CN104177520A - Solid catalyst component for preparing olefin polymer - Google Patents
Solid catalyst component for preparing olefin polymer Download PDFInfo
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- CN104177520A CN104177520A CN201310190424.4A CN201310190424A CN104177520A CN 104177520 A CN104177520 A CN 104177520A CN 201310190424 A CN201310190424 A CN 201310190424A CN 104177520 A CN104177520 A CN 104177520A
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Abstract
The invention provides a solid catalyst component for an olefin polymerization reaction. The solid catalyst component comprises magnesium, titanium, halogen and an electron donor. The electron donor is at least one of diol ester compounds shown in the general formula (I). The catalyst provided by the invention has greatly improved polymerization activity, hydrogen response and stereospecificity. Through the solid catalyst component and the catalyst, a polymer having a high fusion index and high isotacticity is obtained. Compared with the prior art, the solid catalyst component has the advantages that if polymer melt indexes are the same, in other words, hydrogen response is the same, isotactic indexes are improved, and if polymer isotactic indexes are the same, the polymer melt indexes are improved, in other words, the hydrogen response is improved.
Description
Technical field
The present invention relates to a kind of ingredient of solid catalyst, be specifically related to a kind of for the preparation of the molten ingredient of solid catalyst that refers to high isotactic olefin polymer of height.The invention still further relates to containing catalyst system and this catalyst body of this ingredient of solid catalyst and tie up to the application in olefinic polyreaction.
Background technology
As everyone knows, with magnesium, titanium, halogen and electron donor are as the solid titanium catalyst component of basal component, can be used for olefinic polyreaction, particularly in the alpha-olefine polymerizing with 3 carbon or more carbon atoms, can obtain the polymkeric substance of higher yields and higher taxis, wherein electron donor compound is one of requisite composition in catalyst component, and along with having caused polyolefin catalyst, the development of internal electron donor compound constantly updates, at present, multiple electron donor compound is disclosed in a large number, for example polycarboxylic acid, monocarboxylic ester or multi-carboxylate, acid anhydrides, ketone, monoether or polyether, alcohol, amine etc. and derivative thereof.
There is at present document to disclose a kind of dibasic alcohol ester compound, in olefin polymerization catalysis, by using this diol ester compound as electron donor, can obtain the catalyzer of high comprehensive performance.This catalyzer is when for propylene polymerization, there are higher polymerization activity and stereospecificity, the molecular weight distribution of resulting polymers is also wider, but the activity of catalyzer, hydrogen response and stereospecificity are also not too satisfactory, while particularly producing high fusion index polymkeric substance under high hydrogen concentration, the isotactic index of resulting polymers is high not enough, needs further to be improved.
Summary of the invention
For deficiency of the prior art, contriver, through deeply test, is surprised to find that to have 1 of ad hoc structure, and ingredient of solid catalyst prepared by 3-glycol benzoic acid ester compounds is for alkene, and especially when propylene polymerization, polymerization activity is high; There is better hydrogen response or can obtain gratifying high degree of isotacticity in the time of the high molten finger polymkeric substance of preparation.
According to an aspect of the present invention, provide a kind of ingredient of solid catalyst for olefinic polyreaction, it comprises magnesium, titanium, halogen and electron donor, and described electron donor is selected from least one in the diol ester compound shown in following logical formula I;
In logical formula I, R
1and R
2can be identical or different, be selected from hydrogen, halogen atom, 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 and C
7-C
10aralkyl;
R
3and R
4can be identical or different, be selected from hydrogen, 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 and C
7-C
10aralkyl, R
3and R
4optionally be keyed to ring;
R
5be selected from C
2-C
10straight chained alkyl, C
3-C
10branched-chain alkyl, C
3-C
10cycloalkyl, C
6-C
10aryl, C
7-C
10alkaryl and C
7-C
10aralkyl;
N is 1～5 integer;
R
6be selected from C
1-C
10straight chained alkyl, C
3-C
10branched-chain alkyl, C
3-C
10cycloalkyl, C
6-C
10aryl, C
7-C
15alkaryl and C
7-C
15aralkyl.
In a specific embodiment of above-mentioned ingredient of solid catalyst, the hydrogen on described alkyl or aryl is by halo.
In an example of above-mentioned ingredient of solid catalyst, R
1and R
2in have one at least for hydrocarbyl substituent.
In a preferred embodiment of above-mentioned ingredient of solid catalyst, R
1and R
2group is selected from halo or not by the C of halo
1-C
6straight chained alkyl and C
3-C
6branched-chain alkyl.In a further advantageous embodiment, R
3and R
4be selected from hydrogen, halogen atom, C
1-C
6straight chained alkyl and C
3-C
6branched-chain alkyl, or hydrogen on described alkyl is by halo.In a further advantageous embodiment, R
5be selected from C
2-C
6straight chained alkyl and C
3-C
6branched-chain alkyl.
In above-mentioned ingredient of solid catalyst, the n in described general formula represents substituent number on phenyl ring.Preferably n is 1 or 2; More preferably n=1, and be contraposition or ortho position replacement, the substituting group on phenyl ring is ortho position or contraposition.
In an embodiment of above-mentioned ingredient of solid catalyst, R
6be selected from halo or not by the C of halo
4-C
10straight or branched alkyl, C
5-C
10cycloalkyl, C
6-C
10aryl, C
7-C
10alkaryl and C
7-C
10aralkyl.
According to the present invention, the specific examples of the diol ester compound that described general formula is (I) can be selected from but be not limited to: 2,4-hexylene glycol two (4-ethylamino benzonitrile acid esters), 2,4-hexylene glycol two (4-propyl group yl benzoic acid ester), 2,4-hexylene glycol two (4-butylbenzoic acid ester), 2,4-hexylene glycol two (4-isobutyl-benzene manthanoate), 2,4-hexylene glycol two (4-p t butylbenzoic acid ester), 2,4-hexylene glycol two (4-hexyl benzene manthanoate), 3-methyl-2,4-hexylene glycol two (4-ethylamino benzonitrile acid esters), 3-methyl-2,4-hexylene glycol two (4-propyl group yl benzoic acid ester), 3-methyl-2,4-hexylene glycol two (4-butylbenzoic acid ester), 3-methyl-2,4-hexylene glycol two (4-isobutyl-benzene manthanoate), 3-methyl-2,4-hexylene glycol two (4-p t butylbenzoic acid ester), 3-methyl-2,4-hexylene glycol two (4-hexyl benzene manthanoate), 3-ethyl-2,4-hexylene glycol two (4-ethylamino benzonitrile acid esters), 3-ethyl-2,4-hexylene glycol two (4-propyl group yl benzoic acid ester), 3-ethyl-2,4-hexylene glycol two (4-butylbenzoic acid ester), 3-ethyl-2,4-hexylene glycol two (4-isobutyl-benzene manthanoate), 3-ethyl-2,4-hexylene glycol two (4-p t butylbenzoic acid ester), 3-ethyl-2,4-hexylene glycol two (4-hexyl benzene manthanoate), 3,5-heptanediol two (4-ethylamino benzonitrile acid esters), 3,5-heptanediol two (4-propylbenzoic acid ester), 3,5-heptanediol two (4-isopropyl acid ester), 3,5-heptanediol two (4-butylbenzoic acid ester), 3,5-heptanediol two (4-isobutyl-benzene manthanoate), 3,5-heptanediol two (4-p t butylbenzoic acid ester), 3,5-heptanediol two (4-amylbenzene manthanoate), 3,5-heptanediol two (4-hexyl benzene manthanoate), 3,5-heptanediol-styracin-4-ethylamino benzonitrile acid esters, 4-methyl-3,5-heptanediol two (4-ethylamino benzonitrile acid esters), 4-methyl-3,5-heptanediol two (4-propylbenzoic acid ester), 4-methyl-3,5-heptanediol two (4-isopropyl acid ester), 4-methyl-3,5-heptanediol two (4-butylbenzoic acid ester), 4-methyl-3,5-heptanediol two (4-isobutyl-benzene manthanoate), 4-methyl-3,5-heptanediol two (4-p t butylbenzoic acid ester), 4-methyl-3,5-heptanediol two (4-amylbenzene manthanoate), 4-methyl-3,5-heptanediol two (4-hexyl benzene manthanoate), 4-methyl-3,5-heptanediol-styracin-4-ethylamino benzonitrile acid esters, 4-ethyl-3,5-heptanediol two (4-ethylamino benzonitrile acid esters), 4-ethyl-3,5-heptanediol two (4-propylbenzoic acid ester), 4-ethyl-3,5-heptanediol two (4-isopropyl acid ester), 4-ethyl-3,5-heptanediol two (4-butylbenzoic acid ester), 4-ethyl-3,5-heptanediol two (4-isobutyl-benzene manthanoate), 4-ethyl-3,5-heptanediol two (4-p t butylbenzoic acid ester), 4-ethyl-3,5-heptanediol two (4-amylbenzene manthanoate), 4-ethyl-3,5-heptanediol two (4-hexyl benzene manthanoate), 4-ethyl-3,5-heptanediol-styracin-4-ethylamino benzonitrile acid esters, 4-propyl group-3,5-heptanediol two (4-p t butylbenzoic acid ester), 4-butyl-3,5-heptanediol two (4-p t butylbenzoic acid ester), 2,4-dimethyl-3,5-heptanediol two (4-p t butylbenzoic acid ester), 2,6-dimethyl-3,5-heptanediol two (4-p t butylbenzoic acid ester), 4,4-dimethyl-3,5-heptanediol two (4-p t butylbenzoic acid ester), 2,2-dimethyl-3,5-heptanediol two (4-p t butylbenzoic acid ester), 2-methyl-4-ethyl-3,5-heptanediol two (4-butylbenzoic acid ester), 4-methyl-4-ethyl-3,5-heptanediol two (4-p t butylbenzoic acid ester), 2-methyl-4-propyl group-3,5-heptanediol two (4-p t butylbenzoic acid ester), 3-methyl-3-propyl group-3,5-heptanediol two (4-p t butylbenzoic acid ester), 4-methyl-4-propyl group-3,5-heptanediol two (4-p t butylbenzoic acid ester), 3-methyl-2,4-heptanediol two (4-propylbenzoic acid ester), 3-methyl-2,4-heptanediol two (3-propylbenzoic acid ester), 3,6-dimethyl-2,4-heptanediol two (4-p t butylbenzoic acid ester), 2,2,6,6-tetramethyl--3,5-heptanediol two (4-p t butylbenzoic acid ester), 4-methyl-3,5-ethohexadiol two (4-butylbenzoic acid ester), 4-ethyl-3,5-ethohexadiol two (4-p t butylbenzoic acid ester), 4-propyl group-3,5-ethohexadiol two (4-p t butylbenzoic acid ester), 4-butyl-3,5-ethohexadiol two (4-p t butylbenzoic acid ester), 4,4-dimethyl-3,5-ethohexadiol two (4-butylbenzoic acid ester), 4,4-diethyl-3,5-ethohexadiol two (4-propylbenzoic acid ester), 4,4-dipropyl-3,5-ethohexadiol two (4-p t butylbenzoic acid ester), 4-methyl-4-ethyl-3,5-ethohexadiol two (4-second butylbenzoic acid ester), 2-methyl-4-ethyl-3,5-ethohexadiol two (4-p t butylbenzoic acid ester), 2-methyl-6-ethyl-3,5-ethohexadiol two (4-p t butylbenzoic acid ester), 4,6-nonanediol two (4-ethylamino benzonitrile acid esters), 4,6-nonanediol two (4-propylbenzoic acid ester), 4,6-nonanediol two (4-butylbenzoic acid ester), 4,6-nonanediol two (4-isobutyl-benzene manthanoate), 4,6-nonanediol two (4-p t butylbenzoic acid ester), 4,6-nonanediol two (4-hexyl benzene manthanoate), 4,6-nonanediol-styracin-4-ethylamino benzonitrile acid esters, 5-methyl-4,6-nonanediol two (4-ethylamino benzonitrile acid esters), 5-methyl-4,6-nonanediol two (4-propylbenzoic acid ester), 5-methyl-4,6-nonanediol two (4-butylbenzoic acid ester), 5-methyl-4,6-nonanediol two (4-isobutyl-benzene manthanoate), 5-methyl-4,6-nonanediol two (4-p t butylbenzoic acid ester), 5-methyl-4,6-nonanediol two (4-hexyl benzene manthanoate), 5-ethyl-4,6-nonanediol two (4-ethylamino benzonitrile acid esters), 5-ethyl-4,6-nonanediol two (4-propylbenzoic acid ester), 5-ethyl-4,6-nonanediol two (4-butylbenzoic acid ester), 5-ethyl-4,6-nonanediol two (4-isobutyl-benzene manthanoate), 4,6-nonanediol two (4-p t butylbenzoic acid ester), 5-ethyl-4,6-nonanediol two (4-hexyl benzene manthanoate), 5-propyl group-4,6-nonanediol two (4-p t butylbenzoic acid ester), 5-butyl-4,6-nonanediol two (4-butylbenzoic acid ester), 5,5-dimethyl-4,6-nonanediol two (4-p t butylbenzoic acid ester), 5,5-diethyl-4,6-nonanediol two (4-hexyl benzene manthanoate), 5,5-dipropyl-4,6-nonanediol two (4-amylbenzene manthanoate), 5,5-dibutyl-4,6-nonanediol two (4-p t butylbenzoic acid ester) etc.
Of the present invention for olefinic polyreaction ingredient of solid catalyst, be preferably by the carrying out reaction of the diol ester compound shown in magnesium compound, titanium compound and above-mentioned logical formula I prepared.What particularly point out is, described reaction preparation comprises magnesium compound is dissolved in the solvent system being made up of organic epoxy compounds, organo phosphorous compounds and inert diluent, after forming homogeneous solution, mix with titanium compound, then, under precipitation additive exists, separate out solids; The compound that last this solids by using is selected from logical formula I is processed.Can make the compound of logical formula I be attached on solids by processing, if desired, then solids be processed with titanium tetrahalide and inert diluent.Specifically referring to patent CN85100997.
Described magnesium compound is selected from hydrate or the alcohol adduct of magnesium dihalide, alkoxyl Mei ﹑ Wan Ji Mei ﹑ magnesium dihalide, and the derivative that replaces of halogen atom alkoxy in magnesium dihalide or halogenated alkoxy; Preferably magnesium dihalide and alcohol adduct, for example magnesium dichloride, dibrominated magnesium, two magnesium iodides and their alcohol adduct.
The general formula of preferred described titanium compound is TiX
m(OR
1)
4-m, R in formula
1for C
1～C
20alkyl, X is halogen, 1≤m≤4.For example: titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium, wherein preferred titanium tetrachloride.
Described organic epoxy compounds comprises that carbonatoms is at 2～8 aliphatics alkene, diolefine, halogenated aliphatic alkene or diolefine oxide compound, 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).
Described organo phosphorous compounds is 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.
Described precipitation additive is selected from organic acid anhydride, organic acid, ether and ketone, concrete 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 etc.
In the present invention, also magnesium compound can be dissolved in the solvent system containing organic alcohol compound, organic alcohol compound is carbonatoms at 2～8 monohydroxy-alcohol.
In ingredient of solid catalyst of the present invention, described each component is in every mole of magnesium halide, organic epoxy compounds is 0.2～10 mole, organo phosphorous compounds is 0.1～3 mole, precipitation additive is 0～1.0 mole, titanium compound is 0.5～150 mole, and the propylene glycol ester compound of logical formula I is 0.02～0.4 mole.
Above-mentioned ingredient of solid catalyst, based on the gross weight of ingredient of solid catalyst, shown in described logical formula I, the content of diol ester compound is 3～25wt%, and the content of titanium is 1～8wt%, and the content of magnesium is 8～30wt%.Preferably, shown in described logical formula I, the content of diol ester compound is 5～20wt%, and the content of titanium is 1～6wt%, and the content of magnesium is 10～25wt%.
Ingredient of solid catalyst described in the present invention also can be by the method preparation of enumerating below.
Method one: as according to the disclosed method Kaolinite Preparation of Catalyst of patent CN1040379 component.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, by magnesium/acid anhydride mol ratio 5～10 reaction 1～5 hour.Then the alcohol adduct that is chilled to room temperature is joined in advance in the compound titanium solution that is chilled to-15～-40 DEG C according to titanium/magnesium mol ratio 20～50, be warming up to 90～110 DEG C, add a kind of being selected to lead to the compound shown in formula I 100～130 DEG C of reactions 1～3 hour according to magnesium/internal electron donor mol ratio 2～10, 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 being dried, obtain catalyst component.
Method two: by titanium compound of the present invention, concrete as TiCl
4, with general formula be MgCl
2the adducts reaction of pROH and prepare ingredient of solid catalyst.At MgCl
2in pROH, p is 0.1～6 number, 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 existing with the miscible unreactive hydrocarbons of adducts, by alcohol (ROH) and MgCl
2mix, make the rapid chilling of this emulsion, thereby adducts is solidified with the form of spheroidal particle.The adducts so obtaining can directly react with titanium compound, or its dealcoholization (80～130 DEG C) that can pass through thermal control in advance before reacting with titanium compound is to obtain a kind of adducts, wherein the mole number of alcohol is generally lower than 3, preferably between 0.1～2.7.Can be by adducts (dealcoholysis or itself) be suspended in to cold TiCl
4in (general 0 DEG C), and by mixture temperature programming to 80～130 DEG C and keep at this temperature 0.1～2 hour, carry out and the reacting of titanium compound.TiCl
4processing can be carried out once or repeatedly.Using TiCl
4during processing, can add the logical formula I compound of above-mentioned the present invention to process, this processing also can repeat once or repeatedly.
Specifically can be according to the disclosed method Kaolinite Preparation of Catalyst of patent CN1091748 component.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, forms 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 through washing, be dried as ball type carrier, the mol ratio of its alcohol and magnesium chloride is 2～3, with 2～2.5 for well.Diameter of carrier is 10～300 microns, best with 30～150 microns.
, progressively heat up at the above-mentioned ball type carrier of subzero treatment with excessive titanium tetrachloride, in treating processes, add the electron donor shown in the logical formula I of the present invention, after processing, repeatedly wash with inert solvent, after being dried, obtain the spherical catalyst component of solid powdery.The mol ratio of titanium tetrachloride and magnesium chloride is 20～200, with 30～60 for well; Initiated process temperature is-30～0 DEG C, taking-25～-20 DEG C as good; Final treatment temp is 80～136 DEG C, taking 100～130 DEG C as good.
Method three: also can add in arene compound and stir with dialkoxy magnesium, form suspension; Suspension uses tetravalence titanium chloride-20～100 DEG C of processing, and 0～130 DEG C of reaction, in this process, adds the logical formula I electron donor of the present invention to react at-20～130 DEG C, and the solid obtaining washs with arene compound; Then at 0～130 DEG C in aromatic hydrocarbon solvent, then use the processing of tetravalence titanium chloride, finally, with inert solvent washing, drain, obtain ingredient of solid catalyst.Wherein every mole of tetravalence titanium chloride 0.5～100mol for dialkyl magnesium, 0.01～10mol for electron donor.
Method four: use TiCl
4or its aromatic hydrocarbons solution carries out halogenation to two magnesium alkoxide compounds such as dialkoxy magnesium or two aryloxy magnesium at 80～130 DEG C, use TiCl
4or its aromatic hydrocarbons solution processes and can repeat one or many, and in the such processing of one or many, add the compound of the logical formula I of the present invention.
Method five: according to the disclosed method Kaolinite Preparation of Catalyst of patent US4540679 component.First, magnesium alkoxide and carbon dioxide reaction make alkyl magnesiumcarbonate carrier.Then transistion metal compound (being preferably tetravalent titanium compound) and alkyl magnesiumcarbonate carrier react in certain proportion with the electron donor of the logical formula I of the present invention in inert solvent, wherein the mol ratio of transition metal and magnesium elements is at least 0.5:1, and the electron donor consumption of the logical formula I of the present invention mostly is 1.0 moles of every gram of titanium atoms most.Inert solvent must, through purifying, easily make the material of poisoning of catalyst to slough water, oxygen, carbonic acid gas etc.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 also just like magnesium compound, electron donor etc. being formed in thinner to emulsion, add titanium compound to make it fixedly obtain spherical solid, the more treated ingredient of solid catalyst that obtains.
In any above-mentioned preparation method, needed electron donor compound (I) can add with the form of compound; Also can add in other mode, as can be by adopting the applicable precursor original position of electron donor compound (I) to obtain, this front physical efficiency by example as is known chemical reaction as esterification etc. becomes needed electron donor compound.
According to another aspect of the present invention, provide a kind of catalyzer for olefinic polyreaction, comprised following component:
The above-mentioned ingredient of solid catalyst of component a.; With
Components b. alkylaluminium cpd.
In above-mentioned catalyzer, described alkylaluminium cpd is that general formula is AlR
nx
3-ncompound, in formula, R is the alkyl that hydrogen, carbonatoms are 1～20, X is halogen, the number that n is 1≤n≤3; Specifically can be selected from triethyl aluminum, tri-propyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-octylaluminium, three iso-octyl aluminium, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethyl aluminum chloride, ethyl aluminum dichloride, preferably triethyl aluminum, triisobutyl aluminium.
In above-mentioned catalyzer, described catalyzer also comprises amount of component b. external electron donor, described external electron donor is silicoorganic compound, ethers, ester class or its mixture.Add external donor compound, can obtain the olefin polymer that taxis is very high.For example general formula is R
nsi (OR ')
4-nsilicoorganic compound, 0≤n≤3 in formula, R and R ' they are of the same race or different alkyl, cycloalkyl, aryl, haloalkyl, amidos, R can be also halogen or hydrogen atom.For example: trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, vinyltrimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, methyl-t-butyldimethoxysilane, preferably Cyclohexyl Methyl Dimethoxysilane, dimethoxydiphenylsilane.As the compound of external electron donor, can also be ether compound as 1,3-diether, and ester compound is as phenylformic acid monoesters, phenylformic acid diester, diol ester compound, can be also the mixture of silicoorganic compound, ethers, ester class.
In above-mentioned catalyzer, wherein the ratio of component a, components b is taking titanium: the molar ratio computing of aluminium is as 1:(5～1000).Ratio between described component a and amount of component b is with titanium: the molar ratio computing between silicon (or ether, or ester) is 1:(0～500).
Catalyzer of the present invention can directly add in reactor for polymerization process, or catalyzer can participate in prepolymerization before adding first reaction, and in the present invention, term " prepolymerization " refers to lower transforming degree polymerization.According to the present invention, described pre-polymerized catalyst comprises above-mentioned ingredient of solid catalyst and carries out the prepolymer of prepolymerization gained with alkene, and pre-polymerization multiple is 0.1～1000g olefin polymer/g ingredient of solid catalyst.
Can adopt the alpha-olefin identical with aforementioned alkene to carry out prepolymerization, wherein carry out prepolymerized alkene and be preferably ethene or propylene.Specifically, particularly preferably be the mixture that adopts ethene or propylene and amount to be up to one or more alpha-olefins of 20mol% and carry out prepolymerization.Preferably, the transforming degree of pre-polymerized catalyst components is about 0.2～800g polymkeric substance/gram ingredient of solid catalyst.
Prepolymerization operation can, at-40～80 DEG C, preferably, at the temperature of-20～50 DEG C, be carried out in liquid or in gas phase.The part that prepolymerization step can be used as in continuous polymerization technique is carried out online, or carries out independently in periodical operation.For preparation amount is the polymkeric substance of 0.5～20g/g ingredient of solid catalyst, 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, described alkene carries out polymerization under the existence of above-mentioned ingredient of solid catalyst, catalyzer or pre-polymerized catalyst.
Catalyzer of the present invention can directly add in reactor for polymerization process, or catalyzer and alkene pre-polymerization obtain adding in reactor after pre-polymerized catalyst.
Olefinic polyreaction of the present invention carries out according to known polymerization process, can in liquid phase or gas phase, carry out, or also can under the operation of liquid and gas polymerization stage combination, carry out.Adopt conventional technology as slurry process, gas-phase fluidized-bed etc.To adopt following reaction conditions preferably: 0～150 DEG C of polymerization temperature, 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 be selected from ethene, propylene, 1-butylene, 4-methyl-1-pentene and 1-hexene.Be preferably selected from ethene and propylene.As the equal polymerization of propylene with or the copolymerization of other alkene of propylene.The inventive method is also applicable to as the homopolymerization of ethene and ethene and alpha-olefin, as the copolymerization of propylene, butylene, amylene, hexene, octene, 4-methyl-1-pentene.
It is worthy of note, in catalyst component of the present invention, used on the straight chain that contains special construction and contained 6 non-end group glycol more than carbon atom and at least contain 1 C
mthe benzoic acid of (m>=2) hydrocarbyl substituent and the diol ester that obtains (as shown in logical formula I), the diol ester of this special construction can further improve hydrogen response and the polymerization activity of catalyzer.
According to the present invention, adopt the catalyst system of diol ester compound provided by the invention for olefinic polymerization, particularly under high hydrogen concentration, the isotactic index that the hydrogen response of catalyzer improves or resulting polymers represents with boiling heptane extracting insolubles has had raising significantly, is conducive to the exploitation of the different trades mark of polymkeric substance.
The ingredient of solid catalyst and the catalyzer that improve according to the present invention, can make the polymkeric substance of high fusion index and high isotactic.Compared with prior art, the melting index of polymkeric substance is when hydrogen response is suitable at once mutually, and isotactic index improves; When the isotactic index of polymkeric substance is suitable, melting index improves, and hydrogen response improves.
Embodiment
Embodiment given below, only for the present invention is explained and illustrated, does not form any limitation of the invention.
Testing method
1. polymkeric substance isotactic index (TII) adopts heptane extraction process to measure (heptane boiling extracting 6 hours): the polymer samples that 2g is dry, be placed in extractor and use the extracting of boiling heptane after 6 hours, the polymer weight (g) that residuum is dried to constant weight gained is isotactic index with 2 ratio.
2. the melting index of polymkeric substance (MI) is measured by testing standard GB/T3682-2000.
3. the content liquid chromatogram measuring of diol ester (II), liquid chromatography is Waters-600E high performance liquid chromatography, the pillar of C-18, column temperature is 30 DEG C, methanol-water is moving phase, flow velocity 1.0ml/min, UV-detector.
4.Ti content is measured with ultraviolet-visible spectrophotometer 752S, taking 1mol sulfuric acid as blank solution.
5.Mg 0.02 equivalent for content/L EDTA solution carries out titrimetry.
One, the preparation of ingredient of solid catalyst
In the reactor of fully replacing through high pure nitrogen, add successively magnesium chloride 6.0g, toluene 119ml, epoxy chloropropane 5ml, tributyl phosphate (TBP) 15.6ml, is warming up to 50 DEG C, and maintains 2.5 hours under stirring, and solid dissolves completely.Then add Tetra hydro Phthalic anhydride 1.7g, temperature continues to maintain 1 hour; Solution is cooled to below-25 DEG C, in 1 hour, drips 70ml TiCl
4.Slowly be warming up to 80 DEG C, in temperature-rise period, separate out gradually solids.Add diol ester compound (I) 4.6mmol in table 1, holding temperature 1 hour, after filtration, adds toluene 80ml, and washed twice, obtains solid sediment.
Then add toluene 60ml, TiCl
440ml, is warmed up to 108 DEG C, processes 2 hours, after venting filtrate, then adds toluene 60ml, TiCl
440ml, is warmed up to 108 DEG C, processes venting filtrate 2 hours; Add toluene 60ml, boiling state is washed once, then adds hexane 60ml, and boiling state washed twice, adds hexane 60ml, after normal temperature washed twice, obtains ingredient of solid catalyst.
Two, propylene polymerization experiment
The catalyst component of above-described embodiment is carried out respectively to propylene polymerization.Propylene polymerization program is: the stainless steel cauldron that volume is 5L, after gaseous propylene is fully replaced, adds AlEt
32.5mmol, Cyclohexylmethyldimethoxysilane (CHMMS) 0.l mmol, then add ingredient of solid catalyst 8-10mg and a certain amount of hydrogen of above-described embodiment, and 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 1-6 and comparative example 1.The results are shown in Table 1
Table 1 propylene polymerization result
ID1:2,4-hexylene glycol two (4-propylbenzoic acid ester)
ID2:3,5-heptanediol two (4-p t butylbenzoic acid ester)
ID3:3,5-heptanediol two (4-propylbenzoic acid ester)
ID4:3,5-heptanediol two (4-butylbenzoic acid ester)
ID5:3,5-heptanediol dibenzoate
ID6:3,5-heptanediol styracin (4-propylbenzoic acid) ester
ID7:4-ethyl-3,5-heptanediol two (4-p t butylbenzoic acid ester)
Can find out from data above, when adopting the diol ester compound of special construction, not only can significantly improve the activity of catalyzer, particularly, under high hydrogen concentration, the hydrogen response of catalyzer improves (melting index that is resulting polymers is high) or has further improved the isotactic index of catalysis resulting polymers.
It should be noted in the discussion above that above-described embodiment, only for explaining the present invention, does not form any limitation of the invention.By with reference to exemplary embodiments, invention has been described, be descriptive and explanatory vocabulary but should be understood to word wherein used, instead of limited vocabulary.Can in the scope of the claims in the present invention, modify the present invention in accordance with regulations, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention who wherein describes relates to specific method, material and embodiment, and does not mean that the present invention is limited to wherein disclosed particular case, on the contrary, the present invention can extend to other all methods and applications with identical function.
Claims (12)
1. for an ingredient of solid catalyst for olefinic polyreaction, it comprises magnesium, titanium, halogen and electron donor, and described electron donor is selected from least one in diol ester compound shown in following logical formula I;
In formula, R
1and R
2can be identical or different, be selected from hydrogen, halogen atom, 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 and C
7-C
10aralkyl;
R
3and R
4can be identical or different, be selected from hydrogen, 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 and C
7-C
10aralkyl, R
3and R
4optionally be keyed to ring;
R
5be selected from C
2-C
10straight chained alkyl, C
3-C
10branched-chain alkyl, C
3-C
10cycloalkyl, C
6-C
10aryl, C
7-C
10alkaryl and C
7-C
10aralkyl;
N is 1～5 integer;
R
6be selected from C
1-C
10straight chained alkyl, C
3-C
10branched-chain alkyl, C
3-C
10cycloalkyl, C
6-C
10aryl, C
7-C
15alkaryl and C
7-C
15aralkyl.
2. ingredient of solid catalyst according to claim 1, is characterized in that, the hydrogen on described alkyl or aryl is by halo.
3. ingredient of solid catalyst according to claim 1 and 2, is characterized in that, R
1and R
2in have one at least for hydrocarbyl substituent.
4. according to the ingredient of solid catalyst described in any one in claim 1～3, it is characterized in that R
1and R
2group is selected from halo or not by the C of halo
1-C
6straight chained alkyl and C
3-C
6branched-chain alkyl; R
3and R
4be selected from hydrogen, halogen atom, C
1-C
6straight chained alkyl and C
3-C
6branched-chain alkyl, or hydrogen on described alkyl is by halo; R
5be selected from C
2-C
6straight chained alkyl and C
3-C
6branched-chain alkyl; N is 1 or 2, preferably n=1 and replacing for contraposition or ortho position; R
6be selected from halo or not by the C of halo
4-C
10straight or branched alkyl, C
5-C
10cycloalkyl, C
6-C
10aryl, C
7-C
10alkaryl and C
7-C
10aralkyl.
5. according to the ingredient of solid catalyst described in any one in claim 1～4, it is by preparing the carrying out reaction of the diol ester compound shown in magnesium compound, titanium compound and logical formula I.
6. ingredient of solid catalyst according to claim 5, it is characterized in that, described reaction preparation comprises magnesium compound is dissolved in the solvent system being made up of organic epoxy compounds, organo phosphorous compounds and inert diluent, after forming homogeneous solution, mix with titanium compound, then under precipitation additive exists, separate out solids, last described solids by using is selected from the compound of logical formula I and processes.
7. ingredient of solid catalyst according to claim 6, it is characterized in that, described magnesium compound is selected from hydrate or the alcohol adduct of magnesium dihalide, alkoxyl Mei ﹑ Wan Ji Mei ﹑ magnesium dihalide, and the halogen atom alkoxy of magnesium dihalide or derivative that halogenated alkoxy replaces, be preferably selected from magnesium dihalide and alcohol adduct thereof;
Described titanium compound general formula is TiX
m(OR
1) 4-m, R in formula
1for C
1～C
20alkyl, X is halogen, 1≤m≤4, preferably titanium tetrachloride;
Described organic epoxy compounds comprises oxide compound, glycidyl ether and the inner ether of carbonatoms at 2～8 aliphatics alkene, diolefine, halogenated aliphatic alkene or diolefine;
Described organo phosphorous compounds is hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid;
Described precipitation additive is selected from organic acid anhydride, organic acid, ether and ketone.
8. according to the ingredient of solid catalyst described in any one in claim 1～7, it is characterized in that, in every mole of magnesium halide, the amount of described organic epoxy compounds is 0.2～10 mole, the amount of described organo phosphorous compounds is 0.1～3 mole, the amount of described precipitation additive is 0～1.0 mole, and the amount of described titanium compound is 0.5～150 mole, and the amount of the propylene glycol ester compound of described logical formula I is 0.02～0.4 mole.
9. for a catalyzer for olefinic polyreaction, comprise following component:
Ingredient of solid catalyst in component a. claim 1～8 described in any one; With
Components b. alkylaluminium cpd.
10. catalyzer according to claim 9, is characterized in that, described catalyst system also comprises amount of component b. external electron donor, described external electron donor is selected from silicoorganic compound, ethers and ester class.
11. 1 kinds of pre-polymerized catalysts for olefinic polyreaction, comprise and a kind ofly carry out the prepolymer of prepolymerization gained according to the catalyzer described in claim 9 or 10 and with alkene, pre-polymerization multiple is 0.1～1000g olefin polymer/g ingredient of solid catalyst, and preferred described alkene is ethene or propylene.
The method of 12. 1 kinds of olefinic polymerizations, described the alkene catalyzer described in ingredient of solid catalyst, the claim 9 or 10 described in any one or the pre-polymerized catalyst described in claim 11 in claim 1～8 carry out polymerization under existing.
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|---|---|---|---|
| CN201310190424.4A CN104177520B (en) | 2013-05-21 | 2013-05-21 | It is used to prepare the ingredient of solid catalyst of olefin polymer |
| TW103117524A TWI644896B (en) | 2013-05-21 | 2014-05-19 | Catalyst component, catalyst and application for olefin polymerization |
| RU2015154533A RU2673083C2 (en) | 2013-05-21 | 2014-05-21 | Catalyst component for olefin polymerisation, catalyst and use thereof |
| SG11201509482XA SG11201509482XA (en) | 2013-05-21 | 2014-05-21 | Catalyst component for olefin polymerization, catalyst, and use thereof |
| BR112015028908-8A BR112015028908B1 (en) | 2013-05-21 | 2014-05-21 | CATALYST COMPONENT FOR OLEFINE POLYMERIZATION, CATALYST FOR OLEFINE POLYMERIZATION, PREPOLIMERATION CATALYST FOR OLEFINE POLYMERIZATION, METHOD FOR OLEFINE POLYMERIZATION |
| DE112014002517.8T DE112014002517T5 (en) | 2013-05-21 | 2014-05-21 | Catalyst component for olefin polymerization, catalyst and use thereof |
| ES201590123A ES2557178B2 (en) | 2013-05-21 | 2014-05-21 | Catalyst component for the polymerization of olefins, catalyst and use thereof |
| KR1020157036140A KR102174946B1 (en) | 2013-05-21 | 2014-05-21 | Catalyst component for use in olefin polymerization reaction, catalyst, and application |
| PCT/CN2014/078050 WO2014187323A1 (en) | 2013-05-21 | 2014-05-21 | Catalyst component for use in olefin polymerization reaction, catalyst, and application |
| US14/892,533 US9751960B2 (en) | 2013-05-21 | 2014-05-21 | Catalyst component for olefin polymerization, catalyst, and use thereof |
| GB1522379.5A GB2530212B (en) | 2013-05-21 | 2014-05-21 | Catalyst component for olefin polymerization reaction, catalyst, and use thereof |
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| CN112707979A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, preparation method thereof, catalyst and application thereof |
| CN112707980A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization and application thereof |
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|---|---|---|---|---|
| CN101864009A (en) * | 2009-04-17 | 2010-10-20 | 中国石油化工股份有限公司 | Preparation method of catalyst component for polymerization reaction of olefins and catalyst thereof |
| CN102234337A (en) * | 2010-04-22 | 2011-11-09 | 中国石油化工股份有限公司 | Catalyst components for olefin polymerization reaction, and catalyst thereof |
| CN103012625A (en) * | 2011-09-23 | 2013-04-03 | 中国石油化工股份有限公司 | Olefin polymerization catalyst ingredient, preparation method and use of the olefin polymerization catalyst ingredient, catalyst system, use of the catalyst system, and olefin polymerization method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864009A (en) * | 2009-04-17 | 2010-10-20 | 中国石油化工股份有限公司 | Preparation method of catalyst component for polymerization reaction of olefins and catalyst thereof |
| CN102234337A (en) * | 2010-04-22 | 2011-11-09 | 中国石油化工股份有限公司 | Catalyst components for olefin polymerization reaction, and catalyst thereof |
| CN103012625A (en) * | 2011-09-23 | 2013-04-03 | 中国石油化工股份有限公司 | Olefin polymerization catalyst ingredient, preparation method and use of the olefin polymerization catalyst ingredient, catalyst system, use of the catalyst system, and olefin polymerization method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112707979A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, preparation method thereof, catalyst and application thereof |
| CN112707980A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization and application thereof |
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