CN1923862A - Mesoporous molecular sieve carried olefin polymerization catalyst, preparation method and application thereof - Google Patents
Mesoporous molecular sieve carried olefin polymerization catalyst, preparation method and application thereof Download PDFInfo
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- CN1923862A CN1923862A CNA200610116336XA CN200610116336A CN1923862A CN 1923862 A CN1923862 A CN 1923862A CN A200610116336X A CNA200610116336X A CN A200610116336XA CN 200610116336 A CN200610116336 A CN 200610116336A CN 1923862 A CN1923862 A CN 1923862A
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Abstract
The invention discloses an olefin polymeric catalyst and preparing method and reacting technology, which is characterized by the following: the expression formula of catalyst is [SiO2-Cat], wherein Cat represents semi-sandwich homogeneous phase catalyst of transient element metallic titanium (IV) or zirconium (IV); SiO2 represents dielectric molecular sieve SBA-15 decorated by methyl alundum alkyl, which can synthesize polyethylene; the catalyst possesses high ethylene polymeric activity, which displays ultrahigh molecule with different patterns.
Description
Technical field
The invention belongs to the olefin polymerization catalysis technical field, be specifically related to olefin polymerization catalysis of a kind of mesoporous molecular sieve carriedization and its production and application.
Background technology
As the mainstay industry of modern macromolecular material, the development of polyolefin industry is an important symbol of weighing a national petrochemical complex development, and olefin polymerization catalysis then is the key and the core of development polyolefine industry.Can obtain the polyolefin product of specific morphology and performance by the structure of modified catalyst.Therefore, the research and development of catalyzer are the prime mover that polyolefin products updates, updates.Since nineteen fifty-three, olefin polymerization catalysis came out, developed already and three big catalyst system: Ziegler-Natta catalyst system, metallocene catalysis system and " luxuriant afterwards " transition metal-catalyzed system.
Up to the present, people have successfully synthesized many high catalytic activities, have the catalyzer of the polymkeric substance of some premium properties.But, use these homogeneous catalysts and also have many problems for existing industrial fluidized bed production.The high reactivity that mainly shows catalyzer causes " implode " serious in the polymerization process and sticking still phenomenon, needs to use a large amount of expensive promotor methylaluminoxane (MAO), polymer morphologies to be difficult to control etc.One of important channel that addresses these problems is exactly with the homogeneous catalyst loadization.Carrier commonly used at present has SiO
2, Al
2O
3, MgCl
2Deng organic carriers such as inorganic carrier and polystyrene, cyclodextrin.In recent years, the mesoporous material development rapidly, because it has particular structure and nature and characteristic, have many new constructional features and aggregation features with its carried catalyst that is carrier obtains, since first kind mesopore molecular sieve--after M41S series was succeeded in developing by Mobil company, people were carried on olefin polymerization catalysis and have carried out a large amount of research and development on the mesoporous material.
As the novel mesoporous material of a class, SBA-15 has high-specific surface area (900～1000m
2/ g), narrow pore size distribution, wide aperture (6.0～7.0nm), large pore volume (～1.5cm
3/ g) and high mechanical strength, be a kind of carrier of very ideal olefin polymerization catalysis.In recent years, more and more be subjected to people's attention and interest, therefore, the present invention has very important realistic meaning and potential application prospect with SBA-15 as the research of carrier loaded homogeneous catalyst.
Summary of the invention
The purpose of this invention is to provide a kind of catalytic activity height, the application of the reaction process of load olefin polymerization catalysis and preparation method thereof and this carried catalyst catalyzed ethylene polymerization is easily controlled in reaction.
Load olefin polymerization catalysis provided by the invention, its expression formula are [SiO
2-Cat], wherein Cat is transition metal Ti (IV) or Zr (IV) semi-sandwich alum compound homogeneous catalyst, SiO
2Presentation surface utilizes the mesoporous molecular sieve SBA-15 carrier of MAO (methylaluminoxane) modified, and concrete structure is shown below:
The carried catalyst homogeneous catalyst
Wherein, M is central metal Ti or Zr; Cp is a cyclopentadiene; R is H or CH
3L is part 4-methyl-2,6 di t butyl phenol salt, remembers that this catalyzer is the A component.
The single crystal structure of homogeneous catalyst is as follows as mentioned above:
(a) titanium homogeneous catalyst (b) zirconium homogeneous catalyst
The employed promotor of carried catalyst of the present invention is methylaluminoxane (MAO), is designated as the B component.
The present invention proposes the load olefin polymerization catalysis and compares with its homogeneous catalyst, still can keep quite high catalytic activity under the same terms; Carried catalyst is eliminated reaction to B-H and is reduced, and can obtain very high molecular, more dystectic relatively polymkeric substance; Based on the masterplate effect of molecular sieve, the hexagonal duct of the sequential 2 D of SBA-15 and nano level aperture can obtain nano-polyethylene fiber shape product; By the adjusting of temperature of reaction, can obtain the polyethylene fibre of different shape under the different temperature.
Each method of catalyzer system that the present invention proposes is as follows:
(1) preparation of transition metal Ti (IV) semi-sandwich alum compound homogeneous catalyst, step is as follows:
-78 ℃, toward 4～6mmol part 4-methyl-2, add 30～40ml ether solvent in the trichlorine one luxuriant titanium solid mixture of 6-di-tert-butyl phenates and amount of substance such as grade, stir and be warming up to room temperature down gradually, react 8～10 hours after-filtration, vacuum is drained solvent, gets red solid, and it is dissolved in a small amount of CH
2Cl
2In, the upper strata adds a small amount of ether or normal hexane ,-30 ℃ refrigerate red crystallite CpTi (OAr) Cl
2(Ar=4-Me-2,6-
tBu
2C
6H
2).
(2) preparation of transition metal Zr (IV) semi-sandwich alum compound homogeneous catalyst (a), step is as follows:
-78 ℃, with 4～6mmol part 4-methyl-2, the toluene solution of 6-di-tert-butyl phenates slowly is added dropwise to etc. in the normal hexane suspension liquid of trichlorine one luxuriant zirconium of amount of substance, stirs and is warming up to room temperature down gradually, react 10～12 hours after-filtration, vacuum is drained solvent, gets light yellow solid, and it is used a large amount of n-hexane extractions, after extraction liquid concentrates ,-30 ℃ refrigerate yellow crystallite CpZr (OAr) Cl
2(Ar=4-Me-2,6-
tBu
2C
6H
2).
(3) preparation method of load olefin polymerization catalysis, concrete steps are as follows:
Take by weighing mesoporous molecular sieve SBA-15 3.0-5.0 gram, 150～180 ℃ of following vacuum heat-preservings 8～10 hours; Behind the cool to room temperature, add 20～30mL toluene; Add 8～10mLMAO subsequently, stirring at room 15～20h after-filtration with the toluene wash solids for several times, mixes with the toluene solution that is dissolved with homogeneous catalyst then; Continue to stir 18～25 hours, toluene wash is used in centrifugation, and vacuum-drying promptly gets required catalyzer; Wherein homogeneous catalyst is transition metal Ti (IV) or Zr (IV) semi-sandwich alum compound.
Load olefin polymerization catalysis of the present invention is used for the catalyzed ethylene polymerization reaction, and concrete steps are as follows:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene 50ml successively, catalyst B component MAO (methylaluminoxane) 0.5-5.0ml (concentration is 1.7mol/L), catalyst A component load olefin polymerization catalysis 0.1-0.15 gram, and Al/M=1000～5000 (M=Ti, Zr), ethylene pressure 1～15atm, 15～100 ℃ of temperature of reaction, reaction times 0.5-1.0 hour, with the ethanolic soln termination reaction that contains 1% hydrochloric acid; Products therefrom is filtered, with washing with alcohol for several times, in 35～45 ℃ of vacuum-dryings to mass conservation.Its active amt level is 10
4～10
6GPE/ (molMh), the molecular weight of polyethylene order of magnitude are 10
5～10
6
Analyze the resulting poly microscopic pattern of catalyzer of SBA-15 loadization, from Fig. 1 and the visible single bundle of Fig. 2 or multiply and sheet polyethylene fibre; This shows the hexagonal pore passage structure of the sequential 2 D of SBA-15, effectively controlled poly formation direction, and the nano level aperture can obtain nano level polyethylene fibre (Fig. 3); With the difference of temperature of reaction, the variation of polymerization velocity has formed the polymer fiber of different shape in addition.
Description of drawings
Fig. 1 is SBA-15 load titanium (IV) the poly sem photograph of catalyzer gained (SEM).Wherein, Fig. 1 (a) is single bundle polyethylene fibre, the poly different shape of Fig. 1 (a)～1 (d) for preparing under the differing temps, (a) 40 ℃; (b) 20 ℃; (c) 40 ℃; (d) 60 ℃.
Fig. 2 is that SBA-15 load zirconium (IV) catalyzer is at 40 ℃ of poly sem photographs of following catalysis gained (SEM).
Fig. 1 and Fig. 2 gained polyethylene fibre are preparation under 10 normal atmosphere.
Fig. 3 is the polyethylene fibre synoptic diagram of growing in the mesopore molecular sieve duct.
Embodiment
The preparation of embodiment 1 transition metal Ti (IV) semi-sandwich alum compound homogeneous catalyst:
-78 ℃, in part 5mmol 4-methyl-2,6 di t butyl phenol salt and 5mmol trichlorine one luxuriant titanium solid mixture, add the 40ml ether solvent, stir down and slowly be warming up to room temperature, react 8 hours after-filtration, vacuum is drained solvent.Resistates is dissolved in a small amount of CH
2Cl
2In, the upper strata adds a small amount of ether or normal hexane ,-30 ℃ refrigerate red crystallite CpTi (OAr) Cl
2(Ar=4-Me-2,6-
tBu
2C
6H
2), productive rate 83%.
Embodiment 2 transition metal Zr (preparation of IV semi-sandwich alum compound homogeneous catalyst:
-78 ℃, with the toluene solution of part 5mmol4-methyl-2,6 di t butyl phenol salt, slowly be added dropwise in the normal hexane suspension liquid of 5mmol trichlorine one luxuriant zirconium, stir down and slowly be warming up to room temperature, react 12 hours after-filtration, vacuum is drained solvent.The a large amount of n-hexane extractions of resistates, after concentrating ,-30 ℃ refrigerate yellow crystallite CpZr (OAr) Cl
2(Ar=4-Me-2,6-
tBu
2C
6H
2), productive rate 78%.
The preparation of embodiment 3 load olefin polymerization catalysis:
Take by weighing mesoporous molecular sieve SBA-15 3.0 gram, 150～180 ℃ of following vacuum heat-preservings 8～10 hours; Behind the cool to room temperature, add 20mL toluene; Add 10mLMAO subsequently, stirring at room 20h after-filtration is used toluene wash solids three times, mixes with the toluene solution that is dissolved with 0.052g homogeneous catalyst titanium (IV) then; Continue to stir 18～20 hours, toluene wash is used in centrifugation, and vacuum-drying obtains the catalyst A component of loadization, and recording titanium content is 0.364wt%.
The preparation of embodiment 4 load olefin polymerization catalysis:
Take by weighing mesoporous molecular sieve SBA-15 3.0 gram, 150～180 ℃ of following vacuum heat-preservings 8～10 hours; Behind the cool to room temperature, add 25mL toluene; Add 10mLMAO subsequently, stirring at room 25h after-filtration is used toluene wash solids three times, mixes with the toluene solution that is dissolved with 0.069g homogeneous catalyst zirconium (IV) then; Continue to stir 18～20 hours, toluene wash is used in centrifugation, and vacuum-drying obtains the catalyst A component of loadization, and recording zirconium content is 0.143wt%.
The reaction of embodiment 5 catalyzed ethylene polymerizations:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene 50ml successively, embodiment 3 catalyst A component load olefin polymerization catalysis 2.5 μ mol, Al/Ti=2000, ethylene pressure 10atm, 20 ℃ of temperature of reaction, after 0.5 hour,, products therefrom is filtered with the ethanolic soln termination reaction that contains 1% hydrochloric acid, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings to mass conservation.Its activity is 4.11 * 10
4GPE/ (molTih), molecular weight of polyethylene are 1.5 * 10
6
The reaction of embodiment 6 catalyzed ethylene polymerizations:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene 60ml successively, embodiment 3 catalyst A component load olefin polymerization catalysis 2.5 μ mol, Al/Ti=2000, ethylene pressure 10atm, 40 ℃ of temperature of reaction, after 0.5 hour,, products therefrom is filtered with the ethanolic soln termination reaction that contains 1% hydrochloric acid, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings to mass conservation.Its activity is 6.62 * 10
4GPE/ (molTih), molecular weight of polyethylene are 1.2 * 10
6
The reaction of embodiment 7 catalyzed ethylene polymerizations:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene 50ml successively, embodiment 3 catalyst A component load olefin polymerization catalysis 1.5 μ mol, Al/Ti=2000, ethylene pressure 10atm, 60 ℃ of temperature of reaction, after 0.5 hour,, products therefrom is filtered with the ethanolic soln termination reaction that contains 1% hydrochloric acid, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings to mass conservation.Its activity is 2.85 * 10
5GPE/ (molTih), molecular weight of polyethylene are 1.5 * 10
6
The reaction of embodiment 8 catalyzed ethylene polymerizations:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene 50ml successively, embodiment 3 catalyst A component load olefin polymerization catalysis 1.8 μ mol, Al/Ti=2000, ethylene pressure 10atm, 80 ℃ of temperature of reaction, after 0.5 hour,, products therefrom is filtered with the ethanolic soln termination reaction that contains 1% hydrochloric acid, with washing with alcohol for several times, in 80 ℃ of vacuum-dryings to mass conservation.Its activity is 3.46 * 10
5GPE/ (molTih), molecular weight of polyethylene are 4.3 * 10
5
The reaction of embodiment 9 catalyzed ethylene polymerizations:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene 50ml successively, embodiment 3 catalyst A component load olefin polymerization catalysis 1.8 μ mol, Al/Ti=2000, ethylene pressure 6atm, 40 ℃ of temperature of reaction, after 0.5 hour,, products therefrom is filtered with the ethanolic soln termination reaction that contains 1% hydrochloric acid, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings to mass conservation.Its activity is 3.8 * 10
5GPE/ (molTih), molecular weight of polyethylene are 1.3 * 10
6
The reaction of embodiment 10 catalyzed ethylene polymerizations:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene 50ml successively, embodiment 4 catalyst A component load olefin polymerization catalysis 2.8 μ mol, Al/Zr=2000, ethylene pressure 10atm, 20 ℃ of temperature of reaction, after 0.5 hour,, products therefrom is filtered with the ethanolic soln termination reaction that contains 1% hydrochloric acid, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings to mass conservation.Its activity is 2.58 * 10
5GPE/ (molZrh).
The reaction of embodiment 11 catalyzed ethylene polymerizations:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene 50ml successively, embodiment 4 catalyst A component load olefin polymerization catalysis 1.7 μ mol, Al/Zr=2000, ethylene pressure 10atm, 40 ℃ of temperature of reaction, after 0.5 hour,, products therefrom is filtered with the ethanolic soln termination reaction that contains 1% hydrochloric acid, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings to mass conservation.Its activity is 3.98 * 10
5GPE/ (molZrh).
The reaction of embodiment 12 catalyzed ethylene polymerizations:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene 50ml successively, embodiment 4 catalyst A component load olefin polymerization catalysis 1.2 μ mol, Al/Zr=2000, ethylene pressure 10atm, 60 ℃ of temperature of reaction, after 0.5 hour,, products therefrom is filtered with the ethanolic soln termination reaction that contains 1% hydrochloric acid, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings to mass conservation.Its activity is 1.29 * 10
6GPE/ (molZrh).
The reaction of embodiment 13 catalyzed ethylene polymerizations:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene 50ml successively, embodiment 4 catalyst A component load olefin polymerization catalysis 1.8 μ mol, Al/Zr=2000, ethylene pressure 10atm, 80 ℃ of reaction temperature, after 0.5 hour,, products therefrom is filtered with the ethanolic soln termination reaction that contains 1% hydrochloric acid, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings to mass conservation.Its activity is 2.15 * 10
6GPE/ (molZrh).
The reaction of embodiment 14 catalyzed ethylene polymerizations:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene 50ml successively, embodiment 4 catalyst A component load olefin polymerization catalysis 2.5 μ mol, Al/Zr=2000, ethylene pressure 10atm, 100 ℃ of temperature of reaction, after 0.5 hour,, products therefrom is filtered with the ethanolic soln termination reaction that contains 1% hydrochloric acid, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings to mass conservation.Its activity is 2.76 * 10
6GPE/ (molZrh).
The reaction of embodiment 15 catalyzed ethylene polymerizations:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene 50ml successively, embodiment 4 catalyst A component load olefin polymerization catalysis 1.5 μ mol, Al/Zr=1000, ethylene pressure 5atm, 60 ℃ of temperature of reaction, after 0.5 hour,, products therefrom is filtered with the ethanolic soln termination reaction that contains 1% hydrochloric acid, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings to mass conservation.Its activity is 3.85 * 10
5GPE/ (molZrh).
Claims (5)
1, a kind of load olefin polymerization catalysis is characterized in that expression formula is [SiO
2-Cat], wherein Cat is transition metal Ti (IV) or Zr (IV) semi-sandwich alum compound homogeneous catalyst, SiO
2Presentation surface utilizes the mesoporous molecular sieve SBA-15 carrier of methylaluminoxane modified; Concrete structure is as follows:
The carried catalyst homogeneous catalyst
Wherein, M is central metal Ti or Zr; Cp is a cyclopentadiene; R is H or CH
3L is part 4-methyl-2,6 di t butyl phenol salt.
2, a kind of preparation method of load olefin polymerization catalysis as claimed in claim 1 is characterized in that concrete steps are as follows:
Take by weighing mesoporous molecular sieve SBA-15 3.0-5.0 gram, 150～180 ℃ of following vacuum heat-preservings 8～10 hours; Behind the cool to room temperature, add 20～30mL toluene; Add 8～10mL methylaluminoxane subsequently, stirring at room 15～20h after-filtration with the toluene wash solids for several times, mixes with the toluene solution that is dissolved with homogeneous catalyst then; Continue to stir 18～25 hours, toluene wash is used in centrifugation, and vacuum-drying promptly gets required catalyzer; Wherein homogeneous catalyst is transition metal Ti (IV) or Zr (IV) semi-sandwich alum compound.
3,, it is characterized in that the preparation process of described transition metal Ti (IV) semi-sandwich alum compound homogeneous catalyst is as follows according to the preparation method of the described load olefin polymerization catalysis of claim 2:
-78 ℃, in the trichlorine one luxuriant titanium solid mixture of 4～6mmol part 4-methyl-2,6 di t butyl phenol salt and amount of substance such as grade, add 30～40ml ether solvent, stir and be warming up to room temperature down gradually, react 8～10 hours after-filtration, vacuum is drained solvent, gets red solid; It is dissolved in CH
2Cl
2In, the upper strata adds a small amount of ether or normal hexane ,-30 ℃ refrigerate red crystallite CpTi (OAr) Cl
2(Ar=4-Me-2,6-
tBu
2C
6H
2).
4,, it is characterized in that the preparation process of described transition metal Zr (IV) semi-sandwich alum compound homogeneous catalyst is as follows according to the preparation method of the described load olefin polymerization catalysis of claim 2:
-78 ℃, with 4～6mmol part 4-methyl-2, the toluene solution of 6-di-tert-butyl phenates slowly is added dropwise to etc. in the normal hexane suspension liquid of trichlorine one luxuriant zirconium of amount of substance, stirs and is warming up to room temperature down gradually, react 10～12 hours after-filtration, vacuum is drained solvent, gets light yellow solid, and it is used a large amount of n-hexane extractions, after extraction liquid concentrates ,-30 ℃ refrigerate yellow crystallite CpZr (OAr) Cl
2(Ar=4-Me-2,6-
tBu
2C
6H
2).
5, the described load olefin polymerization catalysis of claim 1 is used for catalyzed ethylene polymerization, concrete steps are as follows:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene 50ml successively, concentration is the catalyst B component methylaluminoxane 0.5-5.0mL of 1.7mol/L, catalyst A component load olefin polymerization catalysis 0.1-0.15 gram, Al/M=1000～5000, M is Ti or Zr, ethylene pressure 1～15atm, 15～100 ℃ of temperature of reaction were reacted 0.5-1.0 hour; With the ethanolic soln termination reaction that contains 1% hydrochloric acid, products therefrom is filtered, with washing with alcohol for several times, in 35～45 ℃ of vacuum-dryings to mass conservation.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453124A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Supported metallocene catalyst and olefin polymer, and preparation methods thereof |
| CN102453134A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Olefin polymerization method |
| CN102453141A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Loaded metallocene catalyst and preparation method thereof |
| CN114031703A (en) * | 2021-11-29 | 2022-02-11 | 万华化学集团股份有限公司 | Binuclear metal catalyst, preparation method and application |
-
2006
- 2006-09-21 CN CNA200610116336XA patent/CN1923862A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453134A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Olefin polymerization method |
| CN102453141A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Loaded metallocene catalyst and preparation method thereof |
| CN102453134B (en) * | 2010-10-19 | 2013-07-03 | 中国石油化工股份有限公司 | Olefin polymerization method |
| CN102453141B (en) * | 2010-10-19 | 2013-09-25 | 中国石油化工股份有限公司 | Loaded metallocene catalyst and preparation method thereof |
| CN102453124A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Supported metallocene catalyst and olefin polymer, and preparation methods thereof |
| CN114031703A (en) * | 2021-11-29 | 2022-02-11 | 万华化学集团股份有限公司 | Binuclear metal catalyst, preparation method and application |
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