Catalyst for olefin polymerization and olefin polymerization method
阅读说明：本技术 一种用于烯烃聚合的催化剂和烯烃聚合方法 (Catalyst for olefin polymerization and olefin polymerization method ) 是由 韩书亮 金钊 王路生 宋文波 李昊坤 方园园 于 2020-10-28 设计创作，主要内容包括：本发明公开了一种乙烯聚合用催化剂,包括主催化剂和助催化剂,所述主催化剂为式I所示的双苯酚金属配合物,助催化剂包括有机铝化合物和有机硼化合物；式I中,R-1、R-1＇、R-2、R-2＇相同或不同,各自独立地选自氢和取代或未取代的C-1-C-(20)的烃基；R-3-R-7、R-3＇-R-7＇相同或不同,各自独立地选自氢和取代或未取代的C-1-C-(20)的烃基；R-8和R-9相同或不同,各自独立地选自氢和取代或未取代的C-1-C-(20)的烃基；M和M＇相同或不同,选自IV族金属；X为卤素；(The invention discloses a catalyst for ethylene polymerization, which comprises a main catalyst and a cocatalyst, wherein the main catalyst is a biphenol metal complex shown in a formula I, and the cocatalyst comprises an organic aluminum compound and an organic boron compound; in the formula I, R 1 、R 1 ＇、R 2 、R 2 Are identical or different and are each independently selected from hydrogen and substitutionOr unsubstituted C 1 ‑C 20 A hydrocarbon group of (a); r 3 ‑R 7 、R 3 ＇‑R 7 ' same or different, each independently selected from hydrogen and substituted or unsubstituted C 1 ‑C 20 A hydrocarbon group of (a); r 8 And R 9 Same or different, each independently selected from hydrogen and substituted or unsubstituted C 1 ‑C 20 A hydrocarbon group of (a); m and M', which are identical or different, are selected from group IV metals; x is halogen;)
1. A catalyst for olefin polymerization comprises a main catalyst and a cocatalyst, wherein the main catalyst is a biphenol metal complex shown in a formula I, and the cocatalyst comprises an organic aluminum compound and an organic boron compound;
in the formula I, R1、R1＇、R2、R2' same or different, each independently selected from hydrogen and substituted or unsubstituted C1-C20A hydrocarbon group of (a); r3-R7、R3＇-R7' same or different, each independently selected from hydrogen and substituted or unsubstituted C1-C20A hydrocarbon group of (a); r8And R9Same or different, each independently selected from hydrogen and substituted or unsubstituted C1-C20A hydrocarbon group of (a); m and M', which are identical or different, are selected from group IV metals; x is halogen.
2. The catalyst of claim 1, wherein in formula I, R is1、R1＇、R2、R2Identical or different, each independently selected from hydrogen, substituted or unsubstituted C1-C20Straight or branched alkyl and substituted or unsubstituted C1-C20Is preferably selected from hydrogen and substituted or unsubstituted C1-C10Linear or branched alkyl of (a); r3-R7、R3＇-R7' same or different, each independently selected from hydrogen and substituted or unsubstituted C1-C20Is preferably selected from hydrogen and substituted or unsubstituted C1-C10Linear or branched alkyl of (a); r8And R9Same or different, each independently selected from hydrogen and substituted or unsubstituted C1-C20Is preferably selected from hydrogen and substituted or unsubstituted C1-C10Linear or branched alkyl of (a); m and M', which are identical or different, are chosen from titanium, zirconium and hafnium, preferably titanium; x is selected from fluorine, chlorine, bromine and iodine, preferably chlorine.
3. The catalyst of claim 1 or 2, wherein the metal bis-phenol complex of formula I is prepared by a process comprising the steps of:
1) reacting a biphenol compound shown in a formula II with a metal compound shown in a formula III to obtain a compound shown in a formula IV;
2) reacting a compound shown in a formula IV with a metal complex shown in a formula V to obtain a biphenol metal complex shown in a formula I;
in formulae II and IV, R1、R1＇、R2、R2＇、R8And R9Have the same definitions as in formula I;
in the formula III, M1Selected from group IA metals, preferably lithium, sodium or potassium, R is hydrogen or C1-C10Linear or branched alkyl of (a);
in the formula V, R3-R7Have the same definitions as in formula I.
4. The catalyst according to any one of claims 1 to 3, characterized in that the organoaluminum compound comprises an alkylaluminum and/or an alkylaluminum halide.
5. A catalyst as claimed in any one of claims 1 to 4 wherein said organoboron compound is selected from aryl boron and/or borate salts.
6. The catalyst of any one of claims 1 to 5, wherein the molar ratio of the procatalyst, the organoaluminum compound, and the organoboron compound is 1: (200-2000): (1-10).
7. Use of a catalyst as claimed in any one of claims 1 to 6 in the polymerisation of olefins.
8. A process for the polymerization of olefins by homopolymerization or copolymerization of olefins in the presence of a catalyst as claimed in any of claims 1 to 6.
9. The olefin polymerization process of claim 8, wherein the homopolymerization comprises ethylene homopolymerization; and/or the copolymerization comprises copolymerization of ethylene with other alpha-olefins; and/or the alpha-olefin comprises one or more of propylene, butene, pentene, hexene, octene and 4-methyl-1-pentene.
10. Process for the polymerization of olefins according to claim 8 or 9, characterized in that the homopolymerization or copolymerization is carried out in an inert solvent, which can be an aromatic hydrocarbon or an alkane, preferably comprising benzene, toluene, hexane, heptane and mixtures thereof.
11. An olefin polymer produced by the method according to any one of claims 8 to 10.
Technical Field
The invention relates to a catalyst for olefin polymerization and an olefin polymerization reaction thereof, belonging to the field of olefin polymerization.
Background
Because the polyolefin raw materials are rich and cheap and easy to process and form, the polyolefin products produced worldwide each year exceed one hundred million tons, and become one of the largest-scale industries; the polyolefin material has the characteristics of relatively low density, good chemical resistance, water resistance, good mechanical strength, electrical insulation and the like, can be used for films, pipes, plates, various molded products, wires, cables and the like, has wide application in the aspects of daily sundry products such as agriculture, packaging, automobiles, electric appliances and the like, provides convenience for human clothes, eating and housing, and plays a great role in strategic items such as national defense, energy, aerospace and the like.
The ethylene copolymer product has excellent performance, and various comonomers comprise 1-octene, 1-hexene, 1-butene, propylene, polar monomers and the like. By adjusting the kind and the amount of the comonomer, not only linear low-density polyethylene, but also thermoplastic elastomer and rubber can be obtained, and the application is very wide. Particularly, the special structure of the elastomer endows the elastomer with excellent mechanical property, rheological property and aging resistance, and when the elastomer is used as a plastic impact resistant agent, the elastomer has good low-temperature toughness, small using amount and high cost performance, and is widely used for plastic modification.
Coordination polymerization represented by a Ziegler-Natta catalyst has promoted rapid development of the polyolefin industry and has gradually matured. Nowadays, metal catalysts for solution polymerization are hot spots of research in the field of coordination polymerization, and the catalysts generally consist of a procatalyst and a cocatalyst, which also plays a crucial role in olefin polymerization. Under the action of the cocatalyst, the main catalyst is firstly converted into an active center, and then forms an anion-cation pair with catalytic performance with the cocatalyst to synthesize the polymer. The nature of the cocatalyst can affect the activity, lifetime, high temperature stability, solubility of the catalytic system and the structure of the polymer. The emergence of Methylaluminoxane (MAO) in the early 80's of the 20 th century promoted the vigorous development of metallocene catalysts, changing the problem of low activity when alkylaluminum was used as a cocatalyst in the past. MAO, however, has poor solubility in alkanes, and is expensive in high quantities.
CN101864010B discloses a bimetallic catalyst precursor for catalyzing olefin polymerization or copolymerization. The catalyst precursor is based on a salicylaldimine ligand and a group IV transition metal. The catalyst precursor is mainly prepared by condensing pentafluoroaniline and bridged salicylaldehyde to obtain a ligand and complexing the ligand and Ti to obtain the catalyst, but the catalyst is low in activity, and the alpha-olefin ratio is low and the molecular weight distribution is wide when alpha-olefin and ethylene are copolymerized.
Therefore, how to obtain a metal catalyst with high catalytic efficiency, high copolymerization ratio and low cost is still a technical problem to be solved urgently.
Disclosure of Invention
The present invention aims to overcome the defects of the prior art and provide a catalyst for olefin polymerization, which comprises a main catalyst of a metal complex of biphenol and a cocatalyst.
According to one aspect of the present invention, there is provided a catalyst for olefin polymerization comprising a procatalyst and a cocatalyst, the procatalyst comprising a biphenol metal complex represented by formula I, and the cocatalyst comprising an organoaluminum compound and an organoboron compound;
in the formula I, R1、R1＇、R2、R2' same or different, each independently selected from hydrogen and substituted or unsubstituted C1-C20A hydrocarbon group of (a); r3-R7、R3＇-R7' same or different, each independently selected from hydrogen and substituted or unsubstituted C1-C20A hydrocarbon group of (a); r8And R9Same or different, each independently selected from hydrogen or substituted or unsubstituted C1-C20A hydrocarbon group of (a); m and M', which are identical or different, are selected from group IV metals; x is halogen.
According to a preferred embodiment of the invention, in formula I, R1、R1＇、R2、R2Identical or different, each independently selected from hydrogen, substituted or unsubstituted C1-C20Straight or branched alkyl and substituted or unsubstituted C1-C20Is preferably selected from hydrogen and substituted or unsubstituted C1-C10More preferably selected from hydrogen and substituted or unsubstituted C1-C6Linear or branched alkyl of (a); r3-R7、R3＇-R7' same orEach independently selected from hydrogen and substituted or unsubstituted C1-C20Is preferably selected from hydrogen and substituted or unsubstituted C1-C10More preferably selected from hydrogen and substituted or unsubstituted C1-C6Linear or branched alkyl of (a); r8And R9Same or different, each independently selected from hydrogen and substituted or unsubstituted C1-C20Is preferably selected from hydrogen and substituted or unsubstituted C1-C10More preferably selected from hydrogen and substituted or unsubstituted C1-C6Linear or branched alkyl of (a); m and M', which are identical or different, are chosen from titanium, zirconium and hafnium, preferably titanium; x is selected from fluorine, chlorine, bromine and iodine, preferably chlorine.
According to the invention, said substitution means R1-R7、R1＇-R7＇、R8And R9The hydrocarbon group in (1), preferably alkyl group, aryl group, may be optionally substituted with hetero atom at the carbon atom on the main chain, and the hydrogen atom bonded to the carbon atom may be optionally substituted with hetero atom, alkyl group or alkoxy group; the hetero atom includes an oxygen atom, a nitrogen atom, a boron atom, a sulfur atom, a phosphorus atom, a silicon atom, a germanium atom, a tin atom, a halogen atom and the like.
According to some embodiments of the invention, the metal bis-phenol complex is selected from at least one of the complexes represented by formula I below:
bisphenol metal complex 1: r1＝R2＝R1＇＝R2＇＝Me，R3＝R4＝R5＝R6＝R7＝R3＇＝R4＇＝R5＇＝R6＇＝R7＇＝R8＝R9＝H，M＝M＇＝Ti，X＝Cl；
Bisphenol metal complex 2: r1＝R2＝R1＇＝R2＇＝Et，R3＝R4＝R5＝R6＝R7＝R3＇＝R4＇＝R5＇＝R6＇＝R7＇＝R8＝R9＝H，M＝M＇＝Ti，X＝Cl；
Bisphenol metal complex 3: r1＝R2＝R1＇＝R2＇＝iPr，R3＝R4＝R5＝R6＝R7＝R3＇＝R4＇＝R5＇＝R6＇＝R7＇＝R8＝R9＝H，M＝M＇＝Ti，X＝Cl；
Bisphenol metal complex 4: r1＝R2＝R1＇＝R2＇＝tBu，R3＝R4＝R5＝R6＝R7＝R3＇＝R4＇＝R5＇＝R6＇＝R7＇＝R8＝R9＝H，M＝M＇＝Ti，X＝Cl；
Bisphenol metal complex 5: r1＝R2＝R1＇＝R2＇＝Me，R3＝R4＝R5＝R6＝R7＝R3＇＝R4＇＝R5＇＝R6＇＝R7＇＝Me，R8＝R9＝H，M＝M＇＝Ti，X＝Cl；
Bis-phenol metal complex 6: r1＝R2＝R1＇＝R2＇＝Et，R3＝R4＝R5＝R6＝R7＝R3＇＝R4＇＝R5＇＝R6＇＝R7＇＝Me，R8＝R9＝H，M＝M＇＝Ti，X＝Cl；
Bisphenol metal complex 7: r1＝R2＝R1＇＝R2＇＝iPr，R3＝R4＝R5＝R6＝R7＝R3＇＝R4＇＝R5＇＝R6＇＝R7＇＝Me，R8＝R9＝H，M＝M＇＝Ti，X＝Cl；
Bisphenol metal complex 8: r1＝R2＝R1＇＝R2＇＝tBu，R3＝R4＝R5＝R6＝R7＝R3＇＝R4＇＝R5＇＝R6＇＝R7＇＝Me，R8＝R9＝H，M＝M＇＝Ti，X＝Cl。
According to some embodiments of the invention, the metal bis-phenol complex is prepared by a process comprising the steps of:
1) reacting a biphenol compound shown in a formula II with a metal compound shown in a formula III to obtain a compound shown in a formula IV;
2) reacting a compound shown in a formula IV with a metal complex shown in a formula V to obtain a biphenol metal complex shown in a formula I;
in formulae II and IV, R1、R1＇、R2、R2＇、R8And R9Have the same definitions as in formula I;
in the formula III, M1Selected from group IA metals, preferably lithium, sodium or potassium, R is hydrogen or C1-C10Linear or branched alkyl of (a);
in the formula V, R3-R7Have the same definitions as in formula I.
According to a preferred embodiment of the present invention, the preparation method comprises: reacting a biphenol compound shown in a formula II with a metal compound shown in a formula III in an organic solvent to obtain a compound shown in a formula IV, and then reacting with a metal complex shown in a formula V in the organic solvent to obtain a biphenol metal complex shown in a formula I.
According to some embodiments of the invention, the organic solvent is selected from tetrahydrofuran, diethyl ether, 1, 4-dioxane and dichloromethane.
According to a preferred embodiment of the present invention, the bisphenol compound is at least one selected from the group consisting of bisphenol compounds represented by the following formula II:
bisphenol compound 1: r1＝R2＝R1＇＝R2＇＝Me，R8＝R9＝H；
Bisphenol compound 2: r1＝R2＝R1＇＝R2＇＝Et，R8＝R9＝H；
Bisphenol compound 3: r1＝R2＝R1＇＝R2＇＝iPr，R8＝R9＝H；
Bisphenol compound 4: r1＝R2＝R1＇＝R2＇＝tBu，R8＝R9＝H。
According to a preferred embodiment of the present invention, the metal compound represented by formula III is selected from at least one of KH, NaH, MeLi, EtLi, PrLi, and BuLi.
According to a preferred embodiment of the invention, the compound of formula IV is selected from at least one of the following compounds:
compound 1: r1＝R2＝R1＇＝R2＇＝Me，R8＝R9＝H，M1＝Li；
Compound 2: r1＝R2＝R1＇＝R2＇＝Et，R8＝R9＝H，M1＝Li；
Compound 3: r1＝R2＝R1＇＝R2＇＝iPr，R8＝R9＝H，M1＝Li；
Compound 4: r1＝R2＝R1＇＝R2＇＝tBu，R8＝R9＝H，M1＝Li；
Compound 5: r1＝R2＝R1＇＝R2＇＝Me，R8＝R9＝H，M1＝Na；
Compound 6: r1＝R2＝R1＇＝R2＇＝Et，R8＝R9＝H，M1＝Na；
Compound 7: r1＝R2＝R1＇＝R2＇＝iPr，R8＝R9＝H，M1＝Na；
Compound 8: r1＝R2＝R1＇＝R2＇＝tBu，R8＝R9＝H，M1＝Na；
Compound 9: r1＝R2＝R1＇＝R2＇＝Me，R8＝R9＝H，M1＝K；
Compound 10: r1＝R2＝R1＇＝R2＇＝Et，R8＝R9＝H，M1＝K；
Compound 11: r1＝R2＝R1＇＝R2＇＝iPr，R8＝R9＝H，M1＝K；
Compound 12: r1＝R2＝R1＇＝R2＇＝tBu，R8＝R9＝H，M1＝K。
According to a preferred embodiment of the present invention, the metal complex is at least one selected from the group consisting of metal complexes represented by the following formula V:
metal complex 1: r3＝R4＝R5＝R6＝R7＝H，M＝Ti，X＝Cl；
Metal complex 2: r3＝R4＝R5＝R6＝R7＝Me，M＝Ti，X＝Cl。
According to a preferred embodiment of the present invention, the molar ratio of the bisphenol compound represented by formula II to the compound represented by formula III is 1: (1-20), such as 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, 1:10, 1:10.5, 1:11, 1:11.5, 1:12, 1:12.5, 1:13, 1:13.5, 1:14, 1:14.5, 1:15, 1:15.5, 1:16, 1:16.5, 1:17, 1:17.5, 1:18, 1:18.5, 1:19, 1:19.5, 1:20 and any value in between them, preferably 1: (2-10), preferably 1: (4-8).
According to a preferred embodiment of the present invention, the reaction temperature of the reaction of the biphenol compound represented by the formula II with the compound represented by the formula III is-78 ℃ to 60 ℃, for example-60 ℃, -50 ℃, -40 ℃, -30 ℃, -20 ℃, -10 ℃, 0 ℃, 10 ℃, 20 ℃, 30 ℃ and any value therebetween, preferably-10 ℃ to 40 ℃.
According to a preferred embodiment of the present invention, the reaction time of the reaction of the biphenol compound represented by formula II with the compound represented by formula III is 1 to 10 hours, such as 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5 and any value therebetween, preferably 1.5 to 3 hours.
According to a preferred embodiment of the invention, the molar ratio of the compound of formula IV to the metal compound of formula V is 1: (1.8-2.4), e.g. 1:1.9, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4 and any value in between, preferably 1:2. wherein the number of moles of the compound represented by formula IV is determined as the number of moles of the biphenol compound.
According to a preferred embodiment of the invention the reaction temperature of the reaction of the compound of formula IV with the metal compound of formula V is in the range of-78 ℃ to 60 ℃, such as-60 ℃, -50 ℃, -40 ℃, -30 ℃, -20 ℃, -10 ℃, 0 ℃, 10 ℃, 20 ℃, 30 ℃ and any value in between, preferably in the range of-10 ℃ to 40 ℃.
According to a preferred embodiment of the invention, the reaction time of the reaction of the compound of formula IV with the metal compound of formula V is 6 to 24 hours, such as 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 and any value in between, preferably 6 to 19 hours.
According to some embodiments of the invention, the organoaluminum compound comprises an alkylaluminum and/or an alkylaluminum halide. Specific examples of the organoaluminum compound include, but are not limited to: trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, trioctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichloride. Preferably trimethylaluminum, triethylaluminum or triisobutylaluminum.
According to a preferred embodiment of the invention, the organoboron compound is selected from an aryl boron and/or a borate. The arylborole is preferably a substituted or unsubstituted phenylborone, more preferably tris (pentafluorophenyl) boron. The borate is preferably N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and/or triphenylmethyl tetrakis (pentafluorophenyl) borate.
According to a preferred embodiment of the present invention, the molar ratio of the main catalyst, the organoaluminum compound and the organoboron compound is 1: (200-2000): (1-10), preferably 1: (300-1000): (4-16).
According to another aspect of the present invention there is provided the use of a catalyst as described above in the polymerisation of olefins.
According to a further aspect of the present invention there is provided an olefin polymerisation process in which an olefin is homopolymerised or copolymerised in the presence of a catalyst as claimed in any one of claims 1 to 7.
According to a preferred embodiment of the invention, said homopolymerization comprises ethylene homopolymerization.
According to a preferred embodiment of the present invention, the copolymerization comprises copolymerization of ethylene with other alpha-olefins; preferably the alpha-olefins comprise one or more of propylene, butene, pentene, hexene, octene and 4-methyl-1-pentene.
The polymerization reaction of the present invention may be carried out in an inert solvent. The solvent used may be an aromatic hydrocarbon or an alkane, such as benzene, toluene, hexane, heptane and mixtures thereof.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention in any way.
In the following examples, the evaluation and testing methods involved are as follows:
1. the nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum of the catalyst are tested on a Bruker-400 nuclear magnetic resonance instrument by using deuterated chloroform as a solvent at normal temperature. Polymeric cores
2. High resolution mass spectra were determined on a Bruker ESI-Q/TOF MS mass spectrometer using acetonitrile as the dispersing solvent.
3. Polymerization Activity: the polymer obtained by polymerization was dried and weighed, and the catalyst activity was obtained by dividing the amount of the catalyst added at the time of polymerization.
4. Molecular weight and molecular weight distribution PDI (PDI ═ Mw/Mn) of the polymer: measured at 150 ℃ using PL-GPC220 and 1,2, 4-trichlorobenzene as a solvent (standard: PS, flow rate: 1.0mL/min, column: 3 XPlgel 10um M1 XED-B300X 7.5 nm).
5. The melting point of the polymer was measured using Differential Scanning Calorimetry (DSC): 10mg of the sample was placed in a crucible and measured on a Pekin Elmer DSC 8500 differential scanning calorimeter. Heating from-70 ℃ to 200 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, preserving heat for l min, cooling to-70 ℃ at 10 ℃/min, preserving heat for 3min, then heating to 200 ℃ at 10 ℃/min, and recording second heating scanning data.
6. The comonomer content in the polymer was determined by high temperature nuclear magnetic carbon spectroscopy.
Example 1
Preparation of bisphenol Metal Complex 7
Bisphenol compound 3(2.24mmol) was dissolved in ether solvent, pure KH solid (8.96mmol) was added to the solution at-78 deg.C and reacted for 1 hour, and the reaction was returned to room temperature and continued for 2 hours. Thereafter, the solution was transferred to a dichloromethane solution of metal complex 2(4.48mmol) at-78 ℃ through a double-horn needle and reacted at that temperature for 1 hour, and then the system was gradually returned to room temperature and reacted for another 12 hours. After the reaction was complete, the solvent was removed using a vacuum line, the residue was washed with dichloromethane and filtered through celite, the filtrate was drained and the crude product was recrystallized from dichloromethane/n-hexane to give an orange product (yield 90%) with the following characterization data:
1H NMR(CDCl3,400MHz):δ＝7.45(dd,J＝7.6,2.0Hz,2H,aryl-H),7.25(s,4H,aryl-H),7.14-7.21(m,4H,aryl-H),3.13(m,4H,CH),2.18(s,30H,CH3),1.80(s,6H,CH3),1.03(d,J＝6.8Hz,24H,CH3)；
13C NMR(CDCl3,100MHz):δ＝159.1,146.9,138.9,133.5,132.8,130.6,130.4,130.0,124.5,122.9,34.3,33.9,26.3,24.3,13.1；
ESI-MS for C59H72Cl4O3Ti2(M/Z＝1064.32),Found:M＝1064.34。
example 2
Preparation of bisphenol Metal Complex 7
Bisphenol compound 3(2.24mmol) was dissolved in ether solvent, pure KH solid (2.24mmol) was added to the solution at-78 deg.C and reacted for 1 hour, and the reaction was returned to room temperature and continued for 8 hours. Thereafter, the solution was transferred to a dichloromethane solution of metal complex 2(4.00mmol) at-78 ℃ through a double-horn needle and reacted at that temperature for 1 hour, and then the system was gradually returned to room temperature and reacted for another 18 hours. After the reaction was complete, the solvent was removed using a vacuum line, the residue was washed with dichloromethane and filtered through celite, the filtrate was dried and the crude product was recrystallized from dichloromethane/n-hexane to give an orange product (yield 61%).
Example 3
Preparation of bisphenol Metal Complex 7
Bisphenol compound 3(2.24mmol) was dissolved in ether solvent, pure KH solid (22.4mmol) was added to the solution at 40 ℃ and the reaction was allowed to proceed for 1 hour, then returned to room temperature and continued for 0.5 hour. After this time, the solution was transferred via a double-pointed needle at 40 ℃ into a solution of metal complex 2(4.93mmol) in dichloromethane and reacted at this temperature for 6 hours, after the reaction was complete, the solvent was removed using a vacuum line, the residue was washed with dichloromethane and filtered through celite, the filtrate was drained and the crude product was recrystallized from dichloromethane/n-hexane to give an orange product (73% yield).
Example 4
Preparation of bisphenol Metal Complex 4
Dissolving the biphenol compound 4(2.00mmol) in tetrahydrofuran solvent, adding pure NaH solid (12.00mmol) into the solution at-10 deg.C, reacting for 1 hr, returning to room temperature, and continuing to react for 1 hrThen (c) is performed. Thereafter, the solution was transferred to a tetrahydrofuran solution of metal complex 1(4.00mmol) at-10 ℃ through a double-horn needle and reacted at that temperature for half an hour, and then the system was gradually returned to room temperature and reacted for another 8 hours. After the reaction was complete, the solvent was removed using a vacuum line, the residue was washed with dichloromethane and filtered through celite, the filtrate was drained and the crude product was recrystallized from dichloromethane/n-hexane to give an orange product (92% yield) with the following characterization data: ESI-MS for C51H56Cl4O3Ti2:M/Z＝954.21。
Example 5
Preparation of bisphenol Metal Complex 4
Bisphenol compound 4(2.00mmol) was dissolved in methylene chloride solvent, and 1.0mol/L BuLi solution (2.00mmol) was added to the solution at-10 ℃ to react for 1 hour, and the reaction was returned to room temperature and continued for 4 hours. Thereafter, the solution was transferred to a dichloromethane solution of metal complex 1(4.00mmol) through a double-horn needle at-10 ℃ and reacted at that temperature for half an hour, and then the system was gradually returned to room temperature and reacted for another 15 hours. After the reaction was complete, the solvent was removed using a vacuum line, the residue was washed with dichloromethane and filtered through celite, the filtrate was dried and the crude product was recrystallized from dichloromethane/n-hexane to give an orange product (84% yield).
Example 6
The 500mL polymerization reactor after heating and drying was evacuated twice and purged with nitrogen, further evacuated and purged with ethylene, then 2mL (0.5mmol/mL) of an n-hexane solution of triisobutylaluminum, 150mL of an n-hexane solution subjected to anhydrous oxygen-free treatment and 1mL (2.5. mu. mol/mL) of a toluene solution containing a biphenol metal complex 7 were sequentially added, and a boron-containing reagent [ Ph ] was further added3C][B(C6F5)4]2mL (5. mu. mol/mL). Introducing ethylene under the condition of mechanical stirring and pressure of 1.0MPa, making reaction at 80 deg.C for 20min, then adding ethyl alcohol to stop reaction to obtain 5.1g of polymer, and its polymerization activity is 3.06X 106g·mol-1(Ti)·h-1。
Melting point 133.3 ℃ by DSC; GPC determination of M of the polyethylenewIs 1.8X 105，Mw/MnWas 6.84.
Example 7
The 500mL polymerization reactor after heating and drying was evacuated twice and purged with nitrogen, further evacuated and purged with ethylene, then 2mL (0.5mmol/mL) of an n-hexane solution of triisobutylaluminum, 150mL of an n-hexane solution subjected to anhydrous oxygen-free treatment and 1mL (2.5. mu. mol/mL) of a toluene solution containing a biphenol metal complex 7 were sequentially added, and a boron-containing reagent [ Ph ] was further added3C][B(C6F5)4]2mL (5. mu. mol/mL). Introducing ethylene under 0.5MPa and reacting at 40 deg.C for 20min under mechanical stirring, adding ethanol to terminate the reaction to obtain 2.6g of polymer with polymerization activity of 1.56 × 106g·mol-1(Ti)·h-1。
Melting point 130.6 ℃ by DSC; GPC measured M of polyethylenewIs 2.0X 105，Mw/MnIt was 7.05.
Example 8
The 500mL polymerization reactor after heating and drying was evacuated twice and purged with nitrogen, further evacuated and purged with ethylene, then 2mL (0.5mmol/mL) of an n-hexane solution of triisobutylaluminum, 150mL of an n-hexane solution subjected to anhydrous oxygen-free treatment and 1mL (2.5. mu. mol/mL) of a toluene solution containing a biphenol metal complex 7 were sequentially added, and a boron-containing reagent [ Ph ] was further added3C][B(C6F5)4]2mL (5. mu. mol/mL). Ethylene was passed under mechanical stirring at a pressure of 0.1MPa and reacted at 0 ℃ for 20min under this pressure, after which ethanol was added to terminate the reaction to give 1.15g of a polymer whose polymerization activity was determined by calculation to be 6.90X 105g·mol-1(Ti)·h-1。
Melting point by DSC is 131.5 ℃; GPC measured M of polyethylenewIs 1.7X 105，Mw/MnIt was 8.97.
Example 9
Vacuumizing the 500mL polymerization kettle after being heated and dried, introducing nitrogen twice, vacuumizing, introducing ethylene gas, and sequentially adding triisobutylaluminum normal5mL (0.5mmol/mL) of a hexane solution, 150mL of anhydrous and anaerobic n-hexane, and 1mL (2.5. mu. mol/mL) of a toluene solution containing the biphenol metal complex 7, and a boron-containing reagent [ Ph ] was added3C][B(C6F5)4]4mL (5. mu. mol/mL). Introducing ethylene under the condition of mechanical stirring and pressure of 0.5MPa, making reaction at 80 deg.C for 20min, then adding ethyl alcohol to stop reaction to obtain 3.4g of polymer, and its polymerization activity is 2.04X 106g·mol-1(Ti)·h-1。
Melting point 130.3 ℃ by DSC; GPC measured M of polyethylenewIs 1.5X 105，Mw/MnIs 4.10.
Example 10
The 500mL polymerization reactor after heating and drying was evacuated twice and purged with nitrogen, further evacuated and purged with ethylene, then 1.5mL (0.5mmol/mL) of an n-hexane solution of triisobutylaluminum, 150mL of an n-hexane solution subjected to anhydrous oxygen-free treatment and 1mL (2.5. mu. mol/mL) of a toluene solution containing a biphenol metal complex 7 were sequentially added, and a boron-containing reagent [ Ph ] was further added3C][B(C6F5)4]8mL (5. mu. mol/mL). Introducing ethylene under the condition of mechanical stirring and pressure of 0.5MPa, making reaction at 80 deg.C for 20min, then adding ethyl alcohol to stop reaction to obtain 2.3g of polymer, and its polymerization activity is 1.38X 106g·mol-1(Ti)·h-1。
Melting point by DSC is 134.1 ℃; GPC measured M of polyethylenewIs 1.9X 105，Mw/MnIs 5.93.
Example 11
The 500mL polymerization reactor after heating and drying was evacuated twice and purged with nitrogen, further evacuated and purged with ethylene, and then 4mL (0.5mmol/mL) of an n-hexane solution of triisobutylaluminum, 150mL of an n-hexane solution subjected to anhydrous oxygen-free treatment and 2mL (2.5. mu. mol/mL) of a toluene solution containing a biphenol metal complex 7 were sequentially added, followed by addition of a boron-containing reagent [ Ph3C][B(C6F5)4]4mL (5. mu. mol/mL). Ethylene is introduced under mechanical stirring at a pressure of 0.5MPa and at this pressureReacting at 80 deg.C for 20min, adding ethanol to terminate the reaction to obtain 5.9g of polymer with polymerization activity of 1.77 × 106g·mol-1(Ti)·h-1。
Melting point by DSC is 134.3 ℃; GPC measured M of polyethylenewIs 2.0X 105，Mw/MnIt was 7.94.
Example 12
The 500mL polymerization reactor after heating and drying was evacuated twice and purged with nitrogen, further evacuated and purged with ethylene, then 2mL (0.5mmol/mL) of a toluene solution of triisobutylaluminum, 150mL of toluene subjected to anhydrous oxygen-free treatment and 1mL (2.5. mu. mol/mL) of a toluene solution containing biphenol metal complex 7 were sequentially added, and a boron-containing reagent [ Ph ] was further added3C][B(C6F5)4]2mL (5. mu. mol/mL). Introducing ethylene under the condition of mechanical stirring and pressure of 0.5MPa, making reaction at 80 deg.C for 40min, then adding ethyl alcohol to stop reaction to obtain 6.3g of polymer, and its polymerization activity is 1.89X 106g·mol-1(Ti)·h-1。
Melting point 131.0 ℃ by DSC; GPC measured M of polyethylenewIs 1.9X 105，Mw/MnIs 5.54.
Example 13
The 500mL polymerization vessel heated and dried was evacuated twice and purged with nitrogen, further evacuated and purged with ethylene, then 2mL (0.5mmol/mL) of a toluene solution of triisobutylaluminum, 150mL of n-heptane subjected to anhydrous oxygen-free treatment and 1mL (2.5. mu. mol/mL) of a toluene solution containing biphenol metal complex 7 were sequentially added, and further a boron-containing reagent [ Ph ] was added3C][B(C6F5)4]2mL (5. mu. mol/mL). Introducing ethylene under the condition of mechanical stirring and pressure of 0.5MPa, making reaction at 80 deg.C for 10min, then adding ethyl alcohol to stop reaction to obtain 2.6g of polymer, and its polymerization activity is 3.12X 106g·mol-1(Ti)·h-1。
Melting point 133.0 ℃ by DSC; GPC measured M of polyethylenewIs 1.6X 105，Mw/MnIs 4.99.
Example 14
The 500mL polymerization reactor after heating and drying was evacuated twice and purged with nitrogen, further evacuated and purged with ethylene, then 2mL (0.5mmol/mL) of an n-hexane solution of triisobutylaluminum, 87mL of an n-hexane subjected to anhydrous and anaerobic treatment, 8mL of 1-octene and 1mL (2.5. mu. mol/mL) of a toluene solution containing the biphenol metal complex 7 were sequentially added, and then a boron-containing reagent [ Ph ] was added3C][B(C6F5)4]2mL (5. mu. mol/mL) of the toluene solution (2 mL). Introducing ethylene under the condition of mechanical stirring and pressure of 0.5MPa, reacting at 80 deg.C for 20min under the condition of said pressure, adding ethyl alcohol to stop reaction so as to obtain 9.6g of polymer whose polymerization activity is 5.76X 106g·mol-1(Ti)·h-1。
The melting point of the polymer was 94 ℃ as determined by DSC; m of the Polymer by GPCwIs 1.16X 105，Mw/MnIs 4.08; the content of 1-octene is 8.9% by high temperature nuclear magnetic carbon spectrum.
Example 15
The 500mL polymerization reactor after heating and drying was evacuated twice and purged with nitrogen, further evacuated and purged with ethylene, then 2mL (0.5mmol/mL) of an n-hexane solution of triisobutylaluminum, 87mL of an n-hexane subjected to anhydrous and anaerobic treatment, 8mL of 1-octene and 1mL (2.5. mu. mol/mL) of a toluene solution containing the biphenol metal complex 7 were sequentially added, and then a boron-containing reagent [ Ph ] was added3C][B(C6F5)4]2mL (5. mu. mol/mL) of the toluene solution (2 mL). Introducing ethylene under 0.1MPa under mechanical stirring, reacting at 0 deg.C for 20min under the pressure, adding ethanol to terminate the reaction to obtain 3.9g of polymer with polymerization activity of 2.34 × 106g·mol-1(Ti)·h-1。
The melting point of the polymer cannot be detected by DSC; m of the Polymer by GPCwIs 7.3X 104，Mw/MnIs 3.87; the content of 1-octene is 19.4% by high temperature nuclear magnetic carbon spectrum.
Example 16
Vacuumizing the 500mL polymerization kettle after being heated and dried for twice, introducing nitrogen, vacuumizing again, and introducing ethylene gasThen, 2mL (0.5mmol/mL) of an n-hexane solution of triisobutylaluminum, 87mL (2.5. mu. mol/mL) of an anhydrous and oxygen-free-treated n-hexane, 8mL (1-octene) of an anhydrous and oxygen-free-treated n-hexane solution and 1mL (2.5. mu. mol/mL) of a toluene solution containing the biphenol metal complex 7 were added in this order, and a boron-containing reagent [ Ph ] was added3C][B(C6F5)4]2mL (5. mu. mol/mL) of the toluene solution (2 mL). Introducing ethylene under 2.0MPa under mechanical stirring, reacting at 40 deg.C for 20min under the pressure, adding ethanol to terminate the reaction to obtain 18.0g of polymer with polymerization activity of 1.08 × 107g·mol-1(Ti)·h-1。
The melting point of the polymer was 113 ℃ by DSC; m of the Polymer by GPCwIs 1.51X 105，Mw/MnIs 3.47; the content of 1-octene is 3.3% by high temperature nuclear magnetic carbon spectrum.
Example 17
The 500mL polymerization reactor after heating and drying was evacuated twice and purged with nitrogen, further evacuated and purged with ethylene, then 2mL (0.5mmol/mL) of an n-hexane solution of triisobutylaluminum, 79mL of an n-hexane subjected to anhydrous and anaerobic treatment, 16mL of 1-octene and 1mL (2.5. mu. mol/mL) of a toluene solution containing the biphenol metal complex 7 were sequentially added, and then a boron-containing reagent [ Ph ] was added3C][B(C6F5)4]2mL (5. mu. mol/mL) of the toluene solution (2 mL). Introducing ethylene under the condition of mechanical stirring and pressure of 0.5MPa, reacting at 80 deg.C for 20min under the condition of said pressure, adding ethyl alcohol to stop reaction so as to obtain polymer 12.3g with polymerization activity of 7.38X 106g·mol-1(Ti)·h-1。
Melting point of the polymer was 56 ℃ by DSC; m of the Polymer by GPCwIs 1.0X 105，Mw/MnIs 2.58; the content of 1-octene is 13.8% by high temperature nuclear magnetic carbon spectrum.
Example 18
The 500mL polymerization vessel heated and dried was evacuated twice and purged with nitrogen, further evacuated and purged with ethylene, and then 2mL (0.5mmol/mL) of an n-hexane solution of triisobutylaluminum, 81mL of an n-hexane solution subjected to anhydrous and anaerobic treatment, 14mL of 1-hexene and 1mL (2.5. mu. mol. ANG.) of a toluene solution containing the biphenol metal complex 7 were sequentially addedmL), and a boron-containing reagent [ Ph ] is added thereto3C][B(C6F5)4]2mL (5. mu. mol/mL) of the toluene solution (2 mL). Introducing ethylene under 0.5MPa under mechanical stirring, reacting at 80 deg.C for 20min under the pressure, adding ethanol to terminate the reaction to obtain polymer 8.8g with polymerization activity of 5.28 × 106g·mol-1(Ti)·h-1。
The melting point of the polymer was not determined by DSC; m of the Polymer by GPCwIs 9.7 multiplied by 104，Mw/MnIs 2.44; the content of 1-hexene measured by high temperature nuclear magnetic carbon spectrum was 14.8%.
Example 19
The 500mL polymerization reactor which had been heated and dried was evacuated twice and purged with nitrogen, further evacuated and purged with ethylene, 2mL (0.5mmol/mL) of an n-hexane solution of triisobutylaluminum, 81mL of an anhydrous oxygen-free-treated n-hexane, 3.73g of 1-butene and 1mL (2.5. mu. mol/mL) of a toluene solution containing the biphenol metal complex 7 were sequentially added, and then a boron-containing reagent [ Ph ] was added3C][B(C6F5)4]2mL (5. mu. mol/mL) of the toluene solution (2 mL). Introducing ethylene under the condition of mechanical stirring and pressure of 0.5MPa, reacting at 80 deg.C for 20min under the condition of said pressure, adding ethyl alcohol to stop reaction so as to obtain 8.4g of polymer whose polymerization activity is 5.04X 106g·mol-1(Ti)·h-1。
Melting point of the polymer was 123 ℃ by DSC; m of the Polymer by GPCwIs 1.7X 105，Mw/MnIs 2.34; the 1-butene content was 4.6% by high temperature nuclear magnetic carbon spectroscopy.
Example 20
Vacuumizing a 500mL polymerization kettle which is heated and dried and introducing nitrogen twice, vacuumizing the polymerization kettle again and introducing ethylene gas, then sequentially adding 2mL (0.5mmol/mL) of an n-hexane solution of triethyl aluminum, 81mL of the n-hexane subjected to anhydrous and anaerobic treatment, 16mL of 1-octene and 1mL (2.5 mu mol/mL) of a toluene solution containing a biphenol metal complex 7, and adding a boron-containing reagent [ PhNMe ]2][B(C6F5)4]2mL (5. mu. mol/mL) of the toluene solution (2 mL). Ethylene under a pressure of 0.5MPa is introduced with mechanical stirring and reacted at 80 ℃ under this pressureAfter 20min, ethanol was added to terminate the reaction, to give 11.2g of a polymer having a polymerization activity of 6.72X 106g·mol-1(Ti)·h-1。
The melting point of the polymer was not determined by DSC at 53 ℃; m of the Polymer by GPCwIs 8.1 × 104，Mw/MnIs 2.63; the content of 1-octene is 15.3% by high temperature nuclear magnetic carbon spectrum.
Example 21
The 500mL polymerization kettle which is heated and dried is vacuumized and introduced with nitrogen twice, then vacuumized and introduced with ethylene gas, then 2mL (0.5mmol/mL) of toluene solution of triisobutylaluminum, 87mL of toluene which is subjected to anhydrous anaerobic treatment, 8mL of 1-octene and 1mL (2.5 mu mol/mL) of toluene solution containing biphenol metal complex 7 are added in sequence, and then boron-containing reagent [ PhNMe ] is added2][B(C6F5)4]2mL (5. mu. mol/mL) of the toluene solution (2 mL). Introducing ethylene under 0.5MPa under mechanical stirring, reacting at 80 deg.C for 20min under the pressure, adding ethanol to terminate the reaction to obtain 9.9g of polymer with polymerization activity of 5.94 × 106g·mol-1(Ti)·h-1。
Melting point of the polymer was 91 ℃ by DSC; m of the Polymer by GPCwIs 1.6X 105，Mw/MnIs 2.23; the content of 1-octene is 9.3% by high temperature nuclear magnetic carbon spectrum.
Example 22
The 500mL polymerization kettle which is heated and dried is vacuumized and introduced with nitrogen twice, then vacuumized and introduced with ethylene gas, then 2mL (0.5mmol/mL) of triisobutylaluminum normal hexane solution, 87mL of anhydrous anaerobic treated toluene, 8mL of 1-octene and 1mL (2.5 mu mol/mL) of biphenol metal complex 7-containing toluene solution are added in sequence, and then boron-containing reagent [ PhNMe ] is added2][B(C6F5)4]2mL (5. mu. mol/mL) of the toluene solution (2 mL). Introducing ethylene under the condition of mechanical stirring and pressure of 0.5MPa, reacting at 80 deg.C for 10min under the condition of said pressure, adding ethyl alcohol to stop reaction so as to obtain 5.8g of polymer whose polymerization activity is 6.96X 106g·mol-1(Ti)·h-1。
The melting point of the polymer was 91 ℃ by DSC(ii) a M of the Polymer by GPCwIs 1.4X 105，Mw/MnIs 2.03; the content of 1-octene is 9.7% by high temperature nuclear magnetic carbon spectrum.
Example 23
The 500mL polymerization kettle which is heated and dried is vacuumized and introduced with nitrogen twice, then vacuumized and introduced with ethylene gas, then 2mL (0.5mmol/mL) of triisobutylaluminum normal hexane solution, 87mL (2.5 mu mol/mL) of anhydrous anaerobic treated normal hexane, 8mL (1-octene) and 1mL (2.5 mu mol/mL) of biphenol metal complex 7 toluene solution are added in sequence, and then boron-containing reagent [ PhNMe ] is added2][B(C6F5)4]2mL (5. mu. mol/mL) of the toluene solution (2 mL). Introducing ethylene under the condition of mechanical stirring and pressure of 0.5MPa, reacting at 80 deg.C for 40min under the condition of said pressure, adding ethyl alcohol to stop reaction so as to obtain 15.7g of polymer whose polymerization activity is 4.71X 106g·mol-1(Ti)·h-1。
Melting point of the polymer was 95 ℃ by DSC; m of the Polymer by GPCwIs 1.7X 105，Mw/MnIs 2.33; the content of 1-octene is 8.5% by high temperature nuclear magnetic carbon spectrum.
TABLE 1 amounts of raw materials and reaction conditions in examples 6-23
In Table 1, A represents triisobutylaluminum, B represents triethylaluminum, and C represents [ Ph ]3C][B(C6F5)4]D represents [ PhNMe2][B(C6F5)4]。
TABLE 2 results of the reactions of examples 6 to 23
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or a value of a process variable such as temperature, pressure, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88 … …, and 69 to 71, and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
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