene, MAO toluene solution, 0.01 gram catalyst A and 10 milliliters of vinylbenzene of 7 milliliters in reaction flask, making the Al/Ti ratio is 500.React after 1 hour, with acidifying ethanol termination reaction, polymkeric substance water and ethanol wash respectively three times, in 70 ℃ of vacuum-dryings, obtain polystyrene.Activity of such catalysts is 1.2 * 10
5Gram polystyrene/mole titanium hour.Polystyrene molecular weight M
wBe 3.2 * 10
4, molecular weight distribution M
w/ M
nBe 4.15, a normality is 92.8%, fusing point T
mBe 262.3.
In the above-mentioned test data between polystyrene normality decide by the amount of insolubles by continuous extraction after 3 hours in ebullient acetone.Fusing point is measured with differential scanning calorimetry (DSC).
Example 20
This example carries out the copolyreaction of ethene and 1-hexene.
Underpressure distillation again after the 1-hexene dewatered with hydrolith is preserved under the lucifuge.Method by example 10 is carried out polyreaction, and different is adds 2 milliliters of 1-hexenes in the solution of toluene and MAO earlier, and then adds the toluene solution of catalyzer K and MAO, is condition under to carry out polymerization, collected polymer at 500: 1 at Al/Zr.The activity of catalyzer K is 2.3 * 10
5Gram polymkeric substance/mole zirconium hour, the weight-average molecular weight M of polymkeric substance
wBe 3.12 * 10
5, molecular weight distribution M
w/ M
nBe 2.56.
Table 1
| Instance number | The catalyzer numbering | The catalyzer expression formula | Catalyst activity when mole M (gram polyethylene /) * | Polymkeric substance | |
| Molecular weight Mw (* 10 4) | Molecular weight distribution mw/mn | ||||
| 10 | A | (Pr)(Cp)TiCl 2 | 1.2×10 5 | 34.0 | 2.19 |
| 11 | B | (Id)(Cp)TiCl 2 | 1.3×10 5 | 27.5 | 2.12 |
| 12 | C | (Mz)(Cp)TiCl 2 | 3.2×10 4 | - | - |
| 13 | D | (Ai)(Cp)TiCl 2 | 2.6×10 4 | - | - |
| 14 | E | (Iz)(Cp)TiCl 2 | 1.2×10 5 | 30.0 | 6.50 |
| 15 | F | (Bi)(Cp)TiCl 2 | 1.4×10 5 | 35.8 | 2.31 |
| 16 | G | (Pr)(Ind)TiCl 2 | 3.2×10 5 | 37.2 | 2.38 |
| 17 | H | (Pr)(Flu)TiCl 2 | 4.3×10 5 | 39.5 | 2.17 |
| 18 | K | (Pr)(Ind)ZrCl 2 | 1.5×10 5 | 28.5 | 2.30 |
*M in M and the example 10～18 refers to titanium or zirconium herein
Claims (17)
1, a kind of olefin polymerization catalysis has following general expression:
L contains the indyl that contains a nitrogen-atoms on the ligand groups of imidazole skeleton or the phenyl ring in the formula, two nitrogen-atoms in the described imidazole skeleton be between position or ortho position arrange, 1～4 substituent R is arranged on the five-membered ring of imidazole skeleton
1, two adjacent substituting groups can be connected with each other and form the above condensed ring of binary on its skeleton; Cp is the ligand groups that contains cyclopentadienyl skeleton, and 1～5 substituent R is arranged on the cyclopentadienyl skeleton
2, two adjacent substituting groups on its skeleton can be connected with each other and form the above condensed ring of binary; Described R
1And R
2Be selected from hydrogen, C respectively
1～C
18Alkyl or perfluoroalkyl, C
6～C
24Aralkyl or alkaryl, M is selected from IVB family metal, X and Y are selected from halogen, C respectively
1～C
24Alkyl, alkoxyl group, siloxy or alkaryl.
2, according to the described catalyzer of claim 1, it is characterized in that M is selected from titanium or zirconium, X and Y are selected from halogen or benzyl respectively.
3, according to the described catalyzer of claim 1, it is characterized in that R
1, R
2Be selected from hydrogen, C respectively
1～C
6Alkyl, C
1～C
6Perfluoroalkyl, C
6～C
24Aralkyl or alkaryl.
4,, it is characterized in that ligand L is imidazolyl, pyrazolyl, benzimidazolyl-, indazolyl, 7-azaindolyl, or contain the above-mentioned group of single replacement or multi-substituent that described substituting group is C according to the described catalyzer of claim 1
1～C
6Alkyl or perfluoroalkyl.
5, according to the described any catalyzer of claim 1～4, it is characterized in that Cp is cyclopentadienyl, indenyl, fluorenyl, or single the replacement or polysubstituted above-mentioned group, described substituting group is C
1～C
8Alkyl or perfluoroalkyl.
6, the described Preparation of catalysts method of a kind of claim 1 comprises the steps:
(1) in ether solvent, the strongly alkaline compound of equimolar amount is fully contacted with ligand compound HL, remove then and desolvate, obtain the salt of ligand compound,
(2) in organic solvent, making the salt and the general formula of the above-mentioned ligand compound of equimolar amount is CpMX
2The compound of Y fully contacts, and removes solid matter, the solvent in the gained liquid is removed obtained catalyzer.
7, in accordance with the method for claim 6, it is characterized in that the strongly alkaline compound described in (1) is basic metal, alkali-metal alkylide or hydride, alkyl magnesium bromide.
8, in accordance with the method for claim 7, it is characterized in that described basic metal is lithium, sodium or potassium, the alkyl in alkali metal alkyl compound or the alkyl magnesium bromide is selected from C
1～C
8Alkyl or aralkyl.
9, in accordance with the method for claim 6, it is characterized in that described ether solvent is ether or tetrahydrofuran (THF), organic solvent is ether, methylene dichloride, trichloromethane or toluene.
10, the described Preparation of catalysts method of a kind of claim 1 may further comprise the steps:
(1) in ether solvent, make the strongly alkaline compound and the abundant contact reacts of Cyclopeutadiene type ligand compound of equimolar amount, remove desolvate the salt of Cyclopeutadiene type ligand compound,
(2) in organic solvent, make LMX
3Mol ratio abundant contact reacts under agitation condition such as press with the salt of Cyclopeutadiene type ligand compound, remove solid matter, the solvent in the gained liquid is removed promptly got catalyzer.
11, in accordance with the method for claim 10, it is characterized in that described ether solvent is ether or tetrahydrofuran (THF), organic solvent is ether, methylene dichloride, trichloromethane or toluene.
12, in accordance with the method for claim 10, it is characterized in that described strongly alkaline compound is basic metal, alkali-metal alkylide or hydride, alkyl magnesium bromide.
13, in accordance with the method for claim 12, it is characterized in that described basic metal is lithium, sodium or potassium, the alkyl in alkali metal alkyl compound or the alkyl magnesium bromide is selected from C
1～C
8Alkyl or aralkyl.
14, the described Preparation of catalysts method of a kind of claim 1 is included in the organic solvent, and making general formula is CpMX
2The Y compound fully contacts with mol ratios such as ligand compound HL press, and then the trialkylamine of adding and HL equimolar amount, fully stirs the mixture, and removes solid matter, the solvent in the gained liquid is removed promptly got catalyzer.
15, in accordance with the method for claim 14, it is characterized in that described trialkylamine is triethylamine or tripropyl amine, organic solvent is ether, methylene dichloride or toluene.
16, a kind of method of olefinic polymerization, comprise that with the described catalyzer of claim 1 be Primary Catalysts, with aikyiaiurnirsoxan beta, aluminum alkyls, alkyl aluminum halide or their mixture is promotor, make alpha-olefin carry out polyreaction under 0～150 ℃, 0.01～10.0MPa condition, the Al/M mol ratio is 10～10000 during reaction.
17, in accordance with the method for claim 16, it is characterized in that described aikyiaiurnirsoxan beta is methylaluminoxane, ethyl aikyiaiurnirsoxan beta or isobutyl aluminium alkoxide, aluminum alkyls is trimethyl aluminium, triethyl aluminum or triisobutyl aluminium, and alkyl aluminum halide is aluminium diethyl monochloride or sesquialter aluminium diethyl monochloride; And the Al/M mol ratio is 50～5000 during reaction.
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| JP2019172954A (en) * | 2018-03-26 | 2019-10-10 | 三井化学株式会社 | Catalyst for olefin polymerization, transition metal compound, method for producing olefin polymer, and cyclic olefin copolymer |
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| JP2019172954A (en) * | 2018-03-26 | 2019-10-10 | 三井化学株式会社 | Catalyst for olefin polymerization, transition metal compound, method for producing olefin polymer, and cyclic olefin copolymer |
| JP7175692B2 (en) | 2018-03-26 | 2022-11-21 | 三井化学株式会社 | Catalyst for olefin polymerization and method for producing olefin polymer |
| JP2021073223A (en) * | 2021-01-18 | 2021-05-13 | 三井化学株式会社 | Manufacturing method of transition metal compound, olefin polymerization catalyst, and olefin polymer |
| JP6997887B2 (en) | 2021-01-18 | 2022-01-18 | 三井化学株式会社 | Methods for Producing Transition Metal Compounds, Catalysts for Olefin Polymerization, and Olefin Polymers |
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