CN103772552A - Catalyst ingredient and catalyst used for ethylene polymerization or copolymerization - Google Patents
Catalyst ingredient and catalyst used for ethylene polymerization or copolymerization Download PDFInfo
- Publication number
- CN103772552A CN103772552A CN201210407851.9A CN201210407851A CN103772552A CN 103772552 A CN103772552 A CN 103772552A CN 201210407851 A CN201210407851 A CN 201210407851A CN 103772552 A CN103772552 A CN 103772552A
- Authority
- CN
- China
- Prior art keywords
- titanium
- compound
- magnesium
- catalyst component
- ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a catalyst ingredient used for ethylene polymerization or copolymerization. The catalyst ingredient is characterized in that: the catalyst ingredient is obtained via loading a magnesium/titanium-containing solid material with at least one organic aluminium compound. The magnesium/titanium-containing solid material is selected as a carrier, so that when the catalyst ingredient is used for ethylene polymerization, catalyst activity and hydrogen response are relatively high; an obtained polymer is low in fine powder content; the catalyst ingredient is suitable for ethylene slurry polymerization or gas phase polymerization, and is especially suitable for ethylene gas phase fluidized bed polymerization technology in which the catalyst is charged in a slurry form.
Description
Technical field
The present invention relates to a kind of catalyst component for vinyl polymerization or copolymerization, its preparation method and the application at vinyl polymerization thereof.More particularly, relate to a kind of catalyst component, its preparation method and catalyzer thereof of introducing organo-aluminium compound and electron donor compound in preparation method.
Background technology
In the polyreaction of alkene, particularly, in the copolymerization of vinyl polymerization or ethene and alpha-olefin, mostly adopt the catalyst component using magnesium, titanium, halogen and electron donor as basal component.When this class catalyzer is when for gas-phase fluidized bed polymerization process, for the form and the size-grade distribution that guarantee granules of catalyst are more suitable for fluidized state operation, normally above-mentioned catalyst component is carried on the carriers such as silica gel.For example: US4,302,565, US4,379,759 and CN 1064870A in the disclosed catalyzer for gas-phase fluidized-bed reaction, be that the precursor components of being prepared by titanium compound, magnesium compound and electron donor compound is immersed on the carrier substance such as silica gel, then process impregnated precursor components with active compound and prepare.
In above-mentioned disclosed patent, in order to make catalyzer be applicable to gas-phase fluidized bed polymerization process, all there is stricter requirement in median size to used carrier silicon-dioxide, surface-area, aperture, and the price of this carrier substance is more expensive, need before use silica supports to carry out strict activation, these all cause the increase of the production cost of catalyzer simultaneously; And catalyst activity component is to load on carrier by impregnating method, owing to carrying a titanium quantitative limitation, its catalyst efficiency is also unsatisfactory.In addition, use in the polyethylene powder of this Catalyst Production fine powder amount larger, common 150 microns of following particles account for the 15Wt% left and right of whole powders, and this point is very undesirable in industrial production.
The Catalyst Production method that Chinese patent CN 1085915A mentions, although overcome foregoing some shortcomings, but need to use in process of production MAGNESIUM METAL as reductive agent, and still need to use a large amount of silica supports materials, finally to obtain catalyst particles granule product and also will adopt spray-dired method, facility investment is large, complicated operation, makes its overall manufacturing cost still higher.
CN85100997A discloses a kind of for olefin polymerization catalysis, it is to be dissolved in organic epoxy compounds, organo phosphorous compounds formation homogeneous solution by magnesium halide, prepare with halogenide and the derivative effect thereof of at least one precipitation additive, a kind of multi-carboxylate's electron donor and transition metals Ti again, when this catalyzer is used for propylene polymerization, higher polymerization activity and stereospecificity are preferably shown, but during for vinyl polymerization, activity is on the low side, and the broad particle distribution of polymkeric substance, and the hydrogen response of this catalyzer is bad.
On the basis of CN85100997A, CN1229092A discloses a kind of catalyzer for vinyl polymerization or copolymerization, it is to be dissolved in organic epoxy compounds, organo phosphorous compounds by magnesium halide to add electron donor activator to form homogeneous solution again, prepare with halogenide and the derivative effect thereof of at least one precipitation additive and transition metals Ti again, this catalyzer has shown very high activity during for the slurry polymerization of ethene, the particle form of resulting polymers is better simultaneously, and apparent density is also higher.This catalyst component that has added alcohols activator is for ethene gas-phase polymerization technique, particularly when fluidized bed polymerization process, in the starting stage of polyreaction, polyreaction is very fast, make the easily fragmentation of polymkeric substance generating, polymer beads is thinner, 70～150 microns of size-grade distribution account for 50Wt%～60Wt%, and morphology is also bad.
On the basis of above-mentioned Chinese patent CN85100997, Chinese patent CN1463991A discloses again a kind of catalyzer for vinyl polymerization or copolymerization, magnesium compound is dissolved in the solvent system that contains organic epoxy compounds and organo phosphorous compounds, after forming homogeneous solution, mix with titanium compound, under precipitation additive exists, separate out solids; Under the existence of electron donor compound, obtained solids is reacted with titanium compound, then adopt activator to activate reaction product, obtain catalyst component.Catalyzer prepared by this technique during for fluidized bed polymerization process reactive behavior higher, the fine powder content of polymer powders also has substantial degradation, but this catalyst preparation process flow process is longer, complex process.
Therefore, the slurry polymerization or the vapour phase polymerization that provide a kind of technique simply and to be efficiently suitable for ethene are provided, particularly be applicable to the ingredient of solid catalyst of catalyzer with the gas-phase fluidized bed polymerization process of the ethene of slurries form charging, this catalyst component should have relatively narrow particle size dispersion and less median size, has higher catalytic activity, high hydrogen response and can obtain the polymkeric substance of low fine content.
Summary of the invention
The invention provides one and be suitable for ethene slurry polymerization or vapour phase polymerization, be particularly useful for the ingredient of solid catalyst with the ethene gas-phase fluidized bed polymerization process of slurries form charging.This catalyst component has higher activity, higher hydrogen response, and can obtain the polymkeric substance of low fine content.
For a catalyst component for vinyl polymerization or copolymerization, it is characterized in that, its be a kind of containing on the solids of magnesium/titanium, at least one organo-aluminium compound of load and the catalyst component that obtains;
The general formula of described organo-aluminium compound is AlR '
cx '
dh
e, in formula, R ' is C
1～C
14saturated hydrocarbyl, X ' is halogen atom, c is 1～3 integer, d is 0～2 integer, e is 0 or 1, c+d+e=3.
Specifically:
The solids containing magnesium/titanium described in catalyst component of the present invention can adopt the solids of a large amount of magnesium/titanium well-known to those skilled in the art, wherein comparatively preferably the compound dissolution of magnesium is formed to uniform solution, then under the existence of the halogenide or derivatives thereof of titanium, again separate out the precipitation of solid material containing magnesium/titanium, can add if desired suitable precipitation additive.
Highly preferred scheme is that magnesium compound is dissolved in the solvent system containing organic epoxy compounds and organo phosphorous compounds, add alcohol compound, optionally add the thinner of alkane or aromatic hydrocarbons, form after homogeneous solution again the halogenide or derivatives thereof hybrid reaction with titanium, under precipitation additive exists, separate out the solids containing magnesium/titanium.The preparation method of this solids containing magnesium/titanium is disclosed in CN85100997, at this, its full content is introduced to the present invention as a reference.
Wherein said magnesium compound is selected from the one in the derivative that one of them halogen atom in the hydrate of magnesium dihalide, magnesium dihalide or alcohol adduct and magnesium dihalide molecular formula replaced by-oxyl or halo-oxyl, or their mixture.Above-mentioned magnesium dihalide is specially: magnesium dichloride, dibrominated magnesium, two magnesium iodides, preferably magnesium dichloride.
Wherein said organic epoxy compounds is selected from least one in oxide compound, glycidyl ether and the inner ether of 2～8 aliphatics alkene, diolefine or halogenated aliphatic alkene or diolefine of carbonatoms.For example: oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether etc.
Wherein said organo phosphorous compounds is hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid.For example: ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate or phosphorous acid benzene methyl etc.
In order to make dissolving more abundant, in this solvent system, optionally add inert diluent, common this inert diluent comprises arene compounds or alkane derivative, and arene compounds comprises benzene,toluene,xylene, monochloro-benzene, dichlorobenzene, trichloro-benzene, monochlorotoluene and derivative thereof; Alkane comprises that carbonatoms is a kind of in 3～20 straight-chain paraffin, branched paraffin or naphthenic hydrocarbon or their mixture, as butane, and pentane, hexane, hexanaphthene, heptane etc., as long as can using of contributing to that magnesium halide dissolves.Above-mentioned inert diluent can be used alone, also use capable of being combined.
Wherein said alcohol compound comprises C
1～C
20straight chain alcohol or isomery alcohol, for example: methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, 2-Ethylhexyl Alcohol, n-Octanol, lauryl alcohol, glycerol, amylalcohol, decyl alcohol, dodecanol, Stearyl alcohol, Bian alcohol, phenylethyl alcohol, with C
1～C
8straight chain alcohol be best.
Wherein said precipitation additive is the mixture of at least one material in a kind of and titanous chloride, the aluminum chloride in organic acid anhydride, organic acid, ether, ketone.Concrete as: the mixture of at least one material in diacetyl oxide, Tetra hydro Phthalic anhydride, Succinic anhydried, MALEIC ANHYDRIDE, pyromellitic acid anhydride, acetic acid, propionic acid, butyric acid, vinylformic acid, methacrylic acid, acetone, methylethylketone, benzophenone, methyl ether, ether, propyl ether, butyl ether, amyl ether etc. and titanous chloride, aluminum chloride.
The general formula of the halogenide or derivatives thereof of described transition metals Ti is Ti (OR)
ax
b, in formula, R is C
1～C
14aliphatic alkyl or aromatic hydrocarbyl, X is halogen atom, a is 0～4 integer, b is 0～4 integer, a+b=3 or 4.Concrete compound is as a kind of in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium or their mixture, preferably titanium tetrachloride.
Catalyst component of the present invention is containing the further mixture of at least one organo-aluminium compound of load or at least one organo-aluminium compound and at least one electron donor compound again on the solids of magnesium/titanium above-mentioned.
The general formula of the organo-aluminium compound described in catalyst component of the present invention is AlR '
cx '
dh
e, in formula, R ' is C
1～C
14saturated hydrocarbyl, X ' is halogen atom, c is 1～3 integer, d is 0～2 integer, e is 0 or 1, c+d+e=3.Specifically can select AlMe
3, AlEt
3, AlEt
2h, AlEt
2cl, AlEtCl
2, Al (n-Bu)
3, Al (i-Bu)
3, Al (n-C
6h
13)
3, Al (n-C
8h
17)
3in one or more.
Electron donor compound described in catalyst component of the present invention is selected from ester, aliphatic ether, cyclic aliphatic ether and aliphatic ketone; Be preferably C
1～C
4the alkyl ester of aliphatic saturated monocarboxylic acid, C
7～C
8the alkyl ester of aromatic carboxylic acid, C
2～C
6aliphatic ether, C
3～C
4cyclic ethers, C
3～C
6saturated fatty ketone.Be specially methyl-formiate, ethyl acetate, butylacetate, ether, hexyl ether, tetrahydrofuran (THF), acetone and methyl iso-butyl ketone (MIBK) etc., this class electron donor can use separately or several being used in conjunction with.
The wherein ratio between each component, in every mole of magnesium compound, alcohol compound is 0.1～3 mole, organic epoxy compounds is 0.2～10 mole, organo phosphorous compounds is 0.1～3 mole, and precipitation additive is 0.03～1.0 mole, and the halogenide or derivatives thereof of transition metals Ti is 0.5～120 mole, 0.01～1 mole of organo-aluminium compound, 0～1 mole of electron donor compound.
Above-mentioned catalyst component of the present invention, preferably adopts the following step to be prepared:
1) containing the preparation of the solids of magnesium/titanium: magnesium compound is dissolved in the solvent system containing alcohol compound, organic epoxy compounds and organo phosphorous compounds, form after homogeneous solution, mix with the halogenide or derivatives thereof of titanium again, under precipitation additive exists, separate out the solids containing magnesium/titanium;
The wherein ratio between each component, in every mole of magnesium compound, alcohol compound is 0.1～3 mole, organic epoxy compounds is 0.2～10 mole, organo phosphorous compounds is 0.1～3 mole, and precipitation additive is 0.03～1.0 mole, 0.5～120 mole, the halogenide of titanium and derivative thereof;
2) mixture of at least one organo-aluminium compound or at least one organo-aluminium compound and at least one electron donor compound is reacted with the solids containing magnesium/titanium under the condition of 10 ℃～30 ℃, obtain catalyst component of the present invention through hexane washing, nitrogen drying.
The wherein ratio between each component, in every mole of magnesium compound, 0.01～1 mole of organo-aluminium compound, 0～1 mole of electron donor compound.
In the catalyst component obtaining in the present invention, titanium: 1～10%, aluminium: 0.1～2%, electron donor 1～40%(weight content).
The invention still further relates to a kind of catalyzer for vinyl polymerization or copolymerization, it contains above-mentioned catalyst component of the present invention and the reaction product of organo-aluminium compound, and wherein the general formula of organo-aluminium compound used is AlR "
nx
3-n, R " and be C
1～C
8alkyl, particularly alkyl, aralkyl, aryl; X is halogen atom, particularly chlorine and bromine; N is the integer of 0 < n≤3; Can select one or more organo-aluminium compound to mix use.Preferably AlEt
3, Al (iso-Bu)
3, Al (n-C
6h
13)
3, Al (n-C
8h
17)
3, AlEt
2cl etc.Ratio between catalyst component and organo-aluminium compound, in every gram of catalyst component, organo-aluminium compound consumption is: 0.1mmol～10mmol, is preferably 0.5mmol～3mmol.
The catalyzer the present invention relates to is applicable to the equal polymerization of ethene or the copolymerization of ethene and other alpha-olefins, and wherein alpha-olefin adopts the one in propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 4-methylpentene-1.Its polymerization technique adopts vapor phase process, slurry process and solution method, is more suitable in gas fluidised bed polymerisation, particularly gas-phase fluidized-bed condensation technology.Meanwhile, because the activity of catalyzer of the present invention is very high, therefore can adopt inert diluent by catalyst dilution, for example mineral wet goods, realizes catalyst slurry charging equably by pumping feeding manner, and charging is even, stable operation.
The present invention compared with the prior art tool has the following advantages:
The invention provides one and be suitable for ethene slurry polymerization or vapour phase polymerization, be particularly useful for the ingredient of solid catalyst with the ethene gas-phase fluidized bed polymerization process of slurries form charging.This catalyst component has higher activity, higher hydrogen response, and can obtain the polymkeric substance of low fine content.
Embodiment
Embodiment given below is for the present invention is described, rather than limits the invention.
Testing method:
1, melting index (MI) is to measure according to ASTM D1238-99;
2, size-grade distribution: according to the method for the optical diffraction principle based on one-wavelength laser, with " Malvern Instr.2600 " tester.
Embodiment 1
1, the preparation of catalyst component
Under nitrogen protection, by 4.8 grams of magnesium chlorides, 90 milliliters of toluene, 4.0 milliliters of epoxy chloropropane, 12.5 milliliter tributyl phosphate, 0.5ml ethanol joins in reactor, at mixing speed 450rpm, temperature is under the condition of 60 ℃, react two hours, add 1.5 grams of titanous chlorides and add 1.4 grams of Tetra hydro Phthalic anhydrides, continue reaction one hour, be cooled to-28 ℃, drip 56 milliliters of titanium tetrachlorides, be warming up to gradually 85 ℃, constant temperature one hour, elimination mother liquor, it is dry after inert diluent toluene and organic solvent hexane repeatedly wash, obtain the solids A containing magnesium/titanium.
Solids A by 6 grams containing magnesium/titanium join in another reactor, add 120ml hexane, under the condition of 0 ℃, drip 5ml AlEt stirring 320rpm, temperature
2cl, wherein AlEt
2the concentration of Cl is 28wt%, is, under the condition of 10 ℃, to react 2 hours in mixing speed 320rpm, temperature, with 120ml hexane washing solids, and repeats above treatment step.With 120ml hexane washing solids, obtain 8.5 grams of particulate solid thing B component through evaporation drying, wherein contain Ti 4.5%(weight).
2, polymerization
Volume is the stainless steel cauldron of 2 liters, after hydrogen gas is fully replaced, be pressed into approximately 0.5 liter of hexane with nitrogen, with syringe implantation concentration be 1mmol/ml triethyl aluminum-hexane solution 2ml, under stirring, add again the above-mentioned solid ingredient B of 20mg, supplement hexane total amount and be about 1 liter.
After reinforced, heat up and successively pass into hydrogen and ethene, 2.8 × 10
5pa H
2, 7.5 × 10
5pa ethene, polymerization temperature is 85 ℃, reacts two hours, and overbottom pressure in the still of lowering the temperature, drain, emits polymer syrup liquid material, and elimination hexane is dried polymkeric substance, obtains polyethylene powder, the results are shown in Table 1.
Embodiment 2
Method for preparing catalyst is with embodiment 1.
Polymerization appreciation condition: volume is the stainless steel cauldron of 2 liters, after hydrogen gas is fully replaced, be pressed into approximately 0.5 liter of hexane with nitrogen, with syringe implantation concentration be 1mmol/ml triethyl aluminum-hexane solution 2ml, under stirring, add again the catalyst component B of 50mg, supplement hexane total amount and be about 1 liter.
After reinforced, heat up and successively pass into hydrogen and ethene, 6.8 × 10
5pa H2,3.5 × 10
5pa ethene, polymerization temperature is 85 ℃, reacts two hours, and overbottom pressure in the still of lowering the temperature, drain, emits polymer syrup liquid material, and elimination hexane is dried polymkeric substance, obtains polyethylene powder, the results are shown in Table 1.
Embodiment 3
Method for preparing catalyst is with embodiment 1, and titanous chloride consumption changes 3 grams into.Obtain 9.3 grams of particulate solid thing component C, wherein contain Ti 4.9%(weight).
Polymerization appreciation condition, with embodiment 1, the results are shown in Table 1.
Embodiment 4
6 grams of solids A are joined in another reactor, add 120ml hexane, under the condition of 0 ℃, drip 2.5mlAlEt stirring 320rpm, temperature
2cl, wherein AlEt
2the concentration of Cl is 28wt%, is, under the condition of 10 ℃, to react 2 hours, with 120ml hexane washing solids in mixing speed 320rpm, temperature.Obtain 8.1 grams of particulate solid thing component D through evaporation drying, wherein contain Ti 4.2%(weight).
Polymerization appreciation condition, with embodiment 1, the results are shown in Table 1.
Embodiment 5
6 grams of solids A are joined in another reactor, add 120ml hexane, under the condition of 0 ℃, drip 13mlAlEt stirring 320rpm, temperature
3, wherein AlEt
3concentration be 1mmol/ml, be under the condition of 20 ℃ in mixing speed 320rpm, temperature, reaction half an hour, with 120ml hexane washing solids.Obtain 8.3 grams of particulate solid thing component E through evaporation drying, wherein contain Ti 4.2%(weight).
Polymerization appreciation condition, with embodiment 1, the results are shown in Table 1.
Embodiment 6
6 grams of solids A are joined in a reactor, add 120ml hexane, under the condition of 0 ℃, drip 2.5mlAlEt stirring 320rpm, temperature
2the mixture of Cl and 1mlTHF, wherein AlEt
2the concentration of Cl is 14wt%, is being under the condition of 10 ℃ in mixing speed 320rpm, temperature, and reaction half an hour, with 120ml hexane washing solids.Obtain 9.3 grams of particulate solid thing component F through evaporation drying, wherein contain Ti 3.5%(weight).
Polymerization appreciation condition, with embodiment 1, the results are shown in Table 1.
Comparative example 1
According to the disclosed method Kaolinite Preparation of Catalyst of Chinese patent CN1463991A component:
By 4.8 grams of Magnesium Chloride Anhydrouss, 93 milliliters of toluene, 4.0 milliliters of epoxy chloropropane, 12.5 milliliters of tributyl phosphates join in the reactor of fully replacing through nitrogen, at mixing speed 450rpm, temperature is under the condition of 60 ℃, react two hours, add 1.4 grams of Tetra hydro Phthalic anhydrides, continue reaction one hour, be cooled to-28 ℃, with within 1 hour, dripping 56 milliliters of titanium tetrachlorides, be warming up to gradually 85 ℃ with 2 hours, constant temperature one hour, in temperature-rise period, separate out gradually solids, elimination mother liquor, dry after toluene and twice washing of hexane, obtain the solids H containing magnesium/titanium.
10 grams of solids H are joined in another reactor of fully replacing through nitrogen, add 90ml iso-pentane, 0.3 gram of titanous chloride and 30 milliliters of tetrahydrofuran (THF)s, under normal temperature, react one hour, filter solution, add again 90ml iso-pentane, the aluminium diethyl monochloride hexane solution of 3.5 ml volumes concentration 26.43% at room temperature reacts one hour, obtains particulate solid thing component J through evaporation drying.
Polymerization appreciation condition, with embodiment 1, the results are shown in Table 1.
Comparative example 2
Method for preparing catalyst is with comparative example 1.
Polymerization appreciation condition is with embodiment 2.
Comparative example 3
According to US4,302,565, US4,379,759 disclosed composition and content, adopt the method Kaolinite Preparation of Catalyst component of pickling process:
The activation of silica gel: 948# spherical silica gel (Grace company of the U.S.) is activated to 4 hours at 600 ℃,
In reactor, add 100mlTHF, titanous chloride 0.74g, magnesium chloride 1.13g, be warming up to 70 ℃, react 1 hour, for subsequent use as masterbatch.Add iso-pentane 60ml to another reactor, add silica gel 10g, triethyl aluminum 4.3ml after above-mentioned activation, normal-temperature reaction 30min, iso-pentane at 55 ℃ in still kettle to the content of aluminium in material in reactor is 1.65%, then ready masterbatch is transferred in this reactor, being warming up to refluxes produces, constant temperature 1 hour.THF in distillation reactor to material THF content in still be 12.6%, add under iso-pentane 86ml, aluminium diethyl monochloride 5.3ml normal temperature and react 30min, add under tri-n-hexyl aluminum 3.3ml normal temperature and react 30min.Obtain particulate solid K through vacuum-drying.In final catalyst component, contain Ti 0.78%(weight), Mg 1.58%(weight), tetrahydrofuran (THF) 10.9%(weight).
Polymerization appreciation condition, with embodiment 1, the results are shown in Table 1.
Table 1 polymerization result
As can be seen from Table 1, catalyst component of the present invention has higher active and higher hydrogen response, and resulting polymers has low fine content.Catalyzer of the present invention is suitable for slurry polymerization or the vapour phase polymerization of ethene, is specially adapted to the gas-phase fluidized bed polymerization process of catalyzer with the ethene of slurries form charging.
Claims (15)
1. for a catalyst component for vinyl polymerization or copolymerization, it is characterized in that, it is to contain on the solids of magnesium/titanium a kind of, at least one organo-aluminium compound of load; The general formula of described organo-aluminium compound is AlR '
cx '
dh
e, in formula, R ' is C
1～C
14saturated hydrocarbyl, X ' is halogen atom, c is 1～3 integer, d is 0～2 integer, e is 0 or 1, c+d+e=3.
2. the catalyst component for vinyl polymerization or copolymerization according to claim 1, it is characterized in that, wherein prepare by following method containing the solids of magnesium/titanium: magnesium compound is dissolved in the solvent system that contains alcohol compound, organic epoxy compounds and organo phosphorous compounds, form after homogeneous solution, add again the halogenide or derivatives thereof of transition metals Ti to mix, under the condition existing at precipitation additive, separate out the solids containing magnesium/titanium; Described precipitation additive is the mixture of at least one material in a kind of and titanous chloride, the aluminum chloride in organic acid anhydride, organic acid, ether, ketone; The halogenide or derivatives thereof of described transition metals Ti is a kind of in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium or their mixture.
3. the catalyst component for vinyl polymerization or copolymerization according to claim 2, it is characterized in that, described magnesium compound is selected from the one in the derivative that one of them halogen atom in the hydrate of magnesium dihalide, magnesium dihalide or alcohol adduct and magnesium dihalide molecular formula replaced by-oxyl or halo-oxyl, or their mixture.
4. the catalyst component for vinyl polymerization or copolymerization according to claim 2, it is characterized in that, described organic epoxy compounds comprises at least one in 2～8 fatty oxide compound, glycidyl ether and the inner ether of organizing alkene or diolefine of aliphatics alkene, diolefine or halo of carbonatoms.
5. the catalyst component for vinyl polymerization or copolymerization according to claim 2, is characterized in that, described organo phosphorous compounds is hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid.
6. the catalyst component for vinyl polymerization or copolymerization according to claim 2, is characterized in that, described alcohol compound is to contain 1 fatty alcohol compounds to 10 carbon atoms.
7. the catalyst component for vinyl polymerization or copolymerization according to claim 2, it is characterized in that, described precipitation additive is selected from the mixture of a kind of material at least one and titanous chloride, the aluminum chloride in diacetyl oxide, Tetra hydro Phthalic anhydride, MALEIC ANHYDRIDE, pyromellitic acid anhydride, acetic acid, propionic acid, butyric acid, vinylformic acid, methacrylic acid, acetone, methylethylketone, benzophenone, methyl ether, ether, propyl ether, butyl ether, amyl ether.
8. the catalyst component for vinyl polymerization or copolymerization according to claim 1, is characterized in that, described organo-aluminium compound is selected from AlMe
3, AlEt
3, AlEt
2h, AlEt
2cl, AlEtCl
2, Al (n-Bu)
3, Al (i-Bu)
3, Al (n-C
6h
13)
3, Al (n-C
8h
17)
3in one or more.
9. the catalyst component for vinyl polymerization or copolymerization according to claim 1, it is characterized in that containing on the solids of magnesium/titanium, at least one organo-aluminium compound of load and at least one electron donor compound, described electron donor compound is selected from ester, aliphatic ether, cyclic aliphatic ether and aliphatic ketone.
10. the catalyst component for vinyl polymerization or copolymerization according to claim 9, is characterized in that, described electron donor compound is C
1～C
4the alkyl ester of aliphatic saturated monocarboxylic acid, C
7～C
8the alkyl ester of aromatic carboxylic acid, C
2～C
6aliphatic ether, C
3～C
4cyclic ethers, C
3～C
6at least one in saturated fatty ketone.
11. catalyst components for vinyl polymerization or copolymerization according to claim 9, it is characterized in that, described electron donor compound is at least one in methyl-formiate, ethyl acetate, butylacetate, ether, hexyl ether, tetrahydrofuran (THF), acetone, methyl iso-butyl ketone (MIBK).
The preparation method of the catalyst component for vinyl polymerization or copolymerization described in one of 12. claims 1～11, comprises the steps:
(1) magnesium compound is dissolved in the solvent system that contains alcohol compound, organic epoxy compounds and organo phosphorous compounds, form after homogeneous solution, add again the halogenide or derivatives thereof of transition metals Ti to mix, under precipitation additive exists, separate out the solids containing magnesium/titanium;
(2) mixture of at least one organo-aluminium compound or at least one organo-aluminium compound and at least one electron donor compound is reacted with the solids containing magnesium/titanium, through washing, the dry catalyst component that obtains;
In every mole of magnesium compound, alcohol compound is 0.1～3 mole, organic epoxy compounds is 0.2～10 mole, organo phosphorous compounds is 0.1～3 mole, precipitation additive is 0.03～1.0 mole, the halogenide or derivatives thereof of transition metals Ti is 0.5～120 mole, and organo-aluminium compound is 0.01～1 mole, and electron donor compound is 0 ~ 1 mole.
13. 1 kinds of catalyzer for vinyl polymerization or copolymerization, comprise the reaction product of following two components:
1) the described catalyst component of one of claim 1～11;
2) organoaluminum component: general formula is AlR "
nx
3-n, R " and be C
1～C
8alkyl, X is halogen atom, n is the integer of 0 < n≤3;
In every gram of catalyst component, the consumption of organoaluminum component is: 0.1mmol～10mmol.
The application that the catalyzer for vinyl polymerization or copolymerization of 14. claims 13 closes at the alpha-olefin copolymer of vinyl polymerization or ethene and C3～C8.
The application of the catalyzer of 15. claims 13 in ethene gas-phase polymerization or slurry polymerization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210407851.9A CN103772552B (en) | 2012-10-23 | 2012-10-23 | A kind of catalytic component for vinyl polymerization or combined polymerization and catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210407851.9A CN103772552B (en) | 2012-10-23 | 2012-10-23 | A kind of catalytic component for vinyl polymerization or combined polymerization and catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103772552A true CN103772552A (en) | 2014-05-07 |
| CN103772552B CN103772552B (en) | 2016-07-06 |
Family
ID=50565361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210407851.9A Active CN103772552B (en) | 2012-10-23 | 2012-10-23 | A kind of catalytic component for vinyl polymerization or combined polymerization and catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103772552B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566523A (en) * | 2014-10-10 | 2016-05-11 | 中国石油化工股份有限公司 | Catalyst component used for ethylene homopolymerization or copolymerization reaction, and catalyst thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4352915A (en) * | 1979-06-07 | 1982-10-05 | Sumitomo Chemical Company, Limited | Process for the polymerization of ethylene |
| CN85100997A (en) * | 1985-04-01 | 1987-01-10 | 化工部北京化工研究院 | The catalyst system that is used for olefinic polymerization and copolymerization |
| CN1229092A (en) * | 1998-03-17 | 1999-09-22 | 中国石油化工集团公司 | Catalyst for ethylene polymerization or copolymerization and preparation method thereof |
| CN1532211A (en) * | 2003-03-18 | 2004-09-29 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization or copolymerization and its preparing method |
| CN101376680A (en) * | 2007-08-30 | 2009-03-04 | 中国石油化工股份有限公司 | Polymerization of ethylene catalyst component having high output ratio, preparation and use |
| CN101942050A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization in slurry process and preparation method thereof |
-
2012
- 2012-10-23 CN CN201210407851.9A patent/CN103772552B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4352915A (en) * | 1979-06-07 | 1982-10-05 | Sumitomo Chemical Company, Limited | Process for the polymerization of ethylene |
| CN85100997A (en) * | 1985-04-01 | 1987-01-10 | 化工部北京化工研究院 | The catalyst system that is used for olefinic polymerization and copolymerization |
| CN1229092A (en) * | 1998-03-17 | 1999-09-22 | 中国石油化工集团公司 | Catalyst for ethylene polymerization or copolymerization and preparation method thereof |
| CN1532211A (en) * | 2003-03-18 | 2004-09-29 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization or copolymerization and its preparing method |
| CN101376680A (en) * | 2007-08-30 | 2009-03-04 | 中国石油化工股份有限公司 | Polymerization of ethylene catalyst component having high output ratio, preparation and use |
| CN101942050A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization in slurry process and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566523A (en) * | 2014-10-10 | 2016-05-11 | 中国石油化工股份有限公司 | Catalyst component used for ethylene homopolymerization or copolymerization reaction, and catalyst thereof |
| CN105566523B (en) * | 2014-10-10 | 2018-01-19 | 中国石油化工股份有限公司 | For ethylene homo conjunction or the catalytic component and its catalyst of copolymerization |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103772552B (en) | 2016-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101376680B (en) | Polymerization of ethylene catalyst component having high output ratio, preparation and use | |
| CN102432716B (en) | Catalyst component used for vinyl polymerization, preparation method and application | |
| CN1194993C (en) | Solid catalyst component for ethylene polymerization and catalyst therefor | |
| CN104974283A (en) | Catalyst component used in ethylene polymerization reaction, catalyst and preparation method thereof | |
| CN106478845A (en) | For the catalytic component of olefinic polymerization, catalyst and preparation method thereof | |
| CN101724104A (en) | Catalyst component for ethylene polymerization and catalyst thereof | |
| CN101864013A (en) | Catalyst for gas-phase polymerization or copolymerization of ethylene and preparation method thereof | |
| CN104974279A (en) | Catalyst component used in ethylene polymerization reaction, catalyst and preparation method thereof | |
| CN103087227B (en) | Catalyst component used in ethylene polymerization, and preparation method and application thereof | |
| CN103772550A (en) | Catalyst ingredient used for ethylene polymerization, and catalyst thereof | |
| CN101113182A (en) | Catalyst component, catalyst, preparation method and its application | |
| CN102295716B (en) | Catalyst used for vinyl polymerization and preparation method as well as application thereof | |
| CN103772552A (en) | Catalyst ingredient and catalyst used for ethylene polymerization or copolymerization | |
| CN101962417B (en) | Catalyst for vinyl polymerization and preparation and application thereof | |
| CN1948352B (en) | Catalyst components used for olefin hydrocarbon polymerization and its catalyst | |
| CN103087229B (en) | Catalyst component and catalyst used in ethylene polymerization | |
| CN102585057B (en) | Catalyst for vinyl polymerization reaction | |
| CN103772549A (en) | Catalyst ingredient and catalyst used for ethylene polymerization or copolymerization | |
| CN102260360B (en) | Catalyst for ethylene polymerization, preparation and application thereof | |
| CN105622789A (en) | Small pore size catalyst component for olefin polymerization, preparation method and applications thereof | |
| CN101565476B (en) | Catalyst for ethylene polymerization or copolymerization through slurry method and preparation method and application thereof | |
| CN105085735B (en) | A kind of preparation method of catalytic component for olefinic polymerization | |
| CN103772546A (en) | Catalyst component for ethylene polymerization and catalyst thereof | |
| CN100389134C (en) | Catalyst used for ethylene polymerization or copolymerization, its preparation method and application | |
| CN114426605A (en) | Catalyst component for olefin polymerization and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |