CN104513327B - Olefin polymerization catalyst composition and applications thereof - Google Patents
Olefin polymerization catalyst composition and applications thereof Download PDFInfo
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Abstract
The present invention discloses an olefin polymerization catalyst composition, which contains the reaction product of the following components: A, solid catalyst components, wherein the solid catalyst components contain magnesium, titanium, halogen and an internal electron donor phthalate compound; B, an alkyl aluminum compound; and C, compounded external electron donors, wherein the compounded external electron donors comprise a first class of external electron donors C1 and a second class of external electron donors C2, wherein the first class of the external electron donors C1 are one or a plurality of materials selected from silanes, diethers and amine compounds, and the second class of the external electron donors C2 are malonate compounds. With the catalyst composition, the high activity of the catalyst can be maintained while the hydrogen response of the catalyst and the polymer isotacticity are improved, and the molecular weight distribution of the polymer is broadened.
Description
Technical field
The invention belongs to field of olefin polymerisation is and in particular to a kind of carbon monoxide-olefin polymeric containing compounding external electron donor.This
Invention further relates to the application of above-mentioned carbon monoxide-olefin polymeric.
Background technology
It is known that using magnesium, titanium, halogen and electron donor as the solid titanium catalyst component of basis, can be used for
Olefinic polyreaction, particularly can obtain higher yields and relatively in having the alpha-olefine polymerizing of 3 carbon or more carbon atom
The polymer of high stereospecificity, wherein electron donor compound are one of requisite compositions in catalytic component, and
Development with internal electron donor compound result in polyolefin catalyst and is continuously updated the replacement, external electron donor be also required to
The supporting development of internal electron donor.At present, multiple electron donor compounds, such as internal electron donor unitary carboxylic have been disclosed in a large number
Acid esters or multi-carboxylate, ketone, monoether or polyether, amine etc. and its derivative, external electron donor monocarboxylic esters, amine, amino silicone
Alkane etc. and its derivative.
In recent years, people attempt to develop again new for the external electron donor chemical combination in catalytic systems for polymerization of olefins
Thing, the catalyst more excellent to obtain combination property, and then develop the polymer of different performance.
Content of the invention
For deficiency of the prior art, the invention provides a kind of carbon monoxide-olefin polymeric for olefinic polymerization, it is adopted
With compounding external electron donor system.When described carbon monoxide-olefin polymeric is used for olefinic polymerization, especially propylene polymerization, present
Significantly act synergistically, while keeping catalyst high polymerization activity, improve isotacticity and the melt index of polymer, also
Improve the molecular weight distribution of polymer.
According to an aspect of the invention, it is provided a kind of carbon monoxide-olefin polymeric for olefinic polymerization, comprise with the following group
The product divided：
A ingredient of solid catalyst, comprises magnesium, titanium, halogen and internal electron donor phthalate compound；
B alkyl aluminum compound；
C compounds external electron donor, including first kind external electron donor C1With Equations of The Second Kind external electron donor C2, the described first kind
External electron donor C1For one or more of silanes, two ethers, aminated compounds, described Equations of The Second Kind external electron donor C2For
Malonate compound.
In a preferred embodiment of above-mentioned carbon monoxide-olefin polymeric, described first kind external electron donor C1Outside Equations of The Second Kind
Electron donor compound C2Mol ratio be (1～100):(100～1), preferably（1～50）:（50～1）, more preferably
（1～20）:（20～1）.
In a preferred embodiment of above-mentioned carbon monoxide-olefin polymeric, described internal electron donor phthalate compound
Formula as follows：
Wherein, R1For C1～C10Straight chained alkyl, C3～C15Branched alkyl, C3～C15Cycloalkyl, C6～C20Aryl or C7~
C20Alkaryl or aralkyl, preferably C2～C8Straight chained alkyl, C3～C10Branched alkyl, C5～C10Cycloalkyl, C6～C15Aryl,
Or C7～C15Alkaryl or aralkyl, more preferably C3～C8Straight chained alkyl, C3～C10Branched alkyl, C6～C10Aryl or C7~
C10Alkaryl or aralkyl；R2～R5Can be identical or differ, selected from hydrogen, halogen and substituted or unsubstituted C1～C10Straight chain alkane
Base, C3～C15Branched alkyl, C3～C15Cycloalkyl, C6～C20Aryl or C7～C20Alkaryl or aralkyl, be preferably selected from hydrogen,
Halogen and substituted or unsubstituted C1～C6Straight chained alkyl, C3～C10Branched alkyl, C5～C10Cycloalkyl, C6～C20Aryl or C7
～C20Alkaryl or aralkyl, are more preferably selected from hydrogen, halogen and substituted or unsubstituted C1～C6Straight chained alkyl, C3～C8Side chain
Alkyl.
In the present invention, mean hydrogen on described group optionally by alkyl or halogen atom institute for described " substituted "
Replace, as described substituted C1～C10Straight chained alkyl, C3～C15Branched alkyl, C3～C15Cycloalkyl, C6～C20Aryl or C7~
C20Alkaryl or aralkyl, refer to if the hydrogen on described alkyl, aryl, alkaryl or aralkyl carbon is optionally by alkyl or halogen
Atom is replaced.
In above-mentioned carbon monoxide-olefin polymeric, described phthalate compound is selected from such as following compounds：O-phthalic
Dimethyl phthalate, diethyl phthalate, n-propyl phthalate, diisopropyl phthalate, phthalic acid two
N-butyl, diisobutyl phthalate, amyl phthalate, di-iso-amyl phthalate, phthalic acid two
Just own ester, o-phthalic acid ester, di-n-octyl phthalate, diisooctyl phthalate, phthalic acid two
Bian ester, tetramethyl repefral, tetramethyl diethyl phthalate, tetramethyl n-propyl phthalate,
Tetramethyl diisopropyl phthalate, tetramethyl n-butyl phthalate, tetramethyl diisobutyl phthalate, four
The just own ester of methylphthalic acid two n-pentyl ester, tetramethyl di-iso-amyl phthalate, tetramethyl phthalic acid two, tetramethyl
Base o-phthalic acid ester, tetramethyl di-n-octyl phthalate, tetramethyl diisooctyl phthalate, tetramethyl
Phthalic acid two Bian ester, tetrabromophthalate dimethyl ester, tetrabromophthalate diethylester, tetrabromophthalate two are just
Propyl ester, tetrabromophthalate diisopropyl ester, tetrabromophthalate di-n-butyl, tetrabromophthalate diisobutyl ester, four
The just own ester of phthalate bromine two n-pentyl ester, tetrabromophthalate diisoamyl ester, tetrabromophthalate two, tetrabromo-phthalic two
Formic acid two dissident's ester, tetrabromophthalate di-n-octyl, tetrabromophthalate di-isooctyl and tetrabromophthalate two
Bian ester.
Ingredient of solid catalyst for olefinic polymerization of the present invention（A）Preferably comprise titanium compound, magnesium chemical combination
Thing and selected from having above-mentioned formula（Ⅰ）The product of shown compound.
Magnesium compound wherein used is selected from magnesium dihalide, the hydrate of alkoxyl magnesium alkyl magnesium magnesium dihalide or alcohol and closes
The derivative that in thing and magnesium dihalide molecular formula, one of halogen atom is replaced by oxyl or halo oxyl；It is preferably
Magnesium dihalide or the alcohol adduct of magnesium dihalide.Instantiation such as magnesium dichloride, dibrominated magnesium, magnesium diiodide and their alcohol close
Thing.
It is TiX that titanium compound wherein used can be selected for formulam(OR1)4-mCompound, R in formula1For C1～C20Hydrocarbon
Base, X is halogen, 1≤m≤4.For example：Titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine
Triethoxy titanium, dichlorodiethyl epoxide titanium, trichlorine one ethanolato-titanium, preferably titanium tetrachloride.
Heretofore described ingredient of solid catalyst（A）Can be by the method preparation being exemplified below.
Method one：Method as disclosed according to patent CN1506384 prepares catalytic component.First, by magnesium compound
Mix by 2～5 mol ratios and atent solvent with organic alcohol compound, be warming up to 120～150 DEG C, by magnesium/acid anhydride mol ratio 5～10
Reaction 1～5 hour.Then according to the alcohol adduct being cooled to room temperature is added to by titanium/magnesium mol ratio 20～50 pre- is cooled to -15～-40
DEG C compound titanium solution in, be warming up to 90～110 DEG C, according to magnesium/internal electron donor mol ratio 2～10 add a kind of selected from logical
Formula（Ⅰ）Shown compound reacts 1～3 hour at 100～130 DEG C, filters to isolate solid particle.According still further to titanium/magnesium mole
Than 20～50, solid particle is added in compound titanium solution, stirring is simultaneously reacted 1.5～3 hours at 100～130 DEG C, filters
Isolate solid particle.Finally wash solid particle with 50～80 DEG C of atent solvent, after being dried, obtain catalytic component.
Method two：First magnesium compound is dissolved in and comprises organic epoxide, organic phosphorus compound and inert diluents
In the dicyandiamide solution of agent composition, mix with titanium compound after forming homogeneous solution, in the presence of precipitation additive, separate out solids；
This solids is using selected from formula（Ⅰ）Compound processed so as to be attached on solids, if necessary, then use four halogenations
Titanium and inert diluent are processed to solids.
Wherein said magnesium compound, titanium compound and formula（Ⅰ）Shown compound is as described in aforementioned.Described have
Machine epoxide, organic phosphorus compound and precipitation additive etc. are disclosed in Chinese patent CN85100997, and its related content exists
This is incorporated as reference.As organic epoxide be selected from carbon number 2～8 aliphatic olefin, alkadienes or halo
The oxide of aliphatic olefin or alkadienes, glycidol ether and inner ether.Particular compound is such as：Oxirane, expoxy propane, ring
Oxygen butane, butadiene oxide, butadiene double oxide, epoxychloropropane, methyl glycidyl ether, diglycidyl ether, four
Hydrogen furans.As organic phosphorus compound can comprise hydrocarbyl carbonate or the halogenated hydrocarbons base ester of orthophosphoric acid or phosphorous acid, specifically such as：Orthophosphoric acid three
Methyl esters, orthophosphoric acid triethyl, orthophosphoric acid tributyl, orthophosphoric acid triphenylmethyl methacrylate, Trimethyl phosphite, triethyl phosphite, phosphorous acid
Tributyl, phosphorous triphenyl phosphate methyl esters.As described precipitation additive is selected from organic acid anhydride, organic acid, ether, ketone and ester.Specifically comprise
As：Acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic acid anhydride, acetic acid, propionic acid, butyric acid, third
Olefin(e) acid, methacrylic acid, acetone, MEK, benzophenone, methyl ether, ether, propyl ether, butyl ether, amyl ether, succinate, malonic acid
Ester, glutarate, 2,4-PD ester, 3,5- heptandiol ester.Described each component in terms of every mole of magnesium compound, organic epoxidation
The consumption of compound is 0.2～10 mole, and the consumption of organic phosphorus compound is 0.1～3 mole, and the consumption of precipitation additive is 0～1.0
Mole, the consumption of titanium compound is 0.5～150 mole, described formula（Ⅰ）The consumption of shown compound rubs for 0.01～1.0
You.
Method three：By titanium compound of the present invention, concrete such as TiCl4, it is MgCl with formula2The adduct of pROH
React and prepare ingredient of solid catalyst.In MgCl2In pROH, p is 0.1～6 number, preferably 2～3.5, and R is that have 1
The alkyl of～18 carbon atoms.Adduct can be conveniently made spherical by the following method：Not miscible with adduct lazy
In the presence of property hydrocarbon, by alcohol（ROH）And MgCl2Mixing, makes the rapid chilling of this emulsion, so that adduct is in the form of spheric granules
Solidification.So obtained adduct can directly be reacted with titanium compound, or it can be in advance before reacting with titanium compound
Dealcoholization through thermal control（80～130 DEG C）To obtain a kind of adduct, the molal quantity of wherein alcohol is generally below 3, preferably
Between 0.1～2.7.Can pass through adduct（Dealcoholysis or itself）It is suspended in cold TiCl4（General 0 DEG C）In, and
Mixture temperature programming is kept 0.1～2 hour to 80～130 DEG C and at this temperature, to carry out the reaction with titanium compound.
TiCl4Process can carry out once or repeatedly.With TiCl4Above-mentioned formula of the present invention can be added during process（Ⅰ）Chemical combination
Thing is processed, and this process can also be repeated once or repeatedly.
Specifically catalytic component can be prepared according to the method disclosed in patent CN1091748.Chlorination magnesium alcoholate melt exists
Disperse through high-speed stirred in white oil and the dispersant system of silicone oil, form emulsion, be discharged in coolant rapid cooling and shaping, shape
Become chlorination magnesium alcoholate microballoon.Coolant is the relatively low inert hydrocarbon solvent of boiling point, such as petroleum ether, pentane, hexane, heptane etc..
Gained chlorination magnesium alcoholate microballoon is scrubbed, drying is ball type carrier, and its alcohol is 2～3 with the mol ratio of magnesium chloride, with 2～2.5
Preferably.Diameter of carrier is 10～300 microns, best with 30～150 microns.
With excessive titanium tetrachloride in the above-mentioned ball type carrier of K cryogenic treatment, progressively heat up, processing procedure adds this
Bright formula（Ⅰ）Shown electron donor, is repeatedly washed with atent solvent after process, obtains the spherical of solid powdery and urge after being dried
Agent component.Titanium tetrachloride is 20～200 with the mol ratio of magnesium chloride, preferably 30～60；Initiated process temperature is -30～0
DEG C, it is preferred with -25～-20 DEG C；Final process temperature is 80～136 DEG C, is preferred with 100～130 DEG C.
Method four：Also can be added in arene compound with dialkoxy magnesium and stir, form suspension；Suspension tetravalence
Titanium chloride is processed at -20～100 DEG C, and reacts at 0～130 DEG C, in the process, adds formula of the present invention at -20～130 DEG C
（Ⅰ）Electron donor is reacted, and the solid obtaining is washed with arene compound；Then at 0～130 DEG C in aromatic hydrocarbon solvent
In, then processed with tetravalence titanium chloride, finally washed with atent solvent, drain, obtain ingredient of solid catalyst.Wherein every mole two
Alkyl magnesium tetravalence titanium chloride 0.5～100mol, electron donor is with 0.01～10mol.
Method five：Use TiCl4Or its arene solution at 80～130 DEG C to such as dialkoxy magnesium or two aryloxy group magnesium it
Two magnesium hydrocarbyloxy compound of class carry out halogenation, use TiCl4Or its arene solution carries out process and can be repeated one or more times, and
Add formula of the present invention in the such process of one or many（Ⅰ）Compound.
Method six：Prepare catalytic component according to the method disclosed in patent US4540679.First, magnesium alkoxide and titanium dioxide
Carbon reaction is obtained alkyl carbonic acid magnesium carrier.Then transistion metal compound（It is preferably tetravalent titanium compound）Carry with alkyl magnesium carbonate
Body and formula of the present invention（Ⅰ）Electron donor reacted in atent solvent in certain proportion, wherein transition metal
It is at least 0.5 with the mol ratio of magnesium elements:1, formula of the present invention（Ⅰ）Electron donor consumption be up to 1.0 moles of every gram of titaniums former
Son.Atent solvent must easily make the material of catalyst poisoning through purifying to slough water, oxygen, carbon dioxide etc..React -10
～170 DEG C are carried out, and the reaction time is a few minutes to a few houres.
Prepare ingredient of solid catalyst（A）Method also formed in diluent just like by magnesium compound, electron donor etc.
Emulsion, adds titanium compound to make its fixation obtain spherical solid, treated obtains ingredient of solid catalyst.
In any above-mentioned preparation method, required electron donor compound（Ⅰ）I.e. can be with the shape of compound
Formula adds；Can also add in other manners, such as can be by using electron donor compound（Ⅰ）Suitable precursor original position obtains
, this front physical efficiency passes through the electron donor compound required for for example known chemical reaction such as esterification etc. becomes.
In above-mentioned carbon monoxide-olefin polymeric so that, in a preferred embodiment, the formula of described alkyl aluminum compound is AlR 'nX3-n, in formula, R ' is selected from hydrogen and C1～C20Alkyl, X be halogen, 1≤n≤3.The instantiation bag of described alkyl aluminum compound
Containing triethyl aluminum, tri-propyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-octylaluminium, triisobutyl aluminium, a hydrogen diethyl aluminum,
One hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium and ethyl aluminum dichloride, preferably three
Aluminium ethide, triisobutyl aluminium.
In above-mentioned carbon monoxide-olefin polymeric, as first kind external electron donor C1Compound be prior art in be commonly used for
The compound of external electron donor.Described amine as being the amine of band shape structure, piperidines that such as piperidines, 2,6- replace, 2,
5- substituted piperidine etc..In a specific embodiment, described first kind external electron donor C1It is preferably selected from cyclohexyl methyl two
Methoxy silane, diphenyl dimethoxy silicon, phenyltriethoxy silane, diisopropyl dimethoxy silane, dipropyl dimethoxy
Base silane, dicyclopentyl dimethoxyl silane, diphenyldimethyl silane, tetraalkoxysilane, butyl trimethoxy silane, 2-
Isopropyl -2- isopentyl -1,3- dimethoxy propane, 9,9- bis-（Methoxy）Fluorenes, 2,2- dibutyl -1,3- dimethoxy
In propane, 2,2- diisobutyl -1,3- dimethoxy propane, 2- isobutyl group -2- isopentyl -1,3- dimethoxy propane etc. one
Plant or several.
In a specific embodiment of above-mentioned carbon monoxide-olefin polymeric, the described malonic acid as Equations of The Second Kind external electron donor
The formula of ester compounds is as follows
Wherein, R6For C1～C10Straight chained alkyl, C3～C10The alkyl of side chain, C3～C10Cycloalkyl, C6～C10Aryl, C7~
C10Alkaryl or aralkyl, preferably C2～C8Straight chained alkyl, C3～C8The alkyl of side chain, C5～C10Cycloalkyl or C7～C10Alkane
Virtue；R7And R8May be the same or different, be hydrogen, C1～C10Straight chained alkyl, C3～C10The alkyl of side chain, C3～C10Cycloalkyl, C6～C10
Aryl, C7～C10Alkaryl or aralkyl, preferably hydrogen, C1～C6Straight chained alkyl, C3～C8The alkyl of side chain, C5～C10Cycloalkanes
Base or C7～C10Alkaryl.
In above-mentioned carbon monoxide-olefin polymeric, the malonate compound as Equations of The Second Kind external electron donor is selected from following chemical combination
Thing：Diethyl malonate, dipropyl malonate, Diisopropyl malonate, dibutyl malonate, malonic acid diisobutyl ester, methyl
Diethyl malonate, methylmalonic acid dipropyl, methylmalonic acid diisopropyl ester, methylmalonic acid di-n-butyl, methyl-prop two
Sour diisobutyl ester, methylmalonic acid di tert butyl carbonate, ethyl malonic acid diethylester, ethyl malonic acid dipropyl, ethyl malonic acid two
Isopropyl ester, ethyl malonic acid di-n-butyl, ethyl malonic acid diisobutyl ester, ethyl malonic acid di tert butyl carbonate, propylmalonic acid two
Ethyl ester, propylmalonic acid dipropyl, propylmalonic acid diisopropyl ester, propylmalonic acid di-n-butyl, propylmalonic acid two isobutyl
Ester, propylmalonic acid di tert butyl carbonate, diethyl isopropyl, isopropyl-malonic acid dipropyl, isopropyl-malonic acid two are different
Propyl ester, isopropyl-malonic acid di-n-butyl, isopropyl-malonic acid diisobutyl ester, isopropyl-malonic acid di tert butyl carbonate, phenyl the third two
Diethyl phthalate, phenylmalonic acid dipropyl, phenylmalonic acid diisopropyl ester, phenylmalonic acid di-n-butyl, phenylmalonic acid two
Isobutyl ester, phenylmalonic acid di tert butyl carbonate etc., benzyl group diethyl malonate, benzyl group dipropyl malonate, benzyl group malonic acid two are different
Propyl ester, benzyl group malonic acid di-n-butyl, benzyl group malonic acid diisobutyl ester, benzyl group malonic acid di tert butyl carbonate etc., dimethyl malonic acid
Diethylester, ethyl diethylmalonate, Methylethyl diethyl malonate, methyl butyl diethyl malonate, methyl tert-butyl
Propylmalonic acid diethylester, methyl-propyl diethyl malonate, isopropyl methyl diethyl malonate, diη-propyl malonic acid diethyl
Ester, di-n-butyl diethyl malonate, diisopropyl diethyl malonate, diisobutyl diethyl malonate and diallyl third
Diethyl adipate etc..
In a specific embodiment of above-mentioned carbon monoxide-olefin polymeric, the mol ratio of described component A and component B is with titanium:Aluminium
It is calculated as 1:(5～5000), preferably 1:(20～500)；The mol ratio of component A and component C is with titanium:External donor compound is calculated as
1:(0.1～500), preferably 1:(3～100).
According to another aspect of the present invention, there is provided a kind of Prepolymerized catalyst system for olefinic polymerization, institute
State that Prepolymerized catalyst system comprises a kind of above-mentioned carbon monoxide-olefin polymeric and alkene carries out the prepolymer of prepolymerization gained, pre-polymerization
Multiple is 0.1～1000g olefin polymer/g ingredient of solid catalyst A.
In the present invention, " pre-polymerized catalyst " refers to the catalyst with relatively low transforming degree through polymerization procedure.According to this
Invention, can using be polymerized used by alkene identical alpha-olefin to carry out prepolymerization, wherein carry out prepolymerized alkene preferred
For propylene.Specifically it is therefore particularly preferred that using propylene or its be up to one or more alpha-olefin of 20mol% with amount
Mixture carries out prepolymerization.Preferably, the transforming degree of pre-polymerized catalyst components is about 0.2～500 gram of polymer/gram solid
Body catalyst component A.
Prepolymerization operation can be carried out in a liquid or in gas phase at -20～80 DEG C, at a temperature of preferably 0～50 DEG C.In advance
Polymerization procedure can be carried out online as a part of in continuous polymerization technique, or independently carries out in intermittently operated.For system
The standby polymer measured as 0.5～20g/g catalytic component, the batch pre-polymerization of particularly preferred catalyst of the present invention and propylene.Poly-
Resultant pressure is 0.01～10MPa.
According to a further aspect in the invention, there is provided a kind of olefine polymerizing process, wherein said alkene is in above-mentioned catalyst
It is polymerized in the presence of composition or Prepolymerized catalyst system.
The catalyst of the present invention can be directly added in reactor and be used in polymerization process, or catalyst and alkene pre-polymerization
Add in reactor after obtaining pre-polymerized catalyst.
The olefinic polyreaction of the present invention is carried out according to known polymerization, can carry out in liquid phase or gas phase, or
Person can also be carried out under the operation of liquid and gas polymerization stage combination.Using conventional technique such as slurry process, gas phase fluidization
Bed etc..It is preferably using following reaction condition：0～150 DEG C of polymerization temperature, preferably 60～90 DEG C.
The formula of heretofore described alkene is CH2=CHR, wherein R are hydrogen or C1～C12Alkyl or aryl, be such as selected from
Ethene, propylene, 1- butylene, 4-methyl-1-pentene and 1- hexene.Be preferably selected from propylene, such as all polymerizations of propylene with or propylene its
The combined polymerization of his alkene.
The carbon monoxide-olefin polymeric being provided according to the present invention, using being internal electron donor containing phthalate compound, existing
The conventional external donor compound of technology and malonate compound is had to compound as external electron donor system.Described catalyst
Composition is used for olefinic polymerization, especially propylene polymerization, shows obvious synergy, and polymerization activity is high, the polymerization obtaining
The isotacticity of thing and melt index significantly improve, and the molecular weight distribution of polymer is also improved, and are advantageous to the different trades mark
The exploitation of resin is favourable.
Specific embodiment
Example given below is to further illustrate the present invention, rather than limits the invention.
Method of testing
1. the melt index of polymer（MI）Measure by testing standard GB/T3682 2000.
2. polymer isotactic index adopts heptane extraction process to measure（Heptane boiling extracting 6 hours）：The polymer that 2g is dried
Sample, is placed on after being extracted 6 hours with boiling heptane in extractor, by the polymer weight of residue drying to constant weight gained（g）
It is isotactic index with 2 ratio.
3. polymer molecular weight and molecular weight distribution MWD（MWD=Mw/Mn）：Using gel permeation chromatography method, use PL-
GPC220 is measured with trichloro-benzenes for solvent at 150 DEG C（Standard specimen：Polystyrene, flow velocity：1.0ml/min, pillar：
3xPlgel10um M1xED-B300x7.5nm）.
First, the preparation of ingredient of solid catalyst A
Under nitrogen protection, 4.8g anhydrous magnesium chloride, 19.5g isooctanol and 19.5g decane solvent are added to equipped with stirring
Mix in the 500ml reactor of device, be heated to 130 DEG C, reaction is completely dissolved to magnesium chloride for 1.5 hours, add 1.1g phthalic anhydride, continue
130 DEG C of reactions are maintained to obtain alcohol adduct in 1 hour；Alcohol adduct is cooled to room temperature.
Under nitrogen protection, by above-mentioned alcohol adduct be added drop-wise to pre- be cooled in -22 DEG C of 120ml titanium tetrachloride solution, slowly
It is warming up to 100 DEG C, add the internal electron donor compound in 10mmol table 1（Ⅰ）, it is warming up to 110 DEG C and maintain 2 hours, mistake while hot
Filter, plus titanium tetrachloride 120ml, it is raised to 110 DEG C and reacts 1 hour, filter, with anhydrous hexane solid particle 4 times, after being dried
To solid catalyst.
2nd, propylene polymerization experiment
The ingredient of solid catalyst A of above-described embodiment is carried out propylene polymerization respectively.Propylene polymerization program is：Volume is 5L
Stainless steel cauldron, after being sufficiently displaced from through gaseous propylene, add AlEt32.5mmol, polynary external electron donor（C）0.l
Mmol, adds ingredient of solid catalyst 8～10mg and the 1.2NL hydrogen of above-described embodiment, is passed through liquid propene 2.3L, rises
Temperature, to 70 DEG C, maintains this temperature 1 hour；Cooling, pressure release, obtain the PP powder of embodiment 1～6 and comparative example.Data is shown in Table 1.
Comparative example is to use Cyclohexyl Methyl Dimethoxysilane respectively（CHMMS）And diethyl malonate（DEM）Replace many
First external electron donor（C）, remaining is constant.
Hydrogen is changed into 7.2NL, remaining constant polymerization carrying out propylene, the results are shown in Table 2.
Wherein：
C1：Cyclohexyl Methyl Dimethoxysilane:Diethyl malonate=1:20；
C2：Dicyclopentyl dimethoxyl silane:Methyl-malonic ester=1:5；
C3：Butyl trimethoxy silane:Diethyl benzyl malonate=18:1；
C4：Dicyclopentyl dimethoxyl silane:Diethyl malonate=1:2；
C5：9,9- bis-（Methoxy）Fluorenes:Dipropyl diethyl malonate=6:1；
C6：Cyclohexyl Methyl Dimethoxysilane:Diethyl malonate=4:1.
Table 1 propylene polymerization result
Can see from table 1, at identical conditions, using compounding external electron donor（As embodiment 6）, and individually make
Use any of which external electron donor（Comparative example 1 and comparative example 2）Compare, gather when the carbon monoxide-olefin polymeric obtaining is used for alkene
When conjunction, especially propylene polymerization, polymerization activity is high, improves the isotactic index of polymer simultaneously, improves the molecular weight of polymer
Distribution, shows obvious synergy.
Table 2
From Table 2, it can be seen that at identical conditions, using compounding external electron donor（As embodiment 6）, and individually make
Use any of which external electron donor（Comparative example 1 and comparative example 2）Compare, gather when the carbon monoxide-olefin polymeric obtaining is used for alkene
When conjunction, especially propylene polymerization, show obvious synergy, the high melt index of polymer, the described catalyst obtaining
Composition has preferable hydrogen response.
From Tables 1 and 2 it is known that obvious synergy is presented according to the carbon monoxide-olefin polymeric that the present invention provides,
Not only there is higher catalysis activity, hydrogen response and vertical structure directionality, and the molecular weight distribution of the polymer obtaining also obtains
Arrive improvement.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute any to the present invention
Limit.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive
With explanatory vocabulary, rather than limited vocabulary.Within the scope of the claims the present invention can be made by regulation
Modification, and in without departing substantially from scope and spirit of the present invention, the present invention is revised.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, on the contrary, this
Bright can be extended to other all methods and applications with identical function.
Claims (19)
1. a kind of carbon monoxide-olefin polymeric for olefinic polymerization, comprises the product of following components：
A ingredient of solid catalyst, comprises magnesium, titanium, halogen and internal electron donor phthalate compound；
B alkyl aluminum compound；
C compounds external electron donor, including first kind external electron donor C1With Equations of The Second Kind external electron donor C2, give outside the described first kind
Electron C1For one or more of silane, two ethers, aminated compounds, described Equations of The Second Kind external electron donor C2For malonic acid
Ester compounds.
2. carbon monoxide-olefin polymeric according to claim 1 is it is characterised in that described first kind external electron donor C1With second
Class external donor compound C2Mol ratio be (1～100):(100～1).
3. carbon monoxide-olefin polymeric according to claim 1 is it is characterised in that described first kind external electron donor C1With second
Class external donor compound C2Mol ratio be (1～50):(50～1).
4. carbon monoxide-olefin polymeric according to claim 1 is it is characterised in that described first kind external electron donor C1With second
Class external donor compound C2Mol ratio be (1～20):(20～1).
5. the carbon monoxide-olefin polymeric according to any one in Claims 1 to 4 is it is characterised in that give outside described Equations of The Second Kind
The formula of electron malonate compound is as follows
Wherein, R6For C1～C10Straight chained alkyl, C3～C10The alkyl of side chain, C3～C10Cycloalkyl, C6～C10Aryl, C7～C10Alkane
Aryl or aralkyl；R7And R8May be the same or different, be hydrogen, C1～C10Straight chained alkyl, C3～C10The alkyl of side chain, C3～C10Ring
Alkyl, C6～C10Aryl, C7～C10Alkaryl or aralkyl.
6. carbon monoxide-olefin polymeric according to claim 5 is it is characterised in that R6For C2～C8Straight chained alkyl, C3～C8Side chain
Alkyl, C5～C10Cycloalkyl or C7～C10Alkaryl；R7And R8May be the same or different, be hydrogen, C1～C6Straight chained alkyl, C3～C8
The alkyl of side chain, C5～C10Cycloalkyl or C7～C10Alkaryl.
7. the carbon monoxide-olefin polymeric according to any one in Claims 1 to 4 is it is characterised in that give outside described Equations of The Second Kind
Electron malonate compound is selected from following compounds：Diethyl malonate, dipropyl malonate, Diisopropyl malonate,
Dibutyl malonate, malonic acid diisobutyl ester, methyl-malonic ester, methylmalonic acid dipropyl, methylmalonic acid two are different
Propyl ester, methylmalonic acid di-n-butyl, methylmalonic acid diisobutyl ester, methylmalonic acid di tert butyl carbonate, ethyl malonic acid diethyl
Ester, ethyl malonic acid dipropyl, ethyl malonic acid diisopropyl ester, ethyl malonic acid di-n-butyl, ethyl malonic acid diisobutyl ester,
Ethyl malonic acid di tert butyl carbonate, propylmalonic acid diethylester, propylmalonic acid dipropyl, propylmalonic acid diisopropyl ester, propyl group
Malonic acid di-n-butyl, propylmalonic acid diisobutyl ester, propylmalonic acid di tert butyl carbonate, diethyl isopropyl, isopropyl
Propylmalonic acid dipropyl, isopropyl-malonic acid diisopropyl ester, isopropyl-malonic acid di-n-butyl, isopropyl-malonic acid two isobutyl
Ester, isopropyl-malonic acid di tert butyl carbonate, phenyl ethyl malonate, phenylmalonic acid dipropyl, phenylmalonic acid diisopropyl ester,
Phenylmalonic acid di-n-butyl, phenylmalonic acid diisobutyl ester, phenylmalonic acid di tert butyl carbonate, benzyl group diethyl malonate, Bian
Propylmalonic acid dipropyl, benzyl group Diisopropyl malonate, benzyl group malonic acid di-n-butyl, benzyl group malonic acid diisobutyl ester, benzyl group
Malonic acid di tert butyl carbonate, dimethyl malonic ester, ethyl diethylmalonate, Methylethyl diethyl malonate, first
Base diethyl butylmalonate, methyl-isobutyl diethyl malonate, methyl-propyl diethyl malonate, isopropyl methyl the third two
Diethyl phthalate, diη-propyl diethyl malonate, di-n-butyl diethyl malonate, diisopropyl diethyl malonate, two different
Diethyl butylmalonate and diallyl diethyl malonate.
8. the carbon monoxide-olefin polymeric according to any one in Claims 1 to 4 is it is characterised in that described phthalic acid
The formula of ester compounds is as follows：
Wherein, R1For C1～C10Straight chained alkyl, C3～C15Branched alkyl, C3～C15Cycloalkyl, C6～C20Aryl or C7～C20Alkane
Aryl or aralkyl；R2～R5Can be identical or differ, selected from hydrogen, halogen and substituted or unsubstituted C1～C10Straight chained alkyl, C3
～C15Branched alkyl, C3～C15Cycloalkyl, C6～C20Aryl or C7～C20Alkaryl or aralkyl.
9. carbon monoxide-olefin polymeric according to claim 8 is it is characterised in that R1For C2～C8Straight chained alkyl, C3～C10Side chain
Alkyl, C5～C10Cycloalkyl, C6～C15Aryl or C7～C15Alkaryl or aralkyl；R2～R5Can be identical or differ, it is selected from
Hydrogen, halogen and substituted or unsubstituted C1～C6Straight chained alkyl, C3～C10Branched alkyl, C5～C10Cycloalkyl, C6～C20Aryl,
Or C7～C20Alkaryl or aralkyl.
10. carbon monoxide-olefin polymeric according to claim 8 is it is characterised in that R1For C3～C8Straight chained alkyl, C3～C10?
Alkyl group, C6～C10Aryl or C7～C10Alkaryl or aralkyl；R2～R5Can be identical or differ, selected from hydrogen, halogen with take
Generation or unsubstituted C1～C6Straight chained alkyl, C3～C8Branched alkyl.
11. carbon monoxide-olefin polymerics according to any one in Claims 1 to 4 are it is characterised in that described phthalic acid
Ester compounds are selected from following compounds：Repefral, diethyl phthalate, n-propyl phthalate,
Diisopropyl phthalate, n-butyl phthalate, diisobutyl phthalate, amyl phthalate,
The just own ester of di-iso-amyl phthalate, phthalic acid two, o-phthalic acid ester, di-n-octyl phthalate,
Diisooctyl phthalate, phthalic acid two Bian ester, tetramethyl repefral, tetramethyl phthalic acid two
Ethyl ester, tetramethyl n-propyl phthalate, tetramethyl diisopropyl phthalate, the positive fourth of tetramethyl phthalic acid two
Ester, tetramethyl diisobutyl phthalate, tetramethyl amyl phthalate, tetramethyl phthalic acid diisoamyl
The just own ester of ester, tetramethyl phthalic acid two, tetramethyl o-phthalic acid ester, tetramethyl phthalic acid two are just pungent
Ester, tetramethyl diisooctyl phthalate, tetramethyl phthalic acid two Bian ester, tetrabromophthalate dimethyl ester, tetrabromo
Diethyl phthalate, tetrabromophthalate di-n-propyl ester, tetrabromophthalate diisopropyl ester, tetrabromophthalate
Di-n-butyl, tetrabromophthalate diisobutyl ester, tetrabromophthalate two n-pentyl ester, tetrabromophthalate diisoamyl
The just own ester of ester, tetrabromophthalate two, tetrabromophthalate two dissident's ester, tetrabromophthalate di-n-octyl, tetrabromo
Diisooctyl phthalate and tetrabromophthalate two Bian ester.
12. carbon monoxide-olefin polymerics according to any one in Claims 1 to 4 are it is characterised in that described alkyl aluminum chemical combination
The formula of thing is AlR 'nX3-n, in formula, R ' is selected from hydrogen and C1～C20Alkyl, X be halogen, 1≤n≤3.
13. carbon monoxide-olefin polymerics according to any one in Claims 1 to 4 are it is characterised in that give as outside the first kind
Electron C1Compound, selected from Cyclohexyl Methyl Dimethoxysilane, diphenyl dimethoxy silicon, phenyltriethoxy silane, two
Isopropyl dimethoxysilane, dipropyl dimethoxysilane, dicyclopentyl dimethoxyl silane, diphenyldimethyl silane,
Tetraalkoxysilane, butyl trimethoxy silane, 2- isopropyl -2- isopentyl -1,3- dimethoxy propane, 9,9- bis- (methoxy
Ylmethyl) fluorenes, 2,2- dibutyl -1,3- dimethoxy propane, 2,2- diisobutyl -1,3- dimethoxy propane and 2- isobutyl
One or more of base -2- isopentyl -1,3- dimethoxy propane.
14. carbon monoxide-olefin polymerics according to any one in Claims 1 to 4 are it is characterised in that described component A and group
The mol ratio dividing B is with titanium:Aluminium is calculated as 1:(5～1000)；The mol ratio of component A and component C is with titanium:External donor compound meter
For 1:(0.1～100).
15. carbon monoxide-olefin polymerics according to any one in Claims 1 to 4 are it is characterised in that described component A and group
The mol ratio dividing B is with titanium:Aluminium is calculated as 1:(20～250)；The mol ratio of component A and component C is with titanium:External donor compound meter
For 1:(1～50).
A kind of 16. Prepolymerized catalyst system for olefinic polymerization, described Prepolymerized catalyst system comprises one kind according to power
Profit requires catalyst system any one of 1～15 and alkene to carry out the prepolymer of prepolymerization gained, and pre-polymerization multiple is 0.1
～1000g olefin polymer/g ingredient of solid catalyst A.
A kind of 17. methods of olefinic polymerization, carbon monoxide-olefin polymeric any one of in claim 1～15 for the alkene or right
It is polymerized in the presence of requiring the Prepolymerized catalyst system described in 16.
18. methods according to claim 17 are it is characterised in that the formula of described alkene is CH2=CHR, wherein R are hydrogen
Or C1～C12Alkyl or aryl.
19. methods according to claim 17 are it is characterised in that described alkene is propylene.
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| CN201310459838.2A CN104513327B (en) | 2013-09-30 | 2013-09-30 | Olefin polymerization catalyst composition and applications thereof |
| TW103133626A TWI639626B (en) | 2013-09-30 | 2014-09-26 | Catalyst composition for olefin polymerization and application thereof |
| ES14848074T ES2736026T3 (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerization and application thereof |
| BR112016007091-7A BR112016007091B1 (en) | 2013-09-30 | 2014-09-28 | CATALYST COMPOSITION FOR POLYMERIZATION OF OLEFINS AND USE OF IT |
| US15/025,698 US9822196B2 (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerization and application of same |
| RU2016117106A RU2715995C2 (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerisation and use thereof |
| TR2019/08294T TR201908294T4 (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerization and its application. |
| KR1020217009920A KR20210040186A (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerization and application of same |
| SG11201602505PA SG11201602505PA (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerization and application of same |
| KR1020167011538A KR20160065181A (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerization and application of same |
| PCT/CN2014/087709 WO2015043526A1 (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerization and application of same |
| MYPI2016701051A MY174892A (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerization and use thereof |
| EP14848074.2A EP3053935B1 (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerization and application of same |
| JP2016518715A JP6681827B2 (en) | 2013-09-30 | 2014-09-28 | Olefin polymerization catalyst composition and use thereof |
| CA2925614A CA2925614C (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerization and application of same |
| JP2019021064A JP6745366B2 (en) | 2013-09-30 | 2019-02-07 | Olefin polymerization catalyst composition and use thereof |
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| CN101155838A (en) * | 2005-03-29 | 2008-04-02 | 三星Total株式会社 | Method for producing a propylene polymer having a very high melt flowability |
| EP1970388A1 (en) * | 2006-01-04 | 2008-09-17 | China Petroleum & Chemical Corporation | Catalyst component for olefin polymerization or copolymerization,preparation method thereof, catalyst containing said catalyst component and use thereof |
| CN101687940A (en) * | 2007-05-22 | 2010-03-31 | 博里利斯技术有限公司 | Catalyst system for polypropylene copolymers |
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| CN101155838A (en) * | 2005-03-29 | 2008-04-02 | 三星Total株式会社 | Method for producing a propylene polymer having a very high melt flowability |
| EP1970388A1 (en) * | 2006-01-04 | 2008-09-17 | China Petroleum & Chemical Corporation | Catalyst component for olefin polymerization or copolymerization,preparation method thereof, catalyst containing said catalyst component and use thereof |
| CN101687940A (en) * | 2007-05-22 | 2010-03-31 | 博里利斯技术有限公司 | Catalyst system for polypropylene copolymers |
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