CN1542025A - Alkene polymerization catalyst loaded by mesoporous materials and method for preparing the same - Google Patents
Alkene polymerization catalyst loaded by mesoporous materials and method for preparing the same Download PDFInfo
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- CN1542025A CN1542025A CNA2003101084383A CN200310108438A CN1542025A CN 1542025 A CN1542025 A CN 1542025A CN A2003101084383 A CNA2003101084383 A CN A2003101084383A CN 200310108438 A CN200310108438 A CN 200310108438A CN 1542025 A CN1542025 A CN 1542025A
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Abstract
The present invention is one kind of supported olefin polymerizing catalyst of metallocene and post-transition metal and its reaction process of catalyzing ethylene polymerization. The catalyst consists of two components, the component A has the expression of SiO2-Cat, where SiO2 is mesoporous molecular sieve carrier SBA-15 to support catalyst and Cat is metallocene or post-transition metal; and the component B is methyl aluminoxane or modified methyl aluminoxane. The catalyst has high catalytic activity of catalyzing ethylene polymerization, is suitable for use in vapor and slurry polymerization. Using the catalyst can obtain nano fibrous polyethylene product with high molecular weight, high melting point and high ageing resistance.
Description
Technology neck city
The invention belongs to catalyst technical field, be specifically related to a kind of metallocene that is carried on mesoporous material SBA-15 and late transition metal catalyst for olefin polymerization and preparation method thereof, and this catalyst ethylene polymerization technology.
Background technology
Polyolefine is the mainstay industry of modern macromolecular material industry, and olefin polymerization catalysis then is the core of polyolefine industry.Because the organo-metallic olefin polymerization catalysis not only can efficient catalytic olefinic polymerization under the condition of gentleness, and microtexture that can the cutting polymkeric substance, so can on molecular level, design the new function polyolefine material and improve existing polymer properties, so the research in this field is one of contemporary chemical forward position and focus always.Since nineteen fifty-three, olefin polymerization catalysis came out, Ziegler-Natta catalyst system, metallocene catalysis system and three important milestones of rear transition metal catalyst system have appearred in short 50 years.
Traditional catalyzer has been finished industrialization at present, but metallocene catalysis system and rear transition metal catalyst system also have many problems to wait to solve in actual applications.For metallocene catalyst, its catalytic activity increased and reduces rapidly with the reaction times, sticking still phenomenon appears in polymerization process, can not be used for the gentle phase production technique of slurry, the form that is difficult to controlling polymers, and need a large amount of expensive promotors (methylaluminoxane MAO or improvement methylaluminoxane MMAO) just can make catalytic activity reach the highest; For late transition metal catalyst, particularly the polyolefin products molecular weight that obtains in short polymerization time of Fe-series catalyst is very low.One of important channel that addresses these problems is exactly with the homogeneous catalyst loadization.It is the chromium-based catalysts of carrier late 1950s with silica gel that the loadization of olefin polymerization catalysis starts from Phillips company.The carrier that is used for load at present is a lot, as SiO
2, MgCl
2, molecular sieve, clay, autohemagglutination type polymkeric substance, polystyrene, cyclodextrin etc.The mesoporous molecular sieve SBA-15 of nineteen nineties rise has become the research focus of organic catalysis, and SBA-15 has high-specific surface area (900～1000m
2/ g), narrow pore size distribution, wide aperture (6.0～7.0nm), large pore volume (～1.5ml/g) and the high mechanical strength that keeps of heavy wall, for industrial application very important meaning is arranged so homogeneous catalyst is loaded on the research of mesoporous molecular sieve SBA-15.
Summary of the invention
The purpose of this invention is to provide olefin polymerization catalysis of a kind of loadization and preparation method thereof; And provide the reaction process of this catalyst vinyl polymerization.
Load alkene dimerization agent provided by the invention, its expression formula is [SiO
2-Cat], wherein Cat is a kind of metallocene or late transition metal catalyst, SiO
2BA-15 is with catalyst cupportization for expression mesopore molecular sieve carrier S, remembers that this catalyzer is the A component.
In the above-mentioned carried catalyst A component, metallocene or late transition metal catalyst can be zirconium system, iron system or nickel catalyst, so the structural formula of A component is as shown in the formula shown in (1):
Wherein, M be central metal Zr, Fe, Ni one of them; X be halogen atom Cl, Br one of them; Part (ligand) is cyclopentadienyl or diimine class part.The structural formula of diimine class part is a kind of of a, b in the following formula (2).
In the above-mentioned carried catalyst A component, used zirconium system, iron system, nickel catalyst wherein typically have bis cyclopentadienyl zirconium dichloride, pyridine diimine iron, diimine nickel respectively.Its structural formula is respectively as shown in the formula shown in (3).
(a) bis cyclopentadienyl zirconium dichloride (b) pyridine diimine iron (c) diimine nickel
The promotor that carried catalyst of the present invention was used is methylaluminoxane (MAO) or improves methylaluminoxane (MMAO), is designated as the B component.
The present invention proposes the catalyzer of loadization under promotor consumption situation seldom, still can keep quite high catalytic activity; Simultaneously, the catalyzer of loadization can reduce the generation of β-H elimination reaction, thereby obtains high molecular, high-melting-point, ageing-resistant polymkeric substance; In addition, the hexagonal pore passage structure of the sequential 2 D of mesoporous material SBA-15 can be controlled the relative position between the macromolecular chain, is template with the molecular sieve during polymer growth; And SBA-15 has the nano level aperture, can effectively limit the direction and the size of olefinic polymerization.What use that the catalyst polyreaction of this loadization obtains is nano-polyethylene fiber shape product, is unformed pulverulence and adopt the resulting polyethylene form of homogeneous catalyst.
The activated silica hydroxyl is contained on surface, mesoporous molecular sieve SBA-15 duct, during load and homogeneous catalyst have an effect, obtain different carrier formats.With the diimine nickel is example (formula (4) as follows), and (formula (4) a) exists the situation (formula (4) b) that two bromines are left away simultaneously again, and the former accounts for the overwhelming majority, has realized the carrierization of catalyzer more satisfactoryly both the form that a bromine leaves away.
The olefin polymerization catalysis preparation method of the loadization that the present invention proposes is as follows:
(1) preparation of the olefin polymerization catalysis A component of mesoporous molecular sieve SBA-15 physical load:
Take by weighing mesoporous molecular sieve SBA-15 3.0-5.0 gram, 150～160 ℃ of following vacuum heat-preservings 6～8 hours.Behind the cool to room temperature, add 15～20ml toluene.Under stirring state, add the toluene solution that is dissolved with homogeneous phase metallocene or rear transition metal polymerizing catalyst 0.05-1.50mmol.(general 0.5 hour to 20 hours) stirs under the room temperature.Toluene wash is used in centrifugation, and vacuum-drying promptly obtains the catalyst A component of loadization.
(2) preparation of the olefin polymerization catalysis A component of mesoporous molecular sieve SBA-15 chemical load:
Take by weighing mesoporous molecular sieve SBA-15 3.0-5.0 gram, 150～160 ℃ of following vacuum heat-preservings 6～10 hours.Behind the cool to room temperature, add 15～20ml toluene.Under stirring state, add the toluene solution that is dissolved with homogeneous phase metallocene or rear transition metal polymerizing catalyst 0.05-1.50mmol.The n-Butyl Lithium (1.6mmol/ml) that adds 1.0-10ml after stirring under the room temperature.Continue to stir 18～20 hours, toluene wash is used in centrifugation, and vacuum-drying promptly obtains the catalyst A component of loadization.
Utilize load olefin polymerization catalysis catalyzed ethylene polymerization reaction process of the present invention as follows:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene 50ml, catalyst B component methylaluminoxane (MAO) 0.5-5.0ml successively or improve methylaluminoxane (MMAO) 1.0-2.5ml, catalyst A component load olefin polymerization catalysis 0.01-0.15 gram, Al/M=100～10000), vinyl polymerization pressure is 1～18atm (normal atmosphere), temperature of reaction is-20～80 ℃, and the reaction times was generally 0.5 hour to 1 hour.With the ethanolic soln termination reaction that contains a little hydrochloric acid, products therefrom is filtered, with washing with alcohol for several times, vacuum-drying gets final product again.Its active amt level is 10
5～10
6GPE/ (molMh), the molecular weight of polyethylene order of magnitude are 10
4～10
6
Analyze the resulting poly microscopic pattern of catalyzer of SBA-15 loadization, can clearly see polyethylene fibre from Fig. 1, the hexagonal pore passage structure of the sequential 2 D of this explanation SBA-15 can be controlled the relative position between the macromolecular chain really; During polymer growth with molecular sieve as template, SBA-15 has the nano level aperture, can effectively limit the direction and the size (Fig. 2) of vinyl polymerization, so all obtains nanometer polyolein fiber shape product after metallocene and the late transition metal catalyst load.
Description of drawings
Fig. 1 is poly SEM figure.Wherein, the polyethylene microscopic pattern that Fig. 1 (a) obtains for the load zirconium-based catalyst, the polyethylene microscopic pattern that Fig. 1 (b) obtains for the load Fe-series catalyst, the polyethylene microscopic pattern that Fig. 1 (c) obtains for the load nickel catalyst, the polyethylene microscopic pattern that Fig. 1 (d) obtains for the load nickel catalyst.
Fig. 2 is ethene growth figure in the mesoporous molecular sieve SBA-15.
Embodiment
Embodiment 1: the preparation of the olefin polymerization catalysis A component of mesoporous molecular sieve SBA-15 physical load:
Take by weighing mesoporous molecular sieve SBA-15 (5.0g), 150 ℃ of following vacuum heat-preservings 6 hours.Behind the cool to room temperature, add 15ml toluene.Under stirring state, adding is dissolved with 0.020g Cp
2ZrCl
2(formula (1) toluene solution a).Stirred 0.5 hour under the room temperature.Centrifugation with toluene wash 3 times, vacuum-drying, obtains the catalyst A component of loadization, and measuring zirconium content is 0.085wt%.
Embodiment 2: the preparation of the olefin polymerization catalysis A component of mesoporous molecular sieve SBA-15 physical load:
Take by weighing mesoporous molecular sieve SBA-15 (4.0g), 160 ℃ of following vacuum heat-preservings 8 hours.Behind the cool to room temperature, add 20ml toluene.Under stirring state, add the toluene solution that is dissolved with 0.520g diimine nickel (formula (1) c).Stirred 0.5 hour under the room temperature.Centrifugation with toluene wash 3 times, vacuum-drying, obtains the catalyst A component of loadization, and measuring nickel content is 0.158wt%.
Embodiment 3: the preparation of the olefin polymerization catalysis A component of mesoporous molecular sieve SBA-15 physical load:
Take by weighing mesoporous molecular sieve SBA-15 (4.0g), 155 ℃ of following vacuum heat-preservings 8 hours.Behind the cool to room temperature, add 20ml toluene.Under stirring state, add the toluene solution that is dissolved with 0.520g diimine nickel (formula (1) c).Stirred 20 hours under the room temperature.Centrifugation with toluene wash 3 times, vacuum-drying, obtains the catalyst A component of loadization, and measuring nickel content is 0.347wt%.
Embodiment 4: the preparation of the olefin polymerization catalysis A component of mesoporous molecular sieve SBA-15 chemical load:
Take by weighing mesoporous molecular sieve SBA-15 (5.0g), 150 ℃ of following vacuum heat-preservings 6 hours.Behind the cool to room temperature, add 15ml toluene.Under stirring state, adding is dissolved with 0.020g Cp
2ZrCl
2(formula (1) toluene solution a).Stir under the room temperature and add the 1.0ml n-Butyl Lithium after 30 minutes.Continue to stir 18 hours, centrifugation with toluene wash 3 times, vacuum-drying, obtains the catalyst A component of loadization, and measuring zirconium content is 0.111wt%.
Embodiment 5: the preparation of the olefin polymerization catalysis A component of mesoporous molecular sieve SBA-15 chemical load:
Take by weighing mesoporous molecular sieve SBA-15 (3.0g), 150 ℃ of following vacuum heat-preservings 6 hours.Behind the cool to room temperature, add 15ml toluene.Under stirring state, add the toluene solution that is dissolved with 0.330g pyridine diimine iron (formula (1) b).Stir under the room temperature and add the 1.0ml n-Butyl Lithium after 30 minutes.Continue to stir 18 hours, centrifugation with toluene wash 3 times, vacuum-drying, obtains the catalyst A component of loadization, and the mensuration iron level is 0.588wt%.
Embodiment 6: the preparation of the olefin polymerization catalysis A component of mesoporous molecular sieve SBA-15 chemical load:
Take by weighing mesoporous molecular sieve SBA-15 (5.0g), 160 ℃ of following vacuum heat-preservings 10 hours.Behind the cool to room temperature, add 20ml toluene.Under stirring state, add the toluene solution that is dissolved with 0.700g pyridine diimine iron (formula (1) b).Stir under the room temperature and add the 10ml n-Butyl Lithium after 30 minutes.Continue to stir 20 hours, centrifugation with toluene wash 3 times, vacuum-drying, obtains the catalyst A component of loadization, and the mensuration iron level is 0.781wt%.
Embodiment 7: the preparation of the olefin polymerization catalysis A component of mesoporous molecular sieve SBA-15 chemical load:
Take by weighing mesoporous molecular sieve SBA-15 (4.0g), 160 ℃ of following vacuum heat-preservings 8 hours.Behind the cool to room temperature, add 20ml toluene.Under stirring state, add the toluene solution that is dissolved with 0.520g diimine nickel (formula (1) c).Stir under the room temperature and add the 10ml n-Butyl Lithium after 30 minutes.Continue to stir 20 hours, centrifugation with toluene wash 3 times, vacuum-drying, obtains the catalyst A component of loadization, and measuring nickel content is 0.730wt%.
Embodiment 8: the catalyzed ethylene polymerization reaction:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, the catalyst A component load olefin polymerization catalysis 0.108g (pressing Al/Zr=1700) that in reaction system, adds toluene 50ml, catalyst B component methylaluminoxane (MAO) 1.0ml, embodiment 1 preparation successively, ethene 1atm, in 16 ℃ of reactions 0.5 hour,, products therefrom is filtered with the ethanolic soln termination reaction that contains a little hydrochloric acid, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings 10 hours, get polyethylene 0.091g, activity is 1.82 * 10
5GPE/ (molZrh), molecular weight of polyethylene are 6.65 * 10
4
Embodiment 9: the catalyzed ethylene polymerization reaction:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, the catalyst A component load olefin polymerization catalysis 0.069g (pressing Al/Ni=2500) that in reaction system, adds toluene 50ml, catalyst B component improvement methylaluminoxane (MMAO) 2.1ml, embodiment 2 preparations successively, ethene 1atm, in 14 ℃ of reactions 0.5 hour, with the ethanolic soln termination reaction that contains a little hydrochloric acid, products therefrom is filtered, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings 10 hours, get polyethylene 0.794g, activity is 8.58 * 10
5GPE/ (molNih).
Embodiment 10: the catalyzed ethylene polymerization reaction:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, the catalyst A component load olefin polymerization catalysis 0.022g (pressing Al/Ni=2500) that in reaction system, adds toluene 50ml, catalyst B component improvement methylaluminoxane (MMAO) 1.5ml, embodiment 3 preparations successively, ethene 1atm, in 2 ℃ of reactions 0.5 hour, with the ethanolic soln termination reaction that contains a little hydrochloric acid, products therefrom is filtered, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings 10 hours, get polyethylene 0.391g, activity is 6.06 * 10
5GPE/ (molNih), molecular weight of polyethylene are 6.70 * 10
5
Embodiment 11: the catalyzed ethylene polymerization reaction:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, the catalyst A component load olefin polymerization catalysis 0.031g (pressing Al/Ni=2500) that in reaction system, adds toluene 50ml, catalyst B component improvement methylaluminoxane (MMAO) 2.1ml, embodiment 3 preparations successively, ethene 1atm, in 14 ℃ of reactions 0.5 hour, with the ethanolic soln termination reaction that contains a little hydrochloric acid, products therefrom is filtered, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings 10 hours, get polyethylene 0.453g, activity is 4.95 * 10
5GPE/ (molNih).
Embodiment 12: the catalyzed ethylene polymerization reaction:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, the catalyst A component load olefin polymerization catalysis 0.135g (pressing Al/Zr=1000) that in reaction system, adds toluene 50ml, catalyst B component methylaluminoxane (MAO) 1.0ml, embodiment 4 preparations successively, ethene 1atm, in 16 ℃ of reactions 0.5 hour,, products therefrom is filtered with the ethanolic soln termination reaction that contains a little hydrochloric acid, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings 10 hours, get polyethylene 0.112g, activity is 1.37 * 10
5GPE/ (molZrh), molecular weight of polyethylene are 7.43 * 10
5
Embodiment 13: the catalyzed ethylene polymerization reaction:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, the catalyst A component load olefin polymerization catalysis 0.019g (pressing Al/Fe=1700) that in reaction system, adds toluene 50ml, catalyst B component methylaluminoxane (MAO) 2.0ml, embodiment 5 preparations successively, ethene 1atm, in 16 ℃ of reactions 0.5 hour,, products therefrom is filtered with the ethanolic soln termination reaction that contains a little hydrochloric acid, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings 10 hours, get polyethylene 0.375g, activity is 3.75 * 10
5GPE/ (molFeh).
Embodiment 14: the catalyzed ethylene polymerization reaction:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, the catalyst A component load olefin polymerization catalysis 0.011g (pressing Al/Fe=2500) that in reaction system, adds toluene 50ml, catalyst B component methylaluminoxane (MAO) 2.2ml, embodiment 6 preparations successively, ethene 1atm, in 28 ℃ of reactions 0.5 hour,, products therefrom is filtered with the ethanolic soln termination reaction that contains a little hydrochloric acid, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings 10 hours, get polyethylene 0.329g, activity is 4.39 * 10
5GPE/ (molFeh).
Embodiment 15: the catalyzed ethylene polymerization reaction:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, the catalyst A component load olefin polymerization catalysis 0.011g (pressing Al/Fe=1000) that in reaction system, adds toluene 50ml, catalyst B component methylaluminoxane (MAO) 0.gml, embodiment 6 preparations successively, ethene 1atm, in 28 ℃ of reactions 0.5 hour,, products therefrom is filtered with the ethanolic soln termination reaction that contains a little hydrochloric acid, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings 10 hours, get polyethylene 0.094g, activity is 1.25 * 10
5GPE/ (molFeh).
Embodiment 16: the catalyzed ethylene polymerization reaction:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, the catalyst A component load olefin polymerization catalysis 0.011g (pressing Al/Fe=5500) that in reaction system, adds toluene 50mL, catalyst B component methylaluminoxane (MAO) 4.9ml, embodiment 6 preparations successively, ethene latm, in 28 ℃ of reactions 0.5 hour,, products therefrom is filtered with the ethanolic soln termination reaction that contains a little hydrochloric acid, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings 10 hours, get polyethylene 0.731g, activity is 9.75 * 10
5GPE/ (molFeh).
Embodiment 17: the catalyzed ethylene polymerization reaction:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, the catalyst A component load olefin polymerization catalysis 0.011g (pressing Al/Fe=2500) that in reaction system, adds toluene 50ml, catalyst B component methylaluminoxane (MAO) 2.2ml, embodiment 6 preparations successively, ethene 1atm, in 0 ℃ of reaction 0.5 hour,, products therefrom is filtered with the ethanolic soln termination reaction that contains a little hydrochloric acid, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings 10 hours, get polyethylene 0.101g, activity is 1.35 * 10
5GPE/ (molFeh).
Embodiment 18: the catalyzed ethylene polymerization reaction
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, the catalyst A component load olefin polymerization catalysis 0.011g (pressing Al/Fe=2500) that in reaction system, adds toluene 50ml, catalyst B component methylaluminoxane (MAO) 2.2ml, embodiment 6 preparations successively, ethene 1atm, in 75 ℃ of reactions 0.5 hour,, products therefrom is filtered with the ethanolic soln termination reaction that contains a little hydrochloric acid, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings 10 hours, get polyethylene 0.289g, activity is 3.85 * 10
5GPE/ (molFeh).
Embodiment 19: the catalyzed ethylene polymerization reaction:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, the catalyst A component load olefin polymerization catalysis 0.021g (pressing Al/Fe=2500) that in reaction system, adds toluene 50ml, catalyst B component methylaluminoxane (MAO) 4.4ml, embodiment 6 preparations successively, ethene 4atm, in 40 ℃ of reactions 1 hour,, products therefrom is filtered with the ethanolic soln termination reaction that contains a little hydrochloric acid, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings 10 hours, get polyethylene 1.078g, activity is 3.59 * 10
5GPE/ (molFeh).
Embodiment 20: the catalyzed ethylene polymerization reaction:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, the catalyst A component load olefin polymerization catalysis 0.021g (pressing Al/Fe=2500) that in reaction system, adds toluene 50ml, catalyst B component methylaluminoxane (MAO) 4.4ml, embodiment 6 preparations successively, ethene 8atm, in 40 ℃ of reactions 1 hour,, products therefrom is filtered with the ethanolic soln termination reaction that contains a little hydrochloric acid, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings 10 hours, get polyethylene 0.592g, activity is 1.97 * 10
5GPE/ (molFeh).
Embodiment 21: the catalyzed ethylene polymerization reaction:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, the catalyst A component load olefin polymerization catalysis 0.014g (pressing Al/Ni=2500) that in reaction system, adds toluene 50ml, catalyst B component improvement methylaluminoxane (MMAO) 1.9ml, embodiment 7 preparations successively, ethene 1atm, in 2 ℃ of reactions 0.5 hour, with the ethanolic soln termination reaction that contains a little hydrochloric acid, products therefrom is filtered, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings 10 hours, get polyethylene 0.252g, activity is 2.96 * 10
5GPE/ (molNih), molecular weight of polyethylene are 7.41 * 10
5
Embodiment 22: the catalyzed ethylene polymerization reaction:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, the catalyst A component load olefin polymerization catalysis 0.014g (pressing Al/Ni=2500) that in reaction system, adds toluene 50ml, catalyst B component improvement methylaluminoxane (MMAO) 2.0ml, embodiment 7 preparations successively, ethene 1atm, in 14 ℃ of reactions 0.5 hour, with the ethanolic soln termination reaction that contains a little hydrochloric acid, products therefrom is filtered, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings 10 hours, get polyethylene 0.195g, activity is 2.24 * 10
5GPE/ (molNih).
Claims (4)
1, a kind of load olefin polymerization catalysis is characterized in that expression formula is [SiO
2-Cat], wherein Cat is a kind of metallocene or late transition metal catalyst, SiO
2BA-15 is with catalyst cupportization for expression mesopore molecular sieve carrier S, and concrete structure is as shown in the formula shown in (1):
Wherein, M be central metal Zr, Fe, Ni one of them; X be halogen atom Cl, Br one of them; Part is cyclopentadienyl or diimine class part.
2, a kind of preparation method of load olefin polymerization catalysis is characterized in that concrete steps are as follows:
Take by weighing mesoporous molecular sieve SBA-15 3.0-5.0 gram, 150～160 ℃ of following vacuum heat-preservings 6～8 hours; Behind the cool to room temperature, add 15～20ml toluene; Under stirring state, add the toluene solution that is dissolved with homogeneous phase metallocene or transition metal catalyst for olefin polymerization 0.05-1.50mmol, stirred 0.5 hour to 20 hours; Toluene wash is used in centrifugation, vacuum-drying.
3, a kind of preparation method of load olefin polymerization catalysis is characterized in that concrete steps are as follows:
Take by weighing mesoporous molecular sieve SBA-15 3.0-5.0 gram, 150～160 ℃ of following vacuum heat-preservings 6～10 hours; Behind the cool to room temperature, add 15～20ml toluene; Under stirring state, add the toluene solution that is dissolved with homogeneous phase metallocene or transition metal catalyst for olefin polymerization, add the n-Butyl Lithium that 1.0-10ml concentration is 1.6mmol/ml again; Continue to stir 18～20 hours, toluene wash is used in centrifugation, vacuum-drying.
4, a kind of reaction process that utilizes the described load olefin polymerization catalysis of claim 1 catalyzed ethylene polymerization is characterized in that concrete steps are as follows:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene 50ml, catalyst B component methylaluminoxane 0.5-5.0ml (concentration is 1.7mmol/ml) successively, or improvement methylaluminoxane 1.0-2.5ml (concentration is 2.2mmol/ml), catalyst A component load olefin polymerization catalysis 0.01-0.15 gram, Al/M=100～10000, ethene 1～18atm, in-20～80 ℃ of reactions 0.5 hour to 1 hour, with the ethanolic soln termination reaction that contains a little hydrochloric acid, products therefrom is filtered, use washing with alcohol, last vacuum-drying.
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| CN100341904C (en) * | 2005-07-21 | 2007-10-10 | 浙江大学 | Method of preparing nano-polyethylene fiber by normal pressure extrusion polymerization |
| CN101376113B (en) * | 2007-08-27 | 2010-09-29 | 中国石油天然气股份有限公司 | Molecular sieve supported ethylene oligomerization catalyst, and preparation and application thereof |
| CN101376725B (en) * | 2007-08-27 | 2011-12-07 | 中国石油天然气股份有限公司 | High-impact linear low-density polyethylene/molecular sieve composite material and preparation method thereof |
| CN102453140A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Load type metallocene catalyst and preparation method thereof |
| CN102453140B (en) * | 2010-10-19 | 2013-08-14 | 中国石油化工股份有限公司 | Load type metallocene catalyst and preparation method thereof |
| WO2012171090A1 (en) * | 2011-06-16 | 2012-12-20 | Universidade Federal Do Rio Grande Do Sul-Ufrgs | Zeolite and mesoporous materials used as fillers in the formulation of rubber compounds, thermoplastic rubber, plastics and for manufacturing products |
| CN104017117A (en) * | 2014-06-19 | 2014-09-03 | 中国科学院长春应用化学研究所 | Metallocene catalyst and preparation method thereof, and preparation method of polyethylene nanofiber |
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