CN104974283B - Catalyst component used in ethylene polymerization reaction, catalyst and preparation method thereof - Google Patents
Catalyst component used in ethylene polymerization reaction, catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a catalyst component used in ethylene polymerization reaction, a preparation method of the catalyst component and a catalyst thereof. The catalyst component is formed by supporting at least one inorganic titanium compound, at least one organic titanium compound, at least one electron donor compound and at least one activating agent onto a solid substance containing magnesium/titanium. The solid substance containing magnesium/titanium is prepared by dissolving a magnesium compound in a solvent system containing an organic epoxy compound and an organic phosphorus compound to form a uniform solution, and performing co-precipitation to a titanium compound with one or more organic ester compounds in the presence of a composite precipitation aid. The catalyst component is narrow in particle distribution and is less in average particle size. The catalyst is high in activity and hydrogen regulation sensitivity and can be used for preparing low-fine-powder-content polymers.
Description
Technical field
The invention belongs to field of olefin polymerisation, relates in particular to a kind of catalyst closed for ethylene homo with combined polymerization
Component, the preparation method of the catalytic component, corresponding catalyst and its application in vinyl polymerization.
Background technology
In olefinic polyreaction, particularly ethylene homo is closed or ethylene is closed in reaction with alpha-olefin copolymer, is adopted mostly
Using magnesium, titanium, halogen and electron donor as the catalytic component of basis.When this kind of catalyst is for gas-phase fluidized-bed poly-
When closing technique, it is to ensure that catalyst granules form and particle size distribution are more suitable for fluidized state operation, typically by above-mentioned catalyst
Component is carried on the carriers such as silica gel.For example：Disclosed in US4,302,565, US4,379,759 and CN1064870A for gas
The catalyst of phase fluidized-bed reaction, is the precursor components dipping prepared by titanium compound, magnesium compound and electron donor compound
On the carrier mass such as silica gel, then process impregnated precursor components to prepare with reactive compound.US4,302,565,
US4, the mean diameter of the silica gel used in 379,759 is 50～150 microns, and surface area is more than 50 meters2/ gram, average pore size
More than 80 angstroms.
In patent disclosed above, in order that catalyst is applicable to gas-phase fluidized bed polymerization process, to what is used
The mean diameter of carrier silicas, surface area, aperture have compared with strict requirements, and the price of this carrier mass compared with
Expensive, while need to carry out strict activation to silica supports using front, these all cause the increasing of the production cost of catalyst
Plus；And catalyst activity component is supported on carrier by impregnating method, due to carrying the restriction of titanium amount, its catalyst is imitated
Rate is also unsatisfactory.In addition, it is larger using fine powder amount in the polyethylene powder of the Catalyst Production, usual less than 150 microns
Granule accounts for 15Wt% of whole powders or so, and this point is highly undesirable in the industrial production.Meanwhile, the catalyst is in application
When ethylene gas fluidised bed polymerisation device, catalyst is fed using solid form mostly, and charging process stability is poor, is easily occurred
Plugging and arch formation.And the catalyst of the present invention is due to being enhanced in terms of catalysis activity, therefore can adopt lazy
Property diluent by catalyst dilution, realize that by pumping feeding manner uniform liquid feeds, to solve above-mentioned catalyst charge
Middle produced problem.
And the catalyst manufacturing process being previously mentioned in the Chinese patent of Publication No. CN1085915A, although before overcoming
Some shortcomings described in face, but need to use in process of production magnesium metal as reducing agent, and still need to using substantial amounts of
Silicon dioxide is used as carrier, in addition it is also necessary to obtain catalyst particles granule product using the method being spray-dried, and equipment investment is big, operation is multiple
It is miscellaneous, make overall manufacturing cost still higher.
Disclose a kind of for olefin polymerization catalysis in Chinese patent CN85100997, which is dissolved in by magnesium halide
Organic epoxy compound thing, organic phosphorus compound form homogeneous solution, then give with least one precipitation additive, a kind of multi-carboxylate
What the halogenide and its derivant of electron and transition metals Ti was acted on and was prepared, when the catalyst is used for propylene polymerization, show
Show higher polymerization activity and preferably stereoselectivity, but it is low for activity during vinyl polymerization, and the grain of polymer
Degree wider distribution, and the hydrogen response of the catalyst is bad.
On the basis of CN85100997, Chinese patent CN1229092A discloses one kind again for vinyl polymerization or copolymerization
The catalyst of conjunction, which is to be dissolved in organic epoxy compound thing, organic phosphorus compound by magnesium halide and add electron donor to intensify
Dosage form uniformly solution, then with the halogenide and its derivant effect of at least one precipitation additive and transition metals Ti and prepare
, the catalyst is used for showing very high activity during the slurry polymerization of ethylene, while the particle shape of resulting polymers is preferably,
Apparent density is also higher.This catalytic component for adding alcohols activator is being used for ethene gas-phase polymerization technique, particularly
During fluidized bed polymerization process, especially starting stage of polyreaction, polyreaction are very fast, the polymer of generation is easily broken
Broken, polymer beads are thinner, and 70～150 microns of particle size distribution accounts for 50Wt%～60Wt%, and morphology is not yet
It is good, it is as a result unsatisfactory.
Therefore it is highly desirable to a kind of efficient, high hydrogen response to be provided and solid of the low fine containing weight polymers is obtained and urges
Agent component, makes this kind of catalytic component have the distribution of particles and less mean diameter of opposite, narrow, and catalyst activity is higher,
Slurry polymerization or the gas-phase polymerization of ethylene is suitable to, the gas-phase fluidized-bed of the ethylene that catalyst is fed as a slurry is particularly well-suited to
Polymerization technique.Through inventor design and test repeatedly, invent and need not adopt silica-gel carrier, but will consolidate containing magnesium titanium
Body thing is used as carrier components, and loads upper certain titanium compound, electron donor and activator, and the mean diameter of granule is obtained
Catalyst that is less and being evenly distributed, the catalyst have high catalytic activity, high hydrogen response and low fine are obtained and contain
Weight polymers, it is adaptable to the homopolymerization of ethylene or copolymerization.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of catalytic component and its catalyst for vinyl polymerization, should
Catalyst activity is high, with high hydrogen response and the polymer of low fine content is obtained, and makes this kind of catalytic component
Distribution of particles with opposite, narrow and less mean diameter, are suitable to slurry polymerization or the gas-phase polymerization of ethylene, are particularly well-suited to
The ethylene gas-phase fluidized bed polymerization process that catalyst is fed as a slurry.
An object of the present invention is to provide a kind of catalytic component for ethylene polymerization, and which is contained in one kind
On the solidss of magnesium titanium, in load, at least one inorganic titanium compound, at least one organic titanic compound, at least one are to electricity
Donor compound and at least one activator, the solidss containing magnesium titanium are prepared by following methods：Magnesium compound is dissolved
In the dicyandiamide solution containing organic epoxy compound thing and organic phosphorus compound, after forming homogeneous solution, in compound precipitation additive
In the presence of obtain the solidss containing magnesium titanium with titanium compound and the co-precipitation of one or more organic esterses；Described answers
Conjunction precipitation additive be organic acid anhydride, organic acid, ether, a kind of and titanous chloride. in ketone, a kind of material in aluminum chloride it is mixed
Compound；Aromatic carboxylic acids alkyl of the described organic esterses selected from the Arrcostab or C7～C8 of C1～C4 aliphatic saturated monocarboxylic acids
One kind or their mixture in ester；Described titanium compound is titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four butoxy
One kind in titanium, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl epoxide titanium, one ethanolato-titanium of trichlorine or theirs is mixed
Compound.
The formula of described inorganic titanium compound and organic titanic compound is Ti (OR)aXb, in formula, R is C1～C14Fat
Race's alkyl or aromatic hydrocarbyl, X is halogen atom, and a is 0～4 integer, and b is 0～4 integer, a+b=3 or 4.
Described electron donor compound is selected from aliphatic ether, cyclic aliphatic ether or aliphatic ketone.
The formula of described activator is AlR 'cX’dHe, in formula, R ' is C1～C14Saturated hydrocarbyl, X ' be halogen atom, c
It is 1～3 integer, d is 0～2 integer, and e is 0 or 1, c+d+e=3.
Wherein described magnesium compound is selected from magnesium dihalide, the hydrate of magnesium dihalide or alcohol adduct and magnesium dihalide point
One kind in the minor derivant replaced by oxyl or halo oxyl by one of halogen atom, or their mixing
Thing.
Described organic epoxy compound thing selected from carbon number 2～8 aliphatic olefin, alkadienes or halogenated aliphatic group
At least one in the oxide of alkene or alkadienes, glycidyl ether and inner ether, for example：Oxirane, expoxy propane, epoxy
Butane, butadiene oxide, butadiene double oxide, epoxychloropropane, methyl glycidyl ether, diglycidyl ether etc..
Described organic phosphorus compound is hydrocarbyl carbonate or the halogenated hydrocarbons base ester of orthophosphoric acid or phosphorous acid, specifically such as：Orthophosphoric acid
Trimethyl, orthophosphoric acid triethyl, orthophosphoric acid tributyl, orthophosphoric acid triphenylmethyl methacrylate, NSC 6513, NSC 5284, phosphorous
Sour tributyl or phosphorous acid benzene methyl etc..
In order that dissolving is more fully, inert diluent is can be optionally added in the dicyandiamide solution, generally this inertia
Diluent includes arene compounds or alkane derivative, arene compounds include benzene,toluene,xylene, monochlor-benzene,
Dichlorobenzene, trichloro-benzene, monochlorotoluene and its derivant；Alkane includes linear paraffin, branched paraffin or the ring of 3～20 carbon
One kind or their mixture in alkane, such as butane, pentane, hexane, hexamethylene, heptane etc., as long as it is molten to contribute to magnesium halide
What is solved can use.Above-mentioned inert diluent can be used alone, and also can be combined and uses.
Described organic esterses are selected from C1～C4The Arrcostab or C of aliphatic saturated monocarboxylic acid7～C8Aromatic carboxylic acids alkane
One kind or their mixture in base ester；Preferably in methyl acetate, ethyl acetate, essence of Niobe, ethyl benzoate
One or more.
Described compound precipitation additive is organic acid anhydride, organic acid, ether, the one kind in ketone and titanous chloride., aluminum chloride
In a kind of material mixture, specifically such as：Acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, equal benzene four
Formic acid dianhydride, acetic acid, propanoic acid, butanoic acid, acrylic acid, methacrylic acid, acetone, butanone, benzophenone, methyl ether, ether, propyl ether,
A kind of a kind of mixture of the material in and titanous chloride., aluminum chloride in butyl ether, amyl ether；Wherein organic acid anhydride, organic acid,
A kind of mol ratio in a kind of and titanous chloride., aluminum chloride in ether, ketone is 0.1～10:1.
Catalytic component of the present invention is further to load at least one inorganic titanium on the above-mentioned solidss containing magnesium titanium
Compound, at least one organic titanic compound, at least one electron donor and at least one activator.
The formula of described inorganic titanium compound and organic titanic compound is Ti (OR)aXb, in formula, R is C1～C14Fat
Race's alkyl or aryl, X is halogen, and a is 0～4 integer, and b is 0～4 integer, a+b=3 or 4；Specially titanous chloride., tribromo
Change titanium, titanium triiodide, titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, purity titanium tetraethoxide, four titanium propanolates, four titanium butoxides, one
Chlorine triethoxy titanium, dichlorodiethyl epoxide titanium, one ethanolato-titanium of trichlorine, three titanium butoxide of a chlorine, dichloro dibutoxy titanium, trichlorine
One kind or their mixture in one titanium butoxide, preferably titanous chloride., titanium tetrachloride, purity titanium tetraethoxide, four titanium butoxides
Deng.
Described suitable electron donor compound is selected from aliphatic ether, cyclic aliphatic ether and aliphatic ketone；Preferably C1～C4Saturation
The Arrcostab of aliphatic carboxylic acid, C7～C8The Arrcostab of aromatic carboxylic acids, C2～C6Aliphatic ether, C3～C4Cyclic ethers, C3～C6Saturated fat
Ketone.Specially methyl formate, ethyl acetate, butyl acetate, ether, hexyl ether, tetrahydrofuran, acetone and methyl iso-butyl ketone (MIBK)
Can be used alone Deng, this kind of electron donor or several use cooperatively.
The formula of described activator is AlR 'cX’dHe, in formula, R ' is C1～C14Saturated hydrocarbyl, X ' be halogen atom, c
It is 1～3 integer, d is 0～2 integer, and e is 0 or 1, c+d+e=3.AlEt is can select specifically3、Al(n-C6H13)3、Al(n-
Bu)3、Al(i-Bu)3、AlEt2Cl etc..
The catalytic component of the present invention can also contain alcohol compound, and alcohol compound is containing 2 to 10 carbon originals
The aliphatic alcohol compound of son, in terms of every mole of magnesium compound, the consumption of alcohol compound is 0.1～3 mole.
The second object of the present invention is to provide a kind of preparation method of catalyst component for polymerization of ethylene, it is preferred to use following
Step is prepared：
1) preparation of the solidss A containing magnesium titanium：Magnesium compound is dissolved in into organic epoxy compound thing and organic phosphorus compound
Dicyandiamide solution in, after forming homogeneous solution, then the halogenide with titanium and its derivant mix, in compound precipitation additive and one kind
Or in the presence of several organic esterses, separate out the solidss A containing magnesium titanium；
Ratio wherein between each component, in terms of every mole of magnesium compound, organic epoxy compound thing is 0.2～10 mole,
Organic phosphorus compound is 0.1～3 mole, and it is 0.03～1.0 mole to be combined precipitation additive, 0～1 mole of organic esterses,
The halogenide of titanium and its derivant are 0.5～120 mole；
2) preparation of B solution：At least one inorganic titanium compound and at least one organic titanic compound are dissolved in electricity
In donor compound, B solution is formed.Ratio wherein between each component, in terms of every mole of inorganic titanium compound, organic titanium chemical combination
Thing is 0.1～10 mole, and electron donor compound is 1～50 mole；
3) B solution is reacted with the solid content A containing magnesium titanium for being separated out.Ratio wherein between each component, with
Every mole of magnesium compound meter, 0.1～10 mole of inorganic titanium compound；
4) formula is adopted for AlR 'cX’dHeActivator is to step（3）The product for obtaining is activated, and obtains catalyst
Component, in terms of every mole of magnesium compound, 0.01～10 mole of activator.
In the catalytic component obtained by the present invention, titanium：1～10%, aluminum：0.1～2%, electron donor：1～40%（Weight
Amount content）.
The invention further relates to a kind of for vinyl polymerization or the catalyst of combined polymerization, it contains above-mentioned catalyst of the present invention
The product of component and organo-aluminum compound, the formula of organo-aluminum compound wherein used is AlR "3, R " and for identical or not
Identical C1～C8Alkyl, wherein one or two alkyl can replace by chlorine, can select one or more alkyl
Aluminum is used in mixed way, preferably AlEt3、Al(iso-Bu)3、Al(n-C6H13)3、Al(n-C8H17)3、AlEt2Cl etc..Catalytic component with
In terms of every gram of catalytic component, organo-aluminum compound consumption is ratio between organo-aluminum compound：0.1mmol～10mmol,
Preferably 0.5mmol～3mmol.
The catalyst of the present invention is applied to the combined polymerization of the homopolymerization of ethylene or ethylene and other alpha-olefins, wherein alpha-olefin
Using the one kind in propylene, 1-butylene, 1- amylenes, 1- hexenes, 1- octenes, 4- methylpentenes -1.Its polymerization technique adopts gas phase
Method, slurry process and solwution method, more suitable for gas fluidised bed polymerisation, particularly gas-phase fluidized-bed condensation technology.Simultaneously as
The activity of catalyst of the present invention is very high, therefore can be using inert diluent by catalyst dilution, such as mineral oil etc., by being pumped into
Realizing equably catalyst slurry charging, charging is uniform, stable operation for material mode.
Specific embodiment
Method of testing：
1st, melt index（MI）It is to be determined according to ASTM D1238-99；
2nd, flow index（FI）It is to be determined according to ASTM D1238-99；
3rd, melt flow ratio（MFR）It is the ratio of melt index and flow index；
4th, density polymer is determined according to GB-1033；
5th, particle size distribution：According to the method for the optical diffraction principle based on one-wavelength laser, use " Malvern Instr.2600 "
Tester.
Following examples are citing descriptions more detailed to the present invention, but the invention is not limited in these embodiments.
Embodiment 1：
1st, the preparation of catalytic component
Under nitrogen protection, by 4.8 grams of magnesium chlorides, 90 milliliters of toluene, 4.0 milliliters of epoxychloropropane, 12.5 milliliters of phosphoric acid
Tributyl, 0.5ml ethanol are added in reactor, and under conditions of speed of agitator 450rpm, temperature are 60 DEG C, reaction two is little
When, add 1.5 grams of titanous chloride .s and add 1.4 grams of phthalic anhydrides, continue reaction one hour, be cooled to -28 DEG C, add
1.4ml ethyl benzoate, 56 milliliters of Deca titanium tetrachloride are gradually heating to 85 DEG C, constant temperature one hour, filter off mother solution, Jing inertia
Diluent toluene and organic solvent hexane are dried after repeatedly washing, and obtain the solidss A containing magnesium titanium.
Tetra- titanium butoxides of 10ml and 10ml tetrahydrofurans are added in dissolution kettle, 1 gram of trichlorine after stirring, is added
Change titanium, dissolving under conditions of speed of agitator 450rpm forms compound titanium solution B.
11 grams of solidss A are added in another reactor, 100ml isopentane are added, is 10 in stirring 200rpm, temperature
Deca 10ml compound titanium solution B under conditions of DEG C.React one hour under room temperature, filter solution, and washed twice with hexane,
60ml isopentane is added, the aluminium diethyl monochloride solution reaction of 3.5 milliliters of volumetric concentrations 26.43% one hour is dried by evaporation
Granular solids thing component C19.6 gram is obtained, wherein contains Ti2.52%（Weight）、Mg15.63%（Weight）, aluminum 1.23%（Weight
Amount）, tetrahydrofuran 28.66%（Weight）.
2nd, it is polymerized
Volume is 2 liters of stainless steel cauldron, Jing after hydrogen gas are sufficiently displaced from, is pressed into about 0.5 liter of hexane with nitrogen, uses
Syringe implantation concentration is 1mmol/ml triethyl aluminum hexane solution 2ml, adds above-mentioned solid constituents C of 20mg under stirring,
Supplement about 1 liter of hexane total amount.
Feed, 2.8 × 105Pa H2, 7.5 × 105Pa ethylene, polymerization temperature
Spend for 85 DEG C, react two hours, lower the temperature, overbottom pressure in kettle of draining, release polymer syrup liquid material, filter off hexane, polymer is dried,
Polyethylene powder is obtained, 1 is the results are shown in Table.
Embodiment 2
Tetra- titanium butoxides of 5ml and 10ml tetrahydrofurans are added in dissolution kettle, 1 gram of tri-chlorination after stirring, is added
Titanium, dissolving under conditions of speed of agitator 450rpm form compound titanium solution D.
In a kettle., A11 gram of the solidss prepared in embodiment 1 are added, 100ml isopentane is added, is being stirred
200rpm, temperature are Deca 10ml compound titanium solution D under conditions of 10 DEG C.React one hour under room temperature, filter solution, and
Washed twice with hexane, add 60ml isopentane, the aluminium diethyl monochloride solution reaction one of 3.5 milliliters of volumetric concentrations 26.43%
Hour, it is dried by evaporation and obtains granular solids thing component E16.3 gram, wherein contains Ti1.96%（Weight）、Mg15.47%（Weight
Amount）, aluminum 0.242%（Weight）, tetrahydrofuran 27.65%（Weight）.
Polymerization evaluation condition the results are shown in Table 1 with embodiment 1.
Embodiment 3
Tetra- titanium butoxides of 3ml and 10ml tetrahydrofurans are added in dissolution kettle, 1 gram of tri-chlorination after stirring, is added
Titanium, dissolving under conditions of speed of agitator 450rpm form compound titanium solution F.
In a kettle., A11 gram of the solidss prepared in embodiment 1 are added, 100ml isopentane is added, is being stirred
200rpm, temperature are Deca 10ml compound titanium solution F under conditions of 10 DEG C.React one hour under room temperature, filter solution, and
Washed twice with hexane, add 60ml isopentane, the aluminium diethyl monochloride solution reaction one of 3.5 milliliters of volumetric concentrations 26.43%
Hour, it is dried by evaporation and obtains granular solids thing component G15.6 gram, wherein contains Ti1.88%（Weight）、Mg15.35%（Weight
Amount）, aluminum 0.49%（Weight）, tetrahydrofuran 29.63%（Weight）.
Polymerization evaluation condition the results are shown in Table 1 with embodiment 1.
Embodiment 4
Method for preparing catalyst is changed to 3 grams with embodiment 1, the titanous chloride. consumption before Deca is separated out.Obtain graininess solid
Body thing component H22.2 gram, wherein contains Ti1.99%（Weight）.
Polymerization evaluation condition the results are shown in Table 1 with embodiment 1.
Embodiment 5
Method for preparing catalyst is with embodiment 3
Polymerization evaluation condition：Volume is 2 liters of stainless steel cauldron, Jing after hydrogen gas are sufficiently displaced from, is pressed into nitrogen
About 0.5 liter of hexane, is 1mmol/ml triethyl aluminum hexane solution 2ml with syringe implantation concentration, adds 50mg under stirring
Catalytic component C, supplements about 1 liter of hexane total amount.
Feed, 6.8 × 105Pa H2, 3.5 × 105Pa ethylene, polymerization temperature
Spend for 85 DEG C, react two hours, lower the temperature, overbottom pressure in kettle of draining, release polymer syrup liquid material, filter off hexane, polymer is dried,
Polyethylene powder is obtained, 1 is the results are shown in Table.
Comparative example 1
4.8 grams of magnesium chlorides, 90 milliliters of toluene, 4.0 milliliters of epoxychloropropane, 12.5 milliliters of tributyl phosphates are added to instead
Answer in kettle, under conditions of speed of agitator 450rpm, temperature are 60 DEG C, react two hours, add 1.4 grams of phthalic anhydrides,
Continue reaction one hour, be cooled to -28 DEG C, 56 milliliters of Deca titanium tetrachloride is gradually heating to 85 DEG C, constant temperature one hour, filter off
Mother solution, is dried Jing after inert diluent toluene and organic solvent hexane are repeatedly washed, obtains the solidss J containing magnesium titanium.
Tetra- titanium butoxides of 3ml and 10ml tetrahydrofurans are added in dissolution kettle, 1 gram of tri-chlorination after stirring, is added
Titanium, dissolving under conditions of speed of agitator 450rpm form compound titanium solution K.
In a kettle., J11 gram of the solidss for preparing are added, 100ml isopentane is added, in stirring 200rpm, temperature is
Deca 10ml compound titanium solution K under conditions of 10 DEG C.React one hour under room temperature, filter solution, and two are washed with hexane
It is secondary, add 60ml isopentane, the aluminium diethyl monochloride solution reaction of 3.5 milliliters of volumetric concentrations 26.43% one hour, Jing evaporations
Granular solids thing component L14.1 gram is dried to obtain, wherein contains Ti1.83%（Weight）、Mg11.84%（Weight）, aluminum 0.77%
（Weight）, tetrahydrofuran 32.28%（Weight）.
Polymerization evaluation condition the results are shown in Table 1 with embodiment 1.
Comparative example 2
Catalytic component is prepared according to the method disclosed in Chinese patent CN1463991A：
4.8 grams of anhydrous magnesium chlorides, 93 milliliters of toluene, 4.0 milliliters of epoxychloropropane, 12.5 milliliters of tributyl phosphates are added
To in the reactor being sufficiently displaced from through nitrogen, under conditions of speed of agitator 450rpm, temperature are 60 DEG C, react two hours,
1.4 grams of phthalic anhydrides are added, is continued reaction one hour, is cooled to -28 DEG C, with 56 milliliters of 1 hour Deca titanium tetrachloride, used
85 DEG C are gradually heating within 2 hours, constant temperature one hour. solidss are gradually separated out in temperature-rise period. filter off mother solution, Jing toluene Radix Chloranthi Serrati
Alkane is dried after washing twice, obtains the solidss M containing magnesium titanium.
10 grams of solidss A are added in another reactor being sufficiently displaced from through nitrogen, add 90ml isopentane, 0.3
Gram titanous chloride. and 30 milliliters of tetrahydrofurans, react one hour under room temperature, filter solution, add 90ml isopentane, 3.5 milliliters
The aluminium diethyl monochloride hexane solution of volumetric concentration 26.43% reacts one hour at room temperature, is dried by evaporation and obtains graininess admittedly
Body thing component N.
Polymerization evaluation condition the results are shown in Table 1 with embodiment 7.
Comparative example 3
According to US4,302,565, US4, the composition and content disclosed in 379,759 is prepared using the method for infusion process and is urged
Agent component：
The activation of silica gel：By 948# spherical silica gels（Grace companies of the U.S.）Activate 4 hours at 600 DEG C,
100mlTHF, titanous chloride. 0.74g, magnesium chloride 1.13g is added into reactor, 70 DEG C are warming up to, and reaction 1 is little
When, it is standby as masterbatch.Isopentane 60ml is added to another reactor, the silica gel 10g after above-mentioned activation, triethyl aluminum is added
4.3ml, normal-temperature reaction 30min, in the isopentane in distillating still at 55 DEG C to material in reactor, the content of aluminum is 1.65%,
Then ready masterbatch is transferred in the reactor, has been warming up to backflow and has produced, constant temperature 1 hour.In distillation reactor
THF is 12.6% to material THF contents in kettle, to add and react 30min under isopentane 86ml, aluminium diethyl monochloride 5.3ml room temperature,
Add 30min is reacted under tri-n-hexyl aluminum 3.3ml room temperature.It is vacuum dried to obtain granular solids P.In final catalytic component
Containing Ti0.78%（Weight）、Mg1.58%（Weight）, tetrahydrofuran 10.9%（Weight）.
Polymerization evaluation condition the results are shown in Table 1 with embodiment 7.
Comparative example 4
Catalytic component is prepared according to the method disclosed in Chinese patent CN1229092A：
In Jing high-purity Ns2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2, 60ml toluene,
0.032mol epoxychloropropane, 0.022mol tributyl phosphates, 0.017mol ethanol, are warming up to 80 DEG C, and maintain 15 under stirring
Minute solid is completely dissolved, and forms homogeneous solution, is subsequently adding phthalic anhydride 0.0074mol, then maintains 1 hour, should
Solution is cooled to -25 DEG C, then 0.5mol titanium tetrachlorides are instilled in which, is then to slowly warm up to 80 DEG C, reacts 3 hours, filters
Washed 6 times with toluene and hexane respectively afterwards, be vacuum dried, obtain solid catalyst Q.
Vinyl polymerization：Volume is 2 liters of rustless steel kettle Jing N2After being sufficiently displaced from, hexane 1000ml, three second are added wherein
Base aluminum 2.5mmol/l hexanes, above-mentioned 2.4 milligrams prepared of ingredient of solid catalyst（0.0025mmol is calculated as with titanium）, heat up
To 70 DEG C, then being passed through ethylene makes kettle interior up to 0.6MPa（Gauge pressure）, at 70 DEG C, it is polymerized 2 hours, the results are shown in Table 1.
The polymerization result of 1 embodiment of table and comparative example
Claims (18)
1. a kind of catalytic component for ethylene polymerization, which is on a kind of solidss containing magnesium titanium, in load at least
A kind of inorganic titanium compound, at least one organic titanic compound, at least one electron donor compound and at least one activator,
Characterized in that, the solidss containing magnesium titanium are prepared by following methods：Magnesium compound is dissolved in containing organic epoxidation
In the dicyandiamide solution of compound and organic phosphorus compound, after forming homogeneous solution, with titanium compound in the presence of compound precipitation additive
The solidss containing magnesium titanium are obtained with one or more organic esterses co-precipitation；Described compound precipitation additive is organic
A kind of a kind of mixture of the material in and titanous chloride., aluminum chloride in anhydride, organic acid, ether, ketone；Described organic ester
Class compound selected from C1～C4 aliphatic saturated monocarboxylic acids Arrcostab or C7～C8 aromatic carboxylic acids Arrcostab in one kind or they
Mixture；Described titanium compound be titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide, one
One kind or their mixture in chlorine triethoxy titanium, dichlorodiethyl epoxide titanium, one ethanolato-titanium of trichlorine.
2. the catalytic component for ethylene polymerization according to claim 1, it is characterised in that described inorganic titanium
The formula of compound and organic titanic compound is Ti (OR)aXb, in formula, R is C1～C14Aliphatic alkyl or aromatic hydrocarbyl, X
For halogen atom, a is 0～4 integer, and b is 0～4 integer, a+b=3 or 4；Described electron donor compound is selected from aliphatic series
Ether, cyclic aliphatic ether or aliphatic ketone；The formula of described activator is AlR 'cX’dHe, in formula, R ' is C1～C14Saturated hydrocarbyl, X '
For halogen atom, c is 1～3 integer, and d is 0～2 integer, and e is 0 or 1, c+d+e=3.
3. the catalytic component for ethylene polymerization according to claim 1, it is characterised in that described compound to help
Precipitation agent is acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic acid anhydride, acetic acid, propanoic acid, fourth
Acid, acrylic acid, methacrylic acid, acetone, butanone, benzophenone, methyl ether, ether, propyl ether, butyl ether, the one kind and three in amyl ether
A kind of mixture in titanium chloride, aluminum chloride.
4. the catalytic component for ethylene polymerization according to claim 1, it is characterised in that described compound to help
Precipitation agent is phthalic anhydride and titanous chloride..
5. the catalytic component for ethylene polymerization according to claim 1, it is characterised in that described organic acid
A kind of a kind of mol ratio of the material in and titanous chloride., aluminum chloride in acid anhydride, organic acid, ether, ketone is 0.1～10:1.
6. the catalytic component for ethylene polymerization according to claim 1, it is characterised in that described organic ester
Class compound is methyl acetate, ethyl acetate, essence of Niobe, at least one in ethyl benzoate.
7. the catalytic component for ethylene polymerization according to claim 1, it is characterised in that with every mole of magnesium
Compound meter, organic epoxy compound thing are 0.2～10 mole, and organic phosphorus compound is 0.1～3 mole, and compound precipitation additive is
0.03～1.0 mole, organic esterses are 0～1 mole, and titanium compound is 0.5～120 mole, and inorganic titanium compound is
0.1～10 mole, activator is 0.01～10 mole；In terms of every mole of inorganic titanium compound, organic titanic compound is 0.1～10
Mole, electron donor compound is 1～50 mole.
8. the catalytic component for ethylene polymerization according to claim 1, it is characterised in that also including alcohols
Compound, in terms of every mole of magnesium compound, the consumption of alcohol compound is 0.1～3 mole.
9. the catalytic component for ethylene polymerization according to claim 1, it is characterised in that described magnesium chemical combination
Thing is selected from one of halogen atom in magnesium dihalide, the hydrate of magnesium dihalide or alcohol adduct and magnesium dihalide molecular formula by hydrocarbon
One kind in the derivant replaced by epoxide or halo oxyl, or their mixture.
10. the catalytic component for ethylene polymerization according to claim 1, it is characterised in that described organic ring
Oxygen compound selected from carbon number 2～8 aliphatic olefin, alkadienes or halogenated aliphatic alkene or alkadienes oxidation
At least one in thing, glycidyl ether and inner ether.
11. catalytic components for ethylene polymerization according to claim 1, it is characterised in that described organophosphors
Compound is hydrocarbyl carbonate or the halogenated hydrocarbons base ester of orthophosphoric acid or phosphorous acid.
12. catalytic components for ethylene polymerization according to claim 1, it is characterised in that described inorganic titanium
Compound and organic titanic compound are selected from titanous chloride., titanium tribromide, titanium triiodide, titanium tetrachloride, titanium tetrabromide, tetraiodide
Titanium, purity titanium tetraethoxide, four titanium propanolates, four titanium butoxides, a chlorine triethoxy titanium, dichlorodiethyl epoxide titanium, one ethoxy of trichlorine
One kind or their mixture in base titanium, three titanium butoxide of a chlorine, dichloro dibutoxy titanium, one titanium butoxide of trichlorine.
13. catalytic components for ethylene polymerization according to claim 1, it is characterised in that described electron
Body compound is selected from methyl formate, ethyl acetate, butyl acetate, ether, hexyl ether, tetrahydrofuran, acetone and methyl-isobutyl
At least one in ketone.
14. catalytic components for ethylene polymerization according to claim 1, it is characterised in that described activator
Selected from AlEt3、Al(n-C6H13)3、Al(n-Bu)3、Al(i-Bu)3、AlEt2Cl。
The preparation method of the catalytic component for ethylene polymerization described in one of 15. claim 1-7 and 9-14, including
Following steps：(1) preparation of the solidss A containing magnesium titanium：Magnesium compound is dissolved in into organic epoxy compound thing and organophosphors chemical combination
In the dicyandiamide solution of thing, after forming homogeneous solution, then mix with titanium compound, in compound precipitation additive and organic esterses
In the presence of, separate out the solidss A containing magnesium titanium；(2) preparation of B solution：At least one inorganic titanium compound and at least one are had
Machine titanium compound is dissolved in electron donor compound, forms B solution；(3) by B solution and the solid containing magnesium titanium for being separated out
Thing A is reacted；(4) product that step (3) is obtained is activated using activator, obtains catalytic component.
The preparation method of 16. catalytic components for ethylene polymerization according to claim 15, it is characterised in that
In terms of every mole of magnesium compound, organic epoxy compound thing is 0.2～10 mole, and organic phosphorus compound is 0.1～3 mole, is combined
Precipitation additive is 0.03～1.0 mole, and organic esterses are 0～1 mole, and titanium compound is 0.5～120 mole, inorganic
Titanium compound is 0.1～10 mole, and activator is 0.01～10 mole；In terms of every mole of inorganic titanium compound, organic titanium chemical combination
Thing is 0.1～10 mole, and electron donor compound is 1～50 mole.
A kind of 17. catalyst for ethylene polymerization, including the product of following two component：(1) claim 1～14
One of the catalytic component；(2) organic al composition.
Application of the catalyst described in 18. claim 17 in ethene gas-phase polymerization or slurry polymerization.
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| CN106632754B (en) * | 2015-10-29 | 2019-09-27 | 中国石油化工股份有限公司 | A kind of catalytic component and its preparation method and application for vinyl polymerization |
| CN110862472A (en) * | 2018-08-28 | 2020-03-06 | 中国石油化工股份有限公司 | Olefin polymerization reaction catalyst, preparation method and composite catalyst |
| CN112707981A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, catalyst and application |
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