CN115894748B - Composite precipitating agent for precipitating magnesium chloride solution as well as preparation method and application thereof - Google Patents
Composite precipitating agent for precipitating magnesium chloride solution as well as preparation method and application thereof Download PDFInfo
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- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 title claims abstract description 147
- 229910001629 magnesium chloride Inorganic materials 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 41
- 230000001376 precipitating effect Effects 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 73
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 34
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 30
- 238000001556 precipitation Methods 0.000 claims abstract description 27
- -1 polyethylene Polymers 0.000 claims abstract description 22
- 239000004698 Polyethylene Substances 0.000 claims abstract description 14
- 229920000573 polyethylene Polymers 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000002002 slurry Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 3
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 4
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical group CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 4
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 36
- 229920013716 polyethylene resin Polymers 0.000 abstract description 24
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000004458 analytical method Methods 0.000 description 17
- 229910052782 aluminium Inorganic materials 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000002539 nanocarrier Substances 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012802 nanoclay Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a composite precipitating agent for precipitating magnesium chloride solution, and a preparation method and application thereof, and belongs to the technical field of high polymer materials. The composite precipitating agent comprises carbon nano tubes, a solvent and chloralkylaluminum. The application of the composite separating agent comprises the following steps: (1) Placing magnesium chloride into a container, adding normal hexane, heating and stirring; (2) further adding an alcohol; (3) Dropwise adding the magnesium chloride carrier solution into the composite separating out agent; (4) adding a titanium compound; (5) Stopping stirring, standing the slurry, adding a hydrocarbon solvent to wash and dry the catalyst particles after the slurry is layered. The composite precipitating agent provided by the invention has the advantages that the precipitating rate of the carrier is low, the uniformity and regularity of the obtained carrier are good, and meanwhile, the invention provides a simple and convenient preparation method; the magnesium chloride carrier type polyethylene catalyst prepared by the composite precipitation agent has good polymerization performance, and the obtained polyethylene resin particles are uniformly distributed.
Description
Technical Field
The invention relates to a composite precipitating agent for precipitating magnesium chloride solution, and a preparation method and application thereof, and belongs to the technical field of high polymer materials.
Background
Polyethylene is widely used in various fields with its excellent properties, and China has become a large country for polyethylene production and consumption. In the polyolefin production technology, catalyst technology is still the core of the polyethylene industry and mainly comprises Ziegler-Natta catalysts, chromium-based catalysts, metallocene catalysts, transition metal catalysts and the like. The catalysts for polyethylene resin production in the industry at present mainly comprise Ziegler-Natta catalysts and chromium catalysts, and the development of the catalysts for polyethylene resin with excellent performance is a focus of attention in the industry.
Among the numerous polyolefin catalysts, supported catalysts have found wide application due to their own advantages and good device applicability. Among these catalysts supported on magnesium chloride are one of the most widely used types.
In general, the magnesium chloride carrier cannot be directly used for the preparation of the catalyst, and must be activated to convert the crystal form into a crystal form suitable for the preparation of the catalyst, which would otherwise affect the polymerization characteristics, particle state, etc. of the catalyst. When the carrier is activated, a chemical activation method is a common method, and the common method is to put magnesium chloride into a solution containing an alcohol component, dissolve the magnesium chloride, and then add a component capable of precipitating the magnesium chloride to precipitate the magnesium chloride from the solution, so that the conversion of the crystal form can be completed.
In the prior art, titanium tetrachloride, titanate, aluminum alkyl and other substances can be used for selecting the separating agent, and the required catalyst can be obtained after active components are loaded by controlling the separated carrier particles. In the above scheme, after the carrier crystal forms are transformed, the shape of the formed particles directly affects the performance of the catalyst and the morphology of the polymer, and the catalyst particles can be controlled by optimizing stirring, reaction conditions and the like, and grinding and the like, so that equipment is basically increased or control difficulty is increased.
CN201310211103 relates to a nano-carrier catalyst for producing reinforced polyethylene, a preparation method and application thereof, and nano-clay or modified nano-clay is used as a first component of nano-carrier; the carbon nano tube or the modified carbon nano tube is used as a second component of the nano carrier; the reactive magnesium chloride system or the silicon dioxide system is used as a third component of the nano-carrier and is used for fully compounding the two components to form carrier particles with a certain shape; loading carbon tetrachloride on the obtained nano composite carrier to obtain a nano carrier catalyst; the reactive magnesium chloride system consists of anhydrous magnesium chloride and an electron donor solvent, and then the electron donor solvent is removed through subsequent treatment, so as to obtain the active magnesium chloride. The technology mainly uses a nano material as a carrier of an olefin polymerization catalyst, loads an olefin polymerization active center between nano surfaces or sheets, and carries out in-situ olefin polymerization reaction to obtain the multidimensional nano reinforced polyethylene-based composite material. When the magnesium chloride electron donor solvent is removed, the main function of the separating agent is titanium tetrachloride. The TEA used for treating the nano composite carrier has the main function of removing impurities on the carrier, thus being beneficial to improving the activity of in-situ polymerization reaction. The preparation method has the advantages that the clay and the rod-shaped carbon nano tube in the lamellar can be uniformly dispersed in the composite material obtained by olefin polymerization, the strength and the toughness of the composite material are enhanced, the mutual dispersion of the components is more uniform, and the particle control technology of the magnesium chloride carrier is not involved.
CN102731693 provides a polyolefin catalyst with carbon nanotubes as carrier and a preparation method thereof. The carbon nano tube supported polyolefin catalyst provided by the invention comprises the following components: a carbon nanotube catalyst support, a transition metal compound, and a metal compound; wherein the carbon nanotube catalyst carrier consists of spherical carbon nanotubes; the transition metal compound is selected from at least one of Ziegler-Natta catalyst, metallocene catalyst and non-metallocene catalyst; the metal compound is selected from at least one of a magnesium-containing compound and an aluminum-containing compound. In the implementation, magnesium chloride is dissolved into an alcohol solution to form magnesium chloride alcohol compound, then the magnesium chloride alcohol compound is added into a carbon nano tube solution to react, the carbon nano tube and magnesium chloride compound is obtained after washing and drying, and the catalyst is obtained after titanium tetrachloride and an internal electron donor are loaded. The carbon nano tube supported polyolefin catalyst provided by the invention not only has the apparent morphology of spherical particles, but also has the catalytic active components uniformly distributed on the surface and inside of the spherical carbon nano tube catalyst. Nor how to precipitate magnesium chloride after dissolution to control the magnesium chloride particle process.
CN100379680C relates to a method for obtaining a composite material comprising at least one polymer matrix, and carbon nanotubes dispersed to act as filler. After modifying the carbon nano tube by using an alkyl aluminum cocatalyst, carrying out olefin polymerization after loading a metallocene compound, a Ziegler-Natta titanium catalyst and the like, wherein the mechanical strength of the obtained product is higher than that of a carbon nano tube blending modified material. The carbon nano tube is used as a filler, the aluminum alkyl function is mainly to remove poison in the filler, and then the active component is loaded to initiate olefin reaction, and the invention belongs to the traditional in-situ polymerization technology, and the preparation system does not contain magnesium chloride, does not involve the control of magnesium chloride carrier particles, and has no instructive effect on the invention.
In the prior literature, little research is carried out on the composite precipitating agent, and no report is available that the composite precipitating agent is applied to the preparation process of the magnesium chloride carrier polyethylene catalyst, so that the particle morphology of polymer resin is improved and the particle uniformity is improved.
Disclosure of Invention
The invention aims to provide a composite precipitating agent for precipitating magnesium chloride solution, which enables the precipitating rate of a carrier to be low, and the obtained carrier has good uniformity and regularity, and simultaneously the invention provides a simple and convenient preparation method; in addition, the magnesium chloride carrier type polyethylene catalyst prepared by the composite precipitation agent has good polymerization performance, and the obtained polyethylene resin particles are uniformly distributed.
The composite precipitating agent for precipitating the magnesium chloride solution comprises a carbon nano tube, a solvent and chloralkylaluminum.
Preferably, the chloroalkyl aluminum is diethylaluminum chloride or diisobutylaluminum chloride.
Preferably, the carbon nano tube is used in an amount of 5 to 15 percent of the mass of the magnesium chloride.
The preparation method of the composite separating agent comprises the following steps:
1) Placing the carbon nano tube into a container with stirring under the protection of nitrogen, spraying methanol, soaking for 10-14 hours, and drying;
2) Adding n-hexane into the carbon nanotubes obtained in the step 1), and stirring until the mixture is fully mixed;
3) Adding chlorine-containing alkyl aluminum to react;
4) After the reaction is completed, leaching the mixture three times by using normal hexane, and adding the normal hexane to obtain the composite separating agent.
The magnesium chloride carrier type polyethylene catalyst prepared by the composite precipitation agent comprises the following steps:
(1) Preparation of magnesium chloride carrier solution: under the protection of inert gas, magnesium chloride is put into a container with a stirring device, then n-hexane is added, and the temperature is raised and stirred;
(2) Adding alcohol and magnesium chloride to form a magnesium alkoxide compound, and stirring at constant temperature for 0.5-3 hours to obtain a magnesium chloride carrier solution;
(3) And (3) separating out a carrier: dropwise adding a magnesium chloride carrier solution into the composite separating out agent, stirring at a constant temperature for reaction, wherein the reaction temperature is between-5 ℃ and-20 ℃ and the reaction time is between 2 hours and 4 hours;
(4) Active center loading: slowly adding a titanium compound, and stirring at constant temperature for 1-3 hours;
(5) And (3) drying: stopping stirring, standing the slurry, sucking out the clear liquid without catalyst particles after the slurry is layered, adding a hydrocarbon solvent to wash the catalyst particles, and drying to obtain the magnesium chloride carrier polyethylene catalyst.
According to the invention, the chloralkyl aluminum component is anchored on the surface of the carbon nano tube by preparing the composite precipitating agent, and as the carbon nano tube has a larger specific surface area, enough anchoring points can be ensured, and the requirement of magnesium chloride precipitation is met; after the chloralkyl aluminum is anchored on the carbon nano tube, the chloralkyl aluminum can react with magnesium chloride alcohol compound more gently, so that the precipitation rate of the magnesium chloride carrier is reduced, the precipitation rate is controlled, and the obtained magnesium chloride carrier has better uniformity.
In the precipitation of the magnesium chloride carrier of the present invention, the reaction temperature is controlled, and it is generally required to react at a temperature of 0℃or less, preferably from-5℃to-20 ℃. The control has the advantages that the precipitation effect of the composite precipitating agent can be further ensured, the composite precipitating agent is precipitated at a lower temperature, and the precipitation speed can be controlled more easily; and at low temperature, after the carrier is separated out, collision and aggregation among particles can be reduced, and the regularity of the carrier particles is ensured.
In the invention, the catalyst is used as a main catalyst, alkyl aluminum is used as a cocatalyst, and a slurry polymerization process is adopted to carry out ethylene polymerization to obtain polyethylene resin.
Specifically, the preparation method comprises the steps of firstly drying a polymerization reaction kettle, vacuumizing, adding n-hexane solvent, starting stirring, then adding cocatalyst and main catalyst, heating, introducing ethylene monomer, initiating ethylene monomer by the catalyst to carry out polymerization reaction, controlling the reaction temperature by jacket cooling circulating water, suspending the generated resin particles in the solvent to form polymer slurry, discharging after polymerization is finished, and removing the solvent in the polymer to obtain the required resin product.
Compared with the prior art, the invention has the following beneficial effects:
(1) The composite precipitating agent prepared by the invention has the advantages that the precipitating rate of the carrier is lower, and the uniformity and regularity of the obtained carrier are better;
(2) The magnesium chloride carrier polyethylene catalyst is prepared by using the composite precipitation agent, the polymerization performance of the catalyst is good, and the obtained polyethylene resin particles are uniformly distributed.
Detailed Description
The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples.
The main performance test methods for the catalyst performance and the polymerization product in the examples of the present specification are as follows:
calculation of catalyst polymerization activity: the ratio of the total weight of PE obtained by polymerization to the catalyst addition amount in unit time is KgPE/gCat.
Particle distribution of polyethylene resin particle size and distribution were tested by wet method using a malvern Mastersizer2000 laser particle sizer. Distilled water is selected as a dispersion medium, corresponding sample parameters such as refractive index, absorptivity and the like are set, and volume average particle size and particle size distribution data of the sample parameters are obtained under the appropriate experimental conditions such as pump speed, shading degree and the like.
Example 1:
(1) Preparation of magnesium chloride supported catalyst
Preparation of I and composite precipitant
1) A glass flask equipped with a stirring device and a reflux condensing system was sufficiently purged with nitrogen, and 0.1g of carbon nanotubes were placed in a vessel with stirring under nitrogen protection, then 2mL of methanol was added, immersed for 12 hours, and then dried.
2) To the carbon nanotubes, 40mL of n-hexane was added and stirred until thoroughly mixed.
3) Continuously adding 0.05mol of diethyl aluminum chloride for reaction at the temperature of 70 ℃ for 4 hours.
4) Eluting twice with n-hexane, and adding 40mL of n-hexane to obtain the composite separating agent.
II preparation of magnesium chloride Carrier solution
4) Under the protection of inert gas, 1g of anhydrous magnesium chloride is placed in a container with a stirring device, 60mL of normal hexane is added, and the temperature is raised and the stirring is carried out.
5) Adding 5mL of n-butanol, forming a magnesium alkoxide compound with magnesium chloride, and stirring for 0.5h at 60 ℃;
III, precipitation of the carrier
6) Dropwise adding a magnesium chloride carrier solution into the composite separating-out agent solution, controlling the reaction temperature to be minus 10 ℃, and stirring for 4 hours at constant temperature;
IV active center load
7) 4mL of titanium tetrachloride was slowly added and stirred at 60℃for 2h.
V, drying
8) Stopping stirring, standing the slurry, sucking out the clear liquid without catalyst particles after the slurry is layered, adding n-hexane to wash the catalyst particles, and drying to obtain catalyst powder.
(2) Preparation of polyethylene resin
Drying and vacuumizing a 2L stainless steel polymerization kettle, adding 1.2L dehydrated normal hexane as a solvent, adding 3mL of triethylaluminum as a cocatalyst and 1.5mg of the main catalyst, starting stirring at a stirring speed of 210 revolutions per minute, increasing the temperature in the kettle to 60 ℃ through jacket circulating water, introducing ethylene to the polymerization kettle at a pressure of 0.6MPa, keeping the temperature and the pressure of the polymerization kettle constant, cooling after polymerization for 1 hour, discharging and drying to obtain powdery polyethylene resin. The analysis results are shown in Table 1.
Example 2:
(1) Preparation of magnesium chloride supported catalyst
The same preparation as in example 1 was used, but the amount of carbon nanotubes used in the preparation was 0.02g.
(2) Preparation of polyethylene resin
The same polymerization conditions as in example 1 were used and the analysis results are shown in Table 1.
Example 3:
(1) Preparation of magnesium chloride supported catalyst
The same preparation as in example 1 was used, but the amount of carbon nanotubes used in the preparation was 0.05g.
(2) Preparation of polyethylene resin
The same polymerization conditions as in example 1 were used and the analysis results are shown in Table 1.
Example 4:
(1) Preparation of magnesium chloride supported catalyst
The same catalyst component was used as in example 1, but the amount of carbon nanotubes used in the preparation was 0.15g.
(2) Preparation of polyethylene resin
The same polymerization conditions as in example 1 were used and the analysis results are shown in Table 1.
Example 5:
(1) Preparation of magnesium chloride supported catalyst
The same preparation as in example 1 was used, but the amount of carbon nanotubes used in the preparation was 0.2g.
(2) Preparation of polyethylene resin
The same polymerization conditions as in example 1 were used and the analysis results are shown in Table 1.
Example 6:
(1) Preparation of magnesium chloride supported catalyst
The same preparation as in example 1 was employed, but the carrier precipitation reaction temperature was 0℃during the preparation.
(2) Preparation of polyethylene resin
The same polymerization conditions as in example 1 were used and the analysis results are shown in Table 1.
Example 7:
(1) Preparation of magnesium chloride supported catalyst
The same preparation as in example 1 was employed, but the carrier precipitation reaction temperature was-5℃during the preparation.
(2) Preparation of polyethylene resin
The same polymerization conditions as in example 1 were used and the analysis results are shown in Table 1.
Example 8:
(1) Preparation of magnesium chloride supported catalyst
The same preparation as in example 1 was employed, but the carrier precipitation reaction temperature was-15℃during the preparation.
(2) Preparation of polyethylene resin
The same polymerization conditions as in example 1 were used and the analysis results are shown in Table 1.
Example 9:
(1) Preparation of magnesium chloride supported catalyst
The same preparation as in example 1 was employed, but the carrier precipitation reaction temperature was-20℃during the preparation.
(2) Preparation of polyethylene resin
The same polymerization conditions as in example 1 were used and the analysis results are shown in Table 1.
Example 10:
(1) Preparation of magnesium chloride supported catalyst
The same preparation as in example 1 was employed, but the carrier precipitation reaction temperature was-25℃during the preparation.
(2) Preparation of polyethylene resin
The same polymerization conditions as in example 1 were used and the analysis results are shown in Table 1.
Example 11:
(1) Preparation of magnesium chloride supported catalyst
The same preparation procedure as in example 1 was employed, except that triethylaluminum was used in the preparation of the composite precipitation agent.
(2) Preparation of polyethylene resin
The same polymerization conditions as in example 1 were used and the analysis results are shown in Table 1.
Example 12:
(1) Preparation of magnesium chloride supported catalyst
The same preparation procedure as in example 1 was employed, except that triisobutylaluminum was used in the preparation of the composite precipitant.
(2) Preparation of polyethylene resin
The same polymerization conditions as in example 1 were used and the analysis results are shown in Table 1.
Example 13:
(1) Preparation of magnesium chloride supported catalyst
The same procedure as in example 1 was employed, except that methylaluminoxane was used in the preparation of the composite precipitating agent.
(2) Preparation of polyethylene resin
The same polymerization conditions as in example 1 were used and the analysis results are shown in Table 1.
Example 14:
(1) Preparation of magnesium chloride supported catalyst
The same procedure as in example 1 was employed, except that diisobutylaluminum chloride was used in the preparation of the composite precipitant.
(2) Preparation of polyethylene resin
The same polymerization conditions as in example 1 were used and the analysis results are shown in Table 1.
Comparative example 1:
(1) Preparation of magnesium chloride supported catalyst
Fully cleaning a glass flask equipped with a stirring device and a reflux condensing system by using nitrogen, adding 60mL of n-hexane, 1g of anhydrous magnesium chloride and 5mL of n-butanol under the protection of the nitrogen, stirring at 60 ℃, and stirring at constant temperature for 0.5 hour to obtain a magnesium alkoxide compound solution; cooling to-10 ℃, slowly dropwise adding 0.05mol of diethyl aluminum chloride, stirring for 3 hours, adding 4mL of titanium tetrachloride, and stirring for 2 hours at 60 ℃; the catalyst particles were washed with n-hexane several times and dried to obtain a catalyst powder.
(2) Preparation of polyethylene resin
The same polymerization conditions as in example 1 were used and the analysis results are shown in Table 1.
Comparative example 2:
(1) Preparation of magnesium chloride supported catalyst
Fully cleaning a glass flask equipped with a stirring device and a reflux condensing system by using nitrogen, dispersing 1g of anhydrous magnesium chloride and 5mL of n-butanol in 60mL of n-hexane under the protection of nitrogen, heating to 60 ℃, and stirring at constant temperature for 0.5 hour to obtain a magnesium chloride alkoxide; the magnesium chloride alkoxide was added dropwise to a suspension of 0.1g of carbon nanotubes and 40mL of n-hexane, reacted at a constant temperature of 60℃for 2.0 hours, then washed 3 times with n-hexane, and cooled to-10 ℃. 4mL of titanium tetrachloride was added to the above solution and stirred at-10℃for 2 hours; then reacting for 2 hours at 60 ℃, cleaning the catalyst particles with normal hexane for several times, and drying to obtain catalyst powder.
(2) Preparation of polyethylene resin
The same polymerization conditions as in example 1 were used and the analysis results are shown in Table 1.
Table 1 analysis results
Claims (8)
1. A composite precipitating agent for precipitating magnesium chloride solution is characterized in that: comprises carbon nano-tubes, a solvent and chloralkylaluminum;
the preparation method of the composite separating agent comprises the following steps:
1) Placing the carbon nano tube into a container with stirring under the protection of nitrogen, spraying methanol, soaking for 10-14 hours, and drying;
2) Adding n-hexane into the carbon nanotubes obtained in the step 1), and stirring;
3) Adding chlorine-containing alkyl aluminum to react;
4) After the reaction is completed, eluting with normal hexane, and adding normal hexane to obtain the composite separating agent.
2. The composite precipitation agent for precipitation of magnesium chloride solution according to claim 1, wherein: the chloralkylaluminum is diethylaluminum chloride or diisobutylaluminum chloride.
3. The composite precipitation agent for precipitation of magnesium chloride solution according to claim 1, wherein: the dosage of the carbon nano tube is 5-15% of the mass of magnesium chloride.
4. Use of a composite precipitation agent according to any one of claims 1-3, characterized in that: and (3) preparing the magnesium chloride carrier type polyethylene catalyst by using the composite precipitation agent.
5. The use of a composite precipitation agent according to claim 4, wherein: the method comprises the following steps:
(1) Under the protection of inert gas, magnesium chloride is put into a container with a stirring device, then n-hexane is added, and the temperature is raised and stirred;
(2) Adding alcohol, stirring at constant temperature to obtain magnesium chloride carrier solution;
(3) Dropwise adding the magnesium chloride carrier solution into the composite separating out agent, and stirring at constant temperature for reaction;
(4) Adding a titanium compound, and stirring at constant temperature;
(5) Stopping stirring, standing the slurry, sucking out the clear liquid without catalyst particles after the slurry is layered, adding a hydrocarbon solvent to wash the catalyst particles, and drying to obtain the magnesium chloride carrier polyethylene catalyst.
6. The use of a composite precipitation agent according to claim 5, wherein: the method comprises the following steps: in the step (2), stirring is carried out at constant temperature for 0.5-3 hours.
7. The use of a composite precipitation agent according to claim 5, wherein: the method comprises the following steps: in the step (3), the reaction temperature is between-5 ℃ and-20 ℃ and the reaction time is between 2 and 4 hours.
8. The use of a composite precipitation agent according to claim 5, wherein: the method comprises the following steps: in the step (4), stirring is carried out at constant temperature for 1-3 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103450381A (en) * | 2013-05-30 | 2013-12-18 | 上海化工研究院 | Nano-carrier catalyst for producing reinforced polyethylene as well as preparation method and application of catalyst |
| CN105859919A (en) * | 2016-04-17 | 2016-08-17 | 北京化工大学 | Complex support type catalyst, preparation method and application |
| KR20200065148A (en) * | 2018-11-29 | 2020-06-09 | 롯데케미칼 주식회사 | Carrier composition for polyolefin polymerization catalyst, catalyst composition comprising carrier and method for preparing catalyst |
| CN112759686A (en) * | 2021-01-19 | 2021-05-07 | 上海簇睿低碳能源技术有限公司 | Catalyst for improving processability of ultrahigh molecular weight polyethylene, preparation and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450381A (en) * | 2013-05-30 | 2013-12-18 | 上海化工研究院 | Nano-carrier catalyst for producing reinforced polyethylene as well as preparation method and application of catalyst |
| CN105859919A (en) * | 2016-04-17 | 2016-08-17 | 北京化工大学 | Complex support type catalyst, preparation method and application |
| KR20200065148A (en) * | 2018-11-29 | 2020-06-09 | 롯데케미칼 주식회사 | Carrier composition for polyolefin polymerization catalyst, catalyst composition comprising carrier and method for preparing catalyst |
| CN112759686A (en) * | 2021-01-19 | 2021-05-07 | 上海簇睿低碳能源技术有限公司 | Catalyst for improving processability of ultrahigh molecular weight polyethylene, preparation and application |
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