CN104177521A - Method for preparing solid catalyst component for olefin polymerization and catalyst for olefin polymerization - Google Patents
Method for preparing solid catalyst component for olefin polymerization and catalyst for olefin polymerization Download PDFInfo
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- CN104177521A CN104177521A CN201310190990.5A CN201310190990A CN104177521A CN 104177521 A CN104177521 A CN 104177521A CN 201310190990 A CN201310190990 A CN 201310190990A CN 104177521 A CN104177521 A CN 104177521A
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Abstract
The invention discloses a method for preparing a solid catalyst component for an olefin polymerization reaction. The method comprises the following steps of dissolving a magnesium compound in a solvent system containing a hydrocarbon compound and an alcohol compound, mixing a titanium compound and the above solution at a temperature of -40 to 0 DEG C, adding an electron donor compound into the mixture at a temperature of 50-150 DEG C, and carrying out washing by an inert diluent to obtain the solid catalyst component. The used electron donor is at least one of diol ester compounds shown in the general formula (I). The catalyst system 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, pass through to use this diol ester compound as electron donor, can obtain the catalyzer of high comprehensive performance, 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 during for alkene especially propylene polymerization, and polymerization activity is high; There is better hydrogen response or in the time of the high molten finger polymkeric substance of preparation, can obtain gratifying high degree of isotacticity.
According to an aspect of the present invention, a kind of method of preparing olefinic polyreaction ingredient of solid catalyst is provided, comprise magnesium compound is dissolved in the solvent system of hydrocarbon-containifirst compound and alcohol compound, then at-40～40 DEG C, titanium compound is mixed with above-mentioned solution, at 50-40～150 DEG C, add electron donor compound, and obtain ingredient of solid catalyst after inert diluent washing; Described electron donor is selected from least one in diol ester compound shown in following logical formula I;
（Ⅰ）
In logical formula I, R
1and R
2can be identical or not identical, 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 not identical, 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 and C
7-C
10alkaryl or aralkyl;
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 and C
7-C15 alkaryl or aralkyl.
In a specific embodiment of aforesaid method, the hydrogen on described alkyl or aryl is by halo.
In an embodiment of aforesaid method, R
1and R
2has one at least for hydrocarbyl substituent.In a preferred embodiment of aforesaid method, 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.
In aforesaid method, 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 contraposition 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.
In aforesaid method, described magnesium compound is selected from hydrate or the alcohol adduct of magnesium dihalide, alkoxyl Mei ﹑ Wan Ji Mei ﹑ magnesium dihalide, and in the derivative that in magnesium dihalide, halogen atom alkoxy or halogenated alkoxy are replaced, preferably magnesium compound is selected from magnesium dihalide and alcohol adduct and alkoxyl magnesium.
It is TiX that described titanium compound can be selected general formula
m(OR
1)
4-mcompound, 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, preferably titanium tetrachloride.
Described hydrocarbon compound comprises the C of straight or branched
6-C
12alkane and C
6-C
15aromatic hydrocarbon, concrete as hexane, heptane, octane, nonane, decane, benzene,toluene,xylene etc.Alcohol compound comprises fatty alcohol, alicyclic ring alcohol and aromatic alcohol, the C that wherein fatty alcohol is straight or branched
1-C
10fatty alcohol, alicyclic ring alcohol is C
3-C
10ring family fatty alcohol, aromatic alcohol is C
6-C
20aryl alcohol or alkylaryl alcohol; Concrete as: ethanol, propyl alcohol, butanols, amylalcohol, hexanol, octanol, isooctyl alcohol etc., or their mixture.
Described inert diluent is selected from hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene.
In the ingredient of solid catalyst preparing at aforesaid method, based on the gross weight of ingredient of solid catalyst, the content of the diol ester compound shown in described logical formula I is 1～20wt%, and the content of titanium is 1～6wt%, and the content of magnesium is 3～25wt%.Preferably, the content of the diol ester compound shown in described logical formula I is 5～15wt%, and the content of titanium is 1～5wt%, and the content of magnesium is 13～20wt%.
Ingredient of solid catalyst described in the present invention can be prepared by the following method.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/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 ingredient of solid catalyst.
In 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, the reaction product that comprises following component:
The ingredient of solid catalyst that component a. is above-mentioned; With
Components b. alkylaluminium cpd.
In above-mentioned catalyst system, 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 a specific embodiment of above-mentioned catalyst system, described catalyst system comprises the reaction product of amount of component b and component a and b, and described amount of component b is 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 catalyst system, wherein the ratio of component a and components b is with titanium: aluminium is counted 1:(5～1000); Ratio between described component a and amount of component b, with titanium: the molar ratio computing between silicon (or ether, or ester) is 1:(0～500).
Catalyst system of the present invention can directly add in reactor for polymerization process, or catalyst system 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, catalyst system or pre-polymerized catalyst.
Catalyst system of the present invention can directly add in reactor for polymerization process, or catalyst system 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 ingredient of solid catalyst 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 make catalyst system further improve its hydrogen response and polymerization activity.
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, it is that hydrogen response improves that melting index 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.
One, the preparation of ingredient of solid catalyst
Under nitrogen protection, 4.8g Magnesium Chloride Anhydrous, 19.5g isooctyl alcohol and 19.5g decane solvent are joined in the 500ml reactor that agitator is housed, be heated to 130 DEG C, react and dissolve completely to magnesium chloride for 1.5 hours, add 1.1g phthalic anhydride, continue to maintain 130 DEG C of reactions and within 1 hour, obtain alcohol adduct; Alcohol adduct is cooled to room temperature.
Under nitrogen protection; above-mentioned alcohol adduct is added drop-wise in advance in the 120ml titanium tetrachloride solution that is chilled to-22 DEG C, is slowly warming up to 100 DEG C, add the diol ester compound that the general formula in 10mmol table 1 is (I); be warming up to 110 DEG C and maintain 2 hours, mixture filtered while hot.And then add 120 milliliters of titanium tetrachlorides, and be warmed up to 110 DEG C of reactions 1 hour, filter, use anhydrous hexane solid particulate 4 times, after being dried, obtain 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 1-5 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-propylbenzoic acid ester)
ID3:3,5-heptanediol two (4-butylbenzoic acid ester) ID4:3,5-heptanediol dibenzoate
ID5:3,5-heptanediol styracin (4-propylbenzoic acid) ester
ID6:4-ethyl-3,5-heptanediol two (4-p t butylbenzoic acid ester)
Can find out from embodiment above, when adopting the diol ester compound of special construction, not only can significantly improve the activity of catalyzer, and under high hydrogen concentration, the hydrogen response of catalyzer improves (melting index of resulting polymers improves), or has further improved the isotactic index of catalyzer resulting polymers.
The foregoing is only the preferred embodiment of the present invention; but protection scope of the present invention is not limited to this; any those skilled in the art is in technical scope disclosed by the invention; can change easily or change, and this change or change be all encompassed in protection scope of the present invention within.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (10)
1. prepare the method for olefinic polyreaction ingredient of solid catalyst for one kind, comprise magnesium compound is dissolved in the solvent system of hydrocarbon-containifirst compound and alcohol compound, then at-40～40 DEG C, titanium compound is mixed with above-mentioned solution, and at-40～150 DEG C, add electron donor compound, after inert diluent washing, obtain described ingredient of solid catalyst; Described electron donor is selected from least one in diol ester compound shown in following logical formula I;
（Ⅰ）
In formula, R
1and R
2can be identical or not identical, 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 not identical, 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 and C
7-C
10alkaryl or aralkyl;
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 and C
7-C
15alkaryl or aralkyl.
2. method according to claim 1, is characterized in that, the hydrogen on described alkyl or aryl is by halo.
3. method according to claim 1 and 2, is characterized in that, R
1and R
2has one at least for hydrocarbyl substituent.
4. according to the method 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. method according to claim 1, is characterized in that, described hydrocarbon compound comprises the C of straight or branched
6-C
12alkane and C
6-C
15aromatic hydrocarbon;
Described alcohol compound comprises fatty alcohol, alicyclic ring alcohol and aromatic alcohol, the C that wherein fatty alcohol is straight or branched
1-C
10fatty alcohol, alicyclic ring alcohol is C
3-C
10ring family fatty alcohol, aromatic alcohol is C
6-C
20aryl alcohol or alkylaryl alcohol;
Described magnesium compound is selected from hydrate or the alcohol adduct of magnesium dihalide, alkoxyl magnesium, alkyl magnesium, magnesium dihalide, and the derivative that in magnesium dihalide, halogen atom alkoxy or halogenated alkoxy are replaced, preferably magnesium compound is selected from magnesium dihalide and alcohol adduct and alkoxyl magnesium;
Described titanium compound is selected from titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide one chlorine triethoxy titanium, dichloro diethoxy titanium and trichlorine ethanolato-titanium, preferably titanium tetrachloride;
Described inert diluent is selected from hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene.
6. according to the method described in any one in claim 1～5, it is characterized in that, based on the gross weight of ingredient of solid catalyst, the content of the diol ester compound shown in described logical formula I is 1～20wt%, the content of titanium is 1～8wt%, and the content of magnesium is 3～25wt%; Preferably, the content of the diol ester compound shown in described logical formula I is 5～15wt%, and the content of titanium is 1～5wt%, and the content of magnesium is 13～20wt%.
7. for a catalyzer for olefinic polyreaction, the reaction product that comprises following component:
The ingredient of solid catalyst that in component a. claim 1～6, described in any one prepared by method; With
Components b. alkylaluminium cpd.
8. catalyzer according to claim 7, is characterized in that, described catalyst system comprises the reaction product of amount of component b and component a and b, and described amount of component b is external electron donor, is selected from silicoorganic compound, ethers, ester class and its mixture.
9. the pre-polymerized catalyst for olefinic polyreaction, comprise and a kind ofly carry out the prepolymer of prepolymerization gained according to the catalyst system described in claim 7 or 8 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.
10. an olefine polymerizing process, carries out polymerization under the existence of pre-polymerized catalyst described in the catalyst system described in described alkene described in any one prepared by method in claim 1～6 ingredient of solid catalyst, claim 7 or 8 or claim 9.
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| CN201310190990.5A CN104177521B (en) | 2013-05-21 | 2013-05-21 | Prepare method and the catalyst of solid catalyst component for olefine polymerization |
| TW103117524A TWI644896B (en) | 2013-05-21 | 2014-05-19 | Catalyst component, catalyst and application for olefin polymerization |
| 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 |
| GB1522379.5A GB2530212B (en) | 2013-05-21 | 2014-05-21 | Catalyst component for olefin polymerization reaction, catalyst, and use thereof |
| US14/892,533 US9751960B2 (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 |
| DE112014002517.8T DE112014002517T5 (en) | 2013-05-21 | 2014-05-21 | Catalyst component for olefin polymerization, catalyst and use thereof |
| SG11201509482XA SG11201509482XA (en) | 2013-05-21 | 2014-05-21 | Catalyst component for olefin polymerization, catalyst, and use thereof |
| RU2015154533A RU2673083C2 (en) | 2013-05-21 | 2014-05-21 | Catalyst component for olefin polymerisation, 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 |
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| 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 |
| CN103012632A (en) * | 2011-09-23 | 2013-04-03 | 中国石油化工股份有限公司 | Preparation method of propylene polymer |
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| 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 |
| CN103012632A (en) * | 2011-09-23 | 2013-04-03 | 中国石油化工股份有限公司 | Preparation method of propylene polymer |
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