CN102453124A - Supported metallocene catalyst and olefin polymer, and preparation methods thereof - Google Patents
Supported metallocene catalyst and olefin polymer, and preparation methods thereof Download PDFInfo
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- CN102453124A CN102453124A CN2010105216748A CN201010521674A CN102453124A CN 102453124 A CN102453124 A CN 102453124A CN 2010105216748 A CN2010105216748 A CN 2010105216748A CN 201010521674 A CN201010521674 A CN 201010521674A CN 102453124 A CN102453124 A CN 102453124A
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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 terminal olefin, cycloolefin etc. and ethene is had very high active and excellent copolymerization and ability, tradition is thought can not monomer polymerized be participated in ethylene copolymer.Metallocene catalyst belongs to the catalyzer in single active site, and its excellent performance can be controlled poly molecular weight and MWD, molecular chain branched structure and co-monomer content and the distribution on main chain.In the 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 the organic polymer.Silicon-dioxide, magnesium chloride, organic polymer etc. all are the carriers of using always, can be used for the load single metallocene-titanium catalyst.Supported catalyst is used for vinyl polymerization, has good polymerization activity, but this single metallocene-titanium catalyst need 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 when carrying out olefinic polymerization; Obtained reactive behavior preferably, but experiment showed, that the polyolefine bulk density that this method makes is lower.
Summary of the invention
In order to overcome above-mentioned defective, the invention provides a kind ofly when in polymerization system, not adding alkylaluminoxane and carrying out olefinic polymerization, reactive behavior is higher and can obtain the carried metallocene catalyst of the higher olefin polymer of bulk density.
When contriver's discovery of the present invention is chosen as the compound with formula 1 structure with the metallocene compound in the carried metallocene catalyst, in olefin polymerization system, do not add under the condition of alkylaluminoxane, can obtain the higher polyolefine of bulk density yet.
The invention provides a kind of carried metallocene catalyst, it is characterized in that, this catalyzer comprise carrier with load on alkylaluminoxane and the metallocene compound on the said carrier, said metallocene compound has the structure shown in the 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 a 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, this 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 this 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, and said 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 comprise carrier with load on alkylaluminoxane and the metallocene compound on the said carrier, said metallocene compound has the structure shown in the formula 1,
Formula 1
Wherein, R
1, R
2, R
3, R
4, R
5Can be hydrogen or C independently separately
1-C
5Alkyl, for example 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, for example methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-etc., M is a 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, be benchmark with the total amount of said carried metallocene catalyst, the total amount of said metallocene compound and alkylaluminoxane can be 20-50 weight %, is preferably 23-35 weight %; The content of said carrier can be 50-80 weight %, is preferably 65-77 weight %.
According to carried metallocene catalyst provided by the invention, wherein, the mol ratio of the titanium elements in aluminium element in the said alkylaluminoxane and the said 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, said carried metallocene catalyst is prone to preparation.
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, for example 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, for example methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-etc.; Under this preferred implementation, said carried metallocene catalyst can have advantages of high 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
5Be methyl, R
1' and R
2' be sec.-propyl; Under this preferred implementation, said carried metallocene catalyst is prone to preparation, 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
5Be methyl, R
1' and R
2' be sec.-propyl; Under this preferred implementation, said carried metallocene catalyst is prone to preparation, and has advantages of high catalytic activity.
According to carried metallocene catalyst provided by the invention, wherein, the alkyl in the said alkylaluminoxane can be the alkyl of 1-5 for carbonatoms, and preferred said alkylaluminoxane is MAO, ethyl aikyiaiurnirsoxan beta etc., further is preferably MAO.
According to a kind of preferred implementation of carried metallocene catalyst provided by the invention, wherein, said metallocene compound is a pentamethyl-cyclopentadienyl moiety-2, and 6-di-isopropyl phenoxy-titanium dichloride, said alkylaluminoxane are MAO.The carried metallocene catalyst that adopts above-mentioned metallocene compound and MAO to obtain has excellent catalytic activity.
According to carried metallocene catalyst provided by the invention, wherein metallocene compound can be purchased acquisition, 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) provide.
According to carried metallocene catalyst provided by the invention, wherein, said carrier can be in silicon-dioxide, aluminum oxide and the magnesium chloride one or more.
According to a kind of preferred implementation of carried metallocene catalyst provided by the invention, wherein, said 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, Said metallocene compound is a pentamethyl-cyclopentadienyl moiety-2; 6-di-isopropyl phenoxy-titanium dichloride, said alkylaluminoxane are MAO, and said carrier is the mixture of silicon-dioxide, silicon-dioxide and aluminum oxide or the mixture of silicon-dioxide and magnesium chloride; The High molecular weight polyethylene that obtains when the carried metallocene catalyst catalytic preparation of using this preferred implementation has higher bulk density.
Among 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 said silicon-dioxide and aluminum oxide or said silicon-dioxide and magnesium chloride; Weight ratio between weight ratio between silicon-dioxide and the aluminum oxide or silicon-dioxide and the magnesium chloride can at random be selected; 0.01-100 for example: 1, under the preferable case, be 0.1-50: 1.
Said silicon-dioxide, aluminum oxide and magnesium chloride can be catalyst field various silicon-dioxide, aluminum oxide and the magnesium chlorides of making carrier commonly used.
The present invention also provides the preparation method of above-mentioned carried metallocene catalyst, and this method comprises: under protection of inert gas, and successively said alkylaluminoxane of load and said metallocene compound on said carrier.
According to the preparation method of carried metallocene catalyst of the present invention, wherein, this method also is included in before the load alkylaluminoxane, under protection of inert gas, said carrier is 300-900 ℃ in temperature heated 7-30 hour down.
Preparing method according to carried metallocene catalyst of the present invention; The method of said load can be confirmed according to known content in the olefin polymerization catalysis preparation field; The present invention is restriction especially not, and for example, preferred a kind of carrying method may further comprise the steps:
The first step, preparation activatory carrier: under nitrogen protection, carrier (for example silica gel (trade mark ES757)) is maintained 500-700 ℃ of following 18-30 hour, obtain the activatory carrier.
Second step, load alkylaluminoxane: under protection of inert gas, the activatory carrier is in the organic solvent (for example toluene), and adds alkylaluminoxane (like alkylaluminoxane), and under 40-60 ℃, kept 3-7 hour, obtain the carrier of load alkylaluminoxane.
The 3rd step; Load metallocene compound: under protection of inert gas; The carrier of load alkylaluminoxane is in the organic solvent (for example toluene); And add metallocene compound (like pentamethyl-cyclopentadienyl moiety-2,6-di-isopropyl phenoxy-titanium dichloride), and under 10-40 ℃, kept 20-40 minute.
In the above-mentioned steps, with respect to the activatory carrier 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 for preparing.
The present invention also provides a kind of method for preparing olefin polymer, and this method comprises: under the olefinic polymerization condition, catalyzer is contacted with olefinic monomer, said catalyzer is above-mentioned carried metallocene catalyst.
According to the method for preparing olefin polymer of the present invention; Wherein, Said contact can be carried out in organic solvent, and said organic solvent has no particular limits, and for example is in hexane, pentane, heptane, benzene, toluene, methylene dichloride, chloroform and the methylene dichloride one or more.
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, said olefinic polymerization condition can comprise: in metallocene compound, the concentration of said carried metallocene catalyst in organic solvent is 1 * 10
-8-1 * 10
-5Mol is preferably 5 * 10
-8-5 * 10
-6Mol, the 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.
Based on the method for preparing olefin polymer provided by the invention, wherein, said olefinic monomer can be ethene, can be the alpha-olefin of 4-20 for ethene and carbon number perhaps.
A kind of preferred implementation of the method for preparing olefin polymer that also provides according to the present invention, said carbonatoms are that the terminal olefin of 4-20 can be in 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, the 1-eicosylene one or more.
The present invention further provides a kind of olefin polymer, and said 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 said 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 said 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 said olefin polymer
2.16Can be 0.001-100g/min, be preferably 0.01-10g/min.
Among the present invention, the weight-average molecular weight of olefin polymer and MWD are to record according to gel permeation chromatography method (with THF room temperature wash-out, PS is demarcated).
Among 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 and is 2.16KG.
Following examples are used to specify the present invention, but scope of the present invention is not limited in the following example.
Preparation embodiment 1
This preparation embodiment is used for preparation formula 1 R
1, R
2, R
3, R
4And R
5Be methyl and R
1' and R
2' be the metallocene compound of sec.-propyl.
250 milliliters of there-necked flasks of two thorough dryings are placed ice bath, and nitrogen is fully replaced three times.Add 1.78 grams 2 to one of them there-necked flask, 6-diisopropyl phenol and 50 milliliters of dry toluene, be stirred to abundant dissolving after, in 10 minutes, slowly drip the hexane solution of the butyllithium of 4.2 milliliters of 2.5mol/L concentration.After dropwising, remove ice bath, stirring reaction is 4 hours under the room temperature, obtains 2, the reacted reaction solution of 6-diisopropyl phenol and butyllithium.Add pentamethyl-cyclopentadienyl moiety titanous chloride (available from Strem company) 2.89 grams to the another one there-necked flask; Add 50 milliliters of dry tetrahydrofuran; Start stirring; Fully after the dissolving, 2 in 30 minutes, slowly dripping in the above-mentioned there-necked flask, the reacted reaction solution of 6-diisopropyl phenol and butyllithium.After dropwising, remove ice bath, stirring reaction spends the night under the room temperature.Under 50 ℃ of oil bath conditions, removal of solvent under reduced pressure (toluene and THF) obtains orange solids, after this orange solids of toluene recrystallization, obtains purified 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 the spectrogram; Explain that thus this orange solids is a pentamethyl-cyclopentadienyl moiety-2,6-di-isopropyl phenoxy-titanium dichloride, i.e. R
1, R
2, R
3, R
4And R
5Be methyl and R
1' and R
2' for the metallocene compound with formula 1 of sec.-propyl.
Preparation embodiment 2
This preparation embodiment is used for preparation formula 1 R
1, R
2, R
3, R
4And R
5Be methyl and R
1' and R
2' be the metallocene compound of phenyl.
250 milliliters of there-necked flasks of two thorough dryings are placed ice bath, and nitrogen is fully replaced three times.Add 2.48 grams 2 to one of them there-necked flask, 6-phenylbenzene phenol and 50 milliliters of dry toluene, be stirred to abundant dissolving after, in 10 minutes, slowly drip the hexane solution of the butyllithium of 4.2 milliliters of 2.5mol/L concentration.After dropwising, remove ice bath, stirring reaction is 4 hours under the room temperature, obtains 2, the reacted reaction solution of 6-diisopropyl phenol and butyllithium.Add pentamethyl-cyclopentadienyl moiety titanous chloride 2.89 grams to an other there-necked flask, add 50 milliliters of exsiccant THFs, start stirring, fully after the dissolving, slowly drip 2, the reacted reaction solution of 6-phenylbenzene phenol and butyllithium.After dropwising, remove ice bath, stirring reaction spends the night under the room temperature.Under 50 ℃ of oil bath conditions, removal of solvent under reduced pressure (toluene and THF) obtains the wine red solid, uses the toluene recrystallization, obtains 4.05 gram purified wine red solids.Process
1H-NMR (C
6D
6) identify, following characteristic peak: δ 1.89 (15H), 6.94-7.48 (13H) appear on the spectrogram; Prove that thus this solid is a pentamethyl-cyclopentadienyl moiety-2,6-phenylbenzene phenoxy-titanium dichloride, i.e. R
1, R
2, R
3, R
4And R
5Be methyl and R
1' and R
2' for the metallocene compound with formula 1 of phenyl.
Preparation embodiment 3
This preparation embodiment is used for preparation formula 1 R
1, R
2, R
3, R
4And R
5Be H atom and R
1' and R
2' be the metallocene compound of sec.-propyl.
250 milliliters of there-necked flasks of two thorough dryings are placed ice bath, and nitrogen is fully replaced three times.Add 1.78 grams 2 to one of them there-necked flask, 6-diisopropyl phenol and 50 milliliters of dry toluene, be stirred to abundant dissolving after, in 10 minutes, slowly drip the hexane solution of the butyllithium of 4.2 milliliters of 2.5mol/L concentration.After dropwising, remove ice bath, stirring reaction is 4 hours under the room temperature, obtains 2, the reacted reaction solution of 6-diisopropyl phenol and butyllithium.Add cyclopentadienyl moiety titanous chloride 2.19 grams to the another one there-necked flask; Add 50 milliliters of exsiccant THFs, start stirring, fully after the dissolving; In in 30 minutes, slowly dripping in the above-mentioned there-necked flask 2, the reacted reaction solution of 6-diisopropyl phenol and butyllithium.After dropwising, remove ice bath, stirring reaction spends the night under the room temperature.Under 50 ℃ of oil bath conditions, removal of solvent under reduced pressure (toluene and THF) obtains the deep yellow solid, behind this deep yellow solid of toluene recrystallization, obtains purified 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 the spectrogram; Prove that thus this orange solids is a cyclopentadienyl moiety-2,6-di-isopropyl phenoxy-titanium dichloride, i.e. R
1, R
2, R
3, R
4And R
5Be H atom and R
1' and R
2' for the metallocene compound with formula 1 of sec.-propyl.
Embodiment 1
Present embodiment is used to prepare carried metallocene catalyst A1.
In a vacuum, restrain silica gel (ES757) 600 ℃ of following activation 24 hours with 100.
Silica gel after the 4.0g activation is added in the reactor drum, behind the adding 30ml toluene, add 30 milliliters of MAO toluene solutions that contain the 2.0g MAO; 50 ℃ were reacted 4 hours down; After reaction finishes, leave standstill and filtering reaction after reaction solution, the solid that filtration is obtained is with 100 milliliters of toluene wash three times; After nitrogen dries up, obtain the carrier of the mobile pulverous load MAO of 6g white.
The carrier of above-mentioned load MAO all placed 50ml reaction of toluene device is housed; Add 0.06g and prepare the metallocene compound that embodiment 1 obtains; 25 ℃ down behind the reaction 30min, leave standstill and filtering reaction after reaction solution, with the solid that filters with hexane wash three times; Nitrogen dries up hexane, obtains yellow mobile pulverous carried metallocene catalyst A1.Calculating is learnt according to charging capacity; Total amount with said carried metallocene catalyst is a benchmark; The total amount of said metallocene compound and alkylaluminoxane is 33.5 weight %; The content of said carrier is 66.5 weight %, and the mol ratio of the titanium elements in aluminium element in the said alkylaluminoxane and the said metallocene compound is 200: 1.
Comparative Examples 1
Present embodiment is used to prepare carried metallocene catalyst X.
In a vacuum, restrain silica gel (ES757) 600 ℃ of following activation 24 hours with 100.
Silica gel after the 4.0g activation is added in the reactor drum, behind the adding 30ml toluene, add 30 milliliters of MAO toluene solutions that contain the 2.0g MAO; 50 ℃ were reacted 4 hours down; After reaction finishes, leave standstill and filtering reaction after reaction solution, the solid that filtration is obtained is with 100 milliliters of toluene wash three times; After nitrogen dries up, obtain the carrier of the mobile pulverous load MAO of 6g white.
The carrier of above-mentioned load MAO all placed 50ml reaction of toluene device is housed; The pentamethyl-cyclopentadienyl moiety titanous chloride (available from Strem company) that adds 0.06g; 25 ℃ down behind the reaction 30min, leave standstill and filtering reaction after reaction solution, with the solid that filters with hexane wash three times; Nitrogen dries up hexane, obtains carried metallocene catalyst X.
Embodiment 2
Present embodiment is used to prepare carried metallocene catalyst A2.
In a vacuum, 100 gram silica gel (ES757) and 20 gram magnesium chlorides are mixed afterwards 600 ℃ of following activation 24 hours, obtain the carrier after the activation.
Carrier after the 4.0g activation is added in the reactor drum, behind the adding 30ml toluene, add 15 milliliters of MAO toluene solutions that contain the 1.0g MAO; 50 ℃ were reacted 4 hours down; After reaction finishes, leave standstill and filtering reaction after reaction solution, the solid that filtration is obtained is with 100 milliliters of toluene wash three times; After nitrogen dries up, obtain the carrier of the mobile pulverous load MAO of 5g white.
The carrier of above-mentioned load MAO all placed 50ml reaction of toluene device is housed, add 0.06g and prepare the metallocene compound that embodiment 2 obtains, 25 ℃ down behind the reaction 30min; Leave standstill and filtering reaction after reaction solution, with hexane wash three times, nitrogen dries up hexane with the solid that filters; Obtain carried metallocene catalyst A2; Calculating according to charging capacity and to learn, is benchmark with the total amount of said carried metallocene catalyst, and the total amount of said metallocene compound and alkylaluminoxane is 21 weight %; The content of said carrier is 79 weight %, and the mol ratio of the titanium elements in aluminium element in the said alkylaluminoxane and the said metallocene compound is 50: 1.
Embodiment 3
Present embodiment is used to prepare carried metallocene catalyst A3.
In a vacuum, 100 gram silica gel (ES757) and 20 gram aluminum oxide are mixed afterwards 600 ℃ of following activation 24 hours, obtain the carrier after the activation.
Carrier after the 4.0g activation is added in the reactor drum, behind the adding 30ml toluene, add 45 milliliters of MAO toluene solutions that contain the 3.0g MAO; 50 ℃ were reacted 4 hours down; After reaction finishes, leave standstill and filtering reaction after reaction solution, the solid that filtration is obtained is with 100 milliliters of toluene wash three times; After nitrogen dries up, obtain the carrier of the mobile pulverous load MAO of 7g white.
The carrier of above-mentioned load MAO all placed 50ml reaction of toluene device is housed; Add 0.02g and prepare the metallocene compound that embodiment 3 obtains, 25 ℃ down behind the reaction 30min, leave standstill and filtering reaction after reaction solution; With the solid that filters with hexane wash three times; Nitrogen dries up hexane, obtains carried metallocene catalyst A3, calculates according to charging capacity and learns; Total amount with said carried metallocene catalyst is a benchmark; The total amount of said metallocene compound and alkylaluminoxane is 43.0 weight %, and the content of said carrier is 57.0 weight %, and the mol ratio of the titanium elements in aluminium element in the said alkylaluminoxane and the said metallocene compound is 400: 1.
Polymerization embodiment 1
Present embodiment working load type metallocene catalyst A1 polymerising ethylene and 1-hexene.
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 200 milliliters of hexanes then; With still temperature rise to 80 ℃; Add 800 milliliters of hexanes and 10 milliliters of 1-hexenes again, along with the adding of hexane, the concentration that adds 2 milliliters is triethyl aluminum (TEA) hexane solution of 1 mol; (wherein, the content of metallocene compound is 7 * 10 then to add 200 milligrams of carried metallocene catalyst A1
-6Mol), feed ethene pressure is risen to 1MPa and is maintained 1MPa, 80 ℃ of reactions 1 hour.Obtain 140 gram ethene and 1-hexene polymkeric substance, the weight-average molecular weight that GPC measures this ethene and 1-hexene polymkeric substance is 3.2 * 10
5, melting index MI
2.16=0.021g/10min, MWD is 2.7.Confirm that through calculating the efficient of catalyzer is 700g PE/gcath (that is, 3.0 * 10
6G PE/ (mol Ti h)).The bulk density of ethene that obtains and 1-hexene polymkeric substance is 0.32g/cm
3
Polymerization Comparative Examples 1
Present embodiment working load type metallocene catalyst X polymerising ethylene and 1-hexene.
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 200 milliliters of hexanes then; With still temperature rise to 80 ℃; Add 800 milliliters of hexanes and 10 milliliters of 1-hexenes again, along with the adding of hexane, the concentration that adds 2 milliliters is triethyl aluminum (TEA) hexane solution of 1 mol; (wherein, the content of metallocene compound is 8 * 10 then to add 200 milligrams of carried metallocene catalyst X
-6Mol), feed ethene pressure is risen to 1MPa and is maintained 1MPa, 80 ℃ of reactions 1 hour.Obtain 53 gram ethene and 1-hexene polymkeric substance, the weight-average molecular weight that GPC measures this ethene and 1-hexene polymkeric substance is 2.1 * 10
5, melting index MI
2.16=0.032g/10min, MWD is 3.1.Confirm that through calculating the efficient of catalyzer is 265g PE/gcath (that is, 1.1 * 10
6G PE/ (mol Tih)).The bulk density 0.27g/cm of ethene that obtains and 1-hexene polymkeric substance
3
Polymerization embodiment 2
Present embodiment working load type metallocene catalyst A1 polymerising ethylene and 1-hexene.
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 200 milliliters of hexanes then; With still temperature rise to 80 ℃; Add 800 milliliters of hexanes and 10 milliliters of 1-hexenes again, along with the adding of hexane, the concentration that adds 2 milliliters is triethyl aluminum (TEA) hexane solution of 1 mol; (wherein, the content of metallocene compound is 3.5 * 10 then to add 100 milligrams of carried metallocene catalyst A1
-6Mol), feed ethene pressure is risen to 1MPa and is maintained 1MPa, 80 ℃ of reactions 1 hour.Obtain 85 gram ethene and 1-hexene polymkeric substance, the weight-average molecular weight that GPC measures this ethene and 1-hexene polymkeric substance is 3.6 * 10
5, melting index MI
2.16=0.018g/10min, MWD is 2.8.Confirm that through calculating the efficient of catalyzer is 850g PE/gcath (that is, 3.67 * 10
6G PE/ (mol Ti h)).The bulk density of ethene that obtains and 1-hexene polymkeric substance is 0.31g/cm
3
Polymerization embodiment 3
Present embodiment working load type metallocene catalyst A1 polymerising ethylene.
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 200 milliliters of hexanes then; With still temperature rise to 80 ℃; Add 800 milliliters of hexanes again, along with the adding of hexane, the concentration that adds 2 milliliters is triethyl aluminum (TEA) hexane solution of 1 mol; (wherein, the content of metallocene compound is 7 * 10 then to add 200 milligrams of carried metallocene catalyst A1
-6Mol), feed 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, MWD is 3.2.Confirm that through calculating the efficient of catalyzer is 450gPE/gcath (that is, 1.9 * 10
6G PE/ (mol Ti h)).The ethene polymers bulk density that obtains is 0.32g/cm
3
Polymerization embodiment 4
Present embodiment working load type metallocene catalyst A2 polymerising ethylene and 1-hexene.
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 200 milliliters of hexanes then; With still temperature rise to 80 ℃; Add 800 milliliters of hexanes and 10 milliliters of 1-hexenes again, along with the adding of hexane, the concentration that adds 2 milliliters is triethyl aluminum (TEA) hexane solution of 1 mol; (wherein, the content of metallocene compound is 1 * 10 then to add 50 milligrams of carried metallocene catalyst A2
-6Mol), feed ethene pressure is risen to 1MPa and is maintained 1MPa, 80 ℃ of reactions 1 hour.Obtain 25 gram ethene and 1-hexene polymkeric substance, the weight-average molecular weight that GPC measures this ethene and 1-hexene polymkeric substance is 3.3 * 10
5, melting index MI
2.16=0.025g/10min, MWD is 3.2.Confirm that through calculating the efficient of catalyzer is 475g PE/gcath (that is, 2.0 * 10
6G PE/ (mol Ti h)).The bulk density of ethene that obtains and 1-hexene polymkeric substance is 0.30g/cm
3
Polymerization embodiment 5
Present embodiment working load type metallocene catalyst A3 polymerising ethylene and 1-hexene.
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 200 milliliters of hexanes then; With still temperature rise to 80 ℃; Add 800 milliliters of hexanes and 10 milliliters of 1-hexenes again, along with the adding of hexane, the concentration that adds 2 milliliters is triethyl aluminum (TEA) hexane solution of 1 mol; (wherein, the content of metallocene compound is 2 * 10 then to add 10 milligrams of carried metallocene catalyst A3
-7Mol), feed ethene pressure is risen to 1MPa and is maintained 1MPa, 80 ℃ of reactions 1 hour.Obtain 6 gram ethene and 1-hexene polymkeric substance, the weight-average molecular weight that GPC measures this ethene and 1-hexene polymkeric substance is 3.1 * 10
5, melting index MI
2.16=0.022g/10min, MWD is 3.1.Confirm that through calculating the efficient of catalyzer is 515g PE/gcath (that is, 2.2 * 10
6G PE/ (mol Ti h)).The bulk density of ethene that obtains and 1-hexene polymkeric substance is 0.30g/cm
3
Can find out from above-mentioned polymerization embodiment; Carried metallocene catalyst provided by the invention with the carried metallocene catalyst in the polymerization Comparative Examples is compared; Has higher catalytic activity; And in polymerization system, do not add under the situation of alkylaluminoxane, catalytic activity is still higher, and can obtain the higher polymkeric substance of bulk density.
Claims (19)
1. a carried metallocene catalyst is characterized in that, this catalyzer comprise carrier with load on alkylaluminoxane and the metallocene compound on the said carrier, said metallocene compound has the structure shown in the 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 a titanium, X
1, X
2Be halogen independently of one another.
2. carried metallocene catalyst according to claim 1 wherein, is a benchmark with the total amount of said carried metallocene catalyst, and the total amount of said metallocene compound and alkylaluminoxane is 20-50 weight %, and the content of said carrier is 50-80 weight %.
3. carried metallocene catalyst according to claim 2 wherein, is a benchmark with the total amount of said carried metallocene catalyst, and the total amount of said metallocene compound and alkylaluminoxane is 23-35 weight %, and the content of said carrier is 65-77 weight %.
4. according to claim 1,2 or 3 described carried metallocene catalysts, wherein, the mol ratio of the titanium elements in aluminium element in the said alkylaluminoxane and the said metallocene compound is 20-500: 1.
5. carried metallocene catalyst according to claim 4, wherein, the mol ratio of the titanium elements in aluminium element in the said alkylaluminoxane and the said metallocene compound is 100-300: 1.
6. according to claim 1,2 or 3 described carried metallocene catalysts, wherein, X
1And X
2Be chlorine.
7. according to claim 1,2 or 3 described carried metallocene catalysts, wherein, R
1, R
2, R
3, R
4And R
5Be methyl, R
1', R
2' be phenyl.
8. according to claim 1,2 or 3 described carried metallocene catalysts, wherein, R
1, R
2, R
3, R
4And R
5Be methyl, R
1' and R
2' be sec.-propyl.
9. according to claim 1,2 or 3 described carried metallocene catalysts, wherein, said alkylaluminoxane is a MAO.
10. according to claim 1,2 or 3 described carried metallocene catalysts, wherein, said metallocene compound is a pentamethyl-cyclopentadienyl moiety-2, and 6-di-isopropyl phenoxy-titanium dichloride, said alkylaluminoxane are MAO.
11. according to any described carried metallocene catalyst among the claim 1-3,5 and 8, wherein, said carrier is one or more in silicon-dioxide, aluminum oxide and the magnesium chloride.
12. carried metallocene catalyst according to claim 11, wherein, said carrier is the mixture of silicon-dioxide, silicon-dioxide and aluminum oxide or the mixture of silicon-dioxide and magnesium chloride.
13. a method for preparing any described carried metallocene catalyst among the claim 1-12 is characterized in that, this method comprises: under protection of inert gas, and successively load alkylaluminoxane and metallocene compound on carrier.
14. method according to claim 13, wherein, this method also is included in before the load alkylaluminoxane, under protection of inert gas, said carrier is 300-900 ℃ in temperature heated 7-30 hour down.
15. a method for preparing olefin polymer, this method comprises: under the olefinic polymerization condition, catalyzer is contacted with olefinic monomer; Wherein, said catalyzer is any described carried metallocene catalyst among the claim 1-12.
16. method according to claim 15, wherein, said olefinic polymerization condition comprises: said being aggregated in the organic solvent carried out; In metallocene compound, the concentration of said carried metallocene catalyst in organic solvent is 1 * 10
-8-1 * 10
-5Mol, the contact temperature is 25-500 ℃, and contact pressure is 0.1-5MPa, and be 1-24 hour duration of contact.
17. according to claim 15 or 16 described methods, wherein, said olefinic monomer is an ethene, perhaps is that ethene and carbonatoms are the terminal olefin of 4-20.
18. according to claim 15 or 16 described methods; Wherein, said carbonatoms is that the terminal olefin of 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, the 1-eicosylene.
19. an olefin polymer, said olefin polymer are that any described method prepares among the claim 15-18.
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| CN104059179A (en) * | 2013-03-21 | 2014-09-24 | 中国石油化工股份有限公司 | Supported single metallocene catalyst for ethylene polymerization |
| CN104059177A (en) * | 2013-03-21 | 2014-09-24 | 中国石油化工股份有限公司 | Supported single metallocene catalyst used for ethylene polymerization |
| CN104059174A (en) * | 2013-03-21 | 2014-09-24 | 中国石油化工股份有限公司 | Supported single metallocene catalyst used for ethylene polymerization |
| EP3015502A1 (en) | 2014-10-27 | 2016-05-04 | China Petroleum&Chemical Corporation | A polyethylene composition and a film formed therefrom |
| CN108456273A (en) * | 2017-02-17 | 2018-08-28 | 旭化成株式会社 | Polyethylene based polymers and its manufacturing method |
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