CN1021230C - Polymerigation process of olefin - Google Patents
Polymerigation process of olefin Download PDFInfo
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- CN1021230C CN1021230C CN 88102963 CN88102963A CN1021230C CN 1021230 C CN1021230 C CN 1021230C CN 88102963 CN88102963 CN 88102963 CN 88102963 A CN88102963 A CN 88102963A CN 1021230 C CN1021230 C CN 1021230C
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- aikyiaiurnirsoxan beta
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Abstract
The present invention relates to a polymerization of olefin. The method comprises the steps that a catalyst composed of transition metal of a group IVB of a periodic table, such as a compound of zirconium, alumina alkane formed by trimethylaluminium, and the alumina alkane which is combined with at least one alkyl except a positive alkyl on an aluminum atom is used for carrying out olefinic polymerization. In the method, even if the use level of the alumina alkane formed by the trimethylaluminium with high price is reduced, the olefinic polymerization can also be carried out under excellent polymerization activity, and a polymer with large molecular weight can be made.
Description
The present invention relates to a kind of polymerization process of alkene.In detail, the present invention relates to a kind of olefinic polymerization of under the polymerization activity of excellence, carrying out, and make the method for macromolecule olefin copolymer.In more detail, the present invention relates to a kind ofly when being applicable to narrow molecular weight distribution and two or more olefin-copolymerization, under the polymerization activity of excellence, make molecular weight distribution and form the method for the olefin copolymer of narrowly distributing.
As alpha-olefinic polymer, the manufacture method of ethene polymers or ethylene particularly, known in the presence of Titanium series catalyst of forming by titanium compound and organo-aluminium compound or the vanadium series catalyst formed by vanadium compound and organo-aluminium compound, carry out the method for ethene or ethene and alpha-olefin copolymer.
On the other hand, the Ziegler-type olefin polymerization catalysis as new has proposed the catalyzer of being made up of zirconium compounds and aikyiaiurnirsoxan beta recently.
Open in the clear 58-19309 communique the spy and to have recorded and narrated a kind of polymerization process, this method is to be contained in the presence of the catalyzer that transistion metal compound and wire aikyiaiurnirsoxan beta or ring-type aikyiaiurnirsoxan beta form by following, under-50～200 ℃ of temperature, make ethene and one or more C
3～C
12The alpha-olefin method of carrying out copolymerization.This contains transistion metal compound and can be represented by the formula:
(luxuriant)
2MeRHal
(in the formula, R is cyclopentadienyl, C
1～C
6Alkyl, halogen atom, Me are transition metal, and Hal is a halogen atom)
This wire aikyiaiurnirsoxan beta can be represented by the formula:
(in the formula, R is methyl or ethyl, and n is 4～20 number) this ring-type aikyiaiurnirsoxan beta can be represented by the formula:
(in the formula, the definition of R and n is same as described above)
In the disclosure communique, recorded and narrated the poly density that can make, should be in 10%(weight for regulating) below a spot of long-chain alpha-olefin or its mixture in the presence of carry out vinyl polymerization.
Open the invention of having recorded and narrated relevant wire aikyiaiurnirsoxan beta and ring-type aikyiaiurnirsoxan beta method for making in the clear 59-95292 communique the spy.This wire aikyiaiurnirsoxan beta can be represented by the formula:
(in the formula, n is 2～40 number, and R is C
1～C
6Alkyl) this ring-type aikyiaiurnirsoxan beta can be represented by the formula:
(in the formula, the definition of n and R is same as described above) in this communique, also recorded and narrated as making with this method for making, mix mutually with two (luxuriant) compound of titanium or zirconium such as methylaluminoxane, and the words of carrying out olefinic polymerization, so, every gram transition metal, and in 1 hour, can make polyethylene more than 2500 myriagrams.
Open the method for making that discloses a kind of alkene usefulness polymerizing catalyst in the clear 60-35005 communique the spy, this method is at first to make aluminium alkoxide compound and magnesium compound reaction, then make the resultant of reaction chlorination, handle with Ti, V, Zr or Cr compound again, to make the method for alkene with polymerizing catalyst.This aluminium alkoxide compound can be represented by the formula:
(in the formula, R
1Be C
1～C
10Alkyl, R
0Be R
1Or combine and represent-O-)
In this communique, record and narrate above-mentioned catalyzer and be specially adapted to ethene and C
3～C
12The copolymerization of the mixture of alpha-olefin.
Open the spy and to disclose a kind of reactor blending of polymers catalyst for producing system in the clear 60-35006 communique, it is to be combined by one, two or three of different two or more transition metal-luxuriant or derivatives thereof (a) and aikyiaiurnirsoxan beta (b).Disclose in the embodiment 1 of this communique that a kind of dimethyl two (pentamethyl-is luxuriant) closes zirconium and aikyiaiurnirsoxan beta is a catalyzer, make ethene and propylene polymerization, can make number-average molecular weight and be 15300, weight-average molecular weight be 36400 and propylene component content be the 3.4%(mole) poly method.In addition, in the embodiment 2 of this communique, close zirconium with dichloro two (pentamethyl-is luxuriant), dichloro two (methyl is luxuriant) closes zirconium and aikyiaiurnirsoxan beta is a catalyzer, make ethene and propylene polymerization, having made by number-average molecular weight is 2200, weight-average molecular weight be 11900 and propylene component content be the 30%(mole) toluene soluble part and number-average molecular weight be 3000, weight-average molecular weight be 7400 and propylene component content be the 4.8%(mole) the number-average molecular weight partly formed of toluene insoluble be 2000, weight-average molecular weight be 8300 and propylene component content be the 7.1%(mole) polyethylene and the adulterant of ethylene propylene copolymer.Equally, in embodiment 3, recorded and narrated by molecular weight distribution (Mw/ Mn) be 4.57 and propylene component content be the 20.6%(mole) soluble fractions and molecular weight distribution be 3.04 and propylene component content be the 2.9%(mole) the adulterant of the linear low density polyethylene (LLDPE) formed of insoluble part and ethylene propylene copolymer.
The spy open recorded and narrated in the clear 60-35007 communique a kind of make ethylene homo or with the method for carbonatoms greater than 3 alpha-olefine polymerizing, this method is to carry out containing in the presence of the catalyst system of metallocene (metallocene) and following ring-type aikyiaiurnirsoxan beta.This ring-type aikyiaiurnirsoxan beta can be represented by the formula:
(in the formula, R is that carbonatoms is 1～5 alkyl, the definition of n and above-mentioned same) according to this communique record, with the polymkeric substance that this method makes, its weight-average molecular weight is about 500～1,400,000, and molecular weight distribution is 1.5～4.0.
In addition, open the spy and to have recorded and narrated the catalyst system that a kind of use contains two kinds of metallocenes and aikyiaiurnirsoxan beta at least in the clear 60-35008 communique, can make polyethylene or ethene and C with wide molecular weight distribution
3～C
10The method of multipolymer of alpha-olefin.The molecular weight distribution (Mw/ Mn) of having recorded and narrated above-mentioned multipolymer in this communique is 2～50.
Also have, open clear 60-260602 communique and special opening proposed a kind of use and be mixed with the catalyzer that machine aluminium compound forms by what transistion metal compound and aikyiaiurnirsoxan beta and organo-aluminium compound were formed in the clear 60-130604 communique the spy, and make the method for olefinic polymerization.According to the record of this communique, can improve the polymerization activity of per unit transition metal by being added with machine aluminium compound.
The objective of the invention is to provide a kind of polymerization process of alkene, this method is to use the high aikyiaiurnirsoxan beta of a small amount of valency, but can carry out the industrial advantageous method of olefinic polymerization under excellent polymerization activity.
The method that another object of the present invention is to provide a kind of olefin homo of under the polymerization activity of excellence, making narrow molecular weight distribution or molecular weight distribution and composition to distribute all narrow olefin copolymer, especially molecular weight distribution and the ethylene of composition narrowly distributing.
A further object of the present invention is to provide a kind of above-mentioned homopolymer of higher molecular weight or olefine polymerizing process of multipolymer of making.
A further object of the present invention and advantage can be made clear from following explanation.
According to the present invention, above-mentioned purpose of the present invention and advantage can realize by the polymerization process by following alkene, and the feature of this polymerization process is, by
(A) compound of periodictable IV B group 4 transition metal,
(B) aikyiaiurnirsoxan beta that is formed by trimethyl aluminium reaches
(C) in the presence of the catalyzer of forming in conjunction with the aikyiaiurnirsoxan beta of the alkyl beyond 1 positive alkyl at least on the Al atom, make polymerization of alkene alkene or copolymerization.
Below, the present invention is described in detail.
In the present invention, so-called polymerization one speech not only comprises homopolymerization, and comprises the meaning of copolymerization, and so-called polymkeric substance one speech not only comprises homopolymer, and comprises the meaning of multipolymer.
Used catalyst component (A) is the compound of periodictable IV B group 4 transition metal in method provided by the invention.It specifically is the compound of the transition metal from titanium, zirconium and hafnium, selected.As the transition metal in the catalyst component (A), titanium and zirconium are more satisfactory, and be ideal with zirconium especially.
Having with the base that has conjugated pi electron as the compound of the periodictable IV B group 4 transition metal in the catalyst component (A) is the zirconium compounds of dentate.
With the base that has above-mentioned conjugated pi electron as the zirconium compounds of dentate such as the compound that has available formula I down to represent:
In the formula, R
1Represent alicyclic dialkylene, R
2, R
3And R
4Identical or different, be alicyclic dialkylene, aryl, alkyl, aralkyl, halogen atom or hydrogen atom,
K≥1，
K+1+m+n＝4。
Alicyclic dialkylene is such as cyclopentadienyl, methyl cyclopentadienyl, ethyl cyclopentadienyl, dimethyl cyclopentadienyl, indenyl, tetrahydro indenyl are arranged.As R
2, R
3And R
4The alkyl of expression is such as methyl, ethyl, propyl group, sec.-propyl, butyl etc. are arranged.As aryl such as phenyl, tolyl etc. are arranged.As aralkyl benzyl, 2 methyl-2-hydrocinnamyl etc. are arranged.As halogen atom fluorine, chlorine, bromine etc. are arranged.As this zirconium compounds following compounds is arranged:
One chlorine, one hydrogen two (luxuriant) closes zirconium
Monobromo one hydrogen two (luxuriant) closes zirconium
Hydrogenation two (luxuriant) methylcyclopentadienyl zirconium
Hydrogenation two (luxuriant) ethyl zirconium
Hydrogenation two (luxuriant) phenyl zirconium
Hydrogenation two (luxuriant) benzyl zirconium
Hydrogenation two (luxuriant) neo-pentyl zirconium
One chlorine, one hydrogen two (methyl is luxuriant) closes zirconium
One chlorine, one hydrogen two (indenes) closes zirconium
Dichloro two (luxuriant) closes zirconium
Dibromo two (luxuriant) closes zirconium
One chlorine two (luxuriant) methylcyclopentadienyl zirconium
One chlorine two (luxuriant) ethyl zirconium
One chlorine two (luxuriant) cyclohexyl zirconium
One chlorine two (luxuriant) phenyl zirconium
One chlorine two (luxuriant) benzyl zirconium
Dichloro two (methyl is luxuriant) closes zirconium
Dichloro two (indenes) closes zirconium
Dibromo two (indenes) closes zirconium
Phenylbenzene two (luxuriant) closes zirconium
Dibenzyl two (luxuriant) closes zirconium
Dimethyl two (luxuriant) closes zirconium
The multiple tooth coordination compound that combines by low-grade alkylidene with at least 2 bases selecting from indenyl, substituted indenyl and partial hydrogenation thing thereof is the zirconium compounds of dentate in addition.As this zirconium compounds following compounds is arranged:
Ethylene (indenes) zirconium dimethyl
Ethylene (indenes) diethyl zirconium
Ethylene (indenes) phenylbenzene zirconium
One chlorethylidene two (indenes) methylcyclopentadienyl zirconium
One chlorethylidene two (indenes) ethyl zirconium
Monobromo ethylene (indenes) methylcyclopentadienyl zirconium
Dichloro ethylene (indenes) closes zirconium
Dibromo ethylene (indenes) closes zirconium
Ethylene (4,5,6,7-tetrahydrochysene-1-indenes) zirconium dimethyl
One chlorethylidene two (4,5,6,7-tetrahydrochysene-1-indenes) methylcyclopentadienyl zirconium
Dichloro ethylene (4,5,6,7-tetrahydrochysene-1-indenes) closes zirconium
Dibromo ethylene (4,5,6,7-tetrahydrochysene-1-indenes) closes zirconium
Dichloro ethylene (4-methyl isophthalic acid-indenes) closes zirconium
Dichloro ethylene (5-methyl isophthalic acid-indenes) closes zirconium
Dichloro ethylene (6-methyl isophthalic acid-indenes) closes zirconium
Dichloro ethylene (7-methyl isophthalic acid-indenes) closes zirconium
Dichloro ethylene (5-methoxyl group-1-indenes) closes zirconium
Dichloro ethylene (2,3-dimethyl-1-indenes) closes zirconium
Dichloro ethylene (4,7-dimethyl-1-indenes) closes zirconium
Dichloro ethylene (4,7-dimethoxy-1-indenes) closes zirconium
Catalyst component (B) used in method provided by the invention is the aikyiaiurnirsoxan beta that is formed by trimethyl aluminium, more specifically says so and reacts resulting aikyiaiurnirsoxan beta by trimethyl aluminium and water.The organo-aluminium compound that logical formula II, (III) expression are arranged as the used aikyiaiurnirsoxan beta of catalyst component (B):
In last formula II and (III), m is the number greater than 2, and ideal is the number greater than 5, it would be desirable 6～40 number.
Used catalyst component (C) is at least in conjunction with the aikyiaiurnirsoxan beta of the alkyl beyond 1 positive alkyl on the aluminium atom in method provided by the invention.
This aikyiaiurnirsoxan beta specifically is to be made by aluminum compound with positive alkyl alkyl in addition and water reaction.The alkyl, cycloalkyl, aryl of side chain such as band iso-alkyl etc. are arranged as the alkyl beyond the positive alkyl.Trialkylaluminiums such as triisopropylaluminiuand, triisobutyl aluminium, three-2-methyl butyl aluminium, three-3-methyl butyl aluminium, three-2-methyl amyl aluminium, three-3-methyl amyl aluminium, three-4-methyl amyl aluminium, three-2-methyl hexyl aluminium, three-3-methyl hexyl aluminium, three-2-ethylhexyl aluminium are specifically arranged as this organo-aluminium compound; Tricyclic alkyl aluminium such as thricyclohexyl aluminium; Triaryl aluminums such as triphenyl aluminum, trimethylphenyl aluminium; Hydrogenation aluminum dialkyls such as diisobutylaluminium hydride; Alkoxyalkyl aluminium such as methoxyl group aluminium isobutyl, oxyethyl group aluminium isobutyl, isopropoxy aluminium isobutyl etc.In these organo-aluminium compounds, the aluminum compound of band branch chain type alkyl is comparatively desirable, ideal with trialkyl aluminium compound especially.In addition, available general formula
(in the formula, x, y, z are positive integer, z 〉=2X)
The prenyl aluminium of expression is also more satisfactory.
As catalyst component (B) and method for making (C), such as following method is arranged:
(1) containing the compound of planar water, containing the salt of crystal water, such as adding the method that trialkylaluminium makes it to react in the hydrocarbon suspension liquid of magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, single nickel salt hydrate, cerous chlorate hydrate etc.
(2) in media such as benzene, toluene, ether, tetrahydrofuran (THF), make water directly act on the method for trialkylaluminium.
In these methods, adopt the method for (1) comparatively desirable.Also have, also can contain a spot of organo-metallic component at catalyst component (B) and (C).
In method provided by the invention, catalyst component (A), (B) reach and (C) can distinguish the supply response system, perhaps 2 catalyst components and all the other catalyst components of premix are distinguished the supply response system.Perhaps catalyst component (A), (B) and (C) all after the premixs, the supply response system.When 2 catalyst components of premix, premix catalyst component (A) is with (B) comparatively desirable.
The catalyst component (A) of premix with (B) in, the concentration of this transition metal atoms is generally 2.5 * 10
-4～1.5 * 10
-1Milligram-atom/liter, ideal concentration is 5.0 * 10
-4～1.0 * 10
-1Milligram-atom/liter.The concentration conversion of aikyiaiurnirsoxan beta for the aluminium atom be generally 0.05～5 grammeatom/liter, ideal concentration be 0.1～3 grammeatom/liter.Premix temperature is generally-50～100 ℃, and mixing time is generally 0.1 fen～and 50 hours.
In method provided by the invention, the polyreaction of alkene can adopt any method of liquid polymerizations such as slurry polymerization process, solution polymerization process or gaseous polymerization to carry out.
Implementing method provided by the invention, the usage ratio of the compound of this transition metal atoms (A) is generally 10 with the densitometer of this transition metal atoms in the polymerization reaction system
-8～10
-2Grammeatom/liter, ideal concentration is 10
-7～10
-3Grammeatom/liter.
In addition, in method provided by the invention, as the consumption of the aikyiaiurnirsoxan beta of catalyst component (B) be scaled aluminium atom in the reactive system to be lower than 3 milligram-atoms/liter, ideal value be 0.02～1 milligram-atom/liter.Moreover in reactive system, the ratio that the aluminium atom in the catalyst component (B) accounts for the aluminium atom total amount in catalyst component (B) and the catalyst component (C) is generally 5～80%, and desired proportions is 10～75%, and desired proportions is 15～70%.Equally, the shared ratio of aluminium atom in the catalyst component (C) is generally 20～95%, and desired proportions is 25～90%, and desired proportions is 30～85%.In method provided by the invention, the ratio of this transition metal atoms in the aluminium atom total amount in catalyst component (B) and the catalyst component (C) and the reactive system is generally 20～10000, and ideal ratio is 50～5000, and ideal ratio is 100～2000.
Method provided by the invention is effective for the multipolymer of making olefin polymer, especially ethene polymers and ethene and alpha-olefin.As spendable alkene example among the present invention, it is 3～20 alpha-olefin that ethene and carbonatoms are arranged, such as propylene, butene-1, hexene-1,4-methylpentene-1, octene-1, decylene-1, dodecylene-1, tetradecene-1, cetene-1, vaccenic acid-1, eicosylene-1 etc.Also can carry out polyenoid copolymerization such as diene as required.
In method provided by the invention, olefinic polymerization usually can be in gas phase or liquid phase, such as carrying out under the solution state.In liquid polymerization, both can unreactive hydrocarbons as solvent, also can alkene itself as solvent.
Aliphatic hydrocarbons such as butane, Trimethylmethane, pentane, hexane, octane, decane, dodecane, n-Hexadecane, octadecane are specifically arranged as the hydrocarbon medium; Alicyclic hydrocarbon such as pentamethylene, methylcyclopentane, hexanaphthene, cyclooctane; Aromatic hydrocarbons such as benzene,toluene,xylene; Petroleum fractionss such as gasoline, kerosene, light oil etc.
In method provided by the invention, polymerization temperature is generally-50～200 ℃, and ideal temperature is 0～120 ℃.Polymerization pressure is generally normal pressure～100 kilograms per centimeter
2, desired pressure is normal pressure～50 kilograms per centimeter
2Polymerization can be carried out under any method of intermittent type, semi continuous, continous way.Also can be further reaction conditions be divided into the different polymerizations of carrying out more than two sections.The molecular weight of polymkeric substance can be regulated by hydrogen and polymerization temperature.
With the occasion of olefinic polymerization of the present invention in particular for vinyl polymerization or ethene and alpha-olefin copolymer, compare with former method, it is characterized in that to obtain the polymkeric substance of macromolecule, and, the occasion that is used for two or more olefin-copolymerizations can obtain molecular weight distribution and form the olefin copolymer of narrowly distributing.
(embodiment)
Below, will specify polymerization process provided by the invention by embodiment.Also have, the mensuration of Mw/ Mn value adopts following steps to carry out according to " gel permeation chromatography " of work, the kind distribution of ball in military.
(1) polystyrene standard of use known molecular amount (production of Japan Cao Da company, monodisperse polystyrene), determining molecular weight M and its gel permeation chromatography (GPC) number, the correlogram calibration curve of drafting molecular weight M and elution volume (EV).The concentration of this moment is made as 0.02%(weight).
(2) by measuring the GPC chromatogram that GPC obtains sample, calculate number-average molecular weight Mn, the weight-average molecular weight Mw of polystyrene conversion according to above-mentioned (1), obtain Mw/ Mn value.Specimen preparation condition and the GPC condition determination of this moment are as described below.(specimen preparation)
(1) get 0.1%(weight) sample be scattered in the Erlenmeyer flask with neighbour-dichlorobenzene solvent.
(2) Erlenmeyer flask is heated to 140 ℃, filters after about 30 minutes, its filtrate is measured for GPC.
(GPC condition determination)
Implement under the following conditions.
(1) this (waters) corporate system (150C-ALC/GPC) of device water
(2) post Japan Cao Da corporate system (GMH type)
(3) sample size 400 microlitres
(4) temperature is 140 ℃
(5) flow velocity 1 ml/min
(soluble part content is fewer for n-decane soluble part content in the multipolymer, it is narrower that it forms distribution) be to be added in 450 milliliters of n-decanes by multipolymers with about 3 grams, after dissolving under 145 ℃ of temperature, be cooled to 23 ℃, remove the insoluble part of n-decane after filtration, reclaim the n-decane soluble part by filtrate and measure.
Moreover the B value of vinyl copolymer of the present invention can be as giving a definition:
B= (P
OE)/(2P
O·P
E)
(in the formula, PE represents to contain in the multipolymer molar percentage of ethylene component, Po represents to contain the molar percentage of alpha-olefin component, POE represents the molar percentage of the alpha-olefin ethylene chain of total divalence chain) the B value is the index of each monomer component distribution in the expression copolymer chain, according to GJRay(MacromoIecuIes, 10,773(1977)), JCRandall(MacromoIecuies, 15,353(1982), JPolymer Science, Polymer Physics Ed, 11,275(1973)), KKimura(Polym-er, 25, people's report such as 441(1984)) is by asking for the PE of above-mentioned definition, Po and POE and calculate the B value.Above-mentioned B value is bigger, and then expression is that the block chain is fewer, and the distributing position of ethene and alpha-olefin is identical, forms the multipolymer of narrowly distributing.
Also have, forming distribution B value can be calculated by following method, promptly in diameter is 10 millimeters test tube, about 200 milligrams multipolymer uniform dissolution is made sample in 1 milliliter of hexachlorobutadiene, usually be that 25.05 megahertzes, spectral width are that 1500 hertz, 1500 hertz of optical filtering width, pulse reciprocal time are that 4.2 seconds, pulse width are that 7 microseconds, cumulative frequency are under 2000～5000 times the condition determination in that to measure temperature be 120 ℃, measure frequency, measure sample
13The C nucleus magnetic resonance (
13C-NMR) spectrum, spectrum is asked for PE, Po, POE and is calculated the B value thus.
Embodiment 1
The preparation of catalyst component (B)
In abundant metathetical 400 ml flasks of nitrogen, adding 37 gram Al
2(SO
4)
314H
2O and 125 milliliters of toluene, be cooled to 0 ℃ after, splash into the trimethyl aluminium of 500 mmoles with 125 milliliters of dilution with toluene.Then, be warming up to 40 ℃, successive reaction is 10 hours under this temperature.After the reaction, carry out solid-liquid separation after filtration, from filtrate, remove toluene again, promptly make the aikyiaiurnirsoxan beta solid of 13 gram whites.The depression of the freezing point molecular weight of trying to achieve of utilization in benzene is 930, and the m value of expression is 14 in catalyst component (B).The preparation of catalyst component (C).
In abundant metathetical 400 ml flasks of nitrogen, adding 4.9 gram Al
2(SO
4)
314H
2O and 125 milliliters of toluene, be cooled to 0 ℃ after, splash into the triisobutyl aluminium of 200 mmoles with 125 milliliters of dilution with toluene.Then, be warming up to 40 ℃, successive reaction is 24 hours under this temperature.After the reaction, carry out solid-liquid separation after filtration, gained filtrate partly is used for polymerization.In addition, remove the part of desolvating under reduced pressure from filtrate, the molecular weight that utilizes the cryoscopic method of making solvent with benzene to ask for the gained resultant is 610.
Polymerization
Be to add 500 milliliters of toluene in 1 liter the glass autoclave through the abundant metathetical internal volume of nitrogen, feeding the mixed gas (be respectively 120 liters/hour, 80 liter/hour) of ethene and propylene, placement is 10 minutes under 20 ℃ of temperature.Afterwards, add the catalyst component (C) of 0.25 milligram-atom aluminium, the catalyst component of 0.25 milligram-atom aluminium (B) then adds 2.5 * 10
-3The dichloro two (luxuriant) of mmole closes zirconium, promptly begins polymerization.Supply with continuously the mixed gas of ethene and propylene, polyase 13 is 0 minute under normal pressure and 20 ℃ of temperature.After finishing polymerization, add small amount of methanol and end polymerization.Polymers soln is added in the excessive methyl alcohol, polymkeric substance is separated out, drying under reduced pressure is 12 hours under 130 ℃ of temperature.The result make 15 the gram melt flow rate (MFR)s (MFR) be 0.35 the gram/10 minutes, by
13The ethylene content that C-NMR tries to achieve is the 82.9%(mole), Mw/ Mn is 2.35, the B value is 1.12 polymkeric substance.
Embodiment 2
The preparation of catalyst component (C)
Remove Al used among the embodiment 1
2(SO
4)
314H
2The consumption of O becomes 4.25 grams from 4.9 grams, and the reaction times became outside 5 hours from 24 hours, prepares catalyst component (C) under the condition identical with embodiment 1.After the reaction, carry out solid-liquid separation after filtration, gained filtrate partly is used for polymerization.In addition, remove the part of desolvating under reduced pressure from filtrate, make solvent with benzene, the molecular weight that utilizes cryoscopic method to ask for the gained resultant is 440.
Polymerization
Under the polymerizing condition identical, carry out polymerization with embodiment 1, make 13 gram MFR and be 0.30 gram/10 minutes, by
13The ethylene content that C-NMR tries to achieve is the 82.1%(mole), Mw/ Mn is 2.32, the B value is 1.14 polymkeric substance.
Embodiment 3～5 and comparative example 1
The preparation of catalyst component (C)
Except that will in embodiment 1, changing into respectively three (2-methyl amyl) aluminium, three (2-ethylhexyl) aluminium, prenyl aluminium and three n-butylaluminum by used triisobutyl aluminium, under the condition identical, prepare catalyst component (C) with embodiment 1.
Polymerization
Under the polymerizing condition identical, carry out polymerization with embodiment 1.Polymerization result is as shown in table 1.(table 1 is seen the literary composition back)
Embodiment 6
Polymerization
Being to add 250 milliliters of hexanes and 750 milliliters of 4-methylpentenes-1 in 2 liters the stainless steel autoclave through the abundant metathetical internal volume of nitrogen, be warming up to 35 ℃.Afterwards, add the catalyst component (C) of preparation among the embodiment 2 of catalyst component (B), 0.5 milligram-atom aluminium of preparation among the embodiment 1 of 0.5 milligram-atom aluminium and the dichloro two (luxuriant) of 0.001 mmole respectively and close zirconium.Then, feed ethene, the beginning polymerization.Supplying with ethene continuously makes stagnation pressure remain on 8 kilograms per centimeter
2(gauge pressure), polymerization is 1 hour under 45 ℃ of temperature, finish polymerization after, add a spot of methyl alcohol and end polymerization.Then, whole polymers solns are dropped in the excessive methyl alcohol, reclaim polymkeric substance.Under decompression and 80 ℃ of temperature dry 12 hours, promptly make polymkeric substance.The yield of resulting polymers is 30.1 grams, and its MFR is that 0.24 gram/10 minutes, density are 0.901 gram per centimeter
3, Mw/ Mn is 2.75, decane soluble part weight percent is a 1.8%(weight under the room temperature).
Embodiment 7
Polymerization
Be to add 500 milliliters of toluene in 2 liters the stainless steel autoclave through the abundant metathetical internal volume of nitrogen.In autoclave, add the catalyst component (B) and the catalyst component (C) that prepare among the embodiment 1 of 1 milligram-atom aluminium and 2 milligram-atom aluminium respectively.Add 250 milliliters of propylene liquids in system after, add 0.001 mmole dichloro ethylene (indenes) and close zirconium under-10 ℃ of temperature, polymerization is 6 hours under-10 ℃ of temperature.After 6 hours, in autoclave, add small amount of methanol and end polymerization.After reducing pressure and removing propylene, the toluene slurry of prepared polymkeric substance is added in a large amount of methyl alcohol, reclaims polymkeric substance, through under 80 ℃ of temperature, reduced pressure, being drying to obtain 48.1 gram polypropylene.The limiting viscosity (η) that the gained polypropylene is measured in 135 ℃ of naphthalanes is 0.97 deciliter/gram.
Embodiment 8
Polymerization
Being to add 500 milliliters of hexanes and 500 milliliters of 4-methylpentenes-1 in 2 liters the stainless steel autoclave through the abundant metathetical internal volume of nitrogen, temperature in the system is risen to 55 ℃.Afterwards, in autoclave, add the catalyst component (C) for preparing among the embodiment 2 of 1 milligram-atom aluminium.Then, make the aluminium atomic percent be 0.4 grammeatom/liter embodiment 1 in catalyst component (B) and the zirconium atom concentration of preparation be 0.012 grammeatom/liter dichloro two (luxuriant) close zirconium and under 20 ℃ of temperature, contact 30 minutes with 0.25 milliliter of toluene solution, add in the autoclave again.Feed ethene then, the beginning polymerization.Supplying with ethene continuously makes stagnation pressure remain on 7 kilograms per centimeter
2(gauge pressure), polymerization is 1 hour under 60 ℃ of temperature.After finishing polymerization, add small amount of methanol and end polymerization, then whole polymers solns are dropped in the excessive methyl alcohol, reclaim polymkeric substance.Under decompression, 80 ℃ of temperature dry 12 hours, make polymkeric substance.The yield of resulting polymers is 33.6 grams, and its MFR is that 0.18 gram/10 minutes, density are 0.903 gram per centimeter
3, Mw/ Mn is 2.83, decane soluble part weight percent is a 1.3%(weight under the room temperature).
Claims (7)
1, a kind of polymerization process of alkene, it is characterized in that this method be by
(A) transistion metal compound of periodictable IV B family, described compound have at least one group that contains the cyclopentadienyl structure as dentate,
(B) aikyiaiurnirsoxan beta that is formed by trimethyl aluminium reaches
(C) in the presence of the catalyzer of forming in conjunction with the aikyiaiurnirsoxan beta of the alkyl beyond 1 positive alkyl at least on the aluminium atom, make olefinic polymerization or copolymerization.
2, method according to claim 1 is characterized in that the transition metal of the periodictable IV B family in the compound (A) is titanium, zirconium or hafnium.
3, method according to claim 1 is characterized in that the available following formula II of the aikyiaiurnirsoxan beta (B) that is formed by trimethyl aluminium or descends formula III to represent:
In the formula, m is the number greater than 2,
In the formula, the definition of m is same as described above.
4, method according to claim 1 is characterized in that on the aluminium atom being branched group, cycloalkyl or aryl in conjunction with this alkyl in the aikyiaiurnirsoxan beta (C) of the alkyl beyond 1 positive alkyl at least.
5, method according to claim 1 is characterized in that the consumption of compound (A) counts 10 with the concentration of the transition metal in this compound in polymerization reaction system
-8～10
-2Grammeatom/liter.
6, method according to claim 1, the consumption that it is characterized in that aikyiaiurnirsoxan beta (B) with the densitometer of aluminium atom in polymerization reaction system in this aikyiaiurnirsoxan beta (B) to be lower than 3 milligram-atoms/liter.
7, method according to claim 1, the ratio that it is characterized in that used aikyiaiurnirsoxan beta (C) be the aluminium atom in the aikyiaiurnirsoxan beta (C) account for aluminium atom in this aikyiaiurnirsoxan beta (C) and the aluminium atom total amount in the aikyiaiurnirsoxan beta (B) 20～95%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88102963 CN1021230C (en) | 1988-05-19 | 1988-05-19 | Polymerigation process of olefin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88102963 CN1021230C (en) | 1988-05-19 | 1988-05-19 | Polymerigation process of olefin |
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| Publication Number | Publication Date |
|---|---|
| CN1037715A CN1037715A (en) | 1989-12-06 |
| CN1021230C true CN1021230C (en) | 1993-06-16 |
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| CN 88102963 Expired - Fee Related CN1021230C (en) | 1988-05-19 | 1988-05-19 | Polymerigation process of olefin |
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