CN102272172A - Method for preparing a titanium catalyst component, titanium catalyst component, method for preparing a titanium catalyst and titanium catalyst - Google Patents
Method for preparing a titanium catalyst component, titanium catalyst component, method for preparing a titanium catalyst and titanium catalyst Download PDFInfo
- Publication number
- CN102272172A CN102272172A CN2009801146559A CN200980114655A CN102272172A CN 102272172 A CN102272172 A CN 102272172A CN 2009801146559 A CN2009801146559 A CN 2009801146559A CN 200980114655 A CN200980114655 A CN 200980114655A CN 102272172 A CN102272172 A CN 102272172A
- Authority
- CN
- China
- Prior art keywords
- compound
- titanium
- magnesium
- titanium catalyst
- alcohol
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention relates to a method for preparing a titanium catalyst component, comprising the steps: reacting a magnesium halide in a solvent including an alcohol to obtain a homogeneous solution, reacting at least one organic boron compound with the homogeneous solution, reacting a titanium compound with the homogeneous solution, a titanium catalyst component obtainable by said method, a method for preparing a titanium catalyst and a titanium catalyst obtainable by said method.
Description
Technical field
The present invention relates to a kind of preparation method and titanium catalyst component thereof of titanium catalyst component; A kind of preparation method of titanium catalyst and titanium catalyst thereof.
Can be used for vinyl polymerization and copolymerization based on the titanium catalyst according to titanium catalyst component of the present invention, a kind of high catalytic activity that has is provided, resulting polymers has high bulk density, narrow size distribution and the less catalyzer of fine powder content.
Background technology
In recent years, the research of olefin polymerization catalysis is the hot issue in the polyolefine research field always.Exploitation high catalytic activity, hydrogen response be good, obtain the polyolefin catalyst that polymer particle size is evenly distributed, fine powder is few is the target that the scientific research personnel pursues.
Bibliographical information the magniferous Ti-base catalyst of many usefulness as olefinic polymerization and copolymerization method with catalyzer.These catalyzer can provide high catalytic activity, produce the polymkeric substance of high-bulk-density, go for the slurry and the vapour phase polymerization of ethene.
As obtaining to produce in the catalyzer of high-bulk-density olefin polymer, make magnesium compound and give electron compound prepared in reaction magnesium solution with magnesium solution.Used comprises alcohol, amine, cyclic ethers or organic carboxyl acid to electron compound.Usually magnesium solution prepares in the presence of hydrocarbon solvent.Magnesium-supported catalyzer can prepare by magnesium solution and halogen titanium compound such as titanium tetrachloride reaction.
The method for preparing magnesium solution with alcohol is disclosed among U.S. Pat 3642746, US4336360, US4330649 and the US5106807.
US4477639 and US4518706 also disclose with tetrahydrofuran (THF) or the cyclic ester method as the solvent of the described magnesium compound of dissolving.
Though these catalyzer can be produced the polymkeric substance of high-bulk-density, but still described catalyzer need improved aspect the catalytic activity of catalyzer.In addition, wide size-grade distribution is arranged and contain many fine powders with the polymkeric substance of above-mentioned Catalyst Production, this makes troubles for the production quiet run at the easy blocking pipeline of production process.
The Preparation of catalysts method of disclosed vinyl polymerization and copolymerization among the Japanese Patent JP 4951378 is: magnesium dichloride through grinding and ethanol synthesis generate MgCl
26C
2H
5OH alcohol adduct slurries, again with aluminium diethyl monochloride generation esterification, last and TiCl
4Carry the titanium reaction, obtain MgCl
2Carrier loaded Titanium series catalyst.
This method for preparing catalyst is simple, the reaction conditions gentleness, and activity is very high during the catalyst vinyl polymerization.But this preparation method exists the carrier magnesium chloride can not dissolve in mineral oil, the irregular platy shaped particle that produces when there be former grinding in magnesium chloride in the slurry reaction system causes the solid catalyst particle form that obtains relatively poor, thickness is inhomogeneous, thereby polymer morphology is also bad, fine powder is more, easily produces static and easy blocking pipe.Simultaneously, this catalyzer oligomer in the solvent when polymerization is more, easily blocking pipe and brought bigger trouble for aftertreatment.
For improving these problems, U.S. Pat 4311414 proposes a kind of by making the magnesium hydroxide dry air prepare the method for catalyzer, can produce the improved polymkeric substance of narrow particle size distribution and mean particle size.
U.S. Pat 3953414 and US 4111835 reported by making hydration magnesium dichloride dry air prepare the method for catalyzer, but the production special shape, the great polymkeric substance of mean particle size.
But these methods need optional equipment such as air dry-set, and prepared catalyst activity is lower, and the polymkeric substance that obtains contains very big particle makes the melting process of polymkeric substance become difficulty.
Therefore, needing can be by the simple method catalyzer that is used for vinyl polymerization and copolymerization preparation, that high polymerization activity and hydrogen response are arranged.In addition, also need to produce narrow size-grade distribution of polymerisate and the few catalyzer of fine particle content.
In addition, for using in You Nipa (Unipol) phase fluidised bed processes, a kind of polymerization of typical gaseous ethene adopts the silica gel that has the big particle diameter of activeconstituents (titanium and magnesium) to prepare usually.Because the shape of catalyzer relies on the shape of silica-gel carrier fully, catalyst performance also is the microvoid structure that relies on particle diameter and be used to prepare the silica gel of catalyzer.
For example: the U.S. Pat 4302565 disclosed catalyzer that are used for gas-phase fluidized bed polymerization process, the median size of its used silica gel is generally 40～80 microns.Linear low-density polyethylene film resinoid by this Catalyst Production has good processing properties and mechanical property.The ethylene polymerization activity of this catalyzer is generally about 3500gPE/g Cat on industrialization gas phase fluidization bed apparatus.
But then active significantly reduction when being used for gas-phase fluidized-bed condensation technology owing to the shortening of the catalyzer residence time, thereby cause polyvinyl ash rising and influenced polyvinyl performance, the catalytic activity that therefore improves this type of catalyzer is one of key factor that improves the vinyl polymerization amount.In addition, the form of polymer beads and size distribution are the principal elements that influences gas phase fluidization bed apparatus smooth operation, therefore, except improving catalytic performance, good polymer beads form and size distribution, fine powder content also are the target that such catalyzer is pursued less.
United States Patent (USP) discloses the carrier of catalyzer about US 4302565, caused the repeatability of catalyst preparation process poor on the support of the catalyst owing to adopt pickling process that the activity of such catalysts composition is loaded in, so on support of the catalyst, be difficult to the uniform distribution of control activeconstituents.The catalytic activity of the polymer particle that therefore, obtains, particle shape and size distribution are difficult to satisfactory.
Patent US4376062 and patent CN1493599A are on the basis of above-mentioned catalyst activity component, with the silicon-dioxide of smoke-like as filler, mix with parent, obtain catalyzer by spray-dired method by titanium compound, magnesium compound and electron donor compound.This catalyzer goes for the gas-phase fluidized-bed frozen state and the super frozen state polymerization technique of ethene, control catalyst particle size and the form that obtains easily, and its catalytic efficiency is improved to some extent also.But the catalytic activity of catalyzer and the shape of polymerisate are still unsatisfactory.And when these catalyzer were applied to ethene and higher level alpha-olefin (for example 1-hexene) copolymerization, the n-hexylene extractive content was still very high in the polymkeric substance that obtains, and has reduced the performance of the finished product in the copolymer resin.
Summary of the invention
The object of the invention is to overcome the defective in the art methods, a kind of catalyzer that is used for vinyl polymerization and copolymerization is provided, especially for the ethene gas-phase polymerization that adopts fluidized-bed under frozen state or the super frozen state and copolymerization high catalytic activity, catalyzer that hydrogen response is good, and be that polymkeric substance has high-bulk-density, narrow size-grade distribution and the few catalyzer of fine powder content.
In order to realize the foregoing invention purpose, the invention provides a kind of preparation method of titanium catalytic active component, comprise that step is:
A. make halogenated magnesium compound and contain pure solvent reaction, preparation homogeneous phase magnesium solution;
B. make the reaction of described homogeneous phase magnesium solution and at least a organoboron compound;
C. make the reaction of titanium compound and homogeneous magnesium solution.
According to the present invention, usually under temperature at least-25 ℃, carry out halogenated magnesium compound and solvent reaction in the described preparation titanium catalyst component method, preferable reaction temperature is-10 ℃～200 ℃, more preferably temperature of reaction is 0 ℃～150 ℃.The reaction times of this step is generally 15 minutes～and 5 hours, preferred 30 minutes～4 hours.
According to a kind of preparation method who prepares the titanium catalytic active component of the present invention, halogenated magnesium compound is selected from magnesium dihalide compound, halogenated alkyl magnesium compound, halogenated alkoxy magnesium compound and halogenation aryloxy magnesium compound.
Especially, described magnesium dihalide compound comprises magnesium chloride (MgCl
2), magnesium bromide (MgBr
2), magnesium fluoride (MgF
2) and magnesium iodide (MgI
2); Described halogenated alkyl magnesium compound comprises methylmagnesiumhalide, ethyl-magnesium-halide, halogenation propyl group magnesium, butyl Grignard reagent, halogenation isobutyl-magnesium, halogenation hexyl magnesium and halogenation amyl group magnesium; Described halogenated alkoxy magnesium compound comprises halogenation magnesium methylate, halogenation magnesium ethylate, halogenation isopropoxy magnesium, halogenation butoxy magnesium, halogenation octyloxy magnesium; Halogenation aryloxy magnesium compound comprises halogenation phenoxy group magnesium and halogenation methylphenoxy magnesium.These magnesium compounds can the simplification compounds or are used with the form of the mixture of two or more compounds.
In addition, above-mentioned magnesium compound can be effectively to use with the coordination compound form of other metal.For example, available following compound is as the magnesium metal complex: the compound that obtains by magnesium compound and polysiloxane compound, the silane compound that comprises halogen, ester or alcohol reaction; In the presence of halogenated silanes, phosphorus pentachloride or thionyl chloride, react the compound that obtains by MAGNESIUM METAL and alcohol, phenol or ether.Described magnesium compound can be a magnesium halide, particularly magnesium chloride (MgCl
2) or the alkyl magnesium chloride of the alkyl of 1～10 carbon atom is arranged; The chlorination alkoxyl magnesium that the alkoxyl group of 1～10 carbon atom is arranged; The chlorination aryloxy magnesium that contains the aryloxy of 6～20 carbon atoms.
Preferably, according to the method for preparing titanium catalyst component of the present invention, organoboron compound is the organoboron compound of non-activity hydrogen, particularly has the organoboron compound of following general formula:
R
1 xR
2 yB(OR
3)
z
Wherein, R
1And R
2Be respectively C
1～C
10Alkyl, C
1～C
10-oxyl, C
5～C
10Aryl or halogen;
R
3Be C
1～C
10Alkyl is preferably C
1～C
6Alkyl, aryloxy;
0≤x≤3；
0≤y≤3；
0≤z≤3, and;
x+y+z＝3
Preferably, the represented boron compound of above-mentioned general formula comprises following at least a kind of compound: boric acid methyl dibutyl ester, trimethyl borate, triethyl borate, tripropoxy-boron, tributyl borate, boric acid three monooctyl esters, boric acid benzene diethyl ester, triphenyl borate, trimethyl-boron, triethyl-boron, methyl diethyl boron, diethoxymethyl boron, diethoxy ethyl boron, dibutoxy ethyl boron, dibutoxy butyl boron, two Phenoxyphenyl boron, oxyethyl group diethyl boron, oxyethyl group dibutyl boron, phenoxy group phenylbenzene boron, chlorination diethoxy boron, bromination diethoxy boron, diphenyl antimony chloride oxygen base boron, dichloride oxyethyl group boron, dibrominated oxyethyl group boron, dichloride butoxy boron, dichloride phenoxy group boron and tonsilon oxyethyl group boron etc.
Further, the present invention is a kind of to prepare among the preparation method of titanium catalyst component, and described organoboron compound is selected from following at least a kind of compound: boric acid methyl dibutyl ester, trimethyl borate, triethyl borate, tripropoxy-boron, tributyl borate, boric acid three monooctyl esters, boric acid benzene diethyl ester and triphenyl borate.
Preferably, according to the method for preparing titanium catalyst component of the present invention, titanium compound has following formula:
Ti(OR)
aX
b
Wherein, R is C
1～C
10Aliphatic group, be preferably C
1～C
4Alkyl or C
5～C
10Aryl;
X is fluorine, chlorine, bromine or iodine;
A is 0,1,2 or 3;
B is 1～4 a integer, and
A+b is 3 or 4.
Preferably, according to the method for preparing titanium catalyst component of the present invention, described titanium compound is selected from: TiCl
3, TiCl
4, TiBr
4, TiI
4, Ti (OC
3H
7) Cl
3And Ti (OC
4H
9)
2Cl
2
Described magnesium halide and the solvent that contains alcohol are reacted, prepare described uniform magnesium halide solution (solution that contains magnesium).
The described alcohol that is used to prepare magnesium solution comprises alcohol and the halo derivatives thereof that has 1～20 carbon atom, for example methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, amylalcohol, hexanol, 2-methyl amyl alcohol, 2-Ethylhexyl Alcohol, enanthol, 2-ethyl enanthol, octanol, nonylcarbinol, dodecanol, stearyl alcohol, phenylcarbinol, phenylethyl alcohol, second propylbenzene methyl alcohol and cumic alcohol.Preferably, described alcohol is the alcohol of 1～twelve carbon atom.
Further preferably, according to the method for preparing titanium catalyst component of the present invention, described alcohol is selected from following one or more alcohol mixtures: methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, amylalcohol, hexanol, 2-methyl amyl alcohol, 2-Ethylhexyl Alcohol, enanthol, 2-ethyl enanthol, octanol, nonylcarbinol.
Preferably, according to the method for preparing titanium catalyst component of the present invention, described solvent also contains varsol further.
Further preferably, according to the method for preparing titanium catalyst component of the present invention, described varsol is selected from: aliphatic solvents, alicyclic hydrocarbon solvent, aromatic solvent and halogenated hydrocarbon solvent.
Wherein, aliphatic solvents comprises: pentane, hexane, heptane, octane, decane and kerosene.The clicyclic hydrocarbon solvent comprises: ring benzene, methyl ring benzene, hexanaphthene and methylcyclohexane.Aromatic hydrocarbon solvent comprises: benzene,toluene,xylene, ethylbenzene.Halogenated hydrocarbon solvent comprises: propylene dichloride, Ethylene Dichloride, trieline, tetracol phenixin and chlorobenzene etc.
The mean particle size of gained catalyzer and size-grade distribution can be depending on the ratio of the type of consumption, halogenated magnesium compound of type, alcohol of used alcohol and halogenated magnesium compound and alcohol.
When described magnesium halide solution and titanium compound reaction, the shape and the size of the solid titanium catalyst of separating out depend primarily on reaction conditions.In addition, can carry out by one or many with the reaction of titanium compound.
In order to control particle shape, may preferably make the mixture of described magnesium compound solution and titanium compound, organoboron compound under enough low temperature, react the generation solid substance composition.Preferably, initial temperature is set at-70 ℃～70 ℃, more preferably-50 ℃～50 ℃.Begin when contacting afterreaction, temperature slowly rises and kept 0.5～5 hour down at 50 ℃～150 ℃, continuously finishes reaction so that it to be provided.
Preferably, according to the method for preparing titanium catalyst component of the present invention, described organoboron compound can also can contact back adding system at magnesium compound solution in magnesium compound solution and adding system before titanium compound contacts with titanium compound.
Further preferably, according to the method for preparing titanium catalyst component of the present invention, when adding organoboron compound, add a kind of inorganic carrier.
When inorganic carrier adds in the uniform magnesium halide solution with organoboron compound, obtain the spheric titanium catalyst component, it can provide a kind of highly active spherical titanium catalyst that has, and is particularly suitable for the vapour phase polymerization of ethene.
According to the method for preparing titanium catalyst component of the present invention, before using inorganic carrier, preferably this carrier is carried out the drying and dewatering processing or carry out the alkanisation activation.
Further preferably, according to the method for preparing titanium catalyst component of the present invention, described inorganic carrier is selected from silicon-dioxide, aluminum oxide and their mixture.
Preferably, according to the method for preparing titanium catalyst component of the present invention, inorganic carrier is spherical, and particle diameter is 0.1～150 μ m.
Further preferably, according to the method for preparing titanium catalyst component of the present invention, inorganic carrier is a silicon-dioxide, and specific surface area is 80～300m
2/ g.
When inorganic carrier is specific surface area 80～300m
2During the silicon-dioxide of/g, improved the charge capacity of magnesium in the catalyzer, thus in the catalyzer effectively the charge capacity of catalyst component improve.And, use such inorganic carrier can prevent when Mg content is high, the random gathering of magnesium chloride in the catalyzer guarantees that the catalyst particle that produces forms sphere.
Further preferably, according to the method for preparing titanium catalyst component of the present invention, when halogenated magnesium compound was 1mol, used alcohol was 0.1～10.0mol; Organoboron compound is 0.05～1.0mol; Titanium compound is 1.0～15.0mol.
The method for preparing titanium catalyst component of the present invention, under the situation of using inorganic carrier, when halogenated magnesium compound was 1mol, used alcohol was 0.1～10.0mol so; Organoboron compound is 0.05～1.0mol; Inorganic carrier is that 50～500g and titanium compound are 1.0～15.0mol.
Further preferably, according to the method for preparing titanium catalyst component of the present invention, add after organoboron compound and the titanium compound, add other titanium compound, described other titanium compound is selected from: halogenated titanium or have C
1～C
8The alkyl dioxide of alkoxyl group.
Another purpose of the present invention is to provide a kind of titanium catalyst component, and this component can prepare the method preparation of titanium catalyst component according to the present invention.
Under the corresponding titanium catalyst situation of using described titanium catalyst component as the basis preparation, therefore the titanium catalyst of preparation has high catalytic activity, and it is less to make that in vinyl polymerization and copolymerization polymkeric substance has high bulk density, narrow size-grade distribution and a fine powder content.
In order to be used for vinyl polymerization and copolymerization, titanium catalyst of the present invention must activate, and is included in to make under enough activator effects that titanium atom is in active state in the titanium catalyst component, obtains titanium catalyst.
Therefore, another purpose of real name is to provide a kind of method for preparing titanium catalyst, comprising:
Make the reaction of titanium catalyst component of the present invention and organo-aluminium compound, described organo-aluminium compound has following formula:
AlR
nX
3-n
Wherein, R is hydrogen or C
1～C
20Alkyl is optimized for C
1～C
6Alkyl;
X is fluorine, chlorine, bromine or iodine; And
0＜n≤3。
Preferably, according to the method for preparing titanium catalyst of the present invention, described organo-aluminium compound is selected from: trialkyl aluminium compound, dialkylaluminum halides compound and alkyl dihalo aluminum compound, wherein each alkyl has 1～6 carbon atom, for example methyl, ethyl,, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, neo-pentyl, isopentyl, hexyl and cyclohexyl.
Particularly, described organo-aluminium compound is selected from: triethyl aluminum, triisobutyl aluminium, ethylaluminium dichloride, diethylaluminum chloride, sesquialter ethylaluminium chloride and diisobutylaluminium hydride.
Before actual polyreaction, described titanium catalyst component and ethene or alpha-olefin can be carried out prepolymerization.Described prepolymerization can in the presence of the varsol (as hexane), at low temperatures, under the pressure of ethene or alpha-olefin and as described in carry out under titanium catalyst component and organo-aluminium compound (as the triethyl aluminum) situation about existing.
Another purpose of the present invention is to provide a kind of titanium catalyst, and described titanium catalyst can prepare the method preparation of titanium catalyst according to the present invention.
A kind of titanium catalyst according to the present invention, the mol ratio of organo-aluminium compound and solid titanium catalyst component is 10～1000, is preferably 20～200.
Another purpose of the present invention has been to provide the purposes of catalyzer in vinyl polymerization of the present invention and the copolymerization.
Catalyzer of the present invention can be used for ethene and homopolymerizations other alpha-olefins or copolymerization, and for example described alpha-olefin is propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene and 4-methyl-1-pentene.In polymerization process, can use vapor phase process, slurry process and solution method.
In order to ensure high polyreaction rate, the polyreaction of described use titanium catalyst is carried out under sufficient temp.Usually, polymerization temperature is 20 ℃～200 ℃, is preferably 60 ℃～95 ℃.In polyreaction, monomer pressure is preferably 1atm～100atm, more preferably 2atm～50atm.
Embodiment
Following embodiment is used to illustrate the present invention, its protection domain is not constituted to limit.
First kind of embodiment
Embodiment 1～10 has illustrated that first kind of embodiment of the present invention relates to use halogenated magnesium compound, organoboron compound and titanium compound and prepare titanium catalyst component, and the polyreaction of using the corresponding titanium catalyst of described titanium catalyst component preparation.
Embodiment 1
4.76 gram (50mmol) Magnesium Chloride Anhydrouss, 75 milliliters of decane and 16.3 gram (125mmol) isooctyl alcohol are heated to 130 ℃, make it to react 3 hours, obtain a kind of homogeneous phase solution.In this solution, add the tributyl borate of 15mmol and stir 2 hours so that tributyl borate is dissolved in this solution down at 50 ℃.Above-mentioned all homogeneous phase solutions that obtain are cooled to room temperature, in 1 hour, while stirring it are added drop-wise to then in the 150ml titanium tetrachloride of 0 ℃ of temperature maintenance.Mixture temperature was kept 1 hour down at 0 ℃, under agitation in 2 hours, temperature is carried to 120 ℃ then, and this temperature was kept 2 hours.After reaction in 2 hours finishes, the solid that generates is carried out heat filtering separate.With hexane and decane solid catalyst is carried out thorough washing respectively,, obtain a kind of solid titanium catalyst component after drying until in scavenging solution, can not detecting the titanium compound of separating out.
Vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, adding hexane 1L and concentration is the triethyl aluminum 1.0ml of 1M, the catalyzer that adds the above-mentioned preparation of accurate weighing with syringe, be warming up to 75 ℃, feed hydrogen and make the still internal pressure reach 0.28MPa, feed ethene again and make the interior stagnation pressure of still reach 0.73MPa (gauge pressure), polymerization is 2 hours under 80 ℃ of conditions, and polymerization result sees Table 1.
Embodiment 2
4.76 gram (50mmol) Magnesium Chloride Anhydrouss, 75 milliliters of decane and 16.3 gram (125mmol) isooctyl alcohol are heated to 130 ℃, make it to react 3 hours, obtain a kind of homogeneous phase solution.In this solution, add the boric acid benzene diethyl ester of 15mmol and stir 2 hours so that boric acid benzene diethyl ester is dissolved in this solution down at 50 ℃.Above-mentioned all homogeneous phase solutions that obtain are cooled to room temperature, in 1 hour, while stirring it are added drop-wise to then in the 150ml titanium tetrachloride of 0 ℃ of temperature maintenance.Mixture temperature was kept 1 hour down at 0 ℃, under agitation in 2 hours, temperature is carried to 120 ℃ then, and this temperature was kept 2 hours.After reaction in 2 hours finishes, the solid that generates is carried out heat filtering separate.With hexane and decane solid catalyst is carried out thorough washing respectively,, obtain a kind of solid titanium catalyst component after drying until in scavenging solution, can not detecting the titanium compound of separating out.
Vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, adding hexane 1L and concentration is the triethyl aluminum 1.0ml of 1M, the catalyzer that adds the above-mentioned preparation of accurate weighing with syringe, be warming up to 75 ℃, feed hydrogen and make the still internal pressure reach 0.28MPa, feed ethene again and make the interior stagnation pressure of still reach 0.73MPa (gauge pressure), polymerization is 2 hours under 80 ℃ of conditions, and polymerization result sees Table 1.
Embodiment 3
Embodiment 3 is identical with the method for embodiment 1, and institute's difference is: the tributyl borate that adds 20mmol.Polymerization result sees Table 1.
Embodiment 4
Embodiment 4 is identical with the method for embodiment 1, and institute's difference is: the tributyl borate that adds 10mmol.Polymerization result sees Table 1.
Embodiment 5
Embodiment 5 is identical with the method for embodiment 1, and institute's difference is: the decane that adds 50ml.Polymerization result sees Table 1.
Embodiment 6
4.76 gram (50mmol) Magnesium Chloride Anhydrouss, 75 milliliters of decane and 16.3 gram (125mmol) isooctyl alcohol are heated to 130 ℃, make it to react 3 hours, obtain a kind of homogeneous phase solution.In this solution, add the triphenyl borate of 15mmol and stir 2 hours so that triphenyl borate is dissolved in this solution down at 50 ℃.Above-mentioned all homogeneous phase solutions that obtain are cooled to room temperature, in 1 hour, while stirring it are added drop-wise to then in the 150ml titanium tetrachloride of 0 ℃ of temperature maintenance.Mixture temperature was kept 1 hour down at 0 ℃, under agitation in 2 hours, temperature is carried to 120 ℃ then, and this temperature was kept 2 hours.After reaction in 2 hours finishes, the solid that generates is carried out heat filtering separate.With hexane and decane solid catalyst is carried out thorough washing respectively,, obtain a kind of solid titanium catalyst component after drying until in scavenging solution, can not detecting the titanium compound of separating out.
Vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, adding hexane 1L and concentration is the triethyl aluminum 1.0ml of 1M, the catalyzer that adds the above-mentioned preparation of accurate weighing with syringe, be warming up to 75 ℃, feed hydrogen and make the still internal pressure reach 0.28MPa, feed ethene again and make the interior stagnation pressure of still reach 0.73MPa (gauge pressure), polymerization is 2 hours under 80 ℃ of conditions, and polymerization result sees Table 1.
Embodiment 7
4.76 gram (50mmol) Magnesium Chloride Anhydrouss, 75 milliliters of decane and 16.3 gram (125mmol) isooctyl alcohol are heated to 130 ℃, make it to react 3 hours, obtain a kind of homogeneous phase solution.In this solution, add the boric acid monomethyl dibutyl ester of 15mmol and stir 2 hours so that boric acid monomethyl dibutyl ester is dissolved in this solution down at 50 ℃.Above-mentioned all homogeneous phase solutions that obtain are cooled to room temperature, in 1 hour, while stirring it are added drop-wise to then in the 150ml titanium tetrachloride of 0 ℃ of temperature maintenance.Mixture temperature was kept 1 hour down at 0 ℃, under agitation in 2 hours, temperature is carried to 120 ℃ then, and this temperature was kept 2 hours.After reaction in 2 hours finishes, the solid that generates is carried out heat filtering separate.With hexane and decane solid catalyst is carried out thorough washing respectively,, obtain a kind of solid titanium catalyst component after drying until in scavenging solution, can not detecting the titanium compound of separating out.
Vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, adding hexane 1L and concentration is the triethyl aluminum 1.0ml of 1M, the catalyzer that adds the above-mentioned preparation of accurate weighing with syringe, be warming up to 75 ℃, feed hydrogen and make the still internal pressure reach 0.28MPa, feed ethene again and make the interior stagnation pressure of still reach 0.73MPa (gauge pressure), polymerization is 2 hours under 80 ℃ of conditions, and polymerization result sees Table 1.
Embodiment 8
Embodiment 8 is identical with the method for embodiment 1, and institute's difference is: organoboron compound is a boric acid sec.-propyl dibutyl ester.Polymerization result sees Table 1.
Embodiment 9
Embodiment 9 is identical with the method for embodiment 1, and institute's difference is: organoboron compound is a boric acid triethyl ester.Polymerization result sees Table 1.
Embodiment 10
4.76 gram (50mmol) Magnesium Chloride Anhydrouss, 75 milliliters of decane and 16.3 gram (125mmol) isooctyl alcohol are heated to 130 ℃, make it to react 3 hours, obtain a kind of homogeneous phase solution.In this solution, add the boric acid methyl dibutyl ester of 15mmol and stir 2 hours so that boric acid methyl dibutyl ester is dissolved in this solution down at 50 ℃.Above-mentioned all homogeneous phase solutions that obtain are cooled to room temperature, in 1 hour, while stirring it are added drop-wise to then in the 150ml titanium tetrachloride of 0 ℃ of temperature maintenance.Mixture temperature was kept 1 hour down at 0 ℃, under agitation in 2 hours, temperature is carried to 120 ℃ then, and this temperature was kept 2 hours.After reaction in 2 hours finishes, the solid that generates is carried out heat filtering separate.With hexane and decane solid catalyst is carried out thorough washing respectively,, obtain a kind of solid titanium catalyst component after drying until in scavenging solution, can not detecting the titanium compound of separating out.
Vinyl polymerization is identical with the method for embodiment 1, and polymerization result sees Table 1.
Above-mentioned experimental result shows, can prepare according to the titanium catalyst of titanium catalyst component preparation of the present invention have high bulk density, narrow size distribution and the less polyethylene of fine powder content.
Second kind of embodiment
Embodiment 11～18 and Comparative Examples have illustrated that the first embodiment of the present invention relates to use halogenated magnesium compound, organoboron compound and titanium compound and prepares titanium catalyst component, relate to the polyreaction of use from the corresponding titanium catalyst of described titanium catalyst component preparation.
Embodiment 11
4.76 gram (50mmol) Magnesium Chloride Anhydrouss, 90 milliliters of decane and 16.3 gram (125mmol) isooctyl alcohol are heated to 130 ℃, make it to react 3 hours, obtain a kind of homogeneous phase solution.In this solution, add the triethyl borate of 15mmol and stir 1 hour so that triethyl borate is dissolved in this solution down at 50 ℃.(model: XPO2485 purchases the W.R.Grace﹠amp in the U.S. to add 10 gram silica gel in above-mentioned solution; Co., MD), after stirring 1 hour under 50 ℃, the above-mentioned suspension that obtains is cooled to-10 ℃, in 1 hour, while stirring the 100ml titanium tetrachloride is added drop-wise in the above-mentioned suspension then.Mixture temperature was kept 1 hour down at-10 ℃, under agitation in 3 hours, temperature is carried to 120 ℃ then, and this temperature was kept 2 hours.After reaction in 2 hours finishes, the solid that generates is carried out heat filtering separate.With hexane and decane solid catalyst is carried out thorough washing respectively,, obtain a kind of solid titanium catalyst component of good fluidity after drying until in scavenging solution, can not detecting the titanium compound of separating out.
Vinyl polymerization
The 2L reactor is heated to about 80 ℃,, blows row with hydrogen then with the drying nitrogen displacement.Adding hexane 1L and concentration is the triethyl aluminum 1.0ml of 1M., add the catalyzer of the above-mentioned preparation of accurate weighing with syringe, be warming up to 75 ℃, feed hydrogen and make the still internal pressure reach 0.28MPa, feed ethene again and make that stagnation pressure reaches 1.03MPa (gauge pressure) in the still, polymerization is 2 hours under 80 ℃ of conditions, and polymerization result sees Table 2.
Embodiment 12
4.76 gram (50mmol) Magnesium Chloride Anhydrouss, 90 milliliters of decane and 16.3 gram (125mmol) isooctyl alcohol are heated to 130 ℃, make it to react 3 hours, obtain a kind of homogeneous phase solution.In this solution, add the triethyl borate of 15mmol and stir 1 hour so that triethyl borate is dissolved in this solution down at 50 ℃.(model: XPO2485 purchases the W.R.Grace﹠amp in the U.S. to add 10 gram silica gel in above-mentioned solution; Co., MD), after stirring 1 hour under 50 ℃, the above-mentioned suspension that obtains is cooled to-10 ℃, in 1 hour, while stirring the 100ml titanium tetrachloride is added drop-wise in the above-mentioned suspension then.Mixture temperature was kept 1 hour down at-10 ℃, under agitation in 3 hours, temperature is carried to 120 ℃ then, and this temperature was kept 2 hours.After reaction in 2 hours finishes, the solid that generates is carried out heat filtering separate.With hexane and decane solid catalyst is carried out thorough washing respectively,, obtain a kind of solid titanium catalyst component of good fluidity after drying until in scavenging solution, can not detecting the titanium compound of separating out.
Method according to embodiment 11 is carried out vinyl polymerization, and polymerization result sees Table 2.
Embodiment 13
4.76 gram (50mmol) Magnesium Chloride Anhydrouss, 90 milliliters of decane and 16.3 gram (125mmol) isooctyl alcohol are heated to 130 ℃, make it to react 3 hours, obtain a kind of homogeneous phase solution.In this solution, add the triethyl borate of 7.5mmol and stir 1 hour so that triethyl borate is dissolved in this solution down at 50 ℃.(model: XPO2485 purchases the W.R.Grace﹠amp in the U.S. to add 10 gram silica gel in above-mentioned solution; Co., MD), after stirring 1 hour under 50 ℃, the above-mentioned suspension that obtains is cooled to-10 ℃, in 1 hour, while stirring the 100ml titanium tetrachloride is added drop-wise in the above-mentioned suspension then.Mixture temperature was kept 1 hour down at-10 ℃, in mixture, add the triethyl borate of 7.5mmol then and stir 1h so that system is fully reacted down at-10 ℃, under agitation in 3 hours, temperature is carried to 120 ℃, and this temperature was kept 2 hours.After reaction in 2 hours finishes, the solid that generates is carried out heat filtering separate.With hexane and decane solid catalyst is carried out thorough washing respectively,, obtain a kind of solid titanium catalyst component of good fluidity after drying until in scavenging solution, can not detecting the titanium compound of separating out.
Method according to embodiment 11 is carried out vinyl polymerization, and polymerization result sees Table 2.
Embodiment 14
Embodiment 14 is identical with the method for embodiment 11, and institute's difference is: adopt 15mmol boric acid diethylamino phenyl ester to replace described organoboron compound.
Method according to embodiment 11 is carried out vinyl polymerization, and polymerization result sees Table 2.
Embodiment 15
Embodiment 15 is identical with the method for embodiment 11, and institute's difference is: adopt 15mmol boric acid tributyl ester to replace described organoboron compound.
Method according to embodiment 11 is carried out vinyl polymerization, and polymerization result sees Table 2.
Embodiment 16
4.76 gram (50mmol) Magnesium Chloride Anhydrouss, 90 milliliters of decane and 16.3 gram (125mmol) isooctyl alcohol are heated to 130 ℃, make it to react 3 hours, obtain a kind of homogeneous phase solution.In this solution, add the triethyl borate of 7.5mmol and stir 1 hour so that triethyl borate is dissolved in this solution down at 50 ℃.(model: XPO2485 purchases the W.R.Grace﹠amp in the U.S. to add 10 gram silica gel in above-mentioned solution; Co., MD), after stirring 1 hour under 50 ℃, the above-mentioned suspension that obtains is cooled to-10 ℃, in 1 hour, while stirring the 100ml titanium tetrachloride is added drop-wise in the above-mentioned suspension then.Mixture temperature was kept 1 hour down at-10 ℃.Under agitation in 3 hours, temperature is carried to 120 ℃, and this temperature was kept 2 hours.After reaction in 2 hours finishes, the solid that generates is carried out heat filtering separate.With hexane and decane solid catalyst is carried out thorough washing respectively,, obtain a kind of solid titanium catalyst component of good fluidity after drying until in scavenging solution, can not detecting the titanium compound of separating out.By analysis, titanium content is 3.0% in the titanium catalyst component that obtains.
Accurately a certain amount of above-mentioned titanium catalyst component of weighing adds the 60g hexane and disperses.According to Ti: Al (mol: mol)=add AlEt at 1: 10
2Cl carries out pre-complexing at normal temperatures, reacts to get pre-complex catalyst after 0.5 hour.
Vinyl polymerization
The 2L reactor is heated to about 80 ℃, and air is replaced with drying nitrogen, is blown into hydrogen then.Adding after hexane 1L and concentration is the triethyl aluminum 1.0ml of 1M, the above-mentioned titanium catalyst of 30mg is carried out pre-complexing, be warming up to 75 ℃ subsequently.Feed hydrogen and make the still internal pressure reach 0.28MPa, feed ethene again and make the interior stagnation pressure of still reach 1.03MPa (gauge pressure), polymerization is 2 hours under 80 ℃ of conditions, and polymerization result sees Table 2.
Embodiment 17
Embodiment 17 is identical with the method for embodiment 16, and institute's difference is: according to Ti: Al (mol: mol)=20 add AlEt
2Cl carries out pre-complexing at normal temperatures.
Method according to embodiment 16 is carried out vinyl polymerization, and polymerization result sees Table 2.
Embodiment 18
Embodiment 18 is identical with the method for embodiment 11, and institute's difference is: the amount of silica gel is 15g.
Method according to embodiment 11 is carried out vinyl polymerization, and polymerization result sees Table 2.
Comparative Examples
To process N
2Add 2.0gTiCl in the metathetical 250ml there-necked flask
31/3AlCl
34.6 gram MgCl
2With the 115ml tetrahydrofuran (THF), be warming up to 65 ℃ under stirring, isothermal reaction 2 hours is cooled to 30 ℃.To a process N
2Metathetical 250ml, add in the there-necked flask 6.9 gram silica gel (model: TS-610, available from U.S. Cabot company, MA) after, mother liquor after the cooling is added, keep 30 ℃ of temperature, stirred 2 hours, the mother liquor after stirring is carried out spraying drying with the spraying drying instrument to mother liquor, spray condition: 160 ℃ of inlet temperatures, 80 ℃ of temperature outs obtain ingredient of solid catalyst, and wherein Ti content is 2.41%, Mg content is 6.19%, FHF content is 33%.In the ingredient of solid catalyst that obtains, add mineral oil, be made into the mineral oil solution that contains solids 30%.Add AlEt
2The Cl reaction adds Al (C after 20 minutes again
6H
13)
3Add AlEt
2Cl and Al (C
6H
13)
3, so that THF: AlEt
2Cl: Al (C
6H
13)
3(mol ratio)=1: 0.5: 0.2.
The slurry polymerization of ethene
The 2L reactor is heated to about 80 ℃, vacuumized 1 hour,, blow row with hydrogen then with the drying nitrogen displacement.In polymeric kettle, add the 1L hexane, add 30 milligrams of the triethyl aluminum of 1mmol and above-mentioned catalyzer simultaneously, be warming up to 75 ℃ subsequently, feed hydrogen and make the still internal pressure reach 0.28MPa, feed ethene again and make that stagnation pressure reaches 1.03MPa (gauge pressure) in the still, 80 ℃ of conditions.Polymerization result sees Table 2.
Table 2 experimental result
The result shows, can prepare according to the titanium catalyst of a kind of titanium catalyst component of the present invention preparation have high bulk density, narrow size distribution and the less polyethylene of fine powder, be particularly suitable for using fluidized-bed under frozen state or super frozen state, to prepare the vapour phase polymerization of ethene.
Claims (25)
1. method for preparing titanium catalyst component comprises that step is:
A. make halogenated magnesium compound and contain pure solvent reaction, preparation homogeneous phase magnesium solution;
B. make the reaction of described homogeneous phase magnesium solution and at least a organoboron compound;
C. make the reaction of titanium compound and homogeneous magnesium solution.
2. the described method of claim 1, wherein said halogenated magnesium compound is selected from magnesium dihalide compound, halogenated alkyl magnesium compound, halogenated alkoxy magnesium compound and halogenation aryloxy magnesium compound.
3. claim 1 or 2 described methods, wherein said organoboron compound has following general formula:
R
1 xR
2 yB(OR
3)
z
Wherein, R
1And R
2Be respectively C
1～C
10Alkyl, C
1～C
10-oxyl, C
5～C
10Aryl or halogen;
R
3Be C
1～C
10Alkyl is preferably C
1～C
6Alkyl, aryloxy;
0≤x≤3；
0≤y≤3；
0≤z≤3, and;
x+y+z＝3。
4. the described method of claim 3, wherein said organoboron compound is selected from following at least a kind of compound: boric acid methyl dibutyl ester, trimethyl borate, triethyl borate, tripropoxy-boron, tributyl borate, boric acid three monooctyl esters, boric acid benzene diethyl ester and triphenyl borate.
5. the described arbitrary method of claim 1～4, wherein titanium compound has following formula:
Ti(OR)
aX
b
Wherein, R is C
1～C
10Aliphatic group, perhaps C
5～C
10Replace or unsubstituted aryl;
X is fluorine, chlorine, bromine or iodine;
A is 0,1,2 or 3;
B is 1～4 a integer, and
A+b is 3 or 4.
6. the described method of claim 5, wherein said titanium compound is selected from: TiCl
3, TiCl
4, TiBr
4, TiI
4, Ti (OC
3H
7) Cl
3And Ti (OC
4H
9)
2Cl
2
7. claim described 1～6 described arbitrary method, wherein said alcohol is selected from following one or more alcohol mixtures: methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, amylalcohol, hexanol, 2-methyl amyl alcohol, 2-Ethylhexyl Alcohol, enanthol, 2-ethyl enanthol, octanol, nonylcarbinol.
8. the described arbitrary method of claim 1～7, wherein said solvent also contains varsol further.
9. the described method of claim 8, wherein said varsol is selected from: aliphatic solvents, alicyclic hydrocarbon solvent, aromatic solvent and halogenated hydrocarbon solvent.
10. the described arbitrary method of claim 1～9, wherein said organoboron compound can be in magnesium compound solution and adding system before titanium compound contacts.
11. the described arbitrary method of claim 1～9, wherein said organoboron compound can contact back adding system at magnesium compound solution with titanium compound.
12. the described method of claim 10 wherein adds a kind of inorganic carrier when adding organoboron compound.
13. the described method of claim 10, wherein said inorganic carrier are selected from silicon-dioxide, aluminum oxide and their mixture.
14. the method for claim described 12 or 13, wherein said inorganic carrier are spherical, particle diameter is 0.1～150 μ m.
15. the method for claim described 13 or 14, wherein said inorganic carrier are silicon-dioxide, specific surface area is 80～300m
2/ g.
16. the described arbitrary method of claim 1～11, wherein when halogenated magnesium compound was 1mol, used alcohol was 0.1～10.0mol; Organoboron compound is 0.05～1.0mol; Titanium compound is 1.0～15.0mol.
17. the described arbitrary method of claim 12～15, wherein when halogenated magnesium compound was 1mol, used alcohol was 0.1～10.0mol; Organoboron compound is 0.05～1.0mol; Inorganic carrier is that 50～500g and titanium compound are 1.0～15.0mol.
18. the described arbitrary method of claim 1～17 after wherein said adding organoboron compound and the titanium compound, adds other titanium compound, described other titanium compound is selected from: halogenated titanium or have C
1～C
8The alkyl dioxide of alkoxyl group.
19. titanium catalyst component by the preparation of claim 1～18 method.
20. a method for preparing titanium catalyst comprises that step is:
Make the reaction of titanium catalyst component of the present invention and organo-aluminium compound, described organo-aluminium compound has following formula:
AlR
nX
3-n
Wherein, R is hydrogen or C
1～C
20Alkyl;
X is fluorine, chlorine, bromine or iodine; And
0＜n≤3。
21. the described method of claim 20, wherein said organo-aluminium compound is selected from: trialkyl aluminium compound, dialkylaluminum halides compound and alkyl dihalo aluminum compound, described each alkyl has 1～6 carbon atom.
22. the described method of claim 21, wherein said organo-aluminium compound is selected from: triethyl aluminum, triisobutyl aluminium, ethylaluminium dichloride, diethylaluminum chloride, sesquialter ethylaluminium chloride and diisobutylaluminium hydride.
23. the titanium catalyst of claim 20～22 a method preparation.
24. the described method of claim 23, the mol ratio of wherein said organo-aluminium compound and solid titanium catalyst component are 10～1000.
25. claim 23 or the purposes of 24 described catalyzer in vinyl polymerization and copolymerization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009801146559A CN102272172A (en) | 2008-04-07 | 2009-04-07 | Method for preparing a titanium catalyst component, titanium catalyst component, method for preparing a titanium catalyst and titanium catalyst |
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810088913.8 | 2008-04-07 | ||
| CNA2008100889138A CN101245115A (en) | 2008-04-07 | 2008-04-07 | Homopolymerization and combined polymerization catalyst of ethylene and preparation method thereof |
| CN200810094349.0 | 2008-04-29 | ||
| CNA2008100943490A CN101260166A (en) | 2008-04-29 | 2008-04-29 | Ethene homopolymerization and copolymerization catalyst and preparation method thereof |
| CN2009801146559A CN102272172A (en) | 2008-04-07 | 2009-04-07 | Method for preparing a titanium catalyst component, titanium catalyst component, method for preparing a titanium catalyst and titanium catalyst |
| PCT/EP2009/002566 WO2009124722A1 (en) | 2008-04-07 | 2009-04-07 | Method for preparing a titanium catalyst component, titanium catalyst component, method for preparing a titanium catalyst and titanium catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102272172A true CN102272172A (en) | 2011-12-07 |
Family
ID=40627021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009801146559A Pending CN102272172A (en) | 2008-04-07 | 2009-04-07 | Method for preparing a titanium catalyst component, titanium catalyst component, method for preparing a titanium catalyst and titanium catalyst |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN102272172A (en) |
| DE (1) | DE112009000794T5 (en) |
| WO (1) | WO2009124722A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829758A (en) * | 2015-05-17 | 2015-08-12 | 北京化工大学 | Alkene polymerization catalyst as well as preparation method and application thereof |
| CN107446070A (en) * | 2017-08-29 | 2017-12-08 | 营口风光新材料股份有限公司 | A kind of carrier for olefin polymerization catalysis, preparation method and applications |
| CN111417660A (en) * | 2017-12-05 | 2020-07-14 | 尤尼威蒂恩技术有限责任公司 | Activated spray-dried ziegler-natta catalyst systems |
| CN114539449A (en) * | 2020-11-24 | 2022-05-27 | 中国石油天然气股份有限公司 | Titanium catalyst component for ethylene polymerization and preparation method and application thereof |
| CN114573739A (en) * | 2020-12-02 | 2022-06-03 | 中国石油天然气股份有限公司 | Solid titanium catalyst |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11325928B2 (en) | 2017-12-05 | 2022-05-10 | Univation Technologies, Llc | Modified spray-dried Ziegler-Natta (pro)catalyst systems |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1359395A (en) * | 1999-05-27 | 2002-07-17 | 三星综合化学株式会社 | Catalyst for ethylene homo-and co-polymerization |
| CN1471541A (en) * | 2001-06-21 | 2004-01-28 | ������ѧ��ʽ���� | Catalysts for polymerization and copolymerization of ethylene |
| CN101245115A (en) * | 2008-04-07 | 2008-08-20 | 郭琦 | Homopolymerization and combined polymerization catalyst of ethylene and preparation method thereof |
| CN101260166A (en) * | 2008-04-29 | 2008-09-10 | 郭琦 | Ethene homopolymerization and copolymerization catalyst and preparation method thereof |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA920299A (en) | 1968-08-01 | 1973-01-30 | Mitsui Petrochemical Industries | Process for the polymerization and/or copolymerization of olefins with use of ziegler-type catalytsts supported on carrier |
| NL160286C (en) | 1971-06-25 | |||
| US3953414A (en) | 1972-09-13 | 1976-04-27 | Montecatini Edison S.P.A., | Catalysts for the polymerization of olefins to spherically shaped polymers |
| IT1042667B (en) | 1975-09-18 | 1980-01-30 | Montedison Spa | CATALYSTS FOR THE POLYMERIZATION OF SEROIDAL POLYMER OLEFINS |
| US4302565A (en) | 1978-03-31 | 1981-11-24 | Union Carbide Corporation | Impregnated polymerization catalyst, process for preparing, and use for ethylene copolymerization |
| JPS5590510A (en) * | 1978-12-28 | 1980-07-09 | Mitsubishi Petrochem Co Ltd | Preparation of olefin polymer |
| JPS56811A (en) | 1979-06-18 | 1981-01-07 | Mitsui Petrochem Ind Ltd | Preparation of olefin polymer or copolymer |
| US4376062A (en) | 1979-11-28 | 1983-03-08 | Union Carbide Corporation | Spheroidal polymerization catalyst, process for preparing, and use for ethylene polymerization |
| US4311414A (en) | 1980-02-29 | 1982-01-19 | Halliburton Company | Pile wiper seal |
| GB2101609A (en) * | 1981-07-14 | 1983-01-19 | Ici Plc | Catalyst composition, production and use |
| US4518706A (en) | 1982-09-30 | 1985-05-21 | E. I. Du Pont De Nemours And Company | Hydrocarbon soluble catalyst supports and resultant polymerization catalysts |
| US4477639A (en) | 1983-05-27 | 1984-10-16 | Shell Oil Company | Olefin polymerization catalyst component and composition and method of preparation |
| IT1241062B (en) | 1990-01-10 | 1993-12-29 | Himont Inc | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE |
| US5141910A (en) * | 1990-10-18 | 1992-08-25 | Shell Oil Company | Olefin polymerization catalyst |
| CN1213082C (en) | 2002-10-31 | 2005-08-03 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization |
-
2009
- 2009-04-07 DE DE112009000794T patent/DE112009000794T5/en not_active Ceased
- 2009-04-07 CN CN2009801146559A patent/CN102272172A/en active Pending
- 2009-04-07 WO PCT/EP2009/002566 patent/WO2009124722A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1359395A (en) * | 1999-05-27 | 2002-07-17 | 三星综合化学株式会社 | Catalyst for ethylene homo-and co-polymerization |
| CN1471541A (en) * | 2001-06-21 | 2004-01-28 | ������ѧ��ʽ���� | Catalysts for polymerization and copolymerization of ethylene |
| CN101245115A (en) * | 2008-04-07 | 2008-08-20 | 郭琦 | Homopolymerization and combined polymerization catalyst of ethylene and preparation method thereof |
| CN101260166A (en) * | 2008-04-29 | 2008-09-10 | 郭琦 | Ethene homopolymerization and copolymerization catalyst and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829758A (en) * | 2015-05-17 | 2015-08-12 | 北京化工大学 | Alkene polymerization catalyst as well as preparation method and application thereof |
| CN107446070A (en) * | 2017-08-29 | 2017-12-08 | 营口风光新材料股份有限公司 | A kind of carrier for olefin polymerization catalysis, preparation method and applications |
| CN111417660A (en) * | 2017-12-05 | 2020-07-14 | 尤尼威蒂恩技术有限责任公司 | Activated spray-dried ziegler-natta catalyst systems |
| CN111417660B (en) * | 2017-12-05 | 2023-12-05 | 尤尼威蒂恩技术有限责任公司 | Activated spray-dried Ziegler-Natta catalyst system |
| CN114539449A (en) * | 2020-11-24 | 2022-05-27 | 中国石油天然气股份有限公司 | Titanium catalyst component for ethylene polymerization and preparation method and application thereof |
| CN114573739A (en) * | 2020-12-02 | 2022-06-03 | 中国石油天然气股份有限公司 | Solid titanium catalyst |
| CN114573739B (en) * | 2020-12-02 | 2023-12-22 | 中国石油天然气股份有限公司 | solid titanium catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2009124722A1 (en) | 2009-10-15 |
| DE112009000794T5 (en) | 2011-05-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100554287C (en) | Catalyst component for olefin | |
| CN101096389B (en) | Super-high molecular weight polyethylene catalyzer and preparation method thereof | |
| CN101260166A (en) | Ethene homopolymerization and copolymerization catalyst and preparation method thereof | |
| CN105829438A (en) | Process for producing propylene terpolymer | |
| EP3877391B1 (en) | Alkane-soluble non-metallocene precatalysts | |
| CN102272172A (en) | Method for preparing a titanium catalyst component, titanium catalyst component, method for preparing a titanium catalyst and titanium catalyst | |
| CN106478845B (en) | For the catalytic component of olefinic polymerization, catalyst and preparation method thereof | |
| CN105111336B (en) | A kind of electron donor of ethylene rolymerization catalyst, spherical catalyst, preparation method | |
| CN101245115A (en) | Homopolymerization and combined polymerization catalyst of ethylene and preparation method thereof | |
| CN109320638B (en) | Ziegler-Natta catalyst component and catalyst for ethylene polymerization | |
| CN108727527A (en) | Loaded catalyst and carrying method and application | |
| CN101827867A (en) | Process for the preparation of catalytic support and supported bimetalic catalysts for production of homopolymers and copolymers of ethylene with alfa- olefins, of high and ultra high molecular weight and with broad molecular weight distribution in s | |
| CN107556409B (en) | The internal electron donor of vinyl polymerization Ziegler-Natta catalyst, catalytic component, preparation method | |
| CN102264772A (en) | Method for preparing a titanium catalyst component, titanium catalyst component, method for preparing a titanium catalyst and titanium catalyst | |
| CN103073661B (en) | Magnesium dichloride-based adduct and catalytic component prepared therefrom | |
| WO2001000687A1 (en) | Magnesium/titanium alkoxide complexes and polymerization catalysts made therefrom | |
| US7405176B2 (en) | Solid main catalyst component for ethylene polymerization, a process for preparing the same and a catalyst containing the same | |
| CN103130931A (en) | Ball shape ethylene polymerization solid titanium catalytic agent and preparation and application thereof | |
| CN101880339A (en) | Ziegler-Natta polyethylene catalyst with wide molecular weight distribution, and preparation method thereof | |
| CN106008759B (en) | A kind of electron donor of Ziegler Natta catalyst and its application in ethylene polymerization | |
| CN105859927B (en) | Vinyl polymerization Ziegler-Natta catalyst electron donor, catalytic component, catalyst | |
| CN108440692B (en) | Catalyzed ethylene polymerization Ziegler-Natta catalyst internal electron donor, catalytic component and preparation method | |
| CN107522804B (en) | Internal electron donor, catalytic component, the spherical catalyst of ethylene polymerization | |
| CN105085735B (en) | A kind of preparation method of catalytic component for olefinic polymerization | |
| CN105732853B (en) | The preparation method of Z-N catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: SC INTELLECTUAL PROPERTY JOINT LTD. Free format text: FORMER OWNER: SUED CHEMIE AG Effective date: 20130110 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20130110 Address after: Munich, Germany Applicant after: SUED CHEMIE AG Address before: Munich, Germany Applicant before: Sued Chemie AG |
|
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20111207 |