CN104513331A - Catalyst composition used in olefin polymerization and application thereof - Google Patents
Catalyst composition used in olefin polymerization and application thereof Download PDFInfo
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Abstract
The invention relates to a catalyst composition used in an olefin polymerization reaction. The catalyst composition includes a solid catalyst component A, aluminum alkyl B and an external electron donor halogen-free malonate C, wherein the solid catalyst component A includes at least one of magnesium, titanium, a halogen and an internal electron donor containing lone pair electrons, such as a dialcohol ester compound (I); and the external electron donor C is a halogen-free malonate compound represented as the general formula (II). When the olefin polymerization reaction is carried out with the solid catalyst component A in the presence of the external electron donor C, the solid catalyst component A is very high in activity and especially is greatly enhanced in hydrogen-regulation sensitivity. In addition, some molecular weight distributions of the catalyst become wider and the external electron donor has a high-temperature self-quenching function.
Description
Technical field
The invention belongs to olefin polymerization catalysis technical field, relate to a kind of catalyst composition for olefinic polymerization and application thereof.
Background technology
As everyone knows, using magnesium, titanium, halogen and electron donor as the solid titanium catalyst component of basal component, can be used for olefinic polyreaction, the polymkeric substance of higher yields and higher tacticity particularly can be obtained in the alpha-olefine polymerizing with 3 carbon or more carbon atom, wherein electron donor compound is one of requisite composition in catalyst component, and the development along with internal electron donor compound result in polyolefin catalyst and constantly updates, external electron donor also needs the supporting development with internal electron donor.At present, disclose 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 monocarboxylic ester, amine, aminosilane etc. and derivative thereof.
World patent WO2012052387 discloses a kind of dicarboxylate compounds, this dicarboxylate compounds is containing dicarboxylic esters more than 4 carbon, as adipic acid ester, pimelate, by using this dicarboxylate compounds as external electron donor in olefin polymerization catalysis, the hydrogen response of catalyzer can be made to be greatly improved.But this dicarboxylic ester due to carbochain longer, preparation is complicated, and cost is higher.
Current Problems existing be need to research and develop a kind of with low cost, preparation is simple and have the catalyst composition that higher hydrogen adjusts the olefinic polymerization of susceptibility.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the deficiencies in the prior art, provides a kind of catalyst composition for the preparation of olefin polymer.Said composition comprises ingredient of solid catalyst a, alkylaluminium cpd components b and not halogen-containing malonate compound amount of component b containing diol ester compound.This catalyst composition is used for olefinic polyreaction with not halogen-containing malonate compound for external electron donor, time particularly in propylene polymerization, can obtain the polymkeric substance of high yield; And use not halogen-containing malonate compound to be external electron donor, the hydrogen response of catalyst component a can significantly improve, and the molecular weight distribution of some catalyzer also can be made to broaden.In addition, this external electron donor also has the effect of high temperature self-gravitation.
The present invention still further provides the application in olefin polymerization of a kind of catalyst composition of the present invention.
The present invention also provides a kind of pre-polymerized catalyst composition for olefinic polymerization in addition.
For achieving the above object, according to a first aspect of the invention, provide a kind of catalyst composition for the preparation of olefin polymer, it comprises following component:
A. ingredient of solid catalyst, it contains the internal electron donor compound that Mg, Ti, halogen and at least one contain lone-pair electron;
B. alkylaluminium cpd;
C. as the not halogen-containing malonate compound of external electron donor.
According to the present invention, the general formula of described not halogen-containing malonate compound as shown in (II),
Wherein, R
7and R
8identical or different, be hydrogen, 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.Preferably, R
7and R
8for hydrogen, C
1~ C
8straight chained alkyl, C
3~ C
8the alkyl of side chain, C
3~ C
10cycloalkyl or C
7~ C
10alkaryl, but R
7and R
8can not be hydrogen simultaneously.Further preferably, R
7and R
8for hydrogen, C
1~ C
6straight chained alkyl, C
3~ C
8the alkyl of side chain, C
5~ C
10cycloalkyl or C
7~ C
10alkaryl.
R
9for 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.Preferably, R
9for C
2~ C
10straight chained alkyl, C
3~ C
10the alkyl of side chain, C
3~ C
10cycloalkyl or C
7~ C
10alkaryl.Further preferably, R
9for C
2~ C
8straight chained alkyl, C
3~ C
8the alkyl of side chain, C
5~ C
10cycloalkyl or C
7~ C
10alkaryl.
In a particular embodiment of the present invention, described not halogen-containing malonate compound comprises: 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, 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, 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, dibutyltin diethyl malonate, di-isopropyl diethyl malonate, diisobutyl diethyl malonate, diallyl diethyl malonate etc.
According to the present invention, in described ingredient of solid catalyst a, in described ingredient of solid catalyst a, described internal electron donor compound comprises the compound containing O, N, P, S atom.Be preferably the compound containing O atom.
In an embodiment of the invention, in described ingredient of solid catalyst a, described internal electron donor compound comprises ethers, ester class, phenolic ether class, phenolic ester class and ketone compounds.Be preferably diol ester and succinate compound.More preferably diol ester compound.
In one embodiment of the invention, the general formula of described diol ester compound as shown in formula I,
Wherein, R
1and R
2identical or not identical, be C
3~ C
20cycloalkyl, C
6~ C
20aryl or C
7~ C
20alkaryl or C
7~ C
20aralkyl, and the hydrogen atom in described cycloalkyl, aryl, alkaryl or aralkyl on carbon atom is optionally replaced by alkyl, halogen atom, but R
1and R
2can not be C simultaneously
3~ C
20cycloalkyl.Preferably, described R
1and R
2group is preferably from the alkyl phenyl of the phenyl of phenyl, halo, alkyl phenyl, halo, indenyl, benzyl or phenylethyl.Further preferably, described R
1and R
2be selected from phenyl, C
1~ C
5the phenyl of alkyl phenyl, halo, the C of halo
1~ C
5alkyl phenyl, indenyl, benzyl or styroyl.Even more preferably, described R
1and R
2identical.
R
3and R
4identical or different, be hydrogen, halogen atom, C
1~ C
10straight chained alkyl, C
3~ C
10branched-chain alkyl, C
3~ C
10cycloalkyl, C
6~ C
10aryl or C
7~ C
10alkaryl or aralkyl, and R
3, R
4optionally be keyed to ring.Preferably, R
3and R
4be selected from hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, chlorine atom or bromine atoms.
R
5and R
6identical or different, be halogen atom, C
1~ C
10straight chained alkyl, C
3~ C
10branched-chain alkyl, C
3~ C
10cycloalkyl, C
6~ C
10aryl, C
7~ C
10alkaryl or aralkyl, and described alkyl, aryl,
Hydrogen atom in alkaryl or aralkyl on carbon atom is optionally replaced by alkane or halogen atom.Preferably, R
5and R
6be selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, or the hydrogen atom in described alkyl on carbon atom is replaced by halogen atom.
In a particular embodiment of the present invention, described diol ester compound comprises: 2,4-glycol dibenzoate, 2,4-pentanediol two p-methylbenzoic acid ester, 2,4-pentanediol two m-methyl benzoic acid ester, 2,4-pentanediol two o-toluic acid ester, 2,4-pentanediol two p-ethylbenzoic acid ester, 2,4-pentanediol two n-propyl benzoate ester, 2,4-pentanediol, two pairs of butylbenzoic acid esters, 2,4-pentanediol two p-tert-butyl benzoic acid ester, 3-methyl-2,4-glycol dibenzoate, 3-ethyl-2,4-glycol dibenzoate, 3-propyl group-2,4-glycol dibenzoate, 3-ethyl-2,4-pentanediol two p-methylbenzoic acid ester, 3-ethyl-2,4-pentanediol two p-ethylbenzoic acid ester, 3-ethyl-2,4-pentanediol two n-propyl benzoate ester, 3-ethyl-2,4-pentanediol two pairs of butylbenzoic acid esters, 3-ethyl-2,4-pentanediol two p-tert-butyl benzoic acid ester, 3-butyl-2,4-glycol dibenzoate, 3,3-dimethyl-2,4-glycol dibenzoate, chloro-2, the 4-glycol dibenzoate of 3-, bromo-2, the 4-glycol dibenzoate of 3-, 3,5-heptanediol dibenzoate, 3,5-heptanediol two p-methylbenzoic acid ester, 3,5-heptanediol two p-ethylbenzoic acid ester, 3,5-heptanediol two n-propyl benzoate ester, 3,5-heptanediol, two pairs of butylbenzoic acid esters, 3,5-heptanediol two p-tert-butyl benzoic acid ester, 4-methyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol two p-methylbenzoic acid ester, 4-ethyl-3,5-heptanediol two p-ethylbenzoic acid ester, 4-ethyl-3,5-heptanediol two n-propyl benzoate ester, 4-ethyl-3,5-heptanediol two pairs of butylbenzoic acid esters, 4-ethyl-3,5-heptanediol two p-tert-butyl benzoic acid ester, 4-propyl group-3,5-heptanediol dibenzoate, 4-butyl-3,5-heptanediol dibenzoate, chloro-3, the 5-heptanediol dibenzoates of 4-, bromo-3, the 5-heptanediol dibenzoates of 4-etc.
In an embodiment of the invention, described ingredient of solid catalyst a comprises magnesium, titanium, halogen and the internal electron donor containing lone-pair electron as at least one in diol ester compound (I).
According to the present invention, in described ingredient of solid catalyst a, based on the gross weight of ingredient of solid catalyst a, described diol ester content is 3wt% ~ 25wt%, and the content of titanium is 1wt% ~ 8wt%, and the content of magnesium is 8wt% ~ 25wt%; Preferably, described diol ester content is 5wt% ~ 20wt%, and the content of titanium is 1wt% ~ 6wt%, and the content of magnesium is 15wt% ~ 20wt%.
In an embodiment of the invention, described ingredient of solid catalyst a contains the reaction product of magnesium compound, titanium compound and diol ester compound.
Described magnesium compound comprise 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.Preferably magnesium compound is the alcohol adduct of magnesium dihalide or magnesium dihalide, such as magnesium dichloride, dibrominated magnesium, diiodinating magnesium and their alcohol adduct etc.
The general formula of described titanium compound is TiX
m(OR
a)
4-mcompound, R in formula
afor C
1~ C
20alkyl, X is halogen, 1≤m≤4.Such as titanium compound can be 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 etc., and preferred titanium compound is 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.
Prepare the method for ingredient of solid catalyst a, as in addition magnesium compound, electron donor etc. formed emulsion in thinner, adding titanium compound and making it fixedly obtain spherical solid, more treatedly obtain 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.
According to the present invention, state on the invention in catalyst composition, the general formula of described alkylaluminium cpd b is AlR
bnX
3-n, R in formula
bbe selected from hydrogen and C
1~ C
20alkyl, X is halogen, 1≤n≤3.
In one particular embodiment of the present invention, 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 etc.
According to the present invention, in described catalyst composition, the mol ratio of described component a and components b is with titanium: aluminium counts 1:(5 ~ 1000); Be preferably 1:(20 ~ 250).The mol ratio of described component a and amount of component b is with titanium: c counts 1:(0.1 ~ 100); Be preferably 1:(1 ~ 50).
According to a second aspect of the invention, provide a kind of pre-polymerized catalyst composition for olefinic polymerization, it comprises the prepolymer that the above-mentioned catalyst composition of at least one and alkene carry out prepolymerization gained, and the pre-polymerization multiple of described prepolymer is 0.1 ~ 1000g olefin polymer/g component a.Preferred described alkene is propylene.
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 third aspect of the present invention, provide a kind of olefine polymerizing process, described alkene is polymerized under the effect of above-mentioned catalyst composition or above-mentioned pre-polymerized catalyst composition.
In the present invention, the general formula of described alkene is CH
2=CHR, wherein R is hydrogen or C
1~ C
12alkyl or aryl.Such as, described alkene comprises ethene, propylene, 1-butylene, 4-methyl-1-pentene and 1-hexene, and preferred described alkene is propylene.
In a specific embodiment of the present invention, above-mentioned catalyst composition of the present invention or above-mentioned catalyst composition may be used for propylene all polymerization with or other alkene of propylene copolymerization reaction in.
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.
Detection method of the present invention is as follows:
(1) melting index (MI) of polymkeric substance measures by testing standard GB/T3682-2000.
(2) the content liquid chromatogram measuring of diol ester (II), liquid chromatography is the pillar of Waters-600E high performance liquid chromatography, C-18, and column temperature is 30 DEG C, and methanol-water is moving phase, flow velocity 1.0ml/min, UV-detector.
(3) Ti content ultraviolet-visible spectrophotometer 752S measures, with 1mol sulfuric acid for blank solution.
The present inventor is through many experiments, have been surprisingly found that, the present invention by adopt a kind of cheap general formula be (II) not halogen-containing malonate compound as external electron donor for alkene especially propylene polymerization time, the activity of catalyst component a is very high, particularly hydrogen response has had and has very significantly improved, and the molecular weight distribution of some catalyzer also can be made to broaden.In addition, this external electron donor also has the effect of high temperature self-gravitation.
Embodiment
For making the present invention easier to understand, describe the present invention in detail below in conjunction with embodiment, these embodiments only play illustrative effect, are not limited to range of application of the present invention, NM specific experiment method in the following example, conveniently experimental technique carries out usually.
Embodiment
1. the preparation of ingredient of solid catalyst a
In the reactor of fully replacing through high pure nitrogen, add magnesium chloride 6.0g successively, toluene 119ml, epoxy chloropropane 5ml, tributyl phosphate (TBP) 15.6ml, is warming up to 50 DEG C under stirring, and maintains 2.5 hours, and solid dissolves completely; Add Tetra hydro Phthalic anhydride 1.7g, continue maintenance 1 hour; Solution is cooled to less than-25 DEG C, in 1 hour, drips TiCl
470ml.Slowly be warming up to 80 DEG C, in temperature-rise period, separate out solids gradually; Add 6mmol internal electron donor compound, holding temperature 1 hour, after filtration, add toluene 80ml, wash twice, obtain solid sediment.
Then toluene 60ml is added, TiCl
440ml, is warmed up to 100 DEG C, processes 2 hours, after venting filtrate, then adds toluene 60ml, TiCl
440ml, is warmed up to 100 DEG C, processes 2 hours, venting filtrate; Add toluene 60ml, boiling state washs three times, then adds hexane 60ml, and boiling state washes twice, and adds hexane 60ml, after normal temperature washes twice, obtains ingredient of solid catalyst a.
2. propylene polymerization experiment
Ingredient of solid catalyst a 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 the AlEt of 2.5mmol
3, the diethyl malonate (II) of 0.lmmol, then add the ingredient of solid catalyst of 8 ~ 10mg and the hydrogen of 1.2NL, pass into the liquid propene of 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.
Comparative example replaces not halogen-containing malonic ester (II) with Cyclohexyl Methyl Dimethoxysilane (CHMMS).
The propylene polymerization of above-described embodiment and comparative example the results are shown in Table 1.
Table 1 propylene polymerization result
3. external electron donor (II) is tested the impact property of ingredient of solid catalyst a hydrogen response
Hydrogen is become 7.2NL, and the constant polymerization carrying out propylene of remaining reaction condition, the results are shown in Table 2.
Table 2 external electron donor (II) under high hydrogen concentration on the impact of ingredient of solid catalyst a hydrogen response
As can be seen from Table 2, compared with comparative example, when external electron donor is not halogen-containing malonic ester (II), the hydrogen response of ingredient of solid catalyst a improves a lot.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (15)
1., for the preparation of a catalyst composition for olefin polymer, it comprises following component:
A. ingredient of solid catalyst, it contains the internal electron donor compound that Mg, Ti, halogen and at least one contain lone-pair electron;
B. alkylaluminium cpd;
C. as the not halogen-containing malonate compound of external electron donor.
2. catalyst composition according to claim 1, is characterized in that:
The general formula of described not halogen-containing malonate compound as shown in (II),
Wherein, R
7and R
8identical or different, be hydrogen, 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;
R
9for 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.
3. catalyst composition according to claim 2, is characterized in that:
R
7and R
8for hydrogen, C
1~ C
8straight chained alkyl, C
3~ C
8the alkyl of side chain, C
3~ C
10cycloalkyl or C
7~ C
10alkaryl, but R
7and R
8can not be hydrogen simultaneously;
R
9for C
2~ C
10straight chained alkyl, C
3~ C
10the alkyl of side chain, C
3~ C
10cycloalkyl or C
7~ C
10alkaryl.
4. catalyst composition according to claim 3, is characterized in that:
R
7and R
8for hydrogen, C
1~ C
6straight chained alkyl, C
3~ C
8the alkyl of side chain, C
5~ C
10cycloalkyl or C
7~ C
10alkaryl;
R
9for C
2~ C
8straight chained alkyl, C
3~ C
8the alkyl of side chain, C
5~ C
10cycloalkyl or C
7~ C10 alkaryl.
5. according to the catalyst composition in Claims 1 to 4 described in any one, it is characterized in that, in described ingredient of solid catalyst a, described internal electron donor compound is selected from the compound containing O, N, P, S atom; Be preferably the compound containing O atom.
6. according to the catalyst composition described in claim 5, it is characterized in that, in described ingredient of solid catalyst a, described internal electron donor compound comprises ethers, ester class, phenolic ether class, phenolic ester class and ketone compounds; Be preferably diol ester and succinate compound; More preferably diol ester compound.
7. catalyst system according to claim 6, the general formula of described diol ester compound as shown in formula I,
Wherein, R
1and R
2identical or not identical, be C
3~ C
20cycloalkyl, C
6~ C
20aryl or C
7~ C
20alkaryl or C
7~ C
20aralkyl, and the hydrogen atom in described cycloalkyl, aryl, alkaryl or aralkyl on carbon atom is optionally replaced by alkyl, halogen atom, but R
1and R
2can not be C simultaneously
3~ C
20cycloalkyl;
R
3and R
4identical or different, be hydrogen, halogen atom, C
1~ C
10straight chained alkyl, C
3~ C
10branched-chain alkyl, C
3~ C
10cycloalkyl, C
6~ C
10aryl or C
7~ C
10alkaryl or aralkyl, and R
3, R
4optionally be keyed to ring;
R
5and R
6identical or different, be halogen atom, C
1~ C
10straight chained alkyl, C
3~ C
10branched-chain alkyl, C
3~ C
10cycloalkyl, C
6~ C
10aryl, C
7~ C
10alkaryl or aralkyl, and the hydrogen atom in described alkyl, aryl, alkaryl or aralkyl on carbon atom is optionally replaced by alkane or halogen atom.
8. catalyst composition according to claim 7, is characterized in that,
Described R
1and R
2group is preferably from the alkyl phenyl of the phenyl of phenyl, halo, alkyl phenyl, halo, indenyl, benzyl or phenylethyl;
R
3and R
4be selected from hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, chlorine atom or bromine atoms;
R
5and R
6be selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, or the hydrogen atom in described alkyl on carbon atom is replaced by halogen atom.
9. catalyst composition according to claim 8, is characterized in that, R
1and R
2be selected from phenyl, C
1~ C
5the phenyl of alkyl phenyl, halo, the C of halo
1~ C
5alkyl phenyl, indenyl, benzyl or styroyl.
10. according to the catalyst composition in claim 7 ~ 9 described in any one, it is characterized in that, described R
1and R
2identical.
11., according to the catalyst composition in claim 1 ~ 10 described in any one, is characterized in that, described ingredient of solid catalyst a contains the reaction product of magnesium compound, titanium compound and diol ester compound.
12., according to the catalyst composition described in claim 1 ~ 11, is characterized in that: in described catalyst composition, and 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 described component a and amount of component b is with titanium: amount of component b counts 1:(0.1 ~ 100); Preferred 1:(1 ~ 50).
13. 1 kinds of pre-polymerized catalyst compositions for olefinic polymerization, it comprises the prepolymer that the catalyst composition of at least one according to any one of claim 1 ~ 12 and alkene carry out prepolymerization gained, and the pre-polymerization multiple of described prepolymer is 0.1 ~ 1000g olefin polymer/g component a; Preferred described alkene is propylene.
14. 1 kinds of olefine polymerizing process, are polymerized under the effect of the catalyst composition of described alkene according to any one of claim 1 ~ 12 or pre-polymerized catalyst composition according to claim 13.
15. methods according to claim 14, 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; Preferred described alkene is propylene.
Priority Applications (16)
| Application Number | Priority Date | Filing Date | Title |
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| CN201310461740.0A CN104513331B (en) | 2013-09-30 | 2013-09-30 | Carbon monoxide-olefin polymeric 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 |
| EP14848074.2A EP3053935B1 (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerization and application of same |
| SG11201602505PA SG11201602505PA (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerization and application of same |
| 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 |
| TR2019/08294T TR201908294T4 (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerization and its application. |
| PCT/CN2014/087709 WO2015043526A1 (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 |
| BR112016007091-7A BR112016007091B1 (en) | 2013-09-30 | 2014-09-28 | CATALYST COMPOSITION FOR POLYMERIZATION OF OLEFINS AND USE OF IT |
| MYPI2016701051A MY174892A (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerization and use thereof |
| KR1020217009920A KR20210040186A (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerization and application of same |
| JP2016518715A JP6681827B2 (en) | 2013-09-30 | 2014-09-28 | Olefin polymerization catalyst composition and use thereof |
| CA2925614A CA2925614C (en) | 2013-09-30 | 2014-09-28 | Catalyst composition for olefin polymerization and application of same |
| JP2019021064A JP6745366B2 (en) | 2013-09-30 | 2019-02-07 | Olefin polymerization catalyst composition and use thereof |
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| EP2543684A1 (en) * | 2011-07-07 | 2013-01-09 | Borealis AG | Process for the manufacture of isotactic polypropylene |
| CN102958953A (en) * | 2010-06-24 | 2013-03-06 | 巴塞尔聚烯烃意大利有限责任公司 | Catalyst system for the polymerization of olefins |
| CN103168054A (en) * | 2010-10-19 | 2013-06-19 | 巴塞尔聚烯烃意大利有限责任公司 | Catalyst system for the polymerization of olefins |
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| CN102958953A (en) * | 2010-06-24 | 2013-03-06 | 巴塞尔聚烯烃意大利有限责任公司 | Catalyst system for the polymerization of olefins |
| CN103168054A (en) * | 2010-10-19 | 2013-06-19 | 巴塞尔聚烯烃意大利有限责任公司 | Catalyst system for the polymerization of olefins |
| EP2543684A1 (en) * | 2011-07-07 | 2013-01-09 | Borealis AG | Process for the manufacture of isotactic polypropylene |
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| CN106608939A (en) * | 2015-10-27 | 2017-05-03 | 中国石油化工股份有限公司 | Preparation method of catalyst component for olefin polymerization |
| CN106608939B (en) * | 2015-10-27 | 2019-08-20 | 中国石油化工股份有限公司 | The preparation method of catalytic component for olefinic polymerization |
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