CN117659101A - Synthesis method of racemosilicon bridged metallocene catalyst - Google Patents
Synthesis method of racemosilicon bridged metallocene catalyst Download PDFInfo
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- 239000012968 metallocene catalyst Substances 0.000 title claims abstract description 54
- 238000001308 synthesis method Methods 0.000 title abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 23
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 18
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003446 ligand Substances 0.000 claims abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 7
- 150000003624 transition metals Chemical class 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 23
- 150000001336 alkenes Chemical class 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 14
- OZIJRVRERJTEGQ-UHFFFAOYSA-N dimethyl-bis(2-methyl-4-phenyl-1h-inden-1-yl)silane Chemical compound CC1=CC(C(=CC=C2)C=3C=CC=CC=3)=C2C1[Si](C)(C)C1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 OZIJRVRERJTEGQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000012065 filter cake Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 4
- 239000000377 silicon dioxide Substances 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 15
- 238000003786 synthesis reaction Methods 0.000 abstract description 15
- 239000003054 catalyst Substances 0.000 abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052710 silicon Inorganic materials 0.000 abstract description 7
- 239000010703 silicon Substances 0.000 abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 239000012265 solid product Substances 0.000 description 24
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229910007926 ZrCl Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- ASGNRCDZSRNHOP-UHFFFAOYSA-N 2-methyl-4-phenyl-1h-indene Chemical compound C1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 ASGNRCDZSRNHOP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Abstract
The invention discloses a synthesis method of a racemosilicon bridged metallocene catalyst, which comprises the following steps: under the protection of protective gas, taking a diether reagent as a solvent, and adding and dissolving a bridged double-indene ligand into the solvent; dropwise adding n-hexane solution of butyl lithium into a solvent at the initial system temperature, stirring, and raising the system temperature to a first temperature after stirring is finished to perform a reaction; reducing the temperature of the system to a second temperature, adding transition metal halide salt into the solvent, then raising the temperature of the system to a third temperature, stirring the solvent for coordination reaction, and obtaining suspension after the reaction is finished; and filtering, washing, decompressing and removing the suspension, and recrystallizing to obtain the racemosilicon bridged metallocene catalyst product. The invention adopts a series of simple and easily available diether reagents as the solvent, can selectively synthesize the racemic silicon bridged metallocene catalyst by controlling the reaction conditions, and can greatly improve the synthesis yield of the catalyst.
Description
Technical Field
The invention belongs to the field of metal catalysts, relates to a synthesis technology of a metallocene catalyst, and in particular relates to a synthesis method of a racemosilicon bridged metallocene catalyst.
Background
Metallocene catalysts are compound catalysts formed by eta 5-bonding of a metal, typically titanium, zirconium and hafnium of group IV, with cyclopentadienyl groups and their derived groups, which are required to be used in the catalysis of polyolefins by the co-action of an auxiliary agent. Compared with the traditional Ziegler-Natta catalyst, the metallocene catalyst has more accurate structure regulation capability, which is mainly dependent on the structure of the metallocene ligand: on the one hand, the metallocene ligand is complexed with a metal of group IV to form a single active site; on the other hand, the metallocene ligand "normalizes" the steric geometry around the single site, thus "normalizing" the coordination insertion chain growth reaction of propylene molecules at the site, resulting in a polymer of high stereoregularity, a common catalyst with high catalytic activity and high stereoselectivity, ethyl or silicon bridged dual metallocene catalysts, which occupy quite important positions in metallocene catalysts, however, existing synthesis of these bridged dual metallocene catalysts tend to synthesize chiral mixtures, i.e. a pair of racemates (racemics) and meso (mesomeric), but in most cases only the racemates are needed to prepare isotactic polyolefins.
Spaleck et al initially obtained a metallocene catalyst containing only racemic by recrystallising a mixture containing both isomers in methylene chloride, but the yield in this process was only 10% -30%. The use of this method in catalyst synthesis is greatly limited.
Schmidt et al, by introducing lithium dinaphtalate and other substances into the rac/meso mixed system and converting meso into rac under the condition of illumination with a certain wavelength, but the method needs to introduce photosensitive substances, which is unfavorable for the subsequent purification operation.
The Jordan group of university of chicago selectively synthesizes metallocene catalysts containing only rac configuration by introducing a large steric hindrance aniline chelate into zirconium tetrachloride, but this method requires the advanced synthesis of this part of ancillary ligand and the introduction of THF as ligand in the zirconium center, which increases multiple reaction steps and greatly reduces efficiency and economy.
Disclosure of Invention
The invention aims to: in order to overcome the defects in the prior art, the synthesis method of the racemic silicon bridged metallocene catalyst is provided, a series of simple and easily obtained diether reagents are adopted as solvents, the racemic silicon bridged metallocene catalyst can be selectively synthesized by controlling reaction conditions, and the synthesis yield of the catalyst can be greatly improved.
The technical scheme is as follows: in order to achieve the above purpose, the invention provides a synthesis method of a racemic silicon bridged metallocene catalyst, comprising the following steps:
s1: under the protection of protective gas, taking a diether reagent as a solvent, and adding and dissolving a bridged double-indene ligand into the solvent;
s2: dropwise adding n-hexane solution of butyl lithium into a solvent at the initial system temperature, stirring, and raising the system temperature to a first temperature after stirring is finished to perform a reaction;
s3: after the reaction of the step S2 is finished, the temperature of the system is reduced to a second temperature, equivalent transition metal halide salt of bridged double-indene ligand is added into the solvent, the temperature of the system is increased to a third temperature, the solvent is stirred for coordination reaction, and suspension is obtained after the reaction is finished;
the principle of cooling and heating is as follows: adding transition metal halide salt can cause heat release increase, overtemperature phenomenon exists, and after the metal halide salt is added, the temperature is raised to fully react;
s4: and filtering, washing, decompressing and removing the suspension, and recrystallizing to obtain the racemosilicon bridged metallocene catalyst product.
Further, the shielding gas in the step S1 is an inert gas such as nitrogen or argon.
Further, the structure of the diether reagent in the step S1 is as follows:
wherein R is 1 、R 2 Independently selected from H or C1-C12 linear alkanes or alkenes.
Further, the bridged bis-indene ligand in step S1 is dimethyl bis (2-methyl-4-phenylindenyl) silane.
Further, the bridged bis-indene ligand in the step S1 has the following structural formula:
wherein R is 1 、R 2 Independently selected from H or C1-C12 linear alkanes or alkenes.
Further, the initial system temperature in the step S2 is between-78 ℃ and 20 ℃, and the first temperature is between 0 ℃ and 25 ℃.
Further, the stirring time in the step S2 is 2.5-3.5 h, and the reaction time is 11-13 h.
Further, in the step S3, the second temperature is between-40 ℃ and-20 ℃, and the third temperature is between 0 and 85 ℃;
the transition metal halide salt is one of titanium tetrachloride, zirconium tetrachloride and hafnium tetrachloride.
Further, the washing method in the step S4 is as follows: and washing the filter cake by using diether reagent.
Further, the structural formula of the racemic silicon bridged metallocene catalyst in the step S4 is as follows:
wherein R is 1 、R 2 Independently selected from C1-C12 chain alkanes, alkenes, or branched alkanes, alkenes; r is R 3 、R 4 Independently selected from C1-C12 chain alkanes, alkenes, or branched alkanes, alkenes; r is R 5 、R 6 Independently selected from C1-C12 chain alkanes, alkenes or branched alkanes, alkenes.
The key innovation point of the invention is that the diether reagent is selected as a solvent system, oxygen atoms in the diether solvent can coordinate with zirconium metal centers, and the diether solvent is similar to the coordination of oxygen atoms in tetrahydrofuran in zirconium tetrachloride, but two oxygen atoms contained in the diether solvent can form a product with a certain space structure, the formation of the meso structure can be limited, and the product with only racemization can be selectively synthesized.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
1. the diether reagent is selected as a solvent system, and the coordination effect of the solvent and the transition metal is used for leading the reaction product to be mainly racemized, thereby greatly improving the selectivity of the racemized compound and greatly improving the synthesis yield of the racemized silicon bridged metallocene catalyst.
2. The synthesis method of the invention has simple and convenient operation, does not add extra reaction steps, adopts shorter chemical reaction steps, simplifies the synthesis reaction process and improves the synthesis efficiency.
Detailed Description
The present invention is further illustrated below in conjunction with specific embodiments, it being understood that these embodiments are meant to be illustrative of the invention only and not limiting the scope of the invention, and that modifications of the invention, which are equivalent to those skilled in the art to which the invention pertains, will fall within the scope of the invention as defined in the claims appended hereto.
Example 1:
the embodiment provides a synthesis method of a racemosilicon bridged metallocene catalyst, and the specific synthesis process comprises the following steps:
1) Under the protection of nitrogen, adding 50ML of diether reagent as a solvent, and adding 6g of dimethyl di (2-methyl-4-phenylindenyl) silane into the solvent to dissolve;
the structure of the diether reagent is as follows:
wherein R is 1 、R 2 Independently selected from H or C1-C12 linear alkanes or alkenes;
2) Dropwise adding 10.8mL of n-hexane solution of butyl lithium into a solvent at the initial system temperature of minus 20 ℃ and stirring for 3h, and after stirring, raising the system temperature to 0 ℃ to perform reaction for 12h;
3) After the reaction, the temperature of the system is reduced to-20 ℃, and ZrCl equivalent to dimethyl di (2-methyl-4-phenyl indenyl) silane is added into the solvent 4 The solid powder is heated to 0 ℃ and stirred for a solvent to carry out coordination reaction, the stirring time is 12h, and suspension is obtained after the reaction is finished;
4) The obtained suspension is filtered through a filter funnel to remove lithium chloride, a filter cake is washed by using 50ML of diether reagent, and the filtrate is combined and decompressed to remove 6.2g of solid product;
5) The solid product was recrystallized in toluene to give 5.3g of metallocene catalyst containing only rac-mechanism.
As a result, in step 4 of this example, the yield of 6.2g of the solid product was 74.7%, the ratio of the metallocene catalyst having the rac structure in the solid product obtained in step 4 was 98%, and the yield of 5.3g of the metallocene catalyst containing only the rac structure in step 5 was 63.8%, so that the total yield of the final product was 63.8%.
Example 2:
the embodiment provides a synthesis method of a racemosilicon bridged metallocene catalyst, and the specific synthesis process comprises the following steps:
1) Under the protection of nitrogen, adding 50ML of diether reagent as a solvent, and adding 6g of dimethyl di (2-methyl-4-phenylindenyl) silane into the solvent to dissolve;
the structure of the diether reagent is as follows:
wherein R is 1 、R 2 Independently selected from H or C1-C12 linear alkanes or alkenes;
2) Dropwise adding 10.8mL of n-hexane solution of butyl lithium into a solvent at the initial system temperature of minus 78 ℃ and stirring for 3h, and after stirring, raising the system temperature to 25 ℃ to perform reaction for 12h;
3) After the reaction is finished, the temperature of the system is reduced to-40 ℃, and the dimethyl di (2-methyl-4-phenylindene) and the solvent are addedRadical) silane equivalent ZrCl 4 The solid powder is heated to 85 ℃ and stirred for a solvent to carry out coordination reaction, the stirring time is 12h, and suspension is obtained after the reaction is finished;
4) The obtained suspension is filtered through a filter funnel to remove lithium chloride, a filter cake is washed by using 50ML of diether reagent, and the filtrate is combined and decompressed to remove 5.2g of solid product;
5) The solid product was recrystallized in toluene to give 4.5g of metallocene catalyst containing only rac-units.
As a result, in the present example, the yield of 5.2g of the solid product in step 4 was 62.65%, the ratio of the metallocene catalyst having the rac structure in the solid product obtained in step 4 was 98%, and the yield of 4.5g of the metallocene catalyst containing only the rac structure in step 5 was 54.2%, so that the total yield of the final product was 54.2%.
Example 3:
the embodiment provides a synthesis method of a racemosilicon bridged metallocene catalyst, and the specific synthesis process comprises the following steps:
1) Under the protection of argon, adding 50ML of diether reagent as a solvent, and adding 6g of dimethyl di (2-methyl-4-phenylindenyl) silane into the solvent to dissolve;
the structure of the diether reagent is as follows:
wherein R is 1 、R 2 Independently selected from H or C1-C12 linear alkanes or alkenes;
2) Dropwise adding 10.8mL of n-hexane solution of butyl lithium into a solvent at the initial system temperature of-50 ℃ and stirring for 3h, and after stirring, raising the system temperature to 15 ℃ to perform reaction for 12h;
3) After the reaction, the temperature of the system is reduced to-30 ℃, and HfCl equivalent to dimethyl di (2-methyl-4-phenyl indenyl) silane is added into the solvent 4 The solid powder is heated to 50 ℃ and stirred for a solvent to carry out coordination reaction, the stirring time is 12h, and after the reaction is finishedObtaining a suspension;
4) The obtained suspension is filtered through a filter funnel to remove lithium chloride, a filter cake is washed by using 50ML of diether reagent, and the filtrate is combined and decompressed to remove 5.5g of solid product;
5) The solid product was recrystallized in toluene to give 5.2g of catalyst containing only the racemic structure.
As a result, in the present example, the yield of 5.2g of the solid product in step 4 was 58.13%, the ratio of the metallocene catalyst having the rac structure in the solid product obtained in step 4 was 98%, and the yield of 4.8g of the metallocene catalyst containing only the rac structure in step 5 was 50.74%, so that the total yield of the final product was 50.74%.
Example 4:
the embodiment provides a synthesis method of a racemosilicon bridged metallocene catalyst, and the specific synthesis process comprises the following steps:
1) Under the protection of nitrogen, adding 50ML of diether reagent as a solvent, and adding 6g of dimethyl di (2-methyl-4-phenylindenyl) silane into the solvent to dissolve;
the structure of the diether reagent is as follows:
wherein R is 1 、R 2 Independently selected from H or C1-C12 linear alkanes or alkenes;
2) Dropwise adding 10.8mL of n-hexane solution of tertiary butyl lithium into a solvent at the initial system temperature of minus 40 ℃ and stirring for 3h, and after stirring, raising the system temperature to 20 ℃ to perform reaction for 12h;
3) After the reaction, the temperature of the system is reduced to-20 ℃, and ZrCl equivalent to dimethyl di (2-methyl-4-phenyl indenyl) silane is added into the solvent 4 The solid powder is heated to 40 ℃ and stirred for a solvent to carry out coordination reaction, the stirring time is 12h, and suspension is obtained after the reaction is finished;
4) The obtained suspension is filtered through a filter funnel to remove lithium chloride, a filter cake is washed by using 50ML of diether reagent, and the filtrate is combined and decompressed to remove 5.1g of solid product;
5) The solid product was recrystallized in toluene to give 4.3g of catalyst containing only the racemic structure.
As a result, in step 4 of this example, the yield of 5.1g of the solid product was 61.39%, the ratio of the metallocene catalyst having the rac structure in the solid product obtained in step 4 was 98%, and the yield of 4.3g of the metallocene catalyst containing only the rac structure in step 5 was 51.76%, so that the total yield of the final product was 50.76%.
Comparative example 1:
the embodiment provides a synthesis method of a racemosilicon bridged metallocene catalyst, and the specific synthesis process comprises the following steps:
1) Under the protection of nitrogen, 50ML of anhydrous toluene is taken as a solvent, and 6g of dimethyl di (2-methyl-4-phenyl indenyl) silane is added and dissolved in the solvent;
2) Dropwise adding 10.8mL of n-hexane solution of butyl lithium into a solvent at the initial system temperature of minus 20 ℃ and stirring for 3h, and after stirring, raising the system temperature to 15 ℃ to perform reaction for 12h;
3) After the reaction is finished, the temperature of the system is reduced to minus 20 ℃, zrCl4 solid powder is added into the solvent, the temperature of the system is increased to 30 ℃, the solvent is stirred for carrying out coordination reaction, the stirring time is 12 hours, and suspension is obtained after the reaction is finished;
4) The resulting suspension was filtered through a filter funnel to remove lithium chloride, and the filter cake was washed with 50ML toluene, and the filtrates were combined and removed under reduced pressure to give 2.2g of solid product;
5) The solid product was recrystallized in toluene to give 0.8g of metallocene catalyst containing only rac-mechanism.
As a result, in step 4 of this example, the yield of 2.2g of the solid product was 26.5%, the ratio of the metallocene catalyst having the rac structure in the solid product obtained in step 4 was 51%, and the yield of 0.8g of the metallocene catalyst containing only the rac structure in step 5 was 9.6%, so that the total yield of the final product was 9.6%.
The nuclear magnetic hydrogen spectrum obtained is as follows:
1H NMR(400MHz，CDCl3)::67.0-7.7(m,16H,arom H),6.9(e,2H,H-C(3)),2.2(s,6H,CHs),1.3(s,6H,CH3Si)。
comparative example 2:
the embodiment provides a synthesis method of a racemosilicon bridged metallocene catalyst, and the specific synthesis process comprises the following steps:
1) Under the protection of nitrogen, adding a mixed solvent of 25ML of anhydrous toluene and 25ML of THF, and adding 6g of dimethyl di (2-methyl-4-phenylindenyl) silane into the mixed solvent to dissolve;
2) Dropwise adding 10.8mL of n-hexane solution of butyl lithium into a solvent at the initial system temperature of minus 78 ℃ and stirring for 3h, and after stirring, raising the system temperature to 0 ℃ to perform reaction for 12h;
3) After the reaction is finished, the temperature of the system is reduced to minus 20 ℃, zrCl is added into the solvent 4 The solid powder is heated to 50 ℃ and stirred for a solvent to carry out coordination reaction, the stirring time is 12h, and suspension is obtained after the reaction is finished;
4) The resulting suspension was filtered through a filter funnel to remove lithium chloride, and the cake was washed with 50ML toluene, and the filtrates were combined and removed under reduced pressure to give 2.5g of solid product;
5) The solid product was recrystallized in toluene to give 0.9g of metallocene catalyst containing only rac-mechanism.
As a result, in step 4 of this example, the yield of 2.5g of the solid product was 23.3%, the ratio of the metallocene catalyst having the rac structure in the solid product obtained in step 4 was 53%, and the yield of 0.9g of the metallocene catalyst containing only the rac structure in step 5 was 10.8%, so that the total yield of the final product was 10.8%.
The nuclear magnetic hydrogen spectrum obtained is as follows:
1H NMR(400MHz，CDCl3)::67.0-7.7(m,16H,arom H),6.9(e,2H,H-C(3)),2.2(s,6H,CHs),1.3(s,6H,CH3Si)。
comparative example 3:
in this example, the data of examples 1 and 2 and comparative examples 1 and 2 were subjected to comparative analysis, and specific comparative data are shown in table 1 below:
TABLE 1
| Example 1 | Example 2 | Comparative example 1 | Comparative example 2 | |
| Crude yield | 74.7％ | 62.65％ | 26.5％ | 23.3％ |
| Yield of essence | 63.8％ | 54.2％ | 9.6％ | 10.8％ |
As can be seen from table 1, examples 1 and 2 were far higher in both the crude yield obtained in step 4 and the final refined yield obtained in step 5 than comparative examples 1 and 2, and examples 1 and 2 were substantially identical to comparative examples 1 and 2 except for the solvents, and the effects of anhydrous ethylene glycol dimethyl ether, anhydrous ethylene glycol diethyl ether as solvents were remarkable and not replaced with other solvents, thus verifying the effectiveness of the scheme of the present invention.
Claims (10)
1. A method for synthesizing a racemosilicon bridged metallocene catalyst, which is characterized by comprising the following steps:
s1: under the protection of protective gas, taking a diether reagent as a solvent, and adding and dissolving a bridged double-indene ligand into the solvent;
s2: dropwise adding n-hexane solution of butyl lithium into a solvent at the initial system temperature, stirring, and raising the system temperature to a first temperature after stirring is finished to perform a reaction;
s3: after the reaction of the step S2 is finished, the temperature of the system is reduced to a second temperature, equivalent transition metal halide salt of bridged double-indene ligand is added into the solvent, the temperature of the system is increased to a third temperature, the solvent is stirred for coordination reaction, and suspension is obtained after the reaction is finished;
s4: and filtering, washing, decompressing and removing the suspension, and recrystallizing to obtain the racemosilicon bridged metallocene catalyst product.
2. The method for synthesizing a racemic silica-bridged metallocene catalyst according to claim 1, wherein the shielding gas in step S1 is nitrogen or argon.
3. The method for synthesizing a racemic silica-bridged metallocene catalyst according to claim 1, wherein the diether reagent in the step S1 has the following structure:
wherein R is 1 、R 2 Independently selected from H or C1-C12 linear alkanes or alkenes.
4. The method for synthesizing a racemic silica bridged metallocene catalyst according to claim 1, wherein the bridged bis-indene ligand in step S1 is dimethyl bis (2-methyl-4-phenylindenyl) silane.
5. The method for synthesizing a racemic silica bridged metallocene catalyst according to claim 1, wherein the bridged bis-indene ligand in step S1 has the following structural formula:
wherein R is 1 、R 2 Independently selected from H or C1-C12 linear alkanes or alkenes.
6. The method for synthesizing a racemic silica-bridged metallocene catalyst according to claim 1, wherein the initial system temperature in step S2 is-78 ℃ to 20 ℃ and the first temperature is 0 ℃ to 25 ℃.
7. The method for synthesizing a racemic silica-bridged metallocene catalyst according to claim 1, wherein the stirring time in the step S2 is 2.5-3.5 hours, and the reaction time is 11-13 hours.
8. The method for synthesizing a racemic silica-bridged metallocene catalyst according to claim 1, wherein in the step S3, the second temperature is-40 ℃ to-20 ℃, and the third temperature is 0-85 ℃;
the transition metal halide salt is one of titanium tetrachloride, zirconium tetrachloride and hafnium tetrachloride.
9. The method for synthesizing a racemic silica-bridged metallocene catalyst according to claim 1, wherein the washing method in step S4 is as follows: and washing the filter cake by using diether reagent.
10. The method for synthesizing a racemic silica-bridged metallocene catalyst according to claim 1, wherein the structural formula of the racemic silica-bridged metallocene catalyst in the step S4 is as follows:
wherein R is 1 、R 2 Independently selected from C1-C12 chain alkanes, alkenes, or branched alkanes, alkenes; r is R 3 、R 4 Independently selected from C1-C12 chain alkanes, alkenes, or branched alkanes, alkenes; r is R 5 、R 6 Independently selected from C1-C12 chain alkanes, alkenes or branched alkanes, alkenes.
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