CN115558043A - Polyolefin catalyst and application thereof - Google Patents
Polyolefin catalyst and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 60
- 229920002678 cellulose Polymers 0.000 claims abstract description 57
- 239000001913 cellulose Substances 0.000 claims abstract description 57
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 150000001336 alkenes Chemical class 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000011261 inert gas Substances 0.000 claims abstract description 10
- 239000000725 suspension Substances 0.000 claims abstract description 10
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 28
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 125000003944 tolyl group Chemical group 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 3
- 229920002488 Hemicellulose Polymers 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229920005610 lignin Polymers 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 33
- -1 polyethylene Polymers 0.000 abstract description 22
- 239000004743 Polypropylene Substances 0.000 abstract description 14
- 229920001155 polypropylene Polymers 0.000 abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 9
- 239000004698 Polyethylene Substances 0.000 abstract description 8
- 229920000573 polyethylene Polymers 0.000 abstract description 8
- 238000012685 gas phase polymerization Methods 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract description 3
- 239000012876 carrier material Substances 0.000 abstract description 3
- 239000000805 composite resin Substances 0.000 abstract description 3
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 3
- 230000003014 reinforcing effect Effects 0.000 abstract description 3
- 239000000741 silica gel Substances 0.000 abstract description 3
- 229910002027 silica gel Inorganic materials 0.000 abstract description 3
- 229920005672 polyolefin resin Polymers 0.000 abstract description 2
- 235000010980 cellulose Nutrition 0.000 description 48
- 239000012968 metallocene catalyst Substances 0.000 description 18
- 239000002245 particle Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 6
- 238000002955 isolation Methods 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 238000011068 loading method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a polyolefin catalyst, which takes composite cellulose as a carrier and a metallocene complex as an active component, wherein the composite cellulose is prepared by the following method: adding a solvent into the dried cellulose powder under the protection of inert gas to disperse the cellulose powder into a suspension, continuously adding alkyl aluminoxane into the suspension under the condition of stirring to react, and then distilling the mixture under reduced pressure under the condition of isolating air to obtain the composite cellulose. The invention also relates to the use of the above polyolefin catalyst in the homogeneous polymerization or copolymerization of olefins, and in the gas phase polymerization or slurry polymerization of olefins. The polyolefin product produced by the polyolefin catalyst provided by the invention can be used for preparing cellulose-reinforced polyethylene or polypropylene resin composite materials, and the cellulose component is not only a carrier material, but also a reinforcing component in the final composite material, so that carriers such as inorganic salt, silica gel and the like do not become ash which is difficult to remove in the polyolefin resin material finally.
Description
Technical Field
The invention relates to the field of polyolefin catalysis, in particular to a polyolefin catalyst, and application thereof in homogeneous polymerization or copolymerization of olefin, and application thereof in gas-phase polymerization or slurry polymerization of olefin.
Background
The metallocene catalyst is a pioneering discovery after a Ziegler-Natta catalyst, and has the advantages of high catalytic activity, single active center, narrow molecular weight distribution of polymer products, capability of controlling the product performance of the polymer products by adjusting a catalyst ligand and the like. The metallocene catalyst consumes a large amount of alkylaluminoxane and the product is amorphous when used, so that the metallocene catalyst needs to be subjected to a supporting treatment to reduce the use cost and control the morphology of the polymer product.
Many studies on metallocene catalyst loading have been reported and some of them have been put into production. In which silica, magnesium chloride, etc. are used as carriers in many cases. Although the above method works effectively, the preparation cost of the carrier is high, the process is complex, and the produced polyolefin product is introduced with inorganic impurities which are difficult to remove.
Due to the increasing demand for environmental protection and the increasing severity of relevant laws and regulations, cellulose materials are receiving more attention and being developed in high-end application fields, wherein polypropylene composites reinforced by cellulose materials are one of the current research and development hotspots. But the compatibility of the cellulose material and the polypropylene or polyethylene material is poor, the performance of the composite material obtained by forcibly mixing the cellulose material and the polypropylene or polyethylene material is not obviously improved by simple ball milling, the energy consumption is high, and the industrial mass production is not easy to realize; the chemical pretreatment of the cellulose material to improve the compatibility with the polypropylene material has good use effect, but brings the problems of cost increase and environmental pollution generated in the process amplification process which cannot be ignored.
Disclosure of Invention
Based on the above, one of the objectives of the present invention is to provide a polyolefin catalyst, which uses a metallocene complex as an active component and a cellulose carrier as a carrier, and has the advantages of wide sources of cellulose materials, low production cost, easy control of product morphology, and controllable particle morphology of the supported metallocene catalyst.
Another object of the present invention is to provide a process for producing the above polyolefin catalyst.
It is another object of the present invention to provide the use of the above polyolefin catalyst in homogeneous polymerization or copolymerization of olefins, in gas phase polymerization or slurry polymerization of olefins.
Therefore, the invention provides a polyolefin catalyst, which takes composite cellulose as a carrier and a metallocene complex as an active component, wherein the composite cellulose is prepared by the following method: adding a solvent into the dried cellulose powder under the protection of inert gas to disperse the cellulose powder into a suspension, continuously adding alkyl aluminoxane into the suspension under the condition of stirring to react, and then distilling the mixture under reduced pressure under the condition of isolating air to obtain the composite cellulose.
In particular, the metallocene complex can be any metallocene complex catalyst with polyolefin catalytic capability at present.
The polyolefin catalyst of the present invention, wherein preferably, the drying process of the cellulose powder is: drying the cellulose powder at 45-55 deg.C under vacuum for 24-48 hr.
The polyolefin catalyst of the present invention, wherein the reaction conditions are preferably as follows: 20-30 ℃ for 3-5 hours.
In the polyolefin catalyst of the present invention, preferably, the alkylaluminoxane is methylaluminoxane, ethylaluminoxane or a derivative thereof having the same function as the polyolefin cocatalyst; the metallocene complex has a polyolefin catalytic function.
The polyolefin catalyst of the present invention, wherein preferably, the process of loading the metallocene complex on the composite cellulose is: under the condition of stirring, adding the composite cellulose into a solvent, dropwise adding a solution containing the metallocene complex, reacting to obtain a dispersion liquid, and distilling the dispersion liquid under reduced pressure under the condition of isolating air to obtain the polyolefin catalyst.
The polyolefin catalyst of the present invention, wherein the reaction conditions are preferably as follows: 20-30 ℃ for 3-5 hours.
The polyolefin catalyst of the present invention, wherein preferably the cellulose powder has a diameter of nano-scale and/or micro-scale, and the cellulose powder contains lignin and hemicellulose, and has a purity of 40wt% or more; further preferably, the cellulose powder is chemically modified in advance.
The polyolefin catalyst of the present invention, wherein preferably, the cellulose powder may be white, yellow or brown in color, and the origin thereof may be bacteria or plants.
In the polyolefin catalyst of the present invention, it is preferable that the molar ratio of the aluminum element to the metallocene complex metal element in the polyolefin catalyst is 40 to 100; more preferably, the polyolefin catalyst is used as it is or after being mixed with a technical white oil.
In the polyolefin catalyst of the present invention, it is preferable that the inert gas is nitrogen, helium or argon, and the solvent is toluene or hexane.
Therefore, the invention also provides a preparation method of the polyolefin catalyst, which comprises the following steps: under the protection of inert gas, adding the composite cellulose into a solvent for mixing, then slowly dropwise adding a metallocene complex solution, reacting for 3-5 hours at the temperature of 20-30 ℃, and distilling the dispersion liquid obtained by the reaction under reduced pressure under the condition of air isolation to obtain the composite cellulose supported metallocene catalyst.
In the method for preparing a polyolefin catalyst according to the present invention, preferably, the solvent is toluene or hexane.
Therefore, the invention also provides an application of the polyolefin catalyst in homogeneous polymerization or copolymerization of olefin, the obtained polyolefin can be made into an additive component for preparing a cellulose reinforced polypropylene or polyethylene material, the problem of poor compatibility when the polypropylene or polyethylene material is reinforced by directly using a cellulose material at present can be solved, and the negative effect that the polyolefin catalyst finally necessarily becomes ash when inorganic salt, silica gel and the like are used as carrier materials is avoided.
To this end, the present invention also provides the use of a polyolefin catalyst as described above in gas phase or slurry polymerization of olefins.
Specifically, the preparation method of the polyolefin catalyst comprises the following steps:
step one, cellulose pretreatment: vacuum drying the cellulose powder at 45-55 deg.C for 24-48 hr, and fully drying;
step two, preparing a cellulose carrier: adding the dry cellulose powder obtained in the step (1) into a reactor under the protection of inert rare gas, adding a solvent to disperse the dry cellulose powder into a suspension, continuously adding alkyl aluminoxane, and stirring the mixture to react for 3 to 5 hours at the temperature of between 20 and 30 ℃; then carrying out reduced pressure distillation under the condition of air isolation to obtain a cellulose carrier containing alkylaluminoxane;
step three, preparing a catalyst: under the protection of inert gas, adding the cellulose carrier prepared in the step (2) into a solvent, mechanically stirring, slowly dropwise adding a metallocene catalyst solution, reacting for 3-5 hours at the temperature of 20-30 ℃, and finally distilling the dispersion under reduced pressure under the condition of air isolation to obtain the cellulose-supported metallocene catalyst solid.
The chemical structure of the cellulose material selected by the invention is similar to that of silicon dioxide in that a large number of hydroxyl groups exist on the surface of the material, so that the material can realize the loading of the metallocene catalyst like a silicon dioxide carrier and realize the coating of a polypropylene material in the polymerization process. The operation not only avoids the chemical pretreatment of the cellulose, but also reduces the mixing difficulty of the cellulose material and the polypropylene material, and the polypropylene powder coated with the cellulose material can be mixed with the polypropylene powder/granules only by simple stirring, and can be further used for processing and producing reinforced polypropylene or polyethylene composite materials containing a certain amount of cellulose material.
The beneficial effects of the invention are:
(1) The commercialized cellulose material has rich particle morphology and high selectivity, so the particle morphology of the supported catalyst is easy to control; meanwhile, the cellulose material is low in price, and the preparation cost of the supported metallocene catalyst can be reduced.
(2) The supported metallocene catalyst obtained by the method can be used for catalyzing the copolymerization of propylene or ethylene, and the produced powder can be used for preparing cellulose-reinforced polyethylene or polypropylene resin composite materials, so that the problems of poor compatibility of the composite materials and the need of chemical modification pretreatment on cellulose materials are avoided. Meanwhile, the cellulose component is a carrier material and is also a reinforcing component in the final composite material, and the carriers such as inorganic salt, silica gel and the like do not become ash which is difficult to remove in the polyolefin resin material finally.
(3) The cellulose material loaded metallocene catalyst can be used for a gas phase polymerization process and a slurry polymerization process, and can meet the requirements of different polymerization processes.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions. The percentages referred to in the following examples are percentages by mass.
The polyolefin catalyst provided by the invention takes composite cellulose as a carrier and takes a metallocene complex as an active component, and the composite cellulose is prepared by the following method: adding a solvent into the dried cellulose powder under the protection of inert gas to disperse the cellulose powder into a suspension, continuously adding alkyl aluminoxane into the suspension under the condition of stirring to react, and then distilling the mixture under reduced pressure under the condition of isolating air to obtain the composite cellulose.
In some embodiments, it is preferred that the drying process of the cellulose powder is: drying the cellulose powder at 45-55 deg.C under vacuum for 24-48 hr.
In some embodiments, it is preferred that the conditions of the reaction are: 20-30 ℃ for 3-5 hours.
In some embodiments, it is preferred that the alkylaluminoxane is methylaluminoxane, ethylaluminoxane, or a derivative thereof that also functions as a polyolefin cocatalyst; the metallocene complex has polyolefin catalysis.
In some embodiments, it is preferred that the process of supporting the metallocene complex on the composite cellulose is: under the condition of stirring, adding the composite cellulose into a solvent, dropwise adding a solution containing the metallocene complex, reacting to obtain a dispersion liquid, and distilling the dispersion liquid under reduced pressure under the condition of isolating air to obtain the polyolefin catalyst.
In some embodiments, it is preferred that the reaction conditions are: 20-30 ℃ for 3-5 hours.
In some embodiments, it is preferred that the cellulose powder has a diameter of the nano-scale and/or micro-scale, and the cellulose powder comprises lignin, hemicellulose, and has a purity of 40wt% or more; further preferably, the cellulose powder is chemically modified in advance.
In some embodiments, it is preferred that the polyolefin catalyst has a molar ratio of aluminum element to metallocene complex metal element of 40 to 100; more preferably, the polyolefin catalyst is used as it is or after being mixed with a technical white oil.
In some embodiments, it is preferred that the inert gas is nitrogen, helium or argon and the solvent is toluene or hexane.
The preparation method of the polyolefin catalyst provided by the invention comprises the following steps: under the protection of inert gas, adding the composite cellulose into a solvent for mixing, then slowly dropwise adding a metallocene complex solution, reacting for 3-5 hours at the temperature of 20-30 ℃, and distilling the dispersion liquid obtained by the reaction under reduced pressure under the condition of air isolation to obtain the composite cellulose supported metallocene catalyst.
In some embodiments, it is preferred that the solvent is toluene or hexane.
The invention also provides the application of the polyolefin catalyst in the homogeneous polymerization or copolymerization of olefin.
The present invention also provides the use of the above polyolefin catalyst in gas phase or slurry polymerization of olefins.
Example 1
(1) Drying cellulose whisker powder with purity not lower than 98%, white color, needle leaf wood as source, diameter of about 30 nm and length of about 500 nm in vacuum at 50 deg.C for 24 hr, and fully drying. And then storing the mixture under the protection of nitrogen atmosphere for later use.
(2) Under the protection of nitrogen, 10g of the dried cellulose powder obtained in step (1) was added to a reactor, and the solvent toluene was added to disperse into a suspension, using a ratio of 1g of cellulose powder: 100mL of toluene; and continuously adding 300 ml of methylaluminoxane toluene solution with the mass fraction of 10 percent, stirring and reacting for 4 hours at normal temperature, and then distilling under reduced pressure under the condition of air isolation to obtain the cellulose carrier containing methylaluminoxane.
(3) Under the protection of nitrogen, 5g of the cellulose support containing methylaluminoxane prepared in step (2) was added to toluene and mechanical stirring was applied, and 0.2g of metallocene complex (Cp) 2 ZrCl 2 ) Dissolved in 20mL of toluene and then slowly added dropwise to the reactor. And reacting for 3 hours at normal temperature, and finally washing the dispersion liquid by using toluene under the condition of isolating air and drying in vacuum to obtain the cellulose-supported metallocene catalyst solid.
The obtained solid can be used directly or mixed with industrial white oil. The ICP representation shows that the weight content of Zr in the prepared catalyst is 0.67 percent, and the weight content of Al is 7.2 percent. The particle size of the supported catalyst is not more than 1 micron.
(4) After a 5L high-pressure reaction kettle is purged by nitrogen and impurities are removed by triethyl aluminum, propylene is introduced at the temperature of 35 ℃ until the pressure is 1.0MPa, then 0.2g of the prepared supported metallocene catalyst is added, propylene is introduced again until the pressure of the reaction kettle is 2.0MPa, and polymerization is carried out for 1 hour at the temperature of 60 ℃. The catalyst activity and polymer molecular weight are shown in Table 1.
Example 2
The same procedure as in example 1 was repeated except that microcrystalline cellulose powder having a particle size of about 30 μm and being white and derived from cotton linters was used instead of the cellulose whisker powder, and helium gas was used as a protective gas.
The obtained catalyst had a Zr content of 0.60% by weight and an Al content of 6.9% by weight. The supported catalyst particle size was about 30 microns. The catalyst activity and polymer molecular weight are shown in Table 1.
Example 3
The same as in example 1 is repeated, except that the cellulose whisker powder is replaced by wood powder of a pale yellow color, derived from hardwood, and having a particle size of about 40 μm, and argon is used as a protective gas.
The obtained catalyst had a Zr content of 0.71% by weight and an Al content of 3.5% by weight. The supported catalyst particle size was about 40 microns. The activity and polymer molecular weight are shown in Table 1.
Example 4
The same procedure as in example 1 was repeated except that hydroxyethyl cellulose powder having a milk white color, a molar substitution degree of 1.8 to 2.0 and a particle diameter of about 80 μm was used in place of the cellulose whisker powder, and the resultant was vacuum-dried at 55 ℃ for 48 hours.
The obtained catalyst had a Zr content of 0.63% by weight and an Al content of 2.9% by weight. The supported catalyst had a particle size of about 85 microns. The activity and polymer molecular weight are shown in Table 1.
TABLE 1 catalyst Activity and Polymer molecular weight distribution
| Activity (gPE/g cat.H) | M w /M n | |
| Example 1 | 770 | 1.55 |
| Example 2 | 671 | 1.34 |
| Example 3 | 455 | 1.67 |
| Example 4 | 326 | 1.85 |
As can be seen from table 1, the commercial cellulose material has a rich particle morphology and a high selectivity, and therefore the particle morphology of the catalyst after supporting is also easy to control. Meanwhile, the cellulose material has low price, and the preparation cost of the supported metallocene catalyst can be reduced. The supported metallocene catalyst obtained by the method can be used for catalyzing the copolymerization of propylene or ethylene, and the produced powder can be used for preparing cellulose-reinforced polyethylene or polypropylene resin composite materials, so that the problems of poor compatibility of the composite materials and the need of chemical modification pretreatment on cellulose materials are avoided, and the cellulose component is finally used as a reinforcing component instead of ash. The cellulose material loaded metallocene catalyst can be used for a gas phase polymerization process and a slurry polymerization process, and meets the requirements of different polymerization processes.
The present invention is capable of other embodiments, and various changes and modifications can be made by one skilled in the art without departing from the spirit and scope of the invention.
Claims (11)
1. A polyolefin catalyst is characterized in that composite cellulose is used as a carrier, a metallocene complex is used as an active component, and the composite cellulose is prepared by the following method: adding a solvent into the dried cellulose powder under the protection of inert gas to disperse the cellulose powder into suspension, continuously adding alkyl aluminoxane into the suspension under the condition of stirring to react, and then distilling the mixture under reduced pressure under the condition of isolating air to obtain the composite cellulose.
2. Polyolefin catalyst according to claim 1, characterized in that the drying process of the cellulose powder is: drying the cellulose powder at 45-55 deg.C under vacuum for 24-48 hr.
3. Polyolefin catalyst according to claim 1, characterized in that the reaction conditions are: 20-30 ℃ for 3-5 hours.
4. The polyolefin catalyst according to claim 1, wherein the alkylaluminoxane is methylaluminoxane, ethylaluminoxane or a derivative thereof having the same function as a polyolefin cocatalyst; the metallocene complex has a polyolefin catalytic function.
5. The polyolefin catalyst according to claim 1, wherein the metallocene complex is supported on the composite cellulose by a process comprising: under the condition of stirring, adding the composite cellulose into a solvent, dropwise adding a solution containing the metallocene complex, reacting to obtain a dispersion liquid, and distilling the dispersion liquid under reduced pressure under the condition of isolating air to obtain the polyolefin catalyst.
6. Polyolefin catalyst according to claim 5, characterized in that the reaction conditions are: 20-30 ℃ for 3-5 hours.
7. Polyolefin catalyst according to claim 1, characterized in that the cellulose powder has a diameter in the nanometric and/or micrometric range, comprising lignin, hemicellulose, with a purity above 40% by weight; preferably, the cellulose powder is chemically modified beforehand.
8. The polyolefin catalyst according to claim 1, wherein the molar ratio of the aluminum element to the metallocene complex metal element in the polyolefin catalyst is 40 to 100; preferably, the polyolefin catalyst is used as such or after mixing into a technical white oil.
9. Polyolefin catalyst according to claim 1, wherein the inert gas is nitrogen, helium or argon and the solvent is toluene or hexane.
10. Use of a polyolefin catalyst according to any of claims 1 to 9 for the homogeneous polymerization or copolymerization of olefins.
11. Use of a polyolefin catalyst according to any of claims 1 to 9 in gas phase or slurry polymerization of olefins.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110746795.0A CN115558043A (en) | 2021-07-01 | 2021-07-01 | Polyolefin catalyst and application thereof |
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Citations (4)
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|---|---|---|---|---|
| DE1420618A1 (en) * | 1958-02-11 | 1968-12-12 | Nat Lead Co | Process for the production of cellulosic material |
| JPH1025312A (en) * | 1996-07-11 | 1998-01-27 | Chisso Corp | Olefin polymerization catalyst, production of olefin polymer using the same |
| KR0178822B1 (en) * | 1994-05-03 | 1999-05-15 | 이동호 | Cyclodextrin supported polymeric catalyst for polymerization of olefins or diens and preparation of producing thereof |
| US20100160581A1 (en) * | 2005-08-17 | 2010-06-24 | Wei Xu | Catalyst Composition for Polymerization of Olefins, Polymerization Process Using the Same, and Method for Its Preparation |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1420618A1 (en) * | 1958-02-11 | 1968-12-12 | Nat Lead Co | Process for the production of cellulosic material |
| KR0178822B1 (en) * | 1994-05-03 | 1999-05-15 | 이동호 | Cyclodextrin supported polymeric catalyst for polymerization of olefins or diens and preparation of producing thereof |
| JPH1025312A (en) * | 1996-07-11 | 1998-01-27 | Chisso Corp | Olefin polymerization catalyst, production of olefin polymer using the same |
| US20100160581A1 (en) * | 2005-08-17 | 2010-06-24 | Wei Xu | Catalyst Composition for Polymerization of Olefins, Polymerization Process Using the Same, and Method for Its Preparation |
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