CN114349885B - Preparation method of catalyst carrier, supported catalyst and application thereof - Google Patents
Preparation method of catalyst carrier, supported catalyst and application thereof Download PDFInfo
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- CN114349885B CN114349885B CN202111466743.4A CN202111466743A CN114349885B CN 114349885 B CN114349885 B CN 114349885B CN 202111466743 A CN202111466743 A CN 202111466743A CN 114349885 B CN114349885 B CN 114349885B
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- halogen
- catalyst
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- halogenated
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- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 90
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 63
- 150000002367 halogens Chemical class 0.000 claims abstract description 63
- 229920000642 polymer Polymers 0.000 claims abstract description 63
- 238000002156 mixing Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 36
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- 239000012968 metallocene catalyst Substances 0.000 claims abstract description 24
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 21
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- 239000007788 liquid Substances 0.000 claims abstract description 18
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- 238000000926 separation method Methods 0.000 claims abstract description 13
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- 239000007795 chemical reaction product Substances 0.000 claims abstract description 10
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
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- 238000006243 chemical reaction Methods 0.000 claims description 88
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- CBVJWBYNOWIOFJ-UHFFFAOYSA-N chloro(trimethoxy)silane Chemical compound CO[Si](Cl)(OC)OC CBVJWBYNOWIOFJ-UHFFFAOYSA-N 0.000 claims description 4
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- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- CCZVEWRRAVASGL-UHFFFAOYSA-N lithium;2-methanidylpropane Chemical compound [Li+].CC(C)[CH2-] CCZVEWRRAVASGL-UHFFFAOYSA-N 0.000 description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- DQXKOHDUMJLXKH-PHEQNACWSA-N (e)-n-[2-[2-[[(e)-oct-2-enoyl]amino]ethyldisulfanyl]ethyl]oct-2-enamide Chemical compound CCCCC\C=C\C(=O)NCCSSCCNC(=O)\C=C\CCCCC DQXKOHDUMJLXKH-PHEQNACWSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- SAHIZENKTPRYSN-UHFFFAOYSA-N [2-[3-(phenoxymethyl)phenoxy]-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound O(C1=CC=CC=C1)CC=1C=C(OC2=NC(=CC(=C2)CN)C(F)(F)F)C=CC=1 SAHIZENKTPRYSN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- LIQOCGKQCFXKLF-UHFFFAOYSA-N dibromo(dimethyl)silane Chemical compound C[Si](C)(Br)Br LIQOCGKQCFXKLF-UHFFFAOYSA-N 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- MBMQEIFVQACCCH-QBODLPLBSA-N zearalenone Chemical compound O=C1O[C@@H](C)CCCC(=O)CCC\C=C\C2=CC(O)=CC(O)=C21 MBMQEIFVQACCCH-QBODLPLBSA-N 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of catalysts, and discloses a preparation method of a catalyst carrier, a supported catalyst and application thereof. The preparation method of the catalyst carrier comprises the following steps: 1) Dissolving halogen-containing polymer in a good solvent to obtain a mixed solution; 2) Mixing the mixed solution with a poor solvent to obtain halogen-containing polymer microsphere liquid; 3) Carrying out hydrothermal reaction on the microsphere liquid; 4) Performing solid-liquid separation on the reaction product and carbonizing; 5) And mixing and adsorbing the carbonized product and siloxane, and roasting. The carrier prepared by the method has high specific surface area and pore volume, and the metallocene catalyst prepared by the carrier has high activity.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a preparation method of a catalyst carrier, a supported catalyst and application thereof.
Background
The metallocene catalyst has a single active center, and the product prepared by the metallocene catalyst has high uniformity and can produce a plurality of polyolefin products with high added value; however, the polymer morphology prepared by the metallocene catalyst is difficult to control, and has serious kettle sticking phenomenon, so that the preparation requirement of polyolefin is difficult to meet. Therefore, it is necessary to support the metallocene catalyst, that is, to support the metallocene catalyst on a carrier such as an inorganic, organic, or molecular sieve by a physical or chemical method. The supported metallocene catalyst can improve the polymer morphology of catalytic polymerization, increase the bulk density of the polymer, and control the size and the distribution of polymer particles more easily, and is more suitable for the existing olefin polymerization device and process, thereby promoting the industrialized popularization and application of the metallocene catalyst. The metallocene catalyst supports reported have been mainly divided into: inorganic carrier, polymer organic carrier, inorganic/organic composite carrier, etc., wherein the inorganic carrier is one of the most widely used metallocene catalyst carriers, and generally comprises SiO 2 、MgCl 2 、Al 2 O 3 Etc. Development of a novel metallocene catalyst and high-efficiency loading of the novel metallocene catalyst are important bases for promoting development of the metallocene catalyst.
Disclosure of Invention
The invention aims to provide a preparation method of a catalyst carrier, a supported catalyst and application thereof, wherein the carrier prepared by the method has high specific surface area and pore volume, and the metallocene catalyst prepared by using the carrier has high activity.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a catalyst carrier, comprising the steps of:
1) A step of dissolving a halogen-containing polymer in a good solvent to obtain a mixed solution;
2) Mixing the mixed solution obtained in the step 1) with a poor solvent to obtain a halogen-containing polymer microsphere solution;
3) A step of carrying out a hydrothermal reaction on the halogen-containing polymer microsphere liquid obtained in the step 2);
4) A step of carbonizing the reaction product obtained in the step 3) after solid-liquid separation;
5) And (3) mixing the carbonized product obtained in the step (4) with siloxane for adsorption and roasting.
Preferably, the halogen content of the halogen-containing polymer is 40 to 85 mass% of the total mass of the halogen-containing polymer.
Preferably, the halogen in the halogen-containing polymer is one or more of F, cl, br and I.
Preferably, the total content of carbon, hydrogen and halogen in the halogen-containing polymer is 90 mass% or more of the total mass of the halogen-containing polymer.
Preferably, the halogen-containing polymer is one or more of halogenated polyethylene, halogenated polypropylene, halogenated poly-1-butene, halogenated polyvinyl chloride, halogenated poly-1, 1-dichloroethylene, halogenated poly-1, 2-dichloroethylene, halogenated poly-1, 2-trichloroethylene, halogenated poly-3-chloropropene, halogenated polychloroprene, halogenated poly-bromoethylene, halogenated poly-3-bromopropene, and halogenated poly-bromobutene.
Preferably, the concentration of the halogenated polyolefin polymer in the good solvent is 0.5 to 20 mass%.
Preferably, the good solvent is one or more of tetrahydrofuran, toluene, xylene, chloroform, trichlorobenzene, o-dichlorobenzene, p-dichlorobenzene, 2, 4-dichlorophenol, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
Preferably, the volume ratio of the good solvent to the poor solvent is 1:1-100.
Preferably, the poor solvent is one or more of water, ammonia, methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, glycerol, isopropanol, n-octanol, benzyl alcohol, acetone, butanone, n-hexane, cyclohexane, methyl ether, diethyl ether, n-propyl ether, n-butyl ether, ethyl acetate and butyl acetate.
Preferably, in step 2), the mixing conditions include: the mixing temperature is 0-40deg.C, and the mixing time is 30-120min.
Preferably, the method further comprises the step of concentrating the mixed solution after mixing the mixed solution obtained in the step 1) with the poor solvent;
preferably, the method further comprises the step of removing the solvent and adding the poor solvent after mixing the mixed solution obtained in the step 1) with the poor solvent.
Preferably, the conditions of the hydrothermal reaction include: the reaction temperature is 200-400 ℃ and the reaction time is 1-10h.
Preferably, the carbonization conditions include: heating for 1-10h under inert atmosphere at 200-1000deg.C.
Preferably, the heating carbonization conditions include: heating to 200-1000 deg.C at 1-20deg.C/min under inert atmosphere, and heating at that temperature for 1-10 hr.
Preferably, the method further comprises the step of drying the solid phase obtained by the solid-liquid separation prior to the carbonization.
Preferably, the drying conditions include: the drying temperature is 60-150deg.C, and the drying time is 0.5-10h.
Preferably, in step 5), the siloxane is one or more of tetramethoxysilane, tetraethoxysilane, trimethoxychlorosilane, triethoxychlorosilane, dimethoxy dichlorosilane and ethoxytrichlorosilane.
Preferably, the roasting conditions include: the roasting temperature is 400-800 ℃ and the roasting time is 2-20h.
The invention also provides a supported catalyst, wherein the supported catalyst is obtained by supporting a metallocene compound and an aluminum-containing cocatalyst on the catalyst carrier.
Preferably, the metallocene compound is a compound represented by the following chemical formula (1):
in the formula (1), R 1 -R 8 May be the same or different and are each a hydrogen atom or a C1-C12M is one or more of transition metal elements of groups III, IV, V and VI of the periodic Table of the elements or lanthanides.
Preferably, the method of loading comprises: and a step of carrying out first contact between the catalyst carrier and the solution containing the aluminum cocatalyst and then carrying out second contact between the catalyst carrier and the solution containing the metallocene catalyst.
Preferably, the conditions of the first contact include: the contact temperature is 30-100 ℃, and the contact time is 3-10h.
Preferably, the conditions of the second contact include: the contact temperature is 50-80 ℃, and the contact time is 3-7h.
The invention also provides a catalyst carrier prepared by the preparation method or application of the catalyst in preparation of polyolefin.
Through the technical scheme, the invention provides a preparation method of the catalyst carrier, the specific surface area and pore volume of the carrier prepared by the method are high, and the activity of the metallocene catalyst prepared by using the carrier is high.
Drawings
FIG. 1 is an SEM image of the carrier obtained in example 2.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a method for preparing a catalyst carrier, comprising the steps of:
1) A step of dissolving a halogen-containing polymer in a good solvent to obtain a mixed solution;
2) Mixing the mixed solution obtained in the step 1) with a poor solvent to obtain a halogen-containing polymer microsphere solution;
3) A step of carrying out a hydrothermal reaction on the halogen-containing polymer microsphere liquid obtained in the step 2);
4) A step of carbonizing the reaction product obtained in the step 3) after solid-liquid separation;
5) And (3) mixing the carbonized product obtained in the step (4) with siloxane for adsorption and roasting.
According to the present invention, as the halogen-containing polymer, a halogen-substituted olefin monomer may be polymerized to obtain a halogen-containing polymer microsphere of a suitable size, and preferably, the halogen content in the halogen-containing polymer is 40 to 85 mass% of the total mass of the halogen-containing polymer; more preferably, the halogen content of the halogen-containing polymer is 45 to 80 mass% of the total mass of the halogen-containing polymer; further preferably, the halogen content in the halogen-containing polymer is 60 to 70 mass% of the total mass of the halogen-containing polymer.
According to the present invention, the halogen in the halogen-containing polymer is not particularly limited, and may be, for example, one or more of F, cl, br and I, and the halogen is preferably Cl and/or Br from the viewpoints of reducing the polymer production cost and improving the polymer solubility.
According to the present invention, the halogen-containing polymer may contain other elements than carbon, hydrogen and halogen, but from the viewpoint of improving the solubility of the polymer and reducing the difficulty of the subsequent hydrothermal reaction, it is preferable that the total content of carbon, hydrogen and halogen in the halogen-containing polymer is 90 mass% or more of the total mass of the halogen-containing polymer; more preferably, the total content of carbon, hydrogen and halogen in the halogen-containing polymer is 95 mass% or more of the total mass of the halogen-containing polymer.
According to the present invention, the halogen-containing polymer may be, for example, a halogenated polyolefin or a halogenated polyhaloolefin.
Specifically, the halogen-containing polymer includes, but is not limited to, one or more of halogenated polyethylene, halogenated polypropylene, halogenated poly-1-butene, halogenated polyvinyl chloride, halogenated poly-1, 1-dichloroethylene, halogenated poly-1, 2-dichloroethylene, halogenated poly-1, 2-trichloroethylene, halogenated poly-3-chloropropene, halogenated polychloroprene, halogenated poly-bromoethylene, halogenated poly-3-bromopropene, and halogenated poly-bromobutene; preferably, the halogen-containing polymer is selected from one or more of chlorinated polyethylene, chlorinated polypropylene, chlorinated poly-1-butene, chlorinated polyvinyl chloride, chlorinated poly-1, 1-dichloroethylene, chlorinated poly-1, 2-dichloroethylene, chlorinated poly-1, 2-trichloroethylene, chlorinated poly-3-chloropropene, chlorinated polychloroprene, chlorinated poly-bromoethylene, chlorinated poly-3-bromopropene, chlorinated poly-bromobutene, brominated polyethylene, brominated polypropylene, brominated poly-1-butene, brominated polyvinyl chloride, brominated poly-1, 1-dichloroethylene, brominated poly-1, 2-dichloroethylene, brominated poly-1, 2-trichloroethylene, brominated poly-3-chloropropene, brominated polychloroprene, brominated poly-bromoethylene, brominated poly-3-bromopropene and brominated poly-bromobutene; more preferably, the halogen-containing polymer is selected from one or more of chlorinated polyethylene, chlorinated polypropylene, chlorinated polyvinyl chloride, brominated polyethylene and brominated polypropylene; further preferably, the halogen-containing polymer is selected from chlorinated polyethylene and/or chlorinated polypropylene.
When the halogen-containing polymer is selected from the polymers, the prepared carrier has more pore channel structures, and the obtained supported catalyst has higher catalytic activity.
The dissolution method according to the present invention is not particularly limited as long as the halogen-containing polymer is sufficiently dissolved, and may be, for example: the polymer was added to the good solvent and heated to reflux while stirring.
The conditions for the heating reflux include: the heating reflux temperature is 40-150 ℃, the heating reflux time is 1-5h, and preferably, the heating reflux conditions comprise: the heating reflux temperature is 60-120 ℃, and the heating reflux time is 2-4h.
According to the present invention, in order to facilitate the subsequent precipitation of microspheres of a suitable size, it is preferable that the concentration of the halogenated polyolefin-based polymer in the good solvent is 0.5 to 20 mass%; more preferably, the concentration of the halogenated polyolefin polymer in the good solvent is 0.5 to 10 mass%.
According to the present invention, the good solvent is not particularly limited as long as it can sufficiently dissolve the halogen-containing polymer, and examples of such good solvent include aromatic hydrocarbons, amides and chlorinated hydrocarbons, and specifically include one or more of tetrahydrofuran, toluene, xylene, chloroform, trichlorobenzene, o-dichlorobenzene, p-dichlorobenzene, 2, 4-dichlorophenol, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide; in order to obtain a carrier with more suitable size and pore diameter, the good solvent is preferably one or more of tetrahydrofuran, xylene and dimethyl sulfoxide.
According to the present invention, the ratio of the amount of the good solvent to the amount of the poor solvent may be adjusted in a wide range as long as the microspheres can be precipitated in the mixed solution, and for example, the volume ratio of the good solvent to the poor solvent may be 1:1-100; in order to further obtain microspheres of suitable and uniform size, the volume ratio of good solvent to poor solvent is preferably 1:20-80.
According to the present invention, the poor solvent is not particularly limited as long as the microspheres can be precipitated from the mixed solution, and the poor solvent may be, for example, one or more of water, ammonia, alcohols, ketones, ethers, alkanes and esters, and specifically, one or more of water, ammonia, methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, glycerol, isopropanol, n-octanol, benzyl alcohol, acetone, butanone, n-hexane, cyclohexane, methyl ether, diethyl ether, n-propyl ether, n-butyl ether, ethyl acetate and butyl acetate. In order to obtain a carrier with more suitable size and pore size, the poor solvent is preferably one or more of water, methanol, ethanol, ethyl acetate and acetone.
According to the present invention, the mixing method is not particularly limited as long as the microspheres can be precipitated from the mixed solution, and the mixing conditions preferably include: the mixing temperature is-20-60 ℃ and the mixing time is 0.5-5h; more preferably, the mixing conditions include: the mixing temperature is 0-40deg.C, and the mixing time is 0.5-3h. When the mixing conditions are as described above, precipitation of the microspheres is more complete.
According to the present invention, in order to facilitate the hydrothermal reaction, it is preferable that the method further comprises a step of concentrating the mixed solution obtained in step 1) after mixing the mixed solution with the poor solvent.
The concentration method for reducing the amount of the solvent to promote the hydrothermal reaction according to the present invention is not particularly limited, and any concentration method commonly used in the art may be used, and for example, one or more of evaporation, filtration, and centrifugation may be used, and evaporation is preferable.
The concentration may be performed in an amount of 10 to 90% of the solvent removed, and preferably in an amount of 20 to 80% of the solvent removed in order to further enhance the subsequent hydrothermal reaction rate.
Of course, all solvents may be removed and new solvents may be added to prepare the halogen-containing polymer microsphere fluid. Specifically, the halogen-containing polymer microsphere liquid can be prepared by mixing, then carrying out solid-liquid separation to remove the liquid phase, and then adding the poor solvent. Thus, the solvent in the halogen-containing polymer microsphere liquid can be replaced by a new poor solvent as much as possible, so that the hydrothermal reaction efficiency is higher, the specific surface area of the prepared carrier is larger, and the catalyst activity is higher.
The solid-liquid separation method is not particularly limited, and may be one or more of filtration and centrifugation, which are commonly used in the art.
In order to make the halogen-containing polymer microsphere more fully reactive, preferably, the hydrothermal reaction conditions include: the reaction temperature is 200-400 ℃ and the reaction time is 1-10h; more preferably, the hydrothermal reaction conditions include: the reaction temperature is 250-350 ℃ and the reaction time is 2-8h.
According to the invention, the carbonization is used to convert the hydrothermal reaction product into carbon spheres, and the carbonization conditions include: under inert atmosphere, the carbonization temperature is 200-1000 ℃ and the carbonization time is 1-10h; more preferably, the carbonization conditions include: under inert atmosphere, the carbonization temperature is 250-800 ℃ and the carbonization time is 2-7.
Preferably, the heating carbonization conditions further include: heating to 200-1000 deg.C at 1-20deg.C/min under inert atmosphere, and heating at the temperature for 1-10 hr; more preferably, the conditions for heating carbonization further include: heating to 250-800 deg.C at 1-20deg.C/min under inert atmosphere, and heating at the temperature for 2-7 hr.
According to the present invention, preferably, the method further comprises a step of drying the solid phase obtained by the solid-liquid separation, before the carbonization, the drying being used for removing the solvent to facilitate the carbonization.
Preferably, the drying conditions include: the drying temperature is 50-200 ℃ and the drying time is 1-8h; more preferably, the drying conditions include: the drying temperature is 80-150 ℃ and the drying time is 3-8h.
According to the invention, the siloxane is used for adsorbing/bonding on the surface of the carbon sphere and converting into SiO 2 To form C-SiO 2 The siloxane can be one or more of tetramethoxysilane, tetraethoxysilane, trimethoxychlorosilane, triethoxychlorosilane, dimethoxy dichlorosilane and ethoxytrichlorosilane; in order to allow the siloxane to be more tightly bound to the carbon sphere, preferably, the siloxane is one or more of tetramethoxy siloxane, tetraethoxy siloxane, trimethoxy chlorosilane.
The amount of the siloxane may be such that the carbon sphere is sufficiently bonded to the siloxane, and for example, the mass ratio of the carbon sphere to the siloxane may be 1:20-100; in order to improve the bonding efficiency and facilitate the calcination treatment, it is preferable that the mass ratio of the carbon sphere to the siloxane is 1:20-50.
In order to allow the siloxane to be sufficiently bonded to the carbon spheres, preferably, the conditions of the mixed adsorption include: the mixing temperature is 20-200 ℃, and the mixing time is 1-10h; more preferably, the conditions of the mixed adsorption include: the mixing temperature is 50-150 ℃ and the mixing time is 2-8h.
According to the invention, the calcination is used to convert siloxanes adsorbed on the carbon spheres into SiO 2 As such firing conditions, there may be mentioned: roasting at 400-800 deg.c for 1-8 hr; in order to further improve the conversion efficiency, preferably, the conditions of the firing include: the roasting temperature is 400-700 ℃ and the roasting time is 2-7h.
In a second aspect, the present invention provides a supported catalyst obtained by supporting a metallocene compound and an aluminum-containing cocatalyst on the catalyst support of the present invention.
According to the present invention, preferably, the metallocene compound is a compound represented by the following chemical formula (1):
in the formula (1), R 1 -R 8 And may be the same or different, each is a hydrogen atom or a C1-C12 alkyl group, M is one or more of transition metal elements of groups III, IV, V and VI of the periodic Table of the elements or lanthanides.
The C1-C12 alkyl group may be a straight-chain alkyl group or a branched-chain alkyl group, and examples of the C1-C12 alkyl group include: methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, and the like.
According to the invention, as R 1 -R 8 When the number of atoms is small, the steric hindrance is smaller, and the activity of the compound represented by formula (1) is higher, preferably R in formula (1) 1 -R 8 Each is a hydrogen atom or a C1-C4 alkyl group; more preferably, in formula (1), R 1 -R 8 Each is one or more of a hydrogen atom, a methyl group, an ethyl group, an isopropyl group and an isobutyl group.
In the present invention, examples of the M include: scandium, titanium, vanadium, chromium, yttrium, zirconium, niobium, molybdenum, lanthanum, cerium, hafnium, tantalum, tungsten, and the like.
According to the present invention, when M is a specific element, the compound represented by formula (1) has higher catalytic activity, and preferably, in formula (1), M is one or more of zirconium, titanium, chromium and hafnium.
In a preferred embodiment of the present invention, the compound represented by the formula (1) is selected from one or more of the following compounds,
compound a-1: r is R 1 -R 4 Is H, R 5 -R 8 Methyl, M is zirconium;
compound a-2: r is R 1 -R 4 Is H, R 5 -R 8 Methyl, M is titanium;
compound a-3: r is R 1 -R 4 Is H, R 5 -R 8 Methyl, M is chromium;
compound a-4: r is R 1 -R 4 Is H, R 5 -R 8 Methyl, M is hafnium;
compound B-1: r is R 2 -R 4 Is H, R 1 And R is 5 -R 8 Methyl, M is zirconium;
compound B-2: r is R 2 -R 4 Is H, R 1 And R is 5 -R 8 Methyl, M is titanium;
compound B-3: r is R 2 -R 4 Is H, R 1 And R is 5 -R 8 Methyl, M is chromium;
compound B-4: r is R 2 -R 4 Is H, R 1 And R is 5 -R 8 Methyl, M is hafnium;
compound C-1: r is R 1 -R 8 Methyl, M is zirconium;
compound C-2: r is R 1 -R 8 Methyl, M is titanium;
compound C-3: r is R 1 -R 8 Methyl, M is chromium;
compound C-4: r is R 1 -R 8 Methyl, M is hafnium;
compound D-1: r is R 1 -R 4 Is isopropyl, R 5 -R 8 Methyl, M is zirconium;
compound D-2: r is R 1 -R 4 Is isopropyl, R 5 -R 8 Methyl, M is titanium;
compound D-3: r is R 1 -R 4 Is isopropyl, R 5 -R 8 Methyl, M is chromium;
compound D-4: r is R 1 -R 4 Is isopropyl, R 5 -R 8 Methyl, M is hafnium;
compound E-1: r is R 1 -R 4 Is ethyl, R 5 -R 8 Methyl, M is zirconium;
compound E-2: r is R 1 -R 4 Is ethyl, R 5 -R 8 Methyl, M is titanium;
compound E-3: r is R 1 -R 4 Is ethyl, R 5 -R 8 Methyl, M is chromium;
compound E-4: r is R 1 -R 4 Is ethyl, R 5 -R 8 Methyl, M is hafnium;
compound F-1: r is R 1 -R 4 Is methyl, R 5 -R 8 Is H, M is zirconium;
compound F-2: r is R 1 -R 4 Is methyl, R 5 -R 8 Is H, M is titanium;
compound F-3: r is R 1 -R 4 Is methyl, R 5 -R 8 H and M is chromium;
compound F-4: r is R 1 -R 4 Is methyl, R 5 -R 8 Is H, M is hafnium;
compound G-1: r is R 1 、R 3 Is H, R 2 、R 4 And R is 5 -R 8 Methyl, M is zirconium;
compound G-2: r is R 1 、R 3 Is H, R 2 、R 4 And R is 5 -R 8 Methyl, M is titanium;
compound G-3: r is R 1 、R 3 Is H, R2, R 4 And R is 5 -R 8 Methyl, M is chromium;
compound G-4: r is R 1 、R 3 Is H, R 2 、R 4 And R is 5 -R 8 Methyl, M is hafnium;
compound H-1: r is R 1 -R 8 Is H, M is zirconium;
Compound H-2: r is R 1 -R 8 Is H, M is titanium;
compound H-3: r is R 1 -R 8 H and M is chromium;
compound H-4: r is R 1 -R 8 Is H, M is hafnium;
compound I-1: r is R 1 、R 3 Is isopropyl, R 2 、R 4 Is hydrogen, R 5 -R 8 Methyl, M is zirconium;
compound I-2: r is R 1 、R 3 Is isopropyl, R 2 、R 4 Is hydrogen, R 5 -R 8 Methyl, M is titanium;
compound I-3: r is R 1 、R 3 Is isopropyl, R 2 、R 4 Is hydrogen, R 5 -R 8 Methyl, M is chromium;
compound I-4: r is R 1 、R 3 Is isopropyl, R 2 、R 4 Is hydrogen, R 5 -R 8 Methyl, M is hafnium;
compound J-1: r is R 1 、R 3 Is methyl, R 2 、R 4 Is hydrogen, R 5 -R 8 Methyl, M is zirconium;
compound J-2: r is R 1 、R 3 Is methyl, R 2 、R 4 Is hydrogen, R 5 -R 8 Methyl, M is titanium;
compound J-3: r is R 1 、R 3 Is methyl, R 2 、R 4 Is hydrogen, R 5 -R 8 Methyl, M is chromium;
compound J-4: r is R 1 、R 3 Is methyl, R 2 、R 4 Is hydrogen, R 5 -R 8 Methyl, M is hafnium.
According to the present invention, the method for preparing the metallocene compound may include the steps of:
1) Formylation of compound 1 with an organolithium reagent and/or a turbognard reagent and an amide in the presence of a first organic solvent to give compound 2;
2) Subjecting compound 2 to wittig reaction with wittig reagent and/or wittig-hopanax reagent in the presence of a second organic solvent and a base to obtain compound 3;
3) In the presence of a third organic solvent and a hydrogenation catalyst, carrying out hydrogenation reaction on the compound 3 and hydrogen, and then carrying out hydrolysis reaction to obtain a compound 4;
4) Performing Friedel-crafts acylation reaction on the compound 4 in the presence of polyphosphoric acid to obtain a compound 5;
5) Subjecting compound 5 to carbonyl reduction and elimination in the presence of a fifth organic solvent to obtain compound 6;
6) In the presence of a seventh organic solvent, enabling the compound 6 to react with a deprotonating reagent and then react with halogenated hydrocarbon in a nucleophilic addition reaction, and then enabling the obtained nucleophilic addition product to react with dihalogenated dimethyl silane in a silicon bridging reaction to obtain a compound 7;
7) Reacting compound 7 with a deprotonating agent in the presence of an eighth organic solvent, and then with a salt of metal M to give metallocene compound 8,
wherein, the compounds 1-8 are respectively compounds with the following structures:
in compounds 1-8, R 1 、R 2 、R 5 And R is 6 And may be the same or different, each is a hydrogen atom or a C1-C12 alkyl group, M is one or more of transition metal elements of groups III, IV, V and VI of the periodic Table of the elements or lanthanides.
In the present invention, two monomers linked by a silicon bridge structure are present in the structures of compounds 7 and 8, the above compounds 1 to 6 are used to represent substituents R 1 、R 2 、R 5 、R 6 Monomers of (1) to (6) and R in the following synthetic schemes 1 、R 2 、R 5 、R 6 Respectively replace R 3 、R 4 、R 8 、R 7 The other monomer can be prepared.
As said R 1 -R 8 Examples thereof include: methyl, ethyl, propyl,Isopropyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, and the like.
Preferably, in formula (1), R 1 -R 8 Each is a hydrogen atom or a C1-C4 alkyl group; more preferably, in formula (1), R 1 -R 8 Each is one or more of a hydrogen atom, a methyl group, an ethyl group, an isopropyl group and an isobutyl group.
Examples of the M include: scandium, titanium, vanadium, chromium, yttrium, zirconium, niobium, molybdenum, lanthanum, cerium, hafnium, tantalum, tungsten, and the like; preferably, in formula (1), M is one or more of zirconium, titanium, chromium and hafnium.
The steps are described in detail below.
1) Formylation reaction
In the present invention, compound 2 is obtained by subjecting compound 1 to formylation reaction with an organolithium reagent and/or a turbognard reagent and an amide in the presence of a first organic solvent.
The amide may be DMF (N, N-dimethylformamide).
The molar amount of compound 1 to the amide may be, for example, 1:1-3, preferably 1:2-2.5.
The first organic solvent may be one or more of tetrahydrofuran, toluene, n-hexane and diethyl ether. The amount of the solvent is not particularly limited as long as the reaction proceeds smoothly, and may be a conventional amount in the art.
When an organolithium reagent is used, the molar ratio of compound 1 to organolithium reagent may be 1:1-1.5, preferably 1:1.1-1.3.
In addition, when turbogrignard reagent is used, the molar ratio of compound 1 to turbogrignard reagent may be 1:1.0 to 1.5, preferably 1:1.1-1.3.
The formylation reaction may be a variety of conditions commonly used in the art, for example, the reaction conditions of the formylation reaction may include: the reaction temperature is between-78 and 0 ℃ and the reaction time is between 8 and 12 hours.
After the reaction, the reaction product may be purified by various purification methods commonly used in the art, for example, a dilute hydrochloric acid quenching reaction may be employed, extraction may be performed using an organic solvent (for example, ethyl acetate), and the crude product may be purified by separation by a chromatography column or recrystallization after the solvent is removed.
In a specific embodiment of the present invention, formylation is carried out using iodo-N-phenylimidazole as a starting material under the action of an organolithium reagent and N, N-dimethylformamide to give compound 2.
2) Wittig reaction
In the present invention, compound 2 is subjected to wittig reaction with a wittig reagent or wittig-hall reagent in the presence of a second organic solvent and a base to give compound 3.
The second organic solvent may be one or more of tetrahydrofuran, toluene, n-hexane and diethyl ether. The amount of the solvent is not particularly limited as long as the reaction proceeds smoothly, and may be a conventional amount in the art.
As the base, for example, one or more of NaH, alkyl lithium, sodium alkoxide, and sodium amide; naH is preferred.
The molar ratio of compound 2 to the base may be, for example, 1:1-1.5, preferably 1:1.1-1.3.
The wittig reagent may be: ph (Ph) 3 P＝CR 6 COOEt。
The wittig-hopanax reagent may be (EtO) 2 POCHR 6 CO 2 Et and/or (EtO) 2 POCHR 6 CO 2 Me, preferably (EtO) 2 POCHR 6 CO 2 Et。
R in the above chemical formula 6 Can be correspondingly replaced by R 7 To prepare substituent R 7 Is a compound of (a).
The molar ratio of compound 2 to wittig or wittig-hall agent is 1:1-1.5, preferably 1:1-1.3.
The reaction conditions of the wittig reaction include: the reaction temperature is 0-45 ℃ and the reaction time is 5-20h; preferably, the reaction conditions of the wittig reaction include: the reaction temperature is 0-40 ℃ and the reaction time is 8-15h.
After the reaction, the reaction product may be purified by various purification methods commonly used in the art, for example, water quenching reaction, extraction with an organic solvent (for example, ethyl acetate) may be used, and purification of the crude product by separation by a column chromatography or recrystallization after removal of the solvent.
3) Hydrogenation and hydrolysis reactions
In the present invention, compound 3 is hydrogenated with hydrogen in the presence of a third organic solvent and a hydrogenation catalyst, and then subjected to hydrolysis to obtain compound 4.
Specifically, the compound 3 was subjected to hydrogenation to obtain the following compound 9, and the compound 9 was subjected to hydrolysis to obtain the compound 4.
The hydrogenation catalyst may be a palladium-carbon catalyst.
The amount of the hydrogenation catalyst may be 0.5 to 1.5% by mass based on the total mass of the hydrogenation reaction system.
The third organic solvent can be an alcohol solvent, and can be one or more of ethanol, methanol and isopropanol; ethanol is preferred. The amount of the solvent is not particularly limited as long as the reaction proceeds smoothly, and may be a conventional amount in the art.
The hydrogenation conditions include: the reaction temperature is 5-40 ℃ and the reaction time is 10-48h; preferably, the hydrogenation conditions include: the reaction temperature is 5-30 ℃ and the reaction time is 20-30h.
After the hydrogenation reaction is completed, the reaction product may be purified by various purification methods commonly used in the art, for example, the catalyst may be removed by filtration, and the solvent may be removed, and the resulting solid product may be used for the next hydrolysis reaction.
The hydrolysis reaction may be a hydrolysis reaction in the presence of a fourth organic solvent and an acid, and the acid may be hydrochloric acid. The amount of the acid is not particularly limited and may be a conventional amount used in the art for hydrolysis.
The fourth organic solvent may be an alcohol solvent, and the alcohol solvent may be one or more of methanol, ethanol, and isopropanol; preferably methanol.
The conditions of the hydrolysis reaction are not particularly limited as long as the hydrolysis reaction proceeds sufficiently, and preferably the hydrolysis reaction is performed under reflux, and the reaction time may be, for example, 10 to 50 hours.
The concentration of the acid as the hydrolysis reaction may be 15 to 40 mass%, preferably 25 to 37 mass%.
The post-treatment of the hydrolysis reaction may be performed by a method conventional in the art, and may be, for example: after the solvent is removed, water is added for washing, then an organic solvent (for example, ethyl acetate can be used) is used for extraction, and after the solvent is removed, the crude product is separated by a chromatographic column or is recrystallized, etc. for purification.
4) Friedel-crafts acylation reaction
In the present invention, compound 4 is subjected to friedel-crafts acylation in the presence of polyphosphoric acid to give compound 5.
The amount of the polyphosphoric acid to be used may be in excess as long as the reaction proceeds sufficiently, and for example, may be 1 to 10 parts by weight, preferably 1 to 5 parts by weight, more preferably 1.5 to 2 parts by weight, relative to 1 part by weight of the compound 4.
The reaction conditions of the friedel-crafts acylation reaction include: the reaction temperature is 50-90 ℃ and the reaction time is 3-20h; preferably, the conditions of the friedel-crafts acylation reaction include: the reaction temperature is 70-90 ℃ and the reaction time is 5-10h.
The post-treatment of the friedel-crafts acylation reaction may be performed by a method conventional in the art, for example, may be: the reaction mixture is diluted with ice water, extracted with an organic solvent (for example, ethyl acetate), and the solvent is removed to purify the crude product by separation with a column chromatography or recrystallization.
5) Carbonyl reduction and elimination reactions
In the present invention, the compound 5 is subjected to carbonyl reduction and elimination in the presence of a fifth organic solvent to obtain a compound 6.
Specifically, the carbonyl reduction reaction gives the following compound 10, and the elimination reaction of the compound 10 gives the compound 6.
The fifth organic solvent may be one or more of tetrahydrofuran, toluene, n-hexane and diethyl ether, and preferably diethyl ether. The amount of the solvent is not particularly limited as long as the reaction proceeds smoothly, and may be a conventional amount in the art.
As the reducing agent for the carbonyl reduction reaction, those conventionally used in the art for reducing carbonyl groups can be used, for example, liAlH can be used 4 。
The molar ratio of the compound 5 to the reducing agent may be, for example, 1:1-5, preferably 1:1-3, more preferably 1:2-2.5.
The reaction conditions of the carbonyl reduction reaction include: the reaction temperature is 10-40 ℃ and the reaction time is 10-50h; preferably, the conditions of the carbonyl reduction reaction include: the reaction temperature is 10-30 ℃ and the reaction time is 20-30h.
The post-treatment of the carbonyl reduction reaction may be performed by a method conventional in the art, and may be, for example: after filtering to remove solid substances, the filter cake is washed with an organic solvent (for example, diethyl ether), and the washing solution and the filtered solution are combined and the solvent is removed for the next reaction.
The elimination reaction is an elimination reaction performed in the presence of a sixth organic solvent and a catalyst, and toluene may be used as the sixth organic solvent. The amount of the solvent is not particularly limited as long as the reaction proceeds smoothly, and may be a conventional amount in the art.
As a catalyst for the elimination reactionThe agent can be TsOH, H 2 SO 4 、H 3 PO 4 And Al 2 O 3 Preferably TsOH.
The molar ratio of the catalyst of the elimination reaction to compound 5 may be 0.05 to 0.3:1, preferably 0.08-0.15:1.
the reaction conditions of the elimination reaction include: the reaction temperature is 80-130 ℃ and the reaction time is 10-48h; preferably, the reaction conditions of the elimination reaction include: the reaction temperature is 105-125 ℃ and the reaction time is 20-30h.
The post-treatment of the elimination reaction may be performed by a method conventional in the art, and may be, for example: after the solvent is removed, water is added, and then extraction is performed using an organic solvent (for example, ethyl acetate may be used), and after the solvent is removed, the crude product is purified by separation by a column, recrystallization, or the like.
6) Deprotonation addition reactions and silane bridging reactions.
In the invention, in the presence of a seventh organic solvent, reacting a compound 6 with a deprotonating reagent, then carrying out nucleophilic addition reaction with halogenated hydrocarbon, and then carrying out silicon bridging reaction on the obtained reaction product and dihalogenated dimethyl silane to obtain a compound 7;
specifically, the compound 6 reacts with a deprotonating agent and then carries out nucleophilic addition reaction with halogenated hydrocarbon to obtain a compound 11, and the compound 11 and dihalodimethylsilane carry out silicon bridging reaction to obtain the following compound 7.
The deprotonating agent may be one or more of n-butyllithium, isobutyllithium and tert-butyllithium, preferably n-butyllithium.
The halogenated hydrocarbon is a compound represented by the following formula (2):
R 6 x-type (2),
wherein X is one or more of chlorine, bromine and iodine.
The molar ratio of the deprotonating agent to compound 6 may be 1-1.5:1, preferably 1-1.3:1.
the seventh organic solvent may be one or more of tetrahydrofuran, toluene, n-hexane and diethyl ether, preferably tetrahydrofuran. The amount of the solvent is not particularly limited as long as the reaction proceeds smoothly, and may be a conventional amount in the art.
The reaction conditions of the deprotonation reaction include: the reaction temperature is-78 ℃ to 0 ℃, the reaction time is 5 to 50min, and the preferable reaction time is 25 to 35min.
The molar ratio of halogenated hydrocarbon to compound 6 may be from 1 to 1.5:1, preferably 1-1.3:1.
the reaction conditions for nucleophilic addition reaction with halogenated hydrocarbon include: the reaction temperature is 5-40 ℃ and the reaction time is 0.5-5h; preferably, the reaction conditions for nucleophilic addition reaction with a halogenated hydrocarbon include: the reaction temperature is 10-30 ℃ and the reaction time is 1-2h.
Alternatively, R may be obtained without carrying out the above-mentioned deprotonation and nucleophilic addition reaction 6 A compound which is a hydrogen atom.
Preferably, after the nucleophilic addition reaction is completed, the reaction is quenched with water, extracted with an organic solvent (preferably ethyl acetate), and the solvent is removed and used directly in the next reaction.
Preferably, the silicon bridging reaction with dihalodimethylsilane comprises: the deprotonating agent reacts with the compound 11 in the presence of a solvent, and then dihalodimethylsilane is dropped into the reaction mixture to carry out silicon bridging reaction. The deprotonating agent, solvent and reaction conditions may be the same as those used when the compound 6 reacts with the deprotonating agent.
The dihalodimethylsilane may be dichlorodimethylsilane and/or dibromodimethylsilane.
Since the reaction product is used for the silicon bridging reaction by simple treatments such as extraction after the reaction of the compound 6 with the deprotonating agent and then with the halogenated hydrocarbon, the amount of the dihalodimethylsilane may be selected according to the amount of the compound 6, and preferably, the molar ratio of the dihalodimethylsilane to the compound 6 may be 1 to 1.5:1, more preferably 1-1.3:1.
the reaction conditions of the silicon bridging reaction include: the reaction temperature is 5-40 ℃ and the reaction time is 0.5-5h; preferably, the reaction conditions of the silicon bridging reaction include: the reaction temperature is 10-30 ℃ and the reaction time is 1-2h.
The post-treatment of the silicon bridging reaction may be performed by a method conventional in the art, for example, may be: the reaction is quenched with water, extracted with an organic solvent (preferably ethyl acetate), and the solvent is removed, and the crude product is purified by column chromatography or recrystallization.
7) Preparation of metallocene compounds
In the present invention, compound 7 is reacted with a deprotonating agent in the presence of an eighth organic solvent, and then reacted with a salt of metal M to give compound 8.
The eighth organic solvent may be one or more of tetrahydrofuran, toluene, n-hexane and diethyl ether, preferably tetrahydrofuran. The amount of the solvent is not particularly limited as long as the reaction proceeds smoothly, and may be a conventional amount in the art.
The conditions under which the compound 7 reacts with the deprotonating agent include: the reaction temperature is-78 ℃ to 0 ℃, the reaction time is 5 to 50min, and the preferable reaction time is 25 to 35min.
The deprotonating agent may be one or more of n-butyllithium, isobutyllithium and tert-butyllithium, preferably n-butyllithium.
The molar ratio of the deprotonating agent to compound 7 may be 1-1.5:1, preferably 1-1.3:1.
the salt of the metal M may be, for example, hydrochloride.
Specific examples of the metal M include MCl 4 。
The molar ratio of the salt of the metal M to the compound 7 may be between 0.5 and 2:1, preferably 0.5 to 1.5:1, more preferably 0.5 to 1:1.
after reaction with the deprotonating agent, the conditions for further reaction with the salt of the metal M may include, for example: the reaction temperature is 5-40 ℃ and the reaction time is 10-48h; preferably, the conditions for further reaction with the salt of metal M include: the reaction temperature is 10-30 ℃ and the reaction time is 20-30h.
The post-treatment for the reaction with the salt of the metal M may be carried out by a method conventional in the art, and may be, for example: filtering the reaction solution, washing the precipitate with toluene, combining the filtrates, distilling off part of the solvent under reduced pressure, dropwise adding n-hexane until the precipitate is generated, adding a small amount of toluene to dissolve the precipitate, and crystallizing the solution at-30-0 ℃.
Preferably, the preparation of the compound represented by the formula (1) can be carried out according to the method represented by the following synthesis scheme (1).
Synthetic circuit (1)
The catalyst carrier of the invention has high specific surface area and pore volume, is suitable for loading a metallocene catalyst, is particularly suitable for loading the metallocene compound, and has the advantages of high activity and good fluidity by loading the metallocene compound.
The catalyst carrier of the invention can prepare high-activity metallocene catalyst and improve the preparation efficiency of polyolefin.
The third aspect of the invention provides a catalyst carrier prepared by the preparation method of the catalyst carrier and application of the supported catalyst in preparation of polyolefin.
The present invention will be described in detail by way of examples, but the present invention is not limited to the following examples.
In the following examples, scanning electron microscopes used were HITACHI-S4800 and HITACHI-S1510 manufactured by Hitachi, japan, JEOL JEM-2011 manufactured by Japan electronics, and NOVA3200eandiQ manufactured by instrument, U.S. Kang Da, as BET specific surface area measuring instrument.
Preparation example 1
According to the following combinationSynthesis of metallocene Compound (Compounds 1 to 8: in the Compound of the Structure represented by the formula (1)) in the line (2) 1 -R 4 Is hydrogen, R 5 -R 8 Methyl, M is zirconium)
(1) Formylation reaction
100g (0.37 mol) of iodo-N-phenylimidazole is added into a 1000mL three-necked flask, 200mL of anhydrous tetrahydrofuran is added after nitrogen is fully replaced, and the temperature is cooled to-78 ℃; then 148mL of n-butyllithium solution (2.5M n-hexane solution) was slowly added dropwise; subsequently, 54g (0.74 mol) of anhydrous N, N-dimethylformamide was added dropwise; finally, the temperature is slowly raised to room temperature, and the reaction is carried out overnight. Post-treatment: the reaction was quenched by adding 100mL of dilute hydrochloric acid (10 wt%) and the organic phase was extracted with ethyl acetate, dried and separated by chromatography. Compound 1-2 was obtained in 45.2g and yield was 71%.
(2) Wittig reaction
Taking a 500mL three-neck flask, adding 4.8g of sodium hydride (0.12 mol,60wt% of which is dispersed in mineral oil) and 100mL of dry tetrahydrofuran under the protection of nitrogen, and cooling to 0 ℃; then drop-wise (EtO) 2 POCH(CH 3 )CO 2 Et 28.6g (0.12 mol) and reacted for half an hour; next, a tetrahydrofuran solution (100 mL) of Compound 1-2 (17.2 g,0.1 mol) was added dropwise; finally, the reaction temperature is slowly raised to room temperature for reaction for 10 hours. Post-treatment: adding water to quench reaction, extracting organic phase with ethyl acetate, drying, and separating with chromatographic column. Compound 1-3 was obtained in 25.3g in 99% yield.
(3) Hydrogenation and hydrolysis reactions
A500 mL single-necked flask was charged with 20.5g (0.08 mol) of Compound 1-3, 100mL of ethanol and 1.0g of palladium on carbon (palladium content: 10%) and then a hydrogen balloon was attached thereto, followed by stirring at room temperature for reaction for 24 hours. Post-treatment: the catalyst was removed by filtration and the solvent was evaporated. The obtained solid compound was directly subjected to the next reaction without further purification.
The product obtained in the previous step was dissolved in 200mL of methanol, 20mL of concentrated hydrochloric acid (37 wt%) was added, and the mixture was heated under reflux for 48 hours. Post-treatment: evaporating the solvent, washing with water, extracting the organic phase with ethyl acetate, drying, and separating with chromatographic column. Compounds 1 to 4 were obtained in 15.6g and in 85% yield in two steps.
(4) Friedel-crafts acylation reaction
A250 mL single-necked flask was charged with 11.5g (0.05 mol) of Compound 1-4 and 20g of polyphosphoric acid, and the temperature was raised to 80℃for reaction for 8 hours. Post-treatment: the reaction solution was poured into ice water, extracted with ethyl acetate, dried and separated by a chromatographic column. The yield of the compound 1-5 was 9.5g and 90%.
(5) Carbonyl reduction and elimination reactions
Taking a 100mL single-neck flask, adding 8.5g (0.04 mol) of compound 1-5 and 100mL of anhydrous diethyl ether, and cooling to 0 ℃; 3.0g (0.08 mol) of lithium aluminum hydride are then added in portions; finally, the reaction was carried out at room temperature overnight. Post-treatment: the solid matter is removed by filtration, the filter cake is washed three times with diethyl ether, the filtrates are combined, and the solvent is evaporated for use.
The above product was dissolved in 100mL of toluene, 0.76g (0.004 mol) of p-toluenesulfonic acid monohydrate was added, and the mixture was heated under reflux for 24 hours. Post-treatment: evaporating the solvent, washing with water, extracting with ethyl acetate, and separating with chromatographic column. Compound 1-6 was obtained in 5.7g and yield was 73%.
(6) Deprotonation nucleophilic addition reaction and silicon bridging reaction
Under the protection of nitrogen, adding 19.6g (0.1 mol) of compound 1-6 and 100mL of tetrahydrofuran subjected to drying treatment into a 500mL three-neck flask, and cooling to-78 ℃; then, 40mL (2.5M in n-hexane) of n-butyllithium was added dropwise, and after stirring for 30 minutes, 14.2g (0.1 mol) of methyl iodide was added; finally, the temperature is slowly raised to room temperature, and the reaction is carried out for 1 hour. Post-treatment: adding water to quench the reaction, extracting by adopting ethyl acetate, and evaporating the solvent for later use.
Under the protection of nitrogen, dissolving the product into 100mL of tetrahydrofuran subjected to drying treatment, and cooling to-78 ℃; then, 40mL (2.5M in n-hexane) of n-butyllithium was added dropwise, and after stirring for 30 minutes, 6.45g (0.05 mol) of dichlorodimethylsilane was added; finally, the temperature is slowly raised to room temperature, and the reaction is carried out for 1 hour. Post-treatment: adding water to quench the reaction, extracting with ethyl acetate, and separating with chromatographic column. Compound 1-7 was obtained in 12.2g and yield was 51%.
(7) Preparation of metallocene compounds
Under the protection of nitrogen, 4.79g (0.01 mol) of compound 1-7 is taken and dissolved into 50mL of tetrahydrofuran after drying treatment, and the solution is cooled to-78 ℃; then, 4mL (2.5M in n-hexane) of n-butyllithium was added dropwise, and after stirring for 30 minutes, 1.17g (0.005 mol) of zirconium tetrachloride was added; the reaction was allowed to slowly warm to room temperature for 24 hours. Post-treatment: the precipitate was filtered, washed with 50mL toluene and the filtrates combined. Part of the solvent was distilled off under reduced pressure, n-hexane was added dropwise until precipitation was generated, and then a very small amount of toluene was added to dissolve the precipitate. The solution was crystallized at-20℃and filtered to give orange-red crystals, which were dried to give 3.35g of Compound 1-8 in 60% yield. The structure was confirmed by single crystal diffraction.
Example 1
1g of chlorinated polypropylene (the content of chlorine element is 70 mass percent, the molar ratio of Cl/C is 0.92:1, the CPP-70 model is purchased from Shandong Fangfang Gao Xin chemical industry Co., ltd.) is dissolved in 100ml of tetrahydrofuran as a good solvent, fully stirred and heated to 60 ℃, and nitrogen is used as protective gas for condensation and reflux, and fully dissolved for 2 hours; 1000ml of acetone is placed in a beaker and is rapidly stirred, and a disposable injection needle tube is used for rapidly injecting tetrahydrofuran solution dissolved with chlorinated polypropylene into the rapidly stirred acetone serving as a poor solvent; after all the solutions are injected, preparing chlorinated polypropylene microspheres; taking 100ml of the solution containing chlorinated polypropylene microspheres, adding 100ml of distilled water, and distilling under reduced pressure to remove tetrahydrofuran and acetone; pouring the rest solution into a 50ml high-pressure reaction kettle, heating to 350 ℃ at 10 ℃/min, reacting for 8 hours to obtain liquid containing black precipitate, removing supernatant, washing with ethanol solution, and drying to obtain black powder; and (3) placing the black powder into a quartz tube of a tube furnace, and filling nitrogen into the system to ensure that the quartz tube is free of active gases such as oxygen and the like. The black powder was heated at a rate of 10 c/min to a final carbonization temperature of 800 c and held at that temperature for 3 hours. Slowly cooling to 30 ℃ under nitrogen to obtain the carbon microsphere. Mixing the obtained micron carbon spheres with tetramethoxy siloxane according to a mass ratio of 1:25, mixing and adsorbing for 4 hours at 100 ℃, and roasting the mixed and adsorbed product for 6 hours at 400 ℃ to obtain the catalyst carrier.
Example 2
1g of chlorinated polypropylene (the content of chlorine element is 70 mass percent, the molar ratio of Cl/C is 0.92:1, the CPP-70 model is purchased from Shandong Fangfang Gao Xin chemical industry Co., ltd.) is dissolved in 100ml of dimethyl sulfoxide serving as a good solvent, fully stirred and heated to 120 ℃, and nitrogen is used as protective gas for condensation reflux, and fully dissolved for 2 hours; 1000ml of acetone is placed in a beaker and is rapidly stirred, and a disposable injection needle tube is used for rapidly injecting tetrahydrofuran solution dissolved with chlorinated polypropylene into the rapidly stirred acetone serving as a poor solvent; after all the solutions are injected, preparing chlorinated polypropylene microspheres; taking 100ml of the solution containing chlorinated polypropylene microspheres, and distilling under reduced pressure of-0.1 MPa; pouring the rest solution into a 50ml high-pressure reaction kettle, heating to 350 ℃ at 10 ℃/min, reacting for 8 hours to obtain liquid containing black precipitate, removing supernatant, washing with ethanol solution, and drying to obtain black powder; and (3) placing the black powder into a quartz tube of a tube furnace, and filling nitrogen into the system to ensure that the quartz tube is free of active gases such as oxygen and the like. The black powder was heated at a rate of 10 c/min to a final carbonization temperature of 800 c and held at that temperature for 3 hours. Slowly cooling to 30 ℃ under nitrogen to obtain the carbon microsphere. Mixing the obtained micron carbon spheres with tetramethoxy siloxane according to a mass ratio of 1:25, mixing and adsorbing for 4 hours at 100 ℃, and roasting the mixed and adsorbed product for 4 hours at 400 ℃ to obtain the catalyst carrier.
FIG. 1 is an SEM image of the support obtained in example 2, and the support is shown in FIG. 1 to be in the form of a micron-sized sphere.
Examples 3 to 5
A catalyst support was prepared in the same manner as in example 2, except that the kinds of good solvent, poor solvent and siloxane used were changed, and the mass ratio of the carbon microsphere to the siloxane was as shown in Table 1.
Comparative example 1
A catalyst support was prepared as in example 2, except that no siloxane mixing adsorption was performed.
TABLE 1
| Examples numbering | Good solvent | Poor solvent | Siloxane species | Mass ratio of micrometer carbon spheres to siloxane |
| Example 1 | Tetrahydrofuran (THF) | Acetone (acetone) | Tetramethoxysilane | 1：25 |
| Example 2 | Dimethyl sulfoxide | Acetone (acetone) | Tetramethoxysilane | 1：25 |
| Example 3 | Toluene (toluene) | Ethanol | Tetraethoxysilane | 1：30 |
| Example 4 | Tetrahydrofuran (THF) | Water and its preparation method | Tetraethoxysilane | 1：40 |
| Example 5 | Toluene (toluene) | Ethanol | Trimethoxychlorosilane | 1：45 |
| Comparative example 1 | Dimethyl sulfoxide | Acetone (acetone) | / | / |
Example 6
1.0g of the support obtained in example 1 was dispersed in 5mL of toluene, heated to 60℃with stirring, immersed in 5mL of a toluene solution (1.4 mol/L) of Methylaluminoxane (MAO) for 7 hours, and then washed with 10mL of toluene 5 times to remove excess MAO, thereby obtaining SiO 2 MAO was suspended in 10ml toluene. Then 30mg of Compounds 1-8 are added to SiO 2 Toluene suspension of MAO. After mixing, the mixture was reacted at 50℃for 7 hours, and the unsupported metallocene catalyst was removed by washing 5 times with 10ml of toluene. And (5) drying in vacuum for 5 hours to obtain the supported metallocene catalyst. The mole ratio of the cocatalyst to the metallocene compound in the obtained supported metallocene catalyst calculated by Al element and Zr element is 24:1, the mass ratio of the carrier to the metallocene compound is 1:0.05.
examples 7 to 10
A supported metallocene catalyst was prepared as in example 6, except that the catalyst supports used were the catalyst supports obtained in examples 2-5, respectively.
Comparative example 2
A supported metallocene catalyst was prepared in the same manner as in example 6 except that the catalyst support was the support prepared in comparative example 1.
Test example 1
The average particle diameter of the obtained carrier was measured using a laser particle diameter distribution tester.
The specific surface areas of the obtained support and catalyst and the pore volume of the support and catalyst were measured using a BET specific surface area meter.
The activity of the obtained catalyst was measured by using a propylene bulk polymerization method, and the specific method is as follows:
100mg of metallocene carrier catalyst and 1.2 kg of propylene are added into a 5L steel kettle, the mixture is stirred and reacted for 1 hour at 70 ℃, the reaction is stopped, the material is discharged, and the mixture is dried in a vacuum drying oven for 8 hours to obtain polypropylene. The weight of the obtained polypropylene was weighed, and the catalyst activity was calculated from the weight of the catalyst added.
The average particle diameter, specific surface area and pore volume of the carrier are shown in Table 2, and the catalyst activity is shown in Table 3.
TABLE 2
| Examples numbering | Average particle diameter (μm) | Specific surface area (m) 2 /g) | Pore volume (cm) 3/ g) |
| Example 1 | 5.2 | 315 | 0.32 |
| Example 2 | 6.4 | 250 | 0.35 |
| Example 3 | 5.6 | 449 | 0.41 |
| Example 4 | 7.9 | 289 | 0.39 |
| Example 5 | 4.9 | 464 | 0.53 |
| Comparative example 1 | 4.7 | 203 | 0.29 |
TABLE 2
| Examples numbering | Catalyst Activity (KgPP/gCat.) |
| Example 6 | 25.7 |
| Example 7 | 23.5 |
| Example 8 | 24.8 |
| Example 9 | 20.6 |
| Example 10 | 23.7 |
| Comparative example 2 | 0.89 |
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (20)
1. A method for preparing a catalyst support, comprising the steps of:
1) A step of dissolving a halogen-containing polymer in a good solvent to obtain a mixed solution;
2) Mixing the mixed solution obtained in the step 1) with a poor solvent to obtain a halogen-containing polymer microsphere solution;
3) A step of carrying out a hydrothermal reaction on the halogen-containing polymer microsphere liquid obtained in the step 2);
4) A step of carbonizing the reaction product obtained in the step 3) after solid-liquid separation;
5) Mixing the carbonized product obtained in the step 4) with siloxane for adsorption and roasting,
wherein the halogen content in the halogen-containing polymer is 40 to 85 mass% of the total mass of the halogen-containing polymer, the total content of carbon, hydrogen and halogen in the halogen-containing polymer is 90 mass% or more of the total mass of the halogen-containing polymer,
the conditions of the hydrothermal reaction include: the reaction temperature is 200-400 ℃, the reaction time is 1-10h,
the carbonization conditions include: heating for 1-10h under inert atmosphere at 200-1000 ℃,
the siloxane is one or more of tetramethoxy silane, tetraethoxy silane, trimethoxy chlorosilane, triethoxy chlorosilane, dimethoxy dichlorosilane and ethoxy trichlorosilane,
the roasting conditions include: the roasting temperature is 400-800 ℃ and the roasting time is 2-20h.
2. The method of claim 1, wherein the halogen in the halogen-containing polymer is one or more of F, cl, br, and I.
3. The production method according to claim 2, wherein the halogen-containing polymer is one or more of halogenated polyethylene, halogenated polypropylene, halogenated poly-1-butene, halogenated polyvinyl chloride, halogenated poly-1, 1-dichloroethylene, halogenated poly-1, 2-dichloroethylene, halogenated poly-1, 2-trichloroethylene, halogenated poly-3-chloropropene, halogenated polychloroprene, halogenated polybrominated ethylene, halogenated poly-3-bromopropene and halogenated polybrominated butene.
4. The process according to claim 3, wherein the concentration of the halogenated polyolefin polymer in the good solvent is 0.5 to 20% by mass.
5. The production process according to claim 3, wherein the good solvent is one or more of tetrahydrofuran, toluene, xylene, chloroform, trichlorobenzene, o-dichlorobenzene, p-dichlorobenzene, 2, 4-dichlorophenol, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
6. The process according to claim 3, wherein the volume ratio of the good solvent to the poor solvent is 1:1-100.
7. The production method according to claim 3, wherein the poor solvent is one or more of water, ammonia, methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, glycerol, n-octanol, benzyl alcohol, acetone, butanone, n-hexane, cyclohexane, methyl ether, diethyl ether, n-propyl ether, n-butyl ether, ethyl acetate and butyl acetate.
8. The production method according to claim 3, wherein the poor solvent is one or more of water, ammonia, methanol, ethanol, butanol, ethylene glycol, propylene glycol, glycerol, isopropyl alcohol, n-octanol, benzyl alcohol, acetone, butanone, n-hexane, cyclohexane, methyl ether, diethyl ether, n-propyl ether, n-butyl ether, ethyl acetate and butyl acetate.
9. The production method according to any one of claims 1 to 8, wherein in step 2), the conditions of mixing include: the mixing temperature is 0-40deg.C, and the mixing time is 30-120min.
10. The process according to claim 9, further comprising a step of concentrating the mixed solution obtained in step 1) after mixing the mixed solution with a poor solvent.
11. The process according to claim 10, further comprising the step of removing the solvent and adding the poor solvent after mixing the mixed solution obtained in step 1) with the poor solvent.
12. The production method according to any one of claims 1 to 8, wherein the carbonization conditions include: heating to 200-1000 deg.C at 1-20deg.C/min under inert atmosphere, and heating at that temperature for 1-10 hr.
13. The production method according to claim 12, further comprising a step of drying the solid phase obtained by the solid-liquid separation before the carbonization.
14. The method of manufacturing according to claim 13, wherein the drying conditions include: the drying temperature is 60-150deg.C, and the drying time is 0.5-10h.
15. A supported catalyst characterized by being obtained by supporting a metallocene compound and an aluminum-containing cocatalyst on a catalyst support prepared by the method according to any one of claims 1 to 14.
16. The catalyst according to claim 15, wherein the metallocene compound is a compound represented by the following chemical formula (1):
in the formula (1), R 1 -R 8 And may be the same or different, each being a hydrogen atom or a C1-C12 alkyl group, M being one or more of a transition metal element or a lanthanide of groups IIIB, IVB, VB and VIB of the periodic Table of the elements.
17. The catalyst of claim 15, wherein the loading method comprises: and a step of carrying out first contact between the catalyst carrier and the solution containing the aluminum cocatalyst and then carrying out second contact between the catalyst carrier and the solution containing the metallocene catalyst.
18. The catalyst of claim 17, wherein the conditions of the first contact comprise: the contact temperature is 30-100 ℃, and the contact time is 3-10h.
19. The catalyst of claim 17, wherein the conditions of the second contact comprise: the contact temperature is 50-80 ℃, and the contact time is 3-7h.
20. Use of the catalyst support prepared by the preparation method according to any one of claims 1 to 14 or the catalyst according to any one of claims 15 to 19 in the preparation of a polyolefin.
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| CN1590413A (en) * | 2003-08-29 | 2005-03-09 | 中国石油化工股份有限公司 | Silicon modified aluminium oxide and preparation, and its use in loading metallocene catalyst |
| CN110075900A (en) * | 2019-04-30 | 2019-08-02 | 上海师范大学 | The mesoporous carbon-silica catalyst material and preparation method and application of supported palladium |
| CN110386596A (en) * | 2018-04-18 | 2019-10-29 | 中国科学院化学研究所 | A kind of nanoporous carbon ball and its preparation method and application |
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| CN1590413A (en) * | 2003-08-29 | 2005-03-09 | 中国石油化工股份有限公司 | Silicon modified aluminium oxide and preparation, and its use in loading metallocene catalyst |
| CN110386596A (en) * | 2018-04-18 | 2019-10-29 | 中国科学院化学研究所 | A kind of nanoporous carbon ball and its preparation method and application |
| CN110075900A (en) * | 2019-04-30 | 2019-08-02 | 上海师范大学 | The mesoporous carbon-silica catalyst material and preparation method and application of supported palladium |
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