CN113354759B - Preparation method of silica gel carrier for olefin polymerization metallocene catalyst - Google Patents

Preparation method of silica gel carrier for olefin polymerization metallocene catalyst Download PDF

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CN113354759B
CN113354759B CN202110608446.2A CN202110608446A CN113354759B CN 113354759 B CN113354759 B CN 113354759B CN 202110608446 A CN202110608446 A CN 202110608446A CN 113354759 B CN113354759 B CN 113354759B
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silica gel
olefin polymerization
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ultrasonic
gel carrier
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CN113354759A (en
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彭晓琪
杜刚
彭彦博
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Shanghai Tingjin Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention discloses a preparation method of a silica gel carrier for an olefin polymerization metallocene catalyst, which comprises the following steps: adding a template agent P123 into an acid solution, then sequentially and slowly adding organosilane into the acid solution and then adding a sodium silicate aqueous solution to prepare a silicon source solution; adding a template agent SA-20 into the silicon source solution, uniformly stirring, performing microwave reaction to obtain silica gel, and drying the silica gel to obtain powder; and roasting the obtained powder to remove the template agent, and finally performing hole expansion treatment by using the mixed salt solution. The prepared silica gel is used as a carrier, the metallocene complex is used as an active metal, and the aluminoxane is used as a cocatalyst to prepare a metal catalyst for olefin polymerization; the prepared catalyst can be used for olefin polymerization. The silica gel carrier prepared by the double-template method has the advantages of larger specific surface area, pore size and particle size after being subjected to hole expansion treatment by using a mixed salt solution consisting of sodium chloride, lithium chloride and potassium chloride.

Description

Preparation method of silica gel carrier for olefin polymerization metallocene catalyst
Technical Field
The invention belongs to the technical field of macromolecules, and particularly relates to a preparation method of a silica gel carrier for an olefin polymerization metallocene catalyst.
Background
In the industrial production of polyolefins, in order to meet the production requirements of gas-phase fluidized beds, metallocene catalysts are generally used in a supported type, that is, an active metallocene catalyst is supported on a carrier (research on the supporting of metallocene catalysts in Putengen, wangshihua, lirui. Progress [ J ] synthetic resins and plastics, 2018, 35 (1): 76-80.). Currently, the most commonly used inorganic carriers are silica gel, alumina, montmorillonite, magnesium chloride, molecular sieves, clay, and the like; wherein, the silica gel is the preferred carrier for loading the olefin polymerization metallocene catalyst due to the advantages of stable chemical property, good acid resistance, good wear resistance, good fluidity, high melting point, low price and the like. Although the research on silica gel has been carried out for hundreds of years, because many influencing factors exist in the preparation process, and the technology is strictly kept secret in various countries, so far, no system report on how to adjust the pore structure of a silica gel product exists, so that how to prepare silica gel carrier particles with larger specific surface area and particle size is still one of the challenging problems. Therefore, it is very necessary to develop a method for preparing a silica gel carrier which is easy to handle and can be suitably used for supporting an olefin polymerization metallocene catalyst.
Disclosure of Invention
The invention aims to provide a preparation method of a silica gel carrier for an olefin polymerization metallocene catalyst.
In order to achieve the above purpose, the solution of the invention is:
a preparation method of a silica gel carrier for an olefin polymerization metallocene catalyst comprises the following steps:
(1) Adding a template agent P123 into a hydrochloric acid solution at a constant temperature, and uniformly stirring to obtain a hydrochloric acid solution containing P123;
(2) Slowly adding silane into the hydrochloric acid solution containing P123 prepared in the step (1) under stirring, continuously stirring, and then adding a sodium silicate aqueous solution to prepare a silicon source solution;
(3) Adding a template agent SA-20 into the silicon source solution prepared in the step (2), uniformly stirring to prepare hydrated silicon gel, and transferring the obtained gel into a microwave reaction tank for microwave heat aging;
(4) Cooling and filtering the product obtained in the step (3), washing the obtained solid to be neutral by using ethanol/water, drying, preparing the dried solid into powder, and roasting to remove the template agent;
(5) Dipping the silica gel carrier obtained in the step (4) into a mixed salt solution consisting of NaCl, liCl and KCl, mechanically stirring the obtained mixture, putting the mechanically stirred mixture into an ultrasonic oscillator for ultrasonic dipping, 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;
(6) And (4) adding the dried solid obtained in the step (5) into a hydrochloric acid solution for ultrasonic impregnation, washing with deionized water after filtration until no chloride ion residue exists, and drying to obtain the silica gel carrier for the olefin polymerization metallocene catalyst.
Preferably, the temperature of the hydrochloric acid solution thermostatted in step (1) is 50 ℃.
Preferably, the silane described in step (2) is phenyltrimethoxysilane.
Preferably, the conditions of microwave thermal aging in step (3) are: the microwave power is 350W, the temperature is 85 ℃, and the microwave reaction time is 2.5h.
Preferably, the roasting temperature in the step (4) is 650 ℃, and the roasting time is 12h.
Preferably, the ultrasonic dipping conditions in step (5) are: the ultrasonic immersion temperature is 40 ℃, and the ultrasonic immersion time is 30min.
Preferably, the mixed salt solution composed of NaCl, liCl and KCl in the step (5) is H in mass ratio 2 O:NaCl:LiCl:KCl＝70:20:5:5。
Preferably, the constant-temperature roasting temperature in the step (5) is 800 ℃, and the constant-temperature roasting time is 2 hours.
Preferably, the ultrasonic dipping conditions in the step (6) are as follows: the ultrasonic immersion temperature is 80 ℃, and the ultrasonic immersion time is 40min.
Compared with the prior art, the principle and the gain effect of the invention are as follows:
1. the silica gel carrier for the olefin polymerization catalyst is prepared by combining a sol-gel method with a double template agent, and the silica gel carrier prepared by the double template agent method has larger specific surface area and particle size after being subjected to hole expansion treatment by a mixed salt solution consisting of sodium chloride, lithium chloride and potassium chloride.
2. Compared with the traditional heating mode, the microwave heating can improve the reaction kinetics so as to rapidly and uniformly heat the gel in the aging process, improve the reaction rate, promote the formation of uniform nucleation centers, greatly shorten the time required by gel aging, reduce the time cost, and have the advantages of energy conservation, environmental protection and the like.
3. According to the preparation method of the silica gel carrier, the mixed salt solution composed of NaCl, liCl and KCl is used for carrying out reaming treatment on the silica gel carrier, and then hydrochloric acid is used for carrying out ultrasonic impregnation so that the hydroxyl on the surface of the silica gel is recovered; thus, the specific surface area and the particle size of the prepared silica gel carrier can be successfully improved.
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 specific surface aperture detector of Beschard instruments; the particle size test uses a Beckmann Coulter LS 13 XR laser diffraction particle size analyzer; high temperature 13 C-NMR measurement A Nuclear Magnetic Resonance (NMR) instrument used was of the Bruker Asend TM-600 type; the ultrasonic oscillator used was an ultrasonic oscillator SW-D900S-27 produced by avio of Japan and having a power of 500W.
Example 1:
the preparation method of the silica gel carrier for the olefin polymerization metallocene catalyst comprises the following steps:
(1) Adding 1.0g of template agent P123 (polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer) into 35ml of hydrochloric acid solution with the molar concentration of 1mol/L and keeping the temperature at 50 ℃, and uniformly stirring to prepare hydrochloric acid solution containing P123;
(2) Slowly adding 0.15g of phenyltrimethoxysilane into the hydrochloric acid solution containing the P123 prepared in the step (1) under stirring, continuously stirring, and then adding 5g of sodium silicate aqueous solution with the mass concentration of 40% to prepare silicon source solution;
(3) Adding 1g of template agent peregal SA-20 (fatty alcohol polyoxyethylene (20) ether) into the silicon source solution prepared in the step (2), 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 2 hours at the microwave power of 350W and the temperature of 85 ℃;
(4) Cooling and filtering the product obtained in the step (3), washing the obtained solid with ethanol/water to be neutral (detected by silver nitrate solution until no chloride ion exists), drying, preparing the dried solid into powder, and roasting in a muffle furnace at 650 ℃ for 12 hours to obtain a silica gel carrier of the demoulding agent;
(5) Soaking the silica gel carrier obtained in the step (4) into a mixed salt solution (NaCl, liCl, KCl and water in a mass ratio of H) consisting of sodium chloride, lithium chloride and potassium chloride 2 NaCl, liCl and KCl = 70), 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 with deionized water until no chloride ion remains, and then drying the solid;
(6) And (3) adding the dried solid in the step (5) into 100ml 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 silica gel carrier for the olefin polymerization catalyst. The obtained silica gel is characterized, and the test results of the specific surface area and the pore volume are respectively 516cm 2 G and 2.07cm 3 (ii)/g; results of particle size analysis test: the average particle size was 187.05. Mu.m.
Example 2
The preparation steps of the catalyst for olefin polymerization are as follows:
all operations are carried out under the protection of nitrogen,
(1) 1g of the silica gel prepared in example 1 was dried in an oven at 110 ℃ for 4 hours and then added to a reaction flask protected with dry nitrogen;
(2) Adding 5mmol of Methylaluminoxane (MAO) and 30ml of toluene into a reaction flask, stirring at 50 ℃ for 2 hours, filtering, washing the obtained solid with 15ml of toluene, and repeatedly washing for at least 3 times to obtain a MAO-supported silica gel carrier;
(3) MAO Supported silica support prepared in step (2) and 0.05g of metallocene Complex Me 2 SiCp 2 ZrCl 2 Added to 30ml of toluene and stirred at a temperature of 50 ℃ for 2h. And (3) after filtering, washing the obtained solid by using 15ml of toluene, repeatedly washing for at least 3 times, and drying the obtained solid in vacuum to obtain the catalyst for olefin polymerization.
Example 3
The steps of the catalytic ethylene-norbornene copolymerization are as follows:
all the operations are carried out under the protection of nitrogen, a 1L stainless steel polymerization kettle is replaced by high-purity nitrogen for no less than three times, then 60ml of toluene, 0.94g of norbornene, 0.58g of MAO and 0.02g of the catalyst for olefin polymerization prepared in the example 2 are sequentially added into the polymerization kettle, the system temperature is raised to 60 ℃ after stirring is started, ethylene is injected until the system pressure is 1.2MPa, the temperature and the pressure of the reaction system are kept constant, the temperature is reduced after the polymerization reaction is maintained for 3 hours, the reaction liquid is poured into 100ml of acidified ethanol solution with the mass concentration of 10% (hydrochloric acid/ethanol = 1/10) to terminate the reaction, the obtained copolymerization product is sequentially washed by 30ml of deionized water and 30ml of absolute ethanol after filtration, and finally the copolymerization product is placed in a vacuum drying oven at 60 ℃ and dried to constant weight to obtain the ethylene-norbornene copolymer; the specific conditions for characterizing the resulting ethylene-norbornene copolymer are as follows: DSC of the copolymer is measured on a SHIMADZU DSC-50, and the temperature rising speed is 20 ℃/min; high temperature 13 C-NMR: 50mg of the copolymer is dissolved in deuterated 1, 2-tetrachloroethane as a solvent, and the insertion rate of the bornylene monomer is tested at 100 ℃. The reaction result is: polymerization Activity 78.64 (gCopolymer: gcat) -1 h -1 ) (ii) a The insertion rate of the bornylene in the obtained copolymer is 48.3 percent; the glass transition temperature Tg of the copolymer obtained was 153 ℃.
Comparative example 1
Preparation of silica gel carrier referring to example 1, except that the silicon source solution obtained in step (2) was directly subjected to gel aging without using the template SA-20 in step (3): other conditions are the same. Characterization of the silica gel preparedSpecific surface area and pore volume of 431cm respectively 2 G and 1.37cm 3 (ii)/g; results of particle size analysis test: the average particle size was 133.29. Mu.m.
The obtained support was used for the preparation of an olefin polymerization catalyst according to the procedure of example 2, and the obtained olefin polymerization catalyst was used for the copolymerization of ethylene-norbornene according to the procedure of example 3, and the reaction results were: polymerization activity was 56.71 (gCopolymer: gcat) -1 h -1 ) (ii) a The insertion rate of the bornylene in the obtained copolymer is 41.5 percent; the glass transition temperature Tg of the resulting copolymer was 143 ℃.
Comparative example 2
Preparation of silica gel support referring to example 1, except that no templating agent P123 was used, step (1) and step (2) were combined and adjusted to: slowly adding 0.15g of phenyltrimethoxysilane into 35ml of hydrochloric acid solution with the molar concentration of 1mol/L under stirring, continuing stirring, and then adding 5g of sodium silicate aqueous solution with the mass concentration of 40% to prepare silicon source solution; other conditions are the same. The prepared silica gel is characterized, and the specific surface area and the pore volume are respectively 424cm 2 G and 1.21cm 3 (ii)/g; results of particle size analysis test: the average particle size was 120.83. Mu.m.
The obtained support was used for the preparation of an olefin polymerization catalyst according to the procedure in example 2, and the obtained olefin polymerization catalyst was used for the copolymerization polymerization of ethylene-norbornene according to the procedure in example 3, with the results that: the polymerization activity was 51.02 (gCopolymer: gcat) -1 h -1 ) (ii) a The insertion rate of the bornylene in the obtained copolymer is 40.9 percent; the glass transition temperature Tg of the copolymer obtained is 140 ℃.
Comparative example 3
Preparation of silica gel Carrier reference is made to example 1, except that the reaction conditions in step (5) "put into an ultrasonic oscillator for ultrasonic immersion at 40 ℃ for 30min" are changed to "stirring at 40 ℃ is continued for 6 hours", and the other conditions are the same. The prepared silica gel is characterized, and the specific surface area and the pore volume are respectively 509cm 2 G and 1.97cm 3 (ii)/g; results of particle size analysis test: the average particle size was 181.29. Mu.m.
Reference examples2 the obtained support was used for the preparation of an olefin polymerization catalyst, and the obtained olefin polymerization catalyst was used for the copolymerization of ethylene-norbornene according to the procedure in example 3, with the results that: polymerization activity was 75.91 (gCopolymer: gcat) -1 h -1 ) (ii) a The insertion rate of the bornylene in the obtained copolymer is 46.2%; the glass transition temperature Tg of the copolymer obtained was 151 ℃.
Comparative example 4
Preparation of silica gel carrier referring to example 1, except that the step (5) mixed salt treatment and the step (6) were not performed, the other conditions were the same. The prepared silica gel is characterized, and the specific surface area and the pore volume are 271cm respectively 2 G and 1.05cm 3 (iv) g; results of particle size analysis testing: the average particle size was 95.84. Mu.m.
The obtained support was used for the preparation of an olefin polymerization catalyst according to the procedure in example 2, and the obtained olefin polymerization catalyst was used for the copolymerization of ethylene-norbornene according to the procedure in example 3, with the results that: polymerization Activity 42.16 (gCopolymer: gcat) -1 h -1 ) (ii) a The insertion rate of the bornylene in the obtained copolymer is 33.6 percent; the glass transition temperature Tg of the copolymer obtained was 129 ℃.
From the results of the above examples and comparative examples, it can be seen that: the silica gel carrier for the olefin polymerization catalyst is prepared by combining a sol-gel method with a double template agent, and porous silica gel carrier particles with larger specific surface area and particle size distribution can be prepared by carrying out pore-enlarging treatment on the silica gel carrier prepared by the double template agent method through a mixed salt solution consisting of sodium chloride, lithium chloride and potassium chloride.

Claims (5)

1. A preparation method of a silica gel carrier for an olefin polymerization metallocene catalyst is characterized by comprising the following steps:
(1) Adding a template agent P123 into a hydrochloric acid solution at a constant temperature, and uniformly stirring to obtain a hydrochloric acid solution containing P123;
(2) Slowly adding silane into the hydrochloric acid solution containing P123 prepared in the step (1) under stirring, continuously stirring, and then adding a sodium silicate aqueous solution to prepare a silicon source solution;
(3) Adding a template agent SA-20 into the silicon source solution prepared in the step (2), uniformly stirring to prepare hydrated silicon gel, and transferring the obtained gel into a microwave reaction tank for microwave heat aging; wherein the microwave heat aging conditions are as follows: the microwave power is 350W, the temperature is 85 ℃, and the microwave reaction time is 2.5h;
(4) Cooling and filtering the product obtained in the step (3), washing the obtained solid to be neutral by using ethanol/water, drying, preparing the dried solid into powder, and roasting to remove the template agent;
(5) Dipping the silica gel carrier obtained in the step (4) into a mixed salt solution composed of NaCl, liCl and KCl, mechanically stirring the obtained mixture, putting the mixture into an ultrasonic oscillator for ultrasonic dipping, 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; the ultrasonic impregnation conditions are as follows: the ultrasonic dipping temperature is 40 ℃, and the ultrasonic dipping time is 30min; h is added into the mixed salt solution composed of NaCl, liCl and KCl according to the mass ratio 2 O:NaCl:LiCl:KCl＝70:20:5:5；
(6) Adding the dried solid in the step (5) into a hydrochloric acid solution for ultrasonic impregnation, filtering, washing with deionized water until no chloride ion remains, and drying to obtain the silica gel carrier for the olefin polymerization metallocene catalyst; wherein the ultrasonic impregnation conditions are as follows: the ultrasonic dipping temperature is 80 ℃, and the ultrasonic dipping time is 40min;
the prepared silica gel carrier is used for preparing an olefin polymerization catalyst, and the steps are as follows: all the operations are carried out under the protection of nitrogen, 1g of the obtained silica gel is put into an oven at 110 ℃ for drying for 4 hours and then is added into a reaction flask protected by dry nitrogen; adding 5mmol of Methylaluminoxane (MAO) and 30ml of toluene into a reaction flask, stirring at 50 ℃ for 2 hours, filtering, washing the obtained solid with 15ml of toluene, and repeatedly washing for at least 3 times to obtain a MAO-supported silica gel carrier; to the prepared MAO-supported silica gel support and 0.05g of metallocene complex Me 2 SiCp 2 ZrCl 2 Adding to 30ml of toluene and stirring at 50 ℃ for 2h, filtering and usingAnd washing the obtained solid by 15ml of toluene, repeating the washing for at least 3 times, and drying the obtained solid in vacuum to prepare the catalyst for olefin polymerization.
2. The method for preparing a silica gel support for an olefin polymerization metallocene catalyst according to claim 1, wherein the temperature of the hydrochloric acid solution having the constant temperature in the step (1) is 50 ℃.
3. The method of claim 1, wherein the silane of step (2) is phenyltrimethoxysilane.
4. The method of claim 1, wherein the calcination temperature in the step (4) is 650 ℃ and the calcination time is 12 hours.
5. The method for preparing a silica gel carrier for a metallocene catalyst for olefin polymerization according to claim 1, wherein the isothermal calcination temperature in the step (5) is 800 ℃ and the isothermal calcination time is 2 hours.
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WO2003064322A1 (en) * 2002-01-29 2003-08-07 Imperial Chemical Industries Plc Silica materials with meso- and macropores
CN101423575A (en) * 2007-10-31 2009-05-06 中国石油化工股份有限公司 Supported metallocene catalyst component and preparation method thereof and use

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Publication number Priority date Publication date Assignee Title
EP0399148A2 (en) * 1989-02-27 1990-11-28 Mitsubishi Rayon Co., Ltd. Process for producing metal oxide-based polycondensation powders
WO2003064322A1 (en) * 2002-01-29 2003-08-07 Imperial Chemical Industries Plc Silica materials with meso- and macropores
CN101423575A (en) * 2007-10-31 2009-05-06 中国石油化工股份有限公司 Supported metallocene catalyst component and preparation method thereof and use

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