CN102453124B - Supported metallocene catalyst and olefin polymer, and preparation methods thereof - Google Patents
Supported metallocene catalyst and olefin polymer, and preparation methods thereof Download PDFInfo
- Publication number
- CN102453124B CN102453124B CN201010521674.8A CN201010521674A CN102453124B CN 102453124 B CN102453124 B CN 102453124B CN 201010521674 A CN201010521674 A CN 201010521674A CN 102453124 B CN102453124 B CN 102453124B
- Authority
- CN
- China
- Prior art keywords
- metallocene catalyst
- alkylaluminoxane
- carried
- carried metallocene
- carrier
- 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.)
- Active
Links
Abstract
The invention provides a supported metallocene catalyst, which comprises a carrier, and alkyl aluminoxane and a metallocene compound which are supported on the carrier, wherein the metallocene compound has a structure shown as a formula 1. The invention also provides a method for preparing the supported metallocene catalyst, a method for preparing an olefin polymer by using the catalyst, and the olefin polymer prepared by the method for preparing the olefin polymer. In the olefin polymerization process, the supported metallocene catalyst can reduce the using amount of the alkyl aluminoxane so as to reduce the preparation cost of the olefin polymer; the high molecular weight polyethylene prepared by using the catalyst has a good shape and high bulk density; and the catalyst can be applied to gas-phase polymerization and slurry polymerization processes. The formula 1 is shown as the specifications.
Description
Technical field
The present invention relates to a kind of carried metallocene catalyst and olefin polymer and preparation method thereof.
Background technology
In recent years, in field of olefin polymerisation, the monocyclopentadienes metallic compound more and more gets more and more people's extensive concerning, especially virtue (alkane) oxygen base list metallocene-titanium metal compound has not only showed the high reactivity to ethene, vinylbenzene, non-conjugated diene polymerized hydrocarbon, and the copolymerization of alpha-olefin, cycloolefin etc. and ethene is had to very high active and excellent copolymerization and ability, can also make simultaneously tradition think can not polymerization monomer participate in ethylene copolymer.Metallocene catalyst belongs to the catalyzer in single active centre, and its excellent performance, can control poly molecular weight and molecualr weight distribution, molecular chain branched structure and co-monomer content and the distribution on main chain.In existing report, a lot of single cyclopentadiene titanium compounds are synthesized and are applied to vinyl polymerization.For can be in widespread use on slurry process or these existing polymerization techniques of vapor phase process, people be fixed on single metallocene-titanium catalyst on inorganic carrier or organic polymer.Silicon-dioxide, magnesium chloride, organic polymer etc. are all carriers commonly used, can be used for the load single metallocene-titanium catalyst.Supported catalyst, for vinyl polymerization, have good polymerization activity, but this single metallocene-titanium catalyst needs to add expensive alkylaluminoxane in use simultaneously.
CN101182364A discloses the catalyzer of modified chlorinated magnesium-supported metallocene compound, this loading type list cyclopentadienyl catalyst does not add alkylaluminoxane in polymerization system while carrying out olefinic polymerization, obtained reactive behavior preferably, but experiment showed, that the polyolefine bulk density that the method makes is lower.
Summary of the invention
In order to overcome above-mentioned defect, the invention provides a kind ofly when not adding alkylaluminoxane carrying out olefinic polymerization in polymerization system, reactive behavior is higher and can obtain the carried metallocene catalyst of the olefin polymer that bulk density is higher.
When the present inventor finds the metallocene compound in carried metallocene catalyst is chosen as to the compound with formula 1 structure, do not add in olefin polymerization system under the condition of alkylaluminoxane, can obtain the polyolefine that bulk density is higher yet.
The invention provides a kind of carried metallocene catalyst, it is characterized in that, this catalyzer comprises carrier and load on alkylaluminoxane and the metallocene compound on described carrier, and described metallocene compound has the structure shown in formula 1,
Formula 1
Wherein, R
1, R
2, R
3, R
4, R
5be hydrogen or C independently of one another
1-C
5alkyl, R
1' and R
2' phenyl or C respectively do for oneself
1-C
4alkyl, M is titanium, X
1, X
2be halogen independently of one another.
The present invention also provides the preparation method of above-mentioned carried metallocene catalyst, it is characterized in that, the method comprises: under protection of inert gas, and successively load alkylaluminoxane and metallocene compound on carrier.
The present invention also provides a kind of method for preparing olefin polymer, and the method comprises: under the olefinic polymerization condition, olefinic monomer is contacted with above-mentioned carried metallocene catalyst.
The present invention further provides a kind of olefin polymer, described olefin polymer is that the above-mentioned method for preparing olefin polymer obtains.
Carried metallocene catalyst provided by the invention can reduce the usage quantity of alkylaluminoxane in olefin polymerization process, thereby has reduced the preparation cost of olefin polymer; And the High molecular weight polyethylene form of using this catalyst to prepare is better, and bulk density can be 0.3g/cm
3or more than, and this catalyzer goes for vapour phase polymerization and slurry polymerization processes, for industrial application provides bright prospects.
Embodiment
The invention provides a kind of carried metallocene catalyst, it is characterized in that, this catalyzer comprises carrier and load on alkylaluminoxane and the metallocene compound on described carrier, and described metallocene compound has the structure shown in formula 1,
Formula 1
Wherein, R
1, R
2, R
3, R
4, R
5can be hydrogen or C independently separately
1-C
5alkyl, such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group etc., R
1' and R
2' can be phenyl or C separately
1-C
4alkyl, such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-etc., M is titanium, X
1, X
2can be halogen independently separately, for example fluorine, chlorine, bromine or iodine.
According to carried metallocene catalyst provided by the invention, wherein, the total amount of described carried metallocene catalyst of take is benchmark, and the total amount of described metallocene compound and alkylaluminoxane can be the 20-50 % by weight, is preferably the 23-35 % by weight; The content of described carrier can be the 50-80 % by weight, is preferably the 65-77 % by weight.
According to carried metallocene catalyst provided by the invention, wherein, the mol ratio of the titanium elements in the aluminium element in described alkylaluminoxane and described metallocene compound can be 20-500: 1, be preferably 100-300: 1.
According to a kind of preferred implementation of carried metallocene catalyst provided by the invention, wherein, X
1and X
2be chlorine; Under this preferred implementation, more easily prepared by described carried metallocene catalyst.
According to a kind of preferred implementation of carried metallocene catalyst provided by the invention, wherein, R
1, R
2, R
3, R
4and R
5c respectively does for oneself
1-C
5alkyl, such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group etc.; R
1' and R
2' phenyl or C respectively do for oneself
1-C
4alkyl, such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-etc.; Under this preferred implementation, described carried metallocene catalyst can have higher catalytic activity.
According to a kind of preferred implementation of carried metallocene catalyst provided by the invention, wherein, R
1, R
2, R
3, R
4and R
5for methyl, R
1' and R
2' be sec.-propyl; Under this preferred implementation, more easily prepared by described carried metallocene catalyst, and has excellent catalytic activity.
According to a kind of preferred implementation of carried metallocene catalyst provided by the invention, wherein, R
1, R
2, R
3, R
4and R
5for methyl, R
1' and R
2' be sec.-propyl; Under this preferred implementation, more easily prepared by described carried metallocene catalyst, and has higher catalytic activity.
According to carried metallocene catalyst provided by the invention, wherein, the alkyl in described alkylaluminoxane can be the carbonatoms alkyl that is 1-5, and preferred described alkylaluminoxane is methylaluminoxane, ethylaluminoxane etc., more preferably methylaluminoxane.
According to a kind of preferred implementation of carried metallocene catalyst provided by the invention, wherein, described metallocene compound is pentamethyl-cyclopentadienyl-2,6-di-isopropyl phenoxy group-titanium dichloride, and described alkylaluminoxane is methylaluminoxane.The carried metallocene catalyst that adopts above-mentioned metallocene compound and methylaluminoxane to obtain has excellent catalytic activity.
According to carried metallocene catalyst provided by the invention, wherein metallocene compound can be commercially available, also can prepare voluntarily according to the method that disclosed document (Journal of Molecular Catalysis magazine A volume (J.Mol.Catal.A) .2007 267 volume page 1) provides.
According to carried metallocene catalyst provided by the invention, wherein, described carrier can be one or more in silicon-dioxide, aluminum oxide and magnesium chloride.
According to a kind of preferred implementation of carried metallocene catalyst provided by the invention, wherein, described carrier can be the mixture of silicon-dioxide, silicon-dioxide and aluminum oxide or the mixture of silicon-dioxide and magnesium chloride.
A kind of preferred implementation according to carried metallocene catalyst provided by the invention, wherein, described metallocene compound is pentamethyl-cyclopentadienyl-2,6-di-isopropyl phenoxy group-titanium dichloride, described alkylaluminoxane is methylaluminoxane, the mixture of the mixture that described carrier is silicon-dioxide, silicon-dioxide and aluminum oxide or silicon-dioxide and magnesium chloride; The High molecular weight polyethylene prepared when the carried metallocene catalyst catalysis of using this preferred implementation has higher bulk density.
In the present invention, bulk density is to measure according to the method for GB1636-79 oil national standard.
In the mixture of the mixture of described silicon-dioxide and aluminum oxide or described silicon-dioxide and magnesium chloride, weight ratio between weight ratio between silicon-dioxide and aluminum oxide or silicon-dioxide and magnesium chloride can at random be selected, 0.01-100 for example: 1, under preferable case, be 0.1-50: 1.
Described silicon-dioxide, aluminum oxide and magnesium chloride can be various silicon-dioxide, aluminum oxide and the magnesium chlorides that catalyst field is commonly used for carrier.
The present invention also provides the preparation method of above-mentioned carried metallocene catalyst, and the method comprises: under protection of inert gas, and the successively described alkylaluminoxane of load and described metallocene compound on described carrier.
According to the preparation method of carried metallocene catalyst of the present invention, wherein, before the method also is included in the load alkylaluminoxane, under protection of inert gas, by described carrier, in temperature, be heating 7-30 hour under 300-900 ℃.
Preparation method according to carried metallocene catalyst of the present invention, the method of described load can be determined according to known content in the olefin polymerization catalysis preparation field, the present invention is not particularly limited, and for example, preferred a kind of carrying method comprises the following steps:
The first step, the carrier of preparation activation: under nitrogen protection, carrier (for example silica gel (trade mark ES757)) is maintained to 500-700 ℃ of lower 18-30 hour, obtain the carrier of activation.
Second step; load alkylaluminoxane: under protection of inert gas, make the carrier of activation for example, in organic solvent (toluene), and add alkylaluminoxane (as alkylaluminoxane); and maintain 3-7 hour under 40-60 ℃, obtain the carrier of load alkylaluminoxane.
The 3rd step; load metallocene compound: under protection of inert gas; make the carrier of load alkylaluminoxane for example, in organic solvent (toluene); and add metallocene compound (as pentamethyl-cyclopentadienyl-2; and maintain 20-40 minute under 10-40 ℃ 6-di-isopropyl phenoxy group-titanium dichloride).
In above-mentioned steps, with respect to the carrier of the activation of every gram or the carrier of load alkylaluminoxane, the consumption of organic solvent can be the 20-40 milliliter; The usage quantity of alkylaluminoxane, metallocene compound and carrier is as the criterion with the purpose that can reach the carried metallocene catalyst prepared.
The present invention also provides a kind of method for preparing olefin polymer, and the method comprises: under the olefinic polymerization condition, catalyzer is contacted with olefinic monomer, described catalyzer is above-mentioned carried metallocene catalyst.
According to the method for preparing olefin polymer of the present invention, wherein, described contact can be carried out in organic solvent, and described organic solvent has no particular limits, and is for example one or more in hexane, pentane, heptane, benzene, toluene, methylene dichloride, chloroform and methylene dichloride.
According to the method for preparing olefin polymer of the present invention, wherein, when catalyzer is contacted with olefinic monomer, the alkylaluminoxane in carried metallocene catalyst, can no longer add alkylaluminoxane.
According to the method for preparing olefin polymer provided by the invention, wherein, described olefinic polymerization condition can comprise: in metallocene compound, the concentration of described carried metallocene catalyst in organic solvent is 1 * 10
-8-1 * 10
-5mol/L, be preferably 5 * 10
-8-5 * 10
-6mol/L, Contact Temperature can be 25-500 ℃, is preferably 50-80 ℃; Pressure can be 0.1-5MPa, is preferably 0.5-3MPa, and can be 1-24 hour duration of contact, is preferably 1-4 hour.
According to the method for preparing olefin polymer provided by the invention, wherein, described olefinic monomer can be ethene, or can be ethene and the carbonatoms alpha-olefin that is 4-20.
A kind of preferred implementation of the method for preparing olefin polymer also provided according to the present invention, the alpha-olefin that described carbonatoms is 4-20 can be one or more in 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene.
The present invention further provides a kind of olefin polymer, described olefin polymer is that the above-mentioned method for preparing olefin polymer obtains.
According to olefin polymer provided by the invention, wherein, the weight-average molecular weight of described olefin polymer, can be 1.0 * 10
5-1.0 * 10
6.
According to olefin polymer provided by the invention, wherein, the molecular weight distributing index of described olefin polymer can be between 1.5-3.5, preferably between 2-3.
According to olefin polymer provided by the invention, wherein, the melting index MI of described olefin polymer
2.16can be 0.001-100g/min, be preferably 0.01-10g/min.
In the present invention, the weight-average molecular weight of olefin polymer and molecular weight distribution are to record according to gel permeation chromatography method (with tetrahydrofuran (THF) room temperature wash-out, polystyrene is demarcated).
In the present invention, the melting index of olefin polymer is the described method of ASTM-D1238 standard, on the fusion index instrument of Italian CEAST company, measures, and measures 190 ℃ of temperature, measures load for 2.16KG.
Following examples are for describing the present invention in detail, but scope of the present invention is not limited in the following example.
Preparation Example 1
This Preparation Example is for the preparation of R in formula 1
1, R
2, R
3, R
4and R
5for methyl and R
1' and R
2' be the metallocene compound of sec.-propyl.
Two 250 milliliters of fully dry there-necked flasks are placed in to ice bath, and nitrogen is fully replaced three times.A there-necked flask adds 1.78 gram 2,6-Bis(1-methylethyl)phenols and 50 milliliters of dry toluene wherein, after being stirred to abundant dissolving, slowly drips the hexane solution of the butyllithium of 4.2 milliliters of 2.5mol/L concentration in 10 minutes.After dropwising, remove ice bath, under room temperature, stirring reaction is 4 hours, obtains the reacted reaction solution of 2,6-Bis(1-methylethyl)phenol and butyllithium.Add pentamethyl-cyclopentadienyl titanous chloride (purchased from Strem company) 2.89 grams to the another one there-necked flask, add 50 milliliters of dry tetrahydrofuran, start stirring, after fully dissolving, 2,6-Bis(1-methylethyl)phenol and the reacted reaction solution of butyllithium in slowly dripping in above-mentioned there-necked flask in 30 minutes.After dropwising, remove ice bath, under room temperature, stirring reaction spends the night.Under 50 ℃ of oil bath conditions, removal of solvent under reduced pressure (toluene and tetrahydrofuran (THF)), obtain orange solids, with after this orange solids of toluene recrystallization, obtains refining orange solids 3.85g.Process
1h-NMR (C
6d
6) identify, following characteristic peak: δ 1.26 (12H), 1.89 (15H), 3.34-3.44 (2H), 6.97-7.04 (3H) appear on spectrogram; Illustrate that thus this orange solids is pentamethyl-cyclopentadienyl-2,6-di-isopropyl phenoxy group-titanium dichloride, i.e. R
1, R
2, R
3, R
4and R
5for methyl and R
1' and R
2' for the metallocene compound with formula 1 of sec.-propyl.
Preparation Example 2
This Preparation Example is for the preparation of R in formula 1
1, R
2, R
3, R
4and R
5for methyl and R
1' and R
2' be the metallocene compound of phenyl.
Two 250 milliliters of fully dry there-necked flasks are placed in to ice bath, and nitrogen is fully replaced three times.A there-necked flask adds 2.48 gram 2,6-diphenylphenols and 50 milliliters of dry toluene wherein, after being stirred to abundant dissolving, slowly drips the hexane solution of the butyllithium of 4.2 milliliters of 2.5mol/L concentration in 10 minutes.After dropwising, remove ice bath, under room temperature, stirring reaction is 4 hours, obtains the reacted reaction solution of 2,6-Bis(1-methylethyl)phenol and butyllithium.Add pentamethyl-cyclopentadienyl titanous chloride 2.89 grams to an other there-necked flask, add 50 milliliters of dry tetrahydrofuran (THF)s, start stirring, after fully dissolving, slowly drip the reacted reaction solution of 2,6-diphenylphenol and butyllithium.After dropwising, remove ice bath, under room temperature, stirring reaction spends the night.Under 50 ℃ of oil bath conditions, removal of solvent under reduced pressure (toluene and tetrahydrofuran (THF)), obtain the burgundy solid, uses the toluene recrystallization, obtains the refining burgundy solid of 4.05 grams.Process
1h-NMR (C
6d
6) identify, following characteristic peak: δ 1.89 (15H), 6.94-7.48 (13H) appear on spectrogram; Prove that thus this solid is pentamethyl-cyclopentadienyl-2,6-phenylbenzene phenoxy group-titanium dichloride, i.e. R
1, R
2, R
3, R
4and R
5for methyl and R
1' and R
2' for the metallocene compound with formula 1 of phenyl.
Preparation Example 3
This Preparation Example is for the preparation of R in formula 1
1, R
2, R
3, R
4and R
5for H atom and R
1' and R
2' be the metallocene compound of sec.-propyl.
Two 250 milliliters of fully dry there-necked flasks are placed in to ice bath, and nitrogen is fully replaced three times.A there-necked flask adds 1.78 gram 2,6-Bis(1-methylethyl)phenols and 50 milliliters of dry toluene wherein, after being stirred to abundant dissolving, slowly drips the hexane solution of the butyllithium of 4.2 milliliters of 2.5mol/L concentration in 10 minutes.After dropwising, remove ice bath, under room temperature, stirring reaction is 4 hours, obtains the reacted reaction solution of 2,6-Bis(1-methylethyl)phenol and butyllithium.Add cyclopentadienyl titanous chloride 2.19 grams to the another one there-necked flask, add 50 milliliters of dry tetrahydrofuran (THF)s, start stirring, after fully dissolving, 2,6-Bis(1-methylethyl)phenol and the reacted reaction solution of butyllithium in slowly dripping in above-mentioned there-necked flask in 30 minutes.After dropwising, remove ice bath, under room temperature, stirring reaction spends the night.Under 50 ℃ of oil bath conditions, removal of solvent under reduced pressure (toluene and tetrahydrofuran (THF)), obtain the deep yellow solid, with after this deep yellow solid of toluene recrystallization, obtains refining deep yellow solid 3.2g.Process
1h-NMR (C
6d
6) identify, following characteristic peak: δ 1.25 (12H), 3.43 (2H), 6.12 (5H), 6.94-7.06 (3H) appear on spectrogram; Prove that thus this orange solids is cyclopentadienyl-2,6-di-isopropyl phenoxy group-titanium dichloride, i.e. R
1, R
2, R
3, R
4and R
5for H atom and R
1' and R
2' for the metallocene compound with formula 1 of sec.-propyl.
Embodiment 1
The present embodiment is for the preparation of carried metallocene catalyst A1.
In a vacuum, 100 gram silica gel (ES757) are activated to 24 hours under 600 ℃.
Silica gel after the 4.0g activation is added in reactor, after adding 30ml toluene, add 30 milliliters of methylaluminoxane toluene solutions that contain the 2.0g methylaluminoxane, under 50 ℃, reaction is 4 hours, after reaction finishes, standing and filter reacted reaction solution, 100 milliliters of toluene wash three times for the solid that filtration is obtained, after nitrogen dries up, obtain the carrier of the pulverous load methylaluminoxane of 6g white mobility.
The carrier of above-mentioned load methylaluminoxane all is placed in to the reactor that 50ml toluene is housed, the metallocene compound that adds 0.06g Preparation Example 1 to obtain, after reacting 30min under 25 ℃, standing and filter reacted reaction solution, by filter hexane washing three times for solid, nitrogen dries up hexane, obtains the pulverous carried metallocene catalyst A1 of yellow mobility.Calculate and learn according to charging capacity, the total amount of described carried metallocene catalyst of take is benchmark, the total amount of described metallocene compound and alkylaluminoxane is 33.5 % by weight, the content of described carrier is 66.5 % by weight, and the mol ratio of the titanium elements in the aluminium element in described alkylaluminoxane and described metallocene compound is 200: 1.
Comparative Examples 1
The present embodiment is for the preparation of carried metallocene catalyst X.
In a vacuum, 100 gram silica gel (ES757) are activated to 24 hours under 600 ℃.
Silica gel after the 4.0g activation is added in reactor, after adding 30ml toluene, add 30 milliliters of methylaluminoxane toluene solutions that contain the 2.0g methylaluminoxane, under 50 ℃, reaction is 4 hours, after reaction finishes, standing and filter reacted reaction solution, 100 milliliters of toluene wash three times for the solid that filtration is obtained, after nitrogen dries up, obtain the carrier of the pulverous load methylaluminoxane of 6g white mobility.
The carrier of above-mentioned load methylaluminoxane all is placed in to the reactor that 50ml toluene is housed, the pentamethyl-cyclopentadienyl titanous chloride (purchased from Strem company) that adds 0.06g, after reacting 30min under 25 ℃, standing and filter reacted reaction solution, by filter hexane washing three times for solid, nitrogen dries up hexane, obtains carried metallocene catalyst X.
Embodiment 2
The present embodiment is for the preparation of carried metallocene catalyst A2.
In a vacuum, will after 100 gram silica gel (ES757) and the mixing of 20 gram magnesium chlorides, activate 24 hours under 600 ℃, the carrier after being activated.
Carrier after the 4.0g activation is added in reactor, after adding 30ml toluene, add 15 milliliters of methylaluminoxane toluene solutions that contain the 1.0g methylaluminoxane, under 50 ℃, reaction is 4 hours, after reaction finishes, standing and filter reacted reaction solution, 100 milliliters of toluene wash three times for the solid that filtration is obtained, after nitrogen dries up, obtain the carrier of the pulverous load methylaluminoxane of 5g white mobility.
The carrier of above-mentioned load methylaluminoxane all is placed in to the reactor that 50ml toluene is housed, the metallocene compound that adds 0.06g Preparation Example 2 to obtain, after reacting 30min under 25 ℃, standing and filter reacted reaction solution, by filter hexane washing three times for solid, nitrogen dries up hexane, obtain carried metallocene catalyst A2, calculate and learn according to charging capacity, the total amount of described carried metallocene catalyst of take is benchmark, the total amount of described metallocene compound and alkylaluminoxane is 21 % by weight, the content of described carrier is 79 % by weight, the mol ratio of the titanium elements in the aluminium element in described alkylaluminoxane and described metallocene compound is 50: 1.
Embodiment 3
The present embodiment is for the preparation of carried metallocene catalyst A3.
In a vacuum, will after 100 gram silica gel (ES757) and the mixing of 20 gram aluminum oxide, activate 24 hours under 600 ℃, the carrier after being activated.
Carrier after the 4.0g activation is added in reactor, after adding 30ml toluene, add 45 milliliters of methylaluminoxane toluene solutions that contain the 3.0g methylaluminoxane, under 50 ℃, reaction is 4 hours, after reaction finishes, standing and filter reacted reaction solution, 100 milliliters of toluene wash three times for the solid that filtration is obtained, after nitrogen dries up, obtain the carrier of the pulverous load methylaluminoxane of 7g white mobility.
The carrier of above-mentioned load methylaluminoxane all is placed in to the reactor that 50ml toluene is housed, the metallocene compound that adds 0.02g Preparation Example 3 to obtain, after reacting 30min under 25 ℃, standing and filter reacted reaction solution, by filter hexane washing three times for solid, nitrogen dries up hexane, obtain carried metallocene catalyst A3, calculate and learn according to charging capacity, the total amount of described carried metallocene catalyst of take is benchmark, the total amount of described metallocene compound and alkylaluminoxane is 43.0 % by weight, the content of described carrier is 57.0 % by weight, the mol ratio of the titanium elements in the aluminium element in described alkylaluminoxane and described metallocene compound is 400: 1.
Polymerization embodiment 1
The present embodiment working load type metallocene catalyst A1 polymerising ethylene and 1-hexene.
In the stainless steel polymermaking autoclave of 2 liters, with nitrogen and ethene, respectively replace three times, then add 200 milliliters of hexanes, by still temperature rise to 80 ℃, add again 800 milliliters of hexanes and 10 milliliters of 1-hexenes, along with adding of hexane, triethyl aluminum (TEA) hexane solution that the concentration that adds 2 milliliters is 1 mol/L, (wherein, the content of metallocene compound is 7 * 10 then to add 200 milligrams of carried metallocene catalyst A1
-6mol), pass into ethene pressure is risen to 1MPa and is maintained 1MPa, 80 ℃ of reactions 1 hour.Obtain 140 gram ethene and 1-hexene oligomerization thing, the weight-average molecular weight that GPC measures this ethene and 1-hexene oligomerization thing is 3.2 * 10
5, melting index MI
2.16=0.021g/10min, molecular weight distribution is 2.7.Determine as calculated, the efficiency of catalyzer is 700g PE/gcath (that is, 3.0 * 10
6g PE/ (mol Ti h)).The bulk density of the ethene obtained and 1-hexene oligomerization thing is 0.32g/cm
3.
Polymerization Comparative Examples 1
The present embodiment working load type metallocene catalyst X polymerising ethylene and 1-hexene.
In the stainless steel polymermaking autoclave of 2 liters, with nitrogen and ethene, respectively replace three times, then add 200 milliliters of hexanes, by still temperature rise to 80 ℃, add again 800 milliliters of hexanes and 10 milliliters of 1-hexenes, along with adding of hexane, triethyl aluminum (TEA) hexane solution that the concentration that adds 2 milliliters is 1 mol/L, (wherein, the content of metallocene compound is 8 * 10 then to add 200 milligrams of carried metallocene catalyst X
-6mol), pass into ethene pressure is risen to 1MPa and is maintained 1MPa, 80 ℃ of reactions 1 hour.Obtain 53 gram ethene and 1-hexene oligomerization thing, the weight-average molecular weight that GPC measures this ethene and 1-hexene oligomerization thing is 2.1 * 10
5, melting index MI
2.16=0.032g/10min, molecular weight distribution is 3.1.Determine as calculated, the efficiency of catalyzer is 265g PE/gcath (that is, 1.1 * 10
6g PE/ (mol Tih)).The bulk density 0.27g/cm of the ethene obtained and 1-hexene oligomerization thing
3.
Polymerization embodiment 2
The present embodiment working load type metallocene catalyst A1 polymerising ethylene and 1-hexene.
In the stainless steel polymermaking autoclave of 2 liters, with nitrogen and ethene, respectively replace three times, then add 200 milliliters of hexanes, by still temperature rise to 80 ℃, add again 800 milliliters of hexanes and 10 milliliters of 1-hexenes, along with adding of hexane, triethyl aluminum (TEA) hexane solution that the concentration that adds 2 milliliters is 1 mol/L, (wherein, the content of metallocene compound is 3.5 * 10 then to add 100 milligrams of carried metallocene catalyst A1
-6mol), pass into ethene pressure is risen to 1MPa and is maintained 1MPa, 80 ℃ of reactions 1 hour.Obtain 85 gram ethene and 1-hexene oligomerization thing, the weight-average molecular weight that GPC measures this ethene and 1-hexene oligomerization thing is 3.6 * 10
5, melting index MI
2.16=0.018g/10min, molecular weight distribution is 2.8.Determine as calculated, the efficiency of catalyzer is 850g PE/gcath (that is, 3.67 * 10
6g PE/ (mol Ti h)).The bulk density of the ethene obtained and 1-hexene oligomerization thing is 0.31g/cm
3.
Polymerization embodiment 3
The present embodiment working load type metallocene catalyst A1 polymerising ethylene.
In the stainless steel polymermaking autoclave of 2 liters, with nitrogen and ethene, respectively replace three times, then add 200 milliliters of hexanes, by still temperature rise to 80 ℃, add again 800 milliliters of hexanes, along with adding of hexane, triethyl aluminum (TEA) hexane solution that the concentration that adds 2 milliliters is 1 mol/L, (wherein, the content of metallocene compound is 7 * 10 then to add 200 milligrams of carried metallocene catalyst A1
-6mol), pass into ethene pressure is risen to 1MPa and is maintained 1MPa, 80 ℃ of reactions 1 hour.Obtain 90 gram ethene polymerss, it is 4.3 * 10 that GPC measures this polyvinyl weight-average molecular weight
5, melting index MI
2.16=0.012g/10min, molecular weight distribution is 3.2.Determine as calculated, the efficiency of catalyzer is 450gPE/gcath (that is, 1.9 * 10
6g PE/ (mol Ti h)).The ethene polymers bulk density obtained is 0.32g/cm
3.
Polymerization embodiment 4
The present embodiment working load type metallocene catalyst A2 polymerising ethylene and 1-hexene.
In the stainless steel polymermaking autoclave of 2 liters, with nitrogen and ethene, respectively replace three times, then add 200 milliliters of hexanes, by still temperature rise to 80 ℃, add again 800 milliliters of hexanes and 10 milliliters of 1-hexenes, along with adding of hexane, triethyl aluminum (TEA) hexane solution that the concentration that adds 2 milliliters is 1 mol/L, (wherein, the content of metallocene compound is 1 * 10 then to add 50 milligrams of carried metallocene catalyst A2
-6mol), pass into ethene pressure is risen to 1MPa and is maintained 1MPa, 80 ℃ of reactions 1 hour.Obtain 25 gram ethene and 1-hexene oligomerization thing, the weight-average molecular weight that GPC measures this ethene and 1-hexene oligomerization thing is 3.3 * 10
5, melting index MI
2.16=0.025g/10min, molecular weight distribution is 3.2.Determine as calculated, the efficiency of catalyzer is 475g PE/gcath (that is, 2.0 * 10
6g PE/ (mol Ti h)).The bulk density of the ethene obtained and 1-hexene oligomerization thing is 0.30g/cm
3.
Polymerization embodiment 5
The present embodiment working load type metallocene catalyst A3 polymerising ethylene and 1-hexene.
In the stainless steel polymermaking autoclave of 2 liters, with nitrogen and ethene, respectively replace three times, then add 200 milliliters of hexanes, by still temperature rise to 80 ℃, add again 800 milliliters of hexanes and 10 milliliters of 1-hexenes, along with adding of hexane, triethyl aluminum (TEA) hexane solution that the concentration that adds 2 milliliters is 1 mol/L, (wherein, the content of metallocene compound is 2 * 10 then to add 10 milligrams of carried metallocene catalyst A3
-7mol), pass into ethene pressure is risen to 1MPa and is maintained 1MPa, 80 ℃ of reactions 1 hour.Obtain 6 gram ethene and 1-hexene oligomerization thing, the weight-average molecular weight that GPC measures this ethene and 1-hexene oligomerization thing is 3.1 * 10
5, melting index MI
2.16=0.022g/10min, molecular weight distribution is 3.1.Determine as calculated, the efficiency of catalyzer is 515g PE/gcath (that is, 2.2 * 10
6g PE/ (mol Ti h)).The bulk density of the ethene obtained and 1-hexene oligomerization thing is 0.30g/cm
3.
From above-mentioned polymerization embodiment, can find out, carried metallocene catalyst provided by the invention is compared with the carried metallocene catalyst in the polymerization Comparative Examples, there is higher catalytic activity, and in the situation that do not add alkylaluminoxane in polymerization system, catalytic activity is still higher, and can obtain the polymkeric substance that bulk density is higher.
Claims (18)
1. a carried metallocene catalyst, is characterized in that, this catalyzer comprises carrier and load on alkylaluminoxane and the metallocene compound on described carrier, and described metallocene compound has the structure shown in formula 1,
Wherein, R
1, R
2, R
3, R
4, R
5be hydrogen or C independently of one another
1-C
5alkyl, R
1' and R
2' phenyl or C respectively do for oneself
1-C
4alkyl, M is titanium, X
1, X
2be halogen independently of one another; The total amount of described carried metallocene catalyst of take is benchmark, and the total amount of described metallocene compound and alkylaluminoxane is the 20-50 % by weight, and the content of described carrier is the 50-80 % by weight; The mol ratio of the titanium elements in the aluminium element in described alkylaluminoxane and described metallocene compound is 20-500:1.
2. carried metallocene catalyst according to claim 1, wherein, the total amount of described carried metallocene catalyst of take is benchmark, and the total amount of described metallocene compound and alkylaluminoxane is the 23-35 % by weight, and the content of described carrier is the 65-77 % by weight.
3. carried metallocene catalyst according to claim 1, wherein, the mol ratio of the titanium elements in the aluminium element in described alkylaluminoxane and described metallocene compound is 100-300:1.
4. carried metallocene catalyst according to claim 1 and 2, wherein, X
1and X
2be chlorine.
5. carried metallocene catalyst according to claim 1 and 2, wherein, R
1, R
2, R
3, R
4and R
5for methyl, R
1', R
2' be phenyl.
6. carried metallocene catalyst according to claim 1, wherein, R
1, R
2, R
3, R
4and R
5for methyl, R
1' and R
2' be sec.-propyl.
7. carried metallocene catalyst according to claim 2, wherein, R
1, R
2, R
3, R
4and R
5for methyl, R
1' and R
2' be sec.-propyl.
8. carried metallocene catalyst according to claim 1 and 2, wherein, described alkylaluminoxane is methylaluminoxane.
9. carried metallocene catalyst according to claim 1 and 2, wherein, described metallocene compound is pentamethyl-cyclopentadienyl-2,6-di-isopropyl phenoxy group-titanium dichloride, described alkylaluminoxane is methylaluminoxane.
10. according to the described carried metallocene catalyst of any one in claim 1,2,3,6 and 7, wherein, described carrier is one or more in silicon-dioxide, aluminum oxide and magnesium chloride.
11. carried metallocene catalyst according to claim 10, wherein, the mixture of the mixture that described carrier is silicon-dioxide, silicon-dioxide and aluminum oxide or silicon-dioxide and magnesium chloride.
12. a method for preparing the described carried metallocene catalyst of any one in claim 1-11, is characterized in that, the method comprises: under protection of inert gas, and successively load alkylaluminoxane and metallocene compound on carrier.
13. method according to claim 12 wherein, before the method also is included in the load alkylaluminoxane, under protection of inert gas, is heating 7-30 hour under 300-900 ℃ by described carrier in temperature.
14. a method for preparing olefin polymer, the method comprises: under the olefinic polymerization condition, catalyzer is contacted with olefinic monomer; Wherein, described catalyzer is the described carried metallocene catalyst of any one in claim 1-11.
15. method according to claim 14, wherein, described olefinic polymerization condition comprises: described being aggregated in organic solvent carried out; In metallocene compound, the concentration of described carried metallocene catalyst in organic solvent is 1 * 10
-8-1 * 10
-5mol/L, Contact Temperature is 25-500 ℃, and contact pressure is 0.1-5MPa, and be 1-24 hour duration of contact.
16. according to the described method of claims 14 or 15, wherein, described olefinic monomer is ethene, or is the alpha-olefin that ethene and carbonatoms are 4-20.
17. method according to claim 16, wherein, the alpha-olefin that described carbonatoms is 4-20 is one or more in 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene.
18. an olefin polymer, described olefin polymer is that in claim 14-17, the described method of any one prepares.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010521674.8A CN102453124B (en) | 2010-10-21 | 2010-10-21 | Supported metallocene catalyst and olefin polymer, and preparation methods thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010521674.8A CN102453124B (en) | 2010-10-21 | 2010-10-21 | Supported metallocene catalyst and olefin polymer, and preparation methods thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102453124A CN102453124A (en) | 2012-05-16 |
| CN102453124B true CN102453124B (en) | 2014-01-08 |
Family
ID=46036843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010521674.8A Active CN102453124B (en) | 2010-10-21 | 2010-10-21 | Supported metallocene catalyst and olefin polymer, and preparation methods thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102453124B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788275B (en) * | 2012-10-26 | 2016-05-25 | 中国石油化工股份有限公司 | A kind of method of preparing low density polyethylene (LDPE) |
| CN104059174B (en) * | 2013-03-21 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of supported single metallocene catalyst for vinyl polymerization |
| CN104059177B (en) * | 2013-03-21 | 2016-09-21 | 中国石油化工股份有限公司 | A kind of load single metallocene catalyst for vinyl polymerization |
| CN104059179B (en) * | 2013-03-21 | 2016-09-21 | 中国石油化工股份有限公司 | A kind of supported single metallocene catalyst for vinyl polymerization |
| BR102015027108B1 (en) | 2014-10-27 | 2021-01-12 | China Petroleum & Chemical Corporation | polyethylene composition and film |
| JP6396523B2 (en) * | 2017-02-17 | 2018-09-26 | 旭化成株式会社 | Polyethylene polymer and method for producing the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4897455A (en) * | 1985-06-21 | 1990-01-30 | Exxon Chemical Patents Inc. | Polymerization process |
| CN101121761A (en) * | 2006-08-11 | 2008-02-13 | 住友化学株式会社 | Process for producing prepolymerization catalyst for polymerization of olefin and process for producing olefin polymer |
| CN101182364A (en) * | 2007-12-13 | 2008-05-21 | 中山大学 | Catalyst containing load odd tianocene complexes and method for preparing polyethylene thereby |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0788403B2 (en) * | 1984-11-01 | 1995-09-27 | 昭和電工株式会社 | Method for producing polyolefin |
| CN100475852C (en) * | 2006-05-23 | 2009-04-08 | 中国石油天然气股份有限公司 | Method for polymerizing olefin |
| CN1923862A (en) * | 2006-09-21 | 2007-03-07 | 复旦大学 | Mesoporous molecular sieve carried olefin polymerization catalyst, preparation method and application thereof |
-
2010
- 2010-10-21 CN CN201010521674.8A patent/CN102453124B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4897455A (en) * | 1985-06-21 | 1990-01-30 | Exxon Chemical Patents Inc. | Polymerization process |
| CN101121761A (en) * | 2006-08-11 | 2008-02-13 | 住友化学株式会社 | Process for producing prepolymerization catalyst for polymerization of olefin and process for producing olefin polymer |
| CN101182364A (en) * | 2007-12-13 | 2008-05-21 | 中山大学 | Catalyst containing load odd tianocene complexes and method for preparing polyethylene thereby |
Non-Patent Citations (1)
| Title |
|---|
| JP昭61-108610A 1986.05.27 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102453124A (en) | 2012-05-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102453124B (en) | Supported metallocene catalyst and olefin polymer, and preparation methods thereof | |
| Nomura et al. | Nonbridged half-metallocenes containing anionic ancillary donor ligands: New promising candidates as catalysts for precise olefin polymerization | |
| CN100358922C (en) | Synthesis of polymerization catalyst components | |
| KR102107084B1 (en) | Method for preparing of supported hybrid metallocene catalyst, the supported hybrid metallocene catalyst prepared by the same method, and method for preparing polyolefin using the same | |
| JPH08100018A (en) | Preparation of polyolefin with broad molecular weight distribution | |
| JPH10508630A (en) | Catalyst for bimodal molecular weight distribution ethylene polymers and copolymers | |
| CN101423575A (en) | Supported metallocene catalyst component and preparation method thereof and use | |
| WO1999030822A1 (en) | Group 11 transition metal amine catalysts for olefin polymerization | |
| CN105482000A (en) | Olefin polymerization catalyst as well as preparation method and application method thereof | |
| CN108727527A (en) | Loaded catalyst and carrying method and application | |
| CN104725533A (en) | Olefin polymerization catalyst, olefin polymerization method, and polyolefin | |
| JP2000513761A (en) | Method for producing functional polyolefin | |
| CN100455609C (en) | Olefin polymerization process | |
| Zhang et al. | New Chromium (III) Complexes with Imine− Cyclopentadienyl Ligands: Synthesis, Characterization, and Catalytic Properties for Ethylene Polymerization | |
| CN105037588A (en) | Isoindole rare earth metal catalyst, preparation method and application | |
| EP1958969B1 (en) | A phosphine-substituted vinyl containing metallocene catalyst, preparation process and the application of the same | |
| CN111454300B (en) | Mono-metallocene complex, application thereof and polymerization method of ethylene | |
| CN112778350A (en) | [ OONN ] quadridentate fourth subgroup metal complex, preparation method and application | |
| CN111747977A (en) | Arylamine ether metal complexes, and preparation method and application thereof | |
| CN102405240A (en) | Method for producing olefin polymer | |
| CN113402641B (en) | Metallocene catalyst, preparation method and application | |
| CN102093494A (en) | Metal olefin polymerization catalyst containing 8-hydroxyquinoline imine ligand and preparation method thereof | |
| EP1362066B1 (en) | Catalyst for polymerization of olefin and the method of polymerization of olefin using the same | |
| CN108129593B (en) | Polyolefin epoxy resin and preparation method and application thereof | |
| CN101182337A (en) | Dinuclear metallocene complexes and uses 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 |