CN102050906A - Metallocene catalyst prepolymer and olefin polymerizing method thereof - Google Patents

Metallocene catalyst prepolymer and olefin polymerizing method thereof Download PDF

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CN102050906A
CN102050906A CN2009102366685A CN200910236668A CN102050906A CN 102050906 A CN102050906 A CN 102050906A CN 2009102366685 A CN2009102366685 A CN 2009102366685A CN 200910236668 A CN200910236668 A CN 200910236668A CN 102050906 A CN102050906 A CN 102050906A
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metallocene catalyst
prepolymer
general formula
prepolymerization
polymerization
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于鲁强
王彦荣
宋文波
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The invention provides a metallocene catalyst prepolymer and an olefin polymerizing method thereof, wherein the metallocene catalyst prepolymer is prepared by using the following steps of: carrying out a prepolymerization reaction on a monomer shown in a general formula (1) by using a metallocene catalyst at a temperature of 10-70 DEG C, wherein M represents carbon atoms or silicon atoms, and R1, R2 and R3 are same or different and represents alkyl groups with hydrogen atoms or carbon atoms of 1-6. After the prepolymerization is carried out, propylene homopolymerization or copolymerization is carried out, thus the rigidity and the transparency of the finally obtained polymer product are remarkably improved.

Description

Metallocene catalyst prepolymer and olefine polymerizing process thereof
Technical field
The present invention relates to a kind of metallocene catalyst prepolymer that is used for olefinic polyreaction, and the olefine polymerizing process under this metallocene catalyst prepolymer.
Technical background
Traditionally, preparation has the method for high stiffness acrylic resin and normally adds filler or various nucleator, but because the existence of filler makes the transparent variation of final polymer product, also has tangible material weightening finish problem simultaneously.For nucleator, organic nucleating agent add that affiliation brings that nucleator difficult disperses, easily migration, problem such as cost is higher and nucleating effect is limited.
Select the polymer nucleator for use, especially some dystectic polyolefine can be good at addressing the above problem.People attempt to attempt in polymerization process, and the method that generates some dystectic olefinic polymerization chains on the spot plays the effect of polymer nucleator.For example, before propylene polymerization, select special polymerization single polymerization monomer that catalyzer is carried out prepolymerization and handle, can generate some dystectic polymkeric substance in advance, the catalyzer prepolymer after again prepolymerization being handled carries out propylene polymerization, the polymkeric substance of so prior generation is to the polypropylene of later generation, because its fusing point height can be dispersed in the middle of the polypropylene again preferably, so, the effect of nucleator can be played, the problems referred to above that traditional nucleator exists can be solved again preferably.The special alpha olefin monomers that adopts the special side group of a class band, in the presence of Ziegler-Natta catalyst, carry out prepolymerization and obtain the catalyzer prepolymer, in the presence of the catalyzer prepolymer, carry out propylene polymerization then again, can obtain the propene polymer of high stiffness.This prepolymerized processing not only can improve the structural form of catalyzer, prevent that catalyzer is broken and increase fine polymer powder content in polymerization, and formed a spot of high-melting-point polymer can also play the effect of nucleus in the polymerization process of propylene, thereby improves the performances such as rigidity of final polypropylene product.If described high-melting-point polymer has identical or close crystalline texture with polypropylene, they can further improve nucleating effect, and then improve the mechanical property of the finished product, improve optical property simultaneously.The alpha olefin monomers of the special side group of this class band generally includes: vinyl pentamethylene (VCP), vinyl cyclohexane (VCH), 3-methyl-1-butene (3M1B), 4-methyl-1-pentene (4M1P), cyclopentenes etc.
For example, U.S. Pat 6747103 discloses the method for employing vinyl cyclohexane (VCH) pre-polymerization modification Ziegler-Natta type catalyzer, is specially: at polymerization temperature is that 55 ℃, pressure are 0.5barN 2Under the atmosphere, a certain amount of catalyzer, promotor, specific external electron donor and VCH are carried out polymerization in 20 hours in the grease medium.Get a certain amount of above-mentioned resulting modified catalyst mixture, again with after a certain amount of promotor, specific external electron donor mix, join in the reactor, carry out 70 ℃ of liquid phase bulk propylene polymerizations, the polypropylene articles of gained has higher modulus in flexure, low xylene soluble part, and higher Tc.
Also disclose the method for a kind of employing 3-methyl-1-butene (3M1B) modification Ziegler-Natta type catalyzer in addition, promptly under 20 ℃ of temperature, in the hexane medium,, obtained the catalyzer prepolymer of 10.4g3M1B polymkeric substance/g catalyzer 3M1B polymerization 8 hours.Then this catalyzer through the pre-polymerization modification is used for propylene polymerization, and adopts the method for multi-stage polymeric, obtain the acrylic resin of high degree of isotacticity, wide molecular weight distribution, thereby obtain the polypropylene product of high modulus in flexure.
This type of technology is normally carried out Ziegler-Natta type catalyzer, and for the report of true this type of technology of nothing of single site catalysts.
Summary of the invention
The invention provides a kind of metallocene catalyst prepolymer that is used for olefinic polyreaction, it may further comprise the steps:
Under polymerization temperature, metallocene catalyst exists down, in the inert solvent, carries out the prepolymerization reaction of at least a olefinic monomer shown in the general formula (I):
Figure B2009102366685D0000031
M represents carbon atom or Siliciumatom, R 1, R 2, R 3Identical or different, expression hydrogen atom or carbonatoms are the hydrocarbyl group of 1-6.
The prepolymerization multiple is controlled in 3～100 times with gained prepolymer weight and the calculating recently that adds metallocene catalyst weight, preferably is controlled in 3～50 times.
Above-mentioned prepolymerization temperature of reaction is preferably 10～70 ℃, and the pre-treatment solvent adopts C 6～C 18Inert solvent, preferred hexane, heptane, octane or decane.The prepolymerization reaction times is generally less than 10 hours, controls the time of prepolymerization reaction with the prepolymerization multiple.
In order to obtain the acrylic resin of high degree of isotacticity, wide molecular weight distribution better, can also in above-mentioned prepolymerization reaction, introduce another kind of olefinic monomer, it adopts at least a in the following general formula (II):
HC 2＝CH-CH 2-X (II)
In the general formula (II), X represents cycloalkyl or an aryl or alkaryl that carbonatoms is 6-12 that a carbonatoms is 1-8.
Molar ratio between described general formula (I) and both monomers of general formula (II) is for being 1: 20～1: 0.05.Preferred 1: 5～1: 0.2.
The above-mentioned metallocene catalyst that is used for prepolymerization reaction can adopt the conventional in the industry olefinic polymerization single site catalysts that is used for, and it generally includes the reaction product of following component:
(2) have the Metallocenic compound of general formula for (I):
(C 5R 1 x-mH 5-x)R m 2(C 5R 1 y-mH 5-y) nMQ 3-n (I)
Metal M is Ti, Zr or Hf in the formula; Q is Cl or methyl; C 5R 1 X-mH 5-xAnd C 5R 1 Y-mH 5-yBe to contain identical or different substituent cyclopentadienyl, wherein substituent R 1Be the aromatic base that the alkyl that contains 1～20 carbon atom, alkenyl, aromatic base, alkyl replace, substituting group is identical or different each other, and these substituting groups can contain Si or Ge atom or Si (CH 3) 3, and two or four substituent R of same cyclopentadienyl 1Can constitute one or two ring of 4～6 carbon atoms;
R 2Be the bridged group of two cyclopentadiene parts of connection of one two valency, can be selected from one of following radicals: CR 3 2, C 2R 3 4, SiR 3 2, Si 2R 3 4, GeR 3 2, Ge 2R 3 4, substituent R wherein 3Be R 1Or H, each other can be identical or different, and 2 or 4 s' substituent R 3Can form one or two ring that contains 3～6 carbon atoms;
M=0 or 1, n=0 or 1;
X is one and is not less than m and is not more than 5 integer, and y is one and is not less than m and is not more than 5 integer;
(2) general formula of described aikyiaiurnirsoxan beta is (R-Al-O) n, wherein R is C 1～C 12Alkyl, n is 1～20; The best is 15～20;
The mol ratio of the middle transition metal of Al and component (1) is 30～2000 in the said components (2), is preferably 30～200, and the best is 50～100.
Said components (1) formula of is that the Metallocenic compound of (I) is selected from one or more in the following metallocene compound: Cp2ZrCl 2, Me 2SiCp 2ZrCl 2, Cp 2TiCl 2, Cp 2HfCl 2, Cp 2TiMeCl, Cp 2ZrMe 2, Cp 2TiMe 2, (C 5Me 5) 2ZrCl 2, (MeC 5H 4) 2ZrCl 2, (EtC 5H 4) 2ZrCl 2, (nC 3H 7C 5H 4) 2ZrCl 2, (iC 3H 7C 5H 4) 2ZrCl 2, (nBuC 5H 4) 2ZrCl 2, (iBuC 5H 4) 2ZrCl 2, (tBuC 5H 4) 2ZrCl 2, (1.2-dimethyl C 5H 3) 2ZrCl 2, (1.3-dimethyl C 5H 3) 2ZrCl 2, (1.2.3-trimethylammonium C 5H 2) 2ZrCl 2, (1.3.4-trimethylammonium C 5H 2) 2ZrCl 2, (1.2-diethyl C 5H 3) 2ZrCl 2, (1.3-diethyl C 5H 3) 2ZrCl 2, [O (SiMe 2Cp) 2] ZrCl 2, [O (SiMe 2TBuCp) 2] ZrCl 2, [Et (Ind) 2] ZrCl 2, [Et (2,4,7Me 3Ind) 2] ZrCl 2, [Et (IndH 4) 2] ZrCl 2, [Me 2Si (Cp) (Me 4Cp)] ZrCl 2, (Cp) (Me 4Cp)] ZrCl 2, [Me 2Si (Ind) 2] ZrCl 2, [Ph 2Si (Ind) 2] ZrCl 2, [Bz 2Si (Ind) 2] ZrCl 2, [Me 2Si (2,4,7Me 3Ind) 2] ZrCl 2, [Me 2Si (IndH 4) 2] ZrCl 2, [Me 2Si (2Me-4,6iPr 2Ind) 2] ZrCl 2, [Me 2Si (2Me-4Ph-Ind) 2] ZrCl 2, [Me 2Si (2Me-4,6BEtzInd) 2] ZrCl 2, [Ph 2C (Ind) is (Cp)] ZrCl 2, [Me 2C (Ind) is (Cp)] ZrCl 2, [Me 2C (Ind) is (3MeCp)] ZrCl 2, [Ph 2C (Flu) is (Cp)] ZrCl 2, [Me 2C (Flu) is (Cp)] ZrCl 2, [Me 2Ge (2-Me-4Ph-Ind) 2] ZrCl 2, (MeC 5H 4) 2HfCl 2, (EtC 5H 4) 2HfCl 2, (nC 3H 7C 5H 4) 2HfCl 2, (iC 3H 7C 5H 4) 2HfCl 2, (nBuC 5H 4) 2HfCl 2, (iBuC 5H 4) 2HfCl 2, (tBuC 5H 4) 2HfCl 2, [Et (Ind) 2] HfCl 2, [Me 2C (Flu) is (Cp)] HfCl 2, [Me 2Si (Cp) (Me 4Cp)] HfCl 2Preferred compound is as dicyclopentenyl zirconium dichloride Cp 2ZrCl 2, ethylidene bridging two indenyl zirconium dichloride En (Ind) 2ZrCl 2, En (IndH 4) ZrCl 2, Me 2Si (Ind) 2ZrCl 2, rac-En (4,7-Me-1-Ind) 2ZrCl, Cp 2HfCl 2
In the aluminium alkoxide compound described in the said components (2), R specifically is selected from: methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, the best is a methyl.Mainly be to obtain by alkyl aluminum hydrolysis, for example U.S. Pat 4,544, the method that 762 disclosed employing metal inorganic salts are water source hydrolysis aluminum alkyls; U.S. Pat 4,968, the method that 827 disclosed employing deionized waters are water source hydrolysis aluminum alkyls; The method that Chinese patent 94119050.1 disclosed employing cyclodextrin compounds are water source hydrolysis aluminum alkyls.
The preparation method of the above-mentioned metallocene catalyst that is used for the prepolymerization reaction can adopt the method for industry routine, also can be with reference to disclosed method among patent EP128045, US4530914 and the CN, and the full content of described patent is incorporated herein the present invention as a reference.
The present invention also provides a kind of method of propylene polymerization, it is characterized in that: under polymerization temperature, at least a Ziegler-natta catalyst is or/and metallocene catalyst, exist down with a kind of metallocene catalyst prepolymer of above-mentioned preparation, in the solvent or propylene liquid phase bulk environment down or carry out the equal polymerization or the copolymerization of propylene monomer in the gas phase, polymerization temperature: 60-90 ℃.
In above-mentioned polymerization process, described Ziegler-natta catalyst can adopt the conventional in the industry high reactivity that is used for propylene polymerization, the Ziegler-Natta catalyst of high stereoselective, and it generally includes following component:
(1) with magnesium, titanium, halogen and internal electron donor is the solid active component of main ingredient;
(2) organo-aluminium compound;
(3) randomly, the external electron donor component adopts silicoorganic compound usually, and it mainly acts on is the orientation property that can improve catalyst active center.
Operational with magnesium, titanium, halogen and internal electron donor are that the specific examples of the solid active component of main ingredient is disclosed in Chinese patent CN85100997A, CN1258680A, CN1258683A, CN1258684A, CN1091748A, CN1330086A, CN1298887A, CN1298888A, CN1436796A, CN1047302A, CN1042157A, CN1143651A, CN1021699A, CN1042156A, CN1087094A, US4,547,476, US5,945,366, US4,839,321, US4,816,433, US4,866,022, US5,124,29 grades and Chinese patent application number are 93102795,200410073621 and 200410073623 disclosed catalyzer or catalyst components.
Usually this is that the solid active component of main ingredient is by magnesium chloride, halogenated titanium or derivatives thereof with magnesium, titanium, halogen and internal electron donor, electron donor contact reacts such as ester, ether, alcohol and obtaining.
As the organo-aluminium compound preferred alkyl aluminum compound of catalyzer cocatalyst component, can adopt general formula is AlR nX 3-nCompound, R is a hydrogen in the formula, carbonatoms is 1～20 alkyl, X is a halogen, n is the number of 1＜n≤3; Specifically can be selected from triethyl aluminum, tri-propyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-octylaluminium, triisobutyl aluminium, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethyl aluminum chloride, ethyl aluminum dichloride, preferred triethyl aluminum, triisobutyl aluminium, three n-butylaluminum etc.
Described external electron donor component is preferably silicoorganic compound.It is R that these silicoorganic compound are selected from general formula 1 xR 2 ySi (OR 3) zIn at least a, R wherein 1And R 2Be respectively alkyl or halogen, R 3Be alkyl, 0≤x≤2,0≤y≤2 and 1≤z≤4, and x+y+z=4.General formula is R 1 xR 2 ySi (OR 3) zIn, preferred R 1And R 2Be respectively alkyl or halogen that carbonatoms is 1-10, R 3For carbonatoms is the 1-10 alkyl, x wherein, y, z are positive integer, 0≤x≤2,0≤y≤2 and 1≤z≤4, and x+y+z=4.
Concrete silicoorganic compound have: tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, four (2-ethyl hexyl oxy) silane, ethyl trimethoxy silane, ethyl triethoxysilane, methyltrimethoxy silane, Union carbide A-162, the n-propyl triethoxyl silane, the n-propyl Trimethoxy silane, the decyl Trimethoxy silane, the decyl triethoxyl silane, the cyclopentyl Trimethoxy silane, the cyclopentyl triethoxyl silane, 2-methylcyclopentyl Trimethoxy silane, 2,3-dimethylcyclopentyl Trimethoxy silane, cyclohexyl trimethoxy silane, the cyclohexyl triethoxyl silane, methyltrimethoxy silane, Union carbide A-162, ethyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, tertiary butyl triethoxyl silane, the normal-butyl Trimethoxy silane, ne-butyltriethoxysilaneand, the isobutyl-Trimethoxy silane, the isobutyl-triethoxyl silane, the cyclohexyl triethoxyl silane, cyclohexyl trimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, one chlorine Trimethoxy silane, one chlorine triethoxyl silane, ethyl three isopropoxy silane, vinyl three butoxy silanes, trimethyl phenoxysilane, methyl three allyloxy silane, vinyl nitrilotriacetic base silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, diisopropyl dimethoxy silane, the di-isopropyl diethoxy silane, tertiary butyl methyl dimethoxysilane, tertiary butyl methyldiethoxysilane, the tert-pentyl methyldiethoxysilane, dicyclopentyl dimethoxyl silane, two cyclopentyl diethoxy silanes, the methylcyclopentyl diethoxy silane, methylcyclopentyl dimethoxy silane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, the aminomethyl phenyl diethoxy silane, aminomethyl phenyl dimethoxy silane, two o-tolyl dimethoxy silane, two o-tolyl diethoxy silanes, tolyl dimethoxy silane between two, tolyl diethoxy silane between two, biconjugate tolyl dimethoxy silane, biconjugate tolyl diethoxy silane, the trimethylammonium methoxy silane, trimethylethoxysilane, three cyclopentyl methoxy silane, three cyclopentyl Ethoxysilanes, one or more mixing wherein such as two cyclopentyl-methyl methoxy silane and cyclopentyl dimethyl methyl TMOS are used.
The ratio between each component in the Ziegler-natta catalyst wherein, with titanium: aluminium: the molar ratio computing between the silicon is 1: 5～200: 0.1～100.
In the aforesaid propylene polymerization process, described metallocene catalyst can be selected from employed metallocene catalyst in the prepolymerization reaction, and the two can select identical or different.
Embodiment
With embodiment the present invention is described below, but and unrestricted invention scope.
The testing method or the standard of polymer performance are as follows:
1, melt flow rate (MFR) (MFR) is pressed ISO1133,230 ℃, measures under the 2.16kg load.
2, xylene soluble part is pressed ASTM D5492-98 mensuration.
3, melt temperature, Tc adopt differential scanning calorimeter to press ASTM D3418-03 measurement.
4, resin stretched intensity is pressed ASTM D638-00 measurement.
5, the resin modulus in flexure is pressed ASTM D790-97 measurement.
6, the resin mist degree is pressed ASTM D1003-00 measurement.
Embodiment 1
1, the preparation of metallocene catalyst prepolymer:
With 10mg metallocene catalyst (EBI) ZrCl 2Being dissolved in a certain amount of concentration is in the MAO solution of 1.54M, adds in one 200 milliliters the batch reactor, injects the 150ml hexane, adds and then will 5mlCross through drying treatment 3-methyl-1-butene, then feed a certain amount of in the still Butylene, with the quality of under meter metering butylene.60 ℃ of temperature of reactor, reaction pressure 0.2Mpa, polymerization time 3 hours.Stop to add butylene, in the nitrogen protection bottom discharge, remove liquid portion, add a certain amount of hexane again and carry out carrying out washing treatment 3 times, adding 100ml hexane suspension is standby.Take out 5 milliliters of above-mentioned suspension, dry weighting method confirms that the prepolymerization multiplying power is 10 times.
2, propylene polymerization:
Get the prepolymer suspension 5ml that step 1 obtains, and 15mg catalyzer dry powder (catalyzer among the Chinese patent CN1330086A described in the embodiment 1), 5ml concentration is the hexane solution of the triethyl aluminum of 0.5M, 1.5ml concentration is the hexane solution of the cyclohexyl methyl dimethoxy silane of 0.2M, add in the 5L autoclave, add the hydrogen of 0.5mol successively in reactor, 3 liters of liquid propenes carry out propylene polymerization.70 ℃ of polymerization temperatures, the reaction times is 1 hour.Reaction result and the polymkeric substance Mechanics Performance Testing that obtains the results are shown in Table 1.
Embodiment 2
1, the preparation of metallocene catalyst prepolymer:
With 10mg metallocene catalyst (EBI) ZrCl 2Being dissolved in a certain amount of concentration is in the MAO solution of 1.54M, adds in one 200 milliliters the batch reactor, injects the 150ml hexane, adds and then will The 25ml warpThe 3-methyl-1-butene that super-dry was handled reacts.60 ℃ of temperature of reactor, reaction pressure 0.2Mpa, polymerization time 3 hours.After reaction is finished, in the nitrogen protection bottom discharge, remove liquid portion, add a certain amount of hexane again and carry out carrying out washing treatment 3 times, adding 100ml hexane suspension is standby.Take out 5 milliliters of above-mentioned suspension, dry weighting method confirms that the prepolymerization multiplying power is 10 times.
2, propylene polymerization
Get above-mentioned suspension 5ml, and 15mg catalyzer dry powder (catalyzer among the Chinese patent CN1330086A described in the embodiment 1), 5ml concentration is the triethyl aluminum hexane solution of 0.5M, 1.5ml concentration is the cyclohexyl methyl dimethoxy silane hexane solution of 0.2M, add in the 5L autoclave, add the hydrogen of 0.1mol successively in reactor, 3 liters of liquid propenes carry out propylene polymerization.70 ℃ of polymerization temperatures, the reaction times is 1 hour.Reaction result and the polymkeric substance Mechanics Performance Testing that obtains the results are shown in Table 1.
Comparative Examples 1:
The method of describing among the embodiment 1 among the catalyzer employing Chinese patent CN1330086A obtains, its Ti content: 2.4W t%, Mg content 18.0Wt%, n-butyl phthalate content 13Wt%.With the catalyzer dry powder of 15mg, 5ml concentration is the triethyl aluminium solution of 0.5M, and 1.5ml concentration is the external electron donor CHMDMS solution of 0.2M, add in the 5L autoclave, add the hydrogen of 0.5mol successively in reactor, 3 liters of liquid propenes carry out propylene polymerization.70 ℃ of polymerization temperatures, the reaction times is 1 hour.Reaction result and the polymkeric substance Mechanics Performance Testing that obtains the results are shown in Table 1.
Table 1 polymerization and Mechanics Performance Testing result
Embodiment 1 Embodiment 2 Comparative Examples 1
Polymerization activity (ten thousand times) 2.9 2.7 2.7
MFR(g/10Min) 3.0 3.1 3.2
Xylene soluble part (Wt%) 3.0 2.8 4.8
Melt temperature ℃ 163.8 164.1 158.5
Tc ℃ 116.4 116.9 113.8
Tensile strength (MPa) 54.9 55.1 41.3
Modulus in flexure (GPa) 1.87 1.92 1.63
Izod shock strength (J/m) 31.4 30.3 25.3
Mist degree (%) 29 28 70
By above-mentioned data as can be seen, after the present invention utilizes 3-methyl-1-butene that metallocene catalyst is carried out prepolymerization and handles, carry out propylene homopolymerization or copolymerization again after, can effectively improve the rigidity and the properties of transparency of polypropylene product.

Claims (10)

1. metallocene catalyst prepolymer that is used for olefinic polyreaction, it obtains by following steps:
Under the prepolymerization temperature of reaction, metallocene catalyst exists down, in the inert solvent, carries out the prepolymerization reaction of at least a olefinic monomer shown in the general formula (I):
Figure F2009102366685C0000011
M represents carbon atom or Siliciumatom, R 1, R 2, R 3Identical or different, expression hydrogen atom or carbonatoms are the hydrocarbyl group of 1-6;
The prepolymerization multiple is controlled in 3～100 times with gained prepolymer weight and the calculating recently that adds metallocene catalyst weight.
2. the metallocene catalyst prepolymer that is used for olefinic polyreaction according to claim 1 is characterized in that, 10～70 ℃ of described prepolymerization temperature of reaction, and the prepolymerization reaction times was less than 10 hours.
3. the metallocene catalyst prepolymer that is used for olefinic polyreaction according to claim 1 is characterized in that described prepolymerization multiple is controlled in 3～50 times.
4. the metallocene catalyst prepolymer that is used for olefinic polyreaction according to claim 1 is characterized in that described metallocene catalyst comprises the reaction product of following component:
(1) have the Metallocenic compound of general formula for (I):
(C 5R 1 x-mH 5-x)R m 2(C 5R 1 y-mH 5-y) nMQ 3-n (I)
Metal M is Ti, Zr or Hf in the formula; Q is Cl or methyl; C 5R 1 X-mH 5-xAnd C 5R 1 Y-mH 5-yBe to contain identical or different substituent cyclopentadienyl, wherein substituent R 1Be the aromatic base that the alkyl that contains 1～20 carbon atom, alkenyl, aromatic base, alkyl replace, substituting group is identical or different each other, and these substituting groups can contain Si or Ge atom or Si (CH 3) 3, and two or four substituent R of same cyclopentadienyl 1Can constitute one or two ring of 4～6 carbon atoms;
R 2Be the bridged group of two cyclopentadiene parts of connection of one two valency, can be selected from one of following radicals: CR 3 2, C 2R 3 4, SiR 3 2, Si 2R 3 4, GeR 3 2, Ge 2R 3 4, substituent R wherein 3Be R 1Or H, each other can be identical or different, and 2 or 4 s' substituent R 3Can form one or two ring that contains 3～6 carbon atoms;
M=0 or 1, n=0 or 1;
X is one and is not less than m and is not more than 5 integer, and y is one and is not less than m and is not more than 5 integer;
(2) general formula of described aikyiaiurnirsoxan beta is (R-Al-O) n, wherein R is C 1～C 12Alkyl, n is 1～20; The best is 15～20;
The mol ratio of the middle transition metal of Al and component (1) is 30～2000 in the said components (2), is preferably 30～200, and the best is 50～100.
5. the metallocene catalyst prepolymer that is used for olefinic polyreaction according to claim 1 is characterized in that, introduces another kind of olefinic monomer in the described prepolymerization reaction, and it adopts at least a in the following general formula (II):
HC 2＝CH-CH 2-X (II)
In the general formula (II), X represents cycloalkyl or an aryl or alkaryl that carbonatoms is 6-12 that a carbonatoms is 1-8.
6. the metallocene catalyst prepolymer that is used for olefinic polyreaction according to claim 5 is characterized in that, the molar ratio between described general formula (I) and both monomers of general formula (II) is for being 1:20～1: 0.05.Preferred 1: 5～1: 0.2.
7. the method for a propylene polymerization, it is characterized in that: under polymerization temperature, at least a Ziegler-natta catalyst and/or metallocene catalyst, require the described metallocene catalyst prepolymer of one of 1-6 to exist down with a kind of aforesaid right, in the solvent or propylene liquid phase bulk environment down or carry out the equal polymerization or the copolymerization of propylene monomer in the gas phase.
8. propene polymerizing method according to claim 7, wherein said Ziegler-natta catalyst adopts the conventional in the industry high reactivity that is used for propylene polymerization, the Ziegler-Natta catalyst of high stereoselective, and it generally includes following component:
(1) with magnesium, titanium, halogen and internal electron donor is the solid active component of main ingredient;
(2) organo-aluminium compound;
(3) randomly, the external electron donor component adopts silicoorganic compound usually, and it mainly acts on
It is the orientation property that can improve catalyst active center.
9. propene polymerizing method according to claim 8, the ratio in the wherein said Ziegler-natta catalyst between each component, with titanium: aluminium: the molar ratio computing between the silicon is 1: 5～200: 0.1～100.
10. propene polymerizing method according to claim 8, the described metallocene catalyst prepolymer of one of wherein said Ziegler-natta catalyst and claim 1-6, the adding part by weight scope of the two is 1: 100～1: 0.05, preferred 1: 50～1: 3.
CN2009102366685A 2009-10-27 2009-10-27 Metallocene catalyst prepolymer and olefin polymerizing method thereof Pending CN102050906A (en)

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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
CN113214417A (en) * 2021-03-09 2021-08-06 中国石油化工股份有限公司 Method for preparing polypropylene by using metallocene catalyst

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CN1279694A (en) * 1997-10-22 2001-01-10 智索公司 Supported metalloeene catalyst, process for preparing the same, and process for producing oclefin polymers
CN101003587A (en) * 2006-12-28 2007-07-25 高菲 Method for preparing thermoplastic resin of stereoregularity by using segmented polymerizing body of liquid phase

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CN1102419A (en) * 1993-07-16 1995-05-10 三井石油化学工业株式会社 Polypropylene resin composition and the use of the same
CN1279694A (en) * 1997-10-22 2001-01-10 智索公司 Supported metalloeene catalyst, process for preparing the same, and process for producing oclefin polymers
CN101003587A (en) * 2006-12-28 2007-07-25 高菲 Method for preparing thermoplastic resin of stereoregularity by using segmented polymerizing body of liquid phase

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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
CN113214417A (en) * 2021-03-09 2021-08-06 中国石油化工股份有限公司 Method for preparing polypropylene by using metallocene catalyst

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Application publication date: 20110511