CN102838695A - High hydrogen response polyolefin catalyst component and preparation method thereof, and olefin polymerization method - Google Patents
High hydrogen response polyolefin catalyst component and preparation method thereof, and olefin polymerization method Download PDFInfo
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Abstract
The present invention relates to a high hydrogen response olefin polymerization catalyst component and a preparation method thereof, and an olefin polymerization method. According to the present invention, an organic silane compound and a diether internal electron donor compound are simultaneously introduced during a catalyst component preparation process, and the prepared catalyst component is used for polymerization, particularly for propylene polymerization, such that the hydrogen regulation performance of the catalyst system is increased, the particle morphology of the polymer is improved, and the original isotacticity and other high excellent performances of the catalyst system can be well maintained. In addition, the method of the present invention is suitable for a slurry polymerization method, a bulk polymerization method, a gas phase method, and a plurality of polymerization processes.
Description
Technical field
The present invention relates to the method for a kind of olefin polymerization catalyst components and preparation method thereof and olefinic polymerization with high hydrogen response.
Technical background
The current ordinary method that in field of olefin polymerisation, prepares the high reactivity carried catalyst is common liberation method; At first magnesium halide is dissolved in a kind of solvent system and forms homogeneous solution; With halogenated titanium magnesium halide in active is separated out again, and simultaneously the titanium active ingredient is loaded with up.Patent CN85100997A discloses a kind of catalyst system that is used for olefinic polymerization and copolymerization; This catalyst system comprises: (first) contains the ingredient of solid catalyst of Ti, (second) alkylaluminium cpd, (third) organosilicon; Wherein (first) component is to be dissolved in organic epoxy compounds and organo phosphorous compounds forms homogeneous solution by magnesium halide; This solution mixes with the titanium tetrahalide or derivatives thereof, in the presence of compounds such as precipitation additive such as organic acid anhydrides, organic acid, ether, ketone, separates out solids; This solids is handled with the multi-carboxylate, and it is attached on the solids, handles with titanium tetrahalide and inert diluent and obtains.The degree of isotacticity of resulting polymers was higher when this catalyst system was used for propylene polymerization, and apparent density is big, but catalyst activity is not high.
Two have obtained huge advance made based on the improvement of above-mentioned catalyst system during the last ten years; For example patent CN1955195, patent CN1718594 and patent CN101643519 etc.; The improvement of being reported based on above-mentioned system comprises the selection of technology adjustment and internal electron donor; All make this System Catalyst degree of isotacticity, apparent density, MWD and active aspect original performance is arranged, and in industry, have a wide range of applications.But the hydrogen response that a difficult problem that exists all the time is this System Catalyst is relatively low; Cause the melting index of polyolefin products relatively low; Limited the exploitation of the polyolefin products high fusion index trade mark; Therefore it is constant to be badly in need of a kind of other performances of polyolefine that can keep of research and development, can improve the catalyzer of its hydrogen response ability again, to satisfy the molten demand that refers to trade mark Application and Development of height.
1, the exploitation of 3-diether compound is used, and promotes polyolefin catalyst and has stepped up a new step.Chinese patent CN1042547A and CN1143651 report use 1; The 3-diether compounds is that the catalyzer of internal electron donor preparation has active height in propylene polymerization; Hydrogen response is good, and under the situation that does not add external electron donor, still can keep good characteristics such as tacticity.Just because of 1, the 3-diether has outstanding feature like this, and numerous catalyst systems is competitively introduced diether compound and is wherein obtained the good catalyzer of hydrogen regulation performance with expectation.For example reported among the Chinese patent CN1834117A and on the complex carrier of magnesium chloride and silica gel, used diether compound can effectively improve the hydrogen regulation performance of catalyzer as internal electron donor.
Drawbacks such as patent documentations report proof is used the hydrogen response ability that diether compounds can be good at regulating catalyzer in a large number, and still single use diether compound also can cause narrow molecular weight distribution as internal electron donor, and the polymer processing performance is bad.Therefore many patented inventions can effectively be evaded the drawback that diether compounds produces, for example Chinese patent CN1891722A and patent CN1803863A with diether compound with the composite use of the electron donor of other types.
The inventor discovers, silicoorganic compound and diether compound is incorporated in the above-mentioned catalyst system simultaneously can accesses beyond thought effect.The adding of silicoorganic compound can effectively improve the particle form of this System Catalyst, makes that the segmentation of polymkeric substance is few, and particle form is regular; And organosilyl introducing can be to a certain degree the raising activity of such catalysts.Diether compound can effectively improve the hydrogen response of catalyzer when improving catalyst activity, the melting index of polymkeric substance is increased substantially.The two is used in combination to access has high reactivity, the polyolefin catalyst of good particle form and good hydrogen response.
Summary of the invention
The object of the present invention is to provide a kind of high hydrogen response, highly active olefin polymerization catalyst components and preparation method thereof, and a kind of method of olefinic polymerization is provided.
A kind of high hydrogen response titanium-containing catalyst of olefinic polymerization component that is used for of the present invention, it prepares through following steps:
(1) magnesium compound, organo phosphorous compounds, organic epoxy compounds are contacted in solvent with organic silane compound, form homogeneous solution;
(2) in the presence of precipitation additive, the gained homogeneous solution contacted with titanium compound obtain mixture;
(3) step (2) gained mixture is contacted with two ethers internal electron donor compounds, through filtering, washing, drying obtain olefinic polymerization titanium-containing catalyst component;
At least a in wherein said magnesium compound and the titanium compound is halogen-containing compound;
The general formula of said organic silane compound is R
nSi (OR
1)
4-n, n is 0 to 4 integer in the formula, R is one or more in alkyl, naphthenic base, aryl, halogenated alkyl, halogen, the Wasserstoffatoms, R
1Be in alkyl, naphthenic base, aryl, the halogenated alkyl one or more.
Organic silane compound is one or more in four butoxy silanes, tetraethoxysilane, phenylbenzene diethoxy silane, dimethoxydiphenylsilane, propyl trimethoxy silicane, propyl-triethoxysilicane, cyclohexyl methyl dimethoxy silane, the cyclohexyl methyl diethoxy silane for example, one or more in preferred tetraethoxysilane, four butoxy silanes and the cyclohexyl methyl diethoxy silane.
Described two ethers internal electron donor compounds are preferred 1,3-two ethers electron donor compounds, particularly for example: 2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-isopentyl-1,3-Propanal dimethyl acetal; 2-isobutyl--2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2,2-di-n-butyl-1; The 3-Propanal dimethyl acetal, 2,2-di-isopropyl-1,3-Propanal dimethyl acetal, 2,2-diisobutyl-1; The 3-Propanal dimethyl acetal, 2-cyclopentyl-1,3-Propanal dimethyl acetal, 2-cyclohexyl-1,3-Propanal dimethyl acetal, 2; 2-two cyclopentyl-1,3-Propanal dimethyl acetal, 2,2-dicyclohexyl-1,3-Propanal dimethyl acetal, 2-phenyl-1; The 3-Propanal dimethyl acetal, 2,2-phenylbenzene-1, one or more in the 3-Propanal dimethyl acetal, preferred 2-sec.-propyl-2-isopentyl-1; 3-Propanal dimethyl acetal, 2,2-di-isopropyl-1,3-Propanal dimethyl acetal, 2-cyclopentyl-1,3-Propanal dimethyl acetal and 2-phenyl-1, one or more in the 3-Propanal dimethyl acetal.
Said magnesium compound is at least a in the alcohol adduct of hydrate and the magnesium compound shown in the formula (I) of the magnesium compound shown in the magnesium compound shown in the formula (I), the formula (I),
MgR
4R
5 (I)
In the formula (I), R
4And R
5Halogen, C respectively do for oneself
1-C
5Straight or branched alkoxyl group and C
1-C
5The straight or branched alkyl in a kind of; At least a in the alcohol adduct of the alcohol adduct of the alcohol adduct of magnesium dichloride, dibrominated magnesium, two magnesium iodides, magnesium dichloride, dibrominated magnesium and two magnesium iodides for example; In preferred magnesium dichloride, dibrominated magnesium, two magnesium iodides one or more are good with magnesium dichloride.
Said titanium compound is the compound shown in the formula (II),
TiX
m(OR
6)
4-mFormula (II)
In the formula (II), X is a halogen, R
6Be C
1-C
20Alkyl, m is the integer of 0-4; Be preferably at least a in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium and trichlorine one ethanolato-titanium; In wherein preferred titanium tetrachloride, titanium tetrabromide, the titanium tetra iodide one or more, preferred especially titanium tetrachloride.
Said organic epoxy compounds can be this area various organic epoxides commonly used; For example can be in the oxidation products of the aliphatics alkene of carbonatoms 2-8, halogenated aliphatic alkene one or more; Particularly; One or more in oxyethane, propylene oxide, epoxy monochloroethane, epoxy chloropropane, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, the diglycidylether for example, preferred epoxy chloropropane.
Said precipitation additive can be the various precipitation additives that this area is commonly used, for example is in organic acid, organic acid anhydride, organic ether, the organic ketone one or more, is preferably in organic acid anhydride, organic acid, ether and the ketone of carbonatoms 2-20 one or more; Particularly.For example can be in diacetyl oxide, Tetra hydro Phthalic anhydride, Succinic anhydried, MALEIC ANHYDRIDE, pyromellitic acid anhydride, acetic acid, propionic acid, butyric acid, vinylformic acid, methylacrylic acid, acetone, methylethylketone, benzophenone, methyl ether, ether, propyl ether, butyl ether, the amyl ether one or more, preferred especially Tetra hydro Phthalic anhydride.
Said solvent can for various can the dissolved magnesium compound, this area solvent commonly used of the mixture of silane compound, organic epoxy compounds, organo phosphorous compounds and internal electron donor compound; In concrete for example toluene, ethylbenzene, benzene, YLENE, chlorobenzene, hexane, heptane, octane, the decane one or more, preferred toluene.
Said organo phosphorous compounds can be this area various organo phosphorous compoundss commonly used; The halo hydrocarbyl carbonate of the hydrocarbyl carbonate of phosphoric acid, phosphorous acid and/or phosphoric acid, phosphorous acid for example; Concrete for example can be in trimethyl phosphite 99, triethyl phosphate, tributyl phosphate, triphenylphosphate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, the phosphorous acid benzene methyl one or more, wherein preferably phosphoric acid tri-n-butyl and/or tributyl phosphate.
According to the present invention, although as long as in the process of preparation olefin polymerization catalyst components, introduce silane compound and 1,3-two ethers internal electron donors can be realized the object of the invention; Consumption to said various materials does not have particular requirement, all can allocate with reference to this area conventional amount used, for example the consumption of solvent; Enough dissolve the mixture of various reactants as long as guarantee its consumption, but under preferable case, with respect to every mole of magnesium elements; The consumption of silane compound is the 0.01-5 mole; The consumption of organic epoxy compounds is the 0.2-10 mole, and the consumption of said organo phosphorous compounds is the 0.1-3 mole, and the consumption of titanium compound is the 0.5-20 mole; The consumption of precipitation additive is the 0.03-1 mole, internal electron donor consumption 0.01-5 mole; More preferably the consumption of silane compound is the 0.05-1 mole; The consumption of organic epoxy compounds is the 0.5-4 mole; The consumption of said organo phosphorous compounds is the 0.3-1 mole; The consumption of titanium compound is the 1-15 mole, and the consumption of precipitation additive is the 0.05-0.4 mole, internal electron donor consumption 0.05-1 mole.
The present invention does not have particular requirement to the contact conditions of step (1), (2) and (3), all can carry out with reference to prior art, under the preferable case; The condition of step (1) contact comprises that the temperature of contact is 10-100 ℃; Be preferably 30-80 ℃, the time is 0.5-6 hour, is preferably 1-4 hour; The condition of step (2) contact comprises that the temperature of contact is-30 to 60 ℃, is preferably-30 to 5 ℃, and the time is 0.1-5 hour, is preferably 0.2-4 hour; The condition of step (3) contact comprises that the temperature of contact is 50-200 ℃, is preferably 60-180 ℃, and the time is 0.5-8 hour, is preferably 1-6 hour.
The present invention washs said filtration, and exsiccant method and condition do not have particular requirement, all can carry out with reference to prior art, repeat no more at this.
According to preferred implementation of the present invention, the method for preparing olefin polymerization catalyst components of the present invention comprises the steps:
Under agitation magnesium halide is dissolved in the solvent solution of silane compound, organic epoxy compounds, organo phosphorous compounds, contact is 0.5-6 hour under the 10-100 ℃ of temperature, is preferably under the 30-80 ℃ of temperature and contacts 1-4 hour, forms homogeneous solution; In the presence of precipitation additive, be preferably under-30 to 60 ℃ of temperature under-30 to 5 ℃ of temperature, titanium compound is splashed into above-mentioned homogeneous solution or homogeneous solution is splashed in the titanium compound, contact 0.1-5 hour, be preferably contact 0.2-4 hour; Again reaction mixture is warming up to 50-200 ℃, is preferably 60-180 ℃, whipped state contacts 0.5-8 hour down; Be preferably 1-6 hour, elimination mother liquor, washing composition (for example toluene) washing; Add the internal electron donor compound, use mixture process 3-4 time of halogenide and the washing composition (for example toluene) of titanium again, treatment time 0.5-2 hour; Leach liquid,, make olefinic polymerization titanium-containing catalyst component with washing composition (for example hexane, toluene) wash solids thing.
Olefine polymerizing process of the present invention is included under the olefinic polymerization condition, and each component of olefinic monomer and olefin polymerization catalysis is contacted with one of (B) dual mode according to following (A):
(A) olefinic monomer is contacted with alkylaluminium cpd with olefinic polymerization titanium-containing catalyst component, wherein, the ethene molar content is more than 80% in the said olefinic monomer;
(B) olefinic monomer is contacted with olefinic polymerization titanium-containing catalyst component, alkylaluminium cpd and external electron donor silicoorganic compound;
Wherein, said olefinic polymerization titanium-containing catalyst component is an olefinic polymerization titanium-containing catalyst component of the present invention.
Although when mode contacts, said olefinic monomer is not being limited with (B); For the polyreaction that is mainly used in ethene; Iff is that portion plants alkene respectively, at this time only takes (A) mode to contact and can realize the object of the invention, therefore under preferable case; When mode contacted, the molar content of ethene was below 80% in the said olefinic monomer with (B).
According to the present invention, the mol ratio of the titanium in aluminium in the said alkylaluminium cpd and the said olefin polymerization catalysis is generally 5-5000: 1, be preferably 20-500: 1.The consumption of said external electron donor silicoorganic compound can be regulated according to real needs, and the present invention does not have particular requirement.
According to the present invention, said alkylaluminium cpd is the compound shown in the formula (III),
AlR′
n′X′
3-n′ (III)
In the formula (III), R ' is the alkyl of hydrogen, carbonatoms 1-20 or the aryl of carbonatoms 6-20, and X ' is a halogen, and n ' is the integer of 1-3.At least a in trimethylaluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethyl aluminum chloride and the ethyl aluminum dichloride for example, preferred triethyl aluminum.
The general formula of said external electron donor silicoorganic compound is R
fN " Si (OR
y)
4-n", n in the formula " be 0 to 3 integer, R
fBe in alkyl, naphthenic base, aryl, halogenated alkyl, halogen, the Wasserstoffatoms one or more, R
yBe in alkyl, naphthenic base, aryl, the halogenated alkyl one or more; For example trimethylammonium methoxy silane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyl-t-butyldimethoxysilane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, dicyclohexyl dimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, methylcyclohexyl dimethoxy silane, dicyclopentyl dimethoxyl silane, 2-ethyl piperidine base-2-tertiary butyl dimethoxy silane, (1; 1; 1-three fluoro-2-propyl group)-2-ethyl piperidine base dimethoxy silane and (1; 1; 1-three fluoro-2-propyl group)-and at least a in the methyl dimethoxysilane, preferable methyl cyclohexyl dimethoxy silane.
According to the present invention; Said olefinic monomer can be various alkene commonly used; For example can be in the 1-alkene of carbonatoms 2-6 at least a, at least a in optimal ethylene, propylene, 1-n-butene, the positive amylene of 1-, 1-n-hexylene, the positive octene of 1-and the 4-methyl-1-pentene.Olefine polymerizing process of the present invention is specially adapted to the equal polymerization of propylene, and the random copolymerization of propylene and ethene and heterogeneous crushing-resistant copolymerization close.
According to the present invention, said olefinic polymerization condition can be this area olefinic polymerization condition commonly used, and being generally temperature is 0-150 ℃, and the time is 0.5-5 hour, and pressure is 0.1-10MPa.
Under the preferable case, olefine polymerizing process of the present invention carries out in the presence of solvent, and said contact is carried out in the presence of solvent; Said olefinic polymerization condition comprises: temperature is 0-150 ℃; Time is 0.5-5 hour, and pressure is 0.1-10MPa, in the titanium in the olefin polymerization catalysis; The concentration of said olefin polymerization catalysis in solvent can for example can be the 0.0001-1 mol for the conventional concentration in this area.Under the preferable case, said contact is carried out in the presence of hydrogen, and the add-on of hydrogen can be this area conventional amount used, is generally 0.01-20 liter (under the standard state).
Below describe the present invention through specific embodiment, but do not limit the present invention.
Among the embodiment, the mensuration of titanium content in the catalyzer: carry out colorimetric estimation with ultraviolet-visible spectrophotometer 722 types; Mg content adopts mg ion and the EDTA complexometry records, content of halogen (like chlorine) adopts AgNO
3-NH
4CNS returns the method for dripping and records; Silicon, phosphorus content adopt spectroscopy to record; Internal electron donor compound (diether compound) assay in the catalyzer: adopt chromatography, after diluted acid decomposes,, measure with Agilent 6890N gas chromatograph with extraction agent extraction internal electron donor compound wherein with catalyzer dry powder; The melting index of polymkeric substance (MI) is measured with 6932 type melt indexers of Italian CEAST company, with reference to the GB/T3682-2000 standard; The mensuration of polymer bulk density is with reference to the ASTMD1895-96 standard.
Embodiment 1
Repeating through high pure nitrogen in the metathetical normal-pressure reaction kettle, adding 4.8 gram Magnesium Chloride Anhydrouss, 70 milliliters of toluene, 4.0 milliliters of epoxy chloropropane, 12.5 milliliters of tributyl phosphates and 2.0 milliliters of tetraethoxysilanes successively, is under 60 ℃ the condition, to react 1 hour in temperature; Add 1.4 gram Tetra hydro Phthalic anhydride and 30 milliliters of toluene, continue reaction one hour, be cooled to-28 ℃; Drip 56 milliliters of titanium tetrachlorides (5 milliliters of rate of addition/min), be warming up to gradually 85 ℃ (temperature rise rate be 5 ℃/min), constant temperature one hour; Filter,, add 48 milliliters of titanium tetrachlorides again with toluene wash twice; 72 milliliters of toluene add 2-sec.-propyl-2-isopentyl-1 again, 3-Propanal dimethyl acetal 2mL; 110 ℃ of constant temperature 0.5 hour, add 48 milliliters of titanium tetrachlorides after the filtration again, 72 milliliters of toluene; Handled once in 0.5 hour at 110 ℃ of constant temperature, filter then, the gained solid is obtained solid titanium catalyst component with 5 final vacuum dryings of hexane wash.Wherein, by weight, titanium content is 2.4%, and 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal content are 8.9%, silicone content is 0.1%, Mg content is 17%, cl content is 48%, phosphorus content is 0.12%.
EXPERIMENTAL EXAMPLE 1
5 liters of stainless steel autoclaves are after nitrogen is fully replaced; Add 5 ml concns and be 10 milligrams of the catalyzer of hexane solution and embodiment 1 preparation of hexane solution and the methylcyclohexyl dimethoxy silane (CMMS) that 1 ml concn is 1 mol of the triethyl aluminum of 0.5 mol; Add 10 milliliters of hexane charge lines then, add 1 liter of (under the standard state) hydrogen and 2 liters of refining propylene again; Be warming up to 70 ℃, polyreaction is 1 hour under this temperature.After reaction finishes, with the reaction kettle cooling and stop stirring and discharge reaction product, obtain olefin polymer, concrete outcome sees table 1 for details.
EXPERIMENTAL EXAMPLE 2
5 liters of stainless steel autoclaves are after nitrogen is fully replaced; Add 5 ml concns and be 10 milligrams of the catalyzer of hexane solution and embodiment 1 preparation of hexane solution and the methylcyclohexyl dimethoxy silane (CMMS) that 1 ml concn is 1 mol of the triethyl aluminum of 0.5 mol; Add 10 milliliters of hexane charge lines then, add 4 liters of (under the standard state) hydrogen and 2 liters of refining propylene again; Be warming up to 70 ℃, polyreaction is 1 hour under this temperature.After reaction finishes, with the reaction kettle cooling and stop stirring and discharge reaction product, obtain olefin polymer, concrete outcome sees table 1 for details.
Embodiment 2
Experiment condition uses 2 with embodiment 1,2-di-isopropyl-1, and the 3-Propanal dimethyl acetal replaces 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal.Wherein, by weight, titanium content is 2.7%, 2, and 2-di-isopropyl-1,3-Propanal dimethyl acetal content are 8.1%, silicone content is 0.09%, Mg content is 18%, cl content is 49%, phosphorus content is 0.11%.
EXPERIMENTAL EXAMPLE 3
Experiment condition uses catalyzer prepared as embodiment 2 with EXPERIMENTAL EXAMPLE 1, and concrete outcome sees table 1 for details.
EXPERIMENTAL EXAMPLE 4 experiment conditions are with EXPERIMENTAL EXAMPLE 2, and the catalyzer that uses is prepared as embodiment 2, and concrete outcome sees table 1 for details.
Embodiment 3
Experiment condition uses 2-cyclopentyl-1 with embodiment 1, and the 3-Propanal dimethyl acetal replaces 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal.Wherein, by weight, titanium content is 2.6%, 2-cyclopentyl-1, and 3-Propanal dimethyl acetal content is 8.7%, silicone content is 0.12%, Mg content is 17%, cl content is 48%, phosphorus content is 0.12%.
EXPERIMENTAL EXAMPLE 5
Experiment condition is with EXPERIMENTAL EXAMPLE 1, and catalyst system therefor is that embodiment 3 is prepared, and concrete outcome sees table 1 for details.
EXPERIMENTAL EXAMPLE 6
Experiment condition uses catalyzer prepared as embodiment 3 with EXPERIMENTAL EXAMPLE 2, and concrete outcome sees table 1 for details.
Embodiment 4
The Preparation of catalysts method is used 2-phenyl-1 with embodiment 1, and the 3-Propanal dimethyl acetal replaces 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal.Wherein, by weight, titanium content is 2.4%, and 2-phenyl-1,3-Propanal dimethyl acetal content are 9.0%, silicone content is 0.1%, Mg content is 17%, cl content is 47%, phosphorus content is 0.1%.
EXPERIMENTAL EXAMPLE 7
Experiment condition is with EXPERIMENTAL EXAMPLE 1, uses the prepared catalyzer of embodiment 4, and concrete outcome sees table 1 for details.
EXPERIMENTAL EXAMPLE 8
Experiment condition is with EXPERIMENTAL EXAMPLE 2, uses the prepared catalyzer of embodiment 4, and concrete outcome sees table 1 for details.
Embodiment 5
The Preparation of catalysts process only changes 2.0 milliliters of tetraethoxysilanes wherein into 2.0 milliliter of four butoxy silane with embodiment 1.Wherein, by weight, titanium content is 2.1%, and 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal content are 8.5%, silicone content is 0.1%, Mg content is 17%, cl content is 46%, phosphorus content is 0.1%.
EXPERIMENTAL EXAMPLE 9
Experiment condition is with EXPERIMENTAL EXAMPLE 1, use be the prepared catalyzer of embodiment 5, concrete outcome sees table 1 for details.
EXPERIMENTAL EXAMPLE 10
Experiment condition is with EXPERIMENTAL EXAMPLE 2, uses the prepared catalyzer of embodiment 5, and concrete outcome sees table 1 for details.
Embodiment 6
The Preparation of catalysts process just changes 2.0 milliliters of tetraethoxysilanes into 2.0 milliliters of cyclohexyl methyl diethoxy silanes with embodiment 1.Wherein, by weight, titanium content is 2.4%, and 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal content are 9.1%, silicone content is 0.08%, Mg content is 18%, cl content is 49%, phosphorus content is 0.1%.
EXPERIMENTAL EXAMPLE 11
Experiment condition is with EXPERIMENTAL EXAMPLE 1, and the catalyzer that uses is prepared as embodiment 6, and concrete outcome sees table 1 for details.
EXPERIMENTAL EXAMPLE 12
Experiment condition is with EXPERIMENTAL EXAMPLE 2, and catalyst system therefor is that embodiment 6 is prepared, and concrete outcome sees table 1 for details.
Comparative Examples 1
Repeating through high pure nitrogen in the metathetical normal-pressure reaction kettle, adding 4.8 gram Magnesium Chloride Anhydrouss, 70 milliliters of toluene, 4.0 milliliters of epoxy chloropropane, 12.5 milliliters of tributyl phosphates and 2.0 milliliters of tetraethoxysilanes successively, is under 60 ℃ the condition in temperature; Reacted 1 hour, and added 1.4 gram Tetra hydro Phthalic anhydride and 30 milliliters of toluene, continue reaction one hour; Be cooled to-28 ℃, drip 56 milliliters of titanium tetrachlorides (5 milliliters of rate of addition/min), be warming up to gradually 85 ℃ (temperature rise rate be 5 ℃/min); Add n-butyl phthalate (DNBP) 1.1mL, constant temperature one hour filters; With toluene wash twice, add 48 milliliters of titanium tetrachlorides again, 72 milliliters of toluene; 110 ℃ of constant temperature 0.5 hour, add 48 milliliters of titanium tetrachlorides after the filtration again, 72 milliliters of toluene; Handled once in 0.5 hour at 110 ℃ of constant temperature, filter then, then the gained solid is obtained solid titanium catalyst component with 5 final vacuum dryings of hexane wash.Wherein, by weight, titanium content is 2.4%, and DNBP content is 10.3%, diethyl phthalate content is 0.4%, and silicone content is 0.1%, Mg content is 17%, cl content is 48%, phosphorus content is 0.12%.
Experiment Comparative Examples 1
Experiment condition is with EXPERIMENTAL EXAMPLE 1, and catalyst system therefor is Comparative Examples 1 prepared catalyst, and concrete outcome sees table 1 for details.
Experiment Comparative Examples 2
Experiment condition is with EXPERIMENTAL EXAMPLE 2, and catalyst system therefor is the prepared catalyzer of Comparative Examples 1, and concrete outcome sees table 1 for details.
Comparative Examples 2
Repeating through high pure nitrogen in the metathetical normal-pressure reaction kettle, adding 4.8 gram Magnesium Chloride Anhydrouss, 70 milliliters of toluene, 4.0 milliliters of epoxy chloropropane and 12.5 milliliters of tributyl phosphates successively and be under 60 ℃ the condition, reacting 1 hour in temperature; Add 1.4 gram Tetra hydro Phthalic anhydride and 30 milliliters of toluene, continue reaction one hour, be cooled to-28 ℃; Drip 56 milliliters of titanium tetrachlorides (5 milliliters of rate of addition/min), be warming up to gradually 85 ℃ (temperature rise rate be 5 ℃/min), add 2-sec.-propyl-2-isopentyl-1 again; 3-Propanal dimethyl acetal 2.0mL, constant temperature one hour filters; With toluene wash twice, add 48 milliliters of titanium tetrachlorides again, 72 milliliters of toluene; 110 ℃ of constant temperature 0.5 hour, add 48 milliliters of titanium tetrachlorides after the filtration again, 72 milliliters of toluene; Handled once in 0.5 hour at 110 ℃ of constant temperature, filter then, then the gained solid is obtained solid titanium catalyst component with 5 final vacuum dryings of hexane wash.Wherein, by weight, titanium content is 2.5%, and 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal content are 8.8%, Mg content is 19%, cl content is 49%, phosphorus content is 0.13%.
Experiment Comparative Examples 3
Experiment condition is with EXPERIMENTAL EXAMPLE 1, uses the prepared catalyzer of Comparative Examples 3, and concrete outcome sees table 1 for details.
Experiment Comparative Examples 4
Experiment condition is with EXPERIMENTAL EXAMPLE 2, uses the prepared catalyzer of Comparative Examples 2, and concrete outcome sees table 1 for details.
(embodiment, Comparative Examples refer to the catalyzer compound experiment; EXPERIMENTAL EXAMPLE, experiment Comparative Examples refer to polymerization experiment.)
Table 1
Can find out by table 1; Compare with 2 with experiment Comparative Examples 1; Introduce the hydrogen response that diether compound can effectively improve catalyzer, make the melting index of polymkeric substance under 4L hydrogen state, bring up to about 40g/10min, be doubled by original 20g/10min; The introducing of silicoorganic compound can effectively keep the particle form of compound, makes the tap density of polymkeric substance improve greatly, can find out that from experiment Comparative Examples 3 and 4 when not adding silicon compound, the tap density of polymkeric substance has only 0.40g/cm
3About, and after adding silicon compound, the tap density of polymkeric substance can reach 0.44g/cm
3About, tap density increases substantially; Compare with experiment Comparative Examples 1～4, introduce silicon compound and diether compound simultaneously and can make activity of such catalysts improve 10%～30%; The introducing of silicoorganic compound and diether compound not only hydrogen regulation performance and the particle form to catalyzer is beneficial; Can be good at keeping the premium properties of the original degree of isotacticity of catalyzer simultaneously; Can find out that from table 1 all test polymers obtained degree of isotacticity all more than 97.
Claims (12)
1. one kind is used for the high hydrogen response titanium-containing catalyst of olefinic polymerization component, it is characterized in that it prepares through following steps:
(1) magnesium compound, organo phosphorous compounds, organic epoxy compounds are contacted in solvent with organic silane compound, form homogeneous solution;
(2) in the presence of precipitation additive, the gained homogeneous solution contacted with titanium compound obtain mixture;
(3) step (2) gained mixture is contacted with two ethers internal electron donor compounds, through filtering, washing, drying obtain catalyst component;
At least a in wherein said magnesium compound and the titanium compound is halogen-containing compound;
The general formula of said organic silane compound is R
nSi (OR
1)
4-n, n is 0 to 4 integer in the formula, R is one or more in alkyl, naphthenic base, aryl, halogenated alkyl, halogen, the Wasserstoffatoms, R
1Be in alkyl, naphthenic base, aryl, the halogenated alkyl one or more.
2. titanium-containing catalyst component according to claim 1 is characterized in that, described two ethers internal electron donor compounds are 1,3-two ethers electron donor compounds.
3. titanium-containing catalyst component according to claim 1; It is characterized in that described two ethers internal electron donor compounds are 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2; 2-di-isopropyl-1; 3-Propanal dimethyl acetal, 2-cyclopentyl-1,3-Propanal dimethyl acetal and 2-phenyl-1, one or more in the 3-Propanal dimethyl acetal.
4. titanium-containing catalyst component according to claim 1 is characterized in that, described organic silane compound is one or more in tetraethoxysilane, four butoxy silanes and the cyclohexyl methyl diethoxy silane.
5. titanium-containing catalyst component according to claim 1 is characterized in that, described magnesium compound is at least a in the alcohol adduct of hydrate and the magnesium compound shown in the formula (I) of the magnesium compound shown in the magnesium compound shown in the formula (I), the formula (I),
MgR
4R
5 (I)
In the formula (I), R
4And R
5Halogen, C respectively do for oneself
1-C
5Straight or branched alkoxyl group and C
1-C
5The straight or branched alkyl in a kind of.
6. titanium-containing catalyst component according to claim 1 is characterized in that, described titanium compound is the compound shown in the formula (II),
TiX
m(OR
6)
4-m (II)
In the formula (II), X is a halogen, R
6Be C
1-C
20Alkyl, m is the integer of 0-4.
7. titanium-containing catalyst component according to claim 1; It is characterized in that described titanium compound is a kind of or its mixture in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, titanous chloride, dichloro diethoxy titanium, trichlorine one ethanolato-titanium.
8. titanium-containing catalyst component according to claim 1 is characterized in that, described titanium compound is a titanium tetrachloride.
9. an olefine polymerizing process is characterized in that, under the olefinic polymerization condition, each component of olefinic monomer and olefin polymerization catalysis is contacted with one of (B) dual mode according to following (A):
(A) olefinic monomer is contacted with alkylaluminium cpd with any described high hydrogen response titanium-containing catalyst of the olefinic polymerization component that is used for of claim 1-8, wherein, the ethene molar content is more than 80% in the described olefinic monomer;
(B) with olefinic monomer and claim 1-8 any one describedly be used for the high hydrogen response titanium-containing catalyst of olefinic polymerization component, alkylaluminium cpd contacts with silicoorganic compound;
Described alkylaluminium cpd is the compound shown in the formula (III),
AlR′
n′X′
3-n′ (III)
In the formula (III), R ' is the alkyl of hydrogen, carbonatoms 1-20 or the aryl of carbonatoms 6-20, and X ' is a halogen, and n ' is the integer of 1-3;
The general formula of described silicoorganic compound is R
fN " Si (OR
y)
4-n", n in the formula " be 0 to 3 integer, R
fBe in alkyl, naphthenic base, aryl, haloalkyl, halogen, the Wasserstoffatoms one or more, R
yBe in alkyl, naphthenic base, aryl, the haloalkyl one or more;
Wherein, the mol ratio of the titanium in aluminium in the alkylaluminium cpd and the titanium-containing catalyst component is 5-5000: 1.
10. according to the olefine polymerizing process of claim 9, it is characterized in that the mol ratio of the titanium in aluminium in the alkylaluminium cpd and the titanium-containing catalyst component is 20-500: 1.
11. want 9 olefine polymerizing process, it is characterized in that described olefinic monomer is at least a in ethene, propylene, 1-n-butene, the positive amylene of 1-, 1-n-hexylene, the positive octene of 1-and the 4-methyl-1-pentene according to right.
12. the described olefine polymerizing process of one of claim 9～11 is in the equal polymerization of propylene, the application during the random copolymerization of propylene and ethene and heterogeneous crushing-resistant copolymerization close.
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| CN107629156A (en) * | 2016-07-18 | 2018-01-26 | 中国石油化工股份有限公司 | Catalytic component for olefinic polymerization and preparation method thereof and the catalyst for olefinic polymerization and its application |
| CN109694424A (en) * | 2017-10-24 | 2019-04-30 | 中国石油化工股份有限公司 | Catalytic component for vinyl polymerization and preparation method thereof and catalyst for vinyl polymerization |
| CN114426602A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Preparation method of solid catalyst component for olefin polymerization |
| WO2023072179A1 (en) * | 2021-10-28 | 2023-05-04 | 中国石油化工股份有限公司 | Olefin polymerization catalyst component, catalyst system, prepolymerization catalyst composition and olefin polymerization method |
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| CN114426602A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Preparation method of solid catalyst component for olefin polymerization |
| CN114426602B (en) * | 2020-10-15 | 2023-05-09 | 中国石油化工股份有限公司 | Preparation method of solid catalyst component for olefin polymerization |
| WO2023072179A1 (en) * | 2021-10-28 | 2023-05-04 | 中国石油化工股份有限公司 | Olefin polymerization catalyst component, catalyst system, prepolymerization catalyst composition and olefin polymerization method |
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