CN113278097A - Silica gel supported metallocene catalyst, and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a silica gel supported metallocene catalyst, which takes silica gel as a carrier, a metallocene complex as an active metal and aluminoxane and bis (pentafluorophenyl) zinc as a cocatalyst, wherein the silica gel carrier is prepared by combining a sol-gel method with a double-template method and then carrying out reaming treatment on a double salt solution consisting of sodium chloride, lithium chloride and potassium chloride; the metallocene catalyst is Cp2MCl2、(Me5Cp)2MCl2、(RCp)2MCl2(R ═ Me, n-Bu) orInd2MCl2One kind of (1). The invention also discloses a preparation method of the silica gel loaded metallocene catalyst, which comprises the following steps: and (2) carrying out ultrasonic oscillation on the silica gel carrier, methylaluminoxane, di (pentafluorophenyl) zinc and toluene, then adding the obtained solid and the metallocene complex into the toluene for ultrasonic oscillation, filtering, washing the obtained solid with the toluene, and drying the obtained solid in vacuum. The silica gel supported metallocene catalyst prepared by the invention can be used for catalyzing ethylene-norbornene copolymerization reaction.
Description
Technical Field
The invention belongs to the technical field of macromolecules, and particularly relates to a silica gel supported metallocene catalyst, and a preparation method and application thereof.
Background
In the eighties of the twentieth century, Kaminsky professor, German scientist, discovered that zirconocene dichloride (Cp)2ZrCl2) The homogeneous catalysts with Methylaluminoxane (MAO) exhibit an extraordinarily high activity in the polymerization of ethylene (Sinn H, Kaminsky W, Vollmer K. living polymers on polymerization with ex-tremely producing Ziegler catalysts [ J ]]Angew Chem Int Ed, 1980, 19 (5): 390- & 392-), increasing interest has been drawn from the development and utilization of such metallocene catalysts. The metallocene catalyst is a catalyst system composed of a complex of a group IVB transition metal (such as Ti, Zr or Hf) as a main catalyst and alkylaluminoxane (such as MAO) or an organic boride (such as B (C6F5)3) as a cocatalyst. Although metallocene catalysts have the advantages of high activity, uniform composition of prepared polymers, narrow relative molecular mass distribution and the like, the problems of severe heat release during polymerization, difficulty in controlling the morphology of polymer particles, suitability for solution polymerization and the like still exist (Xujunting, phosphorus sealing first, metallocene catalyst loading research progress [ J]Petrochemical, 1998, 27 (7): 534-535.). Therefore, attempts have been made to prepare supported catalysts by supporting metallocene catalyst systems on a carrier, which can control the morphology and bulk density of the polymer well, and at the same time solve the problem of sticking to the kettle and reduce the amount of Methylaluminoxane (MAO). The most common inorganic carriers include silica gel, alumina, montmorillonite, magnesium chloride, molecular sieves, clay, and the like; a commonly used organic support is polystyrene based polymerization. Metallocene catalysts generally have the following advantages after loading: fixing the metal active center on the carrier improves the stability of the catalyst, reduces the dosage of methylaluminoxane, and can reduce the probability of bimolecular inactivation and beta hydrogen elimination in the polymerization reaction process, thereby improving the molecular weight of the obtained polymer and obtaining the polyolefin powder with regular shape and high apparent density. However, the metallocene catalyst may reduce the activity of the catalyst when supported, and may increase the types of active sites. Therefore, how to increase the activity of supported metallocene catalysts is currently one of the challenging problems.
Disclosure of Invention
The invention aims to provide a silica gel supported metallocene catalyst, and a preparation method and application thereof.
In order to achieve the above purpose, the solution of the invention is:
a silica gel supported metallocene catalyst is prepared by taking silica gel as a carrier, taking a metallocene complex as an active metal and taking aluminoxane and bis (pentafluorophenyl) zinc as a cocatalyst, wherein the silica gel carrier is prepared by combining a sol-gel method and a double-template method, and then carrying out reaming treatment on a double salt solution consisting of sodium chloride, lithium chloride and potassium chloride; the metallocene catalyst is Cp2MCl2、(Me5Cp)2MCl2、(RCp)2MCl2(R ═ Me, n-Bu) or Ind2MCl2One kind of (1).
Preferably, the silica gel carrier prepared by combining the sol-gel method and the double-template method comprises the following steps: adding a template agent P123 into an acid solution to prepare an acid solution containing P123, slowly adding trimethoxy silane while stirring, and then adding a sodium silicate aqueous solution to prepare a silicon source solution; adding an SA-20 template agent into the silicon source solution, uniformly stirring, performing microwave reaction to obtain silica gel, and drying to obtain powder; and carrying out low-temperature plasma treatment on the obtained powder to remove the template agent, thus generating the silica gel carrier in situ.
Preferably, the step of pore-expanding treatment of the silica gel carrier by a double salt solution composed of sodium chloride, lithium chloride and potassium chloride comprises: soaking a silica gel carrier into a double salt solution consisting of sodium chloride, lithium chloride and potassium chloride, mechanically stirring the obtained mixture, placing the mixture into an ultrasonic oscillator for ultrasonic impregnation, filtering, drying the obtained solid, roasting at constant temperature, cooling to room temperature, washing the roasted solid with deionized water until no chloride ion remains, and drying.
Preferably, the specific surface area of the silica gel carrier is 150-550 m2Between/g.
Preferably, the pore volume of the silica gel carrier is 1.2-3.8 cm3Between/g.
Preferably, the particle size of the silica gel carrier is between 30 and 200 mu m.
The preparation method of the silica gel supported metallocene catalyst comprises the following steps:
(1) putting the silica gel carrier into an oven for drying, and then adding the silica gel carrier into a reaction flask protected by dry nitrogen;
(2) adding Methylaluminoxane (MAO), zinc bis (pentafluorophenyl) and toluene into a reaction flask, carrying out ultrasonic oscillation on the obtained mixture, filtering, washing the obtained solid with toluene, and preparing a silica gel carrier loaded with the MAO and the zinc bis (pentafluorophenyl) into the reaction flask;
(3) and (3) adding the MAO prepared in the step (2) and the bis (pentafluorophenyl) zinc supported metallocene complex into toluene, carrying out ultrasonic oscillation on the obtained mixture, filtering, washing the obtained solid with toluene, and drying the obtained solid in vacuum to obtain the silica gel supported metallocene catalyst.
Preferably, the silica gel carrier is prepared by combining a sol-gel method with a double template agent method and then carrying out pore-expanding treatment on a double salt solution consisting of sodium chloride, lithium chloride and potassium chloride.
Preferably, the temperature of the ultrasonic oscillation is 30-50 ℃, and the time of the ultrasonic oscillation is 15-30 min.
The silica gel supported metallocene catalyst is applied to olefin polymerization.
Compared with the prior art, the principle and the gain effect of the invention are as follows:
1. the silica gel supported metallocene catalyst is prepared by combining a sol-gel method with a double template agent to prepare a silica gel carrier, and porous silica gel carrier particles with larger specific surface area, more uniform pore size and more uniform particle size distribution can be prepared by the double template agent method. In addition, the template agent in the prepared silica gel carrier is quickly and efficiently removed at a lower temperature by adopting plasma treatment in the preparation of the silica gel carrier, so that various problems (such as particle growth and agglomeration, collapse of a porous structure and the like) existing in the removal of the template agent through the traditional high-temperature sintering can be effectively avoided, and the stability of the prepared porous silica gel carrier is further improved. In addition, the silica gel carrier obtained after the pore expansion treatment of the selected silica gel carrier by a double salt solution consisting of sodium chloride, lithium chloride and potassium chloride has larger specific surface area and more uniform pore size and particle size distribution.
2. The silica gel supported metallocene catalyst provided by the invention has higher metal loading capacity, because compared with the traditional stirring reaction impregnation method, the ultrasonic oscillation impregnation method adopted by the preparation method of the catalyst provided by the invention not only improves the metal loading capacity, but also greatly shortens the impregnation time, and the preparation method of the catalyst also has the advantages of simple operation and mild conditions.
3. The silica gel loaded metallocene catalyst prepared by the invention can be used for catalyzing ethylene-norbornene copolymerization, and not only can improve the production efficiency of polymerization reaction, but also can improve the glass transition temperature of the obtained copolymer.
Detailed Description
The present invention will be described in further detail with reference to examples. It is also to be understood that the following examples are intended to illustrate the present invention and are not to be construed as limiting the scope of the invention, and that the particular materials, reaction times and temperatures, process parameters, etc. listed in the examples are exemplary only and are intended to be exemplary of suitable ranges, and that insubstantial modifications and adaptations of the invention by those skilled in the art in light of the foregoing description are intended to be within the scope of the invention.
All reagents were commercial reagents unless otherwise indicated and were not further purified prior to use. The specific surface area and pore volume test uses a 3H-2000PS2 model specific surface aperture detector of Bechard instruments; the particle size test uses a Beckmann Coulter LS 13320 XR laser diffraction particle size analyzer; the ICP-OES test used an ICP-OES plasmaQuant 9100 inductively coupled plasma spectrometer from Jena, Germany.
Example 1:
the preparation steps of the silica gel carrier are as follows: the preparation method of the silica gel carrier for loading the metallocene catalyst comprises the following steps: 5.0g of template P123 (polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer) was added to 110ml of a 1mol/L hydrochloric acid solution thermostatted at 50 deg.CUniformly stirring to obtain a hydrochloric acid solution containing P123; slowly adding 0.75g of phenyltrimethoxysilane into the prepared hydrochloric acid solution containing P123 under stirring, continuously stirring, and then adding 25g of sodium silicate aqueous solution with the mass concentration of 40% to prepare silicon source solution; adding 5g of template agent peregal SA-20 (fatty alcohol polyoxyethylene (20) ether) into the silicon source solution prepared in the step (1), uniformly stirring to prepare hydrated silica gel, transferring the obtained gel into a microwave reaction tank for thermal aging, and carrying out microwave reaction for 3 hours at the microwave power of 350W and the temperature of 85 ℃; cooling and filtering the obtained product, washing the obtained solid to be neutral by using ethanol/water (detecting by using a silver nitrate solution until no chloride ion exists), drying, preparing the dried solid into powder, transferring the powder into a Dielectric Barrier Discharge (DBD) device for low-temperature plasma treatment to remove the template agent, treating for 5 hours under the conditions of 200 ℃ of temperature, 220V of voltage and 3.5A of current in oxygen atmosphere, and naturally cooling to room temperature to obtain the silica gel carrier of the template agent; finally, the silica gel support obtained is impregnated with 250ml of a double salt solution consisting of sodium chloride, lithium chloride and potassium chloride (NaCl, LiCl and KCl with water in a mass ratio H)2NaCl, LiCl and KCl (70: 20:5:5), mechanically stirring the obtained mixture, placing the mixture into an ultrasonic oscillator, ultrasonically dipping the mixture for 30min at 40 ℃, filtering the mixture, drying the obtained solid, roasting the solid at the constant temperature of 800 ℃ for 2h, cooling the solid to room temperature, washing the roasted solid by deionized water until no chloride ion remains, and then drying the solid; and adding the dried solid into 300ml of hydrochloric acid solution with the mass concentration of 10%, placing the solution into an ultrasonic oscillator, performing ultrasonic impregnation at 80 ℃ for 40min, filtering, washing the obtained solid with deionized water until no chloride ion remains, and drying to obtain the silica gel carrier for the olefin polymerization metallocene catalyst. The obtained silica gel is characterized, and the test results of the specific surface area and the pore volume are 521cm respectively2G and 2.10cm3(ii)/g; results of particle size analysis test: the average particle size was 194.26 μm.
Example 2:
all operations were carried out under nitrogen protection, and the metallocene catalyst was prepared as follows:
(1) 2g of the silica gel prepared in example 1 were dried in an oven at 110 ℃ for 5 hours and then added to a reaction flask protected with dry nitrogen;
(2) adding 10mmol of Methylaluminoxane (MAO), zinc bis (pentafluorophenyl) and 60ml of toluene into a reaction flask, then transferring the reaction flask into an ultrasonic reactor, carrying out ultrasonic oscillation at 30 ℃ for 30min, filtering, washing the obtained solid with 25ml of toluene, and repeatedly washing for at least 3 times to obtain a MAO-supported silica gel carrier;
(3) the MAO-supported silica gel support prepared in step (2) and 0.1g of metallocene complex Cp2ZrCl2Adding the metallocene catalyst into 60ml of toluene, then transferring a reaction flask into an ultrasonic reactor, carrying out ultrasonic oscillation at 30 ℃ for 30min, filtering, washing the obtained solid with 25ml of toluene, repeatedly washing for at least 3 times, and drying the obtained solid in vacuum to obtain the metallocene catalyst. ICP-OES detection is carried out on the prepared catalyst, active metal components loaded on the catalyst are inspected, and the detection results are as follows: the metallocene catalyst prepared by the ultrasonic impregnation method has the metal Zr loading of 4.09% and the metal Al loading of 10.91%.
(4) The procedure for the catalytic ethylene-norbornene copolymerization was as follows (all operations were carried out under nitrogen protection):
connecting a three-neck polymerization bottle with an ethylene conduit and a vacuum conduit, replacing the three times with high-purity nitrogen, adding 1g of the metallocene catalyst prepared in the step (3) and 20mg of MAO into the polymerization bottle, sequentially injecting 30ml of toluene and 3.2g of norbornene, heating the system to 35 ℃ after stirring, injecting ethylene until the system pressure is 0.2MPa, keeping the temperature and the pressure of the reaction system constant, maintaining the polymerization reaction for 1 hour, cooling, pouring the reaction liquid into 200ml of acidified ethanol solution (hydrochloric acid/ethanol ═ 1/10) with the mass concentration of 10 percent to terminate the reaction, filtering, sequentially washing the product with 40ml of deionized water and 40ml of absolute ethanol to obtain a polymer, finally placing the polymer in a vacuum drying oven at the temperature of 60 ℃ to constant weight to obtain an ethylene-norbornene copolymer, weighing and calculating the activity, as a result, 6.3g of a copolymer was obtained. The ethylene-norbornene copolymer obtained was characterized under the following specific conditions: molecular weight of ethylene-norbornene copolymer gel permeation chromatography model Waters 1515/2414 was usedMeasuring by an instrument: weighing 10mg of polymer, adding 10mL of trichlorobenzene solution into trichlorobenzene as a solvent, dissolving the trichlorobenzene solution in a shaking machine at 150 ℃, preparing a sample, filtering the sample by using a filter disc, putting the filtered sample into a sample bottle for detection, and analyzing the sample according to a standard polyethylene sample calibration curve K which is 5.90 multiplied by 10–2cm3G, alpha is 0.69; the glass softening temperature Tm is determined by means of DSC-Q200 from TA Instruments, USA. The reaction result is: the polymerization activity was 3.7(kg/[ Zr (mol). h)]) (ii) a The molecular weight of the resulting copolymer was 24.31 (10)4g/mol); the Tm of the resulting copolymer product was 162.4 ℃.
Example 3
The silica gel carrier was prepared as in example 1; preparation of the catalyst with reference to example 2, except that in step (3), Cp2ZrCl2Is changed to (Me)5Cp)2ZrCl2，(Me5Cp)2ZrCl2The amount of the catalyst to be used was 1.5g, and the prepared catalyst was subjected to ICP-OES detection under the same conditions, and the active metal component supported on the catalyst was examined, with the following results: the supported amount of Zr metal in the obtained metallocene catalyst was 4.02%, and the supported amount of Al metal was 10.72%.
The conditions for catalyzing the copolymerization of ethylene-norbornene were the same as in example 2, and the reaction results were: the polymerization activity was 3.3(kg/[ Zr (mol). h)]) (ii) a The molecular weight of the resulting copolymer was 24.25 (10)4g/mol); the Tm of the resulting copolymer product was 160.7 ℃.
Example 4
The silica gel carrier was prepared as in example 1; preparation of the catalyst with reference to example 2, except that in step (3), Cp2ZrCl2Switched to (n-BuCp)2ZrCl2，(n-BuCp)2ZrCl2The amount of the catalyst to be used was 1.4g, and the prepared catalyst was subjected to ICP-OES detection under the same conditions, and the active metal component supported on the catalyst was examined, with the following results: the loading of metal Zr and the loading of metal Al in the obtained metallocene catalyst are respectively 4.06% and 10.85%.
The conditions for catalyzing the copolymerization of ethylene-norbornene were the same as in example 2, and the reaction results were: the polymerization activity was 3.9(kg/[ Zr (mol).)h]) (ii) a The molecular weight of the resulting copolymer was 24.34 (10)4g/mol); the Tm of the resulting copolymer product was 159.3 ℃.
Comparative example 1
The silica gel carrier was prepared as in example 1; the catalyst was prepared by referring to example 1 except that the ultrasonic vibration in step (2) was adjusted to conventional mechanical stirring, i.e., stirring at 35 ℃ for 5 hours for the reaction, and the other conditions were the same. ICP-OES detection is carried out on the prepared catalyst, active metal components loaded on the catalyst are inspected, and the detection result is as follows: the supported amount of Zr metal in the obtained metallocene catalyst was 3.34%, and the supported amount of Al metal was 8.28%. The preparation conditions of the catalyst and the conditions for catalyzing the copolymerization of ethylene-norbornene were the same as in example 2, and the reaction results were: the polymerization activity was 2.9(kg/[ Zr (mol). h)]) (ii) a The molecular weight of the resulting copolymer was 20.16 (10)4g/mol); the Tm of the resulting copolymer product was 136.3 ℃.
Comparative example 2
The catalyst was prepared by referring to example 2 except that the silica gel carrier used in the step (1) was changed to ordinary commercially available 955 silica gel powder and the other conditions were the same. ICP-OES detection is carried out on the prepared catalyst, active metal components loaded on the catalyst are inspected, and the detection results are as follows: the supported amount of Zr metal in the obtained metallocene catalyst was 3.11%, and the supported amount of Al metal was 7.58%. The preparation conditions of the catalyst and the conditions for catalyzing the copolymerization of ethylene-norbornene were the same as in example 2, and the reaction results were: the polymerization activity was 2.1(kg/[ Zr (mol). h)]) (ii) a The molecular weight of the resulting copolymer was 11.34 (10)4g/mol); the Tm of the resulting copolymer product was 113.4 ℃.
Claims (10)
1. A silica gel supported metallocene catalyst, characterized in that: the catalyst takes silica gel as a carrier, a metallocene complex as an active metal and aluminoxane and bis (pentafluorophenyl) zinc as a cocatalyst, wherein the silica gel carrier is prepared by combining a sol-gel method and a double-template method and then is subjected to reaming treatment by a double-salt solution consisting of sodium chloride, lithium chloride and potassium chloride; the metallocene catalyst is Cp2MCl2、(Me5Cp)2MCl2、(RCp)2MCl2(R ═ Me, n-Bu) or Ind2MCl2One kind of (1).
2. The silica gel supported metallocene catalyst according to claim 1, wherein the silica gel support is prepared by a sol-gel method combined with a double template method, and the method comprises the following steps: adding a template agent P123 into an acid solution to prepare an acid solution containing P123, slowly adding trimethoxy silane while stirring, and then adding a sodium silicate aqueous solution to prepare a silicon source solution; adding an SA-20 template agent into the silicon source solution, uniformly stirring, performing microwave reaction to obtain silica gel, and drying to obtain powder; and carrying out low-temperature plasma treatment on the obtained powder to remove the template agent, thus generating the silica gel carrier in situ.
3. The silica gel supported metallocene catalyst according to claim 1, wherein the silica gel carrier is subjected to pore expansion treatment by a double salt solution consisting of sodium chloride, lithium chloride and potassium chloride, and the pore expansion treatment comprises the following steps: soaking a silica gel carrier into a double salt solution consisting of sodium chloride, lithium chloride and potassium chloride, mechanically stirring the obtained mixture, placing the mixture into an ultrasonic oscillator for ultrasonic impregnation, filtering, drying the obtained solid, roasting at constant temperature, cooling to room temperature, washing the roasted solid with deionized water until no chloride ion remains, and drying.
4. The silica gel-supported metallocene catalyst according to claim 1, characterized in that: the specific surface area of the silica gel carrier is 150-550 m2Between/g.
5. The silica gel-supported metallocene catalyst according to claim 1, characterized in that: the pore volume of the silica gel carrier is 1.2-3.8 cm3Between/g.
6. The silica gel-supported metallocene catalyst according to claim 1, characterized in that: the particle size of the silica gel carrier is 30-200 mu m.
7. The method of preparing a silica gel supported metallocene catalyst according to claim 1, comprising the steps of:
(1) putting the silica gel carrier into an oven for drying, and then adding the silica gel carrier into a reaction flask protected by dry nitrogen;
(2) adding Methylaluminoxane (MAO), zinc bis (pentafluorophenyl) and toluene into a reaction flask, carrying out ultrasonic oscillation on the obtained mixture, filtering, washing the obtained solid with toluene, and preparing a silica gel carrier loaded with the MAO and the zinc bis (pentafluorophenyl) into the reaction flask;
(3) and (3) adding the MAO prepared in the step (2) and the bis (pentafluorophenyl) zinc supported metallocene complex into toluene, carrying out ultrasonic oscillation on the obtained mixture, filtering, washing the obtained solid with toluene, and drying the obtained solid in vacuum to obtain the silica gel supported metallocene catalyst.
8. The preparation method of the supported metallocene catalyst according to claim 7, wherein the silica gel carrier is prepared by combining a sol-gel method with a double template agent method and then carrying out pore-expanding treatment on the silica gel carrier by using a double salt solution consisting of sodium chloride, lithium chloride and potassium chloride.
9. The method for preparing the supported metallocene catalyst according to claim 7, wherein the temperature of the ultrasonic oscillation is 30 to 50 ℃ and the time of the ultrasonic oscillation is 15 to 30 min.
10. Use of the silica gel supported metallocene catalyst according to claim 1 or the silica gel supported metallocene catalyst prepared by the preparation method according to any one of claim 7 in olefin polymerization.
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| CN113278097B (en) | 2023-03-17 |
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