CN102838696A - Olefin polymerization catalyst component, olefin polymerization method and applications - Google Patents
Olefin polymerization catalyst component, olefin polymerization method and applications Download PDFInfo
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- CN102838696A CN102838696A CN2011101722228A CN201110172222A CN102838696A CN 102838696 A CN102838696 A CN 102838696A CN 2011101722228 A CN2011101722228 A CN 2011101722228A CN 201110172222 A CN201110172222 A CN 201110172222A CN 102838696 A CN102838696 A CN 102838696A
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Abstract
The present invention relates to a catalyst component for olefin polymerization and a preparation method thereof, an olefin polymerization method using the olefin polymerization catalyst, and a slurry preparation method. According to the present invention, an auxiliary dispersing agent is added during a catalyst component preparation process, such that the catalyst component prepared by the method of the present invention has characteristics of good fluidity and low polymer refinement compared with the catalyst component prepared by the method without introduction of the auxiliary dispersing agent in the prior art. The method of the present invention has characteristics of available raw materials and low production cost. The catalyst slurry prepared by the catalyst preparation method of the present invention has better stability compared with the catalyst slurry without addition of the auxiliary dispersing agent.
Description
Technical field
The present invention relates to a kind of olefin polymerization catalyst components and preparation method thereof and a kind of olefine polymerizing process of this olefin polymerization catalysis and method of slurries preparation used.
Technical background
It is normally known to be used to prepare polyolefinic olefin polymerization catalyst components, and in general, in the intermittence type polymerization production process, olefin polymerization catalyst components gets into reactor drum with the powder form through inert gas purge or solvent washing; Therefore the catalyzer of good fluidity helps the discharging in the Catalyst Production, shift, and the charging of catalyzer in the olefinic polymerization.
In the continous way polymerization production process; Olefin polymerization catalyst components generally continuously adds reactor drum through volume pump with the slurries form under whipped state; This feed way has accurate measurement, safety advantage such as controlled, and slurries mainly are made up of catalyst component dry powder and liquid dispersion medium.In order to ensure slurries catalyst component steady concentration property in reinforced process, dispersion medium adopts usually and has the chemically inert MO of having of certain viscosity in the slurries, makes olefin polymerization catalyst components sedimentation in MO slower, disperses more even.If the concentration instability of slurries or olefin polymerization catalyst components disperse inhomogeneous in MO; To cause the polymerization reactor temperature fluctuation; Can make local superheating produce caking when serious; Normal operation to device produces great effect, so olefin polymerization catalysis slurries stability is with dispersed significant to the continuous production of gas-phase polymerization polypropylene device.Solid particulate disperses the preparation slurries normally known in liquid; Can realize through churned mechanically mode, but because olefin polymerization catalyst components is the fine particle in 0.1～100 micrometer range, specific surface area is big; Surface energy is very big; Olefin polymerization catalyst components takes place easily to assemble or reunite in being dried to the process of dry powder, olefin polymerization catalyst components dry powder is added in the MO stir simply, take place to assemble or the dry powder particle of reuniting to be difficult to dispersed with stirring even; Therefore the slurries settling velocity of preparation is fast, less stable.
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 after being mixed with slurries, the slurries sedimentation is very fast.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of olefin polymerization catalyst components and preparation method thereof, and a kind of method of catalyst slurry preparation is provided.
The invention provides a kind of olefin polymerization catalyst components; This catalyst component contains titanium, magnesium, phosphorus, internal electron donor compound; MOX and halogen, said internal electron donor are one or more in alkyl ester, aliphatic ether, cyclic aliphatic ether and the aliphatic ketone that is selected from aliphatic series or aromatic carboxylic acid.
The method for preparing olefin polymerization catalyst components of the present invention; Through in the preparation process, adding dispersion aids; Thereby the catalyst component good fluidity that the catalyst component for preparing is obtained than the method for not introducing dispersion aids of prior art, the polymkeric substance segmentation is few.Method raw material of the present invention is easy to get, and production cost is low.
Has better stability through the existing catalyst slurry that does not add dispersion aids of the catalyst slurry that adopts catalyst preparation of the present invention to obtain.
A kind of catalyst component that is used for olefinic polymerization of the present invention, it prepares through following steps:
(1) magnesium compound, organo phosphorous compounds and organic epoxy compounds are contacted in solvent, 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 the internal electron donor compound, filter, washing;
(4) add dispersion aids, after stirring, drying obtains olefin polymerization catalyst components; At least a in wherein said magnesium compound and the titanium compound is halogen-containing compound;
Described dispersion aids is the compound shown in the formula (III),
M
xO
y (III)
In the formula, M is one to tetravalent metal or nonmetal, and x is 1～3, and y is 1～5; Dispersion aids is of a size of 10nm～500nm, and the amount that adds dispersion aids is 0.01%～2% of a solid catalyst.
Catalyst component of the present invention is generally by a kind of mixture solution and is obtaining solid precipitation in the presence of the precipitation additive with after titanium compound contacts, then with said solid precipitation with after the internal electron donor compound contacts, the product that contacts with dispersion aids again; Wherein, said mixture solution contains magnesium compound, organic epoxy compounds, organo phosphorous compounds and solvent, and at least a in wherein said magnesium compound and the titanium compound is halogen-containing compound.
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 think that especially magnesium dichloride is good.
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; 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 for example; In wherein preferred titanium tetrachloride, titanium tetrabromide, the titanium tetra iodide one or more, preferred especially titanium tetrachloride.
According to the present invention; 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; For example 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 are preferably epoxy chloropropane especially.
Said precipitation additive can be this area various precipitation additives commonly used, for example one or more in organic acid, organic acid anhydride, organic ether, the organic ketone, preferably one or more in organic acid anhydride, organic acid, ether and the ketone of carbonatoms 2-20; Particularly; One or more 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 for example, preferred especially Tetra hydro Phthalic anhydride.
Said solvent is one or more in toluene, ethylbenzene, benzene, YLENE, chlorobenzene, hexane, heptane, octane, the decane, wherein is preferably toluene.
Said organo phosphorous compounds can be this area various organo phosphorous compoundss commonly used; For example can be the halo hydrocarbyl carbonate of the hydrocarbyl carbonate of phosphoric acid, phosphorous acid and/or phosphoric acid, phosphorous acid; In concrete for example 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.
Said internal electron donor compound can be the various internal electron donors that this area is commonly used, for example can be in the alkyl ester that is selected from aliphatic series or aromatic carboxylic acid, aliphatic ether, cyclic aliphatic ether, the aliphatic ketone one or more.
Said aliphatic series or aromatic carboxylic acid's alkyl ester, aliphatic ether, cyclic aliphatic ether, aliphatic ketone all can be the various conventional compounds that use in this area, for example can be for being selected from C
1-C
4The C of aliphatic saturated monocarboxylic acid
1-C
4Alkyl ester, C
7-C
8The C of aromatic carboxylic acid
1-C
4Alkyl ester, C
2-C
6Aliphatic ether, C
3-C
4Cyclic ethers, C
3-C
6Saturated fatty ketone.
Particularly; One or more in diisobutyl phthalate, n-butyl phthalate, dimixo-octyl phthalate, phthalic acid 1,3 diamyl ester, methyl-formiate, ethyl formate, formic acid n-propyl, isopropyl formate, butyl formate, methyl acetate, ETHYLE ACETATE, n-propyl acetate, isopropyl acetate, butylacetate, methyl propionate, ethyl propionate, propionic acid n-propyl, isopropyl propionate, butyl propionate, methyl-butyrate, ethyl n-butyrate, butyric acid n-propyl, isopropyl butyrate, butyl butyrate, ether, propyl ether, butyl ether, amyl ether, hexyl ether, THF (THF), acetone, butanone, 2 pentanone, the MIBK for example; Wherein be preferably diisobutyl phthalate, n-butyl phthalate, phthalic acid 1; In 3 diamyl esters, ethyl formate, formic acid n-propyl, isopropyl formate, butyl formate, methyl acetate, ETHYLE ACETATE, n-propyl acetate, isopropyl acetate, butylacetate, methyl propionate, ethyl propionate, propionic acid n-propyl, isopropyl propionate, butyl propionate, methyl-butyrate, ethyl n-butyrate, butyric acid n-propyl, isopropyl butyrate, the butyl butyrate one or more, preferred especially n-butyl phthalate and/or diisobutyl phthalate.
In the preparation process of olefin polymerization catalyst components; Especially carry out in the process of vacuum drying at catalyst suspension; Can be attended by certain bonding phenomenon, before vacuum-drying, add dispersion aids and help reducing the bonding phenomenon between the catalyzer, the mobile property of catalyzer is better; The catalyst slurry settling velocity that obtains after this catalyzer and the mineral oil is slow, and stability better.
Described dispersion aids is inorganic non-metallic or MOX, is preferably MOX, more preferably charged MOX.Said dispersion aids is the compound shown in the formula (III),
M
xO
y (III)
In the formula (III), M is one to tetravalent metal or nonmetal, and x is 1 to 3, and y is 1 to 5.For example can be silicon-dioxide, silit, tindioxide, aluminium sesquioxide, zinc oxide, titanium oxide, powder blue, nickel oxide, zirconium white, vanadium oxide, weisspiessglanz etc.
The dispersion aids that the present invention added is in nanometer scale, and it is of a size of 10nm～500nm, is preferably 20nm～200nm.
The amount of the dispersion aids that is added is 0.01%～2% of a solid catalyst, is preferably 0.02%～1%, more preferably 0.05%～0.5%.
The described MO of preparation catalyst slurry is white oil; Be the mixture of liquid type hydro carbons, staple is the mixture of the positive isoparaffin of C16～C31, and the molecular weight of white oil is usually all within the 250-450 scope; Has good oxidative stability, chemicalstability.The trade mark of white oil is divided and is divided with the size of 40 ℃ of kinematic viscosity usually.40 ℃ of following kinematic viscosity of white oil that method of the present invention adopts are 10～100mm
2/ s is preferably 20～80mm
2/ s, No. 68 white oils more preferably, 40 ℃ of following kinematic viscosity are 68mm
2/ s.
In the catalyst component of the present invention, by weight, general titanium content is 1-10%, and Mg content is 10-20%, and phosphorus content is 0.01-0.5%, and the internal electron donor compounds content is 5-25%, and content of halogen is 40-70%; Preferred titanium content is 1-5%, and Mg content is 15-20%, and phosphorus content is 0.05-0.2%, and the internal electron donor compounds content is 6-14%, and content of halogen is 45-65%.
According to the present invention, the consumption of said various materials there is not particular requirement, all can allocate with reference to this area conventional amount used, for example the consumption of solvent enough dissolves the mixture of various reactants as long as guarantee its consumption.
According to the present invention, the present invention does not have particular requirement to step (1), (2) and the condition that (3) contact, and 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 ℃, is preferably 30-80 ℃; 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), (4) 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.
Among the present invention, said titanium compound, magnesium compound, internal electron donor compound, organic epoxy compounds, precipitation additive, dispersion aids, solvent types are described in detail in preamble, repeat no more at this.
According to preferred implementation of the present invention, the method for preparing olefin polymerization catalysis of the present invention comprises the steps:
Under agitation magnesium halide is dissolved in the solvent solution of 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 ℃, add the internal electron donor compound, whipped state contacts 0.5-8 hour down; Be preferably 1-6 hour, the elimination mother liquor adds solvent (for example toluene) washing; Use mixture process 3-4 time of halogenide and the solvent (for example toluene) of transition metals Ti again, leach liquid, with solvent (for example hexane, toluene) wash solids thing; Add dispersion aids, after stirring, drying obtains olefin polymerization catalysis.
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 olefin polymerization catalyst components of the present invention, wherein, the ethene molar content is more than 80% in the said olefinic monomer;
(B) olefinic monomer is contacted with olefin polymerization catalyst components of the present invention, alkylaluminium cpd and silicoorganic compound;
When although (B) mode contacts, to the not restriction of said alkene; For the polyreaction that is mainly used in ethene; Iff is other alkene of part, at this time only takes (A) mode to contact and can realize the object of the invention, so under the 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 silicoorganic compound can be regulated according to real needs, and the present invention does not have particular requirement.
Said alkylaluminium cpd is the compound shown in the formula (IV),
AlR′
n′X′
3-n′ (IV)
In the formula (IV), 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.Wherein, Be preferably 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, be preferably triethyl aluminum.
Wherein, the general formula of said silicoorganic compound is R
nSi (OR
1)
4-n, n is 0 to 3 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; Be preferably 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, be preferably methylcyclohexyl 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, be preferably 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.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).
Catalyst slurry stability is demarcated through the slurries settling velocity, in 25 milliliters of band scale Glass tubings, injects 20 milliliters of catalyst slurries, leaves standstill the height that reads supernatant liquid after 72 hours, calculates settling velocity.
Embodiment
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; Phosphorus content adopts spectroscopy to record; Internal electron donor compound (organic ester) 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 ASTM D1895-96 standard.
The flowability of catalyzer characterizes through the slope of repose, and the free surface of powder accumulation horizon is called the slope of repose with maximum angle that horizontal plane forms under the statical equilibrium state.The mensuration at slope of repose is poured powder sample in the funnel into, and sample is dropped on down on the circumference flat board through funnel, and powder is piled up gradually, till can not continuing to pile height.Take the static accumulation form of powder with digital camera, picture is imported computingmachine handle acquisition powder granule slope of repose by two dimensional image.The slope of repose is more little, and the flowability of powder is good more.
Embodiment 1
Repeating through high pure nitrogen in the metathetical normal-pressure reaction kettle, adding 4.8 gram Magnesium Chloride Anhydrouss, 98 milliliters of toluene, 4.0 milliliters of epoxy chloropropane, 12.5 milliliters of tributyl phosphates successively, is under 60 ℃ the condition, to react 2 hours in temperature; Add 1.4 gram Tetra hydro Phthalic anhydrides, continue reaction one hour, be cooled to-28 ℃, drip 56 milliliters of titanium tetrachlorides (5 milliliters of rate of addition/rmin); Be warming up to gradually 85 ℃ (temperature rise rate be 5 ℃/min), add 1.1 milliliters of n-butyl phthalates (DNBP), constant temperature one hour filters; Solid adds 48 milliliters of titanium tetrachlorides again with toluene wash twice, and 72 milliliters of toluene were 110 ℃ of constant temperature 0.5 hour; Add 48 milliliters of titanium tetrachlorides after the filtration again, 72 milliliters of toluene were handled once at 110 ℃ of constant temperature in 0.5 hour; Filter then, then with the gained solid with hexane wash 5 times after, adding Al
2O
37.5mg, after thorough mixing is even, leave standstill, outwell supernatant liquid, vacuum-drying obtains ingredient of solid catalyst again.Wherein, by weight, titanium content is 2.4%, and DNBP content is 10.3%, diethyl phthalate (DEP) content is 0.4%, Mg content is 17%, cl content is 48%, phosphorus content is 0.12%, aluminium content is 0.08%.The slope of repose result of catalyst powder sees table 1 for details.
Polymerization embodiment 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 2 for details.
Slurries embodiment 1
In dry 250ml round-bottomed flask, add 28 gram white oils, add 12 grams again through the solid catalyst that embodiment 1 prepares, under 60 ℃ of water-baths, stirred following 6 hours.Get 20 milliliters of catalyst slurries then and inject 25 milliliters of band scale Glass tubings, leave standstill the height that reads supernatant liquid after 72 hours, calculate settling velocity.
Embodiment 2
Catalyst component preparation is consistent with the method for embodiment 1, after the hexane wash that different is 5 times, and the Al of adding
2O
3Be 25mg, wherein, by weight, titanium content is 2.4%, and DNBP content is 10.3%, diethyl phthalate (DEP) content is 0.4%, Mg content is 17%, cl content is 48%, phosphorus content is 0.12%, aluminium content is 0.27%.The slope of repose result of catalyst powder sees table 1 for details.
Polymerization embodiment 2
The catalyzer consistent with the method for polymerization embodiment 1, that the catalyzer that different is adopts makes for embodiment 2, concrete outcome sees table 2 for details.
Slurries embodiment 2
The catalyzer consistent with the method for slurries embodiment 1, that the catalyzer that different is adopts makes for embodiment 2, concrete outcome sees table 3 for details.
Embodiment 3
Catalyst component preparation is consistent with the method for embodiment 1, after the hexane wash that different is 5 times, and the Al of adding
2O
3Be 2.5mg, wherein, by weight, titanium content is 2.4%, and DNBP content is 10.3%, diethyl phthalate (DEP) content is 0.4%, Mg content is 17%, cl content is 48%, phosphorus content is 0.12%, aluminium content is 0.03%.The slope of repose result of catalyst powder sees table 1 for details.
Polymerization embodiment 3
The catalyzer consistent with the method for polymerization embodiment 1, that the catalyzer that different is adopts makes for embodiment 3, concrete outcome sees table 2 for details.
Slurries embodiment 3
The catalyzer consistent with the method for slurries embodiment 1, that the catalyzer that different is adopts makes for embodiment 3, concrete outcome sees table 3 for details.
Embodiment 4
Catalyst component preparation is consistent with the method for embodiment 1, after the hexane wash that different is 5 times, and the SnO of adding
2Be 5mg, wherein, by weight, titanium content is 2.4%, and DNBP content is 10.3%, diethyl phthalate (DEP) content is 0.4%, Mg content is 17%, cl content is 48%, phosphorus content is 0.12%, tin content is 0.08%.The slope of repose result of catalyst powder sees table 1 for details.
Polymerization embodiment 4
The catalyzer consistent with the method for polymerization embodiment 1, that the catalyzer that different is adopts makes for embodiment 4, concrete outcome sees table 2 for details.
Slurries embodiment 4
The catalyzer consistent with the method for slurries embodiment 1, that the catalyzer that different is adopts makes for embodiment 4, concrete outcome sees table 3 for details.
Embodiment 5
The catalyst component preparation is consistent with the method for embodiment 1; After the hexane wash that different is 5 times; The ZnO that adds is 5mg, wherein, and by weight; Titanium content is 2.4%, and DNBP content is 10.3%, diethyl phthalate (DEP) content is 0.4%, Mg content is 17%, cl content is 48%, phosphorus content is 0.12%, zinc content is 0.08%.The slope of repose result of catalyst powder sees table 1 for details.
Polymerization embodiment 5
The catalyzer consistent with the method for polymerization embodiment 1, that the catalyzer that different is adopts makes for embodiment 5, concrete outcome sees table 2 for details.
Slurries embodiment 5
The catalyzer consistent with the method for slurries embodiment 1, that the catalyzer that different is adopts makes for embodiment 5, concrete outcome sees table 3 for details.
Embodiment 6
Catalyst component preparation is consistent with the method for embodiment 1, after the hexane wash that different is 5 times, and the SiO of adding
2Be 7.5mg, wherein, by weight, titanium content is 2.4%, and DNBP content is 10.3%, diethyl phthalate (DEP) content is 0.4%, Mg content is 17%, cl content is 48%, phosphorus content is 0.12%, silicone content is 0.09%.The slope of repose result of catalyst powder sees table 1 for details.
Polymerization embodiment 6
The catalyzer consistent with the method for polymerization embodiment 1, that the catalyzer that different is adopts makes for embodiment 6, concrete outcome sees table 2 for details.
Slurries embodiment 6
The catalyzer consistent with the method for slurries embodiment 1, that the catalyzer that different is adopts makes for embodiment 6, concrete outcome sees table 3 for details.
Comparative example 1
Repeating through high pure nitrogen in the metathetical normal-pressure reaction kettle, adding 4.8 gram Magnesium Chloride Anhydrouss, 98 milliliters of toluene, 4.0 milliliters of epoxy chloropropane, 12.5 milliliters of tributyl phosphates successively, is under 60 ℃ the condition, to react 2 hours in temperature; Add 1.4 gram Tetra hydro Phthalic anhydrides, 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 1.1 milliliters of n-butyl phthalates (DNBP), constant temperature one hour filters; Solid adds 48 milliliters of titanium tetrachlorides again with toluene wash twice, 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; Handle once 110 ℃ of constant temperature 0.5 hour, filter then, then with the gained solid with hexane wash 5 times after; Leave standstill, outwell supernatant liquid, vacuum-drying obtains ingredient of solid catalyst again.Wherein, by weight, titanium content is 2.4%, and DNBP content is 10.3%, diethyl phthalate (DEP) content is 0.4%, Mg content is 17%, cl content is 48%, phosphorus content is 0.12%.The slope of repose result of catalyst powder sees table 1 for details.
Polymerization Comparative Examples 1
The catalyzer consistent with the method for polymerization embodiment 1, that the catalyzer that different is adopts makes for embodiment 2, concrete outcome sees table 2 for details.
Slurries Comparative Examples 1
The catalyzer consistent with the method for slurries embodiment 1, that the catalyzer that different is adopts makes for embodiment 2, concrete outcome sees table 3 for details.
The foregoing description, polymerization embodiment, slurries embodiment represent catalyzer compound experiment, polymerization experiment and slurries preparation experiment respectively.
Table 1
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | Comparative Examples |
| Slope of repose (degree) | 32 | 30 | 38 | 32 | 34 | 36 | 40 |
Can find out that from table 1 the process dispersion aids is handled, its slope of repose obviously reduces, and explains that the mobile property of catalyzer is better.
Table 2
| Polymerization embodiment | 1 | 2 | 3 | 4 | 5 | 6 | Comparative Examples |
| Active (10 4g?PP/g?cat) | 3.71 | 3.60 | 3.55 | 3.52 | 3.61 | 3.5 | 3.5 |
| Less than 60 order fine powders (%) | ＜0.4 | 0.5 | 0.4 | ＜0.4 | ＜0.4 | 0.5 | 0.6 |
Can find out that from table 2 behind the adding dispersion aids, catalyst activity does not reduce, segmentation reduces
Table 3
| Slurries embodiment | 1 | 2 | 3 | 4 | 5 | 6 | Comparative Examples |
| Settling velocity (mm/h) | 0.11 | 0.14 | 0.20 | 0.10 | 0.18 | 0.19 | 0.25 |
Can find out that from table 3 behind the adding dispersion aids, the settling velocity of catalyst slurry reduces greatly, slurries are more stable.
Show that from experimental result add the better than the mobile property of the catalyzer that does not add dispersion aids of dispersion aids, fine polymer powder is few, resulting slurries stability significantly improves.
Claims (13)
1. a catalyst component that is used for olefinic polymerization is characterized in that, it prepares through following steps:
(1) magnesium compound, organo phosphorous compounds and organic epoxy compounds are contacted in solvent, 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 the internal electron donor compound, filter, washing;
(4) add dispersion aids, after stirring, drying obtains olefin polymerization catalyst components;
At least a in wherein said magnesium compound and the titanium compound is halogen-containing compound;
Described dispersion aids is the compound shown in the formula (III),
M
xO
y (III)
In the formula, M is one to tetravalent metal or nonmetal, and x is 1～3, and y is 1～5; Dispersion aids is of a size of 10nm～500nm, and the amount that adds dispersion aids is 0.01%～2% of a solid catalyst.
2. the catalyst component that is used for olefinic polymerization according to claim 1 is characterized in that described dispersion aids is of a size of 20nm～200nm, and the amount that adds dispersion aids is 0.05%～0.5% of a solid catalyst.
3. the catalyst component that is used for olefinic polymerization according to claim 1; It is characterized in that described dispersion aids is a kind of in silicon-dioxide, tindioxide, aluminium sesquioxide, zinc oxide, titanium oxide, powder blue, nickel oxide, zirconium white, vanadium oxide, the weisspiessglanz.
4. the catalyst component that is used for olefinic polymerization according to claim 1; It 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.
5. the catalyst component that is used for olefinic polymerization 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.
6. the catalyst component that is used for olefinic polymerization 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.
7. the ethylene polymerization catalysts component that is used for according to claim 1 is characterized in that described titanium compound is a titanium tetrachloride.
8. the catalyst component that is used for olefinic polymerization according to claim 1 is characterized in that, said internal electron donor is selected from one or more in aliphatic series or aromatic carboxylic acid's the alkyl ester, aliphatic ether, cyclic aliphatic ether, aliphatic ketone.
9. the catalyst component that is used for olefinic polymerization according to claim 1 is characterized in that, said internal electron donor is n-butyl phthalate and/or diisobutyl phthalate.
10. 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 olefin polymerization catalyst components of claim 1-9, wherein, the ethene molar content is more than 80% in the described olefinic monomer;
(B) olefinic monomer is contacted with claim 1-9 any described olefin polymerization catalyst components, alkylaluminium cpd and silicoorganic compound;
Said alkylaluminium cpd is the compound shown in the formula (IV),
AlR′
n′X′
3-n′ (IV)
In the formula (IV), 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 said silicoorganic compound is R
nSi (OR
1)
4-n, n is 0 to 3 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;
Wherein, the mol ratio of aluminium in the alkylaluminium cpd and the titanium in the olefin polymerization catalyst components is 5-5000: 1.
11. the olefine polymerizing process according to claim 10 is characterized in that, the aluminium in the alkylaluminium cpd and the mol ratio of the titanium in the olefin polymerization catalyst components are 20-500: 1.
12. the olefine polymerizing process according to claim 10 is characterized in that, described alkene 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.
13. the described olefine polymerizing process of one of claim 10～12 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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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106957379A (en) * | 2016-01-12 | 2017-07-18 | 中国石油化工股份有限公司 | A kind of preparation method of catalytic component for vinyl polymerization |
| CN116023527A (en) * | 2021-10-27 | 2023-04-28 | 中国石油化工股份有限公司 | Slurry catalyst and paste catalyst, and preparation methods and applications thereof |
| CN116023549A (en) * | 2021-10-27 | 2023-04-28 | 中国石油化工股份有限公司 | Prepolymerized catalyst, preparation method and application thereof |
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|---|---|---|---|---|
| US4376062A (en) * | 1979-11-28 | 1983-03-08 | Union Carbide Corporation | Spheroidal polymerization catalyst, process for preparing, and use for ethylene polymerization |
| CN1493599A (en) * | 2002-10-31 | 2004-05-05 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization |
| CN101643520A (en) * | 2008-08-07 | 2010-02-10 | 中国石油化工股份有限公司 | Catalyst for propene polymerization |
| CN101906181A (en) * | 2009-06-04 | 2010-12-08 | 中国石油化工股份有限公司 | Catalyst component used for ethylene polymerization and preparation method thereof |
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2011
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|---|---|---|---|---|
| US4376062A (en) * | 1979-11-28 | 1983-03-08 | Union Carbide Corporation | Spheroidal polymerization catalyst, process for preparing, and use for ethylene polymerization |
| CN1493599A (en) * | 2002-10-31 | 2004-05-05 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization |
| CN101643520A (en) * | 2008-08-07 | 2010-02-10 | 中国石油化工股份有限公司 | Catalyst for propene polymerization |
| CN101906181A (en) * | 2009-06-04 | 2010-12-08 | 中国石油化工股份有限公司 | Catalyst component used for ethylene polymerization and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106957379A (en) * | 2016-01-12 | 2017-07-18 | 中国石油化工股份有限公司 | A kind of preparation method of catalytic component for vinyl polymerization |
| CN116023527A (en) * | 2021-10-27 | 2023-04-28 | 中国石油化工股份有限公司 | Slurry catalyst and paste catalyst, and preparation methods and applications thereof |
| CN116023549A (en) * | 2021-10-27 | 2023-04-28 | 中国石油化工股份有限公司 | Prepolymerized catalyst, preparation method and application thereof |
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