CN116120377A - Flexible group-containing zirconocene complex and preparation method thereof - Google Patents
Flexible group-containing zirconocene complex and preparation method thereof Download PDFInfo
- Publication number
- CN116120377A CN116120377A CN202211705623.XA CN202211705623A CN116120377A CN 116120377 A CN116120377 A CN 116120377A CN 202211705623 A CN202211705623 A CN 202211705623A CN 116120377 A CN116120377 A CN 116120377A
- Authority
- CN
- China
- Prior art keywords
- flexible group
- reaction
- complex
- zirconocene
- organic solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The invention discloses a flexible group-containing zirconocene complex and a preparation method thereof. The characteristic structural formula is as follows:. The invention has clear reaction mechanism, is easy for large-scale production, has very important significance for industrial production of polyolefin, and simultaneously provides theoretical support and development thought for future catalyst modification and performance development.
Description
Technical Field
The invention belongs to the field of olefin polymerization catalysts, and in particular relates to a flexible group-containing zirconocene complex and a preparation method thereof
Background
As a new generation of olefin polymerization catalyst, the zirconocene complex has great development potential, and the zirconocene complex is matched with alkyl aluminoxane to form a zirconocene catalyst system. Metallocene catalysts belong to the category of metal organic chemistry, which belongs to a complex interdisciplinary, and are related to the fields of medicine, biology, life science, materials and the like, and have very wide development prospect. The application value of the metallocene catalyst in olefin polymerization is relatively high, so that the metallocene catalyst becomes one of the most internationally popular research fields in the last thirty years.
The metallocene complex has the advantages of clear molecular structure, easy reasoning of reaction mechanism and easy amplified production of related products, has very important significance for theoretical research and industrial production of polyolefin industry, and simultaneously provides theoretical support and development thought for future catalyst modification and novel catalysts with higher performance.
Disclosure of Invention
In order to achieve the above purpose, the invention provides a flexible group-containing zirconocene complex and a preparation method thereof, wherein a flexible group-containing cyclopentadienyl derivative is adopted as a ligand to coordinate with hafnium chloride to obtain the flexible group-containing zirconocene complex, and the structural formula is as follows:
the aforementioned flexible group-containing zirconocene complex, wherein R is
The flexible group-containing zirconocene complex is shown in the specification, wherein X is Cl, br and/or I.
The preparation method of the zirconocene complex containing the flexible group comprises the following synthetic reaction paths:
the preparation method of the zirconocene complex containing the flexible group comprises the following steps:
1) The preparation process is carried out under the inert atmosphere condition;
2) Placing CpM in an anhydrous organic solvent, dropwise adding bromoalkane RX at-10 to-20 ℃ and stirring for reacting for 2-6h, and ending the reaction;
3) Washing and extracting for three times after the reaction is finished to obtain yellow oily liquid, and preparing ligand Cp-R containing a flexible group;
4) Placing ligand Cp-R in an anhydrous organic solvent, dropwise adding n-butyllithium into the anhydrous organic solvent at the temperature of-10 to-20 ℃ and stirring the mixture for reaction for 2 to 4 hours;
5) Putting zirconium tetrachloride into an anhydrous organic solvent, slowly dripping the reaction solution obtained after the reaction in the step (4) at the temperature of minus 10 to minus 20 ℃ for 30min, and stirring for 2-4h at the normal temperature.
6) After the reaction is finished, filtering to obtain colorless clear solution, pumping the solvent by an oil pump, and recrystallizing to obtain the complex.
The preparation method for synthesizing the complex containing the flexible group comprises the following steps of: nitrogen or argon.
In the preparation method for synthesizing the complex containing the flexible group, the CpM and four brominating reagents in the step 2) are added according to the mass ratio of 1:1; the solvent is tetrahydrofuran or toluene; the reaction time is 2-6h, the initial reaction temperature is-10 to-20 ℃, and M is lithium, sodium and potassium.
The preparation method for synthesizing the complex containing the flexible group comprises the following steps of: petroleum ether, hexane, heptane, toluene.
The preparation method of the synthetic flexible group-containing complex comprises the following steps of: tetrahydrofuran or toluene.
The preparation method of the synthetic flexible group-containing complex comprises the following steps of: tetrahydrofuran or toluene; the materials are put in according to the proportion of the amount of the ligand and the zirconium tetrachloride material of 2:1.
The foregoing flexible group-containing zirconocene complexes can be used as olefin polymerization zirconocene catalysts.
The beneficial effects are that:
the invention successfully obtains the cyclopentadienyl zirconium complex containing the flexible group by adopting the cyclopentadienyl derivative containing the flexible group as a ligand to be coordinated with hafnium chloride, has clear reaction mechanism, is easy to realize large-scale production, has very important significance for polyolefin industry and industrial production, and simultaneously provides theoretical support and development thinking for novel catalysts with higher performance for future catalyst modification and development.
Drawings
FIG. 1 is a schematic structural diagram of a flexible group-containing zirconocene complex prepared in example 1;
FIG. 2 is a schematic structural diagram of a flexible group-containing zirconocene complex prepared in example 2;
FIG. 3 is a schematic structural diagram of a flexible group-containing zirconocene complex prepared in example 3;
FIG. 4 is a schematic structural diagram of a flexible group-containing zirconocene complex prepared in example 4.
Detailed Description
The invention is described in detail below by way of examples:
example 1
CpNa 1.76 g (0.02 mol) is weighed into a three-mouth bottle of 100mL, dried THF 20 mL is added under the nitrogen condition, after CpNa is completely dissolved in THF to form a dark red solution, the temperature is reduced to-15 ℃ under the ice salt bath condition, and the temperature is kept for 15min when the temperature is reduced to the required temperature; 2-bromo-1, 1-dimethoxyethane 2.4. 2.4 mL (0.02 mol) was slowly added dropwise using a separating funnel, and after the completion of the addition, the reaction was 3 h. After the reaction is finished, the petroleum ether is washed by water for three times, and the yellow oily liquid, namely ligand (MeO) is obtained by purification 2 -CHCH 2 -Cp. Yield: 70 Percent of the total weight of the composition.
Ligand (MeO) 2 -CHCH 2 Cp 1.54 and g (0.01 mol) was added dropwise to a 100mL three-necked flask under nitrogen, 25 mL dry THF was added, cooled to-20℃in an ice-salt bath and kept at the temperature for 15min, n-BuLi 4 mL (2.5 mol/L in hexane) was added dropwise using a separating funnel, after the completion of the addition for 15min, after the temperature was returned to room temperature, the reaction was continued for 2 h.
Weighing ZrCl 4 1.165 g (0.005 mol) in a 100mL three-neck flask, plugging the bottle stopper, vacuumizing and replacing with nitrogen three times, adding 25 mL dry THF, stirring at normal temperature for 30min until ZrCl is obtained 4 After uniform dispersion, zrCl was obtained by using an ice salt bath 4 The THF system was cooled to-20deg.C and the above-prepared (MeO) was applied to a syringe 2 -CHCH 2 The THF solution of CpLi was slowly added dropwise to the low temperature ZrCl 4 In the THF system, reaction 12 h is carried out after the completion of the dropwise addition. The post-treatment process can be carried out in air, THF and toluene are removed under vacuum condition for recrystallization, crude products are frozen and separated out at low temperature, the crude products are filtered to obtain crude products, petroleum ether and toluene are utilized for secondary recrystallization, crystals are frozen and separated out, white solid is obtained after filtration, and the target products are obtained after washing 3 times with petroleum ether at low temperature, as shown in figure 1. Yield: 71 Percent of the total weight of the composition. 1 H NMR (400 MHz, Chloroform-d) δ 6.32 (s, 8H), 4.49 (t, J = 5.4 Hz, 2H), 3.35 (s, 12H), 2.95 (d, J = 5.4 Hz, 4H). 13 C NMR (101 MHz, Chloroform-d) δ 128.73, 118.39, 112.25, 104.26, 53.47, 33.94. FT-IR(KBr,ν,cm -1 );3120, 2950, 2820, 1500, 1492, 1434, 1340, 1300, 1268, 1116, 1040, 1390, 996, 834。
Example 2
Weighing CpNa 1.76 g (0.02 mol) in a three-mouth bottle of 100mL, adding dried THF 20 mL under the condition of nitrogen, cooling to-15 ℃ under the condition of ice salt bath after CpNa is completely dissolved in THF to form a dark red solution, and preserving heat for 15min when the temperature is reduced to the required temperature; 1-bromo-3-methoxypropane 2.16, 2.16 g (0.02 mol) was slowly added dropwise using a separating funnel, and after the completion of the addition, 3. 3 h was reacted. After the reaction is finished, the petroleum ether is washed by water for three times, and the yellow oily liquid, namely ligand CH, is obtained by purification 3 OCH 2 CH 2 CH 2 -Cp. Yield: 72%.
Ligand CH is taken 3 OCH 2 CH 2 CH 2 CP 1.37 g (0.01 mol) was added dropwise to a 100mL three-necked flask under nitrogen, 25 mL dry THF was added, cooled to-20℃in an ice-salt bath and kept at the temperature for 15min, n-BuLi 4 mL (2.5 mol/L in hexane) was added dropwise using a separating funnel, after the completion of the 15min addition, after the temperature was returned to room temperature, the reaction was continued for 2 h.
Weighing ZrCl 4 1.165 g (0.005 mol) in 100mL three-neck flaskIn the process, the bottle stopper is plugged, vacuumized and replaced by nitrogen for three times, 25 mL dry THF is added, and stirring is carried out for 30min at normal temperature until ZrCl is obtained 4 After uniform dispersion, zrCl was obtained by using an ice salt bath 4 Cooling the THF system to-20 ℃, and using a syringe to prepare the CH 3 OCH 2 CH 2 CH 2 Slowly drop-wise addition of a solution of CPLI in THF to ZrCl at low temperature 4 In the THF system, reaction 12 h is carried out after the completion of the dropwise addition. The post-treatment process can be carried out in air, THF and toluene are removed under vacuum condition for recrystallization, crude products are frozen and separated out at low temperature, the crude products are filtered to obtain crude products, petroleum ether and toluene are utilized for secondary recrystallization, crystals are frozen and separated out, white solid is obtained after filtration, and the target products are obtained after washing 3 times with cold petroleum ether, as shown in figure 2. Yield: 74 Percent of the total weight of the composition. 1 H NMR (400 MHz, Chloroform-d) δ 6.30 (s, 2H), 6.22 (s, 2H), 3.38 (t, J = 6.4 Hz, 2H), 3.33 (s, 3H), 2.71 (s, 2H), 1.83 (s, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 134.29, 116.74, 112.48, 71.87, 58.61, 30.46, 26.74. FT-IR(KBr,ν,cm -1 );3100, 3085, 2976, 2930, 2745, 1651, 1480, 1449, 1387, 1288, 1114, 1044, 873, 826。
Example 3
Weighing CpNa 1.76 g (0.02 mol) in a three-mouth bottle of 100mL, adding dried THF 20 mL under the condition of nitrogen, cooling to-15 ℃ under the condition of ice salt bath after CpNa is completely dissolved in THF to form a dark red solution, and preserving heat for 15min when the temperature is reduced to the required temperature; (2-Bromoethoxy) -t-butyldimethylsilane 4.78, g (0.02 mol) was slowly added dropwise using a separatory funnel and reacted for 3. 3 h after the completion of the addition for 30 minutes. Washing petroleum ether after the reaction is finished, extracting for three times, and purifying to obtain yellow oily liquid, namely ligand H 3 OCH 2 CH 2 CH 2 -Cp. Yield: 73 Percent of the total weight of the composition.
Ligand taking t Bu-(CH 3 CH 3 )SiOCH 2 CH 2 Cp 2.24 g (0.01 mol) was added dropwise to a 100ml three-necked flask under nitrogen, 25: 25 mL dry THF was added, cooled to-20℃in an ice-salt bath and kept at the temperature for 15min, and n-BuLi 4 mL (2.5)mol/L in hexane), after the completion of the dropwise addition for 15min, the reaction was continued for 2 h after the temperature was restored to room temperature.
Weighing ZrCl 4 1.165 g (0.005 mol) in a 100mL three-neck flask, plugging the bottle stopper, vacuumizing and replacing with nitrogen three times, adding 25 mL dry THF, stirring at normal temperature for 30min until ZrCl is obtained 4 After uniform dispersion, zrCl was obtained by using an ice salt bath 4 Cooling the THF system to-20deg.C, and making into the final product by using syringe t Bu-(CH 3 CH 3 )SiOCH 2 CH 2 The THF solution of CpLi was slowly added dropwise to the low temperature ZrCl 4 In the THF system, reaction 12 h is carried out after the completion of the dropwise addition. The post-treatment process can be carried out in air, THF is removed under vacuum condition, toluene is recrystallized, crude products are frozen and separated out at low temperature, the crude products are filtered to obtain crude products, petroleum ether and toluene are utilized for secondary recrystallization of the crude products, crystals are frozen and separated out, white solids are obtained by filtration, and the target products are obtained by washing 3 times with the frozen petroleum ether, as shown in figure 3. Yield: 77 Percent of the total weight of the composition. 1 H NMR (400 MHz, Chloroform-d) δ 6.30 (d, J = 13.4 Hz, 4H), 3.78 (s, 2H), 2.83 (s, 2H), 0.87 (s, 9H), -0.00 (s, 6H). 13 C NMR (101 MHz, Chloroform-d) δ 131.65, 117.70, 112.50, 63.43, 33.86, 25.94, 18.30, -5.35. FT-IR(KBr,ν,cm -1 );3120, 2912, 2905, 2850, 1494, 1300, 1251, 1124, 1098, 932, 805。
Example 4
Weighing CpNa 1.76 g (0.02 mol) in a 100mL three-necked flask, adding dried THF 20 mL under the condition of nitrogen, cooling to-15 ℃ under the condition of ice salt bath after CpNa is completely dissolved in THF to form a dark red solution, and preserving heat for 15min when the temperature is reduced to the required temperature; bromoisooctane 3.86 g (0.02 mol) was slowly added dropwise via a separating funnel, and after completion of the addition, the reaction was 3 h. After the reaction is finished, the petroleum ether is washed by water for three times, and pure yellow oily liquid, namely ligand CH, is obtained by purification 3 CH 2 CH 2 CH 2 C(CH 2 CH 3 )CH 2 -Cp. Yield: 69%.
Ligand CH is taken 3 CH 2 CH 2 CH 2 C(CH 2 CH 3 )CH 2 Cp 1.78 g (0.01 mol) was added dropwise to a 100mL three-necked flask under nitrogen, 25 mL dry THF was added, cooled to-20℃in an ice-salt bath and kept at that temperature for 15min, n-BuLi 4 mL (2.5 mol/L in hexane) was slowly added dropwise using a separating funnel, and the reaction was continued for 2 h after the completion of the 15min addition.
Weighing ZrCl 4 1.165 g (0.005 mol) in a 100mL three-neck flask, plugging the bottle stopper, vacuumizing and replacing with nitrogen three times, adding 25 mL dry THF, stirring at normal temperature for 30min until ZrCl is obtained 4 After uniform dispersion, zrCl was obtained by using an ice salt bath 4 Cooling the THF system to-20 ℃, and using a syringe to prepare the CH 3 CH 2 CH 2 CH 2 C(CH 2 CH 3 )CH 2 The THF solution of CpLi was slowly added dropwise to the low temperature ZrCl 4 In the THF system, reaction 12 h is carried out after the completion of the dropwise addition. The post-treatment process can be carried out in air, THF is removed under vacuum condition, toluene is recrystallized, crude products are frozen and separated out at low temperature, the crude products are filtered to obtain crude products, petroleum ether and toluene are utilized for secondary recrystallization, crystals are frozen and separated out, white solids are obtained by filtration, and the target products are obtained by washing 3 times with the frozen petroleum ether, as shown in figure 4. Yield: 75 Percent of the total weight of the composition. 1 H NMR (400 MHz, Chloroform-d) δ 6.25 (d, J = 39.1 Hz, 8H), 2.57 (s, 4H), 1.47 (s, 2H), 1.26 (s, 16H), 0.87 (s, 12H). 13 C NMR (101 MHz, Chloroform-d) δ 133.18, 132.69, 119.08, 117.96, 117.68, 41.10, 32.47, 28.79, 25.63, 23.01, 14.11, 10.87. FT-IR(KBr,ν,cm -1 );3112, 2980, 2920, 2810, 1502, 1490, 1300, 1250, 1050, 920, 810。
Claims (10)
3. The flexible group-containing zirconocene complex according to claim 1, wherein: wherein X is Cl, br and/or I.
4. A preparation method of a zirconocene complex containing a flexible group is characterized by comprising the following steps: the method comprises the following steps:
1) The preparation process is carried out under the inert atmosphere condition;
2) Placing CpM in an anhydrous organic solvent, dropwise adding bromoalkane RX at-10 to-20 ℃ and stirring for reacting for 2-6h, and ending the reaction;
3) Washing and extracting for three times after the reaction is finished to obtain yellow oily liquid, and preparing ligand Cp-R containing a flexible group;
4) Placing ligand Cp-R in an anhydrous organic solvent, dropwise adding n-butyllithium into the anhydrous organic solvent at the temperature of-10 to-20 ℃ and stirring the mixture for reaction for 2 to 4 hours;
5) Putting zirconium halide into an anhydrous organic solvent, slowly dripping the reaction solution obtained after the reaction in the step 4) at the temperature of minus 10 to minus 20 ℃ for 30min, and stirring for 2-4h at the normal temperature;
6) After the reaction is finished, filtering to obtain colorless clear solution, pumping the solvent by an oil pump, and recrystallizing to obtain the complex.
5. The method for preparing a complex containing a flexible group according to claim 4, wherein: the inert atmosphere in step 1) is: nitrogen or argon.
6. The method for preparing a complex containing a flexible group according to claim 4, wherein: in the step 2), the CpM and four brominating reagents are added according to the mass ratio of 1:1; the solvent is tetrahydrofuran or toluene; the reaction time is 2-6h, the initial reaction temperature is-10 to-20 ℃, and M is lithium, sodium and potassium.
7. The method for preparing a complex containing a flexible group according to claim 4, wherein: the water washing extraction solvent in the step 3) is as follows: petroleum ether, hexane, heptane, toluene.
8. The method for preparing a complex containing a flexible group according to claim 4, wherein: the organic solvent in the step 4) is as follows: tetrahydrofuran or toluene.
9. The method for preparing a complex containing a flexible group according to claim 4, wherein: the organic solvent in the step 5) is as follows: tetrahydrofuran or toluene; the materials are put in according to the proportion of the amount of the ligand and the zirconium tetrachloride material of 2:1.
10. Use of a zirconocene complex containing flexible groups according to claim 1, characterized in that: used as a zirconocene catalyst for olefin polymerization.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211705623.XA CN116120377A (en) | 2022-12-29 | 2022-12-29 | Flexible group-containing zirconocene complex and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211705623.XA CN116120377A (en) | 2022-12-29 | 2022-12-29 | Flexible group-containing zirconocene complex and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN116120377A true CN116120377A (en) | 2023-05-16 |
Family
ID=86311080
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202211705623.XA Pending CN116120377A (en) | 2022-12-29 | 2022-12-29 | Flexible group-containing zirconocene complex and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116120377A (en) |
-
2022
- 2022-12-29 CN CN202211705623.XA patent/CN116120377A/en active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Kucht et al. | New syndiospecific catalysts for styrene polymerization | |
CN108250252B (en) | Bridged metallocene compound containing heterocyclic structure and preparation method and application thereof | |
CN111760593A (en) | Application of deprotonated phenyl bridged beta-ketimine lithium compound in hydroboration reaction | |
CN111420709B (en) | Application of N-heterocyclic carbene-based mixed nickel (II) complex in synthesis of 2-linear alkyl benzothiazole compound | |
CN111763135A (en) | Application of deprotonated phenyl bridged beta-ketimine lithium compound in preparation of alcohol from ester | |
EP2650300B1 (en) | Process for production of racemic-form and racemic-form metallocene complexes | |
EP3050892B1 (en) | Imine catalyst for olefin polymerization, and method for producing olefin polymer | |
CN116120377A (en) | Flexible group-containing zirconocene complex and preparation method thereof | |
US7754835B2 (en) | Polymerisation of ethylene and alpha-olefins with phosphino-iminophenol complexes | |
CN100384893C (en) | Halogen substituent ketoimine front transient metal titanium complex, synthesis method and uses | |
CN111848669A (en) | Vanadium complex catalyst containing phenoxy ligand and preparation method and application thereof | |
CN116178451A (en) | Flexible group-containing hafnocene complex and preparation method thereof | |
JP6957818B2 (en) | Arylaminosilane compounds, propylene polymerization catalysts and their manufacture and application | |
CN116284065A (en) | Flexible group-containing rare earth lanthanum/gadolinium complex and preparation method thereof | |
EP0970964A2 (en) | Method for producing titanium complex | |
JP2006503911A (en) | Racemo-selective synthesis of rac-diorganosilylbis (2-methylbenzo [e] indenyl) zirconium compounds | |
Pang et al. | Synthesis and characterization of bis (guanidinate) zirconium complexes | |
JP4579155B2 (en) | Process for the preparation of partially hydrogenated racemic ansa-metallocene complexes | |
JP4556254B2 (en) | Process for producing alkoxytitanium complex | |
CN116789711A (en) | Flexible group-containing metallocene compound hafnium/zirconium complex and preparation method thereof | |
JP5920539B2 (en) | Novel neodymium compound and diene polymerization catalyst containing the same | |
CN107903346A (en) | A kind of double-core rare earth catalyst and the polymerization of preparation method and syndiotactic polytyrene | |
CN116143845A (en) | Flexible group-containing metallocene mixed rare earth lanthanum/gadolinium complex and preparation method thereof | |
FR2852015A1 (en) | STRESSED GEOMETRY CATALYST COMPONENTS COMPRISING A FLUORENYL LIGANT AND BASED ON GROUP IIIB METALS | |
CN108456233B (en) | Bis-schiff base iron complex, application thereof and method for preparing conjugated diene polymer |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |