CN111484573A - Method for synthesizing olefin polymerization catalyst - Google Patents
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- CN111484573A CN111484573A CN201910479334.4A CN201910479334A CN111484573A CN 111484573 A CN111484573 A CN 111484573A CN 201910479334 A CN201910479334 A CN 201910479334A CN 111484573 A CN111484573 A CN 111484573A
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 26
- 239000002685 polymerization catalyst Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 15
- 230000002194 synthesizing effect Effects 0.000 title claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 56
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000012065 filter cake Substances 0.000 claims abstract description 28
- 238000001914 filtration Methods 0.000 claims abstract description 23
- 239000000706 filtrate Substances 0.000 claims abstract description 18
- 239000003446 ligand Substances 0.000 claims abstract description 14
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000008014 freezing Effects 0.000 claims abstract description 7
- 238000007710 freezing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 30
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 10
- -1 (9-fluorenyl) diphenylmethylene Chemical group 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 101710094396 Hexon protein Proteins 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000001376 precipitating effect Effects 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
- PGTKVMVZBBZCKQ-UHFFFAOYSA-N Fulvene Chemical compound C=C1C=CC=C1 PGTKVMVZBBZCKQ-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- 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 provides a synthesis method of an olefin polymerization catalyst, which comprises the following steps: s1, adding the ligand and anhydrous ether into a first container, and slowly dropwise adding a methyl lithium ether solution into the first container for reaction to obtain a solution A; s2, adding anhydrous ether into a second container, and slowly adding zirconium tetrachloride into the second container to obtain a solution B; s3, slowly adding the solution A in the first container into the second container, filtering to obtain a filter cake A, and transferring the filter cake A to a third container; and S4, adding dry chloroform into the third container for treatment, filtering to obtain a filtrate, freezing the filtrate overnight, filtering to obtain a filter cake B, and drying the filter cake B in vacuum to obtain the olefin polymerization zirconium catalyst. The method has the advantages of simpler operation, greatly improved yield, product purity of over 98 percent and suitability for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of petrochemical industry, in particular to a synthesis method of an olefin polymerization catalyst.
Background
The existing olefin polymerization catalyst synthesis method is to prepare a ligand into lithium salt, purify the lithium salt, and then perform reflux reaction with zirconium tetrachloride in a heptane solvent. However, the above method has the following drawbacks: (1) the lithium salt sensitivity of the ligand is too high, and the ligand is extracted and is not suitable for amplification; (2) the purity of the product generated by the reaction of the ligand lithium salt and the zirconium tetrachloride is extremely poor, and the recrystallization yield is only 30-40%.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a synthesis method of an olefin polymerization catalyst.
The invention provides a synthesis method of an olefin polymerization catalyst, which comprises the following steps:
s1, under the protection of inert gas and with stirring, adding the ligand and anhydrous ether into a first container, and slowly dropwise adding a methyl lithium ether solution into the first container for reaction to obtain a solution A;
s2, adding anhydrous ether into a second container under the protection of inert gas, and slowly adding zirconium tetrachloride into the second container under stirring to obtain a solution B;
s3, slowly adding the solution A in the first container into the second container under stirring, filtering under the protection of inert gas to obtain a filter cake A, and transferring the filter cake A to the third container under the protection of inert gas;
s4, adding dry chloroform into the third container for treatment under stirring, filtering under the protection of inert gas to obtain filtrate, freezing the filtrate overnight, filtering under the protection of inert gas to obtain filter cake B, and drying the filter cake B in vacuum to obtain the olefin polymerization zirconium catalyst.
Preferably, in S1, the ligand is one of (9-fluorenyl) diphenylmethylene (cyclopentadiene), (2, 7-di-tert-butyl-fluorenyl) diphenylmethylene (cyclopentadiene), and (2, 7-di-tert-butyl-fluorenyl) di-p-tolylmethylene (cyclopentadiene).
Preferably, in S1, the molar ratio of ligand to methyl lithium ethyl ether solution is 1: 2-2.2.
Preferably, in S1, slowly dripping methyl lithium ethyl ether solution into the first container at 0-5 ℃, after dripping, preserving heat for 1-1.5h at 0-5 ℃, naturally heating to room temperature and reacting for 2-6h to obtain solution A.
Preferably, in S2, the molar ratio of zirconium tetrachloride to ligand is 1: 1.
Preferably, in S2, slowly adding zirconium tetrachloride into the second container at-10 to-5 ℃, and naturally heating to room temperature for reaction for 1-1.2h after the addition is finished to obtain a solution B.
Preferably, in S3, the solution A in the first container is slowly added into the second container, the temperature of the second container is controlled not to exceed 20 ℃, and the reaction is carried out for 1-6h at room temperature after the addition is finished.
Preferably, in S3, filtration gives filter cake a, which is washed with dry ether.
Preferably, in S4, dry chloroform is added to the third container for treatment, the mixture is stirred for 1-1.2h at room temperature, the mixture is filtered under the protection of inert gas, the filtrate is washed by chloroform, and the filtrate is frozen at-35 ℃ overnight.
The synthesis method of the olefin polymerization catalyst provided by the invention is simpler and easier to operate, the yield is greatly improved, the product purity exceeds 98%, and the method is suitable for large-scale industrial production.
Drawings
FIG. 1 shows a chemical formula of a zirconium catalyst for olefin polymerization in a method for synthesizing a catalyst for olefin polymerization according to the present invention.
Detailed Description
The invention provides a synthesis method of an olefin polymerization catalyst, which comprises the following steps:
s1, under the protection of inert gas and with stirring, adding the ligand and anhydrous ether into a first container, and slowly dropwise adding a methyl lithium ether solution into the first container for reaction to obtain a solution A;
s2, adding anhydrous ether into a second container under the protection of inert gas, and slowly adding zirconium tetrachloride into the second container under stirring to obtain a solution B;
s3, slowly adding the solution A in the first container into the second container under stirring, filtering under the protection of inert gas to obtain a filter cake A, and transferring the filter cake A to the third container under the protection of inert gas;
s4, adding dry chloroform into the third container for treatment under stirring, filtering under the protection of inert gas to obtain filtrate, freezing the filtrate overnight, filtering under the protection of inert gas to obtain filter cake B, and drying the filter cake B in vacuum to obtain the olefin polymerization zirconium catalyst.
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example one
S1, under the protection of inert gas and stirring, adding 1.1L of dry diethyl ether and 120g of (9-fluorenyl) diphenylmethylene (cyclopentadiene) (0.3026mol) into a first container, dropwise adding 380ml of 1.6M methyl lithium diethyl ether solution (0.6053mol) at 0 ℃, controlling the temperature to be between 0 and 5 ℃, finishing dropwise adding for 40 minutes, preserving heat for 1 hour, naturally heating to room temperature and reacting for 2 hours to obtain solution A, wherein a large amount of orange yellow precipitate exists;
s2, under the protection of inert gas, adding 700ml of dry ether into a second container, slowly adding 70.5g (0.3026mol) of zirconium tetrachloride at the temperature of-10 ℃, controlling the temperature to be not more than-5 ℃, completing the addition for 30 minutes, slowly heating to room temperature, keeping the temperature and stirring for 1 hour to obtain a solution B, wherein a large amount of white powder exists in the solution B;
s3, slowly adding the solution A in the first container into the solution B under stirring, controlling the temperature of the solution B not to exceed 20 ℃, adding for 1 hour, continuing stirring for 1 hour at room temperature after the addition is finished, generating a large amount of red powder, filtering under the protection of inert gas, washing a filter cake with dried diethyl ether, and transferring the filter cake to a third container under the protection of inert gas;
s4, adding 1.5L of dry chloroform into a third container under stirring, stirring for 1 hour at normal temperature, filtering under the protection of inert gas, washing with a small amount of chloroform, taking the filtrate as a dark red clear liquid, freezing the filtrate at-35 ℃ overnight, precipitating a large amount of dark red crystals, filtering under the protection of inert gas, and drying a filter cake in vacuum to obtain 152g of dark red crystals, wherein the yield is 90.5%, the dark red crystals are olefin polymerization zirconium catalysts, and the chemical formula is shown in figure 1, wherein R1 and R2 are both H.
In this example, H1-NMR (400MHz, CDCl3): 8.31(m, 2H, Ar-H), 7.93(m, 4H, Ar-H), 7.6(m, 2H, Ar-H), 7.46(m, 2H, Ar-H), 7.35(m, 4H, Ar-H), 7.05(m, 2H, Ar-H), 6.45(m, 2H, Ar-H), 6.41(m, 2H, CP-H), 5.79(m, 2H, CP-H).
Example two
S1, under the protection of inert gas and stirring, adding 1.1L of dried diethyl ether and 153.8g of (2, 7-di-tert-butyl-fluorenyl) diphenylmethylene (cyclopentadiene) (0.3026mol) into a first container, dropwise adding 380ml of 1.6M methyl lithium diethyl ether solution (0.6053mol) at 0 ℃, controlling the temperature to be between 0 and 5 ℃, finishing dropwise adding for 40 minutes, preserving heat for 1 hour, naturally heating to room temperature and reacting for 4 hours to obtain solution A, wherein a large amount of orange yellow precipitates exist;
s2, under the protection of inert gas, adding 700ml of dry ether into a second container, slowly adding 70.5g (0.3026mol) of zirconium tetrachloride at the temperature of-10 ℃, controlling the temperature to be not more than-5 ℃, completing the addition for 30 minutes, slowly heating to room temperature, keeping the temperature and stirring for 1 hour to obtain a solution B, wherein a large amount of white powder exists in the solution B;
s3, slowly adding the solution A in the first container into the solution B under stirring, controlling the temperature of the solution B not to exceed 20 ℃, adding the solution B for 1.5 hours, continuing stirring at room temperature for 3 hours after the addition is finished to generate a large amount of orange-red powder, filtering under the protection of inert gas, washing a filter cake with dried diethyl ether, and transferring the filter cake to a third container under the protection of inert gas;
s4, adding 1L of dry chloroform into a third container under stirring, stirring at room temperature for 1 hour, filtering under the protection of inert gas, washing with a small amount of chloroform, collecting the filtrate as a dark red clear solution, freezing the filtrate at-35 ℃ overnight, precipitating a large amount of orange red crystals, filtering under the protection of inert gas, and vacuum-drying the filter cake to obtain 185g of orange red crystals with a yield of 91.4%, wherein the dark red crystals are zirconium olefin polymerization catalysts, and the chemical formula is shown in fig. 1, wherein R1 is H, and R2 is t-Bu.
In this example, H1-NMR (400MHz, CDCl3) 8.09(m, 2H, Ar-H), 7.98(m, 2H, Ar-H), 7.91(m, 2H, Ar-H), 7.63(m, 2H, Ar-H), 7.40(m, 6H, Ar-H), 6.40(m, 2H, Ar-H), 6.36(m, 2H, CP-H), 5.71(m, 2H, CP-H), 1.06(m, 18H, tBu-H).
EXAMPLE III
S1, under the protection of inert gas and stirring, adding 1.1L of dry diethyl ether and 162.4g of (27-di-tert-butyl-fluorenyl) di-p-toluene methylene cyclopentadiene (0.3026mol) into a first container, dropwise adding 380ml of 1.6M methyl lithium diethyl ether solution (0.6053mol) at 0 ℃, controlling the temperature to be between 0 and 5 ℃, finishing dropwise adding within 60 minutes, preserving heat for 1.2 hours, naturally heating to room temperature, and reacting for 6 hours to obtain solution A, wherein a large amount of orange yellow precipitates exist;
s2, under the protection of inert gas, adding 700ml of dry ether into a second container, slowly adding 70.5g (0.3026mol) of zirconium tetrachloride at the temperature of-10 ℃, controlling the temperature to be not more than-5 ℃, adding the zirconium tetrachloride after 30 minutes, slowly heating to room temperature, keeping the temperature and stirring for 1.2 hours to obtain a solution B, wherein a large amount of white powder exists in the solution B;
s3, slowly adding the solution A in the first container into the solution B under stirring, controlling the temperature of the solution B not to exceed 20 ℃, adding for 2 hours, continuing stirring at room temperature for 6 hours after the addition is finished to generate a large amount of orange-red powder, filtering under the protection of inert gas, washing a filter cake with dried diethyl ether, and transferring the filter cake to a third container under the protection of inert gas;
s4, adding 1L of dry chloroform into a third container under stirring, stirring at normal temperature for 1.2 hours, filtering under the protection of inert gas, washing with a small amount of chloroform, obtaining a filtrate which is a dark red clear liquid, freezing the filtrate at-35 ℃ overnight, separating out a large amount of orange red crystals, filtering under the protection of inert gas, and drying a filter cake in vacuum to obtain 187g of orange red crystals, wherein the yield is 88.6%, the dark red crystals are olefin polymerization zirconium catalysts, and the chemical formula is shown in figure 1, wherein R1 is CH3，R2＝t-Bu。
In this example, H1-NMR (400MHz, CDCl3) 8.06(m, 2H, Ar-H), 7.81(m, 4H, Ar-H), 7.61(m, 2H, Ar-H), 7.22(m, 4H, Ar-H), 6.34(m, 2H, Ar-H), 6.28(m, 2H, CP-H), 5.69(m, 2H, CP-H), 2.36(m, 6H, CH3), 1.06(m, 18H, tBu-H).
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. A method for synthesizing an olefin polymerization catalyst, comprising the steps of:
s1, under the protection of inert gas and with stirring, adding the ligand and anhydrous ether into a first container, and slowly dropwise adding a methyl lithium ether solution into the first container for reaction to obtain a solution A;
s2, adding anhydrous ether into a second container under the protection of inert gas, and slowly adding zirconium tetrachloride into the second container under stirring to obtain a solution B;
s3, slowly adding the solution A in the first container into the second container under stirring, filtering under the protection of inert gas to obtain a filter cake A, and transferring the filter cake A to the third container under the protection of inert gas;
s4, adding dry chloroform into the third container for treatment under stirring, filtering under the protection of inert gas to obtain filtrate, freezing the filtrate overnight, filtering under the protection of inert gas to obtain filter cake B, and drying the filter cake B in vacuum to obtain the olefin polymerization zirconium catalyst.
2. The method for synthesizing an olefin polymerization catalyst as recited in claim 1, wherein in S1, the ligand is one of (9-fluorenyl) diphenylmethylene (cyclopentadiene), (2, 7-di-t-butyl-fluorenyl) diphenylmethylene (cyclopentadiene), and (2, 7-di-t-butyl-fluorenyl) di-p-tolylmethylenecyclopentadiene.
3. The method for synthesizing an olefin polymerization catalyst according to claim 1, wherein the molar ratio of the ligand to the methyl lithium ethyl ether solution in S1 is 1:2 to 2.2.
4. The method for synthesizing the olefin polymerization catalyst according to any one of claims 1 to 3, wherein in S1, a methyl lithium ethyl ether solution is slowly dripped into the first container at 0-5 ℃, after the dripping is finished, the temperature is kept at 0-5 ℃ for 1-1.5h, and the temperature is naturally raised to room temperature for reaction for 2-6h to obtain a solution A.
5. The method for synthesizing an olefin polymerization catalyst according to any one of claims 1 to 3, wherein in S2, the molar ratio of zirconium tetrachloride to the ligand is 1: 1.
6. The method for synthesizing a catalyst for olefin polymerization according to any one of claims 1 to 3, wherein in S2, zirconium tetrachloride is slowly added to the second vessel at-10 ℃ to-5 ℃, and after completion of the addition, the temperature is naturally raised to room temperature to react for 1 to 1.2 hours, thereby obtaining a solution B.
7. The method for synthesizing a catalyst for olefin polymerization according to any one of claims 1 to 3, wherein the solution A in the first vessel is slowly added to the second vessel in S3, the temperature of the second vessel is controlled not to exceed 20 ℃, and the reaction is carried out at room temperature for 1 to 6 hours after the addition is completed.
8. The method for synthesizing an olefin polymerization catalyst according to any one of claims 1 to 3, wherein in S3, filtration is performed to obtain a filter cake A, and the filter cake A is washed with dehydrated ether.
9. The method for synthesizing a catalyst for olefin polymerization according to any one of claims 1 to 3, wherein in S4, dry chloroform is added to the third vessel for treatment, the mixture is stirred at room temperature for 1 to 1.2 hours, the mixture is filtered under an inert gas atmosphere, the filtrate is washed with chloroform, and the filtrate is frozen at-35 ℃ overnight.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022114635A1 (en) * | 2020-11-25 | 2022-06-02 | 한화솔루션 주식회사 | Transition metal compound, catalyst comprising same, and method for preparing same |
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| WO2022114635A1 (en) * | 2020-11-25 | 2022-06-02 | 한화솔루션 주식회사 | Transition metal compound, catalyst comprising same, and method for preparing same |
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