CN104558336B - A kind of propylene copolymer and preparation method thereof - Google Patents
A kind of propylene copolymer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of the high ethylene content propylene copolymer of low energy consumption, this method uses gas phase multi-temperature zone technology, in the presence of the ziegler natta catalyst of high activity, and the second external electron donor is selectively added, propylene or propylene and ethene is carried out propylene homo and copolyreaction at least three continuous zones of convergency of one or more polymer reactors.The method of the invention uses gas phase multi-temperature zone technology, ensures most of polymerization activity of catalyst in low-temperature space, and the heat exchange efficiency of heat exchanger is improved in high-temperature region.In addition, selectively add the second external electron donor, the ingredient of solid catalyst of the titaniferous of second external electron donor and ziegler natta catalyst is coordinated, the ethene reactivity ratio in polymerisation can be effectively improved, ethylene concentration in reducing gas phase composition while guarantee product high ethylene contents, so as to the production capacity for reducing energy consumption, meeting existing apparatus.
Description
Technical field
The invention belongs to polypropylene production technical field, the high ethylene content propylene copolymer of more particularly to a kind of low energy consumption and
Its preparation method.
Background technology
Impact polypropylene product with high ethylene contents, have the rigidity of Noblen and resisting for EP rubbers component concurrently
Impact, there is good rigidity-toughness balanced, be widely used to the fields such as automobile, household electrical appliance and injection moulded containers.
Prepared by the polypropylene generally use multistep polymerization method of high ethylene contents, propylene homo is carried out in first reactor
Or random copolymerization obtains acrylic polymers, the copolymerization that next reactor carries out propylene and ethene is then sent to, third
Polymer of the generation based on ethylene-propylene random copolymer in the hole of alkene polymer particle.
At present, most impact polypropylene trades mark uses ethene as comonomer, and propylene-ethylene copolymerization is anti-
It should be carried out in Gas-phase reactor, and Gas-phase reactor is to remove system response heat by cooling/condensation of circulating air.
When producing high impact resistance polypropylene product, to improve the ethylene contents in product, ethene concentration in gas phase composition can be accordingly improved,
But ethene is a kind of fixed gas, the addition of a large amount of vinyl monomers can be greatly reduced the dew point of circulating air, it is difficult to cool down/condense,
Cause that efficiency of heat exchanger is low, load rise, and then cause device yield reduction, influence economic benefit.
Solves two methods of this problem generally use：First method is to improve the thermic load of circulating air heat exchanger, example
A heat exchanger with more high heat load is such as changed, or a heat exchanger of being connected after existing heat exchanger.But this scheme will
Increase expense is invested, and without the energy consumption level for reducing device.Another method is the reaction temperature by improving copolymerization stage
Degree（Higher than 80 DEG C）To improve the exchange capability of heat of circulating air heat exchanger, as Chinese patent CN1421468A, CN1288175C,
Method disclosed in CN1887917A, CN1887918A and CN100457790A, by increasing between the cold and hot medium of circulating air heat exchanger
The temperature difference, and then effectively improve the heat exchange efficiency of heat exchanger.But the drawbacks of this method is, conventional Zigler-Natta is urged
The rapid decay of agent activity at a temperature of higher than 80 DEG C, causes catalyst consumption cost to greatly improve.Therefore, it is necessary to find one
Kind method, the exchange capability of heat of copolymerization stage circulating air heat exchanger can be improved, reduces energy consumption, while do not increase being transformed into for device
Sheet and the cost of material of production.
The content of the invention
The invention aims to overcome in the prior art when preparing high ethylene content propylene copolymer, copolymerization stage
The defects of circulating air efficiency of heat exchanger is low, device yields poorly down, the consuming cost of raw materials for production is high, there is provided one kind can carry
The exchange capability of heat of high copolymerization stage circulating air heat exchanger, energy consumption is reduced, while do not increase improvement cost and the production of device again
The preparation method of cost of material and the high propylene copolymer of ethylene contents.
It is a further object of the present invention to provide the high ethylene content propylene copolymer that above-mentioned preparation method is prepared.
The invention provides a kind of preparation method of propylene copolymer, the described method comprises the following steps：
（1）Under the first alkene gas-phase polymerization reaction condition or the liquid-phase polymerization of olefins reaction condition, urged in metallocene
In the presence of agent, the first olefin feedstock is subjected to polymerisation, obtains the first polymerization reaction mixture, wherein, described first
Olefin feedstock is propylene or propylene and ethene；
（2）Under the conditions of the second alkene gas-phase polymerization reaction, in the presence of first polymerization reaction mixture, selection
Property add the second external electron donor, by the second olefin feedstock carry out polymerisation, obtain the second polymerization reaction mixture, wherein,
Second olefin feedstock is propylene and ethene；
（3）Under the conditions of alkatrienes gas phase polymerization, in the presence of second polymerization reaction mixture, by
Triolefin hydrocarbon feed carries out polymerisation, obtains propylene copolymer, wherein, the triolefin hydrocarbon feed is propylene and ethene；
Wherein, the temperature in the second alkene gas-phase polymerization reaction condition is less than the alkatrienes gas phase polymerization
Temperature in condition, and the temperature in the alkatrienes gas phase polymerization condition is 90-150 DEG C.
Present invention also offers the propylene copolymer being prepared according to the above method, ethene contains in the propylene copolymer
Measure as 8-30wt%.
The method of the invention uses gas phase multi-temperature zone technology, ensures most of polymerization activity of catalyst in low-temperature space,
The heat exchange efficiency of heat exchanger is improved in high-temperature region.In addition, step（2）And step（3）In, selectively add the second outer electron
Body, the ingredient of solid catalyst of second external electron donor and the titaniferous in ziegler natta catalyst are coordinated, can be with
Effectively improve step（2）And step（3）Polymerisation in ethene reactivity ratio, dropped while product high ethylene contents are ensured
Ethylene concentration in low gas phase composition, so as to the production capacity for reducing energy consumption, meeting existing apparatus.
According to the gas phase multi-temperature zone technology of the present invention and the method for external electron donor regulation and control comonomer reactivity ratio, using three
Step polymerization prepares the process of high ethylene content propylene copolymer, can effectively improve ethene reactivity ratio, reduce exchanger heat load.
In a kind of preferred embodiment of the present invention, due to using solids containing titanium catalytic component and tetrem using alkoxyl magnesium as carrier
TMOS is external electron donor, by（1）After walking propylene homo or propylene-ethylene random copolymerization, the（2）Step and the（3）
The propylene-ethylene copolyreaction of step is in the first external electron donor（Or second external electron donor）In the presence of, ethene reactivity ratio shows
Write and improve, the ethylene contents in gas phase composition can be reduced, so as to reduce energy consumption.In addition, the（2）The typical polymerization temperature of step
Condition can ensure most of polymerization activity of catalyst, the（3）The high temperature polymerization condition of step can further improve heat exchanger
Heat exchange efficiency, reduce energy consumption, the production capacity of expansion instrument.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of preparation method of the high ethylene content propylene copolymer of low energy consumption, this method is more using gas phase
Warm area technology, in the presence of the ziegler natta catalyst (Ziegler-Natta catalyst) of high activity, with propylene or propylene
It is that olefin feedstock carries out polymerisation with ethene, the polymerisation is at least three continuous one or more polymer reactors
The zone of convergency in carry out.Specifically, the described method comprises the following steps：
（1）Under the first alkene gas-phase polymerization reaction condition or the liquid-phase polymerization of olefins reaction condition, urged in metallocene
In the presence of agent, the first olefin feedstock is subjected to polymerisation, obtains the first polymerization reaction mixture, wherein, described first
Olefin feedstock is propylene or propylene and ethene；
（2）Under the conditions of the second alkene gas-phase polymerization reaction, in the presence of first polymerization reaction mixture, selection
Property add the second external electron donor, by the second olefin feedstock carry out polymerisation, obtain the second polymerization reaction mixture, wherein,
Second olefin feedstock is propylene and ethene；
（3）Under the conditions of alkatrienes gas phase polymerization, in the presence of second polymerization reaction mixture, by
Triolefin hydrocarbon feed carries out polymerisation, obtains propylene copolymer, wherein, the triolefin hydrocarbon feed is propylene and ethene；
Wherein, the temperature in the second alkene gas-phase polymerization reaction condition is less than the alkatrienes gas phase polymerization
Temperature in condition, and the temperature in the alkatrienes gas phase polymerization condition is 90-150 DEG C.
In the present invention, it is preferable that step（1）-（3）In polymerisation at least the three of one or more polymer reactors
Carried out in the individual continuous zone of convergency.
According to the present invention, step（1）-（3）In polymerisation at least two series connection polymer reactors in carry out, its
In, the first polymer reactor is first zone of convergency, and the second polymer reactor is divided into the zone of convergency of at least two series connection, extremely
It is respectively second zone of convergency and third polymerization region less；Step（1）Polymerisation carried out in first zone of convergency, it is and right
The form of polymer reactor does not have particular/special requirement；Step（2）With（3）Polymerisation respectively in second zone of convergency and trimerization
Close and carried out in region.Second polymer reactor is Gas-phase reactor, is preferably carried out in horizontal retort Gas-phase reactor, second
The different zones of convergency of polymer reactor have different reaction temperatures, identical or different gas phase composition.
In step（1）In, the first alkene gas-phase polymerization reaction condition or the liquid-phase polymerization of olefins reaction condition bag
Include：Temperature is 50-89 DEG C, preferably 60-80 DEG C；Pressure is 1-6MPa, preferably 2-5MPa；Time is 20-120 minutes, excellent
Elect 30-90 minutes as.
In step（2）In, the second alkene gas-phase polymerization reaction condition includes：Temperature is 50-89 DEG C, preferably 60-
80℃；Pressure is 1-5MPa, preferably 2-4MPa；Time is 20-60 minutes, preferably 30-50 minutes.
In step（3）In, the alkatrienes gas phase polymerization condition includes：Temperature is 90-150 DEG C, and temperature is higher,
More can lifting device condensing plant remove heat energy power, reduce equipment operation load, reduce energy consumption；But higher temperature can influence
The polymerization activity of polymerisation, with the rise of temperature, the ethylene contents and RCC2 of final products can decline, and therefore, be
Take into account condensing plant energy consumption and product ethylene contents, preferably 90-130 DEG C；Pressure is 1-5MPa, preferably 2-4MPa；When
Between be 20-60 minutes, preferably 30-50 minutes.
According to the present invention, step（1）-（3）In, the pressure is meter pressure.
In step（1）In, the additional proportion of the ziegler natta catalyst and the first olefin feedstock, the first olefin feedstock
The additional proportion of middle propylene and ethene, the mol ratio of hydrogen/propylene in gas phase is reacted, is such as not particularly limited, is that this area is normal
Rule selection, has no special requirements.Wherein, in liquid-phase system, the mol ratio of ethene and propylene is 0-0.08 in the first olefin feedstock；
In gas phase system, the mol ratio of ethene and propylene is 0-0.05, and the mol ratio for reacting hydrogen/propylene in gas phase is 0-0.03.
In step（2）In, the addition of second external electron donor and the addition of the second olefin feedstock, the second alkene
The additional proportion of propylene and ethene in raw material, the mol ratio of hydrogen/propylene in gas phase is reacted, is such as not particularly limited, is ability
Domain conventional selection, has no special requirements.Wherein, the addition of second external electron donor meets：（The solid catalyst of titaniferous
The molal quantity of component）：（The molal quantity of alkyl aluminum compound）：（The molal quantity of first external electron donor and the second external electron donor
Sum）Ratio be 1：5-500：0-500, preferably 1：25-100：25-100.Ethylene/propene rubs in second olefin feedstock
Your ratio is 0.2-0.5, and the mol ratio for reacting hydrogen/propylene in gas phase is 0-0.03.
In step（3）In, the addition of propylene and ethene in the addition and triolefin hydrocarbon feed of the triolefin hydrocarbon feed
Ratio, the mol ratio of hydrogen/propylene in gas phase is reacted, is such as not particularly limited, is this area conventional selection, nothing is important to
Ask.Wherein, triolefin hydrocarbon feed is that the mol ratio of ethylene/propene is 0.2-0.5, reacts the mol ratio of hydrogen/propylene in gas phase
For 0-0.03.
In the method for the invention, the Ziegler-Natta catalyst can be selected published in the prior art
Ziegler-Natta catalyst.Preferably, the Ziegler-Natta catalyst contains：
（1）The ingredient of solid catalyst of titaniferous, the ingredient of solid catalyst of the titaniferous is alkoxyl magnesium compound, titanizing
Compound and the catalytic product of internal electron donor compound；
（2）Alkyl aluminum compound；And
（3）The first optional external electron donor；
Wherein, the ingredient of solid catalyst of the titaniferous, the alkyl aluminum compound and first external electron donor
Mol ratio is 1：5-500：0-500, preferably 1：25-100：25-100.
Ziegler-Natta catalyst component of the present invention（1）In the ingredient of solid catalyst of titaniferous,
Described titanium compound can be selected from formula（Ⅰ）Ti(OR)4-nXnAt least one of compound, the R choosings in formula
The aryl that the aliphatic group or carbon number for being 1-14 from carbon number are 7-14, X are halogen atom, and n is selected from 0 to 4 integer；
When n is less than or equal to 2, existing multiple R can be with identical or different.The halogen atom can be chlorine, bromine or iodine.Specifically
, the titanium compound is selected from tetraalkoxy titanium, titanium tetrahalide, three alkyl groups in the halogenalkoxy titaniums, dihalo- dialkoxy titanium and the alkane of single halogen three
At least one of epoxide titanium.More specifically, the tetraalkoxy titanium is selected from titanium tetramethoxide, purity titanium tetraethoxide, four positive third
In epoxide titanium, tetraisopropoxy titanium, four titanium n-butoxides, four isobutoxy titaniums, four cyclohexyloxy titaniums, four phenoxide titaniums at least
It is a kind of；Described titanium tetrahalide is selected from least one of titanium tetrachloride, titanium tetrabromide, titanium tetra iodide；Three described alkyl halide oxygen
Base titanium is in trichloromethoxy titanium, tri-chloroethoxy titanium, trichlorine titanium propanolate, trichlorine titanium n-butoxide, tribromo ethanolato-titanium
At least one；Described dihalo- dialkoxy titanium is selected from dichloro dimethoxy titanium, dichlorodiethyl epoxide titanium, positive third oxygen of dichloro two
At least one of base titanium, dichloro diisopropoxy titanium, dibromo diethoxy titanium；Described single halogen tri-alkoxy titanium is selected from a chlorine
At least one of trimethoxy titanium, a chlorine triethoxy titanium, the positive propoxy titanium of a chlorine three, the titanium isopropoxide of a chlorine three；It is preferred that
Ground, the titanium compound are titanium tetrahalide compound, particularly preferably titanium tetrachloride.
Described alkoxyl magnesium compound can be selected from formula（Ⅱ）Mg(OR1)2-m(OR2)mCompound at least one
Kind, wherein, R1And R2One kind that is identical or different, being respectively selected from the straight or branched alkyl that carbon number is 1-8, it is excellent respectively
Methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, n-hexyl, (2- ethyls) hexyl are elected as, it is further preferred that R1For second
Base, R2For (2- ethyls) hexyl；0≤m≤2, it is preferable that 0.001≤m≤0.5, it is further preferred that 0.001≤m≤0.25,
Most preferably, 0.001≤m≤0.1.It is emphasized that alkoxyl magnesium represented by formula, illustrate only the composition of each alkoxy
Content, i.e. mol ratio, not fully represent the concrete structure of alkoxyl magnesium.
Described alkoxyl magnesium compound outward appearance is spherical, and average grain diameter (D50) is 10-150um, preferably 15-
100um, more preferably 18-80um；Its particle diameter distribution index SPAN<1.1, preferable particle size profile exponent SPAN<1.05, wherein,
SPAN calculation formula is following (V)：
SPAN=（D90-D10）/D50 (V)
In formula (V), D90 is represented to correspond to the particle diameter that accumulating weight divides rate to be 90%, and D10 is represented corresponding to accumulating weight point
Rate is 10% particle diameter, and D50 represents that corresponding accumulating weight divides the particle diameter that rate is 50%.
According to alkoxyl magnesium compound of the present invention, it is preferable that using the alcohol as corresponding to magnesium metal, alkoxy and mix
Closing halogenating agent, back flow reaction is prepared under an inert atmosphere.Wherein mol ratio of the magnesium metal with mixing the halogen atom in halogenating agent
For 1：0.0002-1：0.2, preferably 1：0.001-1：0.08；The weight of alcohol and magnesium ratio is 4：1-50：1, preferably 6：1-25：1.Institute
Reaction is stated to carry out between 0 DEG C to reaction system of reflux temperature.Preferably, the reaction temperature is the backflow temperature of reaction system
Degree.The time of the reaction is 2-30 hours.
The mixing halogenating agent is the combination of halogen and halogen compounds, and the halogen and halogen compounds are non-limiting
Selection：Iodine, bromine, chlorine, magnesium chloride, magnesium bromide, magnesium iodide, potassium chloride, KBr, KI, calcium chloride, calcium bromide, calcium iodide,
Mercury chloride, mercuric bromide, mercuric iodixde, ethyoxyl magnesium iodide, methoxyl group magnesium iodide, isopropyl magnesium iodide, hydrogen chloride, chloracetyl chloride
Deng.It is preferred that the combination of iodine and magnesium chloride.The weight of iodine and magnesium chloride ratio is preferably 1：0.02-1：20, more preferably 1：0.1-1：
10。
Described inert atmosphere, including blanket of nitrogen, argon atmospher etc., preferably blanket of nitrogen.
Described internal electron donor compound includes aliphatic series and Arrcostab, aliphatic series and the aromatic polycarboxylic acid of aromatic monocarboxylate
Arrcostab, aliphatic ether, the one or more in cyclic aliphatic ether and aliphatic ketone；It preferably is selected from the alkyl of C1-C4 aliphatic saturated monocarboxylic acids
Ester, the Arrcostab of C7-C8 aromatic carboxylic acids, C2-C6 aliphatic ethers, C3-C4 cyclic ethers, C3-C6 saturated fats ketone, 1,3- diether compounds
At least one of.
Preferably, above-mentioned interior electronq donor compound can be formula（Ⅲ）Shown phthalate compound,
Formula（III）In, R4And R5Identical or different, respectively carbon number is 1-12 straight or branched alkyl, carbon atom
One kind in number 3-10 cycloalkyl and carbon number 6-20 alkaryl, substitution or unsubstituted aryl.R6、R7、R8And R9Entirely
Portion is hydrogen；Or wherein three are hydrogen, the straight or branched alkyl and carbon atom that another is halogen, carbon number is 1-4
Number is one kind in 1-4 straight or branched alkoxyl.The internal electron donor compound be preferably diethyl phthalate,
N-butyl phthalate, diisobutyl phthalate, DHP, dibutyl phthalate (DHP), adjacent benzene
Diformazan di-isooctyl etc..
Described internal electron donor compound is also selected such as formula（IV）Shown 1,3- diether compounds,
Formula（IV）Middle R10And R11It is identical or different, it is each independently selected from the straight or branched alkane that carbon number is 1-12
One kind in base, the alkaryl of carbon number 3-10 cycloalkyl and carbon number 6-20, substitution or unsubstituted aryl；R13With
R14It is identical or different, it is each independently selected from the straight or branched alkyl that carbon number is 1-10；R12And R15It is identical or different,
The one kind being each independently selected from hydrogen and carbon number 1-10 straight or branched alkyl, optionally, R12、R13、R14And R15Base
One or more of group arbitrarily links up cyclization.Specifically compound is：2- isopropyl -2- isopentyl -1,3- dimethoxies
Base propane, 9,9- bis-（Methoxy）Fluorenes, 2- isobutyl group -2- isopropyl -1,3- dimethoxy propanes, 2,2- bicyclopentyls two
Methoxy propane, 2,2- diphenyl -1,3- dimethoxy propanes, 2- isobutyl group -2- isopropyl -1,3- dimethoxy propanes, 2,
2- bicyclopentyl -1,3- dimethoxy propanes, 2,2- diisobutyl -1,3- dimethoxy propanes etc..
According to the ingredient of solid catalyst of titaniferous of the present invention, can be made by the method for following steps：By alcoxyl
Base magnesium compound, is reacted in the presence of inert diluent with internal electron donor compound and titanium compound；By above-mentioned reaction
Obtained solids is washed to obtain the ingredient of solid catalyst of the titaniferous with atent solvent.
In the preparation method of the ingredient of solid catalyst of the titaniferous, the dosage of the titanium compound is relative to alkoxyl magnesium
The mol ratio of magnesium in compound is（0.5~100）:1, be preferably（1~50）:1.The dosage of the internal electron donor compound
Mol ratio relative to magnesium in alkoxyl magnesium compound is (0.005~10):1, be preferably（0.01~1）：1.The inertia is dilute
The dosage of agent is released relative to the mol ratio of the magnesium in alkoxyl magnesium compound（0.5~100）:1, be preferably（1~50）:1.It is preferred that
Inert diluent is toluene.Reaction temperature is -40~200 DEG C, is preferably -20~150 DEG C；Reaction time is 1 minute~20 small
When, preferably 5 minutes~8 hours.
The atent solvent can be selected from C6~C10 alkane or at least one of aromatic hydrocarbons, preferred hexane, heptane, pungent
At least one of alkane, decane, benzene,toluene,xylene or derivatives thereof etc..
According to the preparation of the ingredient of solid catalyst of titaniferous of the present invention, alkoxyl magnesium compound, internal electron donor
There is no particular limitation for the addition sequence of compound, atent solvent and titanium compound, such as can make in the presence of atent solvent
Each composition mixing, can also dilute each composition with atent solvent in advance mixes them.It is also no special for the number of mixing
Restriction, can mix once, can also mix repeatedly.
According to the preparation of the ingredient of solid catalyst of titaniferous of the present invention, preferably washing is hexane with atent solvent.It is right
In the method for washing, there is no particular limitation, the mode such as is preferably decanted, filters.The usage amount of atent solvent, wash time, washing
Number is not particularly limited, for the magnesium in 1 mole of alkoxyl magnesium compound usually using 1-1000 moles, preferably 10-
500 moles of solvent, generally wash 1-24 hours, preferably 6-10 hours.In addition from the homogeneity of washing and the side of detersive efficiency
Face is set out, and is preferably stirred in washing operation.
Component in catalyst of the present invention（2）It is that formula is (VI) AlRnX3-nAlkyl aluminum compound, R is in formula (VI)
Hydrogen or carbon number are 1-20 alkyl, and X is halogen, n 1<The number of n≤3；Specifically it may be selected from triethyl aluminum, tri-propyl aluminum, three
N-butylaluminum, triisobutyl aluminium, tri-n-octylaluminium, triisobutyl aluminium, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, a chlorine two
At least one of aluminium ethide, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium, ethyl aluminum dichloride, preferably triethyl aluminum or three
Aluminium isobutyl.
Component in catalyst of the present invention（3）The first external electron donor can be known various outer electrons in the industry
Body, it is not particularly limited.Preferred formula（VII）Shown organo-silicon compound,
R1''m''R2''n''Si(OR3'')4-m''-n''（VII）
Formula（VII）In, R1' ' and R2' ' it is identical or different, respectively halogen, hydrogen atom, carbon number be 1-20 alkyl,
One in the haloalkyl that the aryl and carbon number that cycloalkyl that carbon number is 3-20, carbon number are 6-20 are 1-20
Kind；R3' ' be carbon number be 1-20 alkyl, carbon number be 3-20 cycloalkyl, carbon number be 6-20 aryl and carbon
Atomicity is one kind in 1-20 haloalkyl；M'' and n'' is respectively 0-3 integer, and m''+n''<4.The organosilicon
Compound can be trimethylmethoxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, isopropyl
Isobutyl group dimethoxysilane, di-t-butyl dimethoxysilane, tertbutyl methyl dimethoxysilane, t-butylethyl diformazan
TMOS, tert-butyl group propyldimethoxy-silane, ter /-butylisopropyl dimethoxysilane, cyclohexyl methyl dimethoxy silicon
Alkane, Dicyclohexyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane, cyclopentyl-methyl dimethoxysilane, ring penta
It is base ethyldimethoxysilane, dicyclopentyl dimethoxyl silane, cyclopentyl cyclohexyl dimethoxysilane, double（2- methyl rings
Amyl group）Dimethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyl triethoxysilane, methyl
Trimethoxy silane, MTES, ethyl trimethoxy silane, propyl trimethoxy silicane, isopropyl trimethoxy
Base silane, butyl trimethoxy silane, butyl triethoxysilane, trimethoxysilane, amyltrimethoxysilane,
Isopentyl trimethoxy silane, cyclopentyl-trimethoxy-silane, cyclohexyl trimethoxy silane, dimethoxydiphenylsilane,
Diphenyl diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, n-propyl trimethoxy silane, ethene
One or more in base trimethoxy silane, tetramethoxy-silicane, tetraethoxysilane, four butoxy silanes.These are organic
Silicon compound can be used individually, and two or more can also be applied in combination.It is furthermore preferred that given outside described first
Electron contains dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, hexamethylene
In ylmethyl dimethoxysilane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, tetraethoxysilane
At least one, wherein with diisopropyl dimethoxy silane, tetraethoxysilane best results.
If the first external electron donor of the ziegler natta catalyst of selection is not suitable for step（1）In polymerisation
（Propylene homo or propylene-ethylene random copolymerization reaction）Be advantageous to step it is required that can be used（1）The first external electron donor, such as：
First external electron donor is the good external electron donor of vertical structure directional properties, meanwhile, in step（2）With（3）Middle selectivity adds
Enter the second external electron donor, the addition of second external electron donor meets：（Mole of the ingredient of solid catalyst of titaniferous
Number）：（The molal quantity of alkyl aluminum compound）：（The sum of the molal quantity of first external electron donor and the second external electron donor）Ratio
For 1：5-500：0-500, preferably 1：25-100：25-100.Change the first external electron donor or the second external electron donor with
Major catalyst（That is the ingredient of solid catalyst of titaniferous）Coordinated, to improve the ethene reactivity ratio in gas phase copolymerization.The
Two external electron donors can also be that others have substantially to ethene reactivity ratio in addition to the first above-mentioned external electron donor species
The material of effect, such as at least one of chloroform, diethyl zinc.
Ziegler-Natta catalyst of the present invention uses special alkoxyl magnesium component, has the catalyst
The polymerization of unique suitable high temperature polymerization condition, such as：Reactivity is high and release is steady, segments the advantages that reducing.
Present invention also offers the high ethylene content propylene copolymer prepared according to the above method, in the propylene copolymer
Ethylene contents are 8-30wt%.
The present invention will be described in detail by way of examples below.
The relevant data of polymer are obtained by following test method in embodiment：
1. ethene and RCC2 contents：Thermo Nicolet200 type infrared spectrum analysers, 720-730cm-1The peak area pair at place
Answer total ethylene contents；730-740cm-1The peak area at place corresponds to free state ethylene contents, 720cm-1、727cm-1、729cm-1Place
Peak area is correspondingly copolymerized state ethylene contents, and the two ratio is RCC2.
2. bending modulus：Measured according to ASTM D790-97.
3. tensile strength：Measured according to ASTM D638-00.
4. Izod impact strengths：Measured according to ASTM D256-00.
5. the Ti content in catalyst is tested with 721 spectrophotometers.
6. the grain size of dialkoxy magnesium and catalyst, size distribution are swashed with Malvern Mastersizer TM2000
Optical diffraction method measures, and n-hexane is dispersant（Wherein, SPAN=（D90-D10）/D50）.
7. the measure of the m values in carrier：0.1 gram of carrier is taken, adds 10mL1.2mol/L aqueous hydrochloric acid solutions, is shaken 24 hours
Make its decomposition, ethanol therein and 2-Ethylhexyl Alcohol are quantified using gas-chromatography, m values are then calculated as follows：
In formula, w1 is 2-Ethylhexyl Alcohol quality, and w2 is ethanol quality.
8. in catalyst component for olefin polymerization internal electron donor content be measured using Waters600E liquid chromatograies or
Gas Chromatographic Determination.
9. chilling liquid spray flux is the data read from polyplant on chilling nozzle for liquid flowmeter.
10. dew point is the temperature of circulating air heat exchanger exit, can directly read in the controls.
Preparation example：
This preparation example is used for preparing the solids containing titanium catalysis in the high activity Ziegler-Natta catalyst that the present invention uses
Agent component.
After the 16L voltage-resistant reactors with agitator are sufficiently displaced from nitrogen, added into reactor 10L ethanol,
300mL2- ethyl hexanols, 11.2g iodine, 8g magnesium chlorides and 640g magnesium powders.Stirring makes system back flow reaction simultaneously, until there is no
Untill hydrogen is discharged.Stop reaction, washed with 3L ethanol, filtering, dried.Obtained dialkoxy-magnesium support.Gained dialkoxy
Base magnesium carrier D50=30.2um, Span value 0.81, m values 0.015.Above-mentioned dialkoxy-magnesium support 650g and toluene 3250mL is taken to match somebody with somebody
Suspension is made.In the pressure-resistant reactors of 16L of displacement are repeated by high pure nitrogen, toluene 2600mL and titanium tetrachloride are added
3900mL, 80 DEG C are warming up to, then added the suspension prepared in kettle, constant temperature 1 hour, add diethyl phthalate
130mL, 110 DEG C are to slowly warm up to, constant temperature 2 hours, press filtration obtains solid content.Gained solid content adds toluene 5070mL and four chlorinations
Titanium 3380mL mixed liquor is processed as 3 times in 110 DEG C of stir process 1 hour.Press filtration, the solid of gained wash 4 with hexane
It is secondary, each 6000mL, press filtration, drying, produce the ingredient of solid catalyst of titaniferous.Titanium in the ingredient of solid catalyst of gained titaniferous
Atom content 2.4wt%, diethyl phthalate content 10.5wt%.
Embodiment 1：
The present embodiment is used for the preparation method for illustrating the high ethylene content propylene copolymer of low energy consumption of the present invention.
1）Raw material
The ingredient of solid catalyst of the titaniferous obtained in preparation example is major catalyst；Triethyl aluminum is used as co-catalyst；Four
Ethoxysilane（T-Doner）As the first external electron donor；Propylene, ethene and hydrogen are polymer grade, are made after removing water, oxygen
With hexane uses after dehydration.
2）Experimental rig
Using the polymerization technique of two horizontal retort Gas-phase reactor series connection.0.2 cubic metre of horizontal retort Gas-phase reactor volume,
Agitating paddle is T-shaped oblique blade, and angle of inclination is 10 degree, and mixing speed is 100 revs/min.
3）Experimental condition
The（1）Walk gas-phase propene homopolymerization：In the Gas-phase reactor of horizontal retort first（A referred to as area）Addition major catalyst,
Triethyl aluminum, the first external electron donor and propylene, polymerisation is carried out, wherein, major catalyst, triethyl aluminum, first are outside to electricity
The inlet amount of daughter is respectively 0.9g/hr, 0.072mol/hr, 0.012mol/hr, Al/Si (mol/mol)=6.0；Propylene feed
Measure as 15kg/hr；It is 0.0297 to react hydrogen/propylene molar ratio in gas phase；The temperature of polymerisation is 66 DEG C, and pressure is
2.3MPa, time are 60 minutes, obtain the first polymerization reaction mixture；
The（2）Walk the normal temperature gas-phase copolymerization of propylene and ethene：The second polymeric area in the Gas-phase reactor of horizontal retort second
In domain（Referred to as 2nd area）, in the presence of first polymerization reaction mixture, ethene and propylene are added, polymerize instead
Should, ethene and propylene feed amount are respectively 3.6kg/hr, 15kg/hr, and ethylene/propene mol ratio is 0.36；React hydrogen in gas phase
Gas/propylene molar ratio is 0.0094；The temperature of polymerisation is 66 DEG C, pressure 2.3MPa, and the time is 40 minutes, obtains second
Polymerization reaction mixture；
The（3）Walk the high temperature gas-phase copolymerization of propylene and ethene：Third polymerization zone in the Gas-phase reactor of horizontal retort second
In domain（Referred to as 3rd area）, in the presence of second polymerization reaction mixture, ethene and propylene are added, polymerize instead
Should, ethene and propylene feed amount are respectively 3.6kg/hr, 15kg/hr, and ethylene/propene mol ratio is 0.36；React hydrogen in gas phase
Gas/propylene molar ratio is 0.0094, and the temperature of polymerisation is 95 DEG C, pressure 2.3MPa, and the time is 40 minutes, obtains Gao Yi
Alkene content propylene copolymer.
Concrete technology condition is shown in Table 1.
4）Result of the test
The long run test of 48 hours has been carried out according to above-mentioned condition, device stable operation, the polymer that reaction obtains has been entered
Row analysis test, is as a result listed in table 1.
Embodiment 2：
The present embodiment is used for the preparation method for illustrating the high ethylene content propylene copolymer of low energy consumption of the present invention.
1）Raw material
Diisopropyl dimethoxy silane（P-Doner）As the first external electron donor, the other the same as in Example 1.
2）Experimental rig, with embodiment 1.
3）Experimental condition, with embodiment 1.
4）Result of the test
The long run test of 48 hours has been carried out according to above-mentioned condition, device stable operation, the polymer that reaction obtains has been entered
Row analysis test, is as a result listed in table 1.
Embodiment 3：
The present embodiment is used for the preparation method for illustrating the high ethylene content propylene copolymer of low energy consumption of the present invention.
1）Raw material, with embodiment 1.
2）Experimental rig, with embodiment 1.
3）Experimental condition
The（1）Gas-phase propene homopolymerization is walked with embodiment 1；
The（2）The normal temperature gas-phase copolymerization of propylene and ethene is walked with embodiment 1；
The（3）Walk the high temperature gas-phase copolymerization of propylene and ethene：Reaction temperature is 110 DEG C, pressure 2.3MPa, the time 40
Minute；Other conditions are the same as embodiment 1；
4）Result of the test
The long run test of 48 hours has been carried out according to above-mentioned condition, device stable operation, the polymer that reaction obtains has been entered
Row analysis test, is as a result listed in table 1.
Embodiment 4：
The present embodiment is used for the preparation method for illustrating the high ethylene content propylene copolymer of low energy consumption of the present invention.
1）Raw material, with embodiment 1.
2）Experimental rig, with embodiment 1.
3）Experimental condition
The（1）Gas-phase propene homopolymerization is walked with embodiment 1；
The（2）The normal temperature gas-phase copolymerization of propylene and ethene is walked with embodiment 1；
The（3）Walk the high temperature gas-phase copolymerization of propylene and ethene：Reaction temperature is 125 DEG C, pressure 2.3MPa, the time 40
Minute；Other conditions are the same as embodiment 1；
4）Result of the test
The long run test of 48 hours has been carried out according to above-mentioned condition, device stable operation, the polymer that reaction obtains has been entered
Row analysis test, is as a result listed in table 1.
Embodiment 5：
The present embodiment is used for the preparation method for illustrating the high ethylene content propylene copolymer of low energy consumption of the present invention.
1）Raw material, with embodiment 1.
2）Experimental rig, with embodiment 1.
3）Experimental condition
The（1）Walk gas-phase propene-ethylene random copolymerization：Ethene and propylene feed amount are respectively 0.2kg/hr, 15kg/hr,
Ethylene/propene mol ratio is 0.02；Other conditions are the same as embodiment 1；
The（2）Walk the normal temperature gas-phase copolymerization of propylene and ethene：With embodiment 1；
The（3）Walk the high temperature gas-phase copolymerization of propylene and ethene：With embodiment 1.
4）Result of the test
The long run test of 48 hours has been carried out according to above-mentioned condition, device stable operation, the polymer that reaction obtains has been entered
Row analysis test, is as a result listed in table 1.
Embodiment 6：
The present embodiment is used for the preparation method for illustrating the high ethylene content propylene copolymer of low energy consumption of the present invention.
1）Raw material, with embodiment 1.
2）Experimental rig, with embodiment 1.
3）Experimental condition
The（1）Walk gas-phase propene homopolymerization：Major catalyst, triethyl aluminum, the first external electron donor B-Doner inlet amount point
Not Wei 0.9g/hr, 0.072mol/hr, 0.006mol/hr, Al/Si (mol/mol)=12.0；Other conditions are the same as embodiment 1；
The（2）Walk the normal temperature gas-phase copolymerization of propylene and ethene：Second external electron donor T-Doner inlet amount is
0.006mol/hr；Other conditions are the same as embodiment 1；
The（3）Walk the high temperature gas-phase copolymerization of propylene and ethene：Condition is the same as embodiment 1.
4）Result of the test
The long run test of 48 hours has been carried out according to above-mentioned condition, device stable operation, the polymer that reaction obtains has been entered
Row analysis test, is as a result listed in table 1.
Comparative example 1：
1）Raw material
Second, isobutyl dimethoxy silane（B-Doner）As the first external electron donor, the other the same as in Example 1.
2）Experimental rig, with embodiment 1.
3）Experimental condition, with embodiment 1.
4）Result of the test
The long run test of 48 hours has been carried out according to above-mentioned condition, device stable operation, the polymer that reaction obtains has been entered
Row analysis test, is as a result listed in table 1.
Comparative example 2：
1）Raw material, with embodiment 1.
2）Experimental rig, with embodiment 1.
3）Experimental condition
The not subdivided zone of convergency of second Gas-phase reactor, by（2）Step and the（3）The multi-temperature zone polymerization methodses of step change often
Equally distributed 66 DEG C of the temperature of rule, the other the same as in Example 1.
4）Result of the test
The long run test of 48 hours has been carried out according to above-mentioned condition, device stable operation, the polymer that reaction obtains has been entered
Row analysis test, is as a result listed in table 1.
As can be seen from Table 1, the test data of embodiment 1, embodiment 2 and comparative example 1 is mainly reflected outside difference first
Influence of the electron donor to ethene reactivity ratio and plant energy consumption.The second of copolymerization stage is dilute with propylene mole in second Gas-phase reactor
Than under same case, the ethylene contents in product in ethylene contents and rubber phase change with the modulation of the first external electron donor,
Wherein, P-Doner and T-Doner ethylene contents illustrate that ethene exists in P-Doner and T-Doner apparently higher than B-Doner
Under reactivity ratio it is higher.If in product in the case of ethylene contents identical, P-Doner and T-Doner will require than B-Doner
Second is dilute low with propylene mol ratio in gas phase composition, and the reduction of on-condensible gas content will reduce the energy consumption of the condensing plant of device.
It is cold to device in the gas-phase copolymerization stage that the test data of embodiment 1 and comparative example 2 mainly reflects multi-temperature zone technology
The energy consumption of solidifying equipment.When the first external electron donor of addition is identical, second Gas-phase reactor is divided into embodiment 1
Second zone of convergency and third polymerization region, employ multi-temperature zone technology, and the chilling liquid spray flux of copolymerization stage substantially compares ratio
Example 2 is lacked, and illustrates that multi-temperature zone technology can effectively reduce the operating load of device condensing plant, so as to reduce energy consumption.
The test data of embodiment 1,3,4 mainly reflects the different polymerization temperatures of multi-temperature zone technology to device condensing plant
Energy consumption.With the lifting of two area's temperature, the chilling liquid spray flux of copolymerization stage is greatly reduced, and illustrates higher polymerization temperature
What degree was capable of lifting device condensing plant removes heat energy power, equipment operation load is reduced, so as to reduce energy consumption.But at the same time, compared with
High copolymerization temperature can influence the polymerization activity in the stage, be shown from data, with the rise of temperature, ethylene contents and RCC2 meetings
It is slightly decreased.Therefore, three area's polymerization temperatures should be according to needs of production, between condensing plant energy consumption and product ethylene contents
Choose the scheme optimized.
The test data of embodiment 1 and embodiment 5 illustrates, when the first step is polymerized to ethylene-propylene random copolymerization, product
Ethylene contents be significantly higher, but its rigidity can decline, and bending modulus reduces.
The test data of embodiment 1 and embodiment 6 illustrates, when the addition of the first external electron donor is advantageous to improve area production
When the addition of the isotacticity of product, the second external electron donor is advantageous to improve the ethene reactivity ratio of copolymerization stage, final products can
Take into account the rigidity and shock resistance of material.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (25)
1. a kind of preparation method of propylene copolymer, it is characterised in that the described method comprises the following steps：
(1) under the first alkene gas-phase polymerization reaction condition or the liquid-phase polymerization of olefins reaction condition, in ziegler natta catalyst
In the presence of, the first olefin feedstock is subjected to polymerisation, obtains the first polymerization reaction mixture, wherein, first alkene
Raw material is propylene or propylene and ethene；
(2) under the conditions of the second alkene gas-phase polymerization reaction, in the presence of first polymerization reaction mixture, selectivity adds
Enter the second external electron donor, the second olefin feedstock is subjected to polymerisation, obtains the second polymerization reaction mixture, wherein, it is described
Second olefin feedstock is propylene and ethene；
(3) under the conditions of alkatrienes gas phase polymerization, in the presence of second polymerization reaction mixture, by triolefin
Hydrocarbon feed carries out polymerisation, obtains propylene copolymer, wherein, the triolefin hydrocarbon feed is propylene and ethene；
Wherein, the temperature in the second alkene gas-phase polymerization reaction condition is less than the alkatrienes gas phase polymerization condition
In temperature, and the temperature in the alkatrienes gas phase polymerization condition be 90-150 DEG C；
Wherein, the ziegler natta catalyst contains：
(1) ingredient of solid catalyst of titaniferous, the ingredient of solid catalyst of the titaniferous is alkoxyl magnesium compound, titanium compound
With the catalytic product of internal electron donor compound；
(2) alkyl aluminum compound；And
(3) first external electron donors；
Wherein, mole of the ingredient of solid catalyst of the titaniferous, the alkyl aluminum compound and first external electron donor
Than for 1：25-100：25-100；
Wherein, described alkoxyl magnesium compound is selected from formula M g (OR1)2-m(OR2)mAt least one of compound, wherein,
R1And R2One kind that is identical or different, being respectively selected from the straight or branched alkyl that carbon number is 1-8；0.001≤m≤0.5；
Wherein, first external electron donor is general formula R1”m”R2”n”Si(OR3”)4-m”-n”Shown organo-silicon compound, wherein,
R1" and R2" identical or different, the cycloalkanes that alkyl that respectively halogen, hydrogen atom, carbon number are 1-20, carbon number are 3-20
One kind in the haloalkyl that the aryl and carbon number that base, carbon number are 6-20 are 1-20；R3" it is that carbon number is 1-20
Alkyl, carbon number be 3-20 cycloalkyl, carbon number be 6-20 aryl and carbon number be 1-20 haloalkyl
In one kind；M " and n " is respectively 0-3 integer, and m "+n "<4；
Wherein, the second external electron donor described in step (2) is first external electron donor or is in chloroform, diethyl zinc
At least one.
2. according to the method for claim 1, wherein, the polymerisation in step (1)-(3) is anti-in one or more polymerization
Answer and carried out at least three continuous zones of convergency of device.
3. according to the method for claim 2, wherein, the polymerisation in step (1)-(3) is in the poly- of at least two series connection
Close and carried out in reactor, wherein, the first polymer reactor is first zone of convergency, and the second polymer reactor is divided at least two
The zone of convergency of series connection, at least respectively second zone of convergency and third polymerization region；The polymerisation of step (1) is poly- first
Close and carried out in region, the polymerisation of step (2) and (3) is carried out in second zone of convergency and third polymerization region respectively.
4. according to the method for claim 1, wherein, in step (1), the first alkene gas-phase polymerization reaction condition or
The liquid-phase polymerization of olefins reaction condition includes：Temperature is 50-89 DEG C, pressure 1-6MPa, and the time is 20-120 minutes.
5. the method according to claim 11, wherein, the first alkene gas-phase polymerization reaction condition or the olefin liquid phase
Polymeric reaction condition includes：Temperature is 60-80 DEG C, pressure 2-5MPa, and the time is 30-90 minutes.
6. the method according to claim 11, wherein, in step (2), the second alkene gas-phase polymerization reaction condition bag
Include：Temperature is 50-89 DEG C, pressure 1-5MPa, and the time is 20-60 minutes.
7. according to the method for claim 6, wherein, the second alkene gas-phase polymerization reaction condition includes：Temperature is 60-
80 DEG C, pressure 2-4MPa, the time is 30-50 minutes.
8. the method according to claim 11, wherein, in step (3), the alkatrienes gas phase polymerization condition bag
Include：Temperature is 90-150 DEG C, pressure 1-5MPa, and the time is 20-60 minutes.
9. according to the method for claim 8, wherein, the alkatrienes gas phase polymerization condition includes：Temperature is 90-
130 DEG C, pressure 2-4MPa, the time is 30-50 minutes.
10. the method according to claim 11, wherein, R1And R2Respectively methyl, ethyl, propyl group, isopropyl, butyl, different
Butyl, n-hexyl, (2- ethyls) hexyl.
11. the method according to claim 11, wherein, R1For ethyl, R2For (2- ethyls) hexyl.
12. the method according to claim 11, wherein, 0.001≤m≤0.25.
13. the method according to claim 11, wherein, 0.001≤m≤0.1.
14. according to the method for claim 1, wherein, described titanium compound is selected from formula Ti (OR)4-nXnCompound in
At least one, wherein, R is selected from the aryl that the aliphatic group that carbon number is 1-14 or carbon number are 7-14, and X is that halogen is former
Son, n are selected from 0 to 4 integer；When n is less than or equal to 2, existing multiple R are identical or different.
15. according to the method for claim 14, wherein, described titanium compound is selected from tetraalkoxy titanium, titanium tetrahalide, three
At least one of alkyl groups in the halogenalkoxy titanium, dihalo- dialkoxy titanium and single halogen tri-alkoxy titanium.
16. according to the method for claim 1, wherein, described internal electron donor compound includes aliphatic series and aromatics list carboxylic
One or more in the Arrcostab of acid, the Arrcostab of aliphatic series and aromatic polycarboxylic acid, aliphatic ether and aliphatic ketone.
17. according to the method for claim 1, wherein, described internal electron donor compound includes cyclic aliphatic ether.
18. according to the method for claim 16, wherein, the internal electron donor compound is selected from C1-C4 saturated fat carboxylics
Arrcostab, Arrcostab, C2-C6 aliphatic ethers, C3-C4 cyclic ethers, C3-C6 saturated fats ketone and the 1,3- of C7-C8 aromatic carboxylic acids of acid
At least one of diether compounds.
19. according to the method for claim 1, wherein, the alkyl aluminum compound is that formula is AlRnX3-nAlkyl calorize
Compound, wherein, the alkyl that R is hydrogen or carbon number is 1-20, X is halogen, n 1<The number of n≤3.
20. according to the method for claim 19, wherein, the alkyl aluminum compound is selected from triethyl aluminum, tri-propyl aluminum, three
N-butylaluminum, triisobutyl aluminium, tri-n-octylaluminium, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chlorine
At least one of diisobutyl aluminum, sesquialter ethylmercury chloride aluminium, ethyl aluminum dichloride.
21. according to the method for claim 20, wherein, the alkyl aluminum compound is triethyl aluminum or triisobutyl aluminium.
22. according to the method for claim 1, wherein, first external electron donor is trimethylmethoxysilane, two different
Propyldimethoxy-silane, second, isobutyl dimethoxy silane, isopropyl butyldimethoxysilane, di-t-butyl dimethoxy
Base silane, tertbutyl methyl dimethoxysilane, t-butylethyl dimethoxysilane, tert-butyl group propyldimethoxy-silane,
Ter /-butylisopropyl dimethoxysilane, Cyclohexyl Methyl Dimethoxysilane, Dicyclohexyldimethoxysilane, cyclohexyl-
T-butyldimethoxysilane, cyclopentyl-methyl dimethoxysilane, cyclopentyl ethyl dimethoxysilane, bicyclopentyl diformazan
TMOS, cyclopentyl cyclohexyl dimethoxysilane, double (2- methylcyclopentyls) dimethoxysilanes, diphenyl dimethoxy
Silane, diphenyl diethoxy silane, phenyl triethoxysilane, MTMS, MTES, second
Base trimethoxy silane, propyl trimethoxy silicane, isopropyltri-methoxysilane, butyl trimethoxy silane, the second of butyl three
TMOS, trimethoxysilane, amyltrimethoxysilane, isopentyl trimethoxy silane, cyclopenta trimethoxy
Base silane, cyclohexyl trimethoxy silane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyl trimethoxy
Silane, phenyl triethoxysilane, vinyltrimethoxy silane, tetramethoxy-silicane, tetraethoxysilane, four butoxy silicon
One or more in alkane.
23. according to the method for claim 1, wherein, first external electron donor is n-propyl trimethoxy silane.
24. according to the method for claim 22, wherein, first external electron donor is dicyclopentyl dimethoxyl silicon
Alkane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, diphenyl two
At least one of methoxy silane, methyl-t-butyldimethoxysilane, tetraethoxysilane.
25. according to the method for claim 24, wherein, first external electron donor is diisopropyl dimethoxy silane
Or tetraethoxysilane.
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