Metallocene catalyst and its preparation method and application
A nitrogen-containing metallocene catalyst with a modified bridging group enhances the catalytic activity and reduces Tg in COC polymers, addressing the reactivity and Tg challenges of existing zirconium-based catalysts.
Patent Information
- Application Number
- CN202411415893.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-11
- Publication Date
- 2024-12-27
- Estimated Expiration
- 2044-10-11
AI Technical Summary
Existing zirconium-based metallocene catalysts for cycloolefin copolymerization exhibit low reactivity and high glass transition temperature (Tg) due to the large molecular structure of tetracyclododecene (TCD), limiting their effectiveness in producing COC polymers.
A metallocene catalyst with a nitrogen-containing functional group in the bridging unit and ethoxy substituents is synthesized, enhancing the catalytic activity by expanding the bond angle and increasing electron cloud density at the metal center, thereby improving the spatial structure and reducing Tg of the resulting COC polymers.
The new catalyst achieves high catalytic activity with a Tg reduction in ethylene/tetracyclododecene copolymers, producing COC polymers with improved properties and increased catalytic efficiency.
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Figure CN118909005B_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of polymer compounds, and in particular relates to a metallocene catalyst and a preparation method and application thereof. Background Art
[0002] Cyclic olefin copolymer (COC) is an amorphous polymer material that has gradually attracted great attention in recent years. It is widely used in optics, medical treatment, packaging and other fields because of its high transmittance covering the entire spectrum, low birefringence, low water absorption, low density, non-fragile, high Abbe number, stable chemical properties, acid and alkali resistance, and excellent mechanical properties. The preparation of COC depends on polymerization catalysts, among which zirconium-based metallocene catalysts are one of the most important catalysts in cycloolefin copolymerization. In 1998, Wang Qi et al. used Me 2 SiC 2 MCl 2 / MAO (M = Zr, Ti) catalyzes the copolymerization of ethylene and norbornene. Studies have shown that under the same polymerization conditions, Zr has better copolymerization catalytic performance than Ti (ACTA POLYM SIN.1998, 154-159). In 2001, Kaminsky et al. compared a variety of zirconium-based metallocene catalysts with C2 or Cs symmetry to catalyze ethylene cycloolefin copolymerization and found that the C2 symmetric catalyst had the highest catalytic activity and the Cs symmetric catalyst had a higher norbornene insertion rate (MacromolSymp. 2001, 173, 211-225). Walter et al. explored the three zirconocene catalysts Me 2 C(Cp)(fluo)ZrCl 2 , Ph 2 C(Cp)(fluo)ZrCl 2 and Ph 2 C(ind)(Cp)ZrCl 2 The results showed that -Ph 2 Metallocene catalysts with C-as a bridging group can increase the insertion rate of TCD (tetracyclododecene), but the reactivity of the copolymerization reaction is low (Angew. Chem. Int. Ed. 1995, 34(20): 2273-2275).
[0003] TCD is another key monomer of cycloolefin copolymers. Due to its larger molecular structure, TCD leads to low reactivity in E-TCD copolymerization and high Tg (glass transition temperature) of COC polymers containing TCD. Summary of the invention
[0004] The purpose of the present invention is to provide a metallocene catalyst with low cost and high catalytic activity. The present invention also provides a preparation method and application of the metallocene catalyst.
[0005] The metallocene catalyst of the present invention has a structural formula of one of the following structural formulas:
[0006] .
[0007] The preparation method of the metallocene catalyst of the present invention comprises synthesizing component A, component B and catalyst in an anhydrous and oxygen-free environment to obtain the metallocene catalyst; the method comprises the following steps:
[0008] (1) Synthesis of component A
[0009] ① After mixing the ketone with dimethylformamide, add a tetrahydrofuran solution of ethyl chloride and imidazole at -90--50°C, heat to -10-10°C for reaction, filter, and drain the filtrate to obtain solid A;
[0010] ② After the solid A obtained in step ① is dissolved in tetrahydrofuran, a n-butyl lithium n-hexane solution is added at -10-10°C and stirred for reaction for 20-120min, and then hexamethylphosphoric acid triamide is added and stirred for reaction for 20-120min. After the reaction, the solution is cooled to -90--50°C, and carbon tetrabromide is added and stirred for 20-120min, and then heated to room temperature and maintained for 2-4h to obtain a reaction solution;
[0011] ③Saturated NH 4 Cl solution was added to the reaction solution obtained in step ② and stirred for 20-120 min. Then n-hexane was added and mixed to extract the organic phase. Then deionized water was added to wash the organic phase. Saturated CuSO 4 The solution was stirred for 20-120 min, and then extracted to obtain an organic phase, and the solvent was removed in vacuo to obtain solid B;
[0012] ④ After the solid B obtained in step ③ is dissolved in tetrahydrofuran, potassium carbonate, potassium iodide and amine are added, and the reaction is stirred at room temperature. After the reaction is completed, the filtrate is filtered, and the obtained filtrate is washed with deionized water. After washing, the solvent is removed in vacuo to obtain a solid C;
[0013] ⑤ Add the solid C obtained in step ④ to anhydrous ethanol and acetone to dissolve, cool to room temperature after dissolution, filter to obtain crystals, and vacuum dry the crystals to obtain component A;
[0014] (2) Synthesis of component B
[0015] ①ZrCl 4After mixing with dichloromethane, a suspension is obtained; tetrahydrofuran is added to the suspension, stirred, filtered, and a filtrate is obtained; the solvent is removed from the filtrate in vacuo to obtain a solid D;
[0016] ② The solid D obtained in step ① was mixed with n-hexane, filtered, the filter residue was washed, and vacuum dried to obtain component B;
[0017] (3) Catalyst synthesis
[0018] ① Component A is dissolved in tetrahydrofuran, and then a n-butyl lithium n-hexane solution is added and stirred, and the mixture is heated to room temperature and maintained for 1-3 hours to obtain solution A;
[0019] ② Component B is dissolved in tetrahydrofuran to obtain solution B;
[0020] ③ At -80--50°C with stirring, add solution A and solution B to tetrahydrofuran to react for 30-120 min, then return to room temperature to react for 12-24 h, remove tetrahydrofuran from the reaction solution to obtain a solid product A, dissolve the solid product A in dichloromethane, filter to obtain a filtrate, evaporate and concentrate the filtrate to saturation to obtain a liquid product B, add n-hexane to the liquid product B, cool and recrystallize, filter to remove the filtrate, and vacuum dry to obtain a metallocene catalyst.
[0021] In step (1), the ketone in ① is 1-indanone or 2-cyclopentenone; the ratio of ketone, imidazole, tetrahydrofuran solution of ethylene monochloride and dimethylformamide is 1:50-60:500:1300-1500, wherein the ketone is measured in mol, and the imidazole, tetrahydrofuran solution of ethylene monochloride and dimethylformamide are all measured in ml; the concentration of the tetrahydrofuran solution of ethylene monochloride is 1.8-2.2 mol / L, and the reaction time is 1-3 h.
[0022] In step (1) ②, the ratio of solid A, carbon tetrabromide, tetrahydrofuran, n-butyl lithium n-hexane solution and hexamethylphosphoric triamide is 11-16:16.6:120-160:50-70:13-18, wherein solid A and carbon tetrabromide are both measured in g, tetrahydrofuran, n-butyl lithium n-hexane solution and hexamethylphosphoric triamide are all measured in ml; the concentration of n-butyl lithium n-hexane solution is 1 mol / L.
[0023] Step (1) ③ The reaction solution, saturated NH 4 Cl solution, n-hexane, deionized water and saturated CuSO 4 The volume ratio of the solution is 50:7-10:40-60:40-60:15-25.
[0024] In step (1), the amine in step (4) is dimethylamine or pyrrolidine; the ratio of solid B, amine, potassium carbonate, potassium iodide and tetrahydrofuran is 31.2-39.2:7.22-11.38:13.8-41.4:16.6-49.8:500-1000, wherein the solid B, amine, potassium carbonate and potassium iodide are all measured in g, and the tetrahydrofuran is measured in ml; the stirring reaction time is 24-48h.
[0025] In step (1), the ratio of solid C, anhydrous ethanol and acetone is 5:32-45:9-13, wherein solid C is measured in g, and anhydrous ethanol and acetone are both measured in ml; and the dissolution temperature is 55-65°C.
[0026] In step (2) ①, ZrCl 4 , dichloromethane and tetrahydrofuran ratio is 8.8:80-100:5.5, wherein ZrCl 4 The amount of tetrahydrofuran and dichloromethane is measured in g, and the amount of dichloromethane is measured in ml; the stirring time is 30-120 min.
[0027] In step (2) ②, the ratio of solid D to n-hexane is 13:70-100, wherein solid D is measured in g and n-hexane is measured in ml; the stirring time is 10-40 min; washing is washing the filter residue with n-hexane, and the ratio of the filter residue to n-hexane is 13:15-25, wherein the filter residue is measured in g and n-hexane is measured in ml.
[0028] In step (3) ①, the ratio of component A, tetrahydrofuran and n-butyl lithium n-hexane solution is 6.37-9.41:150-200:40-60, wherein component A is measured in g, and tetrahydrofuran and n-butyl lithium n-hexane solution are both measured in ml; the concentration of n-butyl lithium n-hexane solution is 0.8-1.2 mol / L, the stirring temperature is -90--50°C, and the stirring time is 10-30 min.
[0029] In step (3) ②, the ratio of component B to tetrahydrofuran is 7.55:50-70, wherein component B is measured in g and tetrahydrofuran is measured in ml.
[0030] In step (3) ③, the ratio of component A in solution A, component B in solution B and tetrahydrofuran is 6.37-9.41:7.55:40-60, wherein component A and component B are both measured in g, and tetrahydrofuran is measured in ml; and the recrystallization temperature is -24-0°C.
[0031] In step (3) ③, the volume ratio of liquid product B to n-hexane is 1:0.5-1.
[0032] The application of the metallocene catalyst of the present invention is to carry out polymerization reaction of cycloolefin, linear olefin, metallocene catalyst, cocatalyst and solvent to obtain cycloolefin copolymer.
[0033] The cyclic olefin is one or more of tetracyclododecene (TCD) or tetracyclododecene derivatives, and the linear olefin is one or both of ethylene and propylene.
[0034] The co-catalyst is one or more of tri(pentafluorophenyl)boron, triphenylcarbon tetra(pentafluorophenyl)borate, aluminoxane, alkylaluminum or alkylaluminum chloride.
[0035] The aluminoxane is one of methylaluminoxane, ethylaluminoxane or isobutylaluminoxane, the alkylaluminum is one of trimethylaluminum, triethylaluminum, triisobutylaluminum or tri-n-hexylaluminum, and the alkylaluminum chloride is one of diethylaluminum monochloride, sesquiethylaluminum chloride or ethylaluminum dichloride.
[0036] The solvent is one or more of toluene, hexane or heptane.
[0037] The polymerization reaction temperature is 30-100°C, and the polymerization reaction pressure is 0.1-3Mpa.
[0038] The ratio of cycloolefin to metallocene catalyst is 15-20:1, wherein the cycloolefin is measured in g and the metallocene catalyst is measured in μmol.
[0039] The metallocene catalyst of the present invention comprises: metal center-ZrCl 2 -; Bridging group-Pyrrol 2 C- (wherein, pyrrolidinyl, English name: pyrrolidinyl, abbreviated as Pyrrol) or -(NMe 2 ) 2 C-; ligand 3-ethoxy-1H-indene or 2-ethoxycyclopentadiene. The catalyst can make the product E-TCD copolymer have a lower Tg (glass transition temperature). In addition, the catalyst has a high catalytic activity for the ethylene / tetracyclododecene copolymer system, and its catalytic activity can reach 7.0×10 6 g·mol -1 (Zr)·h -1 above.
[0040] The metallocene catalyst of the present invention is (NMe 2 ) 2 C(3-EtO-Ind) 2 ZrCl 2 、Pyrrol 2 C(3-EtO-Ind) 2 ZrCl 2 、(NMe 2 ) 2 C(2-EtO-Cp) 2 ZrCl2 or Pyrrol 2 C(2-EtO-Cp) 2 ZrCl 2 One of them.
[0041] The cycloolefin content in the cycloolefin copolymer prepared by the present invention is 35-50 mol%.
[0042] The beneficial effects of the present invention are as follows:
[0043] The metallocene catalyst prepared by the present invention introduces a nitrogen-containing functional group into the bridging group, expands the bond angle of Cl-Zr-Cl through the electron-rich nitrogen-containing functional group, improves the copolymerization activity of the catalyst for macromolecular cycloolefins, and modifies the spatial structure of the catalyst through the substituent-ethoxy group, so that the steric hindrance of the catalyst is increased to a certain extent, changes the arrangement order of ethylene and tetracyclododecene in the E-TCD polymer, reduces the appearance of TCD concatemer fragments in the polymer chain, and makes TCD distributed in the polymer in the form of isolated sequences as much as possible, thereby reducing the Tg of the COC polymer under the same TCD insertion rate. In addition, the substituent and the bridging structure as electron-donating groups can increase the electron cloud density of the active metal center Zr and enhance the catalytic activity of the catalyst.
[0044] The metallocene catalyst of the invention has the characteristics of simple synthesis and high activity, and the obtained product polymer has low Tg. BRIEF DESCRIPTION OF THE DRAWINGS
[0045] Figure 1 It is the H NMR spectrum of the product obtained in Example 1.
[0046] Figure 2 It is the H NMR spectrum of the product obtained in Example 2.
[0047] Figure 3 It is the H NMR spectrum of the product obtained in Example 3.
[0048] Figure 4 It is the H NMR spectrum of the product obtained in Example 4. DETAILED DESCRIPTION
[0049] The present invention is further described below with reference to the embodiments.
[0050] Example 1
[0051] Metallocene catalyst (NMe 2 ) 2 C(3-EtO-Ind) 2 ZrCl 2 Preparation:
[0052] Component A synthesis, component B synthesis and catalyst synthesis are carried out in an anhydrous and oxygen-free environment to obtain a metallocene catalyst; the method comprises the following steps:
[0053] (1) Synthesis of component A
[0054] ① After 0.15 mol of 1-indanone was mixed with 195 mL of dimethylformamide, 75 mL of a 2 mol / L tetrahydrofuran solution of ethylene monochloride and 7.5 mL of imidazole were slowly added dropwise at -90 °C, and the temperature was gradually raised to -10 °C for 1 h. The mixture was filtered and the solvent was drained from the filtrate to obtain solid A;
[0055] ② Take 16g of the solid A obtained in step ① and dissolve it in 120ml of tetrahydrofuran, start stirring, control the temperature at -10°C, slowly drop 50ml of n-butyl lithium n-hexane solution, react for 20min, add 13ml of hexamethylphosphoric acid triamide (HMPA) and react for 20min, after the reaction, cool the solution to -90°C, slowly drop 16.6g of carbon tetrabromide, stir for 20min, slowly warm to room temperature, keep for 2h, and obtain a reaction solution;
[0056] ③ Add 7 ml saturated NH 4 Cl solution was slowly added to 50 ml of the reaction solution obtained in step ② and stirred for 20 min. After the stirring was completed, the obtained solution was mixed with 40 ml of n-hexane and extracted to obtain an organic phase. Then, 40 ml of deionized water was added to wash the organic phase. 15 ml of saturated CuSO 4 The solution was freed of HMPA, stirred for 20 min, and then extracted to obtain an organic phase, from which the solvent was removed in vacuo to obtain solid B;
[0057] ④ Take 39.2g of the solid B obtained in step ③ and dissolve it in 500ml of tetrahydrofuran, then add 13.8g of potassium carbonate, 16.6g of potassium iodide and 7.22g of dimethylamine, stir at room temperature for 24h, filter after the reaction, wash the filtrate with deionized water, and remove the solvent in vacuo to obtain solid C;
[0058] ⑤ At 55°C and under stirring conditions, add 5g of the solid C obtained in step ④ to 32ml of anhydrous ethanol, and then slowly add 9ml of acetone to completely dissolve it. After the dissolution is completed, slowly cool to room temperature for crystallization, filter to obtain crystals, and vacuum dry the crystals to obtain component A, which is sealed and stored;
[0059] (2) Synthesis of component B
[0060] ①8.8gZrCl 4 Mix with 80 ml of dichloromethane and stir to form a suspension; slowly drop 5.5 g of tetrahydrofuran into the suspension at room temperature, stir for 30 min, and then filter to obtain a filtrate, and remove the solvent from the filtrate in vacuo to obtain solid D;
[0061] ② Mix 13 g of the solid D obtained in step ① with 70 ml of n-hexane, stir for 10 min, filter, wash the filter residue with 15 ml of n-hexane, and dry in vacuo to obtain component B (zirconium tetrachloride tetrahydrofuran complex);
[0062] (3) Catalyst synthesis
[0063] ① Take 8.37g of component A and dissolve it in 150ml of tetrahydrofuran. At -90℃ and under stirring conditions, slowly drop 40ml of 1mol / L n-butyllithium n-hexane solution. Stir for 10min and then slowly warm to room temperature and keep for 1h to obtain solution A.
[0064] ② Take 7.55g of component B and dissolve it in 50ml of tetrahydrofuran to obtain solution B;
[0065] ③ At -60 ° C and stirring conditions, slowly add solution A and solution B to 40 ml of tetrahydrofuran, react at -60 ° C for 80 minutes after the addition, then return to room temperature for 18 hours, remove all the solvent tetrahydrofuran from the reaction solution by vacuum to obtain solid product A, dissolve solid product A in 400 ml of dichloromethane, filter to obtain a filtrate, evaporate and concentrate the filtrate to saturation to obtain liquid product B, slowly add 100 ml of n-hexane to liquid product B, cool to -18 ° C for recrystallization, filter to remove the filtrate, and vacuum dry to obtain 10.53 g of yellow solid product (NMe 2 ) 2 C(3-EtO-Ind) 2 ZrCl 2 , recorded as Zr1; 1HNMR (400MHz, CD 2 Cl 2 ): δ 7.33–7.07 (m, 8H), 5.04 (s, 2H), 4.19–4.02 (m, 4H),1.71 (s, 12H), 1.44–1.39 (m, 6H). The H NMR spectrum of the product is shown in Figure 1 .
[0066] The reaction equation is as follows:
[0067]
[0068] Example 2
[0069] Metallocene Catalyst Pyrrol 2 C(3-EtO-Ind) 2 ZrCl 2 Preparation:
[0070] Component A synthesis, component B synthesis and catalyst synthesis are carried out in an anhydrous and oxygen-free environment to obtain a metallocene catalyst; the method comprises the following steps:
[0071] (1) Synthesis of component A
[0072] ① After 0.15 mol of 1-indanone was mixed with 210 mL of dimethylformamide, 75 mL of a 1.8 mol / L tetrahydrofuran solution of ethylene monochloride and 8 mL of imidazole were slowly added dropwise at -78 °C, and the temperature was gradually raised to 0 °C for 2 h. The mixture was filtered and the solvent was drained from the filtrate to obtain solid A;
[0073] ② Take 15g of the solid A obtained in step ① and dissolve it in 150ml of tetrahydrofuran, start stirring, control the temperature at 0℃, slowly drop 60ml of n-butyl lithium n-hexane solution, react for 60min, add 16ml of hexamethylphosphoric acid triamide (HMPA) and react for 60min, after the reaction, cool the solution to -78℃, slowly drop 16.6g of carbon tetrabromide, stir for 60min, slowly warm to room temperature, keep for 3h, and obtain a reaction solution;
[0074] ③ Add 8.5 ml of saturated NH 4 Cl solution was slowly added to 50 ml of the reaction solution obtained in step ② and stirred for 60 min. After the stirring was completed, the obtained solution was mixed with 50 ml of n-hexane and extracted to obtain an organic phase. Then, 50 ml of deionized water was added to wash the organic phase, and 20 ml of saturated CuSO 4 The solution was freed of HMPA, stirred for 60 min, and then extracted to obtain an organic phase, from which the solvent was removed in vacuo to obtain solid B;
[0075] ④ Take 38.8g of the solid B obtained in step ③ and dissolve it in 750ml of tetrahydrofuran, then add 27.6g of potassium carbonate, 33.2g of potassium iodide and 11.38g of pyrrolidine, stir at room temperature for 36h, filter after the reaction, wash the filtrate with deionized water, and remove the solvent in vacuo to obtain solid C;
[0076] ⑤ At 60°C and under stirring conditions, add 5g of the solid C obtained in step ④ to 38ml of anhydrous ethanol, and then slowly add 11ml of acetone to completely dissolve it. After the dissolution is completed, slowly cool to room temperature for crystallization, filter, and obtain crystals. After the crystals are vacuum dried, component A is obtained, which is sealed and stored;
[0077] (2) Synthesis of component B
[0078] ①8.8gZrCl 4 Mix with 90 ml of dichloromethane and stir to form a suspension; slowly drop 5.5 g of tetrahydrofuran into the suspension at room temperature, stir for 90 min, and then filter to obtain a filtrate, and remove the solvent from the filtrate in vacuo to obtain solid D;
[0079] ② Mix 13 g of the solid D obtained in step ① with 85 ml of n-hexane, stir for 25 min, filter, wash the filter residue with 20 ml of n-hexane, and dry in vacuo to obtain component B (zirconium tetrachloride tetrahydrofuran complex);
[0080] (3) Catalyst synthesis
[0081] ① Take 9.41g of component A and dissolve it in 175ml of tetrahydrofuran. At -78℃ and under stirring conditions, slowly drop 50ml of 1.2mol / L n-butyllithium n-hexane solution. Stir for 20min and then slowly warm to room temperature. Keep for 2h to obtain solution A.
[0082] ② Take 7.55g of component B and dissolve it in 60ml of tetrahydrofuran to obtain solution B;
[0083] ③ At -50 ° C and stirring conditions, slowly add solution A and solution B to 50 ml of tetrahydrofuran, react at -50 ° C for 120 minutes after the addition, then return to room temperature for 12 hours, remove all the solvent tetrahydrofuran from the reaction solution by vacuum to obtain solid product A, dissolve solid product A in 400 ml of dichloromethane, filter to obtain filtrate, evaporate and concentrate the filtrate to saturation to obtain liquid product B, slowly add 130 ml of n-hexane to liquid product B, cool to -24 ° C for recrystallization, filter to remove the filtrate, and vacuum dry to obtain 11.34 g of yellow solid product Pyrrol 2 C(3-EtO-Ind) 2 ZrCl 2 , recorded as Zr2; 1HNMR (400MHz, CD 2 Cl 2 ): δ 7.32–7.12 (m, 8H), 4.79 (s, 2H), 4.19–4.04 (m, 4H),2.81–2.65 (m, 8H), 1.92–1.80 (m, 8H), 1.46–1.42 (m, 6H). The H NMR spectrum of the product is shown in Figure 2 .
[0084] The reaction equation is as follows:
[0085]
[0086] Example 3
[0087] Metallocene catalyst (NMe 2 ) 2 C(2-EtO-Cp) 2 ZrCl 2 Preparation:
[0088] Component A synthesis, component B synthesis and catalyst synthesis are carried out in an anhydrous and oxygen-free environment to obtain a metallocene catalyst; the method comprises the following steps:
[0089] (1) Synthesis of component A
[0090] ① After 0.15 mol of 2-cyclopentenone was mixed with 225 mL of dimethylformamide, 75 mL of a 2.2 mol / L tetrahydrofuran solution of ethylene monochloride and 9 mL of imidazole were slowly added dropwise at -50 °C, and the temperature was gradually raised to 10 °C for 3 h. The mixture was filtered and the solvent was drained from the filtrate to obtain solid A;
[0091] ② Take 11g of the solid A obtained in step ① and dissolve it in 160ml of tetrahydrofuran, start stirring, control the temperature at 10°C, slowly drop 70ml of n-butyl lithium n-hexane solution, react for 120min, add 18ml of hexamethylphosphoric acid triamide (HMPA) and react for 120min, after the reaction, cool the solution to -50°C, slowly drop 16.6g of carbon tetrabromide, stir for 120min, slowly warm to room temperature, keep for 4h, and obtain a reaction solution;
[0092] ③ Add 10 ml saturated NH 4 Cl solution was slowly added to 50 ml of the reaction solution obtained in step ② and stirred for 120 min. After the stirring was completed, the obtained solution was mixed with 60 ml of n-hexane and extracted to obtain an organic phase. Then, 60 ml of deionized water was added to wash the organic phase, and 25 ml of saturated CuSO 4 The solution was freed of HMPA, stirred for 120 min, and then extracted to obtain an organic phase, from which the solvent was removed in vacuo to obtain solid B;
[0093] ④ Take 31.2g of the solid B obtained in step ③ and dissolve it in 1000ml of tetrahydrofuran, then add 41.4g of potassium carbonate, 49.8g of potassium iodide and 7.65g of dimethylamine, stir at room temperature for 48h, filter after the reaction, wash the filtrate with deionized water, and remove the solvent in vacuo to obtain solid C;
[0094] ⑤ At 65°C and under stirring conditions, add 5g of the solid C obtained in step ④ to 45ml of anhydrous ethanol, and then slowly add 13ml of acetone to completely dissolve it. After the dissolution is completed, slowly cool to room temperature for crystallization, filter to obtain crystals, and vacuum dry the crystals to obtain component A, which is sealed and stored;
[0095] (2) Synthesis of component B
[0096] ①8.8gZrCl 4Mix with 100 ml of dichloromethane and stir to form a suspension; slowly drop 5.5 g of tetrahydrofuran into the suspension at room temperature, stir for 120 min, and then filter to obtain a filtrate, and remove the solvent from the filtrate in vacuo to obtain solid D;
[0097] ② Mix 13 g of the solid D obtained in step ① with 100 ml of n-hexane, stir for 40 min, filter, wash the filter residue with 25 ml of n-hexane, and dry in vacuo to obtain component B (zirconium tetrachloride tetrahydrofuran complex);
[0098] (3) Catalyst synthesis
[0099] ① Take 6.37g of component A and dissolve it in 200ml of tetrahydrofuran. At -50℃ and under stirring conditions, slowly drop 60ml of 0.8mol / L n-butyllithium n-hexane solution. Stir for 30min and then slowly warm to room temperature and keep for 3h to obtain solution A.
[0100] ② Take 7.55g of component B and dissolve it in 70ml of tetrahydrofuran to obtain solution B;
[0101] ③ At -80 ° C and stirring conditions, slowly add solution A and solution B to 60 ml of tetrahydrofuran, react at -80 ° C for 30 minutes after the addition, then return to room temperature for 24 hours, remove all the solvent tetrahydrofuran from the reaction solution by vacuum to obtain solid product A, dissolve solid product A in 400 ml of dichloromethane, filter to obtain a filtrate, evaporate and concentrate the filtrate to saturation to obtain liquid product B, slowly add 180 ml of n-hexane to liquid product B, cool to 0 ° C for recrystallization, filter to remove the filtrate, and vacuum dry to obtain 8.23 g of yellow solid product (NMe 2 ) 2 C(2-EtO-Cp) 2 ZrCl 2 , recorded as Zr3; 1H NMR (400MHz, CD 2 Cl 2 ): δ 7.20 (dd, J=7.3, 0.8Hz, 2H), 6.98 (dd, J=7.3, 0.7Hz, 2H),5.06 (s, 2H), 4.15–4.02 (m, 4H), 2.08 (s, 12H), 1.36 (t, J = 5.4 Hz, 6H), the H NMR spectrum of the product is shown in Figure 3 .
[0102] The reaction equation is as follows:
[0103]
[0104] Example 4
[0105] Metallocene Catalyst Pyrrol 2 C(2-EtO-Cp) 2 ZrCl 2 Preparation:
[0106] The dimethylamine was replaced with pyrrolidine, and the other steps were the same as in Example 3 to obtain 9.13 g of a light yellow solid product Pyrrolidine. 2 C(2-EtO-Cp) 2 ZrCl 2 , recorded as Zr4; 1H NMR (400MHz, CD 2 Cl 2 ):δ 7.55 (dd, J = 7.3, 0.9 Hz,2H), 6.98 (dd, J = 7.3, 0.7 Hz, 2H), 5.05 (s, 2H), 4.14–4.03 (m, 4H), 2.74–2.55 (m, 8H), 1.87–1.68 (m, 8H), 1.34 (t, J = 5.2Hz, 6H), see H NMR spectrum of the product. Figure 4 .
[0107] The reaction equation is as follows:
[0108]
[0109] Example 5
[0110] Copolymerization of Ethylene and Tetracyclododecene Catalyzed by Zr1
[0111] The 350 mL polymerization bottle equipped with a stirring magnet was dried continuously at 120 °C for 3 h, and then vacuumed and heated with N 2 Replace 6 times. After the polymerization bottle is cooled down in a nitrogen atmosphere, 80g of tetracyclododecene toluene solution (the mass fraction of tetracyclododecene is 40%) is injected into it with a syringe, and then vacuumed and replaced with ethylene 3 times, and then heated to 50°C. After the heating is completed, 4.5ml of metallocene catalyst Zr1 toluene solution (containing 2μmol of Zr1), 4.5ml of tri(pentafluorophenyl)boron toluene solution and 4.5ml of triisobutylaluminum toluene solution are added to the polymerization bottle in sequence, and the molar ratio of reaction system A1 to Zr is 200, and the molar ratio of B to Zr is 1.5, and then stirred for 3min. After the stirring is completed, ethylene is introduced to keep the ethylene pressure at 0.35Mpa, and the reaction is stirred vigorously for 10min. After the reaction is completed, the temperature is reduced and the pressure is released, and the reaction solution is neutralized with 5% hydrochloric acid acidified ethanol solution to obtain a polymer precipitate, which is washed with ethanol and water several times, vacuum dried to constant weight, and weighed. Catalytic activity: 8.9×10 6 g·mol-1 (Zr)·h -1 ; Polymer Mw: 44.3 kg / mol; Mw / Mn: 2.5; The tetracyclododecene content in the polymer is 43.3 mol%, and the glass transition temperature is 105.2°C.
[0112] Example 6
[0113] Copolymerization of Ethylene and Tetracyclododecene Catalyzed by Zr2
[0114] The metallocene catalyst Zr1 was changed to Zr2, and the other steps were the same as in Example 5. Catalytic activity 1.03×10 7 g·mol -1 (Zr)·h -1 ; Polymer Mw: 45.4 kg / mol; Mw / Mn: 2.1; The tetracyclododecene content in the polymer is 40.6 mol%, and the glass transition temperature is 99.2°C.
[0115] Example 7
[0116] Copolymerization of Ethylene and Tetracyclododecene Catalyzed by Zr3
[0117] The metallocene catalyst Zr1 was changed to Zr3, and the other steps were the same as in Example 5. Catalytic activity: 7.0×10 6 g·mol -1 (Zr)·h -1 ; Polymer Mw: 50.8 kg / mol; Mw / Mn: 2.4; The tetracyclododecene content in the polymer is 47.2 mol%, and the glass transition temperature is 122.9°C.
[0118] Example 8
[0119] Copolymerization of Ethylene and Tetracyclododecene Catalyzed by Zr4
[0120] The metallocene catalyst Zr1 was changed to Zr4, and the other steps were the same as in Example 5. Catalytic activity: 7.2×10 6 g·mol -1 (Zr)·h -1 ; Polymer Mw: 50.3 kg / mol; Mw / Mn: 2.5; The tetracyclododecene content in the polymer is 45.5 mol%, and the glass transition temperature is 116.5°C.
[0121] Example 9
[0122] The temperature was raised from 50°C to 30°C, and the other steps were the same as in Example 6. Catalytic activity: 8.3×10 6 g·mol -1 (Zr)·h -1; Polymer Mw: 55.7 kg / mol; Mw / Mn: 2.6; The tetracyclododecene content in the polymer is 35.3 mol%, and the glass transition temperature is 74.3°C.
[0123] Example 10
[0124] The temperature was raised from 50°C to 80°C, and the other steps were the same as in Example 6. Catalytic activity: 1.22×10 7 g·mol -1 (Zr)·h -1 ; Polymer Mw: 48.6 kg / mol; Mw / Mn: 2.3; The tetracyclododecene content in the polymer is 45 mol%, and the glass transition temperature is 116.3°C.
[0125] Embodiment 11
[0126] The temperature was raised to 100°C instead of 50°C, and the other steps were the same as in Example 6. Catalytic activity: 1.52×10 7 g·mol -1 (Zr)·h -1 ; Polymer Mw: 52.3 kg / mol; Mw / Mn: 2.6; The tetracyclododecene content in the polymer is 49.7 mol%, and the glass transition temperature is 123.2°C.
Claims
1. A metallocene catalyst, characterized in that The structural formula is one of the following: 。 2. A method for preparing the metallocene catalyst according to claim 1, characterized in that Perform component A synthesis, component B synthesis and catalyst synthesis in an anhydrous and oxygen-free environment to obtain a metallocene catalyst; It includes the following steps: (1) Synthesis of component A ① After mixing the ketone with dimethylformamide, add a tetrahydrofuran solution of ethyl chloride and imidazole at -90--50°C, heat to -10-10°C for reaction, filter, drain the filtrate to dry the solvent, and obtain solid A; the ketone is 1-indanone or 2-cyclopentenone; ② After the solid A obtained in step ① is dissolved in tetrahydrofuran, a n-butyl lithium n-hexane solution is added at -10-10°C and stirred for reaction for 20-120min, and then hexamethylphosphoric acid triamide is added and stirred for reaction for 20-120min. After the reaction, the solution is cooled to -90--50°C, and carbon tetrabromide is added and stirred for 20-120min, and then heated to room temperature and maintained for 2-4h to obtain a reaction solution; ③ Add saturated NH4Cl solution to the reaction solution obtained in step ② and stir for 20-120 min, then add n-hexane to mix, extract to obtain an organic phase, then add deionized water to wash the organic phase, add saturated CuSO4 solution and stir for 20-120 min, then extract to obtain an organic phase, remove the solvent in vacuo to obtain solid B; ④ After the solid B obtained in step ③ is dissolved in tetrahydrofuran, potassium carbonate, potassium iodide and amine are added, and the reaction is stirred at room temperature. After the reaction is completed, the filtrate is filtered, and the obtained filtrate is washed with deionized water. After washing, the solvent is removed in vacuo to obtain solid C; the amine is dimethylamine or pyrrolidine; ⑤ Add the solid C obtained in step ④ to anhydrous ethanol and acetone to dissolve, cool to room temperature after dissolution, filter to obtain crystals, and vacuum dry the crystals to obtain component A; (2) Synthesis of component B ① ZrCl4 is mixed with dichloromethane to obtain a suspension; tetrahydrofuran is added to the suspension, stirred, filtered, and a filtrate is obtained; the solvent is removed from the filtrate in vacuo to obtain a solid D; ② The solid D obtained in step ① was mixed with n-hexane, filtered, the filter residue was washed, and vacuum dried to obtain component B; (3) Catalyst synthesis ① Component A is dissolved in tetrahydrofuran, and then a n-butyl lithium n-hexane solution is added and stirred, and the mixture is heated to room temperature and maintained for 1-3 hours to obtain solution A; ② Component B is dissolved in tetrahydrofuran to obtain solution B; ③ At -80--50°C with stirring, add solution A and solution B to tetrahydrofuran to react for 30-120 min, then return to room temperature to react for 12-24 h, remove tetrahydrofuran from the reaction solution to obtain a solid product A, dissolve the solid product A in dichloromethane, filter to obtain a filtrate, evaporate and concentrate the filtrate to saturation to obtain a liquid product B, add n-hexane to the liquid product B, cool and recrystallize, filter to remove the filtrate, and vacuum dry to obtain a metallocene catalyst.
3. The method for preparing the metallocene catalyst according to claim 2, characterized in that In step (1), the ratio of ketone, imidazole, tetrahydrofuran solution of ethylene monochloride and dimethylformamide is 1:50-60:500:1300-1500, wherein the ketone is measured in mol, and the imidazole, tetrahydrofuran solution of ethylene monochloride and dimethylformamide are all measured in ml; the concentration of the tetrahydrofuran solution of ethylene monochloride is 1.8-2.2 mol / L, and the reaction time is 1-3 h.
4. The method for preparing the metallocene catalyst according to claim 2, characterized in that In step (1) ②, the ratio of solid A, carbon tetrabromide, tetrahydrofuran, n-butyl lithium n-hexane solution and hexamethylphosphoric triamide is 11-16:16.6:120-160:50-70:13-18, wherein solid A and carbon tetrabromide are both measured in g, tetrahydrofuran, n-butyl lithium n-hexane solution and hexamethylphosphoric triamide are all measured in ml; the concentration of n-butyl lithium n-hexane solution is 1 mol / L.
5. The method for preparing the metallocene catalyst according to claim 2, characterized in that In step (1) (3), the volume ratio of the reaction solution, saturated NH4Cl solution, n-hexane, deionized water and saturated CuSO4 solution is 50:7-10:40-60:40-60:15-25.
6. The method for preparing the metallocene catalyst according to claim 2, characterized in that In step (1) (4), the ratio of solid B, amine, potassium carbonate, potassium iodide and tetrahydrofuran is 31.2-39.2:7.22-11.38:13.8-41.4:16.6-49.8:500-1000, wherein solid B, amine, potassium carbonate and potassium iodide are all measured in g, and tetrahydrofuran is measured in ml; the stirring reaction time is 24-48h.
7. The method for preparing the metallocene catalyst according to claim 2, characterized in that In step (1), the ratio of solid C, anhydrous ethanol and acetone is 5:32-45:9-13, wherein solid C is measured in g, and anhydrous ethanol and acetone are both measured in ml; and the dissolution temperature is 55-65°C.
8. The method for preparing the metallocene catalyst according to claim 2, characterized in that In step (2) ①, the ratio of ZrCl4, dichloromethane and tetrahydrofuran is 8.8:80-100:5.5, wherein ZrCl4 and tetrahydrofuran are both measured in g, and dichloromethane is measured in ml; the stirring time is 30-120 min; In step (2) ②, the ratio of solid D to n-hexane is 13:70-100, wherein solid D is measured in g and n-hexane is measured in ml; the stirring time is 10-40 min; washing is washing the filter residue with n-hexane, and the ratio of the filter residue to n-hexane is 13:15-25, wherein the filter residue is measured in g and n-hexane is measured in ml.
9. The method for preparing the metallocene catalyst according to claim 2, characterized in that In step (3) ①, the ratio of component A, tetrahydrofuran and n-butyl lithium n-hexane solution is 6.37-9.41:150-200:40-60, wherein component A is measured in g, tetrahydrofuran and n-butyl lithium n-hexane solution are both measured in ml; the concentration of n-butyl lithium n-hexane solution is 0.8-1.2 mol / L, the stirring temperature is -90--50°C, and the stirring time is 10-30 min; In step (3) ②, the ratio of component B to tetrahydrofuran is 7.55:50-70, wherein component B is measured in g and tetrahydrofuran is measured in ml; In step (3) ③, the ratio of component A in solution A, component B in solution B and tetrahydrofuran is 6.37-9.41:7.55:40-60, wherein component A and component B are both measured in g, and tetrahydrofuran is measured in ml; and the recrystallization temperature is -24-0°C.
10. Use of the metallocene catalyst according to claim 1, characterized in that Cyclic olefin, linear olefin, metallocene catalyst, co-catalyst and solvent are polymerized to obtain cycloolefin copolymer; the cycloolefin is one or more of tetracyclododecene or tetracyclododecene derivatives, and the linear olefin is one or both of ethylene and propylene.