CN1092431A - The polymerization process of alpha-olefin - Google Patents

The polymerization process of alpha-olefin Download PDF

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CN1092431A
CN1092431A CN93112706A CN93112706A CN1092431A CN 1092431 A CN1092431 A CN 1092431A CN 93112706 A CN93112706 A CN 93112706A CN 93112706 A CN93112706 A CN 93112706A CN 1092431 A CN1092431 A CN 1092431A
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silane
magnesium
compound
methyl
alkyl
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D·B·莫斯
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Shell USA Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652—Pretreating with metals or metal-containing compounds
    • C08F4/656—Pretreating with metals or metal-containing compounds with silicon or compounds thereof
    • C08F4/6562—Pretreating with metals or metal-containing compounds with silicon or compounds thereof and metals of C08F4/64 or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652—Pretreating with metals or metal-containing compounds
    • C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
    • C08F4/6543—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof halides of magnesium

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Abstract

Carbonatoms comprises one or more alpha-olefins are contacted with catalyst system under polymerizing condition at the polymerization process of one or more alpha-olefins below 20.This catalyst system contains: (a) a kind of halogenated titanium, magniferous procatalyst component of containing, this component is by MgR ' R " magnesium compound of formula; in the presence of the polycarboxylate electron donor(ED), contact with halogenated tetravalent titanium compound (with or without halohydrocarbon) obtain; (b) organoaluminum cocatalyst component and (c) organosilane selective control agent.The catalyst productivity height of this method, and the molecular weight distribution of polymerisate is wide and oligomer content is low.

Description

The polymerization process of alpha-olefin
The invention relates to the method for producing alpha-olefinic polymer.More particularly, the present invention utilizes highly active catalyst for stereospecific polymerization system to come the method for the alpha-olefinic polymer of production modification.
With solid-state transition metal is that basic olefin polymerization catalyst system (comprising titaniferous catalyst component based on magnesium halide) is produced alpha-olefinic polymer, for example the polymkeric substance of ethene, propylene and butene-1 is well known in the prior art.This type of polymerization catalyst system is typically by the method for catalyst component, organo-aluminium compound and one or more electron donor(ED)s that in conjunction with magnesium halide is the basis and obtains.For quoting conveniently, claim solid-state titanium-containing catalyst component to be " procatalyst " at this, claim that organo-aluminium compound be " promotor ", the title electronic donor compound capable be " selective control agent " (SCA).This electron donor(ED) generally is independent use, perhaps with the coordination of organo-aluminium compound part or all coordination uses.Also knownly in the prior art in procatalyst, to add electronic donor compound capable.And electron donor(ED) and titanium-containing compound blended purpose are different with the electron donor(ED) that is called as selective control agent.Compound as electron donor(ED) is identical or inequality with the compound that is used as selective control agent.Above-mentioned high reactivity directional catalyst now is widely used, and in many patents and other document description is arranged all, comprises the people's such as Nestlerode that are referred to herein US4,728,705.
Though very wide as the compound scope of selective control agent usually, this is known in the prior art, a kind of concrete catalyst component can have specific a kind of compound or one group of special and its compatibility of compound.For any given procatalyst and/or promotor, develop a kind of suitable and selective control agent, can improve the utilising efficiency of catalyst efficiency, hydrogen and the performance of polymeric articles greatly.
There have been many class selective control agents in polymerisation catalysts, to use.One of them is exactly a class organosilane.For example, people's such as Hoppin US4,990,478 have reported a class grafted C 3-C 10Alkyl-uncle-butoxy dimethoxy silane.Other fatty silane is described in people's such as Hoppin US4, in 829,038.People's such as Kioka US5 has introduced a kind of catalyst system in 028,671, and this system combines with various alkyl oxyalkyl silane as selective control agent, for example two-just-octadecyl dimethoxy silane and two-just-octadecyl diethoxy silane.
Though known have many methods can produce high directed alpha-olefinic polymer, people still wish to improve activity of such catalysts, produce the polymkeric substance or the multipolymer of modifications such as having high melt flow index and wide molecular weight distribution.Also wish polymkeric substance or multipolymer that the production volatility is low in addition.
Alpha-olefin homo or a kind of of multipolymer of the invention relates to the production modification improve one's methods.
More particularly, the present invention is a kind of method of producing polymkeric substance with highly active olefin polymerization catalyst system, and this catalyst system comprises that (a) contains the procatalyst component of halogenated titanium, and this component is to be C by MgR ' R " magnesium compound of formula (R ' and R in the formula " 1-C 10Alkoxyl group) in the presence of the polycarboxylate electron donor(ED), with or without halon, carry out halogenation with halogenated tetravalent titanium compound and obtain; (b) organoaluminum cocatalyst component; (c) organosilane selective control agent, its general formula is:
Figure 931127068_IMG4
R wherein 1Be C 13-C 30Straight chained alkyl, C 16-C 36Alkaryl or C 16-C 36Aralkyl; R 2And R 3Methyl or C respectively do for oneself 13-C 30Alkyl, or C 1-C 6-oxyl; And R 4Be C 1-C 6-oxyl.
Though there is various compound to can be used to produce procatalyst, R ' during but a kind of typical procatalyst of the present invention is a general formula is MgR ' R " magnesium compound carries out halogenation with halogenated tetravalent titanium compound and prepares in the presence of halon and electron donor(ED); this MgR ' R " is alkoxyl group, aryloxy or alkyl carbonic ether, and R " is alkoxyl group, alkyl carbonic ether, aryloxy or hydrogen.
The used magnesium compound of preparation ingredient of solid catalyst comprises alkoxide, aryl oxide, alkyl carbonic acid or halogen.When alkoxide, contain 1-10 carbon atom, preferably contain the alkoxide of 1-8 carbon atom, more preferably contain the alkoxide of 2-4 carbon atom.When aryl oxide, contain the 6-10 carbon atom, serve as preferred with the 6-8 carbon atom.When the alkyl carbonic ether, contain the 1-10 carbon atom.When halogen, this halogen is bromine, oxygen, iodine or chlorine, is preferred with chlorine.
Suitable magnesium compound is magnesium chloride, magnesium bromide, magnesium fluoride, oxyethyl group magnesium bromide, isobutyl magnesium oxychioride, phenoxy group magnesium iodide, cumyloxy base magnesium bromide, diethoxy magnesium, isopropoxy magnesium, ethyl carbonate magnesium, magnesium ethylate, Magnesium Stearate, Magnesium monolaurate and naphthyloxy magnesium chloride.Particularly preferred magnesium compound is a dialkoxy magnesium.Best magnesium compound is a diethoxy magnesium.
Be to use excessive titanium compound to produce with the halogenated tetravalent titanium compound to the halogenation of magnesium compound.The magnesium compound of every mole is used the 2mole titanium compound at least.Preferably every mole magnesium compound 4-100mole titanium compound, most preferably every mole magnesium compound 4-20mole titanium compound.
Halogenated tetravalent titanium compound takes place by the high temperature contact the halogenation of magnesium compound, and this temperature range is about 60 ℃ to about 150 ℃, preferably about 70 ℃ to about 120 ℃.Usually the time that allows reaction to carry out is 0.1 to 6 hour, is preferably about 0.6 to about 3.5 hours.Halogenated product is a kind of solid, and it is with the filtration of suitable for separation such as routine, separates from the reaction medium of liquid.
The halogenated tetravalent titanium compound that halogenated magnesium compound is used comprises at least 2 halogen atoms, preferably comprises four halogen atoms, this halogen atom chlorine, bromine, iodine or fluorine and all goes.Halogenated tetravalent titanium compound has two alkoxyl groups or aryloxy at most.The example of suitable halogenated tetravalent titanium compound comprises the titanium tetrabromide of diethoxy dibrominated titanium, isopropoxy titanium triiodide, two hexyloxy titanium dichloride, phenoxy group titanous chloride, titanium tetrachloride.Titanium tetrachloride preferably.
This halogenation with halogenated tetravalent titanium compound halogenated magnesium compound is to carry out under usefulness or different halohydrocarbon situation in the presence of the electron donor(ED).If desired, also can there be inert diluent or solvent to exist.
Suitable halohydrocarbon comprises aromatics or aliphatic halogenated hydrocarbons, and they can be the compounds of cyclic and alicyclic ring.Preferred halohydrocarbon contains 1 or 2 halogen atom, but also can be a plurality of halogen atoms if desired.Preferred halogen atom is respectively chlorine, bromine or fluorine.The exemplary of suitable aromatic halohydrocarbons is chlorobenzene, bromobenzene, dichlorobenzene, dichloro dibromobenzene, adjoin-chlorotoluene, toluene(mono)chloride, toluene dichloride, chloronaphthalene.Chlorobenzene, adjoin-chlorotoluene and dichlorobenzene are preferred, and chlorobenzene and adjoin-chlorotoluene are more preferred.
Aliphatic halogenated hydrocarbons can be used the proper of 1-12 carbon atom.The halohydrocarbon of 1-9 carbon atom and have 2 halogen atoms at least preferably.Most preferred halogen is a chlorine.Suitable aliphatic halogenated hydrocarbons comprises methylene bromide, trichloromethane, 1,2-ethylene dichloride, trichloroethane, dichloro one fluoroethane, hexachloroethane, trichloropropane, chlorobutane, dichlorobutane, chloropentane, trichloro-monofluoro octane, tetrachloro octane-iso, dibromo difluoro decane.Preferred aliphatic halogenated hydrocarbons is tetracol phenixin and trichloroethane.
Aromatic halohydrocarbons is preferably used, and specifically is the 6-12 carbon atom, particularly the aromatic halohydrocarbons of 6-10 carbon atom.
The typical electronic that joins in the catalyzer comprises ester (particularly aromatic ester), ether (particularly aromatic oxide), ketone, phenol, amine, acid amides, imines, nitrile, phosphuret-(t)ed hydrogen, phosphite, stibine, hydrogen arsenide, phosphamide and alcoholate to body.Polycarboxylate is that preferred electron is given body.Particularly preferably be aromatic multi-carboxy acid's alkyl ester.The example of suitable many carboxylics ester electron donor(ED) be diethyl phthalate, diisoamyl phthalic ester, ethyl right-ethoxy benzonitrile acid esters, methyl be right-ethoxy benzonitrile acid esters, DI-ISOBUTYL PHTHALATE, dimethylnaphthalene dicarboxylic ester, diisobutyl maleic acid ester, di-isopropyl terephthalate and diisoamyl phthalic ester.DI-ISOBUTYL PHTHALATE and ethyl be right-and the ethoxy benzonitrile acid esters is preferred aromatic carboxylic acid's alkyl ester.
From liquid reaction medium, isolate after the solid halogenated product, use halogenated tetravalent titanium compound treatment one or many again.Preferably halogenated product is repeatedly handled with independent several parts of halogenated tetravalent titanium compounds.If with independent several parts of halogenated tetravalent titanium compounds halogenated product is handled secondary, then can obtain better result.If desired, the mixture process solid product one or many of available halogenated tetravalent titanium compound and halohydrocarbon.Beginning is during halogenation, every mole magnesium compound with to and the 2mole titanium compound, preferably every mole position compound is with the titanium compound of 4mole to 100mole.Most preferably every mol magnesium compound is with the titanium compound of 4mole to 20mole.
Perhaps also alternatively, in the process of handling with other halogenated tetravalent titanium compound, the solid halogenated product is handled once at least with one or more acyl chlorides.Suitable acyl chlorides comprises Benzoyl chloride and phthalyl chloride.Preferred acyl chlorides is a phthalyl chloride.
The solid halogenated products, is separated it once or several times with other halogenated tetravalent titanium compound treatment from fluid reaction medium, use C 10Unreactive hydrocarbons wash at least and once remove unreacted titanium compound, dry then.The example that is suitable for unreactive hydrocarbons of the present invention is iso-pentane, octane-iso, hexane, heptane and hexanaphthene.
Washing at last obtains the titanium content of product, preferably 0.5% weight to 6.0% weight, more preferably 1.5% weight to 4.0% weight.The atomic ratio of titanium and magnesium is between 0.01: 1 and 0.2: 1 in the final product, preferably about 0.02: 1 to 0.15: 1.
Promotor be a kind of be typical organoaluminum with alkylaluminium cpd.Suitable alkylaluminium cpd comprises trialkyl aluminium compound for example triethyl aluminum or triisobutyl aluminium; Dialkyl aluminum halide, for example diethyl aluminum muriate or dipropyl aluminium muriate; To use the aluminum dialkyl alkoxide, diethyl aluminum b-oxide for example.Trialkyl aluminium compound preferably, wherein triethyl aluminum is preferred trialkyl aluminium compound.
Organosilane selective control agent in the catalyst system comprises a silicon-oxygen-carbochain at least.Suitable organic silane compound comprises a following general formula and a compounds:
Figure 931127068_IMG5
R wherein 1Be C 13-C 30Straight chained alkyl, C 16-C 36Alkaryl or C 16-C 36Aralkyl.Preferred R 1Be C 16-C 30Alkyl, C 19-C 30Alkaryl or C 19-C 30Aralkyl.Preferred R 1Be C 18-C 28Alkyl.R 2And R 3Methyl or C respectively do for oneself 13-C 30Alkyl or C 1-C 6-oxyl.Preferred R 2And R 3Methyl or C respectively do for oneself 16-C 30Alkyl or C 1-C 4Alkoxyl group.Preferred R 2Be methyl or C 18-C 28Alkyl or C 1-C 4Alkyl, preferred R 3Be C 1-C 4Alkoxyl group.Preferred R 4Be C 1-C 4Alkoxyl group.R 4Be C 1-C 6-oxyl.Further preferred R 2, R 3And R 4Be ethoxy or methoxyl group.Suitable organosilicon selective control agent just comprising-octadecyltriethoxy silane, just-triacontyl triethoxyl silane, methyl-just-octadecyl dimethoxy silane, methyl-just-octadecyl diethoxy silane, just-octadecyl trimethoxy silane, just-triacontyl Trimethoxy silane and their mixture.Preferred organosilane selective control agent be just-octadecyltriethoxy silane.Just-methyl octadecyl dimethoxy silane and just-octadecyl trimethoxy silane.The present invention also plans with the mixture of two kinds or multiple choices control agent.The consumption of selective control agent is such regulation, promptly in the procatalyst mole of selective control agent and titanium compound than being about 0.5 to about 80.Preferred mole is more preferably about 5 to about 40 than for about 2 to about 60.
By contacting polyreaction is worked under polymeric reaction condition with highly active catalyst for stereospecific polymerization with at least a alpha-olefin.With the procatalyst component, organoaluminum promotor and selective control agent three add respectively in the polymerization reactor according to the present invention, perhaps two kinds of components or all components partly can be mixed before being added to reactor or are all mixed if desired.
The employed particular type of polymerization process is unimportant to operation of the present invention, and thinks the present invention that is suitable for of some conventional polymerization processs at present.Polyreaction is to adopt fluid catalyst to carry out in liquid phase or gas phase under polymerizing condition.
The polyreaction of carrying out in liquid phase, the liquid diluent that adds inert liquid diluent or contain this reaction alkene (for example propylene or 1-butylene) is as reaction diluent.If prepare a kind of multipolymer, wherein a kind of monomer is an ethene, then by ordinary method ethene is added in the thinner.Typical polymerizing condition comprises about 25 ℃ to about 125 ℃ of temperature of reaction, with about 35 ℃ to about 90 ℃ serve as preferably, reaction pressure should be enough to keep the reaction mixture in the liquid phase.This pressure is extremely approximately 1200psi of about 150psi, serves as preferred with the extremely about 900psi of about 250psi.Liquid phase reaction is with intermittent mode or continuous or semicontinuous method operation.Reclaim polymerisate with conventional procedure after the polyreaction.The accurate control of the polymerizing condition of liquid phase process and reaction parameter is to belong to prior art.
Another embodiment of the present invention is to carry out polymerization with gas phase process in the presence of fluid catalyst.So a kind of gas phase polymerization process has been described in this people's such as Gotks that quote U.S. Pat 4,379,759.This gas phase process typically is exactly that the preformed polymer beads of a certain amount and gas phase monomer are added reactor, and separately adds more a spot of every kind of catalyst component.Gas phase monomer (for example propylene) causes and keeps under the temperature and pressure condition of polyreaction being enough to, at a high speed the reaction bed by this solid particulate.Unreacted alkene is separated and recovery, polymeric alkene particle is separated with the speed of in fact quite its reaction.This separation is to carry out with intermittent mode or continuous semi-continuous method, simultaneously with catalyst component and/or alpha-olefin constant speed or be added in the polymerization reactor off and on.The typical polymerization temperature of vapor phase process is about 30 ℃ to about 120 ℃, and typical pressure serves as preferred for approximately arriving 1000psi with about 100 to about 500psi.
In these two kinds of polymerization processs of liquid and gas, molecular hydrogen is arrived the adding reaction mixture as chain transfer, to regulate the molecular weight of polymerisate.Method when hydrogen typically is applied to this purpose is that these those skilled in the art are well-known.How accurately the adding speed of reaction conditions and furnish component and molecular hydrogen control, is prior art fully.
The present invention is used in the polymerization of the alpha-olefin of 20 carbon atoms at the most, for example propylene, dodecylene, comprise the polymerization of their mixture.C preferably 3-C 8Alpha-olefin, for example polymerization of propylene, butene-1 and amylene-1 and hexene-1.
The polymkeric substance that the inventive method is produced is based on isotactic.The productive rate of polymkeric substance is quite high for catalyst levels.Homopolymer and multipolymer that method of the present invention is produced comprise random and impact-resistant multipolymer, and both all have quite high toughness, and their molecular weight distribution is wide simultaneously.And each polymers content is (with C 21The weight fraction of each polymers is determined) less than 300ppm(for homopolymer) and less than 600ppm(for multipolymer).Each polymers content of the preferred homopolymer of the present invention is less than 150ppm, more preferably less than 80ppm.Oligomer content low expression volatile matter (for example cigarette and/or the oil that (for example extrusion molding) discharges in the course of processing afterwards) reduces.
Other characteristic of the present invention disclosed herein, advantage and embodiment for those of ordinary skill, will be to understand easily after the explanation of reading the front.In this respect, though specific embodiments more of the present invention are described in detail, those embodiments can be made changes and improvements, only otherwise leave the illustrated scope with claimed design of the present invention.
At this present invention is described for example, but below the embodiment that enumerates such as comparative example be not restriction the present invention.In all embodiment and comparative example with following these terminology:
ODTMS (just-the octadecyl trimethyl silane)
ODTES (just-octadecyltriethoxy silane)
DNDDMS (two-just-decyl dimethoxy silane)
DDTMS (just-octadecyl trimethoxy silane)
TCTMS (just-the triacontyl Trimethoxy silane)
MNDDMS (methyl-just-decyl dimethoxy silane)
MODDES (methyl-Octadecane base diethoxy silane)
DEEB (ethyl-right-ethoxy benzonitrile acid esters)
NPTMS (just-propyl trimethoxy silicane)
DIBDES (diisobutyl diethoxy silane)
DIBDMS (second, isobutyl dimethoxy silane)
The embodiment I
(a) preparation of procatalyst component
The Preparation of catalysts method is with diethoxy magnesium (2.17g 19mmol) is added to the 50/50(volume/volume of 55ml) TiCl 4In the mixture of/chlorobenzene.Add DI-ISOBUTYL PHTHALATE (0.74ml, 2.75mmol) after, this mixture heated in oil bath and stirred 60 minutes down at 110 ℃.With this mixture heat filtering, and with solid part at 55ml50/50(vol/vol) TiCl 4Make pulpous state in the/chlorobenzene mixture.When certain procatalyst of preparation is that (0.13ml 0.90mmol) is added in this slurry of room temperature with phthalyl chlorination thing.In 110 ℃ of slurries that stir down gained 60 minutes, filter, with resulting solvent at new 50/50TiCl 4Pulping again in the/chlorobenzene mixture.After 110 ℃ are stirred 30 minutes down, filter this mixture and make its cool to room temperature.Wash this procatalyst slurry 6 times with 125ml equal portions octane-iso, under 25 ℃ of nitrogen dry 120 minutes then.
(b) propylene polymerization
Produce several different catalyzer with several organosilanes as selective control agent, wherein some is (TCTMS, ODTES, ODTMS and the MODDES) that belongs in the scope of the invention, other (NPTMS, DNDDMS, DIBDES, DDTMS, MNDDMS and DIBDMS) not within the scope of the present invention.Propylene (2700cc) and molecular hydrogen added in 11 gallon the reactor.Make their temperature be raised to 67 ℃.The procatalyst of organosilane selective control agent, triethyl aluminum and above production is starched premix about 20 minutes, then this mixture is added reactor.Silane amount used in the polyreaction also changes.The amount (making this catalyzer be enough to supply with the titanium of 0.01mmol) of amount of triethyl aluminum (0.70mmol) and procatalyst slurry keeps constant.Then reactor is heated to about 67 ℃, polyreaction was carried out 1 hour under 67 ℃ continuously.Method with routine reclaims polymerisate from the mixture of gained.Weight with this polymkeric substance is calculated reaction yield, and this productive rate calculates (being MMg/g) with every gram titanium production how many hundred myriagram polymerisates in procatalyst.Code name " Q " is the design factor of weight-average molecular weight (Mw) and number-average molecular weight (Mw), by gel chromatography.Code name " M 2" be Z-average molecular weight, referring to " Encyclopedia of Polymer Science and Engineering, 2nd Edition " Vol.10, definition pp.1-19(1987)." R " is M 2And M wCoefficient." melt flow " is according to ASTM D-128-73, and condition L measures." viscosity ratio " is to become assay method (kinetic viscosity measurement) with taper and plane flow to measure, and is that product is at 0.1H 2Viscosity under the frequency is divided by at 1.0H 2The ratio of the viscosity under the frequency.When this viscosity ratio of polymerisate increased, molecular weight distribution increased.
The result of a series of polyreactions represents in the table I.
Figure 931127068_IMG6
1 relatively
The final melt flow of 2 polymerisates
1.0 200 ℃ of 3 viscosity ratio=η 0.1/ η
The procatalyst of 4 usefulness phthalyl chlorides preparation
5 procatalysts without the phthalyl chloride preparation
Comparative example
(a) preparation of procatalyst component
Diethoxy magnesium (50mmol) is added to the 50/50(volume ratio of 150ml) chlorobenzene/TiCl 4Prepare procatalyst in the mixture.Add ethylamino benzonitrile acid esters (16.7mmol) afterwards, this mixture is heated in oil bath, stirred about 60 minutes down at 110 ℃.With the dope filtration of gained and with the new 50/50(volume ratio of 150ml) chlorobenzene/TiCl 4The mixture pulping.In last slurries, add Benzoyl chloride (0.4ml).After 110 ℃ are stirred about 30 minutes down, this mixture is filtered.To wash and starch for several parts with the 150ml iso-pentane and to wash 6 times, under 30 ℃ of nitrogen dry 90 minutes then.
(b) polyreaction
With above-mentioned procatalyst ((a) joint), press the embodiment I, (b) the described method polypropylene of joint, but selective control agent is PEEB.
The embodiment II
For further specifying the advantage of catalyst system of the present invention, produce polymerisate according to the method described in embodiment I and the comparative example, its melt flow is approximately 3.0dg/min.Specifically, with the specific selective control agent (" SCA ") of 0.2mmol with produce the necessary q.s hydrogen of polymkeric substance and produce polymerisate with about 3.0dg/min melt flow.These parameters are shown in the table II
The table II
SCA 1H 2Requirement (mmol)
NPTMS 230
DIBDMS 230
PEEB 3135
MODDES 12
ODTES 13
MNDDMS 17
TCTMS 18
ODTMS 20
DDTMS 22
DNDDMS 29
1. every kind of selection control agent 0.2mmol
2. be used for comparison
3. comparative example
4. for to make polymer product have the needed H of melt flow of about 3dg/min 2Mmol
As shown in Table, catalyst system of the present invention has improved the utilising efficiency of hydrogen.
The embodiment III
To melt flow is that these values of polymer determination viscosity ratio of about 3dg/min are shown in the table III.
The table III
The SCA viscosity ratio
MODDES 1.86
TCTMS 1.80
ODTES 1.78
ODTMS 1.60
DNDDMS 1.62
MNDDMS 1.60
NPTMS 11.58
1 relatively uses
From the table III as seen, can obtain higher viscosity ratio, therefore than wide as the molecular weight distribution of the conventional catalyst system acquisition of selective control agent with NPTMS with catalyst system of the present invention.

Claims (18)

1, carbonatoms is at the polymerization process of one or more alpha-olefins below 20.This method comprises contacts one or more alpha-olefins with catalyst system under polymeric reaction condition, this catalyst system contains:
(a) a kind of procatalyst component of magnesium halide containing, this component contains magnesium, titanium, halogen and a kind of polycarboxylate, and said procatalyst component is to be C by MgR ' R " R ' and R in the magnesium compound of formula, the formula " 1-C 10Alkoxyl group, the polycarboxylate electron donor(ED) is arranged and be with or without halohydrocarbon in the presence of carry out halogenation with halogenated tetravalent titanium compound and obtain;
(b) a kind of organoaluminum cocatalyst component; With
(c) a kind of organosilane selective control agent, its general formula is:
Figure 931127068_IMG1
R in the formula 1Be C 13-C 30Straight chained alkyl, C 16-C 36Alkaryl or C 16-C 36Aralkyl; R 2And R 3Methyl or C respectively do for oneself 13-C 30Alkyl or C 1-C 6-oxyl; R 4Be C 1-C 6-oxyl.
2, the process of claim 1 wherein that the consumption of said organosilicon selection control agent is about 0.5 to about 80 for the mol ratio of this selective control agent and the titanium that exists in the procatalyst component.
3, the method for claim 2, wherein R 1Be C 16-C 30Alkyl, C 19-C 30Alkaryl or C 19-C 30Aralkyl; R 2And R 3Methyl or C respectively do for oneself 16-C 30Alkyl or C 1-C 4Alkoxyl group, and R 4Be C 1-C 4Alkoxyl group.
4, the method for claim 3, wherein the organosilane selective control agent be just-octadecyltriethoxy silane, just-octadecyl Trimethoxy silane, just-triacontyl trimethoxy silane, just-triacontyl triethoxyl silane, methyl-just-octadecyl dimethoxy silane, methyl-just-octadecyl diethoxy silane or their mixture.
5, the method for claim 4, wherein organosilane be just-octadecyl trimethyl silane, just-octadecyltriethoxy silane, methyl-just-octadecyl diethoxy silane or methyl-just-octadecyl dimethoxy silane.
6, the method for claim 5, wherein the halogenated tetravalent titanium compound is a titanium tetrachloride.
7, the method for claim 6, wherein magnesium compound is a magnesium ethylate.
8, the method for claim 7, wherein the polycarboxylate electron donor(ED) is a DI-ISOBUTYL PHTHALATE.
9, the method for claim 8, wherein alpha-olefin is propylene and ethene.
10, the method for claim 9, the wherein propylene of alpha-olefin.
11, the following alpha-olefin of at least a 20 carbon atoms carries out the polymeric method, comprises that in the method at least a alpha-olefin contacts with catalyst system under polymerizing condition, and this catalyst system contains:
(a) a kind of procatalyst of magnesium halide containing, this catalyzer is by MgR ' R " R ' and R in the magnesium compound of formula, the formula " respectively do for oneself alkoxyl group or aryloxy, in the presence of polycarboxylate, use halogenated tetravalent titanium compound, use or carry out halogenation to obtain without halohydrocarbon.
(b) a kind of organoaluminum promotor and
(c) a kind of organosilane selective control agent,
Improvement in the method is that the general formula of organosilane selective control agent wherein is:
Figure 931127068_IMG2
R in the formula 1Be C 13-C 30Alkyl, C 16-C 36Alkaryl or C 16-C 36Aralkyl; R 2And R 3Methyl and C respectively do for oneself 13-C 30Alkyl or C 1-C 6-oxyl; R 4Be C 1-C 6-oxyl.
12, the method for claim 11.R wherein 1Be C 16-C 30Alkyl, C 19-C 30Alkaryl or C 19-C 30Aralkyl; And R 2And R 3Methyl or C respectively do for oneself 16-C 30Alkyl or C 1-C 4Alkoxyl group.
13, the method for claim 12, wherein R 3And R 4Be C 1-C 2Alkoxyl group.
14, the method for claim 13, wherein the organosilane selective control agent is selected from following this group compound: just-octadecyl Trimethoxy silane, just-octadecyltriethoxy silane, just-three the octadecyl Trimethoxy silane, just-triacontyl triethoxyl silane, methyl-Octadecane base dimethoxy silane, methyl-just-octadecyl diethoxy silane and their mixture.
15, a kind of olefin polymerization catalyst system comprises:
(a) a kind of procatalyst component of magnesium halide containing, it be by a kind of magnesium compound in the presence of polycarboxylate, with or without halohydrocarbon, carry out halogenation with halogenated tetravalent titanium compound and obtain,
(b) a kind of organoaluminum cocatalyst component and
(c) a kind of organosilane selective control agent, its general formula is:
Figure 931127068_IMG3
R wherein 1Be C 13-C 30Alkyl, C 16-C 36Alkaryl or C 16-C 36Aralkyl; R 2And R 3Methyl or C respectively do for oneself 13-C 30Alkyl or C 1-C 6-oxyl; And R 4Be C 1-C 6-oxyl.
16, the olefin polymerization catalyst system of claim 15, wherein the mol ratio of the titanium in selective control agent and the procatalyst is about 0.5 to about 80.
17, the alkene catalyst of claim 16, wherein magnesium compound is an alkoxyl magnesium, and halogenated tetravalent titanium compound contains at least four halogen atoms, and the organoaluminum promotor is a trialkyl aluminium compound.
18, the olefin polymerization catalyst system of claim 17, wherein magnesium compound is that diethoxy magnesium, polycarboxylate are that DI-ISOBUTYL PHTHALATE and halohydrocarbon are chlorobenzene or adjoin-chlorotoluene.
CN93112706A 1992-11-06 1993-11-06 The polymerization process of alpha-olefin Pending CN1092431A (en)

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