CN106496374B - A kind of catalyst system being used to prepare olefin polymer and its application - Google Patents
A kind of catalyst system being used to prepare olefin polymer and its application Download PDFInfo
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Abstract
The present invention relates to a kind of catalyst systems for olefinic polymerization, and it includes following components: a. ingredient of solid catalyst, contain Mg, Ti, halogen and at least one internal electron donor compound containing lone pair electrons；B. alkyl aluminum compound；C. external electron donor, the external electron donor include phosphoric acid silicone compounds.When catalyst system of the invention is used for propylene polymerization, available satisfactory polymerization activity, and the hydrogen response of catalyst is more preferable.
Description
Technical field
The present invention relates to field of olefin polymerisation, and in particular to a kind of olefin polymerization containing phosphoric acid silicone compounds is urged
Agent system and its application application.
Background technique
It is well known that can be used for using magnesium, titanium, halogen and electron donor as the solid titanium catalyst component of basis
Olefin polymerization, especially in the alpha-olefine polymerizing with 3 carbon or more available higher yields and compared with
The polymer of high stereospecificity, wherein electron donor compound is one of essential ingredient in ingredient of solid catalyst,
And it is continuously updated the replacement as the development of internal electron donor compound results in polyolefin catalyst, external electron donor also needs
It will be with the mating development of internal electron donor.Currently, largely having disclosed a variety of electron donor compounds, such as internal electron donor one
First carboxylate or multi-carboxylate, ketone, monoether or polyether, diol ester, amine etc. and its derivative, external electron donor monocarboxylic acid
Ester, amine, siloxanes, amino silane etc. and its derivative.The electron donor reported at present is mostly oxygen-containing, nitrogen phosphate and sulfur, silicon
Compound.In these catalyst polymerization systems, electron donor is to activity, stereoselectivity, molecular weight distribution and polymer
Performance has different degrees of influence.However, with the development of technology, it is desirable to develop new electron donor, to adapt to not
Same product demand.
Summary of the invention
The present inventor is had found by a large number of experiments, using the external electron donor of phosphoric acid siloxanes shown in I containing general formula, due to
The phosphoric acid siloxanes contains multiple functional groups, and the validity or selectivity of catalyst active center can be improved.In the present invention
Olefin polymerization catalyst system in by using a kind of new chemical combination combined containing particular functional group's phosphate and siloxanes
The external electron donor of object (i.e. general formula I compound represented), can be obtained the olefin polymer of high comprehensive performance.In the catalysis
When agent system is used for propylene polymerization, catalyst system activity with higher and better hydrogen response.
The present invention provides a kind of novel catalyst systems for olefinic polymerization, using silicon phosphate shown in I containing general formula
The validity or selectivity of catalyst active center can be improved in the external electron donor of oxygen alkane.It is urged in olefinic polymerization of the invention
The olefin polymer of high comprehensive performance can be obtained as external electron donor in agent system.The catalyst system is used for alkene
When polymerization, especially propylene polymerization, catalyst system activity with higher and better hydrogen response.
One of the objects of the present invention is to provide a kind of catalyst system for olefinic polymerization, the catalyst system packets
Containing following components:
A. ingredient of solid catalyst contains Mg, Ti, halogen and at least one internal electron donor containing lone pair electrons
Close object；
B. alkyl aluminum compound；
C. external electron donor, the external electron donor include phosphoric acid silicone compounds.
According to the present invention, comprehensive using the catalyst system of the external donor compound containing novel phosphoric acid siloxanes
Better performances show higher activity and better hydrogen response.
Catalyst system according to the present invention, preferably phosphoric acid silicone compounds are silicon phosphate shown in general formula (I)
Siloxane compound.
Wherein R1、R2Can be identical or not identical, it is C1~C10Linear chain or branched chain alkyl or cycloalkyl；1≤n≤6.It is excellent
Selection of land, R1And R2It is identical or different, it is C1~C4Linear chain or branched chain alkyl；1≤n≤3.Using phosphoric acid shown in logical formula (I)
For silicone compounds as external donor compound, comprehensive performance is preferable, can show that high activity and better hydrogen tune
Sensibility.
A specific embodiment according to the present invention, the phosphoric acid siloxane compound are selected from but not limited to followingization
Close object: solutions of dimethyl phosphoryl methyltrimethoxysilane, diethylphosphoryl methyltrimethoxysilane, solutions of dimethyl phosphoryl ethyl front three
Oxysilane, solutions of dimethyl phosphoryl methyltriethoxysilane, diethylphosphoryl methyltriethoxysilane, diethylphosphoryl ethyl
Trimethoxy silane, solutions of dimethyl phosphoryl ethyl triethoxysilane, diethylphosphoryl ethyl triethoxysilane, dipropyl phosphinylidyne
Ethyl triethoxysilane, solutions of dimethyl phosphoryl propyl trimethoxy silicane, diethylphosphoryl propyl-triethoxysilicane, diethyl
Phosphonoethyl tripropoxy silane, dipropyl phosphinylidyne propyl-triethoxysilicane, dipropyl phosphonoethyl tripropoxy silane, two
At least one of ethyl phosphinylidyne propyl tripropoxy silane and dipropyl phosphinylidyne propyl tripropoxy silane etc..
Another specific embodiment according to the present invention, in the ingredient of solid catalyst a, the internal electron donor chemical combination
Object is selected from the compound containing O, N, P or S atom；Preferably containing the compound of O atom.
In a preferred embodiment of the invention, in the ingredient of solid catalyst a, the internal electron donor chemical combination
Object is selected from least one of ethers, esters, phenolic ether class, phenolic ester class and ketone compounds；It is preferably selected from glycol ester compounds, neighbour
At least one of phthalic acid ester compounds, diether compounds and succinate compound.
Another specific embodiment of catalyst system according to the present invention, it is described to be used as internal electron donor chemical combination
The glycol ester compounds of object can may include but be not limited only to for common glycol ester compounds in the art, specific example:
2,4-PD dibenzoate, two p-methylbenzoic acid ester of 2,4-PD, two m-methyl benzoic acid ester of 2,4-PD, 2,
Two o-toluic acid ester of 4- pentanediol, two p-ethylbenzoic acid ester of 2,4-PD, 2,4-PD two are to n-propylbenzene first
Acid esters, two cumfrey ester of 2,4-PD, 2,4-PD two are right to isobutyl-benzene formic acid esters, 2,4-PD two
N-butylbenzoic acid ester, two p-tert-butyl benzoic acid ester of 2,4-PD, 3- methyl -2,4-PD dibenzoate, 3- second
Base -2,4-PD dibenzoate, 3- n-propyl -2,4-PD dibenzoate, 3- ethyl -2,4-PD two are to first
Yl benzoic acid ester, two p-ethylbenzoic acid ester of 3- ethyl -2,4-PD, 3- ethyl -2,4-PD two are to n-propylbenzene first
Acid esters, two cumfrey ester of 3- ethyl -2,4-PD, 3- ethyl -2,4-PD two to isobutyl-benzene formic acid esters,
3- ethyl -2,4-PD two to n-butylbenzoic acid ester, two p-tert-butyl benzoic acid ester of 3- ethyl -2,4-PD, 3- just
Butyl -2,4-PD dibenzoate, 3,3- dimethyl -2,4-PD dibenzoate, the chloro- 2,4-PD hexichol of 3-
The bromo- 2,4-PD dibenzoate of formic acid esters, 3-, 3,5- heptandiol dibenzoate, 3,5- heptandiol two are to methylbenzene first
Acid esters, two p-ethylbenzoic acid ester of 3,5- heptandiol, 3,5- heptandiol two are to n-propylbenzene formic acid esters, 3,5- heptandiol two to different
Propylbenzoic acid ester, 3,5- heptandiol two are to isobutyl-benzene formic acid esters, 3,5- heptandiol two to n-butylbenzoic acid ester, 3,5- heptan
Two p-tert-butyl benzoic acid ester of glycol, 4- methyl -3,5- heptandiol dibenzoate, 4,4- dimethyl -3,5- heptandiol hexichol
Formic acid esters, 4- ethyl -3,5- heptandiol dibenzoate, two p-methylbenzoic acid ester of 4- ethyl -3,5- heptandiol, 4- ethyl -
Two p-ethylbenzoic acid ester of 3,5- heptandiol, two n-propyl benzoate's ester of 4- ethyl -3,5- heptandiol, 4- ethyl -3,5- heptan two
Alcohol two is to butylbenzoic acid ester, two p-tert-butyl benzoic acid ester of 4- ethyl -3,5- heptandiol, 4- n-propyl -3,5- heptandiol two
Benzoic ether, 4- normal-butyl -3,5- heptandiol dibenzoate, the chloro- 3,5- heptandiol dibenzoate of 4-, 4- bromo- 3,5- heptan
One or more of bisbenzoate etc..
Another specific embodiment of catalyst system according to the present invention, the phthalate compound
Specific example may include but be not limited only to selected from following compounds: repefral, phthalic acid diethyl
Ester, n-propyl phthalate, diisopropyl phthalate, n-butyl phthalate, two isobutyl of phthalic acid
The just own ester of ester, amyl phthalate, di-iso-amyl phthalate, phthalic acid two, two dissident of phthalic acid
Ester, di-n-octyl phthalate, diisooctyl phthalate, two Bian ester of phthalic acid, tetramethyl phthalic acid two
Methyl esters, tetramethyl diethyl phthalate, tetramethyl n-propyl phthalate, tetramethyl phthalic acid diisopropyl
Ester, tetramethyl n-butyl phthalate, tetramethyl diisobutyl phthalate, tetramethyl phthalic acid two positive penta
The just own ester of ester, tetramethyl di-iso-amyl phthalate, tetramethyl phthalic acid two, two dissident of tetramethyl phthalic acid
Ester, tetramethyl di-n-octyl phthalate, tetramethyl diisooctyl phthalate, two Bian ester of tetramethyl phthalic acid,
Tetrabromophthalate dimethyl ester, tetrabromophthalate diethylester, tetrabromophthalate di-n-propyl ester, tetrabromo-phthalic diformazan
Sour diisopropyl ester, tetrabromophthalate di-n-butyl, tetrabromophthalate diisobutyl ester, tetrabromophthalate two positive penta
The just own ester of ester, tetrabromophthalate diisoamyl ester, tetrabromophthalate two, two dissident's ester of tetrabromophthalate, tetrabromo
One of two Bian ester of di-n-octyl phthalate, tetrabromophthalate di-isooctyl and tetrabromophthalate etc. is more
Kind.
Another specific embodiment of catalyst system according to the present invention, it is described to be used as internal electron donor chemical combination
The diether compounds of object are diether compound commonly used in the art, can be selected from but be not limited only to: 2,2- dimethyl -1,3- bis-
Methoxy propane, 2,2- diethyl -1,3- dimethoxy propane, 2,2- dipropyl -1,3- dimethoxy propane, 2,2- diisopropyl
Base -1,3- dimethoxy propane, 2,2- dibutyl -1,3- dimethoxy propane, 2,2- diisobutyl -1,3- dimethoxy third
Alkane, 2,2- diamyl -1,3- dimethoxy propane, 2,2- diisoamyl -1,3- dimethoxy propane, ethyl -1 2- methyl -2-,
3- dimethoxy propane, 2- methyl-2-propyl -1,3- dimethoxy propane, 2- methyl -2- isopropyl -1,3- dimethoxy third
Alkane, 2- methyl -2- butyl -1,3- dimethoxy propane, 2- methyl -2- isobutyl group -1,3- dimethoxy propane, 2- methyl -2-
Amyl -1,3- dimethoxy propane, 2- methyl -2- isopentyl -1,3- dimethoxy propane, 2- ethyl -2- propyl -1,3- diformazan
Oxygroup propane, 2- ethyl -2- isopropyl -1,3- dimethoxy propane, 2- ethyl -2- butyl -1,3- dimethoxy propane, 2- second
Base -2- isobutyl group -1,3- dimethoxy propane, 2- ethyl -2- amyl -1,3- dimethoxy propane, 2- ethyl -2- isopentyl -
1,3- dimethoxy propane, 2- propyl -2- isopropyl -1,3- dimethoxy propane, 2- propyl -2- butyl -1,3- dimethoxy
Propane, 2- propyl -2- isobutyl group -1,3- dimethoxy propane, 2- propyl -2- amyl -1,3- dimethoxy propane, 2- propyl -
2- isopentyl -1,3- dimethoxy propane, 2- isopropyl -2- isobutyl group -1,3- dimethoxy propane, 2- isopropyl -2- amyl -
1,3- dimethoxy propane, 2- isopropyl -2- isopentyl -1,3- dimethoxy propane, 2- butyl -2- isobutyl group -1,3- diformazan
Oxygroup propane, 2- butyl -2- amyl -1,3- dimethoxy propane, 2- butyl -2- isopentyl -1,3- dimethoxy propane, 2- are different
Butyl -2- amyl -1,3- dimethoxy propane, 2- isobutyl group -2- isopentyl -1,3- dimethoxy propane, 2- isobutyl group -2- benzene
Base-1,3- dimethoxy propane, 2- isopentyl-2- phenyl-1,3- dimethoxy propane, 2- (2- methyl butyl) benzyl-1-2-,
3- dimethoxy propane, 2- (2- ethyl-butyl) -2- phenyl -1,3- dimethoxy propane, 2- (2- ethylhexyl) -2- phenyl -
1,3- dimethoxy propane, 2- methyl -2- phenyl -1,3- dimethoxy propane, 2- ethyl -2- phenyl -1,3- dimethoxy third
Alkane, 2- isobutyl group -2- benzyl -1,3- dimethoxy propane, 2- isopentyl -2- benzyl -1,3- dimethoxy propane, 2- (2- first
Base butyl) -2- benzyl -1,3- dimethoxy propane, 2- (2- ethyl-butyl) -2- benzyl -1,3- dimethoxy propane, 2- (2-
Ethylhexyl) -2- benzyl -1,3- dimethoxy propane, 2- propyl -2- benzyl -1,3- dimethoxy propane, 2- isopropyl -2-
Benzyl -1,3- dimethoxy propane, 2- isobutyl group -2- (2- ethyl-butyl) -1,3- dimethoxy propane, 2- isopentyl -2- (2-
Ethyl-butyl) -1,3- dimethoxy propane, 2- (2- methyl butyl) -2- (2- ethyl-butyl) -1,3- dimethoxy propane, 2-
(2- ethylhexyl) -2- (2- ethyl-butyl) -1,3- dimethoxy propane, 2- methyl -2- (2- ethyl-butyl) -1,3- dimethoxy
Base propane, 2- ethyl -2- (2- ethyl-butyl) -1,3- dimethoxy propane, 2- isobutyl group -2- (2- methyl butyl) -1,3- two
Methoxy propane, 2- isopentyl -2- (2- methyl butyl) -1,3- dimethoxy propane, 2- (2- ethyl-butyl) -2- (2- methyl
Butyl) -1,3- dimethoxy propane, 2- (2- ethylhexyl) -2- (2- methyl butyl) -1,3- dimethoxy propane, 2- isobutyl
Base -2- (2- methyl butyl) -1,3- dimethoxy propane, 2- isobutyl group -2- (2- ethylhexyl) -1,3- dimethoxy propane,
2- isopentyl -2- (2- ethylhexyl) -1,3- dimethoxy propane, 2,2- bis- (2- methyl butyl) -1,3- dimethoxy propane,
2- isopropyl -2- isopentyl -1,3- dimethoxy propane, (2- the ethylhexyl) -1,3- dimethoxy propane of 2,2- bis- and 9,9-
One or more of two (methoxy) fluorenes etc..
Another specific embodiment of catalyst system according to the present invention, the succinate compound compound are
Common succinate compound compound in the art, such as 2,3- diη-propyl diethyl succinate, 2,3- diisopropyl succinic acid
Diethylester, 2,3- di-n-butyl diethyl succinate, 2,3- diisobutyl diethyl succinate, 2,3- diη-propyl succinic acid two
Isobutyl ester, 2,3- diisopropyl di-iso-octyl succinate, 2,3- di-n-butyl di-iso-octyl succinate and 2,3- diisobutyl amber
One or more of amber acid diisobutyl ester etc..
According to the present invention, described interior based on the total weight of ingredient of solid catalyst a in the ingredient of solid catalyst a
Electron donor content is 1wt%~25wt%, and such as 3wt%~25wt%, the content of titanium is 0.5wt%~8wt%, the content of magnesium
For 3wt%~25wt%, such as 8wt%~25wt%；Preferably, the internal electron donor content is 5wt%~20wt%, titanium
Content is 1wt%~6wt%, and the content of magnesium is 10wt%~20wt%.It is highly preferred that the content of the internal electron donor is
8wt%~12wt%, the content of titanium are 2wt%~4wt%, and the content of magnesium is 15wt%~20wt%.
Ingredient of solid catalyst a of the present invention for olefinic polymerization, preferably includes titanium compound, magnesium compound
With the reaction product of above-mentioned internal electron donor compound.It is used to prepare titanium compound, the magnesium of the catalyst solid constituent
The dosage for closing object and internal electron donor compound is not particularly limited, and can be respectively the conventional amount used of this field.
Magnesium compound used in it is selected from magnesium dihalide, the hydrate of alkoxy magnesium ﹑ alkane base magnesium ﹑ magnesium dihalide or alcohol and closes
The derivative that one of halogen atom is replaced by oxyl or halogenated oxyl in object and magnesium dihalide molecular formula；Preferably
The alcohol adduct of magnesium dihalide or magnesium dihalide.Specific example such as magnesium dichloride, magnesium dibromide, magnesium diiodide and their alcohol close
Object.
It is TiX that general formula, which can be selected, in titanium compound used in itm(OR1) 4-mCompound, R in formula1For C1~C20Hydrocarbon
Base, X are halogen, 1≤m≤4.Such as: titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide, a chlorine
Triethoxy titanium, dichlorodiethyl oxygroup titanium, one ethanolato-titanium of trichlorine, preferably titanium tetrachloride.
Heretofore described ingredient of solid catalyst a can be prepared by the method being exemplified below.
Method one: as prepared catalyst according to method disclosed in patent CN1506384.Firstly, by magnesium compound with have
Machine alcoholic compound is mixed by 2~5 molar ratios and atent solvent, is warming up to 120~150 DEG C, by magnesium/acid anhydride molar ratio 5~10, magnesium/
Silicon mol ratio 20~50 reacts 1~5 hour.
Then the alcohol adduct for being cooled to room temperature is added to the pre- titanium for being cooled to -15~-40 DEG C according to titanium/magnesium molar ratio 20~50
In compound solution, 90~110 DEG C are warming up to, internal electron donor chemical combination is added according to magnesium/internal electron donor molar ratio 2~10
Object reacts 1~3 hour at 100~130 DEG C, filters to isolate solid particle.
Solid particle is added in compound titanium solution according still further to titanium/magnesium molar ratio 20~50, stir and 100~
130 DEG C are reacted 1.5~3 hours, and solid particle is filtered to isolate.
Solid particle finally is washed with 50~80 DEG C of atent solvent, obtains catalyst after dry.
Method two: it is prepared according to method disclosed in patent CN85100997, firstly, being dissolved in magnesium compound by organic
Epoxide, organic phosphorus compound and inert diluent composition dicyandiamide solution in, formed homogeneous solution after with titanium compound
Solids is precipitated in the presence of precipitation additive in mixing；This solids is handled using internal electron donor compound, makes its load
It invests on solids, when necessary, then with titanium tetrahalide and inert diluent solids is handled, wherein precipitation additive is to have
One of machine acid anhydrides, organic acid, ether, ketone, ester or their mixture.Specifically such as: acetic anhydride, phthalic anhydride, fourth two
Acid anhydrides, maleic anhydride, pyromellitic acid anhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, first and second
Ketone, benzophenone, methyl ether, ether, propyl ether, butyl ether, amyl ether, succinate, malonate, glutarate, 2,4-PD ester, 3,
5- heptandiol ester.
For each component in terms of every mole of magnesium halide, organic epoxy compound object is 0.2~10 mole, and organic phosphorus compound is
0.1~3 mole, precipitation additive is 0~1.0 mole, and titanium compound is 0.5~150 mole, internal electron donor compound 0.02
~0.5 mole.
Method three: catalytic component is prepared according to method disclosed in patent CN1091748.Chlorination magnesium alcoholate melt exists
Disperse in the dispersant system of white oil and silicone oil through high-speed stirred, forms emulsion, be discharged into rapid cooling and shaping, shape in coolant liquid
At chlorination magnesium alcoholate microballoon.Coolant liquid is the lower inert hydrocarbon solvent of boiling point, such as petroleum ether, pentane, hexane, heptane.
Gained chlorination magnesium alcoholate microballoon is washed, it is dry be ball type carrier, the molar ratio of alcohol and magnesium chloride is 2~3, with 2~2.5
Preferably.Diameter of carrier is 10~300 microns, best with 30~150 microns.
It with excessive titanium tetrachloride in the above-mentioned ball type carrier of low-temperature treatment, gradually heats up, is added during processing to electricity
Daughter obtains the spheric catalyst of solid powdery after dry with the multiple unoccupied place of atent solvent after processing.Titanium tetrachloride and chlorination
The molar ratio of magnesium is 20~200, preferably 30~60；Initiated process temperature is -30~0 DEG C, is preferred with -25~-20 DEG C；Finally
Treatment temperature is 80~136 DEG C, is preferred with 100~130 DEG C.
Gained spheric catalyst has the feature that Ti content (weight) 1.5~3.0%, and internal electron donor compound contains
Amount 6.0~20.0%, chlorinity 52~60%, content of magnesium 10~20%, atent solvent content 1~6%, specific surface area of catalyst
Greater than 250m2/g。
Method four: it can also be added in arene compound and be stirred with dialkoxy magnesium, form suspension；Suspension tetravalence
Titanium chloride is handled at -20~100 DEG C, and is reacted at 0~130 DEG C, in the process, in -20~130 DEG C of addition internal electron donors
It is reacted, obtained solid is washed with arene compound；Then at 0~130 DEG C in aromatic hydrocarbon solvent, then with tetravalence chlorine
Change titanium processing, is finally washed, drained with atent solvent, obtain solid catalyst.Wherein every mole of dialkyl magnesium tetravalence chlorination
0.5~100mol of titanium, 0.01~10mol of internal electron donor.
Method five: TiCl is used4Or its arene solution at 80~130 DEG C to such as dialkoxy magnesium or two aryloxy group magnesium it
Two magnesium hydrocarbyloxy compounds of class carry out halogenation, use TiCl4Or its arene solution carries out processing and can be repeated one or more times, and
Internal electron donor compound is added in one or many such processing.
Method six: catalyst is prepared according to method disclosed in patent US4540679.Transistion metal compound is (preferably
Tetravalent titanium compound) and alkoxyl magnesium compound reacted in atent solvent in certain proportion with electron donor, wherein
The molar ratio of transition metal element and magnesium elements is at least 0.5:1, and the dosage of internal electron donor compound is up to 1.0 moles often
Gram titanium atom, atent solvent must facilitate removal, and must dehydration, deoxidation and removing easily make the gas of catalyst poisoning, react -10
~170 DEG C of progress, reaction time are a few minutes to a few houres.
The method of catalyst is prepared also just like by magnesium compound, electron donor etc. forms lotion in diluent, and titanium is added
Compound makes its fixation obtain spherical solid, treated to obtain solid catalyst.
In what above-mentioned a kind of preparation method in office, required internal electron donor compound both can be in the form of compound
It is added；It can also be added, can such as be obtained in situ by using the precursor that internal electron donor compound is suitble in other manners,
The preceding physical efficiency becomes required internal electron donor compound for example, by known chemical reaction such as esterification.
Another specific embodiment of catalyst system according to the present invention, the preferably described alkyl aluminum compound (group
Dividing b) is general formula AlR 'tX3-tShown in alkyl aluminum compound, R ' is selected from hydrogen and C in formula1~C20Alkyl, X is halogen, 1≤t
≤3.The specific example of the alkyl aluminum compound includes triethyl aluminum, tri-propyl aluminum, three n-butylaluminums, triisobutyl aluminium, three
Octyl aluminum, triisobutyl aluminium, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum,
Sesquialter ethylmercury chloride aluminium and ethyl aluminum dichloride, preferably triethyl aluminum, triisobutyl aluminium.Wherein, the use of the alkyl aluminum compound
Amount can be the conventional amount used of this field.A preferred embodiment according to the present invention, mole of the component a and component b
Than with titanium: aluminium is calculated as 1:(5~1000), preferred 1:(20~250).
Goal of the invention according to another preferred, there is provided a kind of method of olefinic polymerization, the alkene is preceding
It states and is polymerize in the presence of catalyst system, obtain olefin polymer.
The reaction of olefinic polymerization of the invention is carried out according to well known polymerization, can be carried out in liquid phase or gas phase,
Or it can also be carried out under the operation that liquid and gas polymerization stage combines.Using conventional technique such as slurry process, gas phase stream
Change bed etc., wherein alkene is selected from ethylene, propylene, 1- butylene, 4-methyl-1-pentene and 1- hexene, the homopolymerization of special propylene with
Or the combined polymerization of propylene other alkene.Preferably it is using following reaction condition: 0~150 DEG C of polymerization temperature, preferably 60~90
℃。
Catalyst system of the invention can be directly added into reactor in polymerization process.Alternatively, prepolymerization is carried out,
Pre-polymerized catalyst is obtained, then is polymerize in first polymer reactor is added.In the present invention, " pre-polymerized catalyst "
Refer to the catalyst for passing through polymerization procedure with lower transforming degree.According to the present invention, the pre-polymerized catalyst includes above-mentioned
Ingredient of solid catalyst and alkene carry out the resulting prepolymer of prepolymerization, and pre-polymerization multiple is that 0.1~1000g olefin polymer/g is solid
Body catalyst component.
Prepolymerization can be carried out using alpha-olefin identical with foregoing alkenes, wherein carrying out prepolymerized alkene and being preferably
Ethylene or propylene.Specifically, it is therefore particularly preferred that be up to one or more α-of 20mol% using ethylene or its surplus
The mixture of alkene carries out prepolymerization.Preferably, the transforming degree of pre-polymerized catalyst components is about 0.2~500 gram of polymerization
Object/gram ingredient of solid catalyst.
Prepolymerization process can carry out in a liquid or in gas phase at a temperature of -20 to 80 DEG C, preferably 0~50 DEG C.In advance
Polymerization procedure can be used as the online progress of a part in continuous polymerization technique, or independently carry out in intermittently operated.For system
Standby amount is the polymer of 0.5~20g/g catalytic component, the batch pre-polymerization of particularly preferred catalyst and ethylene of the present invention.It is poly-
Resultant pressure is 0.01~10MPa.
The general formula of the alkene is CH according to the present invention2=CHR, wherein R is hydrogen or C1-C6Alkyl.The polymerization packet
Include homopolymerization and copolymerization.Described alkene such as ethylene, propylene, butylene, amylene, hexene, octene or 4-methyl-1-pentene etc..
The present invention is used for by using the catalyst system of the external electron donor comprising novel phosphoric acid silicone compounds
When olefinic polymerization, especially propylene polymerization, higher activity and better hydrogen response, the comprehensive performance of catalyst are shown
Preferably.
Specific embodiment
Example given below is in order to illustrate the present invention, without constituting any limitation of the invention.
Test method
Melt index MI: using fusion index instrument under 230 DEG C, 2.16kg pressure, according to ASTMD1238-99
" with the standard test method for squeezing plastometer measurement thermoplasticity fusing flow rate " measurement.
The synthesis of compound
The synthetic route of compound is as follows:
Corresponding di-phosphate ester and haloalkylsiloxanes are used when synthesis, concrete operation step is referring to document Journal
Of Materials Chemistry[2008,18 (17): 2028~2035] or Chinese patent CN101575350A.One, solid
The preparation of body catalyst component
In the 250mL reactor equipped with reflux condenser, mechanical agitator and thermometer and after nitrogen is sufficiently displaced from,
Dehydrated alcohol 36.5mL, anhydrous magnesium chloride 21.3g is added, stirs lower heating, white oil 75mL, silicon is added after magnesium chloride whole dissolution
Oily 75mL maintains 120 DEG C of certain times.In the reaction flask with high speed agitator that another volume is 500mL, it is previously added
The silicone oil of 112.5mL white oil and same volume is preheating to 120 DEG C, and aforementioned mixture is pressed into second reactor rapidly, dimension
120 DEG C are held with 3500rmp stirring 3 minutes, is transferred the material under stirring and is previously added 1600mL hexane and has cooled to -25 DEG C
Third reactor in, until material transfer finish, final temperature be no more than 0 DEG C.It filters, is washed with hexane, be dried in vacuo, obtain
To spherical particle chlorination magnesium alcoholate 41g, the carrier of 100~400 mesh is taken after sieving, the group of analysis test carrier becomes
MgCl2·2.36C2H5OH。
Take above-mentioned MgCl2·2.36C2H5OH ball type carrier 7g be slowly added into equipped with 150mL titanium tetrachloride and is cooled in advance-
In 20 DEG C of reaction flask, 40 DEG C are gradually warming up to, the internal electron donor compound 6mmol in table 1 is added；It is continuously heating to 130
DEG C maintain 2 hours after, filter.Add 120mL TiCl4, 130 DEG C are gradually warming up to, maintains 2 hours, is washed with hexane 60mL
Until repeatedly there is not chloride ion into filtrate, filter cake vacuum drying obtains ingredient of solid catalyst.
Two, propylene polymerization
The catalytic component of above-described embodiment is subjected to propylene polymerization respectively.Propylene polymerization program are as follows: volume be 5L not
Become rusty steel reaction kettle, and after gaseous propylene is sufficiently displaced from, AlEt is added3External donor compound in 2.5mmol, table 1
0.lmmol adds ingredient of solid catalyst 8~10mg and the 1.2L hydrogen of above-mentioned preparation, is passed through liquid propene 2.3L, rises
Temperature maintains this temperature 1 hour to 70 DEG C；Cooling, pressure release obtain the PP powder of Examples 1 to 7 and comparative example 1~4.Polymerization knot
Fruit is shown in Table 1.
1 propylene polymerization result of table
It can be seen that, use phosphoric acid siloxanes shown in general formula (I) for external donor compound, catalyst from table 1
The activity of system preferably, can reach at or above silane external electron donor in the prior art.
Hydrogen is become into 7.2NL, remaining constant polymerization for carrying out propylene the results are shown in Table 2.
Hydrogen response of the table 2 under high hydrogen concentration
As shown in Table 2, when external electron donor is general formula (I) compound represented, the hydrogen response of catalyst system
It improves a lot, is conducive to the polymer for obtaining high fusion index under high hydrogen concentration.
As above data it is known that using phosphoric acid siloxanes shown in general formula (I) for external donor compound, gained
The activity of catalyst system is satisfactory, and hydrogen response is higher.Therefore, the present invention provides a kind of novel caltalysts
System, with wide application prospect.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.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 particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (15)
1. a kind of catalyst system for olefinic polymerization, it includes following components:
A. ingredient of solid catalyst contains Mg, Ti, halogen and at least one internal electron donor chemical combination containing lone pair electrons
Object；
B. alkyl aluminum compound；
C. external electron donor, the external electron donor include phosphoric acid silicone compounds；
The phosphoric acid silicone compounds are phosphoric acid silicone compounds shown in general formula (I),
Wherein R1、R2It is identical or not identical, it is C1-C10Linear chain or branched chain alkyl or cycloalkyl, 1≤n≤6.
2. catalyst system according to claim 1, which is characterized in that R1And R2It is identical or different, it is C1-C4Straight chain or
The alkyl of branch, 1≤n≤3.
3. catalyst system according to claim 1, which is characterized in that phosphoric acid siliconization shown in the general formula (I)
It closes object and is selected from solutions of dimethyl phosphoryl methyltrimethoxysilane, diethylphosphoryl methyltrimethoxysilane, solutions of dimethyl phosphoryl ethyl
Trimethoxy silane, solutions of dimethyl phosphoryl methyltriethoxysilane, diethylphosphoryl methyltriethoxysilane, diethylphosphoryl
Ethyl trimethoxy silane, solutions of dimethyl phosphoryl ethyl triethoxysilane, diethylphosphoryl ethyl triethoxysilane, dipropyl
Phosphonoethyl triethoxysilane, solutions of dimethyl phosphoryl propyl trimethoxy silicane, diethylphosphoryl propyl-triethoxysilicane, two
Ethyl phosphonoethyl tripropoxy silane, dipropyl phosphinylidyne propyl-triethoxysilicane, dipropyl phosphonoethyl tripropoxy silicon
At least one of alkane, diethylphosphoryl propyl tripropoxy silane and dipropyl phosphinylidyne propyl tripropoxy silane.
4. catalyst system according to claim 1, which is characterized in that in the ingredient of solid catalyst a, it is described in give
Electron compound is selected from the compound containing O, N, P or S atom.
5. catalyst system according to claim 4, which is characterized in that in the ingredient of solid catalyst a, it is described in give
Electron compound is the compound containing O atom.
6. catalyst system according to claim 4, which is characterized in that described interior in the ingredient of solid catalyst a
Electron donor compound is selected from least one of ethers, esters, phenolic ether class, phenolic ester class, ether-ether class and ketone compounds.
7. catalyst system according to claim 6, which is characterized in that in the ingredient of solid catalyst a, it is described in give
Electron compound in glycol ester compounds, phthalic acid ester, diether compounds and succinate compound at least
It is a kind of.
8. catalyst system according to claim 1, which is characterized in that the general formula of the alkyl aluminum compound is AlR 'tX3-t, R ' is selected from C in formula1~C20Alkyl, X is halogen, 1≤t≤3.
9. catalyst system according to claim 8, which is characterized in that the alkyl aluminum compound is selected from triethyl group
Aluminium, tri-propyl aluminum, three n-butylaluminums, triisobutyl aluminium, tri-n-octylaluminium, triisobutyl aluminium, a hydrogen diethyl aluminum, a hydrogen two are different
At least one of butyl aluminium, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium and ethyl aluminum dichloride.
10. catalyst system according to claim 1, which is characterized in that in the catalyst system, the component a
Molar ratio with component b is with titanium: aluminium is calculated as 1:(5~1000).
11. catalyst system according to claim 7, which is characterized in that in the catalyst system, the component a
Molar ratio with component b is with titanium: aluminium is calculated as 1:(20~250).
12. catalyst system described in any one of -11 according to claim 1, which is characterized in that in the catalyst system
In, the molar ratio of the component a and component c are with titanium: component c is calculated as 1:(0.1~100).
13. catalyst system according to claim 12, which is characterized in that in the catalyst system, the component a
Molar ratio with component c is with titanium: component c is calculated as 1:(1~50).
14. a kind of method for olefinic polymerization, caltalyst of the alkene described in any one of claim 1-13
Polymerization reaction is carried out in the presence of system, obtains olefin polymer.
15. according to the method for claim 14, which is characterized in that the general formula of the alkene is CH2=CHR, wherein R is hydrogen
Or C1-C6Alkyl.
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