CN1524886A - Compound carrier for olefin polymerization catalyst, catalyst components and the catalyst - Google Patents
Compound carrier for olefin polymerization catalyst, catalyst components and the catalyst Download PDFInfo
- Publication number
- CN1524886A CN1524886A CNA031052142A CN03105214A CN1524886A CN 1524886 A CN1524886 A CN 1524886A CN A031052142 A CNA031052142 A CN A031052142A CN 03105214 A CN03105214 A CN 03105214A CN 1524886 A CN1524886 A CN 1524886A
- Authority
- CN
- China
- Prior art keywords
- electron donor
- catalyst
- complex carrier
- compound
- catalyzer
- 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 discloses a composite carrier and catalyst constituents by using the composite carrier, wherein the composite carrier is a solution formed by contacting magnesium halide with one or multiple electron donor compounds, by mixing the solution with silica sols whose average particle diameter is less than 30 um and spray drying, spherical particles can be obtained. When being used for olefin polymerization along with the catalyst promoter constituents in particular for propone polymerization, the catalyst constituents have shown high polymerization activity and stereospecificity.
Description
Technical field
The present invention relates to a kind of be used for olefinic polymerization particularly propylene polymerization or copolymerization catalyst complex carrier and adopt the catalyst component and the catalyzer of this complex carrier.
Technical background
As everyone knows, efficient carrier model Ziegler-Natta catalyst has been widely used in the copolymerization of the polymerization of ethene, propylene and they and other alpha-olefin.In disclosed patented technology, efficient supported catalyst is single carrier with magnesium chloride usually, in order to improve catalytic activity, at first take different physics or chemical process to prepare magnesium chloride support, then transistion metal compound and electron donor compound formation catalyst active center in the load.From particle shape, this class catalyzer can be divided into particle (non-ball) shape and sphere.US4784983 and US4861847 disclose a kind of particle shape catalyzer, and this catalyzer is to be the particle of main component by dissolving one by one that coprecipitation method obtains with the magnesium chloride, and then obtains with halogen titanium compound and electron donor compound treatment.This catalyzer is being used for olefinic polymerization, particularly during propylene polymerization, shows very high polymerization activity and stereospecificity.But owing to the limitation of granules of catalyst form, be difficult to obtain having the high-impact multipolymer of high ethylene content when the copolymerization that is used for propylene, this also is the total characteristic of this class particle shape catalyzer.Known EP0395083 discloses a kind of catalyzer that is used for olefinic polymerization, it is by magnesium chloride and Fatty Alcohol(C12-C14 and C12-C18) reaction, obtain a kind of spheric magnesium chloride alcohol adduct carrier, halogen titanium compound and electron donor are compound loaded on this ball type carrier then, thereby obtain a kind of catalyzer of high-effective spherical.When this spherical catalyst is used for propylene polymerization, show very high activity and stereospecificity, and the polymer particle form is good, can be used for preparing the high-impact ethylene-propylene copolymer of high ethylene content.But common this granules of catalyst diameter is bigger, and broken phenomenon often takes place during polymerization easily, and especially when the prepolymerization multiplying power was low, this broken phenomenon was comparatively obvious, and the fine polymer powder of generation will influence the steady running of poly-unit.
In addition, also have a class catalyzer be with magnesium chloride load on porous inorganic oxide carriers such as silica gel, and then, finally obtain olefin polymerization catalysis with halogen titanium compound and electron donor compound treatment.For example, English Patent GB2028347 has provided the method that a kind of preparation is loaded in porous inorganic oxide supported catalyst component, promptly use magnesium chloride solution impregnation of silica carrier, make solvent evaporation afterwards, the solid product that obtains again with particularly titanium compound reaction of transistion metal compound.And for example Chinese patent CN1035186C discloses a kind of technology of utilizing silica supports to prepare efficient polypropylene catalyst.It is that the porous silica carrier that hydroxyl is contained on the surface is scattered in the tetrahydrofuran solution of magnesium chloride, and dry above-mentioned suspension obtains MgCl
2/ SiO
2Complex carrier is used titanium tetrachloride and this carrier of electron donor compound treatment again, finally obtains catalyst prod.But this activity of such catalysts is lower.When for example being internal electron donor with the diisobutyl phthalate, two hours polymerization activity was up to 20kgPP/gCat when catalyzer was used for propylene polymerization.Also have many patents to describe this technology, for example in patents such as US5559071, US5625015, WO94/14855, WO94/14856, WO95/11263, WO95/15216, WO95/12622, WO96/16093, WO96/05236, WO97/23518, WO98/01481, WO99/46306, WO00/22011, WO00/40623, WO00/05277 and EP0295312, all disclose this Preparation of catalysts technology by immersion process for preparing complex carrier type catalyzer.
But the prepared catalyzer of carrier that the method that adopts above-mentioned magnesium chloride solution dipping obtains, when being used for propylene polymerization, polymerization activity is all unsatisfactory.This may be because the method for this dipping is to utilize the particle form of silica-gel carrier itself to control the particle form of final catalyzer basically, the particle of the general porous silica gel that adopts is bigger, usually median size is～50 μ m, limited the charge capacity of active ingredient on silica gel, made final activity of such catalysts not high.
U.S. Pat 4376062 discloses a kind of catalyzer of complex carrier type, it is in the electron donor solvent, in tetrahydrofuran (THF), Magnesium Chloride Anhydrous and titanium tetrachloride contact reacts are obtained containing the slurries or the solution of active ingredient, be after the smoke-like silicon-dioxide of 0.007～0.05 μ m mixes then with itself and particle diameter, obtain median size after spray-dried and be the catalyst prod about 25 μ m.Be used for vinyl polymerization after this catalyzer and activator (aluminum alkyls) effect, show high polymerization activity.But,, add internal electron donor and be very important, and above-mentioned preparation method will be unfavorable for stably controlling the composition of each component on carrier in order to obtain high normal propene polymer for being used for propylene polymerization.Owing in the slurries of spraying, contain a large amount of titanium tetrachlorides, easily spray drying device is caused corrosion simultaneously, be unfavorable for suitability for industrialized production.
Summary of the invention
The catalyst component that the purpose of this invention is to provide a kind of complex carrier and adopt this complex carrier to obtain, this catalyst component and cocatalyst component one are used from olefinic polymerization, during especially for propylene polymerization, show high polymerization activity and stereospecificity, and can be used for preparing the high-impact ethylene-propylene copolymer of high ethylene content.
A kind of complex carrier that is used for olefin polymerization catalysis, it is magnesium halide to be contacted with one or more electron donor compounds form solution, this solution mixes with the silica gel of median size less than 30 μ m, the spray-dried spherical particle that makes.
Wherein magnesium halide such as Mg (OR
1)
2-mX
mShown in, R in the formula
1Be C
1～C
14Alkyl, X chooses from F, Cl, Br or its mixture, and m is 1 or 2, R
1Be straight chain, side chain or cyclic alkyl.Concrete compound is as magnesium dichloride, dibrominated magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium, chlorination butoxy magnesium etc., wherein preferred magnesium dichloride.Described halogenated magnesium compound can be used alone or as a mixture.
Suitable electron donor compound comprises the alkyl ester of fat or aromatic alcohol, aliphatic ether, cyclic ethers, aliphatic ketone, fat or aromatic carboxylic acid.Particularly suitable be the alkyl ester that contains the aliphatic saturated monocarboxylic acid of 1-4 carbon atom; The alkyl ester that contains the aromatics of 7-8 carbon atom; Contain 2-8 carbon atom, be preferably the aliphatic ether of 4-5 carbon atom; Contain the cyclic aliphatic ether of 4-5 carbon atom, preferably contain the monoether or the diether of 4 carbon atoms; With contain 3-6 carbon atom, be preferably the aliphatic ketone of 4-5 carbon atom.For example: methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, primary isoamyl alcohol, n-Octanol, isooctyl alcohol, ethylene glycol, propylene glycol, chloroethanol, ethapon, ether, butyl ether, methyl-formiate, ethyl acetate, butylacetate, ether, hexyl ether, tetrahydrofuran (THF) (THF), acetone, methyl iso-butyl ketone (MIBK) etc. are preferably ethanol, Virahol, propyl carbinol, tetrahydrofuran (THF).Electron donor can use separately or several being used.
Suitable electron donor compound also comprises and contains organic epoxy compounds and/or organo phosphorous compounds, and described organic epoxy compounds is selected from and comprises at least a in oxide compound, glycidyl ether and the inner ether of 2～8 aliphatics alkene, diolefine or halo fat group alkene or diolefine of carbonatoms.For example: oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether.Described organo phosphorous compounds is selected from the 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, phosphorous acid benzene methyl.
In order to make magnesium halide and electron donor contact reacts form uniform solution, generally, every mole of magnesium halide needs 3～50 moles of electron donor compounds, is preferably 6～30 moles.The preparation of this solution can be carried out in the presence of a kind of inert organic solvents, and this solvent does not form adducts with magnesium halide.The aromatic hydrocarbons of the preferred alkane of solvent, halohydrocarbon and 6-12 carbon atom, for example hexane, heptane, ethylene dichloride, toluene, dimethylbenzene, ethylbenzene etc.
Obtain more short grained complex carrier for the ease of spray shaping, described silica supports material is generally selected the silica gel of median size less than 30 μ m for use, be preferably less than 10 μ m, more preferably particle diameter also claims aerosil less than the smoke-like silica gel of 1 μ m.The specific surface area of this silica gel is generally 200 ± 50m
2/ g.
With solution and the slurry that obtains after silica gel mixes being suitable for spraying, usually, the add-on of silica gel is 10～200g in every liter of solution.
Spraying drying can be carried out according to the following steps: the slurries that solution is obtained after silica-gel carrier mixes carry out spraying drying with the inertia dry gas by the spraying drying instrument, obtain the globular solid particulate.
In order to make complex carrier of the present invention be applicable to the catalyzer of preparation for olefines polymerization better, needing this complex carrier usually is the spherical particle of mean diameter 5-70 μ m, and preferred average diameter of particles is a 10-60 μ m spherical particle.
The present invention also provides a kind of catalyst component that is used for olefinic polymerization, its contain above-mentioned complex carrier with as general formula Ti (OR
2)
4-mX
mThe reaction product of shown titanium compound, R in the formula
2Be C
1～C
14Aliphatic group, X chooses from F, Cl, Br or its mixture, m is 1～4 integer.Specifically can select 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, the titanous chloride or their mixture for use, preferred titanium tetrachloride.Titanium compound should be a completely soluble liquefied compound under application of temperature, in the non-polar solvent.
Before complex carrier and titanium compound reaction or after the reaction, can also adopt the internal electron donor compound to handle, especially for the catalyst component that is used for propylene polymerization, in order to obtain high normal propene polymer, the adding of this internal electron donor compound is very necessary.Can adopt internal electron donor compound disclosed a large amount of in this area, suitable internal electron donor compound can adopt polyhydric aliphatic family carboxylicesters or aromatic carboxylic acid esters.For example: phthalate, malonic ester class, succinate, glutarate, pivalate or carbonic ether etc.Concrete as: diethyl malonate, butyl ethyl malonate, 2,3-di-isopropyl ethyl succinate, 2,3-di-isopropyl di-iso-octyl succinate, 2,3-di-isopropyl dibutyl succinate, 2,3-di-isopropyl succsinic acid dimethyl esters, 2,2-dimethyl succinate diisobutyl ester, 2-ethyl-2-methylsuccinic acid diisobutyl ester, 2-ethyl-2-methylsuccinic acid diethyl ester, diethylene adipate, Polycizer W 260, ethyl sebacate, Uniflex DBS, the phthalic ester diethyl ester, the phthalic ester diisobutyl ester, the phthalic ester di-n-butyl, the phthalic ester di-isooctyl, diethyl maleate, maleic acid n-butyl, the naphthalene dicarboxylic acids diethyl ester, the naphthalene dicarboxylic acids dibutylester, triethyl trimellitate, tributyl trimellitate, the benzene-1,2,3-tricarboxylic acid triethyl, the benzene-1,2,3-tricarboxylic acid tri-n-butyl, the pyromellitic acid tetra-ethyl ester, pyromellitic acid four butyl esters etc.
Specifically, ingredient of solid catalyst of the present invention can prepare as follows:
(1) preparation magnesium chloride solution
Can prepare magnesium chloride solution according to disclosed certain methods, such as using US4784983 and the disclosed magnesium chloride dissolution system of US4861847 to prepare magnesium chloride solution.
Preferably, among the present invention, magnesium chloride solution prepares as follows:
In the reactor of stirring is housed, add the mixture of a kind of alcohol or two kinds and two or more alcohol, also can add a kind of ether or ester again, add Magnesium Chloride Anhydrous then, heating makes the magnesium chloride dissolving.Wherein alcohol is 3～50: 1 with the mol ratio of magnesium chloride, and the mol ratio of ether or ester and magnesium chloride is 0～20: 1.The dissolving of above-mentioned magnesium chloride also can be carried out in a kind of inert organic solvents, and the consumption of solvent is 0～20ml/gMgCl
2
(2) prepare spherical MgCl
2/ SiO
2Complex carrier
Add smoke-like silica gel in above-mentioned magnesium chloride solution, the add-on of silica gel is 0.1～2g/gMgCl
2, used silica gel is the aerosil of average particulate diameter less than 10 μ m.Stirred 0.5～3 hour down at 10～100 ℃ afterwards, make slurries.Then slurries are carried out spraying drying with the inertia dry gas by the spraying drying instrument, obtaining median size is the spherical MgCl of 5～60 μ m
2/ SiO
2Complex carrier.Inlet air temperature during spraying drying is controlled at 80～300 ℃, and air outlet temperature is controlled at 50～200 ℃.Usually, consisting of of complex carrier:
MgCl
2: 20%～60% (weight)
SiO
2: 10%～60% (weight)
Alcohol: 5%～40% (weight)
Ether: 0～20% (weight)
Solvent:＜5% (weight)
(3) preparation ingredient of solid catalyst
Above-mentioned ball type carrier is suspended in TiCl
4Mixed solution (TiCl with hexane
4Amount is 5～10mlTiCl
4/ g carrier, hexane and TiCl
4Volume ratio be 0～2) in, slowly be warmed up to 80～100 ℃, after keeping for some time under this temperature, liquid is filtered; Add excessive TiCl
4(TiCl
4Amount is 12～16mlTiCl
4/ g carrier), in 1～3 hour, slowly be warming up to 100～120 ℃, and add the internal electron donor compound in temperature-rise period, the add-on of internal electron donor compound is 0.05～0.25mol/molMgCl
2React 1～2 hour after-filtration, randomly, add a certain amount of TiCl
4, kept 1～2 hour at 120 ℃, filtrate is filtered; With the solids washing, then solids is vacuumized drying with inert solvent such as hexane etc. under 30 ℃～50 ℃, promptly get ingredient of solid catalyst of the present invention.
In addition, the invention still further relates to a kind of catalyzer that is used for olefinic polymerization, it comprises the reaction product of following component:
(1) above-mentioned catalyst component of the present invention (active ingredient),
(2) alkylaluminium cpd component, its general formula such as AlR
1 nX
3-nShown in, R in the formula
1Be identical or different C
1～C
20Alkyl can be a straight chain, and side chain or cyclic alkyl, X are halogen, n=1,2 or 3.Preferred triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, chlorination aluminum alkyls, Al (n-C
6H
13)
3, Al (n-C
8H
17)
3, AlEt
2Cl etc.Can select for use one or more aluminum alkyls to mix use.
(3) randomly, a kind of external electron donor compound, for example list or polyfunctional carboxylic acids, carboxylic acid anhydride and carboxylicesters, ketone, ether, alcohol, lactone, and organophosphorus and silicoorganic compound.Preferably have organic silicon compound, as general formula R
nSi (OR)
4-nSilicoorganic compound, 0≤n in the formula≤3, R and R
*Be of the same race or different alkyl, cycloalkyl, aryl, haloalkyl, R also can be halogen or hydrogen atom.
In many cases, particularly when this catalyzer was used for propylene polymerization, the use of external electron donor compound was very necessary.
The ratio between ingredient of solid catalyst (1), alkylaluminium cpd component (2) and the external electron donor component (3) wherein, with titanium: aluminium: the molar ratio computing between the silicon is 1: 5～1000: 0～500.
Wherein component (2) and optional component (3) can be separately or as two kinds of mixture of ingredients and active ingredient contact reacts.
Above-mentioned catalyzer is suitable for alkene CH
2=CHR (wherein R is the alkyl or aryl of hydrogen or 1～6 carbon) and the polyreaction that contains the mixture of (if necessary) a small amount of diolefine.
The polymerization of alkene is carried out according to currently known methods, in liquid monomer or monomer in the liquid phase of the solution in inert solvent, or in gas phase, or by operating in the polymerization mix technology of gas-liquid in mutually.Polymerization temperature is generally 0 ℃～150 ℃, preferably 60 ℃～100 ℃.Polymerization pressure is a normal pressure or higher.
Catalyst component of the present invention is compared with the disclosed spray-dried Technology that directly obtains solid catalyst of US4376062, can control the composition of solid catalyst product better, particularly can regulate the content and the kind of internal electron donor in the ingredient of solid catalyst easily, this for guarantee catalyzer of the present invention have high three-dimensional qualitative be very important.In addition, because it is very little to be present in the primary particle diameter of the silica gel in the catalyzer of the present invention, add catalyzer of the present invention and have very high polymerization activity, thereby when being used for the production of film series products, can be than the generation of more effectively avoiding flake phenomenon on the high side with catalyst prepared.Have again, solid catalyst particle of the present invention has the abundant microporous structure, and catalytic active component is evenly distributed, so this catalyzer has good copolymerization performance, can be used for preparing the high-impact multipolymer of high ethylene content, and be applicable to the gas-phase polymerization process of alkene.In addition, catalyzer of the present invention also is specially adapted to the gas-phase polymerization process of alkene.
Following Example is used for illustrating the present invention, is not to be used for limiting the scope of the invention.
Embodiment 1
1, the preparation of magnesium chloride solution:
Using N
2Fully add 34.5ml ethanol successively, 18.5ml propyl carbinol, 32.4ml tetrahydrofuran (THF) in the glass reactor of metathetical band stirring 350ml.Under the situation that the feed glass reactor temperature does not sharply rise, slowly add Magnesium Chloride Anhydrous 9.5g while stirring, slowly heat up then, temperature makes Magnesium Chloride Anhydrous fully dissolving in this solution in the controlling reactor under stirring about 60 ℃.After the system for the treatment of is dissolved substantially, kept again 2.5 hours, obtain magnesium chloride solution.
2, the preparation of complex carrier:
In above-mentioned solution, add the silica gel 6g of being fuming, fully stirred 1 hour, form slurries.Carry out spraying drying then in the spraying drying instrument, the control inlet air temperature is that 200 ℃, air outlet temperature are 130 ℃, obtains median size and be the spherical complex carrier about 17 μ m.That analyzes the gained carrier consists of (parts by weight): MgCl
2: 43.3%; SO
2: 26.5%; Ethanol: 11.2%; Propyl carbinol: 14.7%; Tetrahydrofuran (THF): 4.2%.
3, Preparation of catalysts:
Get above-mentioned complex carrier 9.1g, slowly add in the titanium tetrachloride of the 100ml that is pre-chilled to 0 ℃, be warmed up to 40 ℃ in 1 hour, add n-butyl phthalate (DNBP) 1.0ml, rose to 100 ℃ in 0.5 hour then, kept 2 hours, mother liquor is filtered at 40 ℃.Add titanium tetrachloride 100ml again, be warmed up to 120 ℃ in 0.5 hour, kept 1 hour, mother liquor is filtered.Wash these solidss 5 times with hexane at 60 ℃, each hexane consumption is 60ml, and washing time is 5 minutes.With the solids drying, obtain ingredient of solid catalyst at last.
Propylene polymerization:
5 liters of autoclaves were purged 1 hour under 70 ℃ with propylene gas earlier, at room temperature introduce the hexane solution (concentration of triethyl aluminum is 0.5mmol/ml) of 5ml triethyl aluminum, hexane solution (concentration of CHMMS is 0.1mmol/ml), 10ml anhydrous hexane and 8.5mg such as the above-mentioned prepared solid spherical catalyst component of 1ml cyclohexyl methyl dimethoxy silane (CHMMS) in the stream of nitrogen gas.Close autoclave, introduce the hydrogen of 1.7NL and the liquid propene of 1.5Kg; In under agitation 5 minutes temperature is risen to 70 ℃.70 ℃ of following polyreactions after 2 hours, stop stirring, remove unpolymerized propylene monomer, with the still internal cooling to room temperature.
Obtain the 310g polypropylene, measure polyacrylic degree of isotacticity (I.I.)=96.0%, melting index (M.I)=5.1g/10min.Activity of such catalysts is 36.5Kg polypropylene/g ingredient of solid catalyst, and polymer stacks density is 0.42g/ml.
Embodiment 2
1, the preparation of magnesium chloride solution:
In the glass reactor that abundant metathetical 350ml band stirs with N2, add 34.5ml ethanol successively, the 45.5ml Virahol.Under the situation that the feed glass reactor temperature does not sharply rise, slowly add Magnesium Chloride Anhydrous 9.5g while stirring, slowly heat up then, temperature makes Magnesium Chloride Anhydrous fully dissolving in this solution in the controlling reactor under stirring about 75 ℃.After the system for the treatment of is dissolved substantially, kept again 2.5 hours, obtain magnesium chloride solution.
2, the preparation of complex carrier:
In above-mentioned solution, add the silica gel 5g of being fuming, fully stirred 1 hour, form slurries.Control inlet air temperature then and be 190 ℃, air outlet temperature and be 110 ℃ and carry out spraying drying, obtain median size and be the spherical complex carrier about 19 μ m.Analyze consist of (parts by weight) of gained carrier:
MgCl
2: 45.7%; SO
2: 24.1%; Ethanol: 13.3%; Virahol: 16.7%.
3, catalyzer is synthetic:
With embodiment 1.
Propylene polymerization:
Polymerization process is with embodiment 1.Activity of such catalysts is 38.0Kg polypropylene/g ingredient of solid catalyst, the polyacrylic degree of isotacticity (I.I.)=96.6% that obtains, and melting index (M.I)=5.2g/10min, polymer stacks density are 0.43g/ml.
Embodiment 3
1, the preparation of magnesium chloride solution:
Using N
2Fully add 23ml ethanol successively, the 36ml propyl carbinol in the glass reactor that metathetical 350ml band stirs.Under the situation that the feed glass reactor temperature does not sharply rise, slowly add Magnesium Chloride Anhydrous 9.5g while stirring, slowly heat up then, temperature makes Magnesium Chloride Anhydrous fully dissolving in this solution in the controlling reactor under stirring about 70.After the system for the treatment of is dissolved substantially, kept again 2.5 hours, obtain magnesium chloride solution.
2, the preparation of complex carrier:
Condition by embodiment 1 is carried out spraying drying, obtains median size and be the spherical complex carrier about 17 μ m.Analyze consist of (parts by weight) of gained carrier:
MgCl
2: 47.5%; SO
2: 23.2%; Ethanol: 5.9%; Propyl carbinol: 23.5%.
3, catalyzer is synthetic: with embodiment 1.
Propylene polymerization:
Polymerization process is with embodiment 1.Activity of such catalysts is 25.1Kg polypropylene/g ingredient of solid catalyst, the polyacrylic degree of isotacticity (I.I.)=96.8% that obtains, and melting index (M.I)=3.0g/10min, polymer stacks density are 0.42g/ml.
Embodiment 4
1, the preparation of magnesium chloride solution:
Using N
2Fully add 46ml ethanol successively, 15.6ml epoxy chloropropane, 32.4ml tetrahydrofuran (THF) in the glass reactor that metathetical 350ml band stirs.Under the situation that the feed glass reactor temperature does not sharply rise, slowly add Magnesium Chloride Anhydrous 9.5g while stirring, slowly heat up then, temperature makes Magnesium Chloride Anhydrous fully dissolving in this solution in the controlling reactor under stirring about 60 ℃.After the system for the treatment of is dissolved substantially, kept again 2.5 hours, obtain magnesium chloride solution.
2, the preparation of complex carrier:
Condition by embodiment 1 is carried out spraying drying, obtains median size and be the spherical complex carrier about 18 μ m.That analyzes the gained carrier consists of (parts by weight): MgCl
2: 48.6%; SO
2: 25.2%; Ethanol: 16.8%; Epoxy chloropropane: 3.6%; Tetrahydrofuran (THF): 5.9%.
3, catalyzer is synthetic: with embodiment 1.
Propylene polymerization:
Polymerization process is with embodiment 1.Activity of such catalysts is 11.6Kg polypropylene/g ingredient of solid catalyst, the polyacrylic degree of isotacticity (I.I.)=96.5% that obtains, and melting index (M.I)=3.6g/10min, polymer stacks density are 0.43g/ml.
Embodiment 5
1, the preparation of magnesium chloride solution:
Using N
2Fully add the 100ml tetrahydrofuran (THF) successively, 4.6ml ethanol in the glass reactor that metathetical 350ml band stirs.Under the situation that the feed glass reactor temperature does not sharply rise, slowly add Magnesium Chloride Anhydrous 8g while stirring, slowly heat up then, temperature makes Magnesium Chloride Anhydrous fully dissolving in this solution in the controlling reactor under stirring about 60 ℃.After the system for the treatment of is dissolved substantially, kept again 2.5 hours, obtain magnesium chloride solution.
2, the preparation of complex carrier:
Condition by embodiment 1 is carried out spraying drying, obtains median size and be the spherical complex carrier about 17 μ m.Analyze consist of (parts by weight) of gained carrier:
MgCl
2: 42.0%; SO
2: 25.9%; Ethanol: 3.6%; Tetrahydrofuran (THF) 28.5%.
3, catalyzer is synthetic: embodiment 1.
Propylene polymerization:
Polymerization process is with embodiment 1.Activity of such catalysts is 16.0Kg polypropylene/g ingredient of solid catalyst, the polyacrylic degree of isotacticity (I.I.)=97.3% that obtains, and melting index (M.I)=2.9g/10min, polymer stacks density are 0.41g/ml.
Embodiment 6
1, the preparation of magnesium chloride solution:
Using N
2Fully add 80ml toluene, 8.2ml tributyl phosphate, 7.8ml epoxy chloropropane, 4.8g Magnesium Chloride Anhydrous successively in the glass reactor of metathetical band stirring 350ml, slowly heat up then, temperature makes Magnesium Chloride Anhydrous fully dissolving in this solution in the controlling reactor under stirring about 55 ℃.After the system for the treatment of is dissolved substantially, kept again 2.5 hours, obtain magnesium chloride solution.
2, the preparation of complex carrier:
In above-mentioned solution, add the silica gel 3.5g of being fuming, fully stirred 1 hour, form slurries.Control inlet air temperature then and be 200 ℃, air outlet temperature and be 130 ℃ and carry out spraying drying, obtain median size and be the spherical complex carrier about 18 m.
3, catalyzer is synthetic: with embodiment 1.
Propylene polymerization:
Polymerization process is with embodiment 1.Activity of such catalysts is 26.0Kg polypropylene/g ingredient of solid catalyst, the polyacrylic degree of isotacticity (I.I.)=96.5% that obtains, and melting index (M.I)=3.1g/10min, polymer stacks density are 0.41g/ml.
Embodiment 7
1, the preparation of magnesium chloride solution:
Using N
2Fully add 150ml ethanol, 9.5g Magnesium Chloride Anhydrous successively in the glass reactor of metathetical band stirring 350ml, slowly heat up then, temperature makes Magnesium Chloride Anhydrous fully dissolving in this solution in the controlling reactor under stirring about 50 ℃.After the system for the treatment of is dissolved substantially, kept again 2.5 hours, obtain magnesium chloride solution.
2, the preparation of complex carrier:
In above-mentioned solution, add the silica gel 6g of being fuming, fully stirred 1 hour, form slurries.Control inlet air temperature then and be 190 ℃, air outlet temperature and be 110 ℃ and carry out spraying drying, obtain median size and be the spherical complex carrier about 16 μ m.
3, catalyzer is synthetic: with embodiment 1.
Propylene polymerization:
Polymerization process is with embodiment 1.Activity of such catalysts is 23.0Kg polypropylene/g ingredient of solid catalyst, the polyacrylic degree of isotacticity (I.I.)=96.0% that obtains, and melting index (M.I)=7.2g/10min, polymer stacks density are 0.42g/ml.
Claims (14)
1, a kind of complex carrier that is used for olefin polymerization catalysis, it is magnesium halide to be contacted with one or more electron donor compounds form solution, this solution mixes the spray-dried spherical particle that makes with the silica supports material of median size less than 30 μ m.
2, the complex carrier that is used for olefin polymerization catalysis according to claim 1, the mean diameter that it is characterized in that described spherical particle is less than 70 μ m.
3, the complex carrier that is used for olefin polymerization catalysis according to claim 1, the mean diameter that it is characterized in that described spherical particle are 10-60 μ m.
4, the complex carrier that is used for olefin polymerization catalysis according to claim 1, its described electron donor compound are selected from the hydrocarbyl carbonate or the halo hydrocarbyl carbonate of alkyl ester, phosphoric acid or phosphorous acid of oxide compound, aliphatic ketone, fat or the aromatic carboxylic acid of fat or aromatic alcohol, aliphatic ether, cyclic ethers, aliphatics alkene or halogenated aliphatic alkene.
5, the complex carrier that is used for olefin polymerization catalysis according to claim 1, the average particle diameter of its described silica gel is less than 1 μ m.
6, the complex carrier that is used for olefin polymerization catalysis according to claim 1, the mol ratio of its described electron donor compound and magnesium halide is 3～50: 1.
7, a kind of catalyst component that is used for olefinic polymerization, its contain the described complex carrier of one of claim 1-6 with as general formula Ti (OR)
4-mX
mThe reaction product of shown titanium compound, R is C in the formula
1～C
14Aliphatic group, X chooses from F, Cl, Br or its mixture, m is 1～4 integer.
8, the catalyst component that is used for olefinic polymerization according to claim 7 is characterized in that, before complex carrier and titanium compound reaction or after the reaction, can also adopt the internal electron donor compound to handle.
9, the catalyst component that is used for olefinic polymerization according to claim 8 is characterized in that, described internal electron donor compound is polyhydric aliphatic family carboxylicesters or aromatic carboxylic acid esters.
10, the catalyst component that is used for olefinic polymerization according to claim 8 is characterized in that, described internal electron donor compound is selected from one or more in phthalic ester, malonic ester, succinate, glutarate, pivalate or the carbonic ether.
11, a kind of CH that is used for
2The catalyzer of=CHR olefinic polyreaction, wherein R is hydrogen or C
1-C
6Alkyl or aryl, comprise the reaction product of following component:
(1) the described ingredient of solid catalyst of one of claim 7-10;
(2) alkylaluminium cpd,
(3) randomly, external electron donor component.
12, catalyzer according to claim 11, wherein alkylaluminium cpd such as AIR
1 nX
3-nShown in, R in the formula
1Be identical or different C
1～C
20Alkyl can be a straight chain, and side chain or cyclic alkyl, X are halogen, n=1,2 or 3.
13, catalyzer according to claim 11, wherein the external electron donor component is a general formula R
nSi (OR ')
4-nSilicoorganic compound, 0≤n in the formula≤3, R is of the same race or different alkyl, cycloalkyl, aryl, haloalkyls with R ', R also can be halogen or hydrogen atom.
14, catalyzer according to claim 13, the ratio between ingredient of solid catalyst (1), alkylaluminium cpd component (2) and the external electron donor component (3) wherein, with titanium: aluminium: the molar ratio computing between the silicon is 1: 5～1000: 0～500.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03105214 CN1218971C (en) | 2003-02-24 | 2003-02-24 | Compound carrier for olefin polymerization catalyst, catalyst components and the catalyst |
| JP2006501450A JP2006523730A (en) | 2003-02-24 | 2004-02-17 | Composite support for propylene polymerization catalyst, catalyst component and catalyst containing the same |
| EP04711555A EP1609805B1 (en) | 2003-02-24 | 2004-02-17 | Complex support suitable for propylene polymerization catalyst, a catalyst component and catalyst containing the same |
| KR1020057015694A KR20060013486A (en) | 2003-02-24 | 2004-02-17 | Complex support suitable for propylene polymerization catalyst, a catalyst component and catalyst containing the same |
| RU2005128272/04A RU2005128272A (en) | 2003-02-24 | 2004-02-17 | COMPLETE CARRIER OF PROPYLENE POLYMERIZATION CATALYSTS, CATALYTIC COMPONENT AND CATALYST INCLUDING THE INDICATED COMPONENT |
| CA002516693A CA2516693A1 (en) | 2003-02-24 | 2004-02-17 | Complex support suitable for propylene polymerization catalyst, a catalyst component and catalyst containing the same |
| PCT/CN2004/000126 WO2004074329A1 (en) | 2003-02-24 | 2004-02-17 | Complex support suitable for propylene polymerization catalyst, a catalyst component and catalyst containing the same |
| US10/783,096 US20040229748A1 (en) | 2003-02-24 | 2004-02-19 | Composite carrier of catalysts for propylene polymerization, a catalyst component and a catalyst comprising the same |
| US11/369,793 US20060154806A1 (en) | 2003-02-24 | 2006-03-07 | Composite carrier of catalysts for propylene polymerization, a catalyst component and a catalyst comprising the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03105214 CN1218971C (en) | 2003-02-24 | 2003-02-24 | Compound carrier for olefin polymerization catalyst, catalyst components and the catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1524886A true CN1524886A (en) | 2004-09-01 |
| CN1218971C CN1218971C (en) | 2005-09-14 |
Family
ID=34282554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03105214 Expired - Lifetime CN1218971C (en) | 2003-02-24 | 2003-02-24 | Compound carrier for olefin polymerization catalyst, catalyst components and the catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1218971C (en) |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100366640C (en) * | 2004-10-29 | 2008-02-06 | 中国石油化工股份有限公司 | Carrier for olefin polymerization catalyst and its preparation method and its uses in preparing olefin polymerization catalyst |
| CN100417669C (en) * | 2005-10-14 | 2008-09-10 | 中国石油化工股份有限公司 | Solid catalyst composition used for olefine polymerization and catalyst thereof |
| CN100443515C (en) * | 2005-12-30 | 2008-12-17 | 中国石油化工股份有限公司 | Loading type bimetal polyethylene catalyst and its preparation method |
| CN102399329A (en) * | 2010-09-16 | 2012-04-04 | 中国石油化工股份有限公司 | Catalyst component used in alkene polymerization, and catalyst |
| CN102399327A (en) * | 2010-09-16 | 2012-04-04 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and its catalyst |
| CN102432706A (en) * | 2011-09-15 | 2012-05-02 | 中国石油天然气股份有限公司 | Magnesium chloride composite spherical carrier, preparation and application |
| CN102464734A (en) * | 2010-11-18 | 2012-05-23 | 中国石油化工股份有限公司 | Olefin polymerization catalyst and preparation method thereof and olefin polymerization method |
| CN102107145B (en) * | 2009-12-23 | 2012-10-17 | 中国石油天然气股份有限公司 | Modified Ti-Mg catalyst and preparation method and application thereof |
| CN101903412B (en) * | 2007-11-30 | 2013-06-05 | 博里利斯技术有限公司 | Catalyst with low surface area |
| CN103524643A (en) * | 2012-07-04 | 2014-01-22 | 中国石油天然气股份有限公司 | Preparation method of polyethylene catalyst |
| CN104177523A (en) * | 2014-09-02 | 2014-12-03 | 淄博新塑化工有限公司 | Polypropylene catalyst spherical carrier and solid catalyst and preparation method thereof |
| CN104403027A (en) * | 2014-12-05 | 2015-03-11 | 中国石油天然气股份有限公司 | Olefin polymerization catalyst, combined catalyst containing olefin polymerization catalyst and application of olefin polymerization catalyst |
| CN104530272A (en) * | 2014-12-23 | 2015-04-22 | 中国科学院长春应用化学研究所 | Catalyst for polydiene synthesis and preparation method thereof |
| WO2016086836A1 (en) * | 2014-12-05 | 2016-06-09 | 中国石油天然气股份有限公司 | Disulfonic acid ester compound, olefin polymerization catalyst component and olefin polymerization catalyst |
| CN106467580A (en) * | 2015-08-17 | 2017-03-01 | 中国石油化工股份有限公司 | The spherical complex carrier in super big hole three-dimensional cubic duct and support type polyethylene catalysts and their preparation method and application |
| CN106632759A (en) * | 2015-10-29 | 2017-05-10 | 中国石油化工股份有限公司 | Solid catalyst component for ethylene polymerization, preparation method and application thereof |
| CN107522800A (en) * | 2016-06-20 | 2017-12-29 | 中国石油化工股份有限公司 | Ball type carrier and olefin polymerization catalysis and its preparation method and application and the method for olefinic polymerization |
| CN107522799A (en) * | 2016-06-20 | 2017-12-29 | 中国石油化工股份有限公司 | Ball type carrier and olefin polymerization catalysis and its preparation method and application and the method for olefinic polymerization |
| CN107522803A (en) * | 2016-06-20 | 2017-12-29 | 中国石油化工股份有限公司 | Ball type carrier and olefin polymerization catalysis and its preparation method and application and the method for olefinic polymerization |
| CN109206546A (en) * | 2017-07-01 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of catalyst support used for olefinic polymerization and its preparation method and application |
| CN110938157A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Catalyst system for olefin polymerization and prepolymerized catalyst composition and use thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110467694B (en) * | 2018-05-09 | 2022-01-04 | 中国石油天然气股份有限公司 | Preparation method of composite carrier of propylene high-temperature polymerization catalyst, propylene high-temperature polymerization catalyst component and propylene high-temperature polymerization catalyst |
-
2003
- 2003-02-24 CN CN 03105214 patent/CN1218971C/en not_active Expired - Lifetime
Cited By (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100366640C (en) * | 2004-10-29 | 2008-02-06 | 中国石油化工股份有限公司 | Carrier for olefin polymerization catalyst and its preparation method and its uses in preparing olefin polymerization catalyst |
| CN100417669C (en) * | 2005-10-14 | 2008-09-10 | 中国石油化工股份有限公司 | Solid catalyst composition used for olefine polymerization and catalyst thereof |
| CN100443515C (en) * | 2005-12-30 | 2008-12-17 | 中国石油化工股份有限公司 | Loading type bimetal polyethylene catalyst and its preparation method |
| CN101903412B (en) * | 2007-11-30 | 2013-06-05 | 博里利斯技术有限公司 | Catalyst with low surface area |
| CN102107145B (en) * | 2009-12-23 | 2012-10-17 | 中国石油天然气股份有限公司 | Modified Ti-Mg catalyst and preparation method and application thereof |
| CN102399329A (en) * | 2010-09-16 | 2012-04-04 | 中国石油化工股份有限公司 | Catalyst component used in alkene polymerization, and catalyst |
| CN102399327A (en) * | 2010-09-16 | 2012-04-04 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and its catalyst |
| CN102399327B (en) * | 2010-09-16 | 2013-06-05 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and its catalyst |
| CN102399329B (en) * | 2010-09-16 | 2013-08-14 | 中国石油化工股份有限公司 | Catalyst component used in alkene polymerization, and catalyst |
| CN102464734A (en) * | 2010-11-18 | 2012-05-23 | 中国石油化工股份有限公司 | Olefin polymerization catalyst and preparation method thereof and olefin polymerization method |
| CN102432706B (en) * | 2011-09-15 | 2014-04-02 | 中国石油天然气股份有限公司 | Magnesium chloride composite spherical carrier, preparation and application |
| CN102432706A (en) * | 2011-09-15 | 2012-05-02 | 中国石油天然气股份有限公司 | Magnesium chloride composite spherical carrier, preparation and application |
| CN103524643B (en) * | 2012-07-04 | 2015-08-19 | 中国石油天然气股份有限公司 | Preparation method of polyethylene catalyst |
| CN103524643A (en) * | 2012-07-04 | 2014-01-22 | 中国石油天然气股份有限公司 | Preparation method of polyethylene catalyst |
| CN104177523A (en) * | 2014-09-02 | 2014-12-03 | 淄博新塑化工有限公司 | Polypropylene catalyst spherical carrier and solid catalyst and preparation method thereof |
| CN104403027A (en) * | 2014-12-05 | 2015-03-11 | 中国石油天然气股份有限公司 | Olefin polymerization catalyst, combined catalyst containing olefin polymerization catalyst and application of olefin polymerization catalyst |
| WO2016086836A1 (en) * | 2014-12-05 | 2016-06-09 | 中国石油天然气股份有限公司 | Disulfonic acid ester compound, olefin polymerization catalyst component and olefin polymerization catalyst |
| WO2016086837A1 (en) * | 2014-12-05 | 2016-06-09 | 中国石油天然气股份有限公司 | Disulfonic acid ester compound and application thereof, olefin polymerization catalyst component and olefin polymerization catalyst |
| CN104530272A (en) * | 2014-12-23 | 2015-04-22 | 中国科学院长春应用化学研究所 | Catalyst for polydiene synthesis and preparation method thereof |
| CN104530272B (en) * | 2014-12-23 | 2017-04-19 | 中国科学院长春应用化学研究所 | Catalyst for polydiene synthesis and preparation method thereof |
| CN106467580B (en) * | 2015-08-17 | 2019-04-19 | 中国石油化工股份有限公司 | The spherical complex carrier and support type polyethylene catalysts in super big hole three-dimensional cubic duct and their preparation method and application |
| CN106467580A (en) * | 2015-08-17 | 2017-03-01 | 中国石油化工股份有限公司 | The spherical complex carrier in super big hole three-dimensional cubic duct and support type polyethylene catalysts and their preparation method and application |
| CN106632759A (en) * | 2015-10-29 | 2017-05-10 | 中国石油化工股份有限公司 | Solid catalyst component for ethylene polymerization, preparation method and application thereof |
| CN107522799A (en) * | 2016-06-20 | 2017-12-29 | 中国石油化工股份有限公司 | Ball type carrier and olefin polymerization catalysis and its preparation method and application and the method for olefinic polymerization |
| CN107522803A (en) * | 2016-06-20 | 2017-12-29 | 中国石油化工股份有限公司 | Ball type carrier and olefin polymerization catalysis and its preparation method and application and the method for olefinic polymerization |
| CN107522800A (en) * | 2016-06-20 | 2017-12-29 | 中国石油化工股份有限公司 | Ball type carrier and olefin polymerization catalysis and its preparation method and application and the method for olefinic polymerization |
| CN107522799B (en) * | 2016-06-20 | 2020-09-15 | 中国石油化工股份有限公司 | Spherical carrier, olefin polymerization catalyst, preparation method and application thereof, and olefin polymerization method |
| CN107522800B (en) * | 2016-06-20 | 2021-02-05 | 中国石油化工股份有限公司 | Spherical carrier, olefin polymerization catalyst, preparation method and application thereof, and olefin polymerization method |
| CN109206546A (en) * | 2017-07-01 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of catalyst support used for olefinic polymerization and its preparation method and application |
| CN109206546B (en) * | 2017-07-01 | 2021-05-11 | 中国石油化工股份有限公司 | Catalyst carrier for olefin polymerization and preparation method and application thereof |
| CN110938157A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Catalyst system for olefin polymerization and prepolymerized catalyst composition and use thereof |
| CN110938157B (en) * | 2018-09-25 | 2022-10-21 | 中国石油化工股份有限公司 | Catalyst system for olefin polymerization and prepolymerized catalyst composition and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1218971C (en) | 2005-09-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1218971C (en) | Compound carrier for olefin polymerization catalyst, catalyst components and the catalyst | |
| CN1229400C (en) | Catalyst compoment used for olefinic polymerization and its catalyst | |
| CN1958621A (en) | Solid catalyst components in use for polymerizing olefin, catalyst, and application of catalyst | |
| CN1955195B (en) | Catalyst, preparation method and application for olefin polymerization or copolymerization | |
| CN1726080A (en) | Magnesium dichloride-based adducts and catalyst components obtained therefrom | |
| CN1035186C (en) | Components and catalysts for polymerization of olefins | |
| CN1718595A (en) | Globular catalyst component used for olefine polymerization and its catalyst | |
| CN1085915A (en) | Production has the polyvinyl method of the hexane extractable content of minimizing | |
| CN1194993C (en) | Solid catalyst component for ethylene polymerization and catalyst therefor | |
| CN1039335C (en) | Solid component of catalyst for (co) polymerization of ethylene | |
| CN100417669C (en) | Solid catalyst composition used for olefine polymerization and catalyst thereof | |
| CN1035383C (en) | Catalyst component for olefin polymerization | |
| CN1803863A (en) | Catalyst components for olefinic polyreaction and catalyst thereof | |
| CN1769337A (en) | Polyolefin composite material and preparation method | |
| CN1213082C (en) | Catalyst for ethylene polymerization | |
| CN101289520A (en) | Catalyst suitable for vinyl polymerization and copolymerisation | |
| CN100400554C (en) | Catalyst components for propylene polymerization and catalyst thereof | |
| CN1310968C (en) | Catalyst used for olefine polymerization or copolymerization, its preparation method and application | |
| CN1948352B (en) | Catalyst components used for olefin hydrocarbon polymerization and its catalyst | |
| CN110467694A (en) | Preparation method, propylene high-temperature polymerization catalyst component and the propylene high-temperature polymerization catalyst of propylene high-temperature polymerization catalyst complex carrier | |
| CN1177873C (en) | Catalyst component for ethylene polymerization or copolymerization, and catalyst and use thereof | |
| CN1891722A (en) | Method for preparing catalyst constituent for olefinic polymerization | |
| CN1279069C (en) | Polyethylene catalyst and its preparation method | |
| CN1274721C (en) | Catalyst for ethene polymerization or multipolymer, preparing method thereof | |
| CN1297574C (en) | Catalyst component for olefine polymerization and catalyst 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 | ||
| CX01 | Expiry of patent term |
Granted publication date: 20050914 |
|
| CX01 | Expiry of patent term |