CN103044593B - Olefin polymer and preparation method thereof - Google Patents
Olefin polymer and preparation method thereof Download PDFInfo
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- CN103044593B CN103044593B CN201110310319.0A CN201110310319A CN103044593B CN 103044593 B CN103044593 B CN 103044593B CN 201110310319 A CN201110310319 A CN 201110310319A CN 103044593 B CN103044593 B CN 103044593B
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Abstract
The invention relates to an olefin polymer and a preparation method thereof. According to the method, an olefin polymerization catalyst system comes into contact with one or more olefins under the condition of olefin polymerization, wherein the olefin polymerization catalyst system contains a solid component, an external electron donor compound and an organic aluminum compound, the solid component contains titanium, magnesium and an internal electron donor compound, the external electron donor compound contains a first external electron donor compound and a second external electron donor compound, the first external electron donor compound is diisobutyldimethoxysilane and the second external electron donor compound is n-propyl trimethoxysilane and/or tetraethoxy-silicone. The olefin polymerization method provided by the invention has excellent hydrogen regulation sensibility and high polymerization efficiency and is applicable to occasions of preparation of propene polymers in a gaseous polymerization way.
Description
Technical field
The present invention relates to a kind of olefin polymer and preparation method thereof.
Background technology
Along with the improvement of the raising of propene polymer production technology level, particularly efficient catalyst and polymerization technique, high fluidity propylene polymers product development and application have made great progress.Employing high fluidity propylene polymers can not only reduce the defect in injection technique, and then rate of reducing the number of rejects and seconds; But also processing temperature, injection pressure and mold clamping pressure etc. can be reduced, thus reduce energy consumption, shorten the shaping cycle of goods.In addition, because the mobility of resin improves, can also thin-gage goods be produced, reduce raw-material usage quantity.In order to improve the melt mass flow rate (MFR) of propene polymer, usually take following two kinds of modes of production: one is edman degradation Edman, another kind is that hydrogen adjusts method.Edman degradation Edman is in extruding pelletization process, in propene polymer, add organo-peroxide, and the macromolecular chain of propene polymer is ruptured, and then reduces the melt viscosity of propene polymer, the melt mass flow rate of corresponding raising propene polymer.But the propene polymer prepared by the method easily turns to be yellow, and with certain smell.
Hydrogen tune method is the density of hydrogen by improving in the course of the polymerization process in polymeric kettle, impels the macromolecular chain generation chain tra nsfer of propene polymer, thus the propene polymer of acquisition high workability.The yellowness index of the propene polymer adopting hydrogen to adjust legal system standby is low, appearance stablity; Volatile content in product is low, can be used in the occasion that automotive upholstery etc. has higher requirements to smell.But in actual mechanical process, when amounts of hydrogen increases to a certain degree, the degree that the melt mass flow rate of propene polymer increases reduces, and also makes the activity decrease of catalyzer, affects polymerization efficiency simultaneously.In addition, the increase of hydrogen usage is also had higher requirement to the pressure control capability of polymerization reactor, the ability of removing heat energy power and bearing high-load.
Therefore, when adopting hydrogen to adjust method to regulate the melt mass flow rate of propene polymer, the hydrogen response (that is, the melting index of polymkeric substance is with the intensity of variation of the add-on of hydrogen) improving the olefin polymerization catalyst system used is crucial.
US5652303, US5844046, US6111039 and US6087459 individually disclose when adopting the polymerization methods of liquid polymerization, two kinds of silane compounds can be used as external donor compound, improve the hydrogen response of Ziegler-Natta catalyst, thus improve the melt mass flow rate of the propene polymer of preparation.Although in alkene (particularly propylene) polymerization process, adopt external donor compound disclosed in US5652303, US5844046, US6111039 and US6087459, the melt mass flow rate of the polymkeric substance finally obtained can be improved to a certain extent, but the hydrogen response of above-mentioned olefin polymerization catalyst system still awaits further raising.Further, above-mentioned two kinds of silane compounds are used still to be difficult to obtain balance between good hydrogen response and high polymerization efficiency as the olefin polymerization catalyst system of external donor compound.In addition, adopt above-mentioned external donor compound, when preparing propene polymer in the mode of vapour phase polymerization, very difficult acquisition has the propene polymer of high melt mass flow index.
To sum up, a kind of method that can have a propene polymer of high melt mass flow rate with high polymerization efficiency and the preparation of low hydrogen usage is provided to remain a technical problem urgently to be resolved hurrily.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of olefine polymerizing process, this olefine polymerizing process not only has good hydrogen response, but also has high polymerization efficiency.
The invention provides a kind of olefine polymerizing process, under the method is included in olefin polymerization conditions, by olefin polymerization catalyst system and one or more olefins contact, described olefin polymerization catalyst system contains solid ingredient, external donor compound and organo-aluminium compound, described solid ingredient contains titanium, magnesium and internal electron donor compound, wherein, described external donor compound comprises the first external donor compound and the second external donor compound, described first external donor compound is second, isobutyl dimethoxy silane, described second external donor compound is n-propyl Trimethoxy silane and/or tetraethoxysilane.
Present invention also offers a kind of olefin polymer prepared by method of the present invention.
Method according to the present invention has good hydrogen response, can prepare the olefin polymer with higher melt mass flow rate under the condition that density of hydrogen is identical; And also have higher polymerization efficiency according to method of the present invention, within the unit time, the olefin polymer catalyst of unit mass can prepare more substantial olefin polymer.Olefine polymerizing process according to the present invention is specially adapted to the occasion being prepared propene polymer by the mode of vapour phase polymerization.
Embodiment
The invention provides a kind of olefine polymerizing process, under the method is included in olefin polymerization conditions, by olefin polymerization catalyst system and one or more olefins contact, described olefin polymerization catalyst system contains solid ingredient, external donor compound and organo-aluminium compound, described solid ingredient contains titanium, magnesium and internal electron donor compound, wherein, described external donor compound comprises the first external donor compound and the second external donor compound, described first external donor compound is second, isobutyl dimethoxy silane, described second external donor compound is n-propyl Trimethoxy silane and/or tetraethoxysilane.
According to olefine polymerizing process of the present invention, described external donor compound be the first external donor compound and the second external donor compound (namely, described outer Donor compound is the mixture of the first external donor compound and the second external donor compound), the relative proportion of described first external donor compound and the second external donor compound can change in wide in range scope.
Preferably, the mol ratio of described first external donor compound and the second external donor compound is 1: 0.5-199.More preferably, the mol ratio of described first external donor compound and the second external donor compound is 1: 1-199.Further preferably, the mol ratio of described first external donor compound and the second external donor compound is 1: 1-99.
Still more preferably, the mol ratio of described first external donor compound and the second external donor compound is 1: 9-39.When the mol ratio of described first external electron donor and the second external donor compound is 1: 9-39, on the one hand there is more excellent hydrogen response according to olefine polymerizing process of the present invention, can have the olefin polymer of high melt mass flow rate with the preparation of the hydrogen of less amount, and the melt mass flow rate of prepared olefin polymer can change in wide in range scope; According to olefine polymerizing process of the present invention, also there is higher polymerization efficiency on the other hand.
Most preferably, according to olefine polymerizing process of the present invention, the mol ratio of described first external donor compound and the second external donor compound is 1: 19-39.
According to method of the present invention, described olefin polymerization catalyst system is also containing solid ingredient and organo-aluminium compound.According to method of the present invention, described olefin polymerization catalyst system is not particularly limited for the kind of described solid ingredient and organo-aluminium compound and consumption, can be that the routine of this area is selected.
According to the present invention, described solid ingredient contains titanium, magnesium and internal electron donor compound, is the reaction product of titanium compound, magnesium compound and internal electron donor compound.
According to the present invention, described titanium compound can be various titanium compounds conventional in olefin polymerization catalysis.Preferably, described titanium compound is the titanium compound shown in formula I,
TiX
1 m(OR
1)
4-m(I)
In formula I, X
1can be the one in chlorine, bromine and iodine, R
1can be C
1-C
5straight or branched alkyl, m can be the integer of 0-4.In formula I, m can be such as 0,1,2,3 or 4.
In the present invention, C
1-C
5straight or branched alkyl example can for but be not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl and neo-pentyl.
In the present invention, the example of described titanium compound can for but be not limited to: one or more in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygen base titanium and trichlorine one ethanolato-titanium.
Preferably, in formula I, X
1for the one in chlorine, bromine and iodine, R
1for C
1-C
5straight or branched alkyl, m is the integer of 1-4, such as: described titanium compound can be one or more in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, a chlorine triethoxy titanium, dichlorodiethyl oxygen base titanium and trichlorine one ethanolato-titanium.
Further preferably, in formula I, m is 4, such as: described titanium compound can be one or more in titanium tetrachloride, titanium tetrabromide and titanium tetra iodide.Most preferably, in formula I, m is 4, and X
1for chlorine, namely described titanium compound is titanium tetrachloride.
According to the present invention, described magnesium compound can be the magnesium compound shown in formula II,
R
3-Mg-R
2(II)
In formula II, R
2and R
3can be chlorine, bromine, iodine, C separately
1-C
5straight or branched alkoxyl group and C
1-C
5straight or branched alkyl in one.In the present invention, C
1-C
5the example of straight or branched alkoxyl group include but not limited to: methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy, isopentyloxy, tertiary pentyloxy and neopentyl oxygen.
Preferably, in formula II, R
2and R
3be the one in chlorine, bromine and iodine separately.Most preferably, in formula II, R
2and R
3be chlorine, namely described magnesium compound is magnesium chloride.
According to the present invention, described internal electron donor compound can be the conventional various internal electron donor compound of field of olefin polymerisation, such as: described internal electron donor compound can be one or more in Bisphthalate based compound.Preferably, described internal electron donor compound is one or more in diisobutyl phthalate, n-butyl phthalate, n-propyl phthalate, diisopropyl phthalate, diethyl phthalate and dimethyl phthalate.
One of the present invention preferred embodiment in, in formula I, X
1for the one in chlorine, bromine and iodine, m is 4; And in formula II, R
2and R
3be the one in chlorine, bromine and iodine separately; Described internal electron donor compound is one or more in diisobutyl phthalate, n-butyl phthalate, n-propyl phthalate, diisopropyl phthalate, diethyl phthalate and dimethyl phthalate.
One of the present invention more preferred embodiment in, described titanium compound is titanium tetrachloride; Described magnesium compound is magnesium chloride; And described internal electron donor compound is one or more in diisobutyl phthalate, n-butyl phthalate, n-propyl phthalate, diisopropyl phthalate, diethyl phthalate and dimethyl phthalate.
According to the present invention, can adopt and well known to a person skilled in the art that various method prepares described solid ingredient.Such as, the preparation method of described solid ingredient can comprise: contacted in organic solvent with internal electron donor compound with titanium compound by described magnesium compound, then carries out solid-liquid separation, and carries out washing and drying.According to the present invention, the consumption of described titanium compound, internal electron donor compound and magnesium compound is with in final solid ingredient, and the content of each component meets concrete service requirements and is as the criterion.Preferably, the mol ratio of described titanium compound, internal electron donor compound and magnesium compound is 0.01-0.5: 0.01-50: 1.
According to method of the present invention, the preparation method of described solid ingredient is preferably: under the existence of hydrocarbon system solvent, at the temperature of 110-150 DEG C, described magnesium compound is contacted 1-3 hour with alcohol; Again at the temperature of 110-150 DEG C, product of contact is contacted with the first internal electron donor compound with titanic acid ester, thus prepares alcohol adduct; At the temperature of-10 DEG C to-30 DEG C, titanium compound is dripped in described alcohol adduct, after being added dropwise to complete, the temperature of the mixture obtained is increased to 100-130 DEG C, and at such a temperature, the second internal electron donor compound is added in described mixture, then at the temperature of 100-130 DEG C, contact 1-3 hour, product of contact is filtered, washed and carry out drying, described solid ingredient can be obtained.Described first internal electron donor compound and described second internal electron donor compound can be previously described internal electron donor compound separately.Described first internal electron donor compound can be identical with described second internal electron donor compound, also can be different, preferably identical.The mol ratio of described first internal electron donor compound and described magnesium compound can be 0.1-0.2: 1.The mol ratio of described titanium compound, the second internal electron donor compound and magnesium compound can be 0.01-0.5: 0.01-50: 1.Described hydrocarbon system solvent can be C
6-C
10straight chain hydrocarbon or branched-chain hydrocarbon, described titanic acid ester can be such as one or more in titanium isopropylate, tetra-n-butyl titanate and tetraethyl titanate.The mol ratio of described titanic acid ester and described magnesium compound can be 0.05-0.1: 1.
According to the present invention, the various organo-aluminium compounds that described organo-aluminium compound can be commonly used for this area.Usually, described organo-aluminium compound can be one or more in the organo-aluminium compound shown in formula III,
Wherein, R
4, R
5and R
6can be chlorine and C separately
1-C
5straight or branched alkyl in one, and R
4, R
5and R
6in at least one is C
1-C
5straight or branched alkyl.
Preferably, described organo-aluminium compound is one or more in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium and diethyl aluminum chloride.Further preferably, described organo-aluminium compound is triethyl aluminum.
One of the present invention preferred embodiment in, described titanium compound is titanium dichloride; Described magnesium compound is magnesium chloride; Described internal electron donor compound is one or more in diisobutyl phthalate, n-butyl phthalate, n-propyl phthalate, diisopropyl phthalate, diethyl phthalate and dimethyl phthalate; And described organo-aluminium compound is triethyl aluminum.
According to olefine polymerizing process of the present invention, the amount of the solid ingredient in described olefin polymerization catalyst system, external donor compound and organo-aluminium compound can carry out appropriate selection according to concrete application scenario.The mol ratio of the titanium in the aluminium in described organo-aluminium compound and described solid ingredient can be 20-2000: 1, is preferably 50-1000: 1.The mol ratio of silicon total in the aluminium in described organo-aluminium compound and described external donor compound can be 1-100: 1, is preferably 5-70: 1.
One of the present invention preferred embodiment in, the mol ratio of the titanium in the aluminium in described organo-aluminium compound and described solid ingredient is 20-2000: 1, and the mol ratio of silicon total in the aluminium in described organo-aluminium compound and described external donor compound is 1-100: 1.
One of the present invention more preferred embodiment in, the mol ratio of the titanium in the aluminium in described organo-aluminium compound and described solid ingredient is 50-1000: 1, and the mol ratio of silicon total in the aluminium in described organo-aluminium compound and described external donor compound is 5-70: 1.
Can by each component in olefin polymerization catalyst system be sent in polymerization reactor according to method of the present invention, after mixing, one or more alkene are sent in described polymerization reactor, to contact with the mixture of described olefin polymerization catalyst system, thus one or more alkene described are polymerized.
Olefine polymerizing process according to the present invention may be used for all polymerizations of alkene, also may be used for multiple alkene to carry out copolymerization.Described alkene can be ethene, C
3-C
101-alkene and C
4-C
8diolefin in one or more.According to olefine polymerizing process of the present invention, described alkene is preferably propylene; Or be propylene and be selected from ethene, C
4-C
101-alkene and C
4-C
8diolefin in one or more comonomers.In the present invention, C
4-C
101-alkene specific examples can for but be not limited to: the positive amylene of 1-n-butene, 1-, 1-n-hexylene, the positive octene of 1-and 4-methyl-1-pentene.In the present invention, C
4-C
8diolefin example can for but be not limited to: 1,3-butadiene and isoprene.
According to olefine polymerizing process of the present invention, described olefin polymerization conditions can be the normal condition of this area.Preferably, described olefin polymerization conditions comprises: temperature is 40-90 DEG C, and pressure is 0.5-4MPa.
According to olefine polymerizing process of the present invention, the contact of one or more alkene and catalyst according to the invention system can be carried out in presence of hydrogen, described hydrogen is for regulating the molecular weight (that is, melt mass flow rate) of the olefin polymer obtained.According to olefine polymerizing process of the present invention, the amount of described hydrogen can carry out appropriate selection according to the kind of used alkene.
One of the present invention preferred embodiment in, under method according to the present invention is included in olefin polymerization conditions, olefin polymerization catalyst system is contacted with propylene.More specifically, this preferred embodiment comprises: to be sent into by olefin polymerization catalyst system in polymerization reactor and to mix, propylene is sent in described polymerization reactor, contact under olefin polymerization conditions with the mixture of described olefin polymerization catalyst system, thus prepare polypropylene.
This preferred embodiment in, the contact of preferred propylene and described olefin polymerization catalyst system is carried out in the presence of hydrogen gas, such hydrogen can as molecular weight regulator to preparation polyacrylic molecular weight regulate.
When the contact of propylene and described olefin polymerization catalyst system is carried out in presence of hydrogen, the consumption of hydrogen can carry out appropriate selection according to the polyacrylic molecular weight of expection.High according to the hydrogen response of olefine polymerizing process of the present invention, the mol ratio of hydrogen and propylene is 0.001-0.1: 1, just can prepare the polypropylene that melt mass flow rate is 10-150 gram/10 minutes.
In another preferred embodiment of the present invention, under method according to the present invention is included in olefin polymerization conditions, by olefin polymerization catalyst system and propylene be selected from ethene, C
4-C
101-alkene and C
4-C
8diolefin in one or more comonomers contact.Can by olefin polymerization catalyst system to be sent in polymerization reactor and after mixing, by propylene be selected from ethene, C
4-C
101-alkene and C
4-C
8diolefin in one or more comonomers send in described polymerization reactor, to contact under olefin polymerization conditions with the mixture of described olefin polymerization catalyst system, thus make propylene and described comonomer carry out copolymerization.Preferably, described comonomer is ethene.
This preferred embodiment in, preferred propylene carries out in the presence of hydrogen gas with described comonomer and contacting of described olefin polymerization catalyst system, such hydrogen can as molecular weight regulator to preparation polyacrylic molecular weight regulate.High according to the hydrogen response of method of the present invention.Such as: when preparing the multipolymer of propylene and ethene, propylene is carried out in presence of hydrogen with ethene and contacting of described olefin polymerization catalyst system, the mol ratio of hydrogen and propylene is 0.001-0.1: 1, and the melt mass flow rate of the propene polymer of preparation can reach 10-60 gram/10 minutes.
According to this preferred embodiment, the ratio between described propylene and described comonomer is not particularly limited, and can carry out appropriate selection, repeat no more herein according to the performance of the propene polymer of expection.
Both can carry out in the liquid phase according to polymerization process of the present invention, and also can carry out in the gas phase, be not particularly limited.Preferably, carry out in the gas phase according to olefine polymerizing process of the present invention.That is, according to olefine polymerizing process of the present invention, one or more alkene described with carry out particularly preferably in gas-phase polymerization reactor according to the contact of olefin polymerization catalyst system of the present invention.The various gas-phase polymerization reactors that described gas-phase polymerization reactor can be commonly used for this area, such as fluidized-bed reactor and horizontal type agitated bed gas-phase polymerization reactor.Olefine polymerizing process according to the present invention is particularly suitable for carrying out in horizontal type agitated bed gas-phase polymerization reactor, to produce granulated polymer.
The present invention is described in detail below in conjunction with embodiment.
Following examples relate to following testing method.
(1) melt mass flow rate: according to the testing method specified in GB/T3682-2000, carries out being purchased on the TP402-2 type melt mass flow rate determinator of Japanese Tester company.Wherein, probe temperature is 230 DEG C, and load is 2.16 kilograms.
(2) ethylene content: adopt infrared spectroscopy, sample pellet is hot pressed into the film that thickness is 200-400 micron on the thermocompressor of 160 DEG C, after naturally cooling to room temperature, tests being purchased on the IR-435 infrared spectrometer of Japanese Shimadzu.
(3) rubber-phase content in ethylene-propylene copolymer: adopt n-decane extraction process to measure, concrete operations are:
The n-decane being 98 quality % by sample and purity mixes, in 145 DEG C of backflows 24 hours in the flask with reflux, be cooled to room temperature, rubber compatibility is in decane, and all the other crystallize out, then filter, and by filtrate added drop-wise in acetone, the rubber phase in filtrate is separated out, after filtration, after drying, weigh, determine the content of rubber phase.
(4) degree of isotacticity: employing carbon-13 nmr spectra method (
13c-NMR), carry out in the AM300 NMR spectrometer with superconducting magnet of Bruker company of Switzerland being purchased, concrete operations condition is:
Sample is dissolved with deuterated orthodichlorobenzene when temperature is 120 DEG C, is mixed with the solution that concentration is 15 volume %, in the oil bath of 120 DEG C, dissolves 4-5 hour.
(5) molecular weight and molecualr weight distribution: adopt gel permeation chromatography, carry out on the WATER GPCV2K gel chromatograph of WATERS company being purchased, the moving phase used is orthodichlorobenzene, and probe temperature is 150 DEG C, adopts monodisperse polystyrene as standard substance.
(6) polymerization efficiency: refer in the unit time, by the quality of the polymkeric substance of the catalyst preparing of unit mass, calculation formula is: quality/(quality of polymerization reaction time × catalyzer) of the polymkeric substance of preparation, wherein, the quality of polymkeric substance in kilogram, the quality of catalyzer in gram, polymerization reaction time in hour.
Preparation example 1-4 is for the preparation of the solid ingredient in olefin polymerization catalyst system.
Preparation example 1
(1) preparation of magnesium chloride alcohol adduct
The there-necked flask nitrogen replacement three times of agitator and thermometer is housed, then adds 5g Magnesium Chloride Anhydrous, 30mL n-decane and 23mL ethanol.Warming while stirring to 130 DEG C, and react 2 hours at this temperature, in advance 1.5mL tetrabutyl titanate and 2mL diisobutyl phthalate are added in 5mL toluene, at room temperature stirring reaction 0.5 hour.Above-mentioned toluene solution is added in there-necked flask, and continues reaction 1 hour at 130 DEG C, after reaction terminates, be cooled to the magnesium chloride alcohol adduct solution that room temperature forms stable and uniform.
(2) preparation of the solid ingredient of catalyzer
The reactor nitrogen replacement three times of agitator and thermometer is housed, and then add 200mL titanium tetrachloride, at-20 DEG C, magnesium chloride alcohol adduct solution step (1) prepared was added drop-wise in this reactor in 30 minutes.After being added dropwise to complete, be warming up to 110 DEG C through 3.5 hours.At 110 DEG C, add 1.2mL diisobutyl phthalate, and react 2 hours at this temperature.Reaction terminates rear filtering liquid, rejoins 2000mL titanium tetrachloride, and then 110 DEG C of reactions 1.5 hours.Reaction terminates rear filtering reaction solution, is washed 60 minutes by the solid trichloromethane obtained at 60 DEG C, and be then washed till without free chlorion in filtrate with normal hexane, remaining solid product obtains the solid ingredient of catalyzer through vacuum-drying.In this solid ingredient, the content of Ti is 2.36wt%.
Preparation example 2
(1) preparation of magnesium chloride alcohol adduct
The method identical with the step (1) in preparation example 1 is adopted to prepare magnesium chloride alcohol adduct, unlike, use n-butyl phthalate to replace diisobutyl phthalate, thus prepare magnesium chloride alcohol adduct solution.
(2) preparation of the solid ingredient of catalyzer
Adopt the solid ingredient of the method Kaolinite Preparation of Catalyst identical with the step (2) in preparation example 1, unlike, use n-butyl phthalate to replace diisobutyl phthalate, thus obtain the solid ingredient of catalyzer.In this solid ingredient, the content of Ti is 2.12wt%.
Preparation example 3
(1) preparation of magnesium chloride alcohol adduct
The method identical with the step (1) in preparation example 1 is adopted to prepare magnesium chloride alcohol adduct, unlike, use n-propyl phthalate to replace diisobutyl phthalate, thus prepare magnesium chloride alcohol adduct solution.
(2) preparation of the solid ingredient of catalyzer
Adopt the solid ingredient of the method Kaolinite Preparation of Catalyst identical with the step (2) in preparation example 1, unlike, use n-propyl phthalate to replace diisobutyl phthalate, thus obtain the solid ingredient of catalyzer.In this solid ingredient, the content of Ti is 2.03wt%.
Preparation example 4
(1) preparation of magnesium chloride alcohol adduct
The method identical with the step (1) in preparation example 1 is adopted to prepare magnesium chloride alcohol adduct, unlike, use diisopropyl phthalate to replace diisobutyl phthalate, thus prepare magnesium chloride alcohol adduct solution.
(2) preparation of the solid ingredient of catalyzer
Adopt the solid ingredient of the method Kaolinite Preparation of Catalyst identical with the step (2) in preparation example 1, unlike, use diisopropyl phthalate to replace diisobutyl phthalate, thus obtain the solid ingredient of catalyzer.In this solid ingredient, the content of Ti is 1.98wt%.
Embodiment 1-18 is used for illustrating according to olefin polymer of the present invention and preparation method thereof.
Embodiment 1
The heating of 5L autoclave is vacuumized, excluding air and water, after nitrogen purging, add catalyst solid constituent prepared by 20mg preparation example 1, triethyl aluminum is added by the amount of Al/Ti (mole)=900, in autoclave, pass into 30mmol hydrogen, add second, isobutyl dimethoxy silane (DB) and tetraethoxysilane (DT) (both mol ratio DB: DT=1: 19 respectively; The mol ratio Al/Si=20 of the total amount of the silicon in triethyl aluminum in the amount of aluminium and second, isobutyl dimethoxy silane and tetraethoxysilane), then add 1.2kg liquid propene.Off-response still, by still temperature rise to 70 DEG C, after polyreaction 2h, discharges unreacting propylene, obtains polypropylene GRANULES.
Embodiment 2
The method identical with embodiment 1 is adopted to prepare polypropylene, unlike, use n-propyl Trimethoxy silane (DN) to replace tetraethoxysilane.
Embodiment 3
The method identical with embodiment 1 is adopted to prepare polypropylene, unlike mol ratio DB: DT=1: 39 of, second, isobutyl dimethoxy silane and tetraethoxysilane.
Embodiment 4
The method identical with embodiment 2 is adopted to prepare polypropylene, unlike, the mol ratio of second, isobutyl dimethoxy silane and n-propyl Trimethoxy silane is DB: DN=1: 39.
Embodiment 5
The method identical with embodiment 1 is adopted to prepare polypropylene, unlike, the mol ratio of second, isobutyl dimethoxy silane and tetraethoxysilane is DB: DT=1: 9.
Embodiment 6
The method identical with embodiment 1 is adopted to prepare polypropylene, unlike, the mol ratio of second, isobutyl dimethoxy silane and tetraethoxysilane is DB: DT=1: 1.
Embodiment 7
The method identical with embodiment 1 is adopted to prepare polypropylene, unlike, the mol ratio of second, isobutyl dimethoxy silane and tetraethoxysilane is DB: DT=1: 99.
Embodiment 8
The method identical with embodiment 2 is adopted to prepare polypropylene, unlike, the mol ratio of second, isobutyl dimethoxy silane and n-propyl Trimethoxy silane is DB: DN=1: 9.
Embodiment 9
The method identical with embodiment 2 is adopted to prepare polypropylene, unlike, the mol ratio of second, isobutyl dimethoxy silane and n-propyl Trimethoxy silane is DB: DN=1: 1.
Embodiment 10
The method identical with embodiment 2 is adopted to prepare polypropylene, unlike, the mol ratio of second, isobutyl dimethoxy silane and n-propyl Trimethoxy silane is DB: DN=1: 99.
Embodiment 11
The method identical with embodiment 1 is adopted to prepare polypropylene, unlike, the consumption of hydrogen is 100mmol.
Embodiment 12
The method identical with embodiment 2 is adopted to prepare polypropylene, unlike, the consumption of hydrogen is 100mmol.
Embodiment 13
The method identical with embodiment 1 is adopted to prepare polypropylene, unlike, the consumption of hydrogen is 200mmol.
Embodiment 14
The method identical with embodiment 2 is adopted to prepare polypropylene, unlike, the consumption of hydrogen is 200mmol.
Comparative example 1
The method identical with embodiment 1 is adopted to prepare polypropylene, unlike, do not use tetraethoxysilane, and second, isobutyl dimethoxy silane add-on makes Al/Si=20.
Comparative example 2
The method identical with embodiment 1 is adopted to prepare polypropylene, unlike, do not use second, isobutyl dimethoxy silane, and tetraethoxysilane add-on makes Al/Si=20.
Comparative example 3
The method identical with embodiment 2 is adopted to prepare polypropylene, unlike, do not use second, isobutyl dimethoxy silane, and the add-on of n-propyl Trimethoxy silane makes Al/Si=20.
Embodiment 15
The method identical with embodiment 1 is adopted to prepare polypropylene, unlike, the mol ratio of second, isobutyl dimethoxy silane and tetraethoxysilane is DB: DT=1: 199.
Embodiment 16
The method identical with embodiment 1 is adopted to prepare polypropylene, unlike, the mol ratio of second, isobutyl dimethoxy silane and tetraethoxysilane is DB: DT=1: 0.67.
Embodiment 17
The method identical with embodiment 2 is adopted to prepare polypropylene, unlike, the mol ratio of second, isobutyl dimethoxy silane and n-propyl Trimethoxy silane is DB: DN=1: 199.
Embodiment 18
The method identical with embodiment 2 is adopted to prepare polypropylene, unlike, the mol ratio of second, isobutyl dimethoxy silane and n-propyl Trimethoxy silane is DB: DN=1: 0.67.
Comparative example 4
The method identical with embodiment 1 is adopted to prepare polypropylene, unlike, replace second, isobutyl dimethoxy silane and tetraethoxysilane with dimethoxydiphenylsilane and four butoxy silanes, and the mol ratio of dimethoxydiphenylsilane and four butoxy silanes is 1: 19.
Comparative example 5
The method identical with embodiment 1 is adopted to prepare polypropylene, unlike, replace second, isobutyl dimethoxy silane and tetraethoxysilane with Cyclohexylmethyldimethoxysilane and tetramethoxy-silicane, and the mol ratio of Cyclohexylmethyldimethoxysilane and tetramethoxy-silicane is 1: 19.
Table 1 lists the polymerization result of embodiment 1-18 and comparative example 1-5.
Table 1
*: dimethoxydiphenylsilane/tetra-butoxy silane
*: Cyclohexylmethyldimethoxysilane/tetramethoxy-silicane
Embodiment 1 and comparative example 1 and 2, embodiment 2 are compared can find out with comparative example 2 and 3, according to olefine polymerizing process of the present invention, not only there is good hydrogen response, and there is higher polymerization efficiency.
Embodiment 19-28 is for illustration of olefin polymer according to the present invention and preparation method thereof.
Embodiment 19
Catalyst solid constituent prepared by preparation example 2 is added 50m continuously with 1.5g/h
3continuous horizontal type agitated bed Gas-phase reactor in, triethyl aluminum is added continuously with pump, the add-on of triethyl aluminum makes the mol ratio Al/Ti=600 of the aluminium in triethyl aluminum and the titanium in catalyst solid constituent, (both molar ratios are DB: DT=1: 39 to add second, isobutyl dimethoxy silane and tetraethoxysilane continuously, the total amount mol ratio Al/Si=20 of the silicon in triethyl aluminum in the amount of aluminium and second, isobutyl dimethoxy silane and tetraethoxysilane), mix.Pass into propylene and hydrogen carries out polyreaction, wherein, the pressure of reactor is 2.25MPa, and temperature of reactor is 65 DEG C, and reactor material level is 80%, hydrogen/propylene ratio (H
2/ C
3) be 0.07 (mol/mol), propylene and hydrogen mean residence time is in the reactor 40min.
Embodiment 20-22
The method identical with embodiment 19 is adopted to prepare polypropylene, unlike, change the mol ratio of second, isobutyl dimethoxy silane and tetraethoxysilane, be respectively: DB: DT=1: 19, DB: DT=1: 12, DB: DT=1: 9.
Embodiment 23
The method identical with embodiment 20 is adopted to prepare polypropylene, unlike, the pressure of reactor is 0.5MPa, and temperature is 40 DEG C, and material level is 80%, hydrogen/propylene ratio (H
2/ C
3) be 0 (mol/mol).
Embodiment 24
The method identical with embodiment 20 is adopted to prepare polypropylene, unlike, the pressure of reactor is 4MPa, and temperature is 90 DEG C, hydrogen/propylene ratio (H
2/ C
3) be 0.1 (mol/mol).
Embodiment 25 and 26
The method identical with embodiment 19 is adopted to prepare polypropylene, unlike, change the mol ratio of second, isobutyl dimethoxy silane and tetraethoxysilane, be respectively: DB: DT=1: 1, DB: DT=1: 99.
Comparative example 6
The method identical with embodiment 19 is adopted to prepare polypropylene, unlike, do not use second, isobutyl dimethoxy silane, the add-on of tetraethoxysilane makes Al/Si=20.
Comparative example 7
The method identical with embodiment 19 is adopted to prepare polypropylene, unlike, do not use tetraethoxysilane, the add-on of second, isobutyl dimethoxy silane makes Al/Si=20.
Embodiment 27 and 28
The method identical with embodiment 19 is adopted to prepare polypropylene, unlike, change the mol ratio of second, isobutyl dimethoxy silane and tetraethoxysilane, be respectively: DB: DT=1: 0.67, DB: DT=1: 199.
Comparative example 8
The method identical with embodiment 20 is adopted to prepare polypropylene, unlike, replace second, isobutyl dimethoxy silane and tetraethoxysilane with dimethoxydiphenylsilane and four butoxy silanes, and the mol ratio of dimethoxydiphenylsilane and four butoxy silanes is 1: 19.
Comparative example 9
The method identical with embodiment 20 is adopted to prepare polypropylene, unlike, replace second, isobutyl dimethoxy silane and tetraethoxysilane with Cyclohexylmethyldimethoxysilane and tetramethoxy-silicane, and the mol ratio of Cyclohexylmethyldimethoxysilane and tetramethoxy-silicane is 1: 19.
Comparative example 10
The method identical with embodiment 19 is adopted to prepare polypropylene, unlike, tetraethoxysilane and second, isobutyl dimethoxy silane are successively sent into continuous horizontal type agitated bed Gas-phase reactor from two charging openings, wherein, first charging opening and second charging opening are arranged along the axis of continuous horizontal type agitated bed Gas-phase reactor, be benchmark along the travel direction of material in described continuous horizontal type agitated bed Gas-phase reactor, the distance that first charging opening is positioned at the initiating terminal of described continuous horizontal type agitated bed Gas-phase reactor is 8% place of the total length of described continuous horizontal type agitated bed Gas-phase reactor, and described first charging opening is for adding tetraethoxysilane, the distance that described second charging opening is positioned at the initiating terminal of described continuous horizontal type agitated bed Gas-phase reactor is 75% of the total length of described Gas-phase reactor, and described second charging opening is for adding second, isobutyl dimethoxy silane.
During polymerization, catalyst solid constituent and triethyl aluminum are sent into described continuous horizontal type agitated bed Gas-phase reactor from first charging opening respectively, and mix with tetraethoxysilane, then pass into propylene and hydrogen from first charging opening, contact with said mixture and be polymerized; Be polymerized the mixture obtained then to contact with second, isobutyl dimethoxy silane, proceed polymerization, thus prepare polypropylene.
Table 2 lists the polymerization result of embodiment 19-28 and comparative example 6-10.
Table 2
*: dimethoxydiphenylsilane/tetra-butoxy silane
*: Cyclohexylmethyldimethoxysilane/tetramethoxy-silicane
Embodiment 29-38 is for illustration of olefin polymer according to the present invention and preparation method thereof.
Embodiment 29
Catalyst solid constituent prepared by preparation example 2 is added 50m continuously with 1.5g/h
3continuous horizontal type agitated bed Gas-phase reactor in, triethyl aluminum is added continuously with pump, the add-on of triethyl aluminum makes the mol ratio Al/Ti=600 of the aluminium in triethyl aluminum and the titanium in catalyst solid constituent, (both molar ratios are DB: DN=1: 39 to add second, isobutyl dimethoxy silane and n-propyl Trimethoxy silane continuously, the total amount mol ratio Al/Si=20 of the silicon in triethyl aluminum in the amount of aluminium and n-propyl Trimethoxy silane and second, isobutyl dimethoxy silane), mix.Pass into propylene and hydrogen carries out polyreaction, wherein, the pressure of reactor is 2.25MPa, and temperature of reactor is 65 DEG C, and reactor material level is 80%, hydrogen/propylene ratio (H
2/ C
3) be 0.07 (mol/mol), propylene and hydrogen mean residence time is in the reactor 40min.
Embodiment 30-32
The method identical with embodiment 29 is adopted to prepare polypropylene, unlike, change the mol ratio of second, isobutyl dimethoxy silane and n-propyl Trimethoxy silane, be respectively: DB: DN=1: 19, DB: DN=1: 12, DB: DN=1: 9.
Embodiment 33
The method identical with embodiment 30 is adopted to prepare polypropylene, unlike, the pressure of reactor is 0.5MPa, and temperature is 40 DEG C, hydrogen/propylene ratio (H
2/ C
3) be 0 (mol/mol).
Embodiment 34
The method identical with embodiment 30 is adopted to prepare polypropylene, unlike, the pressure of reactor is 4MPa, and temperature is 90 DEG C, hydrogen/propylene ratio (H
2/ C
3) be 0.1 (mol/mol).
Embodiment 35 and 36
The method identical with embodiment 29 is adopted to prepare polypropylene, unlike, change the mol ratio of second, isobutyl dimethoxy silane and n-propyl Trimethoxy silane, be respectively: DB: DN=1: 1, DB: DN=1: 99.
Comparative example 11
The method identical with embodiment 29 is adopted to prepare polypropylene, unlike, do not use second, isobutyl dimethoxy silane, the add-on of n-propyl Trimethoxy silane makes Al/Si=20.
Embodiment 37 and 38
The method identical with embodiment 29 is adopted to prepare polypropylene, unlike, change the mol ratio of second, isobutyl dimethoxy silane and n-propyl Trimethoxy silane, be respectively: DB: DN=1: 0.67, DB: DN=1: 199.
Comparative example 12
The method identical with embodiment 29 is adopted to prepare polypropylene, unlike, n-propyl Trimethoxy silane and second, isobutyl dimethoxy silane are successively sent into continuous horizontal type agitated bed Gas-phase reactor from two charging openings, wherein, first charging opening and second charging opening are arranged along the axis of reactor, be benchmark along the travel direction of material in described continuous horizontal type agitated bed Gas-phase reactor, the distance that first charging opening is positioned at the initiating terminal of described continuous horizontal type agitated bed Gas-phase reactor is 8% place of the total length of described continuous horizontal type agitated bed Gas-phase reactor, and described first charging opening is for adding n-propyl Trimethoxy silane, the distance that described second charging opening is positioned at the initiating terminal of described continuous horizontal type agitated bed Gas-phase reactor is 75% of the total length of described first reactor, and described second charging opening is for adding second, isobutyl dimethoxy silane.
During polymerization, catalyst solid constituent and triethyl aluminum are sent into described continuous horizontal type agitated bed Gas-phase reactor from first charging opening respectively, and mix with n-propyl Trimethoxy silane, then pass into propylene and hydrogen from first charging opening, contact with said mixture and be polymerized; Be polymerized the mixture obtained then to contact with second, isobutyl dimethoxy silane, proceed polymerization, thus prepare polypropylene.
Table 3 lists the polymerization result of embodiment 29-38 and comparative example 11-12.
Table 3
Embodiment 19 and comparative example 10 are compared, embodiment 29 and comparative example 12 are compared, can find out, with the solid ingredient making propylene elder generation with olefin polymerization catalyst system, organo-aluminium compound and the contact of a kind of external donor compound, be polymerized to make at least part of propylene, and then compared with the polymerization methods that contacts of the mixture that above-mentioned polymerization is produced and another kind of external donor compound, method according to the present invention contacts with each component in olefin polymerization catalyst system by making propylene simultaneously, the polypropylene with high melt mass flow rate can not only be prepared, and there is higher polymerization efficiency, the polymkeric substance of preparation also has higher degree of isotacticity.
Embodiment 39-50 is for illustration of olefin polymer according to the present invention and preparation method thereof.
Embodiment 39
Catalyst solid constituent prepared by preparation example 3 is added 50m continuously with 1.5g/h
3continuous horizontal type agitated bed Gas-phase reactor in, triethyl aluminum is added continuously with pump, the add-on of triethyl aluminum makes the mol ratio Al/Ti=600 of the aluminium in triethyl aluminum and the titanium in catalyst solid constituent, (both molar ratios are DB: DT=1: 39 to add second, isobutyl dimethoxy silane and tetraethoxysilane continuously, the total amount mol ratio Al/Si=20 of the silicon in triethyl aluminum in the amount of aluminium and tetraethoxysilane and diisobutyl dimethoxy silicon), mix.Then, pass into propylene, ethene and hydrogen and carry out polyreaction, wherein, the pressure of reactor is 2.25MPa, and the temperature of reactor is 65 DEG C, and the material level of reactor is 80%, hydrogen/propylene ratio (H
2/ C
3) be 0.07 (mol/mol), ethylene/propene ratio (C
2/ C
3) be 0.03 (mol/mol), propylene and hydrogen mean residence time is in the reactor 40min.
Embodiment 40-42
The method identical with embodiment 39 is adopted to prepare propene polymer, unlike, change the mol ratio of second, isobutyl dimethoxy silane and tetraethoxysilane, be respectively: DB: DT=1: 19, DB: DT=1: 12, DB: DT=1: 9.
Embodiment 43
The method identical with embodiment 40 is adopted to prepare propene polymer, unlike, the pressure of reactor is 0.5MPa, and temperature is 40 DEG C, hydrogen/propylene ratio (H
2/ C
3) be 0 (mol/mol), ethylene/propene ratio (C
2/ C
3) be 0.001 (mol/mol).
Embodiment 44
The method identical with embodiment 40 is adopted to prepare propene polymer, unlike, the pressure of reactor is 4MPa, and temperature is 90 DEG C, hydrogen/propylene ratio (H
2/ C
3) be 0.1 (mol/mol), ethylene/propene ratio (C
2/ C
3) be 0.5 (mol/mol).
Embodiment 45
The method identical with embodiment 40 is adopted to prepare propene polymer, unlike, the pressure of reactor is 1.8MPa, and temperature is 60 DEG C, and material level is 70%, hydrogen/propylene ratio (H
2/ C
3) be 0.02 (mol/mol), ethylene/propene ratio (C
2/ C
3) be 0.01 (mol/mol).
Embodiment 46
The method identical with embodiment 40 is adopted to prepare propene polymer, unlike, the pressure of reactor is 2.35MPa, and temperature is 70 DEG C, and material level is 85%, hydrogen/propylene ratio (H
2/ C
3) be 0.08 (mol/mol), ethylene/propene ratio (C
2/ C
3) be 0.1 (mol/mol).
Embodiment 47 and 48
The method identical with embodiment 39 is adopted to prepare propene polymer, unlike, change the mol ratio of second, isobutyl dimethoxy silane and tetraethoxysilane, be respectively: DB: DT=1: 1, DB: DT=1: 99.
Comparative example 13
The method identical with embodiment 39 is adopted to prepare propene polymer, unlike, do not use second, isobutyl dimethoxy silane, the add-on of tetraethoxysilane makes Al/Si (mole)=20.
Comparative example 14
The method identical with embodiment 39 is adopted to prepare propene polymer, unlike, do not use tetraethoxysilane, the add-on of second, isobutyl dimethoxy silane makes Al/Si=20.
Embodiment 49 and 50
The method identical with embodiment 39 is adopted to prepare propene polymer, unlike, change the mol ratio of second, isobutyl dimethoxy silane and tetraethoxysilane, be respectively: DB: DT=1: 0.67, DB: DT=1: 199.
Comparative example 15
The method identical with embodiment 40 is adopted to prepare propene polymer, unlike, replace second, isobutyl dimethoxy silane and tetraethoxysilane with dimethoxydiphenylsilane and four butoxy silanes, and the mol ratio of dimethoxydiphenylsilane and four butoxy silanes is 1: 19.
Comparative example 16
The method identical with embodiment 40 is adopted to prepare propene polymer, unlike, replace second, isobutyl dimethoxy silane and tetraethoxysilane with Cyclohexylmethyldimethoxysilane and tetramethoxy-silicane, and the mol ratio of Cyclohexylmethyldimethoxysilane and tetramethoxy-silicane is 1: 19.
Comparative example 17
The method identical with embodiment 40 is adopted to prepare propene polymer, unlike, tetraethoxysilane and second, isobutyl dimethoxy silane are successively sent into continuous horizontal type agitated bed Gas-phase reactor from two charging openings, wherein, first charging opening and second charging opening are arranged along the axis of described continuous horizontal type agitated bed Gas-phase reactor, be benchmark along the travel direction of material in described continuous horizontal type agitated bed Gas-phase reactor, the distance that first charging opening is positioned at the initiating terminal of described continuous horizontal type agitated bed Gas-phase reactor is 8% place of the total length of described continuous horizontal type agitated bed Gas-phase reactor, and described first charging opening is for adding tetraethoxysilane, the distance that described second charging opening is positioned at the initiating terminal of described continuous horizontal type agitated bed Gas-phase reactor is 75% of the total length of described first reactor, and described second charging opening is for adding second, isobutyl dimethoxy silane.
During polymerization, catalyst solid constituent and triethyl aluminum are sent into described continuous horizontal type agitated bed Gas-phase reactor from first charging opening respectively, and mix with tetraethoxysilane, then pass into propylene, ethene and hydrogen from first charging opening, contact with said mixture and be polymerized; Be polymerized the mixture obtained then to contact with second, isobutyl dimethoxy silane, proceed polymerization, thus prepare propene polymer.
Table 4 lists the polymerization result of embodiment 39-50 and comparative example 13-17.
Table 4
*: dimethoxydiphenylsilane/tetra-butoxy silane
*: Cyclohexylmethyldimethoxysilane/tetramethoxy-silicane
Embodiment 51-62 is for illustration of olefin polymer according to the present invention and preparation method thereof.
Embodiment 51
The method identical with embodiment 39 is adopted to prepare propene polymer, unlike, use n-propyl Trimethoxy silane to replace tetraethoxysilane, and the mol ratio of second, isobutyl dimethoxy silane and n-propyl Trimethoxy silane is DB: DN=1: 39.
Embodiment 52-54
The method identical with embodiment 51 is adopted to prepare propene polymer, unlike, change the mol ratio of second, isobutyl dimethoxy silane and n-propyl Trimethoxy silane, be respectively: DB: DN=1: 19, DB: DN=1: 12, DB: DN=1: 9.
Embodiment 55
The method identical with embodiment 52 is adopted to prepare propene polymer, unlike, the pressure of reactor is 0.5MPa, and temperature is 40 DEG C, hydrogen/propylene ratio (H
2/ C
3) be 0 (mol/mol), ethylene/propene ratio (C
2/ C
3) be 0.001 (mol/mol).
Embodiment 56
The method identical with embodiment 52 is adopted to prepare propene polymer, unlike, the pressure of reactor is 4MPa, and temperature is 90 DEG C, hydrogen/propylene ratio (H
2/ C
3) be 0.1 (mol/mol), ethylene/propene ratio (C
2/ C
3) be 0.5 (mol/mol).
Embodiment 57
The method identical with embodiment 52 is adopted to prepare propene polymer, unlike, the pressure of reactor is 1.8MPa, and temperature is 60 DEG C, and reactor material level is 70%, hydrogen/propylene ratio (H
2/ C
3) be 0.02 (mol/mol), ethylene/propene ratio (C
2/ C
3) be 0.01 (mol/mol).
Embodiment 58
The method identical with embodiment 52 is adopted to prepare propene polymer, unlike, the pressure of reactor is 2.35MPa, and temperature is 70 DEG C, and reactor material level is 85%, hydrogen/propylene ratio (H
2/ C
3) be 0.08 (mol/mol), ethylene/propene ratio (C
2/ C
3) be 0.1 (mol/mol).
Embodiment 59 and 60
The method identical with embodiment 51 is adopted to prepare propene polymer, unlike, change the mol ratio of second, isobutyl dimethoxy silane and n-propyl Trimethoxy silane, be respectively: DB: DN=1: 1, DB: DN=1: 99.
Comparative example 18
The method identical with embodiment 51 is adopted to prepare propene polymer, unlike, do not use second, isobutyl dimethoxy silane, the add-on of n-propyl Trimethoxy silane makes Al/Si=20.
Embodiment 61 and 62
The method identical with embodiment 51 is adopted to prepare propene polymer, unlike, change the mol ratio of second, isobutyl dimethoxy silane and n-propyl Trimethoxy silane, be respectively: DB: DN=1: 0.67, DB: DN=1: 199.
Comparative example 19
The method identical with embodiment 51 is adopted to prepare propene polymer, unlike, n-propyl Trimethoxy silane and second, isobutyl dimethoxy silane are successively sent into continuous horizontal type agitated bed Gas-phase reactor from two charging openings, wherein, first charging opening and second charging opening are arranged along the axis of described continuous horizontal type agitated bed Gas-phase reactor, be benchmark along the travel direction of material in described continuous horizontal type agitated bed Gas-phase reactor, the distance that first charging opening is positioned at the initiating terminal of described continuous horizontal type agitated bed Gas-phase reactor is 8% place of the total length of described continuous horizontal type agitated bed Gas-phase reactor, and described first charging opening is for adding n-propyl Trimethoxy silane, the distance that described second charging opening is positioned at the initiating terminal of described continuous horizontal type agitated bed Gas-phase reactor is 75% of the total length of described first reactor, and described second charging opening is for adding second, isobutyl dimethoxy silane.
During polymerization, catalyst solid constituent and triethyl aluminum are sent into described continuous horizontal type agitated bed Gas-phase reactor from first charging opening respectively, and mix with n-propyl Trimethoxy silane, then pass into propylene, ethene and hydrogen from first charging opening, contact with said mixture and be polymerized; Be polymerized the mixture obtained then to contact with second, isobutyl dimethoxy silane, proceed polymerization, thus prepare propene polymer.
Table 5 lists the polymerization result of embodiment 51-62 and comparative example 18-19.
Table 5
Claims (13)
1. an olefine polymerizing process, under the method is included in olefin polymerization conditions, by olefin polymerization catalyst system and one or more olefins contact, described olefin polymerization catalyst system contains solid ingredient, external donor compound and organo-aluminium compound, described solid ingredient contains titanium, magnesium and internal electron donor compound, wherein, described external donor compound comprises the first external donor compound and the second external donor compound, described first external donor compound is second, isobutyl dimethoxy silane, described second external donor compound is n-propyl Trimethoxy silane, the mol ratio of described first external donor compound and the second external donor compound is 1:1-199.
2. method according to claim 1, wherein, the mol ratio of described first external donor compound and the second external donor compound is 1:1-99.
3. method according to claim 2, wherein, the mol ratio of described first external donor compound and the second external donor compound is 1:9-39.
4. method according to claim 1, wherein, the mol ratio of the titanium in the aluminium in described organo-aluminium compound and described solid ingredient is 20-2000:1, and the mol ratio of silicon total in the aluminium in described organo-aluminium compound and described external donor compound is 1-100:1.
5. the method according to claim 1 or 4, wherein, described solid ingredient is the reaction product of titanium compound, magnesium compound and internal electron donor compound.
6. method according to claim 5, wherein, described titanium compound is titanium tetrachloride; Described magnesium compound is magnesium chloride; Described internal electron donor compound is one or more in diisobutyl phthalate, n-butyl phthalate, n-propyl phthalate, diisopropyl phthalate, diethyl phthalate and dimethyl phthalate.
7. method according to claim 5, wherein, the mol ratio of described titanium compound, internal electron donor compound and magnesium compound is 0.01-0.5:0.01-50:1.
8. the method according to claim 1 or 4, wherein, described organo-aluminium compound is triethyl aluminum.
9. method according to claim 1, wherein, described contact is carried out in gas-phase polymerization reactor.
10. method according to claim 9, wherein, described gas-phase polymerization reactor is horizontal type agitated bed gas-phase polymerization reactor.
11. methods according to claim 1, wherein, described alkene is propylene, or is propylene and be selected from ethene, C
3-C
101-alkene and C
4-C
8diolefin in one or more comonomers.
12. methods according to claim 11, wherein, described contact is carried out in presence of hydrogen, and the mol ratio of described hydrogen and described propylene is 0.001-0.1:1.
13. methods according to claim 1, wherein, described olefin polymerization conditions comprises: temperature is 40-90 DEG C, and pressure is 0.5-4MPa.
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| CN104610478B (en) * | 2013-11-05 | 2017-07-25 | 中国石油化工股份有限公司 | A kind of catalyst for olefinic polyreaction |
| CN105294894B (en) * | 2015-11-14 | 2018-09-25 | 新***山子天利高新技术股份有限公司 | Superelevation flows narrow ditribution polypropylene and preparation method thereof |
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| CN110804117A (en) * | 2018-07-20 | 2020-02-18 | 中国科学院化学研究所 | Crosslinked ethylene-propylene copolymer and preparation method and application thereof |
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| CN114426607B (en) * | 2020-10-15 | 2024-02-13 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization, application of catalyst, olefin polymerization method and polymer |
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