CN104513332A - Catalyst system used in olefin polymerization and application thereof - Google Patents
Catalyst system used in olefin polymerization and application thereof Download PDFInfo
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Abstract
The invention discloses a catalyst system used in olefin polymerization. The catalyst system includes following components: (a). a solid catalyst component, comprising magnesium, titanium, a halogen and an internal electron donor diether compound; (b) an alkyl aluminum compound; and (c) a compounded external electron donor, comprising a first external electron donor c1 and a second external electron donor c2, wherein the first external electron donor c1 is selected from one or more of silanes, diethers and amines, and the second external electron donor c2 is a malonate compound. In the invention, by compounding the malonate compound and the external electron donors used in the prior art to obtain the external electron donor for being used in the olefin polymerization, especially in propylene polymerization, the catalyst system, when being used, is high in catalytic activity. An obtained polymer is high in stereo-directionality and hydrogen-regulation sensitivity and further a molecular weight distribution of the polymer becomes wider. The catalyst system is suitable for being used for developing resin in different trademarks.
Description
Technical field
The invention belongs to field of olefin polymerisation, be specifically related to a kind of catalyst system containing composite external electron donor.The invention still further relates to the application of above-mentioned catalyst system.
Background technology
As everyone knows, Zinger-Natta catalyzer can be used for olefinic polyreaction, particularly in the alpha-olefine polymerizing with 3 carbon or more carbon atom, can obtain the polymkeric substance of higher yields and higher tacticity.Wherein electron donor compound is one of composition in catalyzer, and constantly updates along with the development of internal electron donor compound result in polyolefin catalyst, and meanwhile, external electron donor is the development along with the development of internal electron donor also.At present, disclosed multiple electron donor compound in a large number, such as internal electron donor monocarboxylic ester or multi-carboxylate, ketone, monoether or polyether, amine etc. and derivative thereof, external electron donor is as monocarboxylic ester, amine, aminosilane etc. and derivative thereof.
In recent years, people attempt again to develop make new advances for the external donor compound in catalytic systems for polymerization of olefins, such as a kind of in the catalyst system of olefinic polyreaction disclosed in Chinese patent, employing diether compound is internal electron donor, adopting the dicarboxylic ester containing more than 4 carbon if adipic acid ester, pimelate are as external electron donor, the hydrogen response of catalyzer can be made when carrying out propylene polymerization to be greatly improved; But this dicarboxylic ester due to carbochain longer, preparation is complicated, and cost is higher, limits its large-scale application, and meanwhile, it can not change the shortcoming of diether catalyst narrow molecular weight distribution.
Summary of the invention
For deficiency of the prior art, the invention provides a kind of catalyst system for olefinic polymerization, it adopts ingredient of solid catalyst containing diether compounds and composite external electron donor, when described catalyst system is used for olefinic polymerization, present obvious synergy, not only maintain the high catalytic activity of catalyzer, improve the degree of isotacticity of polymkeric substance, also make the molecular weight distribution of obtained polymkeric substance broaden.
According to an aspect of the present invention, provide a kind of catalyst system for olefinic polymerization, comprise the product of following component:
A ingredient of solid catalyst, comprises magnesium, titanium, halogen and internal electron donor diether compounds;
B alkylaluminium cpd;
The external electron donor that c is composite, comprises first kind external electron donor c
1with Equations of The Second Kind external electron donor c
2, described first kind external electron donor c
1be selected from one or more of silicane, two ethers and aminated compounds, described Equations of The Second Kind external electron donor c
2for malonate compound.
In a preferred embodiment of above-mentioned catalyst system, described first kind external electron donor c
1with Equations of The Second Kind external donor compound c
2mol ratio be (1 ~ 100): (100 ~ 1), preferably (1 ~ 50): (50 ~ 1), more preferably (1 ~ 20): (20 ~ 1).
In a specific embodiment of above-mentioned catalyst system, the general formula (I) of the internal electron donor diether compounds in described ingredient of solid catalyst is
Wherein, R
1and R
2can be identical or not identical, be substituted or unsubstituted C
1~ C
10straight chained alkyl, C
3~ C
15branched-chain alkyl, C
3~ C
15cycloalkyl, C
6~ C
20aryl or C
7~ C
20alkaryl or aralkyl, be preferably substituted or unsubstituted C
2~ C
10straight chained alkyl, C
3~ C
10branched-chain alkyl, C
3~ C
10cycloalkyl, C
6~ C
15aryl or C
7~ C
15alkaryl or aralkyl; R
1and R
2optionally can be keyed to ring or not Cheng Huan.
In the present invention, for described " replacement " mean hydrogen on described group optionally by alkyl or halogen atom replace, as described in the C of replacement
1~ C
10straight chained alkyl, C
3~ C
15branched-chain alkyl, C
3~ C
15cycloalkyl, C
6~ C
20aryl or C
7~ C
20alkaryl or aralkyl, refer to as described in hydrogen on alkyl, aryl, alkaryl or aralkyl carbon optionally by alkyl or halogen atom replace.
In above-mentioned catalyst system, the specific examples of described internal electron donor diether compounds can be selected from 2,2-dimethyl-1,3-Propanal dimethyl acetal, 2,2-diethyl-1,3-Propanal dimethyl acetal, 2,2-dipropyl-1,3-Propanal dimethyl acetal, 2,2-di-isopropyl-1,3-Propanal dimethyl acetal, 2,2-dibutyl-1,3-Propanal dimethyl acetal, 2,2-diisobutyl-1,3-Propanal dimethyl acetal, 2,2-diamyl-1,3-Propanal dimethyl acetal, 2,2-diisoamyl-1,3-Propanal dimethyl acetal, 2-methyl-2-ethyl-1,3-Propanal dimethyl acetal, 2-methyl-2-propyl-1,3-Propanal dimethyl acetal, 2-methyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-methyl-2-butyl-1,3-Propanal dimethyl acetal, 2-methyl-2-isobutyl--1,3-Propanal dimethyl acetal, 2-methyl-2-amyl group-1,3-Propanal dimethyl acetal, 2-methyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2-ethyl-2-propyl group-1,3-Propanal dimethyl acetal, 2-ethyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-ethyl-2-butyl-1,3-Propanal dimethyl acetal, 2-ethyl-2-isobutyl--1,3-Propanal dimethyl acetal, 2-ethyl-2-amyl group-1,3-Propanal dimethyl acetal, 2-ethyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2-propyl group-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-propyl group-2-butyl-1,3-Propanal dimethyl acetal, 2-propyl group-2-isobutyl--1,3-Propanal dimethyl acetal, 2-propyl group-2-amyl group-1,3-Propanal dimethyl acetal, 2-propyl group-2-isopentyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isobutyl--1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-amyl group-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2-butyl-2-isobutyl--1,3-Propanal dimethyl acetal, 2-butyl-2-amyl group-1,3-Propanal dimethyl acetal, 2-butyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2-isobutyl--2-amyl group-1,3-Propanal dimethyl acetal, 2-isobutyl--2-isopentyl-1,3-Propanal dimethyl acetal, 2-isobutyl--2-phenyl-1,3-Propanal dimethyl acetal, 2-isopentyl-2-phenyl-1,3-Propanal dimethyl acetal, 2-(2-methyl butyl)-2-benzyl-1,3-Propanal dimethyl acetal, 2-(2-ethyl-butyl)-2-phenyl-1,3-Propanal dimethyl acetal, 2-(2-ethylhexyl)-2-phenyl-1,3-Propanal dimethyl acetal, 2-methyl-2-phenyl-1,3-Propanal dimethyl acetal, 2-ethyl-2-phenyl-1,3-Propanal dimethyl acetal, 2-isobutyl--2-benzyl-1,3-Propanal dimethyl acetal, 2-isopentyl-2-benzyl-1,3-Propanal dimethyl acetal, 2-(2-methyl butyl)-2-benzyl-1,3-Propanal dimethyl acetal, 2-(2-ethyl-butyl)-2-benzyl-1,3-Propanal dimethyl acetal, 2-(2-ethylhexyl)-2-benzyl-1,3-Propanal dimethyl acetal, 2-propyl group-2-benzyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-benzyl-1,3-Propanal dimethyl acetal, 2-isobutyl--2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2-isopentyl-2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2-(2-methyl butyl)-2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2-(2-ethylhexyl)-2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2-methyl-2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2-ethyl-2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2-isobutyl--2-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2-isopentyl-2-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2-(2-ethyl-butyl)-2-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2-(2-ethylhexyl)-2-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2-isobutyl--2-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2-isobutyl--2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal, 2-isopentyl-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal, 2,2-bis-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2,2-bis-(2-ethylhexyl)-1,3-Propanal dimethyl acetal and 9,9-bis-(methoxymethyl) fluorenes etc.
Ingredient of solid catalyst a for olefinic polymerization of the present invention, preferably comprises titanium compound, magnesium compound and is selected from the reaction product with the compound shown in above-mentioned logical formula I.
Magnesium compound wherein used be selected from one of them halogen atom in magnesium dihalide, the hydrate of alkoxyl group magnesium ﹑ alkane base magnesium ﹑ magnesium dihalide or alcohol adduct and magnesium dihalide molecular formula by-oxyl or halo-oxyl the derivative of replacing; Be preferably the alcohol adduct of magnesium dihalide or magnesium dihalide.Specific examples is as magnesium dichloride, dibrominated magnesium, diiodinating magnesium and their alcohol adduct.
Titanium compound wherein used can select general formula to be TiX
m(OR
1)
4-mcompound, R in formula
1for C
1~ C
20alkyl, 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 oxygen base titanium, trichlorine one ethanolato-titanium, preferred titanium tetrachloride.
Ingredient of solid catalyst a described in the present invention is by the following method preparation enumerated.
Method one: as the method Kaolinite Preparation of Catalyst component disclosed according to patent CN1506384.First, magnesium compound is mixed by 2 ~ 5 mol ratios and inert solvent with organic alcohol compound, be warming up to 120 ~ 150 DEG C, react 1 ~ 5 hour by magnesium/acid anhydride mol ratio 5 ~ 10.Then according to titanium/magnesium mol ratio 20 ~ 50 alcohol adduct being chilled to room temperature joined in the compound titanium solution being chilled to-15 ~-40 DEG C in advance, be warming up to 90 ~ 110 DEG C, according to magnesium/internal electron donor mol ratio 2 ~ 10 add a kind of be selected from the compound shown in logical formula I 100 ~ 130 DEG C reaction 1 ~ 3 hour, filter to isolate solid particulate.According to titanium/magnesium mol ratio 20 ~ 50, solid particulate is joined in compound titanium solution again, stir and 100 ~ 130 DEG C of reactions 1.5 ~ 3 hours, filter to isolate solid particulate.Finally with the inert solvent washing solid particulate of 50 ~ 80 DEG C, after drying, obtain catalyst component.
Method two: be first dissolved in by magnesium compound in the solvent system comprising organic epoxy compounds, organo phosphorous compounds and inert diluent composition, mix after forming homogeneous solution with titanium compound, under precipitation additive exists, separates out solids; This solids adopts the compound being selected from logical formula I to process, and makes it be attached on solids, if desired, then processes solids with titanium tetrahalide and inert diluent.
Wherein said magnesium compound, the compound shown in titanium compound and logical formula I are as described in aforementioned.Described organic epoxy compound thing, organo phosphorous compounds and precipitation additive etc. are disclosed in Chinese patent CN85100997, and its associated viscera is incorporated herein by reference.As organic epoxy compounds can be selected from carbonatoms 2 ~ 8 aliphatics alkene, the oxide compound of diolefine or halogenated aliphatic alkene or diolefine, glycidyl ether and inner ether.Particular compound is as oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether, tetrahydrofuran (THF).As organo phosphorous compounds can comprise hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid, concrete as ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, tricresyl phosphite benzene methyl.As described in precipitation additive optional from organic acid anhydride, organic acid, ether, ketone and ester.Specifically comprise as diacetyl oxide, Tetra hydro Phthalic anhydride, Succinic anhydried, MALEIC ANHYDRIDE, pyromellitic acid anhydride, acetic acid, propionic acid, butyric acid, vinylformic acid, methacrylic acid, acetone, methylethylketone, benzophenone, methyl ether, ether, propyl ether, butyl ether, amyl ether, succinate, malonic ester, glutarate, 2,4-pentadiol ester, 3,5-heptanediol esters.Described each component is in every mole of magnesium compound, the consumption of organic epoxy compound thing is 0.2 ~ 10 mole, the consumption of organo phosphorous compounds is 0.1 ~ 3 mole, the consumption of precipitation additive is 0 ~ 1.0 mole, the consumption of titanium compound is 0.5 ~ 150 mole, and the consumption of the compound shown in described logical formula I is 0.01 ~ 1.0 mole.
Method three: by titanium compound of the present invention is concrete as TiCl
4, be MgCl with general formula
2the adducts of pROH reacts and prepares ingredient of solid catalyst.At MgCl
2in pROH, p is the number of 0.1 ~ 6, preferably 2 ~ 3.5, and R is the alkyl with 1 ~ 18 carbon atom.Adducts can be made spherical by the following method aptly: under not miscible with adducts unreactive hydrocarbons exist, by alcohol (ROH) and MgCl
2mixing, makes the rapid chilling of this emulsion, thus adducts is solidified with the form of spheroidal particle.The adducts so obtained can directly and titanium compound react, or its before reacting with titanium compound can in advance through the dealcoholization (80 ~ 130 DEG C) of thermal control to obtain a kind of adducts, wherein the mole number of alcohol is generally lower than 3, preferably between 0.1 ~ 2.7.Can by adducts (dealcoholysis or itself) be suspended in cold TiCl
4in (general 0 DEG C), and mixture temperature programming to 80 ~ 130 DEG C are also kept 0.1 ~ 2 hour at this temperature, carry out the reaction with titanium compound.TiCl
4process can be carried out once or repeatedly.With TiCl
4can add above-mentioned the present invention during process to lead to formula I compound and process, this process also can repeat once or repeatedly.
Specifically can according to the method Kaolinite Preparation of Catalyst component disclosed in patent CN1091748.Magnesium chloride alcohol adduct melt disperses through high-speed stirring in the dispersant system of white oil and silicone oil, forms emulsion, is discharged into rapid cooling and shaping in cooling fluid, formation magnesium chloride alcohol adduct microballoon.Cooling fluid is the inert hydrocarbon solvent that boiling point is lower, as sherwood oil, pentane, hexane, heptane etc.Gained magnesium chloride alcohol adduct microballoon is ball type carrier through washing, drying, and the mol ratio of its alcohol and magnesium chloride is 2 ~ 3, with 2 ~ 2.5 as well.Diameter of carrier is 10 ~ 300 microns, best with 30 ~ 150 microns.
With excessive titanium tetrachloride at the above-mentioned ball type carrier of subzero treatment, progressively heat up, in treating processes, add the present invention lead to the electron donor shown in formula I, repeatedly wash with inert solvent after process, after drying, obtain the spherical catalyst components of solid powdery.The mol ratio of titanium tetrachloride and magnesium chloride is 20 ~ 200, with 30 ~ 60 as well; Initiated process temperature is-30 ~ 0 DEG C, is good with-25 ~-20 DEG C; Final treatment temp is 80 ~ 136 DEG C, is good with 100 ~ 130 DEG C.
Method four: also can add in arene compound with dialkoxy magnesium and stir, forms suspension; Suspension is with tetravalence titanium chloride-20 ~ 100 DEG C of process, and 0 ~ 130 DEG C of reaction, in the process, add the present invention at-20 ~ 130 DEG C and lead to formula I electron donor and react, the solid arene compound obtained washs; Then at 0 ~ 130 DEG C in aromatic hydrocarbon solvent, then use the process of tetravalence titanium chloride, finally with inert solvent washing, drain, obtain ingredient of solid catalyst.Wherein every mole of dialkyl magnesium tetravalence titanium chloride 0.5 ~ 100mol, electron donor 0.01 ~ 10mol.
Method five: use TiCl
4or its arene solution carries out halogenation to two magnesium hydrocarbyloxy compound of such as dialkoxy magnesium or two aryloxy magnesium and so at 80 ~ 130 DEG C, uses TiCl
4or its arene solution carries out process and can repeat one or many, and in the such process of one or many, add the compound that the present invention leads to formula I.
Method six: according to the method Kaolinite Preparation of Catalyst component disclosed in patent US4540679.First, magnesium alkoxide and carbon dioxide reaction obtain alkyl magnesiumcarbonate carrier.Then the electron donor that formula I is led in transistion metal compound (be preferably tetravalent titanium compound) and alkyl magnesiumcarbonate carrier and the present invention reacts in certain proportion in inert solvent, wherein the mol ratio of transition metal and magnesium elements is at least 0.5:1, and the electron donor consumption that formula I is led in the present invention mostly is 1.0 moles of every gram of titanium atoms most.Inert solvent must through purifying, to slough the material that water, oxygen, carbonic acid gas etc. easily make poisoning of catalyst.Reaction is carried out at-10 ~ 170 DEG C, and the reaction times is that several minutes arrives several hours.
The method preparing ingredient of solid catalyst (A) also forms emulsion just like by magnesium compound, electron donor etc. in thinner, adds titanium compound and makes it fixedly obtain spherical solid, more treatedly obtains ingredient of solid catalyst.
In the above-mentioned preparation method of any one, required electron donor compound (I) namely can add with the form of compound; Also can add in other manners, as can be obtained by the precursor original position adopting electron donor compound (I) to be applicable to, this precursor becomes required electron donor compound by example chemical reaction as is known such as esterification etc.
In a specific embodiment of above-mentioned catalyst system, the general formula of described alkylaluminium cpd is AlR '
nx
3-n, wherein R ' is selected from hydrogen and C
1~ C
20alkyl, X is halogen, 1≤n≤3.The specific examples of described alkylaluminium cpd comprises triethyl aluminum, tri-propyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-octylaluminium, triisobutyl aluminium, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium and ethyl aluminum dichloride, preferred triethyl aluminum, triisobutyl aluminium.
In a specific embodiment of above-mentioned catalyst system, the general formula of described Equations of The Second Kind external electron donor malonate compound is
In formula, R
3and R
4may be the same or different, be selected from hydrogen, C
1~ C
10straight chained alkyl, C
3~ C
10the alkyl of side chain, C
3~ C
10cycloalkyl, C
6~ C
10aryl and C
7~ C
10alkaryl or aralkyl, be preferably selected from hydrogen, C
1~ C
6straight chained alkyl, C
3~ C
8the alkyl of side chain, C
5~ C
10cycloalkyl and C
7~ C
10alkaryl; R
5for C
1~ C
10straight chained alkyl, C
3~ C
10the alkyl of side chain, C
3~ C
10cycloalkyl, C
6~ C
10aryl, C
7~ C
10alkaryl or aralkyl, be preferably C
2~ C
8straight chained alkyl, C
3~ C
8the alkyl of side chain, C
5~ C
10cycloalkyl or C
7~ C
10alkaryl.
In above-mentioned catalyst system, described Equations of The Second Kind external electron donor malonate compound is as being selected from following compound: diethyl malonate, dipropyl malonate, Diisopropyl malonate, butyl ethyl malonate, propanedioic acid diisobutyl ester, methyl-malonic ester, Methylpropanedioic acid dipropyl, Methylpropanedioic acid diisopropyl ester, Methylpropanedioic acid di-n-butyl, Methylpropanedioic acid diisobutyl ester, Methylpropanedioic acid di tert butyl carbonate, ethyl malonic acid diethylester, ethyl malonic acid dipropyl, ethyl malonic acid diisopropyl ester, ethyl malonic acid di-n-butyl, ethyl malonic acid diisobutyl ester, ethyl malonic acid di tert butyl carbonate, propylmalonic acid diethyl ester, propylmalonic acid dipropyl, propylmalonic acid diisopropyl ester, propylmalonic acid di-n-butyl, propylmalonic acid diisobutyl ester, propylmalonic acid di tert butyl carbonate, diethyl isopropyl, isopropyl-malonic acid dipropyl, isopropyl-malonic acid diisopropyl ester, isopropyl-malonic acid di-n-butyl, isopropyl-malonic acid diisobutyl ester, isopropyl-malonic acid di tert butyl carbonate, phenyl ethyl malonate, phenylmalonic acid dipropyl, phenylmalonic acid diisopropyl ester, phenylmalonic acid di-n-butyl, phenylmalonic acid diisobutyl ester, phenylmalonic acid di tert butyl carbonate etc., Bian propylmalonic acid diethyl ester, Bian propylmalonic acid dipropyl, Bian propylmalonic acid diisopropyl ester, Bian propylmalonic acid di-n-butyl, Bian propylmalonic acid diisobutyl ester, Bian propylmalonic acid di tert butyl carbonate etc., dimethyl malonic ester, diethyl malonic ester, methylethyl diethyl malonate, methyl butyl diethyl malonate, methyl-isobutyl diethyl malonate, methyl-propyl diethyl malonate, isopropyl methyl diethyl malonate, diη-propyl diethyl malonate, di-n-butyl diethyl malonate, di-isopropyl diethyl malonate, diisobutyl diethyl malonate and diallyl diethyl malonate etc.
In above-mentioned catalyst system, described first kind external electron donor c
1as can be in prior art the compound being commonly used for external electron donor; Described amine, as being the amine of band shape structure, as piperidines, 2, the 6-piperidines replaced, 2, the 5-piperidines etc. replaced.In a preferred embodiment, described first kind external electron donor c
1be selected from Cyclohexyl Methyl Dimethoxysilane, diphenyl dimethoxy silicon, phenyltriethoxy silane, diisopropyl dimethoxy silane, dipropyl dimethoxysilane, dicyclopentyl dimethoxyl silane, diphenyldimethyl silane, tetraalkoxysilane, butyl trimethoxy silane, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 9,9-bis-(methoxymethyl) fluorenes, 2,2-dibutyl-1,3-Propanal dimethyl acetal, 2,2-diisobutyl-1, one or more in 3-Propanal dimethyl acetal and 2-isobutyl--2-isopentyl-1,3-Propanal dimethyl acetal etc.
In a specific embodiment of above-mentioned catalyst system, the mol ratio of described component a and components b is with titanium: aluminium counts 1:(5 ~ 1000), preferred 1:(20 ~ 250); The mol ratio of component a and amount of component b is with titanium: external donor compound counts 1:(0.1 ~ 100), preferred 1:(1 ~ 50).
According to another aspect of the present invention, provide a kind of Prepolymerized catalyst system for olefinic polymerization, described Prepolymerized catalyst system comprises the prepolymer that a kind of above-mentioned catalyst system and alkene carry out prepolymerization gained, and pre-polymerization multiple is 0.1 ~ 1000g olefin polymer/g ingredient of solid catalyst a.
In the present invention, " pre-polymerized catalyst " refers to the catalyzer of lower transforming degree through polymerization procedure.According to the present invention, the alpha-olefin identical with being polymerized alkene used can being adopted to carry out prepolymerization, wherein carrying out prepolymerized alkene and being preferably propylene.Specifically, particularly preferably be, the mixture adopting propylene or itself and amount to be up to one or more alpha-olefins of 20mol% carries out prepolymerization.Preferably, the transforming degree of pre-polymerized catalyst components is about 0.2 ~ 500 gram of polymkeric substance/gram ingredient of solid catalyst a.
Prepolymerization operation can at-20 ~ 80 DEG C, preferably at the temperature of 0 ~ 50 DEG C, carry out in a liquid or in gas phase.Prepolymerization step can carry out online as the part in continuous polymerization technique, or carries out independently in periodical operation.For the polymkeric substance that preparation amount is 0.5 ~ 20g/g catalyst component, the particularly preferably batch pre-polymerization of catalyzer of the present invention and propylene.Polymerization pressure is 0.01 ~ 10MPa.
According to a further aspect in the invention, provide a kind of olefine polymerizing process, wherein said alkene is polymerized under the effect of above-mentioned catalyst system or Prepolymerized catalyst system.
Catalyzer of the present invention can directly add in polymerization process in reactor, or catalyzer and alkene pre-polymerization obtain pre-polymerized catalyst after add in reactor.
Olefinic polyreaction of the present invention carries out according to known polymerization process, can carry out in liquid phase or gas phase, or also can carry out under the operation of liquid and gas polymerization stage combination.Adopt conventional technology as slurry process, gas-phase fluidized-bed etc.Adopt following reaction conditions preferably: polymerization temperature 0 ~ 150 DEG C, preferably 60 ~ 90 DEG C.
The general formula of alkene described in the present invention is CH
2=CHR, wherein R is hydrogen or C
1~ C
12alkyl or aryl, as being selected from propylene, 1-butylene, 4-methyl-1-pentene and 1-hexene.Be preferably selected from propylene, as propylene all polymerizations with or the copolymerization of other alkene of propylene.
The present invention by the external electron donor that adopts a kind of malonate compound and prior art conventional composite as external electron donor be used for alkene particularly propylene polymerization time, present obvious synergy, the high catalytic activity not only maintaining catalyzer also improves the vertical structure directional property of polymkeric substance simultaneously, and widened the molecular weight distribution of polymkeric substance, be conducive to the processing of polymkeric substance, be suitable for the exploitation of different trade mark resin.
Embodiment
Embodiment given below is in order to the present invention is described, instead of limits the invention.
Testing method
1. polymkeric substance isotactic index adopts heptane extraction process to measure (heptane boiling extracting 6 hours): the polymer samples of 2g drying, be placed in extractor and after 6 hours with the extracting of boiling heptane, residuum be dried to the polymer weight (g) of constant weight gained and be isotactic index with the ratio of 2.
2. polymericular weight and molecular weight distribution MWD(MWD=Mw/Mn): adopt gel permeation chromatography method, be that solvent measures (standard specimen: polystyrene at 150 DEG C with PL-GPC220 with trichlorobenzene, flow velocity: 1.0ml/min, pillar: 3xPlgel 10um M1xED-B 300x7.5nm).
One, the preparation of ingredient of solid catalyst a
Reflux exchanger, mechanical stirrer and thermometer are being housed and in 250ml reactor after nitrogen is fully replaced, add dehydrated alcohol 36.5ml, Magnesium Chloride Anhydrous 21.3g, stir lower intensification, add white oil 75ml, silicone oil 75ml after magnesium chloride all dissolves, maintain 120 DEG C of certain hours.Another volume be 500ml with in the reaction flask of high speed agitator, add the silicone oil of 112.5ml white oil and same volume in advance, be preheating to 120 DEG C, aforementioned mixture is pressed into rapidly in the second reactor, maintain 120 DEG C and stir 3 minutes with 3500rmp, be transferred to by material under stirring and add 1600ml hexane in advance and be cooled in the 3rd reactor of-25 DEG C, until material transfer is complete, outlet temperature is no more than 0 DEG C.Suction filtration, with hexanes wash, vacuum-drying, obtains spherical particle magnesium chloride alcohol adduct 41g, gets 100-400 object carrier after sieving, analytical test carrier consist of MgCl
22.38C
2h
5oH.
Get above-mentioned MgCl
22.38C
2h
5oH ball type carrier 7g slowly joins and 150ml titanium tetrachloride is housed and is chilled in advance in the reaction flask of-20 DEG C, is progressively warming up to 40 DEG C, adds the compound 3mmol of general formula for (I); Continue to be warming up to 130 DEG C, maintain 2 hours, suction filtration.Add 120ml TiCl again
4, be progressively warming up to 130 DEG C, maintain 2 hours, wash repeatedly to there is not chlorion in filtrate with hexane 60ml, filter cake vacuum-drying, obtains ingredient of solid catalyst.
Two, propylene polymerization experiment
The ingredient of solid catalyst a of above-described embodiment is carried out propylene polymerization respectively.Propylene polymerization program is: volume is the stainless steel cauldron of 5L, after gaseous propylene is fully replaced, adds AlEt
32.5mmol, composite external electron donor c 0.1mmol, then the ingredient of solid catalyst 8 ~ 10mg and the 1.2NL hydrogen that add above-described embodiment, pass into liquid propene 2.3L, be warming up to 70 DEG C, maintain this temperature 1 hour; Cooling, pressure release, obtains the PP powder of embodiment 1 ~ 9 and comparative example.
Comparative example uses Cyclohexyl Methyl Dimethoxysilane (CHMMS) and diethyl malonate (DEM) to replace composite external electron donor (c) respectively, and all the other are constant.
Experiment the data obtained is see table 1 and table 2.Wherein, the ratio of two kinds of external electron donors is mol ratio, and WMD refers to molecular weight distribution,
1c: Cyclohexyl Methyl Dimethoxysilane (CHMMS): diethyl malonate (DEM)=1:8;
2c: butyl trimethoxy silane: diethyl malonate (DEM)=1:16;
3c: dicyclopentyl dimethoxyl silane: methyl-malonic ester=1:2;
4c:2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal: diethyl malonate (DEM)=3:1;
5c: dicyclopentyl dimethoxyl silane: diethyl malonate (DEM)=7:2;
6c: Cyclohexyl Methyl Dimethoxysilane (CHMMS): Diisopropyl malonate=8:3;
7c: dicyclopentyl dimethoxyl silane: phenyl ethyl malonate=20:1;
8c: Cyclohexyl Methyl Dimethoxysilane (CHMMS): di-n-butyl diethyl malonate=1:4;
9c: Cyclohexyl Methyl Dimethoxysilane (CHMMS): diethyl malonate (DEM)=2:3.
Table 1
As can be seen from Table 1, at identical conditions, use composite external electron donor (as embodiment 9), with be used alone wherein a kind of external electron donor (comparative example 1 and comparative example 2) and compare, when the catalyzer obtained is for olefinic polymerization, especially during propylene polymerization, present obvious synergy, not only maintain the high catalytic activity of catalyzer, also improve the isotactic index of polymkeric substance simultaneously, and widen the molecular weight distribution (MWD) of polymkeric substance.Therefore, according to catalyzer provided by the invention, not only have higher catalyst activity, good hydrogen response is good, and the degree of isotacticity of the polymkeric substance obtained is high; Meanwhile, polymkeric substance has wider molecular weight distribution.
It should be noted that above-described embodiment only for explaining the present invention, not forming any limitation of the invention.By referring to exemplary embodiments, invention has been described, but to should be understood to word wherein used be descriptive and explanatory vocabulary, instead of limited vocabulary.Amendment can be made by the scope being defined in the claims in the present invention to the present invention, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention wherein described relates to specific method, material and embodiment, and do not mean that the present invention is limited to particular case disclosed in it, on the contrary, easily extensible of the present invention is to other all methods and applications with identical function.
Claims (12)
1., for a catalyst system for olefinic polymerization, comprise the product of following component:
A ingredient of solid catalyst, comprises magnesium, titanium, halogen and internal electron donor diether compounds;
B alkylaluminium cpd;
The composite external electron donor of c, comprises first kind external electron donor c
1with Equations of The Second Kind external electron donor c
2, described first kind external electron donor c
1be selected from one or more in silicane, two ethers and aminated compounds, described Equations of The Second Kind external electron donor c
2for malonate compound.
2. catalyst system according to claim 1, is characterized in that, described first kind external electron donor c
1with Equations of The Second Kind external donor compound c
2mol ratio be (1 ~ 100): (100 ~ 1), preferably (1 ~ 50): (50 ~ 1), more preferably (1 ~ 20): (20 ~ 1).
3. catalyst system according to claim 1 and 2, is characterized in that, the general formula of described Equations of The Second Kind external electron donor malonate compound is
In formula, R
3and R
4may be the same or different, be selected from hydrogen, C
1~ C
10straight chained alkyl, C
3~ C
10the alkyl of side chain, C
3~ C
10cycloalkyl, C
6~ C
10aryl and C
7~ C
10alkaryl or aralkyl, be preferably selected from hydrogen, C
1~ C
6straight chained alkyl, C
3~ C
8the alkyl of side chain, C
5~ C
10cycloalkyl and C
7~ C
10alkaryl; R
5for C
1~ C
10straight chained alkyl, C
3~ C
10the alkyl of side chain, C
3~ C
10cycloalkyl, C
6~ C
10aryl, C
7~ C
10alkaryl or aralkyl, be preferably C
2~ C
8straight chained alkyl, C
3~ C
8the alkyl of side chain, C
5~ C
10cycloalkyl or C
7~ C
10alkaryl.
4. according to the catalyst system in claims 1 to 3 described in any one, it is characterized in that, described Equations of The Second Kind external electron donor malonate compound is selected from following compound: diethyl malonate, dipropyl malonate, Diisopropyl malonate, butyl ethyl malonate, propanedioic acid diisobutyl ester, methyl-malonic ester, Methylpropanedioic acid dipropyl, Methylpropanedioic acid diisopropyl ester, Methylpropanedioic acid di-n-butyl, Methylpropanedioic acid diisobutyl ester, Methylpropanedioic acid di tert butyl carbonate, ethyl malonic acid diethylester, ethyl malonic acid dipropyl, ethyl malonic acid diisopropyl ester, ethyl malonic acid di-n-butyl, ethyl malonic acid diisobutyl ester, ethyl malonic acid di tert butyl carbonate, propylmalonic acid diethyl ester, propylmalonic acid dipropyl, propylmalonic acid diisopropyl ester, propylmalonic acid di-n-butyl, propylmalonic acid diisobutyl ester, propylmalonic acid di tert butyl carbonate, diethyl isopropyl, isopropyl-malonic acid dipropyl, isopropyl-malonic acid diisopropyl ester, isopropyl-malonic acid di-n-butyl, isopropyl-malonic acid diisobutyl ester, isopropyl-malonic acid di tert butyl carbonate, phenyl ethyl malonate, phenylmalonic acid dipropyl, phenylmalonic acid diisopropyl ester, phenylmalonic acid di-n-butyl, phenylmalonic acid diisobutyl ester, phenylmalonic acid di tert butyl carbonate etc., Bian propylmalonic acid diethyl ester, Bian propylmalonic acid dipropyl, Bian propylmalonic acid diisopropyl ester, Bian propylmalonic acid di-n-butyl, Bian propylmalonic acid diisobutyl ester, Bian propylmalonic acid di tert butyl carbonate etc., dimethyl malonic ester, diethyl malonic ester, methylethyl diethyl malonate, methyl butyl diethyl malonate, methyl-isobutyl diethyl malonate, methyl-propyl diethyl malonate, isopropyl methyl diethyl malonate, dipropyl diethyl malonate, di-isopropyl diethyl malonate, di-n-butyl diethyl malonate, diisobutyl diethyl malonate and diallyl diethyl malonate.
5. according to the catalyst system in Claims 1 to 4 described in any one, it is characterized in that, the general formula (I) of the internal electron donor diether compounds in described ingredient of solid catalyst is
Wherein, R
1and R
2can be identical or not identical, be substituted or unsubstituted C
1~ C
10straight chained alkyl, C
3~ C
15branched-chain alkyl, C
3~ C
15cycloalkyl, C
6~ C
20aryl or C
7~ C
20alkaryl or aralkyl, be preferably substituted or unsubstituted C
2~ C
10straight chained alkyl, C
3~ C
10branched-chain alkyl, C
3~ C
10cycloalkyl, C
6~ C
15aryl or C
7~ C
15alkaryl or aralkyl; R
1and R
2optionally can be keyed to ring or not Cheng Huan.
6. according to the catalyst system in Claims 1 to 5 described in any one, it is characterized in that, described internal electron donor diether compounds is selected from 2,2-dimethyl-1,3-Propanal dimethyl acetal, 2,2-diethyl-1,3-Propanal dimethyl acetal, 2,2-dipropyl-1,3-Propanal dimethyl acetal, 2,2-di-isopropyl-1,3-Propanal dimethyl acetal, 2,2-dibutyl-1,3-Propanal dimethyl acetal, 2,2-diisobutyl-1,3-Propanal dimethyl acetal, 2,2-diamyl-1,3-Propanal dimethyl acetal, 2,2-diisoamyl-1,3-Propanal dimethyl acetal, 2-methyl-2-ethyl-1,3-Propanal dimethyl acetal, 2-methyl-2-propyl-1,3-Propanal dimethyl acetal, 2-methyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-methyl-2-butyl-1,3-Propanal dimethyl acetal, 2-methyl-2-isobutyl--1,3-Propanal dimethyl acetal, 2-methyl-2-amyl group-1,3-Propanal dimethyl acetal, 2-methyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2-ethyl-2-propyl group-1,3-Propanal dimethyl acetal, 2-ethyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-ethyl-2-butyl-1,3-Propanal dimethyl acetal, 2-ethyl-2-isobutyl--1,3-Propanal dimethyl acetal, 2-ethyl-2-amyl group-1,3-Propanal dimethyl acetal, 2-ethyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2-propyl group-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-propyl group-2-butyl-1,3-Propanal dimethyl acetal, 2-propyl group-2-isobutyl--1,3-Propanal dimethyl acetal, 2-propyl group-2-amyl group-1,3-Propanal dimethyl acetal, 2-propyl group-2-isopentyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isobutyl--1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-amyl group-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2-butyl-2-isobutyl--1,3-Propanal dimethyl acetal, 2-butyl-2-amyl group-1,3-Propanal dimethyl acetal, 2-butyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2-isobutyl--2-amyl group-1,3-Propanal dimethyl acetal, 2-isobutyl--2-isopentyl-1,3-Propanal dimethyl acetal, 2-isobutyl--2-phenyl-1,3-Propanal dimethyl acetal, 2-isopentyl-2-phenyl-1,3-Propanal dimethyl acetal, 2-(2-methyl butyl)-2-benzyl-1,3-Propanal dimethyl acetal, 2-(2-ethyl-butyl)-2-phenyl-1,3-Propanal dimethyl acetal, 2-(2-ethylhexyl)-2-phenyl-1,3-Propanal dimethyl acetal, 2-methyl-2-phenyl-1,3-Propanal dimethyl acetal, 2-ethyl-2-phenyl-1,3-Propanal dimethyl acetal, 2-isobutyl--2-benzyl-1,3-Propanal dimethyl acetal, 2-isopentyl-2-benzyl-1,3-Propanal dimethyl acetal, 2-(2-methyl butyl)-2-benzyl-1,3-Propanal dimethyl acetal, 2-(2-ethyl-butyl)-2-benzyl-1,3-Propanal dimethyl acetal, 2-(2-ethylhexyl)-2-benzyl-1,3-Propanal dimethyl acetal, 2-propyl group-2-benzyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-benzyl-1,3-Propanal dimethyl acetal, 2-isobutyl--2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2-isopentyl-2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2-(2-methyl butyl)-2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2-(2-ethylhexyl)-2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2-methyl-2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2-ethyl-2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2-isobutyl--2-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2-isopentyl-2-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2-(2-ethyl-butyl)-2-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2-(2-ethylhexyl)-2-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2-isobutyl--2-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2-isobutyl--2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal, 2-isopentyl-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal, 2,2-bis-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 3-sec.-propyl-3-isopentyl-1,3-Propanal dimethyl acetal, 2,2-bis-(2-ethylhexyl)-1,3-Propanal dimethyl acetal and 9,9-bis-(methoxymethyl) fluorenes.
7. according to the catalyst system in claim 1 ~ 6 described in any one, it is characterized in that, described first kind external electron donor c
1be selected from Cyclohexyl Methyl Dimethoxysilane, diphenyl dimethoxy silicon, phenyltriethoxy silane, diisopropyl dimethoxy silane, diη-propyl dimethoxysilane, dicyclopentyl dimethoxyl silane, diphenyldimethyl silane, tetraalkoxysilane, butyl trimethoxy silane, 2-sec.-propyl-2-isopentyl-1, 3-Propanal dimethyl acetal, 9, 9-bis-(methoxymethyl) fluorenes, 2, 2-di-n-butyl-1, 3-Propanal dimethyl acetal, 2, 2-diisobutyl-1, 3-Propanal dimethyl acetal and 2-isobutyl--2-isopentyl-1, one or more in 3-Propanal dimethyl acetal.
8. according to the catalyst system in claim 1 ~ 7 described in any one, it is characterized in that, the general formula of described alkylaluminium cpd is AlR '
nx
3-n, wherein R ' is selected from hydrogen and C
1~ C
20alkyl, X is halogen, 1≤n≤3.
9. according to the catalyst system in claim 1 ~ 8 described in any one, it is characterized in that, the mol ratio of described component a and components b is with titanium: aluminium counts 1:(5 ~ 1000), preferred 1:(20 ~ 250); The mol ratio of component a and amount of component b is with titanium: external donor compound counts 1:(0.1 ~ 100), preferred 1:(1 ~ 50).
10. the Prepolymerized catalyst system for olefinic polymerization, described Prepolymerized catalyst system comprises a kind of prepolymer carrying out prepolymerization gained according to the catalyst system according to any one of claim 1 ~ 9 and alkene, and pre-polymerization multiple is 0.1 ~ 1000g olefin polymer/g ingredient of solid catalyst a.
The method of 11. 1 kinds of olefinic polymerizations, is polymerized under the catalyst system of alkene according to any one of claim 1 ~ 9 or Prepolymerized catalyst system according to claim 10 exist.
12. methods according to claim 11, is characterized in that, the general formula of described alkene is CH
2=CHR, wherein R is hydrogen or C
1~ C
12alkyl or aryl, be preferably propylene.
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| CN201310462810.4A CN104513332B (en) | 2013-09-30 | 2013-09-30 | Catalyst system and its application for olefinic polymerization |
| TW103133626A TWI639626B (en) | 2013-09-30 | 2014-09-26 | Catalyst composition for olefin polymerization and application thereof |
| KR1020167011538A KR20160065181A (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerization and application of same |
| ES14848074T ES2736026T3 (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerization and application thereof |
| SG11201602505PA SG11201602505PA (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerization and application of same |
| PCT/CN2014/087709 WO2015043526A1 (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerization and application of same |
| MYPI2016701051A MY174892A (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerization and use thereof |
| CA2925614A CA2925614C (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerization and application of same |
| KR1020217009920A KR20210040186A (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerization and application of same |
| TR2019/08294T TR201908294T4 (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerization and its application. |
| JP2016518715A JP6681827B2 (en) | 2013-09-30 | 2014-09-28 | Olefin polymerization catalyst composition and use thereof |
| US15/025,698 US9822196B2 (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerization and application of same |
| RU2016117106A RU2715995C2 (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerisation and use thereof |
| EP14848074.2A EP3053935B1 (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerization and application of same |
| BR112016007091-7A BR112016007091B1 (en) | 2013-09-30 | 2014-09-28 | CATALYST COMPOSITION FOR POLYMERIZATION OF OLEFINS AND USE OF IT |
| JP2019021064A JP6745366B2 (en) | 2013-09-30 | 2019-02-07 | Olefin polymerization catalyst composition and use thereof |
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