CN102603932A - Solid catalyst component and catalyst for olefinic polymerization - Google Patents
Solid catalyst component and catalyst for olefinic polymerization Download PDFInfo
- Publication number
- CN102603932A CN102603932A CN2011100212478A CN201110021247A CN102603932A CN 102603932 A CN102603932 A CN 102603932A CN 2011100212478 A CN2011100212478 A CN 2011100212478A CN 201110021247 A CN201110021247 A CN 201110021247A CN 102603932 A CN102603932 A CN 102603932A
- Authority
- CN
- China
- Prior art keywords
- compound
- mole
- alkyl
- magnesium
- dicyano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a solid catalyst component and a catalyst for olefinic polymerization. The solid catalyst component uses dialkoxy magnesium as a carrier and toluene as a dispersant to be contacted with at least one 2,3-di-non-linear chain alkyl-2-cyanosuccinic acid dibasic acid ester type compound and a 2-isopropyl-2-(3-methyl-butyl)-1,3-dimethoxypropane compound to react with titanium halide, and then the reaction product is processed by the titanium halide to obtain the solid catalyst component. The polymerization activity of the catalyst is high, the molecule weight distribution of the obtained polymer is wide, the bulk density is high, the hydrogen response and the stereospecificity expression are good, the grain shape is good, the fine powder content is less and the catalyst is suitable for developing the polyolefine grade.
Description
Technical field
The present invention relates to a kind of solid catalyst component for olefine polymerization and catalyzer, belong to field of olefin polymerisation.
Background technology
Field of olefin polymerisation generally adopts the compound of titanium and Z-N (Ziegler-Natta) polymerization catalyst of organo-aluminium compound formation to obtain olefin polymer.For example in polyacrylic preparation, using described in the patent such as CN85100997A, CN1453298A contained mainly the ingredient of solid catalyst that is made up of titanium, magnesium, chlorine and internal electron donor compound and as the organo-aluminium compound of cocatalyst component with as the catalyzer of the organosilicon external electron donor compound of upright structure directional property rising agent, to obtain propene polymer.At present, the research of catalyzer mainly concentrates on following several respects: improve the polymerization activity of catalyzer, improve polyolefinic upright structure directional property, improve the hydrogen response of catalyzer, improve the particle form of olefin polymer, reduce Cl residual in the polymkeric substance etc.
With dialkoxy magnesium is the loaded catalyst component of carrier, resulting propene polymer, and it is good to have a particle form, and fine powder content is few, premium propertiess such as upright structure directional property height.Obtain this good catalyst component for olefin, at first must prepare the dialkoxy magnesium carrier of excellent property.
Use dialkoxy magnesium to have much as the research that carrier prepares olefin polymerization catalyst components.Patent EP0459009 discloses a kind of catalyst component that is used for olefinic polymerization; Its preparation method is that diethoxy magnesium is formed suspension-s in korenyl; And between 80～125 ℃, the dichloride of this suspension-s with titanium tetrachloride and phthalyl contacted, with the korenyl washing, obtained the titanium-containing catalyst component at last; Active high, active lasting during the polymerization catalyst that obtains by this catalyst component, but the tap density of gained propene polymer is lower.
Patent EP0811639 discloses a kind of ingredient of solid catalyst that is used for olefinic polymerization, and it is reacted to each other by a kind of halogenated titanium, a kind of aromatic yl two carboxy acid ester and a kind of alkoxyl magnesium and processes.Tap density through the control alkoxyl magnesium; Indexs such as average particulate size; And the temperature that control begins to contact with alkoxyl magnesium from halogenated titanium rises to the speed (temperature rise rate is controlled between 0.5～20/min) of the temperature that reacts; Thereby obtain a kind of ingredient of solid catalyst, can obtain the polyolefine of a kind of high degree of isotacticity, high bulk density thus, but the resulting polymers fine powder content is higher.
Among the CN101054424A dialkoxy magnesium for preparing is suspended in the toluene, is cooled to 0 ℃, add titanium tetrachloride then; Heat up, add internal electron donor, fully the reaction back adds toluene wash; Handle with toluene and titanium compound then, use hexane wash at last again.The ingredient of solid catalyst polymerization activity is higher, good sphericity, but size distribution is not too concentrated.
In with magnesium, titanium and internal electron donor ingredient of solid catalyst, obtain the polymkeric substance of higher stereospecificity, the internal electron donor compound composition that is absolutely necessary as the olefinic polymerization of basal component.Disclosed electron donor commonly used is the multi-carboxylate.The phthalate of mentioning in for example many patents, concrete as, n-butyl phthalate, diisobutyl phthalate this; The ingredient of solid catalyst that this kind compound obtains is with the catalyzer of cocatalyst component and external electron donor formation, when being used for propylene polymerization; Has high polymerization activity; And the stereospecificity of polymkeric substance is good, but resulting polyacrylic MWD is wide inadequately, and processing characteristics is bad.
The present invention is a carrier with the spherical dialkoxy magnesium of excellent property, is dispersion agent and a kind of 2 with toluene; The alkyl of 3-two non-straight chains-2-cyanic acid succinate compound and 2-sec.-propyl-2-(3-methylbutyl)-1; The mixing of 3-Propanal dimethyl acetal is handled through titanium compound to electron compound contact back and titanium compound reaction again, obtains ingredient of solid catalyst; Be promotor with the organo-aluminium compound during polymerization, be upright structure directing agent with organosilyl compound.Active high during this polymerization catalyst, the molecular weight distribution that obtains is wide, stereospecificity good, particle form is good, fine powder content is few, is applicable to the field higher to the polymer processing performance requriements.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of solid catalyst component for olefine polymerization, catalyst for olefines polymerizing and olefin polymer; The polymerization catalyst of preparation is active high, and the molecular weight distribution that obtains is wide, stereospecificity good, particle form is good.
A kind of ingredient of solid catalyst that is used for olefinic polymerization of the present invention; This catalyst component is a carrier with spherical dialkoxy magnesium, is that dispersion agent and at least a has 2 of general formula (I) with the inert solvent; The alkyl of 3-two non-straight chains-2-cyanic acid succinate compound and 2-sec.-propyl-2-(3-methylbutyl)-1; The mixing of 3-Propanal dimethyl acetal is handled through titanium compound to electron compound contact back and titanium compound reaction again, obtains ingredient of solid catalyst.
Described have 2 of a general formula (I), and the alkyl of 3-two non-straight chains-2-cyanic acid succinate compound is:
Wherein, R
1And R
2Group is independently selected from the C of straight chain
1～C
4The C of alkyl or side chain
1～C
4Alkyl; R is selected from C
3～C
6Iso-alkyl, C
3～C
6Secondary alkyl or C
3～C
6Naphthenic base.
2, the alkyl of 3-two non-straight chains-2-cyanic acid succinate compound can use separately or several kinds be used, its usage quantity is 0.005～10 mole with respect to the magnesium in 1 mole of spherical dialkoxy magnesium compound.
Described 2-sec.-propyl-2-(3-methylbutyl)-1, its usage quantity of 3-Propanal dimethyl acetal is 0.005～10 mole with respect to the magnesium in 1 mole of spherical dialkoxy magnesium compound.
The general formula of described titanium compound is Ti (OR)
4-nX
n, R is C in the formula
1～C
14Aliphatic hydrocarbyl or aromatic hydrocarbyl, X is a halogen atom, n is 0 to 4 integer; N is 2 when following, and a plurality of R can be identical or different;
The usage quantity of titanium compound is 0.5～100 mole with respect to the magnesium in 1 mole of spherical dialkoxy magnesium compound.
Described inert solvent randomly adopts a kind of in hexane, heptane, octane, decane, the benzene,toluene,xylene or their mixture; Its usage quantity is 0.5～100 mole with respect to the magnesium in 1 mole of spherical dialkoxy magnesium compound.
Described spherical dialkoxy magnesium is disclosed in the application of application number 201010522125.2, and the disclosed associated viscera of this application is all introduced the present invention as a reference.
Described have 2 of a general formula (I), and the alkyl of 3-two non-straight chains-2-cyanic acid succinate compound is:
Wherein, R
1And R
2Group is independently selected from the C of straight chain
1～C
4The C of alkyl or side chain
1～C
4Alkyl; R is selected from C
3～C
6Iso-alkyl, C
3～C
6Secondary alkyl or C
3～C
6Naphthenic base;
2; The alkyl of 3-two non-straight chains-2-cyanic acid succinate class electron donor compound can be selected at least a of following compounds for use: 2; 3-di-isopropyl-2-dicyano methyl-succinate, 2,3-di-isopropyl-2-dicyano diethyl succinate, 2,3-di-isopropyl-2-dicyano Succinic Acid di-n-propyl ester, 2; 3-di-isopropyl-2-dicyano diisopropyl ester amber acid, 2; 3-di-isopropyl-2-dicyano Succinic Acid di-n-butyl, 2,3-di-isopropyl-2-dicyano Succinic Acid diisobutyl ester, 2,3-di-isopropyl-2-cyanic acid Succinic Acid-1-methyl esters-4-ethyl ester (R
1=methyl, R
2=ethyl), 2,3-di-isopropyl-2-cyanic acid Succinic Acid-1-ethyl ester-4-methyl esters (R
1=ethyl, R
2=methyl), 2, the positive butyl ester of 3-di-isopropyl-2-cyanic acid Succinic Acid-1--4-ethyl ester (R
1=normal-butyl, R
2=ethyl), 2, the 3-di-isopropyl-positive butyl ester (R of 2-cyanic acid Succinic Acid-1-ethyl ester-4-
1=ethyl, R
2=normal-butyl), 2; 3-diisobutyl-2-dicyano methyl-succinate, 2,3-diisobutyl-2-dicyano diethyl succinate, 2,3-diisobutyl-2-dicyano Succinic Acid di-n-propyl ester, 2; 3-diisobutyl-2-dicyano diisopropyl ester amber acid, 2; 3-diisobutyl-2-dicyano Succinic Acid di-n-butyl, 2,3-diisobutyl-2-dicyano Succinic Acid diisobutyl ester, 2,3-diisobutyl-2-cyanic acid Succinic Acid-1-methyl esters-4-ethyl ester (R
1=methyl, R
2=ethyl), 2,3-diisobutyl-2-cyanic acid Succinic Acid-1-ethyl ester-4-methyl esters (R
1=ethyl, R
2=methyl), 2, the positive butyl ester of 3-diisobutyl-2-cyanic acid Succinic Acid-1--4-ethyl ester (R
1=normal-butyl, R
2=ethyl), 2, the 3-diisobutyl-positive butyl ester (R of 2-cyanic acid Succinic Acid-1-ethyl ester-4-
1=ethyl, R
2=normal-butyl), 2; 3-two sec.-butyls-2-dicyano methyl-succinate, 2,3-two sec.-butyls-2-dicyano diethyl succinate, 2,3-two sec.-butyls-2-dicyano Succinic Acid di-n-propyl ester, 2; 3-two sec.-butyls-2-dicyano diisopropyl ester amber acid, 2; 3-two sec.-butyls-2-dicyano Succinic Acid di-n-butyl, 2,3-two sec.-butyls-2-dicyano Succinic Acid diisobutyl ester, 2,3-two sec.-butyls-2-cyanic acid Succinic Acid-1-methyl esters-4-ethyl ester (R
1=methyl, R
2=ethyl), 2,3-two sec.-butyls-2-cyanic acid Succinic Acid-1-ethyl ester-4-methyl esters (R
1=ethyl, R
2=methyl), 2, the positive butyl ester of 3-two sec.-butyls-2-cyanic acid Succinic Acid-1--4-ethyl ester (R
1=normal-butyl, R
2=ethyl), 2, the 3-two sec.-butyls-positive butyl ester (R of 2-cyanic acid Succinic Acid-1-ethyl ester-4-
1=ethyl, R
2=normal-butyl), 2; 3-two cyclopentyl-2-dicyano methyl-succinate, 2,3-two cyclopentyl-2 dicyano diethyl succinate, 2,3-two cyclopentyl-2-dicyano Succinic Acid di-n-propyl ester, 2; 3-two cyclopentyl-2-dicyano diisopropyl ester amber acid, 2; 3-two cyclopentyl-2-dicyano Succinic Acid di-n-butyl, 2,3-two cyclopentyl-2-dicyano Succinic Acid diisobutyl ester, 2,3-two cyclopentyl-2-cyanic acid Succinic Acid-1-methyl esters-4-ethyl ester (R
1=methyl, R
2=ethyl), 2,3-two cyclopentyl-2-cyanic acid Succinic Acid-1-ethyl ester-4-methyl esters (R
1=ethyl, R
2=methyl), 2, the positive butyl ester of 3-two cyclopentyl-2-cyanic acid Succinic Acid-1--4-ethyl ester (R
1=normal-butyl, R
2=ethyl), 2, the 3-two cyclopentyl-positive butyl ester (R of 2-cyanic acid Succinic Acid-1-ethyl ester-4-
1=ethyl, R
2=normal-butyl), 2; 3-dicyclohexyl-2-dicyano methyl-succinate, 2,3-dicyclohexyl-2-dicyano diethyl succinate, 2,3-dicyclohexyl-2-dicyano Succinic Acid di-n-propyl ester, 2; 3-dicyclohexyl-2-dicyano diisopropyl ester amber acid, 2; 3-dicyclohexyl-2-dicyano Succinic Acid di-n-butyl, 2,3-dicyclohexyl-2-dicyano Succinic Acid diisobutyl ester, 2,3-dicyclohexyl-2-cyanic acid Succinic Acid-1-methyl esters-4-ethyl ester (R
1=methyl, R
2=ethyl), 2,3-dicyclohexyl-2-cyanic acid Succinic Acid-1-ethyl ester-4-methyl esters (R
1=ethyl, R
2=methyl), 2, the positive butyl ester of 3-dicyclohexyl-2-cyanic acid Succinic Acid-1--4-ethyl ester (R
1=normal-butyl, R
2=ethyl), 2, the 3-dicyclohexyl-positive butyl ester (R of 2-cyanic acid Succinic Acid-1-ethyl ester-4-
1=ethyl, R
2=normal-butyl).Wherein, Preferred 2; 3-di-isopropyl-2 dicyano diethyl succinate, 2,3-di-isopropyl-2-dicyano Succinic Acid di-n-propyl ester, 2,3-di-isopropyl-2-dicyano diisopropyl ester amber acid, 2; 3-di-isopropyl-2-dicyano Succinic Acid di-n-butyl, 2,3-di-isopropyl-2-dicyano Succinic Acid diisobutyl ester.Preferred especially 2,3-di-isopropyl-2-dicyano diethyl succinate.
Described have 2 of a general formula (I), and the alkyl of 3-two non-straight chains-2-cyanic acid succinate compound is by the disclosed method preparation of international patent application no PCT/CN2010/000202.
Its usage quantity is generally 0.005～10 mole with respect to the magnesium in 1 mole of spherical dialkoxy magnesium compound, is preferably 0.01～1 mole.
2-sec.-propyl-2-(3-methylbutyl)-1,3-Propanal dimethyl acetal compound press the disclosed method preparation of Chinese patent ZL91108297.2.
Its usage quantity is generally 0.005～10 mole with respect to the magnesium of 1 mole of spherical dialkoxy magnesium compound, is preferably 0.01～1 mole.
The general formula of described titanium compound is Ti (OR)
4-nX
n, R is C in the formula
1～C
14Aliphatic hydrocarbyl or aromatic hydrocarbyl, X is a halogen atom, n is 0 to 4 integer; N is 2 when following, and a plurality of R can be identical or different.X is preferably chlorine atom and bromine atoms, especially preferably the chlorine atom.R can be saturated group or unsaturated group, can also be straight chain shape or the group with side chain, and perhaps cyclic group, particularly preferably is the alkyl of straight or branched at special preferably alkyl, alkenyl, cycloalkenyl group and aralkyl.When having a plurality of R, can be identical between them, also can be different.Object lesson as R can be methyl, ethyl, n-propyl, sec.-propyl, allyl group, normal-butyl, sec.-butyl, isobutyl-, n-pentyl, n-hexyl, n-heptyl, n-octyl, positive decyl, allyl group, crotonyl, cyclopentyl, cyclohexyl, cyclohexenyl, phenyl, tolyl, benzyl, styroyl etc.
Specifically can select four titan-alkoxides such as tetramethoxy titanium, purity titanium tetraethoxide, four positive propoxy titaniums, tetraisopropoxy titanium, four titanium n-butoxide, four isobutoxy titaniums, Fourth Ring hexyloxy titanium, four phenoxide titaniums for use; Titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide, titanium tetra iodide; Three halogenated alkoxy titaniums such as trichlorine methoxyl group titanium, trichlorine ethanolato-titanium, trichlorine titanium propanolate, trichlorine titanium n-butoxide, tribromo ethanolato-titanium; Dihalide dialkoxy titaniums such as dichloro dimethoxy titanium, dichloro diethoxy titanium, dichloro two positive propoxy titaniums, dichloro diisopropoxy titanium, dibromo diethoxy titanium; Single halogenation tri-alkoxy titaniums such as one chlorine trimethoxy titanium, a chlorine triethoxy titanium, a chlorine three positive propoxy titaniums, a chlorine three titanium isopropoxides.Wherein preferred titanium tetrahalide, especially preferably titanium tetrachloride.The usage quantity of titanium compound is generally 0.5～100 mole with respect to the magnesium in 1 mole of spherical dialkoxy magnesium compound, is preferably 1～50 mole.
Described inert solvent can adopt a kind of in hexane, heptane, octane, decane, the benzene,toluene,xylene or their mixture.Preferred toluene.
The usage quantity of inert solvent is generally 0.5～100 mole with respect to the magnesium in 1 mole of spherical dialkoxy magnesium compound, preferred 1～50 mole.
The contact temperature of each composition is generally-40～200 ℃, preferred-20～150 ℃; Be generally 1 minute duration of contact～20 hours, be preferably 5 minutes～8 hours.
Do not have special qualification for each component engagement sequence, for example can in the presence of inert diluent, make each composition contact, can make their contacts again with each composition of inert solvent dilution in advance yet.Number of times for contact does not have special qualification yet, can contact once, can contact repeatedly yet.
The ingredient of solid catalyst that obtains through above contact reacts can wash with inert solvent.As can adopt a kind of in hexane, heptane, octane, decane, the benzene,toluene,xylene or their mixture.The present invention preferably uses hexane wash.Washing methods is not special to limit modes such as preferred decant, filtration.The usage quantity of inert solvent, washing time, washing times are not special to be limited, and uses 1～1000 mole usually, is preferably 10～500 moles solvent with respect to the compound of 1 mole of magnesium, washs usually 1～24 hour, preferred 10～6 hours.From the homogeneity of washing and the aspect of detersive efficiency, preferably in washing operation, stir in addition.Need to prove that the ingredient of solid catalyst of gained can or be preserved under dryness in inert solvent.
The invention still further relates to a kind of solid catalyst that is used for olefinic polymerization, comprise the reaction product of following component:
The ingredient of solid catalyst of A, olefinic polymerization of the present invention;
B, organo-aluminium compound component; Its general formula is AlR
nX
3-n, in the formula R be hydrogen, and carbonatoms be 1～20 alkyl; X is a halogen, and n is the integer of 0＜n≤3;
The silicoorganic compound component of C, a kind of optional adding; Its general formula is R
1R
2Si (OR ')
2, R in the formula
1, R
2Identical or different, be C
1～C
20Alkyl, naphthenic base or aryl, R ' is for containing the alkyl of 1～4 carbon atom.
Have basic aluminum compound concrete as: aluminum alkyl halides such as trimethylaluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, ethyl aluminum dichloride, wherein with triethyl aluminum, triisobutyl aluminium for well.Ratio between B component and the component A is 5～5000 with aluminium and titanium molar ratio computing, is preferably 20～500;
Silicoorganic compound concrete as: trimethylammonium methoxy silane, trimethylethoxysilane, trimethyl phenoxysilane; Dimethyldimethoxysil,ne, dimethyldiethoxysilane, methylcyclohexyl diethoxy silane; Methylcyclohexyl dimethoxy silane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane; Phenyl triethoxysilane, phenyltrimethoxysila,e, vinyltrimethoxy silane etc.Ratio between B component and the component C counts 5～30 with aluminium and silicon mol ratio.
It is carrier that the present invention adopts the alkoxyl magnesium of excellent property; The olefin polymerization catalysis of preparing is active high; Molecular weight distribution is wide, tap density is high, hydrogen response and stereospecificity does very well, particle form keeps and be evenly distributed, and is fit to the exploitation of the polyolefine trade mark.
Embodiment
Through embodiment the present invention is described particularly, the present invention is not limited to following embodiment.
Polyolefinic evaluation method is following:
Titanium content in (1) the 721 spectrophotometer detecting catalyst;
(2) the boiling n-heptane extraction process is measured the isotactic index (II) of polymkeric substance;
(3) press the melting index (MI) that testing standard GB/T3682-2000 measures polymkeric substance;
(4) Malvern Mastersizer
TM2000 normal hexane dispersion agent laser diffractometries are measured grain size, the size-grade distribution of dialkoxy magnesium and catalyzer;
(5) measure tap density with the method for bulk solids weight in the unit volume.
Embodiment 1
(1) 2; The preparation of 3-di-isopropyl-2-dicyano diethyl succinate (in table 1 be called for short " JS "): by international patent application no PCT/CN2010/000202 the disclosed embodiments 1 method, with 10 times of the consumption expansions of reactant and solvent among the embodiment 1, and will be with the chromatography column separation and purification 2 that is filled with silica gel; 3-di-isopropyl-2-dicyano diethyl succinate bullion; Change the underpressure distillation separation and purification into, under 110-120Pa pressure, collect 124-127 ℃ of cut.Product infrared analysis and PCT/CN2010/000202 the disclosed embodiments 1 obtain 2,3-di-isopropyl-2-dicyano diethyl succinate is consistent.
IR(cm
-1)：2979，2881，2246，1733，1469，1394，1371，1299.6，1141。(2) 2-sec.-propyl-2-(3-methylbutyl)-1, the preparation of 3-Propanal dimethyl acetal (in table 1, being called for short " 2# ether "): press the disclosed method preparation of Chinese patent ZL91108297.2.
Embodiment 2
(1) preparation of catalyst component
(d (0.5) is 26.4 μ m to choose alkoxyl magnesium; The Span value is 0.85) 10g and toluene 50ml, the preparation of embodiment 1 method 2; 3-di-isopropyl-2-dicyano diethyl succinate (in table 1, being called for short " JS ") 1.25m l, 2-sec.-propyl-2-(3-methylbutyl)-1,3-Propanal dimethyl acetal (in table 1, being called for short " 2# ether ") 1.25ml is mixed with suspension-s; Repeat to add toluene 10ml and titanium tetrachloride 90ml in the reaction kettle of metathetical 300ml through high pure nitrogen, be warming up to 80 ℃; Then the suspension-s for preparing is added in the still, constant temperature continued to be warming up to 110 ℃ after 1 hour; Constant temperature 2 hours is clean with the liquid press filtration then.The mixed solution that adds toluene 120ml and titanium tetrachloride 30ml then was warming up to 110 ℃ of stir process 1 hour, so handled 3 times, and elimination liquid, the solid of gained are with hexane 150ml washing 4 times, and elimination liquid is also dry, promptly gets ingredient of solid catalyst.
(2) olefinic polymerization
Use propylene as alkene, follow these steps to carry out polymerization:
In one the 5 liters stainless steel autoclaves that have a whisking appliance; Behind nitrogen replacement, at room temperature introduce hexane solution (concentration of triethyl aluminum the is 0.5mmol/m1) 5ml of triethyl aluminum, hexane solution (concentration of CHMMS is 0.10mmol/m1) lml, anhydrous hexane 10ml and the ingredient of solid catalyst 10mg of cyclohexyl methyl dimethoxy silane (CHMMS) in the stream of nitrogen gas.Close autoclave, introduce hydrogen 4.5L (under the standard state) and liquid propene 2.0L; In under agitation 10 minutes temperature is risen to 70 ℃., stop stirring after 2 hours 70 ℃ of following polyreactions, remove unpolymerized propylene monomer, collected polymer.
Embodiment 3
Except in the preparation (1) of catalyst component; With 2 of embodiment 1 gained; 3-di-isopropyl-2-dicyano diethyl succinate (in table 1, being called for short " JS ") and 2-sec.-propyl-2-(3-methylbutyl)-1; The add-on of 3-Propanal dimethyl acetal (in table 1, being called for short " 2# ether ") changes into respectively outside 1.9ml and the 0.6ml, and other is with embodiment 2.
Embodiment 4
Except in the preparation (1) of catalyst component; With 2 of embodiment 1 method preparation; 3-di-isopropyl-2-dicyano diethyl succinate (in table 1, being called for short " JS ") and 2-sec.-propyl-2-(3-methylbutyl)-1; The add-on of 3-Propanal dimethyl acetal (in table 1, being called for short " 2# ether ") changes into respectively outside 0.6ml and the 1.9ml, and other is with embodiment 2.
Comparative example 1
(1) preparation of catalyst component
The alkoxyl magnesium 10g and toluene 50ml, n-butyl phthalate (DNBP) 2.5ml that get with embodiment 2 same specifications are mixed with suspension-s; Repeat to add toluene 10m l and titanium tetrachloride 90ml in the reaction kettle of metathetical 300ml through high pure nitrogen, be warming up to 80 ℃; Then the suspension-s for preparing is added in the still, constant temperature continued to be warming up to 115 ℃ after 1 hour; Constant temperature 2 hours is clean with the liquid press filtration then.The mixed solution that adds toluene 120ml and titanium tetrachloride 30ml then was warming up to 110 ℃ of stir process 1 hour, so handled 3 times, and elimination liquid, the solid of gained are with hexane 150ml washing 4 times, and elimination liquid is also dry, promptly gets ingredient of solid catalyst.
(3) olefinic polymerization
With embodiment 2.
Claims (5)
1. an ingredient of solid catalyst that is used for olefinic polymerization is characterized in that, this catalyst component is a carrier with spherical dialkoxy magnesium; With the inert solvent is dispersion agent; Have 2 of a general formula (I) with at least a, the alkyl of 3-two non-straight chains-2-cyanic acid succinate compound and 2-sec.-propyl-2-(3-methylbutyl)-1, the mixing of 3-Propanal dimethyl acetal is to electron compound contact back and titanium compound reaction; Handle through titanium compound again, obtain ingredient of solid catalyst;
Described have 2 of a general formula (I), and the alkyl of 3-two non-straight chains-2-cyanic acid succinate compound is:
Wherein, R
1And R
2Group is independently selected from the C of straight chain
1～C
4The C of alkyl or side chain
1～C
4Alkyl; R is selected from C
3～C
6Iso-alkyl, C
3～C
6Secondary alkyl or C
3～C
6Naphthenic base;
2, the alkyl of 3-two non-straight chains-2-cyanic acid succinate compound can use separately or several kinds be used, its usage quantity is 0.005～10 mole with respect to the magnesium in 1 mole of spherical dialkoxy magnesium compound;
Described 2-sec.-propyl-2-(3-methylbutyl)-1, its usage quantity of 3-Propanal dimethyl acetal is 0.005～10 mole with respect to the magnesium in 1 mole of spherical dialkoxy magnesium compound;
The general formula of described titanium compound is Ti (OR)
4-nX
n, R is C in the formula
1～C
14Aliphatic hydrocarbyl or aromatic hydrocarbyl, X is a halogen atom, n is 0 to 4 integer; N is 2 when following, and a plurality of R can be identical or different;
The usage quantity of titanium compound is 0.5～100 mole with respect to the magnesium in 1 mole of spherical dialkoxy magnesium compound;
Described inert solvent randomly adopts a kind of in hexane, heptane, octane, decane, the benzene,toluene,xylene or their mixture; Its usage quantity is 0.5～100 mole with respect to the magnesium in 1 mole of spherical dialkoxy magnesium compound.
2. according to the ingredient of solid catalyst described in the claim 1, it is characterized in that described 2, the usage quantity of the alkyl of 3-two non-straight chains-2-cyanic acid succinate compound is 0.01～1 mole with respect to the magnesium in 1 mole of spherical dialkoxy magnesium compound; 2-sec.-propyl-2-(3-methylbutyl)-1, the usage quantity of 3-Propanal dimethyl acetal is 0.01～1 mole with respect to the magnesium in 1 mole of spherical dialkoxy magnesium compound; Titanium compound is a titanium tetrachloride, and its usage quantity is 1～50 mole with respect to the magnesium in 1 mole of spherical dialkoxy magnesium compound; Inert solvent is a toluene, and its usage quantity is 1～50 mole with respect to the magnesium in 1 mole of spherical dialkoxy magnesium compound.
3. according to the ingredient of solid catalyst described in the claim 1; It is characterized in that; Described 2, the alkyl of 3-two non-straight chains-2-cyanic acid succinate compound is 2,3-di-isopropyl-2-dicyano diethyl succinate, 2; 3-di-isopropyl-2 dicyano Succinic Acid di-n-propyl ester, 2; 3-di-isopropyl-2-dicyano diisopropyl ester amber acid, 2,3-di-isopropyl-2-dicyano Succinic Acid di-n-butyl, 2, a kind of in 3-di-isopropyl-2-dicyano Succinic Acid diisobutyl ester or their mixture.
4. according to the ingredient of solid catalyst described in the claim 1, it is characterized in that described 2, the alkyl of 3-two non-straight chains-2-cyanic acid succinate compound is 2,3-di-isopropyl-2-dicyano diethyl succinate.
5. a catalyzer that is used for olefinic polymerization is characterized in that, comprises the reaction product of following component:
The said olefins polymerizing solid catalyst component of one of A, claim 1～4;
B, organo-aluminium compound component; Its general formula is AlR
nX
3-n, R is that hydrogen or carbonatoms are 1～20 alkyl in the formula; X is a halogen, and n is the integer of 0＜n≤3;
The silicoorganic compound component of C, a kind of optional adding; Its general formula is R
1R
2Si (OR ')
2, R in the formula
1, R
2Identical or different, be C
1～C
20Alkyl, C
3～C
20Naphthenic base or aryl, R ' is for containing the alkyl of 1～4 carbon atom;
Ratio between B component and the component A is 5～5000 with aluminium and titanium molar ratio computing; Ratio between B component and the component C counts 5～30 with aluminium and silicon mol ratio.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110021247.8A CN102603932B (en) | 2011-01-19 | 2011-01-19 | Solid catalyst component and catalyst for olefinic polymerization |
| KR1020137021542A KR101928316B1 (en) | 2011-01-19 | 2012-01-19 | Solid catalyst component and catalyst for olefin polymerization |
| EP12736394.3A EP2666790B1 (en) | 2011-01-19 | 2012-01-19 | Solid catalyst component and catalyst for olefin polymerization |
| BR112013018569A BR112013018569B1 (en) | 2011-01-19 | 2012-01-19 | solid catalyst component, catalyst for olefin polymerization and process for olefin polymerization |
| MYPI2013002704A MY162215A (en) | 2011-01-19 | 2012-01-19 | Solid catalyst component and catalyst for olefin polymerization |
| ES12736394.3T ES2537188T3 (en) | 2011-01-19 | 2012-01-19 | Solid catalyst component and catalyst for olefin polymerization |
| US13/980,359 US9376513B2 (en) | 2011-01-19 | 2012-01-19 | Solid catalyst component and catalyst for olefin polymerization |
| SG2013055116A SG192040A1 (en) | 2011-01-19 | 2012-01-19 | Solid catalyst component and catalyst for olefin polymerization |
| PCT/CN2012/000098 WO2012097680A1 (en) | 2011-01-19 | 2012-01-19 | Solid catalyst component and catalyst for olefin polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110021247.8A CN102603932B (en) | 2011-01-19 | 2011-01-19 | Solid catalyst component and catalyst for olefinic polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102603932A true CN102603932A (en) | 2012-07-25 |
| CN102603932B CN102603932B (en) | 2014-03-12 |
Family
ID=46521750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110021247.8A Active CN102603932B (en) | 2011-01-19 | 2011-01-19 | Solid catalyst component and catalyst for olefinic polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102603932B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104479055A (en) * | 2014-11-27 | 2015-04-01 | 任丘市利和科技发展有限公司 | Dialkoxymagnesium support type solid catalyst component and catalyst |
| DE102015013209A1 (en) | 2014-10-10 | 2016-04-14 | Petrochina Company Limited | Olefin polymerization catalyst and combined catalyst containing the same |
| CN116023543A (en) * | 2021-10-27 | 2023-04-28 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, catalyst for olefin polymerization and application thereof |
| CN116023545A (en) * | 2021-10-27 | 2023-04-28 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization, catalyst system, application and olefin polymerization method |
| CN116041586A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method thereof, catalyst and olefin polymerization method |
| CN116041575A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, catalyst and olefin polymerization method |
| CN116041581A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Olefin polymerization catalyst component, preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101165073A (en) * | 2006-10-20 | 2008-04-23 | 中国石油化工股份有限公司 | Catalyst component used for olefin polymerization reaction and catalyst thereof |
-
2011
- 2011-01-19 CN CN201110021247.8A patent/CN102603932B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101165073A (en) * | 2006-10-20 | 2008-04-23 | 中国石油化工股份有限公司 | Catalyst component used for olefin polymerization reaction and catalyst thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102015013209A1 (en) | 2014-10-10 | 2016-04-14 | Petrochina Company Limited | Olefin polymerization catalyst and combined catalyst containing the same |
| CN104479055A (en) * | 2014-11-27 | 2015-04-01 | 任丘市利和科技发展有限公司 | Dialkoxymagnesium support type solid catalyst component and catalyst |
| CN116023543A (en) * | 2021-10-27 | 2023-04-28 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, catalyst for olefin polymerization and application thereof |
| CN116023545A (en) * | 2021-10-27 | 2023-04-28 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization, catalyst system, application and olefin polymerization method |
| CN116041586A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method thereof, catalyst and olefin polymerization method |
| CN116041575A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, catalyst and olefin polymerization method |
| CN116041581A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Olefin polymerization catalyst component, preparation method and application thereof |
| CN116041586B (en) * | 2021-10-28 | 2024-02-13 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method thereof, catalyst and olefin polymerization method |
| CN116041575B (en) * | 2021-10-28 | 2024-05-07 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, catalyst and olefin polymerization method |
| CN116041581B (en) * | 2021-10-28 | 2024-07-02 | 中国石油化工股份有限公司 | Olefin polymerization catalyst component, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102603932B (en) | 2014-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102399326B (en) | Solid catalyst component for olefin polymerization, and catalyst thereof | |
| CN102603932A (en) | Solid catalyst component and catalyst for olefinic polymerization | |
| CN101735346B (en) | Catalyst for propylene homopolymerization and copolymerization, and preparation method and application thereof | |
| CN1726080A (en) | Magnesium dichloride-based adducts and catalyst components obtained therefrom | |
| EP2617739B1 (en) | Catalyst carrier for olefin polymerization, solid catalyst component and catalyst | |
| CN104583244B (en) | Catalyst for olefines polymerizing and preparation method thereof | |
| CN1026003C (en) | Process for manufacturing of catalyst composition used in olefin polymerization | |
| CN102838697A (en) | Catalyst component for high temperature olefin polymerization, and preparation method thereof | |
| CN103788252A (en) | Catalyst solid ingredient, catalyst containing catalyst solid ingredient and use of catalyst in olefin polymerization | |
| CN102603931B (en) | Solid catalyst component for olefin polymerization and catalyst | |
| WO2005103094A1 (en) | Olefin polymerization procatalyst compositions and method of preparation | |
| CN102898558B (en) | Application of catalyst component in olefin polymerization | |
| CN102212153B (en) | Diester-maleate-containing solid catalyst component for olefin polymerization and preparation method thereof | |
| CN102898555B (en) | Application of catalyst component in olefin polymerization | |
| CN100363389C (en) | Catalyst used for ethylene polymerization or copolymerization and its preparation method | |
| CN102898557B (en) | Application of catalyst component in olefin polymerization | |
| EP0677066B1 (en) | Olefin polymerization catalyst | |
| JP3340729B2 (en) | α-Olefin polymerization method | |
| CN101456924B (en) | Catalyst component for olefin polymerization and catalyst thereof | |
| EP2666790B1 (en) | Solid catalyst component and catalyst for olefin polymerization | |
| CN102603933B (en) | Solid catalyst component for olefin polymerization and catalyst | |
| CN108084305A (en) | Ethylene polymerization solid titanium catalyst component, preparation method thereof and ethylene polymerization solid titanium catalyst | |
| CN102898556B (en) | Application of catalyst component in olefin polymerization | |
| CN101519463A (en) | Preparation method of catalyst for ethylene polymerization and copolymerization | |
| CN115975078B (en) | Catalyst component for olefin polymerization, catalyst and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |