CN104177520B - It is used to prepare the ingredient of solid catalyst of olefin polymer - Google Patents
It is used to prepare the ingredient of solid catalyst of olefin polymer Download PDFInfo
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Abstract
The present invention provides a kind of ingredient of solid catalyst for olefinic polyreaction, and comprising magnesium, titanium, halogen and electron donor, the electron donor is selected from the following general formula（Ⅰ）At least one of shown glycol ester compounds.According to catalyst provided by the invention, polymerization activity, hydrogen response and stereoselectivity are greatly improved.According to ingredient of solid catalyst and catalyst that the present invention improves, the polymer of high fusion index and high isotactic can be made.Compared with prior art, mutually when hydrogen response is suitable at once, isotactic index improves the melt index of polymer；When the isotactic index of polymer is suitable, melt index improves, i.e., hydrogen response improves.
Description
Technical field
The present invention relates to a kind of ingredients of solid catalyst, and in particular to one kind is used to prepare the high isotactic olefinic polymerization of high melting means
The ingredient of solid catalyst of object.The invention further relates to tied up to containing the catalyst system of the ingredient of solid catalyst and the caltalyst
Application in olefinic polyreaction.
Background technology
It is well known that it can be used for using magnesium, titanium, halogen and electron donor as the solid titanium catalyst component of basis
Olefinic polyreaction, can particularly be obtained in the alpha-olefine polymerizing with 3 carbon or more carbon atom higher yields and compared with
The polymer of high stereoregularity, wherein electron donor compound are one of essential ingredients in catalytic component, and
The replacement is continuously updated as the development of internal electron donor compound results in polyolefin catalyst, it is at present, largely open
A variety of electron donor compounds, such as polybasic carboxylic acid, monocarboxylic esters or multi-carboxylate, acid anhydrides, ketone, monoether or polyether,
Alcohol, amine etc. and its derivative.
There is document to disclose a kind of dibasic alcohol ester compound at present, by using this glycol in olefin polymerization catalysis
Ester compounds can obtain the catalyst of high comprehensive performance as electron donor.The catalyst when for propylene polymerization, have compared with
High polymerization activity and stereoselectivity, the molecular weight distribution of resulting polymers is also wider, but the activity of catalyst, and hydrogen tune is sensitive
Property and stereoselectivity it is also less than satisfactory, particularly under high hydrogen concentration produce high fusion index polymer when, gained gathers
The isotactic index for closing object is high not enough, needs to be further improved.
Invention content
For deficiency of the prior art, inventor is by deeply experiment, it has unexpectedly been found that, have the 1,3- of specific structure
When ingredient of solid catalyst prepared by glycol benzoic acid ester compounds is used for alkene, especially propylene polymerization, polymerization activity is high；Tool
There is better hydrogen response or can obtain satisfactory high isotacticity when preparing high melting means polymer.
According to an aspect of the invention, there is provided a kind of ingredient of solid catalyst for olefinic polyreaction, packet
Containing magnesium, titanium, halogen and electron donor, the electron donor is selected from the following general formula（Ⅰ）In shown glycol ester compounds at least
It is a kind of；
General formula（Ⅰ）In, R1And R2It may be the same or different, selected from hydrogen, halogen atom, C1-C10Straight chained alkyl, C3-C10The alkane of branch
Base, C3-C10Cycloalkyl, C6-C10Aryl, C7-C10Alkaryl and C7-C10Aralkyl；
R3And R4It may be the same or different, selected from hydrogen, halogen atom, C1-C10Straight chained alkyl, C3-C10Branched alkyl, C3-C10Cycloalkanes
Base, C6-C10Aryl, C7-C10Alkaryl and C7-C10Aralkyl, R3And R4Optionally bonded cyclization；
R5Selected from C2-C10Straight chained alkyl, C3-C10Branched alkyl, C3-C10Cycloalkyl, C6-C10Aryl, C7-C10Alkaryl and
C7-C10Aralkyl；
N is 1~5 integer；
R6Selected from C1-C10Straight chained alkyl, C3-C10Branched alkyl, C3-C10Cycloalkyl, C6-C10Aryl, C7-C15Alkaryl and
C7-C15Aralkyl.
In a specific embodiment of above-mentioned ingredient of solid catalyst, the hydrogen on the alkyl or aryl is halogenated.
In an example of above-mentioned ingredient of solid catalyst, R1And R2In at least one be hydrocarbyl substituent.
In a preferred embodiment of above-mentioned ingredient of solid catalyst, R1And R2Group is selected from halogenated or not by halogenated
C1-C6Straight chained alkyl and C3-C6Branched alkyl.In a further advantageous embodiment, R3And R4Selected from hydrogen, halogen atom, C1-C6Straight chain
Alkyl and C3-C6Hydrogen on branched alkyl or the alkyl is halogenated.In a further advantageous embodiment, R5Selected from C2-C6Straight chain
Alkyl and C3-C6Branched alkyl.
In above-mentioned ingredient of solid catalyst, the n in the general formula represents the number of benzene ring substituents.It is preferred that n for 1 or
2；More preferable n=1, and be contraposition or ortho position substitution, i.e. substituent group on phenyl ring is ortho position or contraposition.
In one embodiment of above-mentioned ingredient of solid catalyst, R6Selected from halogenated or not by halogenated C4-C10Straight chain or
Branched alkyl, C5-C10Cycloalkyl, C6-C10Aryl, C7-C10Alkaryl and C7-C10Aralkyl.
According to the present invention, the general formula is（Ⅰ）The specific examples of glycol ester compounds may be selected from but be not limited to：2,4-
Hexylene glycol two（4- ethylamino benzonitrile acid esters）, 2,4- hexylene glycols two（4- propyl yl benzoic acid esters）, 2,4- hexylene glycols two（4- butyl benzenes
Formic acid esters）, 2,4- hexylene glycols two（4- isobutyl-benzene formic acid esters）, 2,4- hexylene glycols two（4- p t butylbenzoic acid esters）, 2,4- oneself
Glycol two（4- hexyl benzoic ethers）, 3- methyl -2,4- hexylene glycols two（4- ethylamino benzonitrile acid esters）, 3- methyl -2,4- hexylene glycols
Two（4- propyl yl benzoic acid esters）, 3- methyl -2,4- hexylene glycols two（4- butylbenzoic acid esters）, 3- methyl -2,4- hexylene glycols two
（4- isobutyl-benzene formic acid esters）, 3- methyl -2,4- hexylene glycols two（4- p t butylbenzoic acid esters）, 3- methyl -2,4- hexylene glycols two
（4- hexyl benzoic ethers）, 3- ethyl -2,4- hexylene glycols two（4- ethylamino benzonitrile acid esters）, 3- ethyl -2,4- hexylene glycols two（4- third
Base yl benzoic acid ester）, 3- ethyl -2,4- hexylene glycols two（4- butylbenzoic acid esters）, 3- ethyl -2,4- hexylene glycols two（4- isobutyls
Yl benzoic acid ester）, 3- ethyl -2,4- hexylene glycols two（4- p t butylbenzoic acid esters）, 3- ethyl -2,4- hexylene glycols two（4- hexyls
Benzoic ether）, 3,5- heptandiols two（4- ethylamino benzonitrile acid esters）, 3,5- heptandiols two（4- propylbenzoic acid esters）, 3,5- heptan two
Alcohol two（4- isopropyl acid esters）, 3,5- heptandiols two（4- butylbenzoic acid esters）, 3,5- heptandiols two（4- isobutyl-benzene first
Acid esters）, 3,5- heptandiols two（4- p t butylbenzoic acid esters）, 3,5- heptandiols two（4- amyl benzoic ethers）, 3,5- heptandiols
Two（4- hexyl benzoic ethers）, 3,5- heptandiols-cinnamic acid -4- ethylamino benzonitriles acid esters, 4- methyl -3,5- heptandiols two（4- second
Yl benzoic acid ester）, 4- methyl -3,5- heptandiols two（4- propylbenzoic acid esters）, 4- methyl -3,5- heptandiols two（4- isopropyls
Benzoic ether）, 4- methyl -3,5- heptandiols two（4- butylbenzoic acid esters）, 4- methyl -3,5- heptandiols two（4- isobutyl-benzenes
Formic acid esters）, 4- methyl -3,5- heptandiols two（4- p t butylbenzoic acid esters）, 4- methyl -3,5- heptandiols two（4- amylbenzene first
Acid esters）, 4- methyl -3,5- heptandiols two（4- hexyl benzoic ethers）, 4- methyl -3,5- heptandiols-cinnamic acid -4- ethylamino benzonitriles
Acid esters, 4- ethyl -3,5- heptandiols two（4- ethylamino benzonitrile acid esters）, 4- ethyl -3,5- heptandiols two（4- propylbenzoic acid esters）、
4- ethyl -3,5- heptandiols two（4- isopropyl acid esters）, 4- ethyl -3,5- heptandiols two（4- butylbenzoic acid esters）、4-
Ethyl -3,5- heptandiols two（4- isobutyl-benzene formic acid esters）, 4- ethyl -3,5- heptandiols two（4- p t butylbenzoic acid esters）、4-
Ethyl -3,5- heptandiols two（4- amyl benzoic ethers）, 4- ethyl -3,5- heptandiols two（4- hexyl benzoic ethers）, 4- ethyls-
3,5- heptandiols-cinnamic acid -4- ethylamino benzonitriles acid esters, 4- propyl -3,5- heptandiols two（4- p t butylbenzoic acid esters）, 4- fourths
Base -3,5- heptandiols two（4- p t butylbenzoic acid esters）, 2,4- dimethyl -3,5- heptandiols two（4- p t butylbenzoic acid esters）、
2,6- dimethyl -3,5- heptandiols two（4- p t butylbenzoic acid esters）, 4,4- dimethyl -3,5- heptandiols two（4- tert-butyl benzenes
Formic acid esters）, 2,2- dimethyl -3,5- heptandiols two（4- p t butylbenzoic acid esters）, 2- methyl -4- ethyl -3,5- heptandiols two
（4- butylbenzoic acid esters）, 4- methyl -4- ethyl -3,5- heptandiols two（4- p t butylbenzoic acid esters）, 2- methyl -4- propyl -
3,5- heptandiols two（4- p t butylbenzoic acid esters）, 3- methyl -3- propyl -3,5- heptandiols two（4- p t butylbenzoic acid esters）、
4- methyl -4- propyl -3,5- heptandiols two（4- p t butylbenzoic acid esters）, two (4- propylbenzoic acids of 3- methyl -2,4- heptandiols
Ester), 3- methyl -2,4- heptandiols two (3- propylbenzoic acids ester), 3,6- dimethyl -2,4- heptandiols two（4- tert-butyl benzene first
Acid esters）, 2,2,6,6- tetramethyl -3,5- heptandiols two（4- p t butylbenzoic acid esters）, 4- methyl -3,5- ethohexadiols two（4- fourths
Yl benzoic acid ester）, 4- ethyl -3,5- ethohexadiols two（4- p t butylbenzoic acid esters）, 4- propyl -3,5- ethohexadiols two（The tertiary fourths of 4-
Yl benzoic acid ester）, 4- butyl -3,5- ethohexadiols two（4- p t butylbenzoic acid esters）, 4,4- dimethyl -3,5- ethohexadiols two（4-
Butylbenzoic acid ester）, 4,4- diethyl -3,5- ethohexadiols two（4- propylbenzoic acid esters）, 4,4- dipropyl -3,5- ethohexadiols two
（4- p t butylbenzoic acid esters）, 4- methyl -4- ethyl -3,5- ethohexadiols two（4- second butylbenzoic acid esters）, 2- methyl -4- second
Base -3,5- ethohexadiols two（4- p t butylbenzoic acid esters）, 2- methyl -6- ethyl -3,5- ethohexadiols two（4- p t butylbenzoic acids
Ester）, 4,6- nonanediols two（4- ethylamino benzonitrile acid esters）, 4,6- nonanediols two（4- propylbenzoic acid esters）, 4,6- nonanediols two（4-
Butylbenzoic acid ester）, 4,6- nonanediols two（4- isobutyl-benzene formic acid esters）, 4,6- nonanediols two（4- p t butylbenzoic acid esters）、
4,6- nonanediols two（4- hexyl benzoic ethers）, 4,6- nonanediols-cinnamic acid -4- ethylamino benzonitriles acid esters, 5- methyl -4,6- nonyls two
Alcohol two（4- ethylamino benzonitrile acid esters）, 5- methyl -4,6- nonanediols two（4- propylbenzoic acid esters）, 5- methyl -4,6- nonanediols two
（4- butylbenzoic acid esters）, 5- methyl -4,6- nonanediols two（4- isobutyl-benzene formic acid esters）, 5- methyl -4,6- nonanediols two（4-
P t butylbenzoic acid ester）, 5- methyl -4,6- nonanediols two（4- hexyl benzoic ethers）, 5- ethyl -4,6- nonanediols two（4- second
Yl benzoic acid ester）, 5- ethyl -4,6- nonanediols two（4- propylbenzoic acid esters）, 5- ethyl -4,6- nonanediols two（4- butyl benzenes
Formic acid esters）, 5- ethyl -4,6- nonanediols two（4- isobutyl-benzene formic acid esters）, 4,6- nonanediols two（4- p t butylbenzoic acid esters）、
5- ethyl -4,6- nonanediols two（4- hexyl benzoic ethers）, 5- propyl -4,6- nonanediols two（4- p t butylbenzoic acid esters）、5-
Butyl -4,6- nonanediols two（4- butylbenzoic acid esters）, 5,5- dimethyl -4,6- nonanediols two（4- p t butylbenzoic acid esters）、
5,5- diethyl -4,6- nonanediols two（4- hexyl benzoic ethers）, 5,5- dipropyl -4,6- nonanediols two（4- amyl benzoic acid
Ester）, 5,5- dibutyl -4,6- nonanediols two（4- p t butylbenzoic acid esters）Deng.
Ingredient of solid catalyst of the present invention for olefinic polyreaction is preferably by by magnesium chemical combination
Object, titanium compound and above-mentioned general formula（Ⅰ）Shown glycol ester compounds carry out what reaction was prepared.It is emphasized that
Prepared by the reaction includes magnesium compound being dissolved in being made of organic epoxy compound object, organic phosphorus compound and inert diluent
Dicyandiamide solution in, formed homogeneous solution after mix with titanium compound, then in the presence of precipitation additive, precipitation solids；Most
This solids is used selected from general formula afterwards（Ⅰ）Compound handled.General formula can be made by processing（Ⅰ）Compound be attached to it is solid
On body object, when necessary, then with titanium tetrahalide and inert diluent solids is handled.Referring specifically to patent
CN85100997。
The magnesium compound is selected from the hydrate or alcohol adduct of magnesium dihalide, alkoxy Mei ﹑ Wan Ji Mei ﹑ magnesium dihalides, with
And the derivative that the halogen atom in magnesium dihalide is replaced by alkoxy or halogenated alkoxy；It is preferred that magnesium dihalide and its alcohol close
Object, such as magnesium dichloride, dibrominated magnesium, magnesium diiodide and their alcohol adduct.
It is preferred that the general formula of the titanium compound is TiXm(OR1)4-m, R in formula1For C1~C20Alkyl, X is halogen, 1≤m
≤4.Such as：Titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro
Diethoxy titanium, one ethanolato-titanium of trichlorine, wherein it is preferred that titanium tetrachloride.
The organic epoxy compound object includes carbon atom number in 2~8 aliphatic olefin, alkadienes, halogenated aliphatic alkene
Hydrocarbon or diene hydrocarbon oxide, glycidol ether and inner ether, particular compound is such as：Ethylene oxide, propylene oxide, epoxy butane, fourth
Allene oxide object, butadiene double oxide, epoxychloropropane, methyl glycidyl ether, diglycidyl ether, tetrahydrofuran.
The organic phosphorus compound is orthophosphoric acid or the hydrocarbyl carbonate of phosphorous acid or halogenated hydrocarbons base ester, 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.
The precipitation additive is selected from organic acid anhydride, organic acid, ether and ketone, specifically such as：Acetic anhydride, phthalic anhydride, fourth
Dicarboxylic anhydride, 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 etc..
In the present invention, magnesium compound can also be dissolved in the dicyandiamide solution containing organic alcohol compound, organic alcohol compound
Object is monohydric alcohol of the carbon atom number 2~8.
In ingredient of solid catalyst of the present invention, each component is in terms of every mole of magnesium halide, organic epoxidation
It is 0.2~10 mole to close object, and organic phosphorus compound is 0.1~3 mole, and precipitation additive is 0~1.0 mole, titanium compound 0.5
~150 moles, general formula（Ⅰ）Propylene glycol ester chemical combination object be 0.02~0.4 mole.
Above-mentioned ingredient of solid catalyst, the total weight based on ingredient of solid catalyst, the general formula（Ⅰ）Shown glycol esterification
The content for closing object is 3~25wt%, and the content of titanium is 1~8wt%, and the content of magnesium is 8~30wt%.Preferably, the general formula（Ⅰ）
The content of shown glycol ester compounds is 5~20wt%, and the content of titanium is 1~6wt%, and the content of magnesium is 10~25wt%.
Heretofore described ingredient of solid catalyst can also be prepared by the method being exemplified below.
Method one：Method as disclosed according to patent CN1040379 prepares catalytic component.First, by magnesium compound
It is mixed with organic alcohol compound by 2~5 molar ratios and atent solvent, is warming up to 120~150 DEG C, by magnesium/acid anhydride molar ratio 5~10
Reaction 1~5 hour.Then the alcohol adduct for being cooled to room temperature is added to according to titanium/magnesium molar ratio 20~50 and pre- is cooled to -15~-40
DEG C compound titanium solution in, be warming up to 90~110 DEG C, added according to magnesium/internal electron donor molar ratio 2~10 a kind of selected from logical
Formula（Ⅰ）Compound represented is reacted 1~3 hour at 100~130 DEG C, filters to isolate solid particle.According still further to titanium/magnesium mole
Solid particle is added in compound titanium solution than 20~50, stir and is reacted 1.5~3 hours at 100~130 DEG C, filtering
Isolate solid particle.Solid particle finally is washed with 50~80 DEG C of atent solvent, catalytic component is obtained after dry.
Method two：It is specific such as TiCl by titanium compound of the present invention4, it is MgCl with general formula2The adduct of pROH
It reacts and prepares 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 with miscible lazy of adduct
In the presence of property hydrocarbon, by alcohol（ROH）And MgCl2Mixing, makes the rapid chilling of the lotion, so as to make adduct in the form of spheric granules
Curing.Obtained adduct can directly be reacted with titanium compound or it can be advance before being reacted with titanium compound
By the dealcoholization of 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.It can be by by adduct（Dealcoholysis or itself）It is suspended in cold TiCl4（General 0 DEG C）In, and
Mixture temperature programming kept for 0.1~2 hour to 80~130 DEG C and at this temperature, reacted with titanium compound.
TiCl4Processing can carry out primary or multiple.With TiCl4Above-mentioned general formula of the present invention can be added in during processing（Ⅰ）Chemical combination
Object is handled, and this processing can also be repeated once or repeatedly.
Catalytic component specifically can be prepared according to the 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, form emulsion, be discharged into rapid cooling and shaping, shape in coolant
Into chlorination magnesium alcoholate microballoon.The coolant inert hydrocarbon solvent relatively low for boiling point, such as petroleum ether, pentane, hexane, heptane.
Gained chlorination magnesium alcoholate microballoon is washed, dry for ball type carrier, and 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.
With excessive titanium tetrachloride in the above-mentioned ball type carrier of low-temperature treatment, gradually heat up, this hair is added in processing procedure
Bright general formula（Ⅰ）Shown electron donor is repeatedly washed after processing with atent solvent, and the spherical shape that solid powdery is obtained after dry is urged
Agent component.The molar ratio of titanium tetrachloride and magnesium chloride is 20~200, 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 three：Also it can be added in arene compound and stirred with dialkoxy magnesium, form suspension；Suspension tetravalence
Titanium chloride is reacted in -20~100 DEG C of processing, and at 0~130 DEG C, in the process, general formulas of the present invention is added at -20~130 DEG C
（Ⅰ）Electron donor is reacted, and obtained solid is washed with arene compound；Then at 0~130 DEG C in aromatic hydrocarbon solvent
In, then with tetravalence titanium chloride handle, finally washed, drained with atent solvent, obtain ingredient of solid catalyst.Wherein every mole two
Alkyl magnesium tetravalence 0.5~100mol of titanium chloride, 0.01~10mol of electron donor.
Method four：Use TiCl4Or 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
General formula of the present invention is added in one or many such processing（Ⅰ）Compound.
Method five：Catalytic component is prepared according to the method disclosed in patent US4540679.First, magnesium alkoxide and titanium dioxide
Alkyl carbonic acid magnesium carrier is made in carbon reaction.Then transistion metal compound（Preferably tetravalent titanium compound）It is carried with alkyl magnesium carbonate
Body and general formula of the present invention（Ⅰ）Electron donor reacted in atent solvent in certain proportion, wherein transition metal element
It is at least 0.5 with the molar ratio of magnesium elements:1, general formula of the present invention（Ⅰ）Electron donor dosage be up to 1.0 moles of every gram of titanium originals
Son.Atent solvent must pass through purifying, easily make the substance of catalyst poisoning to slough water, oxygen, carbon dioxide etc..Reaction is -10
~170 DEG C of progress, reaction time are a few minutes to a few houres.
The method of ingredient of solid catalyst is prepared also just like magnesium compound, electron donor etc. to be formed to breast in diluent
Liquid, adding in titanium compound makes its fixation obtain spherical solid, treated to obtain ingredient of solid catalyst.
In any above-mentioned preparation method, required electron donor compound（Ⅰ）It can be with the shape of compound
Formula adds in；It can also add in other manners, it such as can be by using electron donor compound（Ⅰ）Suitable precursor obtains in situ
, which becomes required electron donor compound for example, by known chemical reaction such as esterification.
According to another aspect of the present invention, a kind of catalyst for olefinic polyreaction is provided, includes following groups
Point：
The above-mentioned ingredients of solid catalyst of component a.；With
Component b. alkyl aluminum compounds.
In above-mentioned catalyst, the alkyl aluminum compound is that general formula is AlRnX3-nCompound, in formula R be hydrogen, carbon it is former
Subnumber is 1~20 alkyl, and X is halogen, and n is the number of 1≤n≤3；Specifically it may be selected from triethyl aluminum, tri-propyl aluminum, three normal-butyls
Aluminium, triisobutyl aluminium, tri-n-octylaluminium, three iso-octyl aluminium, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride,
One chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium, preferably ethyl aluminum dichloride, triethyl aluminum, triisobutyl aluminium.
In above-mentioned catalyst, the catalyst further includes component c. external electron donors, and the external electron donor is organic
Silicon compound, ethers, esters or its mixture.External donor compound is added in, the very high alkene of stereoregularity can be obtained
Hydrocarbon polymer.Such as general formula is RnSi(OR′)4-nOrgano-silicon compound, 0≤n≤3, R and R ' are of the same race or different in formula
Alkyl, cycloalkyl, aryl, halogenated alkyl, amido, R may be halogen or hydrogen atom.Such as：Trimethylmethoxysilane, three
Methylethoxy base silane, dimethyldimethoxysil,ne, dimethyl diethoxysilane, dimethoxydiphenylsilane, hexichol
Base diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, vinyltrimethoxysilane, cyclohexyl first
Base dimethoxysilane, methyl-t-butyldimethoxysilane, preferably Cyclohexyl Methyl Dimethoxysilane, diphenyl dimethoxy
Base silane.As the compound of external electron donor, ether compound such as 1,3- diether and ester type compound such as benzene first can also be
Acid monoester, benzoic acid diester, glycol ester compounds or organo-silicon compound, ethers, esters mixture.
In above-mentioned catalyst, wherein component a, component b ratio with titanium：The molar ratio computing of aluminium is 1:(5~1000).Institute
The ratio between component a and component c is stated with titanium:Silicon（Or ether or ester）Between molar ratio computing be 1:(0~500).
The catalyst of the present invention can be directly added into reactor can add in for polymerization process or catalyst
Prepolymerization is participated in before one reaction, in the present invention, term " prepolymerization " refers to be polymerize with relatively low transforming degree.According to this hair
Bright, the pre-polymerized catalyst includes above-mentioned ingredient of solid catalyst and its carries out the pre-polymerization obtained by prepolymerization with alkene
Object, pre-polymerization multiple are 0.1~1000g olefin polymers/g ingredients of solid catalyst.
The alpha-olefin identical with foregoing alkenes may be used to carry out prepolymerization, wherein carrying out prepolymerized alkene and being preferably
Ethylene or propylene.Specifically, particularly preferably using ethylene or propylene and amount be up to 20mol% one or more α-
The mixture of alkene carries out prepolymerization.Preferably, the transforming degree of pre-polymerized catalyst components is about 0.2~800g polymerizations
Object/gram ingredient of solid catalyst.
Prepolymerization process can in a liquid or in gas phase be carried out at -40~80 DEG C, at a temperature of preferably -20~50 DEG C.
Prepolymerization step can independently be carried out as the online progress of a part in continuous polymerization technique or in intermittently operated.For
Preparation amount is the polymer of 0.5~20g/g ingredients of solid catalyst, the interval pre-polymerization of particularly preferred catalyst and propylene of the present invention
It closes.Polymerization pressure is 0.01~10MPa.
According to another aspect of the present invention, a kind of olefine polymerizing process is provided, the alkene is in above-mentioned solid catalyst
It is polymerize in the presence of component, catalyst or pre-polymerized catalyst.
The catalyst of the present invention can be directly added into reactor in polymerization process or catalyst and alkene pre-polymerization
It is added in reactor after obtaining pre-polymerized catalyst.
The present invention olefinic polyreaction according to well known polymerization carry out, can be carried out in liquid phase or gas phase or
It is carried out under the operation that person can also combine in liquid and gas polymerization stage.Using conventional technique such as slurry process, gas phase fluidization
Bed etc..Preferably it is using following reaction condition：0~150 DEG C of polymerization temperature, preferably 60~90 DEG C.
The general formula of heretofore described alkene is CH2=CHR, wherein R are hydrogen or C1~C12Alkyl or aryl.Such as it is selected from
Ethylene, propylene, 1- butylene, 4-methyl-1-pentene and 1- hexenes.It is preferably selected from ethylene and propylene.As propylene homopolymerization with or
The combined polymerization of other alkene of propylene.The method of the present invention is also applied for homopolymerization such as ethylene and ethylene and alpha-olefin, such as propylene, fourth
The copolymerization of alkene, amylene, hexene, octene, 4-methyl-1-pentene.
Contain 6 carbon on the straight chain containing special construction it is worth noting that having been used in catalytic component of the invention
Non- end group glycol more than atom is at least containing 1 Cm（m≥2）Diol ester obtained from the benzoic acid of hydrocarbyl substituent
（Such as general formula（Ⅰ）It is shown）, the diol ester of the special construction can further improve the hydrogen response and polymerization activity of catalyst.
According to the present invention, olefinic polymerization is used for using the catalyst system of glycol ester compounds provided by the invention, especially
It is the isotactic that the hydrogen response of catalyst improves or resulting polymers are represented with the heptane extracting insoluble matter that boils under high hydrogen concentration
Index, which has, to be significantly increased, and is conducive to the exploitation of the polymer difference trade mark.
According to the present invention ingredient of solid catalyst and catalyst that improve, high fusion index and high isotactic can be made
Polymer.Compared with prior art, mutually when hydrogen response is suitable at once, isotactic index improves the melt index of polymer；It is poly-
When the isotactic index of conjunction object is suitable, melt index improves, i.e., hydrogen response improves.
Specific embodiment
Example given below is only used for that the present invention is explained and illustrated, and does not form any limit to the present invention
System.
Test method
1. polymer isotactic index（TII）It is measured using heptane extraction process（Heptane boiling extracting 6 hours）：2g dryings gather
Object sample is closed, is placed in extractor after being extracted 6 hours with boiling heptane, by the polymer weight obtained by residue drying to constant weight
（g）Ratio with 2 is isotactic index.
2. the melt index of polymer（MI）It is measured by testing standard GB/T3682-2000.
3. diol ester（Ⅱ）Content liquid chromatogram measuring, liquid chromatogram be Waters-600E high performance liquid chromatography, C-
18 pillar, column temperature are 30 DEG C, and methanol-water is mobile phase, flow velocity 1.0ml/min, UV detector.
4.Ti contents are measured with ultraviolet-visible spectrophotometer 752S, using 1mol sulfuric acid as blank solution.
5.Mg contents carry out titrimetry with 0.02 equivalent/L EDTA solution.
First, the preparation of ingredient of solid catalyst
In the reactor being sufficiently displaced from by high pure nitrogen, magnesium chloride 6.0g, toluene 119ml, epoxy chlorine are sequentially added
Propane 5ml, tributyl phosphate（TBP）15.6ml is warming up to 50 DEG C, and maintains 2.5 hours under stirring, solid is completely dissolved.So
Phthalic anhydride 1.7g is added in afterwards, and temperature continues to 1 hour；Solution is cooled to -25 DEG C hereinafter, being added dropwise in 1 hour
70ml TiCl4.80 DEG C are to slowly warm up to, solids is gradually precipitated in temperature-rise period.Add in the glycol ester compounds in table 1
（Ⅰ）4.6mmol, maintains temperature 1 hour, after filtering, adds in toluene 80ml, washes twice, obtain solid sediment.
Then toluene 60ml, TiCl are added in440ml is warming up to 108 DEG C, handles 2 hours, after venting filtrate, adds first
Benzene 60ml, TiCl440ml is warming up to 108 DEG C, handles 2 hours, venting filtrate；Toluene 60ml is added in, boiling state washed once,
Hexane 60ml is added, boiling state washes twice, adds in hexane 60ml, after room temperature washes twice, obtain ingredient of solid catalyst.
2nd, propylene polymerization is tested
The catalytic component of above-described embodiment is subjected to propylene polymerization respectively.Propylene polymerization program is：Volume for 5L not
Become rusty steel reaction kettle, after gaseous propylene is sufficiently displaced from, adds in AlEt32.5mmol, Cyclohexylmethyldimethoxysilane
（CHMMS）0.l mmol add the ingredient of solid catalyst 8-10mg of above-described embodiment and a certain amount of hydrogen, are passed through liquid
Body propylene 2.3L, is warming up to 70 DEG C, maintains this temperature 1 hour；Cooling, pressure release obtain embodiment 1-6 and the PP powder of comparative example 1
Material.It the results are shown in Table 1
1 propylene polymerization result of table
ID1：2,4- hexylene glycols two（4- propylbenzoic acid esters）
ID2：3,5- heptandiols two (4- p t butylbenzoic acids ester)
ID3：3,5- heptandiols two (4- propylbenzoic acids ester)
ID4：3,5- heptandiols two (4- butylbenzoic acids ester)
ID5：3,5- heptandiol dibenzoates
ID6：3,5- heptandiols cinnamic acid (4- propylbenzoic acids）Ester
ID7：4- ethyl -3,5- heptandiols two (4- p t butylbenzoic acids ester)
From data above as can be seen that when the glycol ester compounds using special construction, it can not only significantly improve and urge
The activity of agent, particularly under high hydrogen concentration, the hydrogen response of catalyst improves（That is the melt index of resulting polymers
It is high）Or further improve the isotactic index of catalysis resulting polymers.
It should be noted that embodiment described above is only used for explaining the present invention, do not form to any of the present invention
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
It changes 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 wherein disclosed particular case, on the contrary, this hair
It is bright to can be extended to other all methods and applications with identical function.
Claims (12)
1. a kind of ingredient of solid catalyst for olefinic polyreaction, described to give it includes magnesium, titanium, halogen and electron donor
Electron is selected from least one of following glycol ester compounds：2,4- hexylene glycols two (4- propylbenzoic acids ester), 2,4- oneself two
Alcohol two (4- butylbenzoic acids ester), 2,4- hexylene glycols two (4- isobutyl-benzenes formic acid esters), (the 4- tert-butyl benzene first of 2,4- hexylene glycols two
Acid esters), 3- methyl -2,4- hexylene glycols two (4- propylbenzoic acids ester), two (4- butylbenzoic acids of 3- methyl -2,4- hexylene glycols
Ester), 3- methyl -2,4- hexylene glycols two (4- isobutyl-benzenes formic acid esters), two (4- p t butylbenzoic acids of 3- methyl -2,4- hexylene glycols
Ester), 3- ethyl -2,4- hexylene glycols two (4- propylbenzoic acids ester), 3- ethyl -2,4- hexylene glycols two (4- butylbenzoic acids ester),
3- ethyl -2,4- hexylene glycols two (4- isobutyl-benzenes formic acid esters), 3- ethyl -2,4- hexylene glycols two (4- p t butylbenzoic acids ester),
3,5- heptandiols two (4- propylbenzoic acids ester), 3,5- heptandiols two (4- isopropyl acids ester), (the 4- fourths of 3,5- heptandiols two
Yl benzoic acid ester), 3,5- heptandiols two (4- isobutyl-benzenes formic acid esters), 3,5- heptandiols two (4- p t butylbenzoic acids ester), 3,
5- heptandiols-cinnamic acid -4- propylbenzoic acids ester, 4- methyl -3,5- heptandiols two (4- propylbenzoic acids ester), 4- methyl -3,
5- heptandiols two (4- isopropyl acids ester), 4- methyl -3,5- heptandiols two (4- butylbenzoic acids ester), 4- methyl -3,5-
Heptandiol two (4- isobutyl-benzenes formic acid esters), 4- methyl -3,5- heptandiols two (4- p t butylbenzoic acids ester), 4- ethyls -3,5-
Heptandiol two (4- propylbenzoic acids ester), 4- ethyl -3,5- heptandiols two (4- isopropyl acids ester), 4- ethyls -3,5- heptan
Glycol two (4- butylbenzoic acids ester), 4- ethyl -3,5- heptandiols two (4- isobutyl-benzenes formic acid esters), 4- ethyls -3,5- heptan two
Alcohol two (4- p t butylbenzoic acids ester), 4- propyl -3,5- heptandiols two (4- p t butylbenzoic acids ester), 4- butyl -3,5- heptan two
Alcohol two (4- p t butylbenzoic acids ester), 2,4- dimethyl -3,5- heptandiols two (4- p t butylbenzoic acids ester), 2,6- dimethyl -
3,5- heptandiols two (4- p t butylbenzoic acids ester), 4,4- dimethyl -3,5- heptandiols two (4- p t butylbenzoic acids ester), 2,2-
Dimethyl -3,5- heptandiols two (4- p t butylbenzoic acids ester), two (4- butylbenzoic acids of 2- methyl -4- ethyl -3,5- heptandiols
Ester), 4- methyl -4- ethyl -3,5- heptandiols two (4- p t butylbenzoic acids ester), 2- methyl -4- propyl -3,5- heptandiols two
(4- p t butylbenzoic acids ester), 3- methyl -3- propyl -3,5- heptandiols two (4- p t butylbenzoic acids ester), 4- methyl -4- third
Base -3,5- heptandiols two (4- p t butylbenzoic acids ester), 3- methyl -2,4- heptandiols two (4- propylbenzoic acids ester), 3- methyl -
2,4- heptandiols two (3- propylbenzoic acids ester), 3,6- dimethyl -2,4- heptandiols two (4- p t butylbenzoic acids ester), 2,2,6,
6- tetramethyl -3,5- heptandiols two (4- p t butylbenzoic acids ester), 4- methyl -3,5- ethohexadiols two (4- butylbenzoic acids ester),
4- ethyl -3,5- ethohexadiols two (4- p t butylbenzoic acids ester), 4- propyl -3,5- ethohexadiols two (4- p t butylbenzoic acids ester),
4- butyl -3,5- ethohexadiols two (4- p t butylbenzoic acids ester), two (4- butylbenzoic acids of 4,4- dimethyl -3,5- ethohexadiols
Ester), 4,4- diethyl -3,5- ethohexadiols two (4- propylbenzoic acids ester), two (4- tertiary butyls of 4,4- dipropyl -3,5- ethohexadiols
Benzoic ether), 4- methyl -4- ethyl -3,5- ethohexadiols two (4- second butylbenzoic acids ester), 2- methyl -4- ethyls -3,5- pungent two
Alcohol two (4- p t butylbenzoic acids ester), 2- methyl -6- ethyl -3,5- ethohexadiols two (4- p t butylbenzoic acids ester), 4,6- nonyls two
Alcohol two (4- propylbenzoic acids ester), 4,6- nonanediols two (4- butylbenzoic acids ester), (the 4- isobutyl-benzene formic acid of 4,6- nonanediols two
Ester), 4,6- nonanediols two (4- p t butylbenzoic acids ester), 5- methyl -4,6- nonanediols two (4- propylbenzoic acids ester), 5- first
Base -4,6- nonanediols two (4- butylbenzoic acids ester), 5- methyl -4,6- nonanediols two (4- isobutyl-benzenes formic acid esters), 5- methyl -
4,6- nonanediols two (4- p t butylbenzoic acids ester), 5- ethyl -4,6- nonanediols two (4- propylbenzoic acids ester), 5- ethyl -4,
6- nonanediols two (4- butylbenzoic acids ester), 5- ethyl -4,6- nonanediols two (4- isobutyl-benzenes formic acid esters), 4,6- nonanediols two
(4- p t butylbenzoic acids ester), 5- propyl -4,6- nonanediols two (4- p t butylbenzoic acids ester), 5- butyl -4,6- nonanediols two
(4- butylbenzoic acids ester), 5,5- dimethyl -4,6- nonanediols two (4- p t butylbenzoic acids ester) and 5,5- dibutyl -4,6-
Nonanediol two (4- p t butylbenzoic acids ester).
2. ingredient of solid catalyst according to claim 1, by by magnesium compound, titanium compound and the glycol
Ester compounds carry out reaction and are prepared.
3. ingredient of solid catalyst according to claim 2, which is characterized in that prepared by the reaction is included magnesium compound
It is dissolved in the dicyandiamide solution being made of organic epoxy compound object, organic phosphorus compound and inert diluent, forms homogeneous solution
It is mixed afterwards with titanium compound, then in the presence of precipitation additive, solids is precipitated, the last solids is used selected from described
Glycol ester compounds are handled.
4. ingredient of solid catalyst according to claim 3, which is characterized in that the magnesium compound be selected from magnesium dihalide,
The hydrate or the halogen atom of alcohol adduct and magnesium dihalide of alkoxy Mei ﹑ Wan Ji Mei ﹑ magnesium dihalides are by alkoxy or alkyl halide
The derivative that oxygroup is replaced；
The titanium compound general formula is TiXm(OR1) 4-m, R in formula1For C1~C20Alkyl, X is halogen, 1≤m≤4；
The organic epoxy compound object include carbon atom number 2~8 aliphatic olefin, alkadienes, halogenated aliphatic alkene or
Oxide, glycidol ether and the inner ether of alkadienes；
The organic phosphorus compound is orthophosphoric acid or the hydrocarbyl carbonate of phosphorous acid or halogenated hydrocarbons base ester；
The precipitation additive is selected from organic acid anhydride, organic acid, ether and ketone.
5. ingredient of solid catalyst according to claim 4, which is characterized in that the titanium compound is titanium tetrachloride.
6. ingredient of solid catalyst according to claim 4, which is characterized in that the magnesium compound be selected from magnesium dihalide and
Its alcohol adduct.
7. the ingredient of solid catalyst according to any one in claim 3~6, which is characterized in that with every mole of halogenation
Magnesium meter, the amount of the organic epoxy compound object is 0.2~10 mole, and the amount of the organic phosphorus compound is 0.1~3 mole, institute
The amount for stating precipitation additive is more than 0~1.0 mole, and the amount of the titanium compound is 0.5~150 mole, the diol ester chemical combination
The amount of object is 0.02~0.4 mole.
8. a kind of catalyst for olefinic polyreaction includes following components：
Ingredient of solid catalyst in component a. claims 1~7 described in any one；With
Component b. alkyl aluminum compounds.
9. catalyst according to claim 8, which is characterized in that the catalyst system further includes the outer electrons of component c.
Body, the external electron donor are selected from organo-silicon compound, ethers and esters.
10. a kind of a kind of pre-polymerized catalyst for olefinic polyreaction, comprising catalysis according to claim 8 or claim 9
Agent and its prepolymer obtained by with alkene progress prepolymerization, pre-polymerization multiple are 0.1~1000g olefin polymers/g solid catalysts
Component.
11. pre-polymerized catalyst according to claim 10, which is characterized in that the alkene is ethylene or propylene.
12. a kind of method of olefinic polymerization, solid catalyst group of the alkene in claim 1~7 described in any one
Divide, polymerize in the presence of the catalyst described in claim 9 or 8 or the pre-polymerized catalyst described in claim 11 or 10.
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310190424.4A CN104177520B (en) | 2013-05-21 | 2013-05-21 | It is used to prepare the ingredient of solid catalyst of olefin polymer |
| TW103117524A TWI644896B (en) | 2013-05-21 | 2014-05-19 | Catalyst component, catalyst and application for olefin polymerization |
| 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 |
| SG11201509482XA SG11201509482XA (en) | 2013-05-21 | 2014-05-21 | Catalyst component for olefin polymerization, 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 |
| RU2015154533A RU2673083C2 (en) | 2013-05-21 | 2014-05-21 | Catalyst component for olefin polymerisation, catalyst and use thereof |
| ES201590123A ES2557178B2 (en) | 2013-05-21 | 2014-05-21 | Catalyst component for the polymerization of olefins, catalyst and use thereof |
| KR1020157036140A KR102174946B1 (en) | 2013-05-21 | 2014-05-21 | Catalyst component for use in olefin polymerization reaction, catalyst, and application |
| GB1522379.5A GB2530212B (en) | 2013-05-21 | 2014-05-21 | Catalyst component for olefin polymerization reaction, catalyst, and use thereof |
| DE112014002517.8T DE112014002517T5 (en) | 2013-05-21 | 2014-05-21 | Catalyst component for olefin polymerization, catalyst and use thereof |
| US14/892,533 US9751960B2 (en) | 2013-05-21 | 2014-05-21 | Catalyst component for olefin polymerization, catalyst, and use thereof |
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| CN201310190424.4A CN104177520B (en) | 2013-05-21 | 2013-05-21 | It is used to prepare the ingredient of solid catalyst of olefin polymer |
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| CN101864009A (en) * | 2009-04-17 | 2010-10-20 | 中国石油化工股份有限公司 | Preparation method of catalyst component for polymerization reaction of olefins and catalyst thereof |
| CN102234337A (en) * | 2010-04-22 | 2011-11-09 | 中国石油化工股份有限公司 | Catalyst components for olefin polymerization reaction, and catalyst thereof |
| CN103012625A (en) * | 2011-09-23 | 2013-04-03 | 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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| CN101864009A (en) * | 2009-04-17 | 2010-10-20 | 中国石油化工股份有限公司 | Preparation method of catalyst component for polymerization reaction of olefins and catalyst thereof |
| CN102234337A (en) * | 2010-04-22 | 2011-11-09 | 中国石油化工股份有限公司 | Catalyst components for olefin polymerization reaction, and catalyst thereof |
| CN103012625A (en) * | 2011-09-23 | 2013-04-03 | 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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