CN104109213A

CN104109213A - Catalyst component for olefin polymerization and catalyst thereof

Info

Publication number: CN104109213A
Application number: CN201410266036.4A
Authority: CN
Inventors: 王志武; 李树行; 李华姝; 张军伟; 章慧; 陈业娜; 代金松; 马庆利; 王敬禹; 李树宾; 陈颢; 雷凤瑶; 白伟; 李利革; 高勇
Original assignee: Beijing Li Hezhixin Science And Technology Ltd
Current assignee: Beijing Li Hezhixin Science And Technology Ltd
Priority date: 2014-06-13
Filing date: 2014-06-13
Publication date: 2014-10-22
Anticipated expiration: 2034-06-13
Also published as: CN104109213B

Abstract

A catalyst component for olefin polymerization is provided. The catalyst component comprises magnesium halide in an active state, a titanium compound containing at least one Ti-halogen bond and supported by the magnesium halide, and at least one unsaturated ring substituted diacid ester compound of the general formula (I) that is supported by the magnesium halide. The catalyst component has excellent activity. The prepared polymer has high isotacticity.

Description

For catalyst component and the catalyzer thereof of olefinic polymerization

Technical field

The unsaturated ring that the present invention relates to contain specific type replace two ester compounds as internal electron donor and/or external electron donor for CH ₂the catalyzer of=CHR olefinic polymerization, wherein R is hydrogen or the hydrocarbyl group containing 1-12 carbon atom.

Background technology

All the time, the catalyzer using as the olefin polymer such as homopolymer or multipolymer for the manufacture of alpha-olefin, the catalyzer of the titanium compound of the magnesium chloride load that comprises activity morphology is known.This olefin polymerization catalyst components contains magnesium, titanium, halogen and internal electron donor.Conventionally in Z-N catalyst system for propylene polymerization, except above-mentioned main catalyst component, aluminum alkyl catalyst, also needing to add the 3rd component is external electron donor, further to improve the stereotaxis performance of catalyzer.

At present, the external electron donor in polypropylene catalyst mainly divides aromatic carboxylic acid esters, organic amine, calixarene, several large classes of organo-siloxane.Polypropylene in producing normal use organo-siloxane have dimethoxydiphenylsilane (DDS) cyclohexyl dimethoxy silane (CMMS), dicyclopentyl dimethoxyl silane (DCPDMS), a second, isobutyl dimethoxy silane (DIBDMS), etc.

External electron donor, for improving Z-N activity and controlling polymkeric substance taxis aspect and also bringing into play very important effect, is therefore found the study hotspot that novel electron donor is Ziegler-Natta catalyst always.In addition, the interaction of main catalyst component, aluminum alkyl catalyst and external electron donor has directly determined the quality of polymerization, if mate properly, can make catalyzer can reach high reactivity and can ensure again high stereospecificity.

Prior art has extensively been narrated the example of above-mentioned electron donor compound, comprises ethers, ketone, ester class, the compound that contains N, P and/or S atom.Preferred kind has 1,3-the third diether compounds, monocarboxylic ester or polycarboxylic acid ester compound, 1,3-diol ester compound.Particularly suitable be monocarboxylic ester or polycarboxylic acid ester compound, concrete example is that aromatic binary carboxylic acid compound is as Bisphthalate or bis--terephthalate.Bisphthalate comprises: dimethyl phthalate, diethyl phthalate, n-propyl phthalate, diisopropyl phthalate, n-butyl phthalate, diisobutyl phthalate, Methyl Benzene-o-dicarboxylate ethyl ester, Methyl Benzene-o-dicarboxylate isopropyl ester, Methyl Benzene-o-dicarboxylate n-propyl, the positive butyl ester of ethyl phthalate(DEP), ethyl phthalate(DEP) isobutyl ester, amyl phthalate, di-iso-amyl phthalate, dihexyl phthalate, heptyl phthalate ester, dinoctyl phthalate, dimixo-octyl phthalate, phthalic acid (2,2-dimethyl hexyl) diester, phthalic acid (2-ethylhexyl) diester, 2-nonyl-phthalate ester, Di Iso Decyl Phthalate, phthalic acid (2,2-dimethyl heptyl) diester, n-butyl phthalate isohexyl ester, n-butyl phthalate (2-ethylhexyl) ester, the just own ester of phthalic acid n-pentyl ester, phthalic acid n-pentyl ester ester in the different ninth of the ten Heavenly Stems, isoamyl phthalate ester in the positive last of the ten Heavenly stems, phthalic acid n-pentyl ester undecane ester, phthalic acid isopentyl isohexyl ester, the just own ester of phthalic acid (2-methyl polyhexamethylene), phthalic acid n-hexyl (2-(ethyl hexyl) ester), the just own ester of phthalic acid (different the ninth of the ten Heavenly Stems ester), phthalic acid n-hexyl (positive the last of the ten Heavenly stems ester), the positive heptyl ester of phthalic acid (2-(ethyl hexyl) ester), the positive heptyl ester of phthalic acid (different the ninth of the ten Heavenly Stems ester), the positive heptyl ester of phthalic acid ester in the new ninth of the ten Heavenly Stems and phthalic acid 2-ethylhexyl (different the ninth of the ten Heavenly Stems ester).These esters can independent or multiple mixing use.Bis--terephthalate comprises: dimethyl terephthalate (DMT), diethyl terephthalate, terephthalic acid di-n-propyl ester, terephthalic acid diisopropyl ester, di-n-butyl terephthalate, di-n-butyl terephthalate, isobutyl terephthalate, terephthaldehyde's acetoacetic ester methyl esters, terephthalic acid methyl esters isopropyl ester, terephthaldehyde's acetoacetic ester (n-propyl), terephthaldehyde's acetoacetic ester (positive butyl ester), terephthaldehyde's acetoacetic ester (isobutyl ester), terephthalic acid two n-pentyl esters, terephthalic acid diisoamyl ester, terephthalic acid dihexyl, the positive heptyl ester of terephthalic acid two, terephthalic acid di-n-octyl, the different n-octyl of terephthalic acid two, terephthalic acid two (2,2-dimethyl hexyl) ester, terephthalic acid two (2-ethylhexyl) ester, terephthalic acid two ester in the positive ninth of the ten Heavenly Stems, terephthalic acid dinonyl, terephthalic acid two isodecyl esters, terephthalic acid two (2,2-dimethyl ethyl heptyl) ester, the positive butyl ester dissident of terephthalic acid ester, the positive butyl ester of terephthalic acid (2 ethylhexyl) ester, the just own ester of terephthalic acid n-pentyl ester, terephthalic acid n-pentyl ester dissident ester, terephthaldehyde's isoamyl valerate (heptyl ester), terephthalic acid, terephthalic acid n-pentyl ester (2-ethylhexyl) ester, terephthalic acid n-pentyl ester (different the ninth of the ten Heavenly Stems ester), terephthaldehyde's isoamyl valerate (positive the last of the ten Heavenly stems ester), terephthalic acid n-pentyl ester undecane ester, terephthaldehyde's isoamyl valerate dissident ester, terephthalic acid n-hexyl (2-(ethyl hexyl) ester), terephthalic acid n-hexyl (different nonyl ester), the just own ester of terephthalic acid (positive the last of the ten Heavenly stems ester), terephthalic acid n-heptyl (2-(ethyl hexyl) ester), terephthalic acid n-heptyl (different nonyl ester), terephthalic acid n-heptyl (new the last of the ten Heavenly stems ester), with terephthalic acid 2-ethylhexyl (different nonyl ester).These esters can independent or multiple mixing use.

Diethyl phthalate most preferably in these diester, dipropyl phthalic butyl ester, terephthalic acid diisopropyl ester, n-butyl phthalate, diisobutyl phthalate, dinoctyl phthalate, dimixo-octyl phthalate, di-n-butyl terephthalate, isobutyl terephthalate, terephthalic acid di-n-octyl, terephthalic acid di-isooctyl, the mixing of one or more in terephthalic acid two (2-ethylhexyl) ester or Di Iso Decyl Phthalate.

Magnesium compound of the present invention preferably adopts magnesium alkoxide compound.

Another preferably adopts the alcohol adduct of magnesium dihalide magnesium compound of the present invention.

Magnesium compound of the present invention one preferably adopts liquid magnesium compound again.

Titanium compound of the present invention comprises titanium tetrachloride, titanium tetrabromide, titanium tetra iodide or alkyl halide titanium, and alkyl halide titanium is as methoxyl group titanous chloride, oxyethyl group titanous chloride, propoxy-titanous chloride, n-butoxy titanous chloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, two n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride or three n-Butoxyl titanium-chlorides.In these halogenated titaniums, can apply one or more and mix use.Wherein preferably adopt titanium tetrachloride.

Ingredient of solid catalyst of the present invention (A) and preparation (a) can be carried out according to the whole bag of tricks.

According to a kind of method wherein, use TiCl ₄or the aromatic hydrocarbons of titanium alkoxides (such as toluene, dimethylbenzene etc.) solution can react with two magnesium alkoxide compounds such as dialkoxy magnesium or two aryloxy magnesium, and carry out halogenation at 80-130 DEG C at-25-0 DEG C.Use TiCl ₄the processing carried out of aromatic hydrocarbons solution can repeat one or many, and add the electron donor compound of choosing any one kind of them in repeatedly such processing.For example can be prepared with reference to the preparation method of disclosed solids containing titanium catalyst component in US5077357: add successively magnesium ethylate, purity titanium tetraethoxide, ortho-cresol, ethanol and chlorobenzene, stir; By TiCl ₄/ chlorobenzene solution adds in aforesaid liquid fast, heats up until completely dissolved, continues to be warming up to specified temp; Utilize N ₂bubbling continues to stir certain hour after taking away ethanol synthesis thing, then adopts hot chlorobenzene to wash once, octane-iso washed twice, then N ₂dry up and can obtain carrier.Or according to another example: successively by TiCl ₄, purity titanium tetraethoxide, magnesium ethylate and ortho-cresol add in chlorobenzene, stir; Add ethanol, under high temperature, after magnesium ethylate dissolves, continue to stir 3h; Then filtered while hot adopts warm chlorobenzene to wash once, and octane-iso washs once, last N ₂dry.

According to another kind of method, the alcoholate of magnesium or chlorohydrin and in solution, contain the excessive TiCl of the electron donor compound of choosing any one kind of them ₄at the temperature of 80-13 DEG C, react.According to preferred method, can be TiX by general formula _n(OR) _4-ntitanium compound, in formula, R is that carbonatoms is the alkyl of 1-20, X is halogen, n=1-4; Preferably TiCl ₄, and be MgCl from general formula ₂the adducts of mROH reacts and prepares ingredient of solid catalyst, the number that in formula, m is 0.1-6, and preferably 2-3.5, and R is the alkyl with 1-20 carbon atom.Adducts can be made spherical by the following method aptly: under not existing with the miscible unreactive hydrocarbons of adducts, alcohol and magnesium chloride are mixed, make the rapid chilling of this emulsion, thereby adducts is solidified with the form of spheroidal particle.The spherical MgCl preparing according to this process ₂the example of mROH adducts is described and is found in US4399054 and US4469648.The adducts so obtaining can directly react with titanium compound, or its can be in advance through 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 to 2.5.Can be by adducts (dealcoholysis or itself) be suspended in to cold TiCl ₄in (general-25-0 DEG C), carry out and the reacting of titanium compound; Mixture is heated to 80-130 DEG C and keep 0.5-2 hour at this temperature.Use TiCl ₄the processing of carrying out can be carried out once or repeatedly.Using TiCl ₄during processing, can add the electron donor compound of choosing any one kind of them to process, this processing can repeat once or repeatedly.

Preparation ingredient of solid catalyst of the present invention another kind of method comprise, by Magnesium Chloride Anhydrous and choose any one kind of them electron donor compound magnesium dichloride occur activation condition under together with grinding.The product so obtaining can be with excessive TiCl at the temperature of 80-130 DEG C ₄process one or many.After processing with the washing of hydro carbons volume until chloride ion-containing not.According to further method, the magnesium dichloride by anhydrous state, titanium compound and the electron donor compound of choosing any one kind of them are carried out to the product that common grinding obtains, adopt and process such as the halohydrocarbon of 1,2-ethylene dichloride, chlorobenzene, methylene dichloride and so on.This processing is carried out 1-4 hour at 40 DEG C to the temperature between halohydrocarbon boiling point.Then conventionally wash and obtain product with the inertia hydro carbons volume of hexane and so on.

According to another kind of method, magnesium dichloride is activated in advance according to the method for knowing, then at the temperature of about 80-135 DEG C with excessive TiCl ₄process, wherein in solution, contain the electron donor compound of choosing any one kind of them.Use TiCl ₄process repeatedly and solid cleaned to remove any TiCl for reaction with hexane ₄.

Further method comprises, also can be prepared with reference to the preparation method of disclosed solids containing titanium catalyst component in CN1208045: first under a kind of compound that is selected from alcohol, phenol, ketone, aldehyde, ether, amine, pyridine and ester exists, liquid magnesium compound is contacted with liquid titanium compound at low temperatures, be settled out solid, be generally-70-200 DEG C of temperature when contact, be preferably-30-130 DEG C, in contact process by the electron donor compound treatment of choosing any one kind of them.

The another kind of method of ingredient of solid catalyst of the present invention 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, under the existence of precipitation additive, wash out solids; The electron donor compound treatment of choosing any one kind of them for this solids, is carried on solids it, if desired, then processes and obtains with titanium tetrahalide and inert diluent, and wherein precipitation additive is the one in organic acid anhydride, organic acid, ether, ketone.Described each component is in every mole of magnesium halide, and organic epoxy compounds is 0.2-10 mole, and organo phosphorous compounds is 0.1-3 mole, and precipitation additive is 0.03-1.0 mole, and the halogenide of transition metal Ti and derivative thereof are 0.5-150 mole.

Ingredient of solid catalyst of the present invention, can also adopt at SiO ₂, the magnesium compound of load is prepared as carrier on the inorganic oxide such as aluminum oxide or porous resin, then activate by the method for knowing, then at the temperature of about 80-135 DEG C with excessive TiCl ₄process, in treating processes, add the electron donor compound of choosing any one kind of them.Above-mentioned reaction causes forming the magnesium halide that is activity morphology.Except these reactions, the method that is also known to other in document makes to form by the compound initial substance that is different from magnesium halide the magnesium halide that is activity morphology.

General crystal magnesium halide compound with regular structure, portative Ti is little, thereby catalytic activity is low, prepare highly active supported catalyst, and magnesium halide must pass through activation treatment.Activating treatment process comprise with physics and/or chemistry method be made into crystallite so that active centre is carried on magnesium halide surface, edge and fault location, the magnesium halide crystallite that is suitable for load Ti of this processing is " magnesium halide that is activity morphology ".

General formula is AlR _nx _(3-n)organo-aluminium compound, in formula, R is the alkyl of hydrogen, carbonatoms 1-20, X is halogen, and the integer that n is 0≤n≤3 is selected from the trialkyl compound such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, trioctylaluminum.Also likely use trialkylaluminium and aluminum alkyl halide, alkyl aluminum hydride or such as AlEt ₂cl and Al ₂et ₃cl ₃and so on the mixture of alkylaluminium sesquichloride, can also use alkyl chloride oxygen alkane.

The present invention requires a kind of external electron donor to use together with catalyst component (a), in the time that the latter is different from catalyst component (A), is at least like this.Described external electron donor, at least one the unsaturated ring that is selected from logical formula I replaces two ester compounds:

Wherein, A, B, C, D and E are all selected from carbon atom or are selected from the heteroatoms in N, O and S; W, X, Y, Z and m are 0 or 1; Condition is

In the time that n equals 0:

XIII) A, B, C and D are carbon atom, and X, Y, Z and W are 1; Or

XIV) A is nitrogen-atoms, and B, C and D are carbon atom, and W is that 0, X, Y and Z are 1; Or

XV) A and D are nitrogen-atoms, and B and C are carbon atom, and W and Z are that 0, X and Y are 1; Or

XVI) D is nitrogen-atoms, and A, B and C are carbon atom, and Z is that 0, W, X and Y are 1; Or

In the time that n equals 1:

X) A, B, C, D and E are carbon atom, and m is that 2, W, X, Y and Z are 1; Or

Xi) E is nitrogen-atoms, and A, B, C and D are carbon atom, and m is that 1, W, X, Y and Z are 1; Or

Xii) E is Sauerstoffatom, and A, B, C and D are carbon atom, and m is that 0, W, X, Y and Z are 1; Or

Vii) E is sulphur atom, and A, B, C and D are carbon atom, and m is that 0, W, X, Y and Z are 1; Or

Viii) D and E are nitrogen-atoms, and A, B and C are carbon atom, and m is that 1, W, X and Y are that 1, Z is 0.

R ¹and R ²for identical or not identical C ₁-C ₂₀alkyl, such as C ₁-C ₂₀straight or branched alkyl, alkenyl, C ₃-C ₂₀cycloalkyl, C ₆-C ₂₀aryl, C ₇-C ₂₀alkaryl and C ₇-C ₂₀aralkyl; Identical or different R ³-R ⁷hydrogen atom, halogen atom, Sauerstoffatom, sulphur atom and C ₁-C ₂₀alkyl, such as C ₁-C ₂₀straight or branched alkyl, C ₃-C ₂₀cycloalkyl, C ₆-C ₂₀aryl, C ₇-C ₂₀alkaryl and C ₇-C ₂₀aralkyl;

Above-mentioned R ¹-R ⁷at random comprise one or several R atom as carbon atom or hydrogen atom or both substituents, R atom is heteroatoms, the C of straight or branched ₁-C ₂₀alkyl, C ₃-C ₂₀cycloalkyl, C ₆-C ₂₀aryl, C ₇-C ₂₀alkaryl and C ₇-C ₂₀aralkyl; Wherein R ¹-R ⁷any two groups mutually bonding generate one or more volutions, condensed ring structure.

Unsaturated ring shown in logical formula I replaces two ester compound specific exampless and is:

3,5-phenylbenzene 2H pyrroles-2,2-dicarboxylate; 3-(3-chloro-phenyl-)-5-methyl-pyrroles-2,2-dicarboxylate; 3-(3-bromophenyl)-5-methyl-pyrroles-2,2-dicarboxylate; Diethyl-3-(to chlorobenzene)-5-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Fluorenes-9,9-dioctyl phthalate dimethyl ester; Fluorenes-9,9-dicarboxylate; Fluorenes-9,9-dioctyl phthalate di-n-propyl ester; Fluorenes-9,9-dioctyl phthalate diisopropyl ester; Fluorenes-9,9-dioctyl phthalate di-n-butyl; Fluorenes-9,9-dioctyl phthalate diisobutyl ester; Fluorenes-9,9-dioctyl phthalate two n-pentyl esters; Fluorenes-9, the just own ester of 9-dioctyl phthalate two; Fluorenes-9, the positive heptyl ester of 9-dioctyl phthalate two; Fluorenes-9,9-dioctyl phthalate di-n-octyl; 9-methyl-formiate-9-ethyl formate-fluorenes; 9-methyl-formiate-9-formic acid n-propyl-fluorenes; 9-methyl-formiate-9-isopropyl formate-fluorenes; 9-methyl-formiate-9-n-buty formate-fluorenes; 9-methyl-formiate-9-tetryl formate-fluorenes; 9-ethyl formate-9-formic acid n-propyl-fluorenes; 9-ethyl formate-9-isopropyl formate-fluorenes; 9-ethyl formate-9-n-buty formate-fluorenes; 9-ethyl formate-9-tetryl formate-fluorenes; Dimethyl 4H-benzo <g> thia <2,3-e> indazole-4,4-dicarboxylic acid esters; 2H-pyrroles-2, diethyl-5-phenyl-3 (to toluene), 2-manthanoate; Diethyl-3 (to anisole)-5-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Diethyl 5-(to nitro)-3-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Diethyl-2,3-phenylbenzene-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-(4-chlorobenzene)-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-(4-p-methoxy-phenyl)-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl 3-(4-methylbenzene)-2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl-3-(4-oil of mirbane)-1H-indenes-1,1-dicarboxylic acid esters; Dimethylamino-4-five methoxycarbonyl-1,2,3,5,5-, five methoxycarbonyl cyclopentadiene; 3-phenyl-indenes-1,1-dioctyl phthalate methyl esters; Dimethyl-5-(to chlorobenzene) 3-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Dimethyl 3,4-bis-(to chlorobenzene) 2H-pyrroles-dicarboxylic acid esters; Dimethyl 3-(p-oil of mirbane)-5-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Dimethyl 3-(m-oil of mirbane)-5-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Dimethyl 5-(m-oil of mirbane)-5-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Dimethyl 5,6-dimethyl-5H, 6H-encircles penta 2 indoles-11,11-dicarboxylic acid esters; 1-(2-oil of mirbane sulphur)-2,3,4,5,5-methyl-formiate-cyclopentadiene; 1-(2,4-dinitrobenzene)-2,3,4,5,5-five methyl-formiates-cyclopentadiene; Methyl-2-the tertiary butyl-3-methyl isophthalic acid H-indenes-1,1-dicarboxylic acid esters; Dimethyl 3-methyl-2-trimethyl silicane-indenes-1,1-dicarboxylic acid esters; Dimethyl 3-methyl-2-phenyl-indenes-1,1-dicarboxylic acid esters; Diethyl-2,3-bis--n-propyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl-3-methylol-2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl-2-the tertiary butyl-5,6-dimethoxy-3-methyl isophthalic acid H-indenes-1,1-dicarboxylic acid esters; Dimethyl-2-phenyl-3-(thia-2-yl)-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl-3-(2-toluene) 2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl 3-(2-methoxycarbonyl phenyl)-2 phenyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl 3-(4-trifluoromethylbenzene) 2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl 3-(4-phenyl methyl ketone) 2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl-2-(hexamethylene 1-alkene)-3-(4-phenyl methyl ketone)-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl 2-[(ethoxy acyl group) methyl]-1H-indenes-1,1-dicarboxylic acid esters; 1,1-diethyl-1H-indenes-1,1-dicarboxylic acid esters; The chloro-5 methyl-pyrazoles of 7-[4,3-d] pyrimidine-3,3-dioctyl phthalate ethyl ester; The chloro-7-methyl-pyrazoles of 5-[4,3-d] pyrimidine-3,3-dioctyl phthalate ethyl ester; 5-amino-7-methyl-pyrazoles [4,3-d] pyrimidine-3,3-dioctyl phthalate ethyl ester; 7-methoxyl group-5-methyl-pyrazoles [4,3-d] pyrimidine-3,3-dioctyl phthalate ethyl ester; 1-p-totuidine base-2,3,4,5,5-, five methoxycarbonyl cyclopentadiene; Dimethyl-3H-phenanthro-< 9,10-c > pyrazoles-3,3-dicarboxylic acid esters; 3,3-bis-(methoxycarbonyl)-3H-indazole; 3,3-bis-(ethoxycarbonyl) 3H-indazole; 1-trichloromethyl-2,3,4,5,5-, five methoxycarbonyl cyclopentadiene; 1-(2-methyl-4-oil of mirbane)-five methoxycarbonyl cyclopentadiene; 1-(the iodo-4-oil of mirbane of 2-)-five methoxycarbonyl cyclopentadiene; 2-(the iodo-4-oil of mirbane of 2-)-1,3,4,5,5-five methoxycarbonyl cyclopentadiene; 1-(2,4-dinitrobenzene)-2,3,4,5,5-five methoxycarbonyl cyclopentadiene; 4-benzyl-1, poly-(methoxycarbonyl) cyclopentadiene of 2,3,5,5-five; 3-benzyl-1, poly-(methoxycarbonyl) cyclopentadiene of 2,4,5,5-five; 2-(trifluoromethyl)-5-carbonyl-3,3-bis-(methoxycarbonyl)-3H-indoles; 2-(trifluoromethyl)-5-carbonyl-7-methyl-3,3-bis-(methoxycarbonyl)-3H-indoles; 3-(trifluoromethyl)-5-hydroxyl-7-methoxyl group-3,3-bis-(methoxycarbonyl)-3H-indoles; 2H-pyrroles-2, diethyl-3-phenyl-5 (to toluene), 2-dicarboxylic acid esters; Diethyl-2-(4-chlorobenzene)-5-morpholine-4H-imidazoles-4,4-dicarboxylic acid esters; 4,5,5-tricarboxylic acid methyl esters-1,2,3-trichlorine cyclopentadiene; Methyl-3-methyl-4-trimethyl silicane-ring penta-2,4-diene-1,1-dicarboxylic acid esters; Diethyl-2,5-phenylbenzene-4H-imidazoles-4,4-dicarboxylic acid esters; Diethyl-3-benzyl-2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-3-(4-(methoxycarbonyl) phenyl) 2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-3-(4-acetylbenzene) 2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-methoxyl methyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl-2-the tertiary butyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-the tertiary butyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl 2-normal-butyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl 2-normal-butyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl 2-n-hexyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-(3-cyano group-1-propyl group)-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-diethoxy methyl isophthalic acid H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-(4-methoxyphenyl)-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-(1-tetrahydrobenzene)-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-(cyclohexyl)-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-3-(3-toluene)-2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-3-(3-oil of mirbane)-2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl 13H-indeno [1,2-e]-Fei-13,13-dicarboxylic acid esters; Diethyl-2-hexyl-3-(4-methoxyphenyl) 1H-indenes-1,1-dicarboxylic acid esters; Ring penta [c] thia-5,5-dioctyl phthalate ethyl ester; 4-[4-[4-(methylsulphonic acid) benzene] 1,1-bis-(methoxyl group) ring penta-2,4-diene-3-yl] pyridine; Fluorenes-4,9, the 9-dioctyl phthalate-4-tertiary butyl-9,9-dimethyl ester; 4-(4-amino-pyridine-3-base carbamyl)-fluorenes-9,9-dioctyl phthalate methyl esters; 4-(3-amino-pyridine-4-base carbamyl)-fluorenes-9,9-dioctyl phthalate dimethyl ester; The iodo-2-phenyl-1H-of diethyl-3-indenes-1,1-dicarboxylic acid esters; The iodo-2-n-pentyl-1H-of diethyl-3-indenes-1,1-dicarboxylic acid esters; The iodo-2-of diethyl-3-(3 methoxyphenyl)-1H-indenes-1,1-dicarboxylic acid esters; The iodo-2-of diethyl-3-(naphthalene-2-yl)-1H-indenes-1,1-dicarboxylic acid esters; Di-n-hexyl-fluorenes-9,9-dicarboxylic acid esters; Two n-heptyls-fluorenes-9,9-dicarboxylic acid esters; Diethyl-2-benzene-3H-indenes-3,3-dicarboxylic acid esters; The bromo-1H-of diethyl-2-indenes-1,1-dicarboxylic acid esters;

1-ethyl-1-methyl-cyclohexyl-2,5-diene-1,1-dicarboxylic acid esters; N, 4,4-, tri-ethoxy carbon back-Isosorbide-5-Nitrae-dihydro-pyridines; 2,6-phenylbenzene-4,4-dimethoxycarbonyl-4H-pyrans; 2,6-phenylbenzene-4,4-dimethoxycarbonyl-Isosorbide-5-Nitrae-dihydropyridine; 2,6-bis-(4-chlorobenzene)-4,4-dimethoxycarbonyl-4H-pyrans; 2,6-bis-(4-methoxyphenyl)-4,4-dimethoxycarbonyl-4H-pyrans; 2,6-bis-(4-chlorobenzene)-4,4-dimethoxycarbonyl-Isosorbide-5-Nitrae-dihydropyridine; 2,6-bis-(4-methoxyphenyl)-4,4-dimethoxycarbonyl-Isosorbide-5-Nitrae-dihydropyridine; 1-cyclopentyl-4,4-bis-(methoxycarbonyl)-Isosorbide-5-Nitrae-dihydropyridine; 1-n-hexyl-4,4-bis-(methoxycarbonyl)-Isosorbide-5-Nitrae-dihydropyridine; 1-methoxy-6,6-bis-methanoyl methyl-cyclohexyl-Isosorbide-5-Nitrae-diene; Dimethyl Isosorbide-5-Nitrae-dihydronaphthalene-1,1-dicarboxylic acid esters; 2,6-bis-(4-chlorobenzene)-4,4-dimethoxy acyl group-4H-thiapyran; Diethyl-3-bromo-Isosorbide-5-Nitrae-dihydro-1-methyl pyridazino[3,4-b] quinoxaline-4,4-dicarboxylic acid esters; The bromo-3-of diethyl-5-phenyl-Isosorbide-5-Nitrae-dihydrogen dazin-4,4-dicarboxylic acid esters; Three hexyls-3-phenyl-Isosorbide-5-Nitrae-dihydrogen dazin-4,4,5-front three acid esters; 1-styroyl-bis-(methoxy acyl group) Isosorbide-5-Nitrae-dihydropyridine; Diethyl-2-methyl-6-benzene (4H-pyrans) 4,4-dicarboxylic acid esters; 1-(2-menaphthyl)-4,4-bis-(methoxy acyl group)-Isosorbide-5-Nitrae-dihydropyridine; Dimethyl-3-ethanoyl-1-toluquinoline-4,4 (1H)-dicarboxylic acid esters.

The compound of logical formula I preferably includes the compound of logical formula II:

Wherein R ¹-R ⁶group is as the definition in logical formula I, R ³-R ⁶for identical or different groups.

The compound of logical formula II preferably includes the compound of logical formula III:

Wherein R ¹-R ²group is as the definition in logical formula I, and R ' is the C of identical or not identical hydrogen, halogen atom, straight or branched ₁-C ₂₀alkyl, C ₃-C ₂₀cycloalkyl, C ₆-C ₂₀aryl, C ₇-C ₂₀alkaryl and C ₇-C ₂₀aralkyl.

In 5-membered ring compounds shown in logical formula III, more suitable particular compound example has:

Fluorenes-9,9-dioctyl phthalate dimethyl ester; Fluorenes-9,9-dicarboxylate; Fluorenes-9,9-dioctyl phthalate di-n-propyl ester; Fluorenes-9,9-dioctyl phthalate diisopropyl ester; Fluorenes-9,9-dioctyl phthalate di-n-butyl; Fluorenes-9,9-dioctyl phthalate diisobutyl ester; Fluorenes-9,9-dioctyl phthalate two n-pentyl esters; Fluorenes-9, the just own ester of 9-dioctyl phthalate two; Fluorenes-9, the positive heptyl ester of 9-dioctyl phthalate two; Fluorenes-9,9-dioctyl phthalate di-n-octyl; 9-methyl-formiate-9-ethyl formate-fluorenes; 9-methyl-formiate-9-formic acid n-propyl-fluorenes; 9-methyl-formiate-9-isopropyl formate-fluorenes; 9-methyl-formiate-9-n-buty formate-fluorenes; 9-methyl-formiate-9-tetryl formate-fluorenes, 9-ethyl formate-9-formic acid n-propyl-fluorenes; 9-ethyl formate-9-isopropyl formate-fluorenes; 9-ethyl formate-9-n-buty formate-fluorenes; 9-ethyl formate-9-tetryl formate-fluorenes.

Catalyzer of the present invention can be used for alkene CH ₂in=CHR (being total to) polymerization, described alkene optimal ethylene, propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene and 1-octene.

For the catalyzer of applying in the present invention carries out olefinic polymerization, homopolymerization and copolymerization can be applied above-mentioned by component a, b, the prepared catalyzer of c.Conventionally the mol ratio of components b and component a is that the every mol of 1-1000mol is contained in the titanium atom in component a, is preferably the every mol of 50-800mol and is contained in the titanium atom in component a; The mol ratio of amount of component b and component a is 0.002-10, is preferably 0.01-2, is preferably 0.01-0.5.

The order of addition(of ingredients) of each component is arbitrarily, joins at first in paradigmatic system with components b, then adds amount of component b, and it is good finally adding component a.

Polymerization technique in the present invention can carry out in the situation that having solvent or there is no solvent.Olefinic monomer can be gas phase or liquid phase.Further add hydrogen to can be used as molecular weight regulator.Certainly polymerization also can be carried out in the situation that there is no molecular weight regulator.Polymerization temperature is higher than 200 DEG C, preferably 20-100 DEG C, the more preferably temperature of 40-80 DEG C.Polymerization pressure does not exceed 10MPa, preferably 1-5MPa.Successive polymerization or batchwise polymerization technique can be applied.And polyreaction can divide a step, two steps or multistep to carry out.

Apply the alkene that catalyzer of the present invention carries out homopolymerization or copolymerization and comprise, normal olefine: ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-nonene, 1-decene; Branched-chain alkene is as 3-methyl-1-butene and 4-methyl-1-pentene; Diolefine is as divinyl, vinyl cyclopentenes and vinyl cyclohexene.Catalyzer of the present invention is preferably applied in polyethylene and polypropylene.These alkene can independent or multiple mixing use.

Apply the polymerization (referring to main body polymerization here) of the alkene that catalyst component a of the present invention, b, c carry out, recommend degree of isotacticity, the particle properties etc. of the reactive polymer that carries out the incompatible increase catalyzer of pre-polymerization.This prepolymerization technology equally can be for vinylbenzene homopolymerization.

In prepolymerization technology, the order of addition(of ingredients) of each component and monomer is arbitrarily.Preferably first components b is joined and contain inertia and maybe will carry out in the alkene gas of polymerization, then after component a, add one or more alkene of wanting polymerization adding.In the prepolymerized process of alkene of application organosilane, suggestion joins components b in the prepolymerization system of olefin gas that rare gas element maybe will carry out polymerization, then adds amount of component b, then adds component a, finally adds alkene again.

The present invention adopts the bifunctional compound with ad hoc structure, the unsaturated ring as shown in logical formula I replaces two ester compounds, the contained specific ring of this compounds replaces structure, there is steric effect and can fix the steric configuration of Liang Ge acid esters functional group, participating in the formation of catalyst active center and the stereospecificity that improves catalyzer is had to positive effect.Because the oxygen of ester bond has stronger coordination effect, and relatively stable in the preparation process of catalyzer, can avoid to a certain extent being extracted by aluminum alkyls in polymerization process, therefore, while adopting compound of the present invention as the internal electron donor of ziegler natta catalyst, the catalyzer of gained has higher activity and stereospecificity conventionally.

If the degree of isotacticity of polymkeric substance is had to higher requirement, can in polymerization process, add external electron donor, the inventor finds, add compound of the present invention as external electron donor in polymerization process time, can keep catalyst activity, can obtain again the polymkeric substance of high isotactic.And for the catalyst component that contains dissimilar internal electron donor, when this unsaturated ring replaces two ester compounds as external electron donor, the activity to catalyst system and stereospecificity all can be brought into play good effect.

Summary of the invention

The present invention makes in view of the aforementioned technical background, and its object is to provide a kind of unsaturated ring taking ad hoc structure to replace the catalyst component for olefinic polymerization of two acid esters as component.

Contriver finds simultaneously, and this unsaturated ring replaces two acid esters compounds and contains two functional groups with superperformance, and has specific ring texture to play the steric configuration of steric hindrance and bifunctional.When the catalyst component that contains different types of internal electron donor when employing carries out propylene polymerization, use unsaturated ring to replace two acid esters for external electron donor, can obtain with high yield having the polypropylene product of high isotactic.

Another object of the present invention is to provide this unsaturated ring to replace the novel catalyst system that two acid esters compounds are external electron donor.

In order to realize object of the present invention, the invention provides a kind of catalyst component of olefinic polyreaction, (CH ₂=CHR alkene, wherein R is hydrogen or the hydrocarbyl group containing 1-12 carbon atom), described catalyst component comprises magnesium halide (the general crystal magnesium halide compound with regular structure that is activity morphology, portative Ti is little, thereby catalytic activity is low, prepare highly active supported catalyst, magnesium halide must pass through activation treatment.Activating treatment process comprise with physics and/or chemistry method be made into crystallite, so that active centre is carried on magnesium halide surface, edge and fault location, the magnesium halide crystallite that is suitable for load Ti of this processing is " magnesium halide in active "), and the carrying titanium compound that contains at least one Ti-halogen key thereon replaces two ester compounds with at least one the unsaturated ring that is selected from following logical formula I:

In the time that n equals 0:

IX) A, B, C and D are carbon atom, and X, Y, Z and W are 1; Or

X) A is nitrogen-atoms, and B, C and D are carbon atom, and W is that 0, X, Y and Z are 1; Or

XI) A and D are nitrogen-atoms, and B and C are carbon atom, and W and Z are that 0, X and Y are 1; Or

XII) D is nitrogen-atoms, and A, B and C are carbon atom, and Z is that 0, W, X and Y are 1; Or

In the time that n equals 1:

Vii) A, B, C, D and E are carbon atom, and m is that 2, W, X, Y and Z are 1; Or

Viii) E is nitrogen-atoms, and A, B, C and D are carbon atom, and m is that 1, W, X, Y and Z are 1; Or

Ix) E is Sauerstoffatom, and A, B, C and D are carbon atom, and m is that 0, W, X, Y and Z are 1; Or

V) E is sulphur atom, and A, B, C and D are carbon atom, and m is that 0, W, X, Y and Z are 1; Or

Vi) D and E are nitrogen-atoms, and A, B and C are carbon atom, and m is that 1, W, X and Y are that 1, Z is 0.

According to another example, the reaction product that olefin polymerization catalysis provided by the invention contains following material:

(A) as the catalyst component limiting above;

(B) at least one general formula is AlR _nx _(3-n)organo-aluminium compound, in formula, R is the alkyl of hydrogen, carbonatoms 1-20; X is halogen, the integer that n is 0≤n≤3; And as optional components,

(C) a kind of electron donor compound.

Wherein, described organo-aluminium compound (B) is a kind of trialkyl aluminium compound.Described trialkyl aluminium compound is selected from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, trioctylaluminum.

It is R that described electron donor compound (C) is selected from general formula _nsi (OR ₁) _4-nsilicone compounds, R and R in formula ₁for C ₁-C ₁₈alkyl, optionally also have heteroatoms; N is the integer of 0≤n≤3.

According to another example, olefin polymerization catalysis provided by the invention comprises that a kind of general formula is AlR _nx _(3-n)organo-aluminium compound (in formula, R is the alkyl of hydrogen, carbonatoms 1-20, X is halogen, n is the integer of 0≤n≤3) and the unsaturated ring of logical formula I replace the reaction product of two ester compounds and a kind of ingredient of solid catalyst (a), this ingredient of solid catalyst (a) contains a kind of magnesium halide that is activity morphology, and the carrying titanium compound that contains at least one Ti-halogen key and a kind of electron donor compound thereon.

Catalyst component (A) is a kind of preferred embodiment of catalyst component (a).

The unsaturated ring as shown in logical formula I that Kaolinite Preparation of Catalyst component (A) adopts replaces two ester compound specific exampless and is:

3,5-phenylbenzene 2H pyrroles-2,2-dicarboxylate; 3-(3-chloro-phenyl-)-5-methyl-pyrroles-2,2-dicarboxylate; 3-(3-bromophenyl)-5-methyl-pyrroles-2,2-dicarboxylate; Diethyl-3-(to chlorobenzene)-5-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Fluorenes-9,9-dioctyl phthalate dimethyl ester; Fluorenes-9,9-dicarboxylate; Fluorenes-9,9-dioctyl phthalate di-n-propyl ester; Fluorenes-9,9-dioctyl phthalate diisopropyl ester; Fluorenes-9,9-dioctyl phthalate di-n-butyl; Fluorenes-9,9-dioctyl phthalate diisobutyl ester; Fluorenes-9,9-dioctyl phthalate two n-pentyl esters; Fluorenes-9, the just own ester of 9-dioctyl phthalate two; Fluorenes-9, the positive heptyl ester of 9-dioctyl phthalate two; Fluorenes-9,9-dioctyl phthalate di-n-octyl; 9-methyl-formiate-9-ethyl formate-fluorenes; 9-methyl-formiate-9-formic acid n-propyl-fluorenes; 9-methyl-formiate-9-isopropyl formate-fluorenes; 9-methyl-formiate-9-n-buty formate-fluorenes; 9-methyl-formiate-9-tetryl formate-fluorenes; 9-ethyl formate-9-formic acid n-propyl-fluorenes; 9-ethyl formate-9-isopropyl formate-fluorenes; 9-ethyl formate-9-n-buty formate-fluorenes; 9-ethyl formate-9-tetryl formate-fluorenes dimethyl 4H-benzo <g> thia <2,3-e> indazole-4,4-dicarboxylic acid esters; 2H-pyrroles-2, diethyl-5-phenyl-3 (to toluene), 2-manthanoate; Diethyl-3 (to anisole)-5-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Diethyl 5-(to nitro)-3-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Diethyl-2,3-phenylbenzene-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-(4-chlorobenzene)-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-(4-p-methoxy-phenyl)-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl 3-(4-methylbenzene)-2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl-3-(4-oil of mirbane)-1H-indenes-1,1-dicarboxylic acid esters; Dimethylamino-4-five methoxycarbonyl-1,2,3,5,5-, five methoxycarbonyl cyclopentadiene; 3-phenyl-indenes-1,1-dioctyl phthalate methyl esters; Dimethyl-5-(to chlorobenzene) 3-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Dimethyl 3,4-bis-(to chlorobenzene) 2H-pyrroles-dicarboxylic acid esters; Dimethyl 3-(p-oil of mirbane)-5-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Dimethyl 3-(m-oil of mirbane)-5-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Dimethyl 5-(m-oil of mirbane)-5-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Dimethyl 5,6-dimethyl-5H, 6H-encircles penta 2 indoles-11,11-dicarboxylic acid esters; 1-(2-oil of mirbane sulphur)-2,3,4,5,5-methyl-formiate-cyclopentadiene; 1-(2,4-dinitrobenzene)-2,3,4,5,5-five methyl-formiates-cyclopentadiene; Methyl-2-the tertiary butyl-3-methyl isophthalic acid H-indenes-1,1-dicarboxylic acid esters; Dimethyl 3-methyl-2-trimethyl silicane-indenes-1,1-dicarboxylic acid esters; Dimethyl 3-methyl-2-phenyl-indenes-1,1-dicarboxylic acid esters; Diethyl-2,3-bis--n-propyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl-3-methylol-2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl-2-the tertiary butyl-5,6-dimethoxy-3-methyl isophthalic acid H-indenes-1,1-dicarboxylic acid esters; Dimethyl-2-phenyl-3-(thia-2-yl)-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl-3-(2-toluene) 2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl 3-(2-methoxycarbonyl phenyl)-2 phenyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl 3-(4-trifluoromethylbenzene) 2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl 3-(4-phenyl methyl ketone) 2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl-2-(hexamethylene 1-alkene)-3-(4-phenyl methyl ketone)-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl 2-[(ethoxy acyl group) methyl]-1H-indenes-1,1-dicarboxylic acid esters; 1,1-diethyl-1H-indenes-1,1-dicarboxylic acid esters; The chloro-5 methyl-pyrazoles of 7-[4,3-d] pyrimidine-3,3-dioctyl phthalate ethyl ester; The chloro-7-methyl-pyrazoles of 5-[4,3-d] pyrimidine-3,3-dioctyl phthalate ethyl ester; 5-amino-7-methyl-pyrazoles [4,3-d] pyrimidine-3,3-dioctyl phthalate ethyl ester; 7-methoxyl group-5-methyl-pyrazoles [4,3-d] pyrimidine-3,3-dioctyl phthalate ethyl ester; 1-p-totuidine base-2,3,4,5,5-, five methoxycarbonyl cyclopentadiene; Dimethyl-3H-phenanthro-< 9,10-c > pyrazoles-3,3-dicarboxylic acid esters; 3,3-bis-(methoxycarbonyl)-3H-indazole; 3,3-bis-(ethoxycarbonyl) 3H-indazole; 1-trichloromethyl-2,3,4,5,5-, five methoxycarbonyl cyclopentadiene; 1-(2-methyl-4-oil of mirbane)-five methoxycarbonyl cyclopentadiene; 1-(the iodo-4-oil of mirbane of 2-)-five methoxycarbonyl cyclopentadiene; 2-(the iodo-4-oil of mirbane of 2-)-1,3,4,5,5-five methoxycarbonyl cyclopentadiene; 1-(2,4-dinitrobenzene)-2,3,4,5,5-five methoxycarbonyl cyclopentadiene; 4-benzyl-1, poly-(methoxycarbonyl) cyclopentadiene of 2,3,5,5-five; 3-benzyl-1, poly-(methoxycarbonyl) cyclopentadiene of 2,4,5,5-five; 2-(trifluoromethyl)-5-carbonyl-3,3-bis-(methoxycarbonyl)-3H-indoles; 2-(trifluoromethyl)-5-carbonyl-7-methyl-3,3-bis-(methoxycarbonyl)-3H-indoles; 3-(trifluoromethyl)-5-hydroxyl-7-methoxyl group-3,3-bis-(methoxycarbonyl)-3H-indoles; 2H-pyrroles-2, diethyl-3-phenyl-5 (to toluene), 2-dicarboxylic acid esters; Diethyl-2-(4-chlorobenzene)-5-morpholine-4H-imidazoles-4,4-dicarboxylic acid esters; 4,5,5-tricarboxylic acid methyl esters-1,2,3-trichlorine cyclopentadiene; Methyl-3-methyl-4-trimethyl silicane-ring penta-2,4-diene-1,1-dicarboxylic acid esters; Diethyl-2,5-phenylbenzene-4H-imidazoles-4,4-dicarboxylic acid esters; Diethyl-3-benzyl-2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-3-(4-(methoxycarbonyl) phenyl) 2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-3-(4-acetylbenzene) 2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-methoxyl methyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl-2-the tertiary butyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-the tertiary butyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl 2-normal-butyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl 2-normal-butyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl 2-n-hexyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-(3-cyano group-1-propyl group)-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-diethoxy methyl isophthalic acid H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-(4-methoxyphenyl)-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-(1-tetrahydrobenzene)-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-(cyclohexyl)-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-3-(3-toluene)-2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-3-(3-oil of mirbane)-2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl 13H-indeno [1,2-e]-Fei-13,13-dicarboxylic acid esters; Diethyl-2-hexyl-3-(4-methoxyphenyl) 1H-indenes-1,1-dicarboxylic acid esters; Ring penta [c] thia-5,5-dioctyl phthalate ethyl ester; 4-[4-[4-(methylsulphonic acid) benzene] 1,1-bis-(methoxyl group) ring penta-2,4-diene-3-yl] pyridine; Fluorenes-4,9, the 9-dioctyl phthalate-4-tertiary butyl-9,9-dimethyl ester; 4-(4-amino-pyridine-3-base carbamyl)-fluorenes-9,9-dioctyl phthalate methyl esters; 4-(3-amino-pyridine-4-base carbamyl)-fluorenes-9,9-dioctyl phthalate dimethyl ester; The iodo-2-phenyl-1H-of diethyl-3-indenes-1,1-dicarboxylic acid esters; The iodo-2-n-pentyl-1H-of diethyl-3-indenes-1,1-dicarboxylic acid esters; The iodo-2-of diethyl-3-(3 methoxyphenyl)-1H-indenes-1,1-dicarboxylic acid esters; The iodo-2-of diethyl-3-(naphthalene-2-yl)-1H-indenes-1,1-dicarboxylic acid esters; Di-n-hexyl-fluorenes-9,9-dicarboxylic acid esters; Two n-heptyls-fluorenes-9,9-dicarboxylic acid esters; Diethyl-2-benzene-3H-indenes-3,3-dicarboxylic acid esters; The bromo-1H-of diethyl-2-indenes-1,1-dicarboxylic acid esters;

Wherein R ¹-R ⁶group is as the definition in logical formula I.

Wherein R ¹, R ²group is as the definition in logical formula I, and R ' is the C of identical or not identical hydrogen, halogen atom, straight or branched ₁-C ₂₀alkyl, C ₃-C ₂₀cycloalkyl, C ₆-C ₂₀aryl, C ₇-C ₂₀alkaryl and C ₇-C ₂₀aralkyl.

Unsaturated ring of the present invention replaces malonic ester can be synthetic by various reactions.One of them is synthetic by following formula three-step reaction: steps A is to react with carbonic acid gas and alkyl lithium reagents encircling accordingly substitution compound, or reacts with alkyl-dimethyl ester and sodium hydride and be prepared into cyclic hydrocarbon radical replacement formic acid (can referring to US4564700A1); Step B is by upper step product and corresponding alcohol R ¹oH reaction esterification is manthanoate, or with suitable ester class precursor direct addition be that cyclic hydrocarbon replaces formic acid fat (can be referring to JournaloftheChemicalSociety, 1949, P2182,2185); Step C be by upper step product with prepare (can referring to Analytical Chemistry, vol.32, NO.4, April1960) with the precursor addition of suitable haloformate.

In addition, when unsaturated ring replaces two ester compound R ¹and R ²when identical, available corresponding unsaturated ring substitution compound directly prepares with lithium reagent (as n-Butyl Lithium or lithium diisopropyl amido) and haloformate single step reaction, and each substituting group leads to together definition in formula I (can referring to TetrahedronLetters50 (2009) 6057-6059):

Ingredient of solid catalyst for olefinic polymerization of the present invention (a), the reaction product that comprises titanium compound, magnesium compound and a kind of electron donor compound, described electron donor compound is the Lewis alkali that contains one or more electronegativity groups, and electron donor atom is wherein selected from the group of N, O, S, P, As or Sn composition; Described magnesium compound precursor is selected from least one: Mg (OR) ₂, X _nmg (OR) _2-n, MgCl ₂mROH, R _2-nmgX _n, MgR ₂, MgCl ₂/ SiO ₂, MgCl ₂/ Al ₂o ₃, or the mixture of magnesium halide and alcohol titanium, the number that in formula, m is 0.1-6,0<n<2, X is halogen, R is C ₁-C ₂₀alkyl; The general formula of described titanium compound is TiX _n(OR) _4-n, in formula, R is that carbonatoms is the alkyl of 1-20, X is halogen, n=1-4.

Embodiment

Further describe the present invention with embodiment below, be conducive to the understanding to the present invention and advantage thereof, better effects if, but described embodiment is only for illustrating the present invention instead of restriction the present invention.

unsaturated ring replaces the preparation of two ester compounds

Synthesizing of embodiment 1 fluorenes-9-methyl-formiate-9-ethyl formate

Steps A: add successively 18g sodium hydride, 50g fluorenes, 150mL toluene in 1000mL there-necked flask under nitrogen protection, open mechanical stirring, be warming up to 125 DEG C of backflows, keep reaction 4h; Be cooled to 90 DEG C, in flask, slowly drip 146.1g diethyl carbonate, in 1.5h, drip off, drip off rear continuation reaction 3h; Be cooled to 20 DEG C, slowly splash into the mixture of 60g concentrated hydrochloric acid and 75g water, and control temperature and be no more than 40 DEG C; Filter, isolate organic phase, wash with water to neutrality, organic phase is revolved steaming, obtains reddish-brown liquid; Reflux and spend the night revolving together with the hydrochloric acid that steams gained liquid and 157.4g acetic acid and 63g10%; Mixture is down to 20 DEG C, separatory; Organic phase adds 30%NaOH solution after revolving steaming, regulates pH value to 8～9, is extracted with ethyl acetate, and retains water.Water adds concentrated hydrochloric acid to regulate pH value to be extracted with ethyl acetate to 5-6, retains organic phase, and organic phase is revolved steaming; Product acetic acid ethyl dissolution, freezing recrystallization; Filter, thick product washs with hexane.Obtain the about 10g of clear crystal, fusing point: 228～230 DEG C.

In step B:250mL there-necked flask, add 9-formic acid fluorenes 2g (9.5mmol), methyl alcohol (30mL), the vitriol oil (0.2mL); Reflux 2h; Be cooled to room temperature; Reaction solution is poured in saturated sodium bicarbonate solution, and ethyl acetate extraction secondary (30mL*2) merges organic phase, saturated common salt washing (30mL*1), underpressure distillation, obtains yellow solid, oil pump is drained, and obtains the thick product of 1.8g, fusing point 62-65 DEG C.

In tri-mouthfuls of round-bottomed flasks of step C:250mL, add methyl alcohol (20mL), sodium Metal 99.5 (0.12g, 5mmol), under ice bath, after sodium Metal 99.5 dissolves emerge without bubble completely, add 9-methyl-formiate fluorenes (0.56g, 2.5mmol), dissolve completely, be yellow, after stirring 5min, add Vinyl chloroformate (0.8g, 7.5mmol); Stir 30min, pour in the aqueous solution, merge organic phase with using ethyl acetate extracting twice (50mL*2) after dichloromethane extraction (20mL*2) instead, saturated common salt washing (50mL*1), revolve and steam liquid, hexane washing, crude product sherwood oil recrystallization, obtain product, 106-109 DEG C.

Fluorenes-9-methyl-formiate-9-ethyl formate ¹h-NMR (CDCl ₃) δ (ppm): 0.982-1.014 (t, 3H, methyl hydrogen), 3.758 (s, 3H, the adjacent methyl hydrogen of oxygen), 4.130-4.156 (m, 2H, the adjacent methylene radical hydrogen of oxygen), 7.356-7.388 (t, 2H, aromatic ring hydrogen), (7.439-7.470 t, 2H, aromatic ring hydrogen), (7.714-7.728 d, 2H, aromatic ring hydrogen), (7.790-7.7804 d, 2H, aromatic ring hydrogen).

Embodiment 2 fluorenes-9,9-dicarboxylate synthetic

By (1.6M, n-Butyl Lithium/hexane solution 15mmol) is added drop-wise in the 20mL tetrahydrofuran solution that contains 16mmol diisopropylamine at-78 DEG C, above-mentioned solution stirs 45 minutes at-78 DEG C, and at 0 DEG C, stirs after 20 minutes and cool to-78 DEG C again.At-78 DEG C, the 20mL tetrahydrofuran solution that contains 7.0mmol fluorenes was added drop-wise in the above-mentioned solution stirring in 30 minutes, the Vinyl chloroformate of 33mmol is added in said mixture.Reaction system is warming up to room temperature, and at room temperature stirs 3 hours.Above-mentioned reaction mixture is poured in 100mL water, and by extracted with diethyl ether (three extractions, each 50mL ether), organic phase dried over mgso, the concentrated rear thick product of gained sherwood oil recrystallization, obtains product, 100-101 DEG C.

Fluorenes-9,9-dicarboxylate ¹h-NMR (CDCl ₃) δ (ppm): 0.932-0.962 (t, 6H, methyl hydrogen), 4.132-4.158 (m, 4H, the adjacent methylene radical hydrogen of oxygen), (7.392-7.424 t, 2H, aromatic ring hydrogen), (7.448-7.480 t, 2H, aromatic ring hydrogen), (7.734-7.748 d, 2H, aromatic ring hydrogen), (7.890-7.906 d, 2H, aromatic ring hydrogen)

Embodiment 3 fluorenes-9,9-dioctyl phthalate dimethyl ester synthetic

Synthesis step is with embodiment 2, and difference is for to be changed to methyl-chloroformate by Vinyl chloroformate.

Fluorenes-9,9-dioctyl phthalate dimethyl ester ¹h-NMR (CDCl ₃) δ (ppm): 3.759 (s, 6H, methyl hydrogen), (7.359-7.392 t, 2H, aromatic ring hydrogen), (7.443-7.475 t, 2H, aromatic ring hydrogen), 7.720-7.735 (d, 2H, aromatic ring hydrogen), 7.799-7.7814 (d, 2H, aromatic ring hydrogen).

Embodiment 4 fluorenes-9,9-dioctyl phthalate di-n-propyl ester synthetic

Synthesis step is with embodiment 2, and difference is for to be changed to chloroformic acid n-propyl by Vinyl chloroformate.

Fluorenes-9,9-dioctyl phthalate di-n-propyl ester ¹h-NMR (CDCl ₃) δ (ppm): 0.936-0.966 (t, 6H, methyl hydrogen), 1.664-1.735 (m, 4H, methylene radical hydrogen), 4.171-4.197 (t, 4H, the adjacent methylene radical hydrogen of oxygen), 7.389-7.421 (t, 2H, aromatic ring hydrogen), (7.449-7.481 t, 2H, aromatic ring hydrogen), (7.737-7.752 d, 2H, aromatic ring hydrogen), (7.887-7.902 d, 2H, aromatic ring hydrogen).

Embodiment 5 fluorenes-9,9-dioctyl phthalate diisopropyl ester synthetic

Synthesis step is with embodiment 2, and difference is for to be changed to isopropyl chlorocarbonate by Vinyl chloroformate.

Fluorenes-9,9-dioctyl phthalate diisopropyl ester ¹h-NMR (CDCl ₃) δ (ppm): 1.282-1.295 (t, 12H, methyl hydrogen), 5.012-5.062 (m, 4H, the adjacent methyne hydrogen of oxygen), (7.215-7.295 t, 2H, aromatic ring hydrogen), (7.307-7.354 t, 2H, aromatic ring hydrogen), (7.356-7.371 d, 2H, aromatic ring hydrogen), (7.654-7.686 d, 2H, aromatic ring hydrogen).

Embodiment 6 fluorenes-9,9-dioctyl phthalate di-n-butyl synthetic

Synthesis step is with embodiment 2, and difference is for to be changed to butyl chloroformate by Vinyl chloroformate.

Fluorenes-9,9-dioctyl phthalate di-n-butyl ¹h-NMR (CDCl ₃) δ (ppm): 0.937-0.967 (t, 6H, methyl hydrogen), (1.363-1.438 m, 4H, methylene radical hydrogen), (1.642-1.699 m, 4H, methylene radical hydrogen), 4.220-4.246 (oxygen faces methylene radical hydrogen for t, 4H), 7.394-7.426 (t, 2H, aromatic ring hydrogen), 7.447-7.479 (t, 2H, aromatic ring hydrogen), 7.734-7.749 (d, 2H, aromatic ring hydrogen), (7.889-7.904 d, 2H, aromatic ring hydrogen).

Embodiment 7 fluorenes-9,9-dioctyl phthalate diisobutyl ester synthetic

Synthesis step is with embodiment 2, and difference is for to be changed to isobutyl chlorocarbonate by Vinyl chloroformate.

Fluorenes-9,9-dioctyl phthalate diisobutyl ester ¹h-NMR (CDCl ₃) δ (ppm): 0.919-0.932 (d, 12H, methyl hydrogen), 1.936-2.016 (m, 2H, methyne hydrogen), 3.982-3.995 (d, 4H, the adjacent methylene radical hydrogen of oxygen), 7.372-7.405 (t, 2H, aromatic ring hydrogen), (7.440-7.473 t, 2H, aromatic ring hydrogen), (7.728-7.743 d, 2H, aromatic ring hydrogen), (7.868-7.883 d, 2H, aromatic ring hydrogen).

Embodiment 8 fluorenes-9,9-dioctyl phthalate dibenzyl ester synthetic

Synthesis step is with embodiment 2, and difference is for to be changed to benzyl chloroformate by Vinyl chloroformate.

Fluorenes-9,9-dioctyl phthalate dibenzyl ester ¹h-NMR (CDCl ₃) δ (ppm): 5.186-5.212 (s, 4H, methylene radical hydrogen), 7.372-7.405 (t, 2H, aromatic ring hydrogen), 7.384-7.426 (t, 6H, aromatic ring hydrogen), 7.440-7.473 (t, 2H, aromatic ring hydrogen), (7.478-7.602 d, 4H, aromatic ring hydrogen), (7.728-7.743 d, 2H, aromatic ring hydrogen), (7.868-7.883 d, 2H, aromatic ring hydrogen).

Table 1 encircles substituted fluorene two acid esters examples

the preparation of ingredient of solid catalyst

In embodiment, the operation of Kaolinite Preparation of Catalyst is all carried out under high pure nitrogen protection.Specific embodiment is as follows.

Embodiment 9

In 5 mouthfuls of flasks with stirring of fully replacing through nitrogen at 500ml, add 10g diethoxy magnesium and the prepare suspension of 80mL toluene, then maintain-15 DEG C and drip titanium tetrachloride 20mL, after system being slowly warming up to 10 DEG C after dropwising, drip titanium tetrachloride 60mL, slowly be warming up to again 80 DEG C afterwards, add 3.5g fluorenes-9,9-dicarboxylate, then continue to be warming up to 120 DEG C of constant temperature 2 hours, then by clean liquid press filtration, elimination liquid, the solid of gained washs 3 times at 125 DEG C with 120mL titanium tetrachloride.The solid of gained washs 2 times at 60 DEG C with 150mL hexane, room temperature washing 2 times, elimination liquid is also dry, obtains 10.34g pressed powder and is ingredient of solid catalyst, analyzing titanium content is 3.04 (wt) %, and fluorenes two acid and esters contents are 16.50 (wt) %.

Embodiment 10

In 5 mouthfuls of flasks with stirring of fully replacing through nitrogen at 500ml, add 10g diethoxy magnesium and the prepare suspension of 80mL toluene, then maintain 10 DEG C and drip titanium tetrachloride 20mL.After dropwising, system is slowly warming up to 80 DEG C, add 3.6mLDNBP (dibutyl phthalate), then continue to be warming up to 110 DEG C of constant temperature 2 hours, then by clean liquid press filtration, elimination liquid, the solid of gained washs 3 times at 90 DEG C with 100mL toluene.Then add the mixed solution of 40mL titanium tetrachloride and 80mL toluene to be warming up to 110 DEG C of stir process 1 hour, elimination liquid, the solid of gained washs 5 times at 60 DEG C with 100mL hexane, elimination liquid is also dry, obtain 9.5g pressed powder and be ingredient of solid catalyst, analyzing titanium content is 2.57 (wt) %, and DNBP content is 13.49 (wt) %.

Embodiment 11

Preparation method is with embodiment 10, difference is with 3.5g9, two (methoxyl methyl) fluorenes of 9-replace dibutyl phthalate, obtain 9.5g pressed powder and be ingredient of solid catalyst, analyzing titanium content is 3.02 (wt) %, two (methoxyl methyl) fluorenes content of 9,9-is 20.42 (wt) %.

polymerization

Component using solid catalyst as olefin polymerization catalysis is carried out polymerization evaluation:

Embodiment 12

At 5L stainless steel cauldron after nitrogen is fully replaced, adding 5mL concentration is the triethyl aluminum hexane solution of 0.5mol/L and the catalyzer 10mg of 1mmol external donor compound CMMS and embodiment 9, then add 10mL hexane to rinse charge line, add again 2L (under standard state) hydrogen, with the refining propylene of 2.5L, control reaction 20 DEG C of pre-polymerizations 5 minutes, be warming up to 70 DEG C, polyreaction 1 hour at this temperature.After reaction finishes, reactor is lowered the temperature and stop stirring and discharge reaction product, drying obtains polymkeric substance.(tap density of polymkeric substance adopts JB/T2412-2008 method, and degree of isotacticity adopts JB/T3682-2000 method.)

Embodiment 13

Polymerization process is with embodiment 12, and difference is for to be changed to DDS by CMMS.

Embodiment 14

Polymerization process is with embodiment 12, and difference is for to be changed to DPDMS by CMMS.

Embodiment 15

Polymerization process is with embodiment 12, and difference is for to be changed to DIBDMS by CMMS.

Embodiment 16

Polymerization process is with embodiment 12, and difference is for to be changed to fluorenes-9 by CMMS, 9-dicarboxylate.

Embodiment 17

Polymerization process is with embodiment 12, and difference is not for adding external electron donor.

Embodiment 18

Polymerization process is with embodiment 12, and difference is for to be changed to embodiment 10 catalyzer by embodiment 9 catalyzer, and CMMS is changed to fluorenes-9,9-dicarboxylate.

Embodiment 19

Polymerization process is with embodiment 12, and difference is for to be changed to embodiment 11 catalyzer by embodiment 9 catalyzer, and CMMS is changed to fluorenes-9,9-dicarboxylate.

Comparative example 1

Polymerization process is with embodiment 12, and difference is for to be changed to embodiment 10 catalyzer by embodiment 9 catalyzer.

Comparative example 2

Polymerization process is with embodiment 12, and difference, for embodiment 9 catalyzer are changed to embodiment 10 catalyzer, does not add external electron donor.

Comparative example 3

Polymerization process is with embodiment 12, and difference, for embodiment 9 catalyzer are changed to embodiment 11 catalyzer, does not add external electron donor.

Comparative example 4

Polymerization process is with embodiment 12, and difference is for to be changed to embodiment 11 catalyzer by embodiment 9 catalyzer.

Table 2 polymerization result

[note] dimethoxydiphenylsilane (DDS)

Cyclohexyl dimethoxy silane (CMMS),

Second, isobutyl dimethoxy silane (DIBDMS),

N-butyl phthalate (DNBP)

Shown by table 2 polymerization result, employing is selected from the catalyzer that fluorenes two acid esters that unsaturated ring replaces diester compound are prepared as internal electron donor, while coordinating different types of external donor compound for propylene polymerization, compare DNBP and 9, the catalyzer of two (methoxyl methyl) fluorenes internal electron donors of 9-, can obtain quite or higher levels of activity, and the polyacrylic degree of isotacticity of gained is higher.In the time that fluorenes two ester compounds use as external electron donor, coordinate different internal electron donor compounds, also can obtain and compare while using other external electron donor polymerizations, quite even higher polymerization activity and degree of isotacticity.

Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.

Claims

1. for the catalyst component of olefinic polymerization, it is characterized in that, comprise the magnesium halide that is activity morphology, and the carrying titanium compound that contains at least one Ti-halogen key thereon replaces two ester compounds with at least one the unsaturated ring that is selected from following logical formula I:

In the time that n equals 0:

I) A, B, C and D are carbon atom, and X, Y, Z and W are 1; Or

II) A is nitrogen-atoms, and B, C and D are carbon atom, and W is that 0, X, Y and Z are 1; Or

III) A and D are nitrogen-atoms, and B and C are carbon atom, and W and Z are that 0, X and Y are 1; Or

IV) D is nitrogen-atoms, and A, B and C are carbon atom, and Z is that 0, W, X and Y are 1; Or

In the time that n equals 1:

I) A, B, C, D and E are carbon atom, and m is that 2, W, X, Y and Z are 1; Or

Ii) E is nitrogen-atoms, and A, B, C and D are carbon atom, and m is that 1, W, X, Y and Z are 1; Or

Iii) E is Sauerstoffatom, and A, B, C and D are carbon atom, and m is that 0, W, X, Y and Z are 1; Or

I) E is sulphur atom, and A, B, C and D are carbon atom, and m is that 0, W, X, Y and Z are 1; Or

Ii) D and E are nitrogen-atoms, and A, B and C are carbon atom, and m is that 1, W, X and Y are that 1, Z is 0.

2. the catalyst component for olefinic polymerization according to claim 1, is characterized in that, the compound of described logical formula I comprises the compound of following logical formula II:

Wherein R ¹-R ⁶group is as the definition in logical formula I.

3. the catalyst component for olefinic polymerization according to claim 2, is characterized in that, the compound of described logical formula II comprises the compound of following logical formula III:

4. the catalyst component for olefinic polymerization according to claim 1, is characterized in that, the compound described in logical formula I is selected from the group that following compounds forms:

5. according to the catalyst component described in any one in claim 1-4, it is characterized in that, the unsaturated ring that comprises titanium compound, magnesium compound and be selected from described logical formula I replaces the reaction product of two ester compounds, and the precursor of described magnesium compound is selected from least one: Mg (OR) ₂, X _nmg (OR) _2-n, MgCl ₂mROH, R _2-nmgX _n, MgR ₂, MgCl ₂/ SiO ₂, MgCl ₂/ Al ₂o ₃, or the mixture of magnesium halide and alcohol titanium, the number that in formula, m is 0.1-6,0<n<2, X is halogen, R is hydrogen or C ₁-C ₂₀alkyl; The general formula of described titanium compound is TiX _n(OR) _4-n, in formula, R is that carbonatoms is the alkyl of 1-20, X is halogen, n=1-4.

6. the method for the preparation catalyst component for olefinic polymerization claimed in claim 5, it is characterized in that, comprise: make magnesium compound and titanium compound and the unsaturated ring that is selected from described logical formula I replace two acid esters internal electron donor compounds and contact, thereby obtain catalyst component.

7. the preparation method of the catalyst component for olefinic polymerization according to claim 6, is characterized in that, described magnesium compound is the one in the derivative that in magnesium dihalide molecular formula, wherein at least one halogen atom is replaced by-oxyl or halo-oxyl; Or described magnesium compound is alkoxyl magnesium or aryloxy magnesium; Or the described magnesium compound alcohol adduct that is magnesium dihalide; Or described magnesium compound is to make general formula R under a kind of existence of the compound that is selected from alcohol, phenol, ketone, aldehyde, ether, amine, pyridine and ester _2-nmgX _nliquid magnesium compound contact redeposition with liquid titanium compound and separate out solid.

8. for a catalyzer for olefinic polymerization, it is characterized in that, comprise the product of following substance reaction:

(A) catalyst component described in any one in claim 1-5;

(B) at least one general formula is AlR _nx _(3-n)organo-aluminium compound, in formula, R is the alkyl of hydrogen, carbonatoms 1-20; X is halogen, the integer that n is 0≤n≤3; With, optionally,

(C) except the unsaturated ring of described logical formula I replaces the electron donor compound two ester compounds.

9. catalyzer according to claim 8, is characterized in that, described organo-aluminium compound (B) is a kind of trialkyl aluminium compound.

10. catalyzer according to claim 9, is characterized in that, described trialkyl aluminium compound is selected from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, trioctylaluminum.

11. catalyzer according to claim 8, is characterized in that, it is R that electron donor compound (C) is selected from general formula _nsi (OR ₁) _4-nsilicone compounds, R and R in formula ₁for C ₁-C ₁₈alkyl, optionally also have heteroatoms; N is the integer of 0≤n≤3.

12. 1 kinds of catalyzer for olefinic polymerization, is characterized in that, comprise the product of following substance reaction:

(a) ingredient of solid catalyst, comprises the magnesium halide that is activity morphology, and the carrying titanium compound that contains at least one Ti-halogen key and a kind of electron donor compound thereon;

(c) external electron donor, at least one the unsaturated ring that is selected from logical formula I replaces two ester compounds:

In the time that n equals 0:

V) A, B, C and D are carbon atom, and X, Y, Z and W are 1; Or

VI) A is nitrogen-atoms, and B, C and D are carbon atom, and W is that 0, X, Y and Z are 1; Or

VII) A and D are nitrogen-atoms, and B and C are carbon atom, and W and Z are that 0, X and Y are 1; Or

VIII) D is nitrogen-atoms, and A, B and C are carbon atom, and Z is that 0, W, X and Y are 1; Or

In the time that n equals 1:

Iv) A, B, C, D and E are carbon atom, and m is that 2, W, X, Y and Z are 1; Or

V) E is nitrogen-atoms, and A, B, C and D are carbon atom, and m is that 1, W, X, Y and Z are 1; Or

Vi) E is Sauerstoffatom, and A, B, C and D are carbon atom, and m is that 0, W, X, Y and Z are 1; Or

Iii) E is sulphur atom, and A, B, C and D are carbon atom, and m is that 0, W, X, Y and Z are 1; Or

Iv) D and E are nitrogen-atoms, and A, B and C are carbon atom, and m is that 1, W, X and Y are that 1, Z is 0.

13. catalyzer according to claim 12, is characterized in that, the compound of described logical formula I comprises the compound of following logical formula II:

Wherein R ¹-R ⁶group is as the definition in logical formula I.

14. catalyzer according to claim 13, the compound of wherein said logical formula II comprises the compound of following logical formula III:

15. catalyzer according to claim 12, is characterized in that, the compound described in logical formula I is selected from following compounds:

16. catalyzer according to claim 12, it is characterized in that, the electron donor compound being carried on ingredient of solid catalyst (a) is the Lewis alkali that contains one or more electronegativity groups, and electron donor atom is wherein selected from the group of N, O, S, P, As or Sn composition; Or phthalic ester; Or 1,3-diether; Or succinate; Or 1,3-diol ester.

17.CH ₂the polymerization process of=CHR alkene or described alkene mixture or described alkene and diolefine mixture, wherein R is hydrogen or the hydrocarbyl group containing 1-12 carbon atom, exist under the condition of catalyzer described in claim 8 or 12, be with or without under aliphatics or aromatic hydrocarbon solvents existence and carry out described method in liquid phase, or in gas phase, carry out described method, or combine to carry out described method by liquid and gas polymerization stage.

18. methods according to claim 17, is characterized in that, described alkene is normal olefine, and described normal olefine is selected from ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-nonene, 1-decene; Described alkene is also branched-chain alkene, and described branched-chain alkene is selected from: 3-methyl-1-butene or 4-methyl-1-pentene; Described alkene is also diolefine, and described diolefine is selected from: divinyl, vinyl cyclopentenes or vinyl cyclohexene.