CN104177521B - Prepare method and the catalyst of solid catalyst component for olefine polymerization - Google Patents
Prepare method and the catalyst of solid catalyst component for olefine polymerization Download PDFInfo
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Abstract
The invention discloses a kind of method preparing olefinic polyreaction ingredient of solid catalyst, including magnesium compound being dissolved in the dicyandiamide solution of hydrocarbon-containifirst compound and alcohol compound, at 40～0 DEG C, titanium compound is mixed with above-mentioned solution, at 50～150 DEG C, add electron donor compound, and obtain ingredient of solid catalyst after inert diluent washs；At least one in diol ester compound shown in following logical formula I of described electron donor.The catalyst system provided according to the present invention, its polymerization activity, hydrogen response and stereoselectivity are greatly improved.The ingredient of solid catalyst improved according to the present invention and catalyst, it is possible to prepare high fusion index and the polymer of high isotactic.Compared with prior art, the melt index of polymer is time hydrogen response is suitable at once mutually, and isotactic index improves；When the isotactic index of polymer is suitable, the i.e. hydrogen response of melt index raising improves.
Description
Technical field
The present invention relates to a kind of ingredient of solid catalyst, be specifically related to a kind of for preparing high melting means height isotactic alkene
The ingredient of solid catalyst of hydrocarbon polymer.The invention still further relates to the catalyst system containing this ingredient of solid catalyst
And this caltalyst ties up to the application in olefinic polyreaction.
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 permissible in there is the alpha-olefine polymerizing of 3 carbon or more carbon atom
Obtaining higher yields and the polymer of higher stereoregularity, wherein electron donor compound is catalytic component
In one of requisite composition, and along with the development of internal electron donor compound result in catalyzed polyolefin
Agent is continuously updated the replacement, at present, discloses multiple electron donor compound, the most polynary carboxylic the most in a large number
Acid, monocarboxylic esters or multi-carboxylate, anhydride, ketone, monoether or polyether, alcohol, amine etc. and derivant thereof.
Document is had to disclose a kind of dibasic alcohol ester compound, by using this in olefin polymerization catalysis at present
Kind diol ester compound, as electron donor, the catalyst of available high comprehensive performance, is gathering for propylene
During conjunction, having higher polymerization activity and stereoselectivity, the molecular weight distribution of resulting polymers is the widest, but
The activity of catalyst, hydrogen response and stereoselectivity are the most less than satisfactory, particularly high hydrogen concentration
During lower production high fusion index polymer, the isotactic index of resulting polymers is the highest, needs to be carried further
High.
Summary of the invention
For deficiency of the prior art, inventor is through deeply test, it has unexpectedly been found that, there is specific knot
Ingredient of solid catalyst prepared by the 1,3-glycol benzoic acid ester compounds of structure is for alkene especially propylene polymerization
Time, polymerization activity is high；There is more preferable hydrogen response or when preparing high melting means polymer, can be made
The high isotacticity that people is satisfied.
According to an aspect of the invention, it is provided one prepares olefinic polyreaction ingredient of solid catalyst
Method, including magnesium compound being dissolved in the dicyandiamide solution of hydrocarbon-containifirst compound and alcohol compound, so
After at-40～40 DEG C, titanium compound is mixed with above-mentioned solution, at 50-40～150 DEG C add electron donor
Compound, and obtain ingredient of solid catalyst after inert diluent washs；Described electron donor is selected from following logical
At least one in diol ester compound shown in formula I；
(I)
In logical formula I, R1And R2Can be identical or differ, selected from hydrogen, halogen atom, C1-C10Straight chain alkane
Base, C3-C10The alkyl of side chain, C3-C10Cycloalkyl, C6-C10Aryl, C7-C10Alkaryl and C7-C10Virtue
Alkyl；
R3And R4Can be identical or differ, selected from hydrogen, halogen atom, C1-C10Straight chained alkyl, C3-C10Side chain
Alkyl, C3-C10Cycloalkyl, C6-C10Aryl, C7-C10Alkaryl and C7-C10Aralkyl, R3And R4Appoint
Selection of land keyed jointing cyclization；
R5Selected from C2-C10Straight chained alkyl, C3-C10Branched alkyl, C3-C10Cycloalkyl, C6-C10Aryl and C7-C10
Alkaryl or aralkyl；
N is the integer of 1～5；
R6Selected from C1-C10Straight chained alkyl, C3-C10Branched alkyl, C3-C10Cycloalkyl, C6-C10Aryl and
C7-C15 alkaryl or aralkyl.
In a specific embodiment of said method, the hydrogen on described alkyl or aryl is by halo.
In an embodiment of said method, R1And R2At least one is hydrocarbyl substituent.Above-mentioned side
In one preferred embodiment of method, R1And R2Group is selected from halo or not by the C of halo1-C6Straight chained alkyl and
C3-C6Branched alkyl.R3And R4Selected from hydrogen, halogen atom, C1-C6Straight chained alkyl and C3-C6Branched alkyl,
Or the hydrogen on described alkyl is by halo.R5Selected from C2-C6Straight chained alkyl and C3-C6Branched alkyl.
In the above-mentioned methods, the n in described formula represents the number of benzene ring substituents.Preferably n is 1 or 2；
More preferably n=1, and replace for para-position or ortho position, i.e. substituent group on phenyl ring is para-position or para-position.
In an embodiment of above-mentioned ingredient of solid catalyst, R6Selected from halo or not by the C of halo4-C10
Straight or branched alkyl, C5-C10Cycloalkyl, C6-C10Aryl, C7-C10Alkaryl and C7-C10Aralkyl.
According to the present invention, the instantiation of the described diol ester compound that formula is (I) be selected from but not
Be confined to: 2,4-hexanediol two (4-ethylamino benzonitrile acid esters), 2,4-hexanediol two (4-propyl group yl benzoic acid ester),
2,4-hexanediol two (4-butylbenzoic acid ester), 2,4-hexanediol two (4-isobutyl-benzene formic acid esters), 2,4-oneself two
Alcohol two (4-p t butylbenzoic acid ester), 2,4-hexanediol two (4-hexyl benzene formic acid esters), 3-methyl-2,4-oneself two
Alcohol two (4-ethylamino benzonitrile acid esters), 3-methyl-2,4-hexanediol two (4-propyl group yl benzoic acid ester), 3-methyl-2,4-
Hexanediol two (4-butylbenzoic acid ester), 3-methyl-2,4-hexanediol two (4-isobutyl-benzene formic acid esters), 3-first
Base-2,4-hexanediol two (4-p t butylbenzoic acid ester), 3-methyl-2,4-hexanediol two (4-hexyl benzene formic acid esters),
3-ethyl-2,4-hexanediol two (4-ethylamino benzonitrile acid esters), 3-ethyl-2,4-hexanediol two (4-propyl group yl benzoic acid
Ester), 3-ethyl-2,4-hexanediol two (4-butylbenzoic acid ester), 3-ethyl-2,4-hexanediol two (4-isobutyl group
Benzoate), 3-ethyl-2,4-hexanediol two (4-p t butylbenzoic acid ester), 3-ethyl-2,4-hexanediol two (4-
Hexyl benzene formic acid esters), 3,5-heptandiol two (4-ethylamino benzonitrile acid esters), 3,5-heptandiol two (4-propylbenzoic acid
Ester), 3,5-heptandiol two (4-isopropyl acid ester), 3,5-heptandiol two (4-butylbenzoic acid ester), 3,5-
Heptandiol two (4-isobutyl-benzene formic acid esters), 3,5-heptandiol two (4-p t butylbenzoic acid ester), 3,5-heptandiol
Two (4-amylbenzene formic acid esters), 3,5-heptandiol two (4-hexyl benzene formic acid esters), 3,5-heptandiol-cinnamic acid-4-
Ethylamino benzonitrile acid esters, 4-methyl-3,5-heptandiol two (4-ethylamino benzonitrile acid esters), 4-methyl-3,5-heptandiol two (4-
Propylbenzoic acid ester), 4-methyl-3,5-heptandiol two (4-isopropyl acid ester), 4-methyl-3,5-heptandiol
Two (4-butylbenzoic acid esters), 4-methyl-3,5-heptandiol two (4-isobutyl-benzene formic acid esters), 4-methyl-3,5-
Heptandiol two (4-p t butylbenzoic acid ester), 4-methyl-3,5-heptandiol two (4-amylbenzene formic acid esters), 4-first
Base-3,5-heptandiol two (4-hexyl benzene formic acid esters), 4-methyl-3,5-heptandiol-cinnamic acid-4-ethylamino benzonitrile acid esters,
4-ethyl-3,5-heptandiol two (4-ethylamino benzonitrile acid esters), 4-ethyl-3,5-heptandiol two (4-propylbenzoic acid ester),
4-ethyl-3,5-heptandiol two (4-isopropyl acid ester), 4-ethyl-3,5-heptandiol two (4-butylbenzoic acid
Ester), 4-ethyl-3,5-heptandiol two (4-isobutyl-benzene formic acid esters), 4-ethyl-3,5-heptandiol two (the tertiary fourth of 4-
Yl benzoic acid ester), 4-ethyl-3,5-heptandiol two (4-amylbenzene formic acid esters), 4-ethyl-3,5-heptandiol two (4-
Hexyl benzene formic acid esters), 4-ethyl-3,5-heptandiol-cinnamic acid-4-ethylamino benzonitrile acid esters, 4-propyl group-3,5-heptandiol
Two (4-p t butylbenzoic acid esters), 4-butyl-3,5-heptandiol two (4-p t butylbenzoic acid ester), 2,4-diformazan
Base-3,5-heptandiol two (4-p t butylbenzoic acid ester), 2,6-dimethyl-3,5-heptandiol two (4-tert-butyl benzene first
Acid esters), 4,4-dimethyl-3,5-heptandiol two (4-p t butylbenzoic acid ester), 2,2-dimethyl-3,5-heptandiol two
(4-p t butylbenzoic acid ester), 2-methyl-4-ethyl-3,5-heptandiol two (4-butylbenzoic acid ester), 4-methyl
-4-ethyl-3,5-heptandiol two (4-p t butylbenzoic acid ester), 2-methyl-4-propyl group-3,5-heptandiol two (uncle 4-
Butylbenzoic acid ester), 3-methyl-3-propyl group-3,5-heptandiol two (4-p t butylbenzoic acid ester), 4-methyl-4-
Propyl group-3,5-heptandiol two (4-p t butylbenzoic acid ester), 3-methyl-2,4-heptandiol two (4-propylbenzoic acid ester),
3-methyl-2,4-heptandiol two (3-propylbenzoic acid ester), 3,6-dimethyl-2,4-heptandiol two (4-tert-butyl benzene first
Acid esters), 2,2,6,6-tetramethyl-3,5-heptandiol two (4-p t butylbenzoic acid ester), 4-methyl-3,5-ethohexadiol two
(4-butylbenzoic acid ester), 4-ethyl-3,5-ethohexadiol two (4-p t butylbenzoic acid ester), 4-propyl group-3,5-are pungent
Glycol two (4-p t butylbenzoic acid ester), 4-butyl-3,5-ethohexadiol two (4-p t butylbenzoic acid ester), 4,4-
Dimethyl-3,5-ethohexadiol two (4-butylbenzoic acid ester), 4,4-diethyl-3,5-ethohexadiol two (4-propylbenzene first
Acid esters), 4,4-dipropyl-3,5-ethohexadiol two (4-p t butylbenzoic acid ester), 4-methyl-4-ethyl-3,5-pungent two
Alcohol two (4-second butylbenzoic acid ester), 2-methyl-4-ethyl-3,5-ethohexadiol two (4-p t butylbenzoic acid ester),
2-methyl-6-ethyl-3,5-ethohexadiol two (4-p t butylbenzoic acid ester), 4,6-nonanediol two (4-ethyl benzoate
Ester), 4,6-nonanediol two (4-propylbenzoic acid ester), 4,6-nonanediol two (4-butylbenzoic acid ester), 4,6-
Nonanediol two (4-isobutyl-benzene formic acid esters), 4,6-nonanediol two (4-p t butylbenzoic acid ester), 4,6-nonanediol
Two (4-hexyl benzene formic acid esters), 4,6-nonanediol-cinnamic acid-4-ethylamino benzonitrile acid esters, 5-methyl-4,6-nonanediol
Two (4-ethylamino benzonitrile acid esters), 5-methyl-4,6-nonanediol two (4-propylbenzoic acid ester), 5-methyl-4,6-nonyl
Glycol two (4-butylbenzoic acid ester), 5-methyl-4,6-nonanediol two (4-isobutyl-benzene formic acid esters), 5-methyl
-4,6-nonanediol two (4-p t butylbenzoic acid ester), 5-methyl-4,6-nonanediol two (4-hexyl benzene formic acid esters),
5-ethyl-4,6-nonanediol two (4-ethylamino benzonitrile acid esters), 5-ethyl-4,6-nonanediol two (4-propylbenzoic acid ester),
5-ethyl-4,6-nonanediol two (4-butylbenzoic acid ester), 5-ethyl-4,6-nonanediol two (4-isobutyl-benzene formic acid
Ester), 4,6-nonanediol two (4-p t butylbenzoic acid ester), 5-ethyl-4,6-nonanediol two (4-hexyl benzene formic acid
Ester), 5-propyl group-4,6-nonanediol two (4-p t butylbenzoic acid ester), 5-butyl-4,6-nonanediol two (4-butyl
Benzoate), 5,5-dimethyl-4,6-nonanediol two (4-p t butylbenzoic acid ester), 5,5-diethyl-4,6-nonyl two
Alcohol two (4-hexyl benzene formic acid esters), 5,5-dipropyl-4,6-nonanediol two (4-amylbenzene formic acid esters), 5,5-bis-fourth
Base-4,6-nonanediol two (4-p t butylbenzoic acid ester) etc..
In the above-mentioned methods, described magnesium compound is selected from magnesium dihalide, alkoxyl magnesium alkyl magnesium dihalide
In the hydrate of magnesium or alcohol adduct, and magnesium dihalide, a halogen atom is put by alkoxyl or halogenated alkoxy
In the derivant changed, preferably magnesium compound is selected from magnesium dihalide and alcohol adduct thereof and alkoxyl magnesium.
It is TiX that described titanium compound can be selected for formulam(OR1)4-mCompound, R in formula1For C1～C20Hydrocarbon
Base, X is halogen, 1≤m≤4.Such as: 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 tetrachloro
Change titanium.
Described hydrocarbon compound includes the C of straight or branched6-C12Alkane and C6-C15Aromatic hydrocarbon, the most such as
Hexane, heptane, octane, nonane, decane, benzene,toluene,xylene etc..Alcohol compound includes fat
Alcohol, alicyclic ring alcohol and aromatic alcohol, wherein fatty alcohol is the C of straight or branched1-C10Fatty alcohol, alicyclic ring alcohol is C3-C10
Ring race fatty alcohol, aromatic alcohol is C6-C20Aryl alcohol or alkylaryl alcohol；Concrete the most such as: ethanol, propanol,
Butanol, amylalcohol, hexanol, capryl alcohol, isooctanol etc., or their mixture.
Described inert diluent is selected from hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene.
In the ingredient of solid catalyst that said method prepares, gross weight based on ingredient of solid catalyst,
The content of the diol ester compound shown in described logical formula I is 1～20wt%, and the content of titanium is 1～6wt%,
The content of magnesium is 3～25wt%.Preferably, the content of the diol ester compound shown in described logical formula I is
5～15wt%, the content of titanium is 1～5wt%, and the content of magnesium is 13～20wt%.
Heretofore described ingredient of solid catalyst can be prepared by the following method.As according to patent
Method disclosed in CN1040379 prepares catalytic component.First, by magnesium compound and organic alcohol compound
Mix by 2～5 mol ratios and atent solvent, be warming up to 120～150 DEG C, anti-by magnesium/acid anhydride mol ratio 5～10
Answer 1～5 hour.Then according to the alcohol adduct being cooled to room temperature is joined pre-being cooled to by titanium/magnesium mol ratio 20～50
-15～the compound titanium solution of-40 DEG C in, be warming up to 90～110 DEG C, according to magnesium/electron donor mol ratio 2～
10 add a kind of being selected from leads to the compound shown in formula I in 100～130 DEG C of reactions 1～3 hour, filtration
Isolate solid particle.According still further to titanium/magnesium mol ratio 20～50, solid particle is joined compound titanium solution
In, stirring is also reacted 1.5～3 hours at 100～130 DEG C, filters to isolate solid particle.Finally with 50～
The atent solvent washing solid particle of 80 DEG C, obtains ingredient of solid catalyst after drying.
In 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, as fitted by using electron donor compound (I)
The precursor closed obtains in situ, and this front physical ability becomes required by such as known chemical reaction such as esterification etc.
The electron donor compound wanted.
According to another aspect of the present invention, it is provided that a kind of catalyst for olefinic polyreaction, comprise
The product of following component:
The ingredient of solid catalyst that component a. is above-mentioned；With
Component b. alkyl aluminum compound.
In above-mentioned catalyst system, alkyl aluminum compound be formula be AlRnX3-nCompound, R in formula
For the alkyl that hydrogen, carbon number are 1～20, X is halogen, and n is the number of 1≤n≤3；Specifically it is selected from three second
Base aluminum, tri-propyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-octylaluminium, three iso-octyl aluminum, a hydrogen
Diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride
Aluminum, ethyl aluminum dichloride, preferably triethyl aluminum, triisobutyl aluminium.
In a specific embodiment of above-mentioned catalyst system, described catalyst system includes component c and group
Dividing the product of a and b, described component c is external electron donor, for organo-silicon compound, ethers, esters
Or its mixture.Add external donor compound, it is possible to obtain the olefin polymer that stereoregularity is the highest.
Such as formula is RnSi(OR′)4-nOrgano-silicon compound, 0≤n≤3 in formula, R and R ' is for of the same race or different
Alkyl, cycloalkyl, aryl, haloalkyl, amido, R can also be halogen or hydrogen atom.Such as: front three
Methoxylsilane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyl diethoxy silicon
Alkane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyl triethoxysilane, phenyl three
Methoxy silane, vinyltrimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, methyl tertbutyl two
Methoxy silane, preferably Cyclohexyl Methyl Dimethoxysilane, dimethoxydiphenylsilane.As giving outward
The compound of electron, it is also possible to be ether compound such as 1,3-diether, and ester type compound such as benzoic acid monoesters,
Benzoic acid diester, diol ester compound, it is also possible to be the mixture of organo-silicon compound, ethers, esters.
In above-mentioned catalyst system, wherein the ratio of component a and component b is with titanium: aluminum is calculated as 1:(5～1000)；
Ratio between described component a and component c, with titanium: the molar ratio computing between silicon (or ether, or ester) is 1:
(0～500).
The catalyst system of the present invention can be directly added into for polymerization process in reactor, or caltalyst
System can participate in prepolymerization before adding first reaction, and in the present invention, term " prepolymerization " refers to relatively low
Transforming degree is polymerized.According to the present invention, described pre-polymerized catalyst comprises above-mentioned ingredient of solid catalyst
And carrying out the prepolymer of prepolymerization gained with alkene, pre-polymerization multiple is that 0.1～1000g olefin polymer/g is solid
Body catalyst component.
The alpha-olefin identical with foregoing alkenes can be used to carry out prepolymerization, wherein carry out prepolymerized alkene
It is preferably ethylene or propylene.Specifically, ethylene or propylene is particularly preferably used to be up to amount
The mixture of one or more alpha-olefins of 20mol% carries out prepolymerization.Preferably, pre-polymerized catalyst group
The transforming degree divided is about 0.2～800g polymer/gram ingredient of solid catalyst.
Prepolymerization operation can be at-40～80 DEG C, at a temperature of preferably-20～50 DEG C, in a liquid or gas phase
In carry out.Prepolymerization step can be carried out online as the part in continuous polymerization technique, or interval behaviour
Work is carried out independently.For the polymer that preparation amount is 0.5～20g/g ingredient of solid catalyst, particularly preferably
Catalyst of the present invention and the batch pre-polymerization of propylene.Polymerization pressure is 0.01～10MPa.
According to a further aspect in the invention, it is provided that a kind of olefine polymerizing process, described alkene is at above-mentioned solid
It is polymerized in the presence of catalytic component, catalyst system or pre-polymerized catalyst.
The catalyst system of the present invention can be directly added in reactor in polymerization process, or catalyst
System 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 enter in liquid phase or gas phase
OK, or can also liquid and gas polymerization stage combination operation under carry out.Use conventional technique such as
Slurry process, gas-phase fluidized-bed etc..It is preferably to use following reaction condition: polymerization temperature 0～150 DEG C, preferably
60～90 DEG C.
The formula of heretofore described alkene is CH2=CHR, wherein R is hydrogen or C1～C12Alkyl or virtue
Base；As selected from ethylene, propylene, 1-butylene, 4-methyl-1-pentene and 1-hexene；It is preferably selected from ethylene and propylene.
All polymerizations and or the combined polymerization of other alkene of propylene such as propylene.It is equal that the inventive method is also applied for such as ethylene
Gather and ethylene and alpha-olefin, such as propylene, butylene, amylene, hexene, octene, the copolymerization of 4-methyl-1-pentene.
It is worthy of note, the ingredient of solid catalyst of the present invention employs on the straight chain containing special construction
Containing non-end group glycol more than 6 carbon atoms with at least contain 1 CmThe benzene of (m >=2) hydrocarbyl substituent
The diol ester (as shown in logical formula I) that formic acid reacts and obtains, the diol ester of this special construction can make catalysis
Agent system improves its hydrogen response and polymerization activity further.
According to the present invention, the catalyst system of the diol ester compound of present invention offer is used to be used for olefinic polymerization,
Particularly under high hydrogen concentration, the hydrogen response of catalyst improves or resulting polymers is with boiling heptane extracting
The isotactic index that insoluble matter represents has had and has significantly increased, the beneficially exploitation of the polymer difference trade mark.
The ingredient of solid catalyst improved according to the present invention and catalyst, it is possible to prepare high fusion index and high
The polymer of normality.Compared with prior art, the melt index of polymer is time hydrogen response is suitable at once mutually,
Isotactic index improves；When the isotactic index of polymer is suitable, the i.e. hydrogen response of melt index raising improves.
Detailed description of the invention
Example given below is only used for being explained and illustrated the present invention, is not intended that the present invention's
Any restriction.
Method of testing
1. polymer isotactic index (TII) uses heptane extraction process to measure (heptane boiling extracting 6 hours): 2g
The polymer samples being dried, is placed in extractor after extracting 6 hours with boiling heptane, is done by residue
The dry polymer weight (g) to constant weight gained with 2 ratio be isotactic index.
2. the melt index (MI) of polymer is measured by testing standard GB/T3682 2000.
3. the content liquid chromatogram measuring of diol ester (II), liquid chromatograph is Waters-600E high-efficient liquid phase color
Spectrum, the pillar of C-18, column temperature is 30 DEG C, and methanol-water is flowing phase, flow velocity 1.0ml/min, ultraviolet
Detector.
4.Ti content ultraviolet-visible spectrophotometer 752S measures, with 1mol sulphuric acid as blank solution.
One, the preparation of ingredient of solid catalyst
Under nitrogen protection, 4.8g anhydrous magnesium chloride, 19.5g isooctanol and 19.5g decane solvent are joined
Equipped with in the 500ml reactor of agitator, it is heated to 130 DEG C, reacts and be completely dissolved to magnesium chloride for 1.5 hours,
Add 1.1g phthalic anhydride, continue to 130 DEG C of reactions and obtain alcohol adduct in 1 hour；Alcohol adduct is cooled to room temperature.
Under nitrogen protection, above-mentioned alcohol adduct is added drop-wise in the pre-120ml titanium tetrachloride solution being cooled to-22 DEG C,
It is to slowly warm up to 100 DEG C, adds the diol ester compound that formula is (I) in 10mmol table 1, heat up
Maintain 2 hours to 110 DEG C, mixture filtered while hot.Add 120 milliliters of titanium tetrachlorides the most again, be warmed up to
110 DEG C are reacted 1 hour, filter, and with anhydrous hexane solid particle 4 times, obtain solid catalysis after drying
Agent component.
Two, propylene polymerization experiment
The catalytic component of above-described embodiment is carried out respectively propylene polymerization.Propylene polymerization program is: volume is
The stainless steel cauldron of 5L, after gaseous propylene is sufficiently displaced from, adds AlEt32.5mmol, methylcyclohexyl
Dimethoxysilane (CHMMS) 0.l mmol, adds the ingredient of solid catalyst 8-10mg of above-described embodiment
And a certain amount of hydrogen, it is passed through liquid propene 2.3L, is warming up to 70 DEG C, maintain this temperature 1 hour；Fall
Temperature, pressure release, obtain the PP powder of embodiment 1-5 and comparative example 1.The results are shown in Table 1.
Table 1 propylene polymerization result
ID1:2,4-hexanediol two (4-propylbenzoic acid ester)
ID2:3,5-heptandiol two (4-propylbenzoic acid ester)
ID3:3,5-heptandiol two (4-butylbenzoic acid ester) ID4:3,5-heptandiol dibenzoate
ID5:3,5-heptandiol cinnamic acid (4-propylbenzoic acid) ester
ID6:4-ethyl-3,5-heptandiol two (4-p t butylbenzoic acid ester)
From above embodiment it can be seen that when the diol ester compound of employing special construction, be possible not only to show
Write the activity improving catalyst, and under high hydrogen concentration, the hydrogen response of catalyst improves (gained
The melt index of polymer improves), or further increase the isotactic index of catalyst resulting polymers.
The foregoing is only the preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any those skilled in the art, in technical scope disclosed by the invention, can be changed easily or become
Change, and this being altered or varied all is contained within protection scope of the present invention.Therefore, the protection of the present invention
Scope should be as the criterion with the protection domain of claims.
Claims (10)
1. the method preparing olefinic polyreaction ingredient of solid catalyst, is dissolved in including by magnesium compound
In the dicyandiamide solution of hydrocarbon-containifirst compound and alcohol compound, then at-40～40 DEG C by titanium compound with above-mentioned
Solution mixes, and adds electron donor compound at-40～150 DEG C, obtains institute after inert diluent washs
State ingredient of solid catalyst；Described electron donor is selected from diol ester compound shown in following logical formula I extremely
Few one；
In formula, R1And R2Can be identical or differ, selected from hydrogen, halogen atom, C1-C10Straight chained alkyl, C3-C10
The alkyl of side chain, C3-C10Cycloalkyl, C6-C10Aryl, C7-C10Alkaryl and C7-C10Aralkyl；
R3And R4Can be identical or differ, selected from hydrogen, halogen atom, C1-C10Straight chained alkyl, C3-C10Branched alkane
Base, C3-C10Cycloalkyl, C6-C10Aryl, C7-C10Alkaryl and C7-C10Aralkyl, R3And R4Optionally
Keyed jointing cyclization；
R5Selected from C2-C10Straight chained alkyl, C3-C10Branched alkyl, C3-C10Cycloalkyl, C6-C10Aryl and C7-C10
Alkaryl or aralkyl；
N is the integer of 1～5；
R6Selected from C1-C10Straight chained alkyl, C3-C10Branched alkyl, C3-C10Cycloalkyl, C6-C10Aryl and C7-C15
Alkaryl or aralkyl；
Diol ester compound shown in described logical formula I selected from 2,4-hexanediol two (4-propylbenzoic acid ester),
2,4-hexanediol two (4-butylbenzoic acid ester), 2,4-hexanediol two (4-isobutyl-benzene formic acid esters), 2,4-oneself two
Alcohol two (4-p t butylbenzoic acid ester), 2,4-hexanediol two (4-hexyl benzene formic acid esters), 3-methyl-2,4-oneself two
Alcohol two (4-propylbenzoic acid ester), 3-methyl-2,4-hexanediol two (4-butylbenzoic acid ester), 3-methyl-2,4-
Hexanediol two (4-isobutyl-benzene formic acid esters), 3-methyl-2,4-hexanediol two (4-p t butylbenzoic acid ester), 3-
Methyl-2,4-hexanediol two (4-hexyl benzene formic acid esters), 3-ethyl-2,4-hexanediol two (4-propylbenzoic acid ester),
3-ethyl-2,4-hexanediol two (4-butylbenzoic acid ester), 3-ethyl-2,4-hexanediol two (4-isobutyl-benzene formic acid
Ester), 3-ethyl-2,4-hexanediol two (4-p t butylbenzoic acid ester), 3-ethyl-2,4-hexanediol two (4-hexyl
Benzoate), 3,5-heptandiol two (4-propylbenzoic acid ester), 3,5-heptandiol two (4-isopropyl acid
Ester), 3,5-heptandiol two (4-butylbenzoic acid ester), 3,5-heptandiol two (4-isobutyl-benzene formic acid esters),
3,5-heptandiol two (4-p t butylbenzoic acid ester), 3,5-heptandiol two (4-hexyl benzene formic acid esters), 3,5-heptan two
Alcohol-cinnamic acid-4-ethylamino benzonitrile acid esters, 4-methyl-3,5-heptandiol two (4-propylbenzoic acid ester), 4-methyl-3,5-
Heptandiol two (4-isopropyl acid ester), 4-methyl-3,5-heptandiol two (4-butylbenzoic acid ester), 4-
Methyl-3,5-heptandiol two (4-isobutyl-benzene formic acid esters), 4-methyl-3,5-heptandiol two (4-p t butylbenzoic acid
Ester), 4-methyl-3,5-heptandiol two (4-hexyl benzene formic acid esters), 4-methyl-3,5-heptandiol-cinnamic acid-4-second
Yl benzoic acid ester, 4-ethyl-3,5-heptandiol two (4-propylbenzoic acid ester), 4-ethyl-3,5-heptandiol two (4-
Isopropyl acid ester), 4-ethyl-3,5-heptandiol two (4-butylbenzoic acid ester), 4-ethyl-3,5-heptandiol
Two (4-isobutyl-benzene formic acid esters), 4-ethyl-3,5-heptandiol two (4-p t butylbenzoic acid ester), 4-ethyl-3,5-
Heptandiol two (4-hexyl benzene formic acid esters), 4-ethyl-3,5-heptandiol-cinnamic acid-4-ethylamino benzonitrile acid esters, 4-third
Base-3,5-heptandiol two (4-p t butylbenzoic acid ester), 4-butyl-3,5-heptandiol two (4-p t butylbenzoic acid ester),
2,4-dimethyl-3,5-heptandiol two (4-p t butylbenzoic acid ester), 2,6-dimethyl-3,5-heptandiol two (uncle 4-
Butylbenzoic acid ester), 4,4-dimethyl-3,5-heptandiol two (4-p t butylbenzoic acid ester), 2,2-dimethyl-3,5-
Heptandiol two (4-p t butylbenzoic acid ester), 2-methyl-4-ethyl-3,5-heptandiol two (4-butylbenzoic acid ester),
4-methyl-4-ethyl-3,5-heptandiol two (4-p t butylbenzoic acid ester), 2-methyl-4-propyl group-3,5-heptandiol two
(4-p t butylbenzoic acid ester), 4-methyl-4-propyl group-3,5-heptandiol two (4-p t butylbenzoic acid ester), 3-
Methyl-2,4-heptandiol two (4-propylbenzoic acid ester), 3-methyl-2,4-heptandiol two (3-propylbenzoic acid ester), 3,6-
Dimethyl-2,4-heptandiol two (4-p t butylbenzoic acid ester), 2,2,6,6-tetramethyl-3,5-heptandiol two (uncle 4-
Butylbenzoic acid ester), 4-methyl-3,5-ethohexadiol two (4-butylbenzoic acid ester), 4-ethyl-3,5-ethohexadiol two
(4-p t butylbenzoic acid ester), 4-propyl group-3,5-ethohexadiol two (4-p t butylbenzoic acid ester), 4-butyl-3,5-
Ethohexadiol two (4-p t butylbenzoic acid ester), 4,4-dimethyl-3,5-ethohexadiol two (4-butylbenzoic acid ester),
4,4-diethyl-3,5-ethohexadiol two (4-propylbenzoic acid ester), 4,4-dipropyl-3,5-ethohexadiol two (the tertiary fourth of 4-
Yl benzoic acid ester), 4-methyl-4-ethyl-3,5-ethohexadiol two (4-second butylbenzoic acid ester), 2-methyl-4-second
Base-3,5-ethohexadiol two (4-p t butylbenzoic acid ester), 2-methyl-6-ethyl-3,5-ethohexadiol two (the 4-tert-butyl group
Benzoate), 4,6-nonanediol two (4-propylbenzoic acid ester), 4,6-nonanediol two (4-butylbenzoic acid ester),
4,6-nonanediol two (4-isobutyl-benzene formic acid esters), 4,6-nonanediol two (4-p t butylbenzoic acid ester), 4,6-
Nonanediol two (4-hexyl benzene formic acid esters), 4,6-nonanediol-cinnamic acid-4-ethylamino benzonitrile acid esters, 5-methyl-4,6-
Nonanediol two (4-propylbenzoic acid ester), 5-methyl-4,6-nonanediol two (4-butylbenzoic acid ester), 5-methyl
-4,6-nonanediol two (4-isobutyl-benzene formic acid esters), 5-methyl-4,6-nonanediol two (4-p t butylbenzoic acid ester),
5-methyl-4,6-nonanediol two (4-hexyl benzene formic acid esters), 5-ethyl-4,6-nonanediol two (4-propylbenzoic acid ester),
5-ethyl-4,6-nonanediol two (4-butylbenzoic acid ester), 5-ethyl-4,6-nonanediol two (4-isobutyl-benzene formic acid
Ester), 5-ethyl-4,6-nonanediol two (4-hexyl benzene formic acid esters), 5-propyl group-4,6-nonanediol two (the 4-tert-butyl group
Benzoate), 5-butyl-4,6-nonanediol two (4-butylbenzoic acid ester), 5,5-dimethyl-4,6-nonanediol two
(4-p t butylbenzoic acid ester), 5,5-diethyl-4,6-nonanediol two (4-hexyl benzene formic acid esters) and 5,5-bis-fourth
Base-4,6-nonanediol two (4-p t butylbenzoic acid ester).
Method the most according to claim 1, it is characterised in that described hydrocarbon compound includes straight chain or props up
The C of chain6-C12Alkane and C6-C15Aromatic hydrocarbon；
Described alcohol compound includes fatty alcohol, alicyclic ring alcohol and aromatic alcohol, and wherein fatty alcohol is straight or branched
C1-C10Fatty alcohol, alicyclic ring alcohol is C3-C10Ring race fatty alcohol, aromatic alcohol is C6-C20Aryl alcohol or alkyl
Aryl alcohol；
Described magnesium compound closes selected from magnesium dihalide, alkoxyl magnesium, alkyl magnesium, the hydrate of magnesium dihalide or alcohol
The derivant that in thing, and magnesium dihalide, a halogen atom is replaced by alkoxyl or halogenated alkoxy；
Described titanium compound is selected from titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, tetraethoxy
Titanium, a chlorine triethoxy titanium, dichlorodiethyl epoxide titanium and tri-chloroethoxy titanium；
Described inert diluent is selected from hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene.
Method the most according to claim 2, it is characterised in that described magnesium compound selected from magnesium dihalide and
Its alcohol adduct and alkoxyl magnesium；Described titanium compound is selected from titanium tetrachloride.
4. according to the method described in any one in claims 1 to 3, it is characterised in that based on solid catalyst
The gross weight of component, shown in described logical formula I, the content of diol ester compound is 1～20wt%, the content of titanium
Being 1～8wt%, the content of magnesium is 3～25wt%.
Method the most according to claim 4, it is characterised in that gross weight based on ingredient of solid catalyst,
Shown in described logical formula I, the content of diol ester compound is 5～15wt%, and the content of titanium is 1～5wt%, magnesium
Content be 13～20wt%.
6., for the catalyst of olefinic polyreaction, comprise the product of following component:
The ingredient of solid catalyst that in component a. Claims 1 to 5 prepared by method described in any one；With
Component b. alkyl aluminum compound.
Catalyst the most according to claim 6, it is characterised in that described catalyst includes component c and group
Dividing the product of a and b, described component c is external electron donor, selected from organo-silicon compound, ethers, ester
Class and its mixture.
8., for a pre-polymerized catalyst for olefinic polyreaction, comprise a kind of according to claim 6 or 7 institute
The catalyst stated and carry out the prepolymer of prepolymerization gained with alkene, pre-polymerization multiple is that 0.1～1000g alkene gathers
Compound/g ingredient of solid catalyst.
Pre-polymerized catalyst the most according to claim 8, it is characterised in that described alkene is ethylene or third
Alkene.
10. an olefine polymerizing process, prepared by described alkene method described in any one in Claims 1 to 5
Ingredient of solid catalyst, the catalyst described in claim 6 or 7 or the pre-polymerization described in claim 8 or 9
Close and be polymerized in the presence of catalyst.
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310190990.5A CN104177521B (en) | 2013-05-21 | 2013-05-21 | Prepare method and the catalyst of solid catalyst component for olefine polymerization |
| TW103117524A TWI644896B (en) | 2013-05-21 | 2014-05-19 | Catalyst component, catalyst and application for olefin polymerization |
| GB1522379.5A GB2530212B (en) | 2013-05-21 | 2014-05-21 | Catalyst component for olefin polymerization reaction, catalyst, and use thereof |
| PCT/CN2014/078050 WO2014187323A1 (en) | 2013-05-21 | 2014-05-21 | Catalyst component for use in olefin polymerization reaction, catalyst, and application |
| US14/892,533 US9751960B2 (en) | 2013-05-21 | 2014-05-21 | Catalyst component for olefin polymerization, catalyst, and use thereof |
| RU2015154533A RU2673083C2 (en) | 2013-05-21 | 2014-05-21 | Catalyst component for olefin polymerisation, catalyst and use thereof |
| KR1020157036140A KR102174946B1 (en) | 2013-05-21 | 2014-05-21 | Catalyst component for use in olefin polymerization reaction, catalyst, and application |
| DE112014002517.8T DE112014002517T5 (en) | 2013-05-21 | 2014-05-21 | Catalyst component for olefin polymerization, catalyst and use thereof |
| ES201590123A ES2557178B2 (en) | 2013-05-21 | 2014-05-21 | Catalyst component for the polymerization of olefins, catalyst and use thereof |
| SG11201509482XA SG11201509482XA (en) | 2013-05-21 | 2014-05-21 | Catalyst component for olefin polymerization, catalyst, and use thereof |
| BR112015028908-8A BR112015028908B1 (en) | 2013-05-21 | 2014-05-21 | CATALYST COMPONENT FOR OLEFINE POLYMERIZATION, CATALYST FOR OLEFINE POLYMERIZATION, PREPOLIMERATION CATALYST FOR OLEFINE POLYMERIZATION, METHOD FOR OLEFINE POLYMERIZATION |
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| CN103012625B (en) * | 2011-09-23 | 2015-03-11 | 中国石油化工股份有限公司 | Olefin polymerization catalyst ingredient, preparation method and use of the olefin polymerization catalyst ingredient, catalyst system, use of the catalyst system, and olefin polymerization method |
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