CN109970890B - Non-metallocene catalyst, preparation method and application - Google Patents

Non-metallocene catalyst, preparation method and application Download PDF

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CN109970890B
CN109970890B CN201910181750.6A CN201910181750A CN109970890B CN 109970890 B CN109970890 B CN 109970890B CN 201910181750 A CN201910181750 A CN 201910181750A CN 109970890 B CN109970890 B CN 109970890B
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CN109970890A (en
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雷剑兰
黄斯璜
黄启谷
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Zhejiang Chain Science And Technology Co ltd
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Beijing Guoda Hengtai Kemao Co ltd
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    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
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    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers

Abstract

The invention relates to a non-metallocene catalyst, a preparation method and application thereof. The non-metallocene catalyst is a compound corresponding to formula 1.
Figure DDA0001991474550000011
Wherein X is selected from halogen, F, cl, br, I, or C 1 ‑C 15 Alkyl of (2), or C 3 ‑C 15 Cycloalkyl of, or C 5 ‑C 20 The heteroaryl group of (a). The catalyst is used for catalyzing ethylene homopolymerization, propylene homopolymerization, ethylene and alpha-olefin copolymerization, propylene and alpha-olefin copolymerization, ethylene and polar olefin monomer copolymerization, propylene and polar olefin monomer copolymerization or nonpolar olefin monomer and polar olefin monomer multi-copolymerization. Suitable for solution polymerization process, gas phase bulk polymerization process, liquid phase bulk polymerization process, loop polymerization process, slurry polymerization process or combined polymerization process, the obtained polymer has a weight average molecular weight of 500 to 7000000g/mol, a polymerization temperature of 0 to 200 ℃, a polymerization time of 0.5 to 5 hours and a polymerization pressure of 0.1mPa to 30MPa.

Description

Non-metallocene catalyst, preparation method and application
Technical Field
The invention relates to an olefin polymerization catalyst, a preparation method and application thereof, in particular to a non-metallocene catalyst, a preparation method and application thereof. More specifically, it is a [ N, P ] type non-metallocene catalyst, a preparation method of [ N, P ] type non-metallocene catalyst and the application of catalyzing olefin homopolymerization or copolymerization, the comonomer includes alpha-olefin or polar alkene monomer.
Background
Non-metallocene catalysts appear in the nineties of the twenty-century, coordination atoms of the catalysts are nitrogen, phosphorus, oxygen, sulfur and the like, oxygen affinity of central metal atoms of the catalysts is weak, and copolymerization of olefin and polar monomers is easily realized, so that a functional polyolefin material with excellent performance is synthesized. In addition, the design and synthesis of the non-metallocene catalyst ligand structure are subject to great variability. It develops rapidly from the beginning and has been regarded by people.
Complexes containing more heteroatoms in the host structure have more variability in structure and have more space for adjusting the structure and performance of the polymer compared with complexes containing only a single heteroatom (such as oxygen, nitrogen and the like). Currently, many non-metallocene ligands have been studied as structures such as [ N, N ], [ N, O ], [ N, N, O ], [ P, N, N ], [ P, N, P ], [ O, N, N, O ], [ N, N, O, O ], and the like.
Yellow Kelvin [ Ma L F, et al. Journal Polymer Science: part A: polymer Chemistry,2008, 46; ma L F, et al. Journal Polymer Science: part A: polymer Chemistry,2010, 48.
Keim [ George J.P et al. Journal of Molecular Catalysis A: chemical 110 (1996): 77-87] synthesized [ N, O ], [ P, O ], [ O, O ], [ S, O ] palladium catalysts, catalyzed styrene and ethylene copolymerization, studied the relationship between the structure and catalytic activity of the catalyst ligand, with the [ P, O ] ligand catalyst having the highest activity.
Sunwawa synthesized a series of catalysts containing [ N, N ] aminoindole [ Zhang W J, et al.J of Organometallic Chem.2006,691:4759-4767], [ N, N, O ] pyridylsalicyl [ Shaofeng Liu, et al.journal of Polymer Science: part A: polymer Chemistry,2008, 46.
Patent 200310108556 reports a polypeptide containing [ O, N, N, O ]]The complex of the type ligand is used as an olefin polymerization catalyst, and the catalytic activity of the catalyst is 10 5 gPE/molTi.h。
CN102030843 discloses a non-metallocene catalyst containing [ N, N, O, O ] structural ligand for olefin polymerization. When the catalyst is used for olefin polymerization, the catalyst has better catalytic activity on ethylene homopolymerization, ethylene/alpha-olefin and ethylene/polar monomer copolymerization.
Patent CN201310108975.1 discloses that a full-heterocyclic non-metallocene catalyst can effectively catalyze ethylene homopolymerization, propylene homopolymerization, ethylene and alpha-olefin copolymerization, propylene and alpha-olefin copolymerization, ethylene and polar alkene monomer copolymerization or propylene and polar alkene monomer copolymerization. However, the synthesis process of the full heterocyclic non-metallocene catalyst is complex and the synthesis steps are long.
The invention unexpectedly discovers a novel non-metallocene catalyst which is an [ N, P ] type non-metallocene catalyst, wherein an [ N, P ] type organic ligand reacts with a transition metal salt to generate the novel [ N, P ] type non-metallocene catalyst, and ethylene homopolymerization, propylene homopolymerization, ethylene and alpha-olefin copolymerization, propylene and alpha-olefin copolymerization, ethylene and polar olefin monomer copolymerization, propylene and polar olefin monomer copolymerization or nonpolar olefin monomer and polar olefin monomer multi-copolymerization are efficiently catalyzed in the presence of a cocatalyst alkoxy aluminum or alkyl aluminum.
Disclosure of Invention
The invention aims to provide an olefin polymerization [ N, P ] type non-metallocene catalyst and a preparation method thereof, which are used for ethylene homopolymerization, propylene homopolymerization, ethylene and alpha-olefin copolymerization, propylene and alpha-olefin copolymerization, ethylene and polar olefin monomer copolymerization, propylene and polar olefin monomer copolymerization or nonpolar olefin monomer and polar olefin monomer multi-copolymerization.
The olefin polymerization catalyst provided by the invention consists of an [ N, P ] type non-metallocene catalyst and a cocatalyst. Wherein the [ N, P ] type non-metallocene catalyst is composed of the [ N, P ] type non-metallocene catalyst which accords with a general formula 1, and is characterized in that: the [ N, P ] type non-metallocene catalyst is generated by the reaction of [ N, P ] type organic ligand and transition metal salt.
Figure BDA0001991474540000031
Wherein, in the general formula 1, R 1 、R 2 Or R 3 Are identical or different substituents, R 1 、R 2 Or R 3 Are respectively selected from C 1 -C 20 Alkyl of (C) 3 -C 20 Cycloalkyl of (C) 6 -C 40 Aryl of (C) 6 -C 40 Halogenated aryl of, C 1 -C 20 Alkoxy group of (1), C 3 -C 20 Cycloalkoxy of (C) 6 -C 40 Aryloxy group of, or C 6 -C 40 The N heteroaryl group of (1); x is selected from halogen, F, cl, br, I, or C 1 -C 15 Alkyl of (2), or C 3 -C 15 Cycloalkyl of, or C 5 -C 20 The heteroaryl group of (a); m represents a transition metal selected from one of IIIB, IVB, VB, VIB or VIII, preferably Ti, zr, hf, fe, co, ni, pd, Y, nd, sm, sc, ru, rh, V or Cr; n is a positive integer greater than or equal to 1 and less than or equal to 3, preferably 1, 2 or 3; m is a positive integer equal to or less than 5, preferably 2, 3, 4 or 5; wherein m is not less than n.
Wherein the cocatalyst is an organometallic aluminium compound selected from alkylaluminums or alkylaluminoxanes which are hydrolysis products of alkylaluminums, preferably trimethylaluminium, triethylaluminium, triisobutylaluminium, tri-n-hexylaluminium, methylaluminoxane (MAO); the molar ratio of the cocatalyst to the [ N, P ] type non-metallocene catalyst is as follows: (50-5000): 1, preferably (100-1000): 1.
the preferred [ N, P ] type non-metallocene catalyst according to formula 1 of the present invention is as follows, but the scope of the present invention is not limited to the following [ N, P ] type non-metallocene catalyst.
Figure BDA0001991474540000041
Figure BDA0001991474540000051
Figure BDA0001991474540000061
Wherein, the preparation method of the [ N, P ] type non-metallocene catalyst conforming to the general formula 1 comprises the following steps:
(1) Adding an [ N, P ] type organic ligand which accords with a general formula 2 into a reaction bottle at the temperature of between 70 ℃ below zero and 100 ℃, adding an inert organic solvent, adding a hydrogen-removing reagent, and reacting for 0.5 to 30 hours; wherein the molar ratio of the [ N, P ] type organic ligand corresponding to the general formula 2 to the hydrogen abstraction reagent is 1: (1-2); wherein the hydrogen abstraction reagent is a Grignard reagent, butyl lithium, sodium or potassium, or the like;
(2) Adding a transition metal salt into the step (1) at the temperature of between 70 ℃ below zero and 200 ℃, reacting for 0.5 to 30 hours, removing the organic solvent, washing with an inert organic solvent, and drying to obtain the [ N, P ] type non-metallocene catalyst which accords with the general formula 1; wherein the molar ratio of the [ N, P ] type organic ligand corresponding to formula 2 to the transition metal salt is 1: (1.1-5); wherein the transition metal salt is a halide of a transition metal; wherein the transition metal is selected from one of IIIB, IVB, VB, VIB or VIII, preferably Ti, zr, hf, fe, co, ni, pd, Y, nd, sm, sc, ru, rh, V or Cr;
Figure BDA0001991474540000071
wherein, R in the general formula 2 1 、R 2 Or R 3 Are identical or different substituents, R 1 、R 2 Or R 3 Are respectively selected from C 1 -C 20 Alkyl of (C) 3 -C 20 Cycloalkyl of, C 6 -C 40 Aryl of (C) 6 -C 40 Halogenated aryl of (2), C 1 -C 20 Alkoxy group of (1), C 3 -C 20 Cycloalkoxy of (A), C 6 -C 40 Aryloxy group of, or C 6 -C 40 The N heteroaryl group of (1);
wherein the inert organic solvent is selected from C 5 ～C 15 Saturated hydrocarbon of (C) 5 ～C 10 Alicyclic hydrocarbon of (2), C 6 ～C 15 Aromatic hydrocarbon of (2), C 2 ～C 10 The saturated heterocyclic hydrocarbon or a mixed solvent composed of the above solvents;
wherein, the preparation method of the [ N, P ] type organic ligand conforming to the general formula 2 comprises the following steps:
(1) Reacting a primary amine R 1 NH 2 Adding the mixture into a reaction bottle, adding an inert organic solvent and a hydrogen-withdrawing reagent, and reacting at the temperature of between 70 ℃ below zero and 200 ℃ for 2 to 24 hours; primary amines R 1 NH 2 The molar ratio of the hydrogen extracting reagent to the hydrogen extracting reagent is 1: (1-1.5); wherein R is 1 Is selected from C 1 -C 20 Alkyl of (C) 3 -C 20 Cycloalkyl of, C 6 -C 40 Aryl of, C 6 -C 40 Halogenated aryl of, C 1 -C 20 Alkoxy group of (1), C 3 -C 20 Cycloalkoxy of (A), C 6 -C 40 Aryloxy group of, or C 6 -C 40 The N heteroaryl group of (1); wherein, the hydrogen-withdrawing reagent is Grignard reagent, butyl lithium, sodium or potassium, etc.;
(2) Adding a dialkylphosphorus halide or diarylphosphorus halide R to step (1) at-70 to 50 deg.C 2 R 3 PCl, the reaction temperature is-30 to 150 ℃, and the reaction time is 1 to 24 hours; removing the solvent, washing by adopting an inert organic solvent, filtering and drying to obtain an organic ligand in accordance with a general formula 2; wherein, the primary amine R 1 NH 2 The molar ratio to dialkylphosphonium halide or diarylphosphonium halide is 1: (1-1.2); wherein, R is 2 Or R 3 Are identical or different substituents, R 2 Or R 3 Are respectively selected from C 1 -C 20 Alkyl of (C) 3 -C 20 Cycloalkyl of, C 6 -C 40 Aryl of (C) 6 -C 40 Halogenated aryl of (2), C 1 -C 20 Alkoxy group of (C) 3 -C 20 Cycloalkoxy of (C) 6 -C 40 Aryloxy group of, or C 6 -C 40 The N heteroaryl group of (1);
wherein the inert organic solvent is selected from C 5 ～C 15 Saturated hydrocarbon of (C) 5 ～C 10 Alicyclic hydrocarbon of (C) 6 ～C 15 Aromatic hydrocarbons of、C 2 ～C 10 The saturated heterocyclic hydrocarbon or the mixed solvent composed of the above solvents.
The invention provides [ N, P]The application of the non-metallocene catalyst is to catalyze ethylene homopolymerization, propylene homopolymerization, copolymerization of ethylene and alpha-olefin, copolymerization of propylene and alpha-olefin, copolymerization of ethylene and polar olefin monomer, copolymerization of propylene and polar olefin monomer, or multipolymerization of non-polar olefin monomer and polar olefin monomer, and the catalytic activity of the catalyst is high. Wherein the alpha-olefin is C 3 -C 2000 Olefins of (2), preferably propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 3-methyl-1-butene, 4-methyl-1-pentene, styrene, α -methylstyrene, norbornene, ethylidene norbornene, butadiene, isopentene, isoprene, 1, 8-nonadiene, 1, 7-octadiene or mixtures thereof, and the like; polar olefinic monomers are compounds containing a carbon-carbon double bond and simultaneously bearing a polar group, selected from compounds according to formula 3, wherein Z is selected from integers from 0 to 50, wherein FG is selected from hydroxy-OH, phenolic hydroxy-C6H 4OH, carboxy-COOH, arylcarboxy-C6H 4COOH, ester-COOR, arylester-C6H 4COOR, halogen, nitrile-CN, -N (H) R, amino acids or amino acid esters, and the like, wherein R is selected from C1 to C30 alkyl, C1 to C30 polyfluoroalkyl, C1 to C30 alkoxy, C1 to C30 siloxane, C1 to C30 silane, C3 to C30 cycloalkyl, C3 to C30 cycloalkoxy, C3 to C30 siloxycycloalkyl, C3 to C30 silacycloalkyl, C6 to C30 aryl, C6 to C30 silaryl, C6 to C30 siloxy, C6 to C30 aryloxy, C6 to C30 pyridyl or C30 pyridyl, C6 to C30 pyridyl, or a derivative of Cl, br, or a derivative thereof, wherein F is selected from C1 to C30 sulfonyl, or a derivative; the polar olefin monomer is preferably the following compounds, but is not limited to these compounds: 6-hydroxy-1-hexene, 10-hydroxy-1-decene, 10-carboxy-1-decene, 10-methylcarboxylate-1-decene, hydroxynorbornene, vinyltyrosine ethyl ester, 8-bromo-1-octene, 6-chloro-1-hexene, acrylonitrile, vinyl chloride, tetrafluoroethylene, perfluoropropene, perfluorobutene-1, perfluorohexene-1, acrylic acid, methacrylic acid, 4-vinyl-1-pentanoic acid, 9-vinyl-1-decanoic acid, vinyl acetate, MMA, MA, butyl methacrylate, perfluorohexyl methacrylateP-hydroxystyrene, 10-methyl carboxylate-1-decene, isobutyl perfluoromethacrylate, or a mixture of two or more polar olefin monomers;
Figure BDA0001991474540000091
further, the [ N, P ]]The application of the non-metallocene catalyst comprises a solution polymerization process, a gas-phase bulk polymerization process, a liquid-phase bulk polymerization process, a loop polymerization process, a slurry polymerization process or a combined polymerization process, wherein the solution polymerization process or the slurry polymerization process needs a solvent selected from water and C 5 To C 20 Aliphatic alkanes or cycloalkanes of (A), or C 6 To C 20 Or a mixed solvent thereof.
Further, the application of the [ N, P ] type non-metallocene catalyst is characterized in that: the catalyst is used for catalyzing ethylene homopolymerization, propylene homopolymerization, ethylene and alpha-olefin copolymerization, propylene and alpha-olefin copolymerization, ethylene and polar olefin monomer copolymerization, propylene and polar olefin monomer copolymerization or nonpolar olefin monomer and polar olefin monomer multi-copolymerization, the weight average molecular weight of the obtained polymer is 500-7000000 g/mol, the polymerization temperature is 0-200 ℃, the polymerization time is 0.5-5 hours, and the polymerization pressure is 0.1 mPa-30 MPa.
The present invention will be further described with reference to the following specific embodiments, but the scope of the present invention is not limited to the following examples.
Detailed Description
Example 1
Synthesis of ligands
50ml of toluene and 5ml of tert-butylamine are taken to be put into a 300ml schlenk bottle, a methyl Grignard reagent with the same mol as the tert-butylamine is added at the temperature of minus 30 ℃, stirred and reacted for 5 hours, diisopropyl phosphonium chloride with the same mol as the tert-butylamine is added, the reaction is carried out for 6 hours at the temperature of minus 30 ℃, the solvent is removed in vacuum, the mixture is washed by n-hexane for 2 times and dried in vacuum, and the product is obtained with the yield of 81 percent.
Synthesis of catalyst (1)
Taking 20ml of toluene and 1g of ligand to a 200ml schlenk bottle, adding n-butyllithium which is equal to the mole of the ligand at the temperature of-40 ℃, stirring, reacting for 4 hours, adding TiCl which is equal to the mole of the ligand 4 Reacting at-30 ℃ for 5 hours, removing the solvent in vacuum, washing with n-hexane for 3 times, and drying in vacuum to obtain the catalyst (1) with the yield of 85%.
After a 2L stainless steel autoclave is fully replaced by nitrogen, 1L of N-hexane is added into the reaction kettle, 5mg of [ N, P ] type non-metallocene catalyst (1) is added, 2.94mmol of MAO is added, ethylene is charged until the pressure is 0.5MPa, the mixture is stirred, the temperature is raised to 75 ℃ for reaction for 0.5 hour, and 735 g of a polymerization product is collected.
Example 2
Synthesis of ligands
60ml of toluene and 5ml of aniline are taken to be put into a 300ml schlenk bottle, a phenyl Grignard reagent with the same mole as the aniline is added at the temperature of minus 50 ℃, the mixture is stirred and reacted for 6 hours, dicyclohexyl phosphine chloride with the same mole as the aniline is added, the reaction is carried out for 5 hours at the temperature of minus 40 ℃, the solvent is removed in vacuum, the mixture is washed by normal hexane for 3 times, and the product is dried in vacuum, so that the yield is 85 percent.
Synthesis of catalyst (2)
20ml of toluene and 1.5g of ligand are taken and put into a 200ml schlenk bottle, n-butyllithium which is equimolar with the ligand is added at the temperature of minus 20 ℃, stirred and reacted for 5 hours, and ZrCl which is equimolar with the ligand is added 4 The reaction was carried out at-30 ℃ for 8 hours, the solvent was removed in vacuo, washed with n-hexane 4 times, and dried in vacuo to obtain catalyst (2) with a yield of 84%.
After a 5L stainless steel autoclave is fully replaced by nitrogen, 2.5L of N-hexane is added into the reaction kettle, 3mg of [ N, P ] type non-metallocene catalyst (2) is added, 3.25mmol of MAO is added, 30 g of 1-hexene is added, ethylene is charged until the pressure is 0.7MPa, the mixture is stirred, the temperature is raised to 80 ℃ for reaction for 1 hour, and 518 g of polymerization product is collected.
Example 3
Synthesis of ligands
50ml of toluene and 5ml of dimethylaniline are taken to be put in a 300ml schlenk bottle, an ethyl Grignard reagent with the same mole as the dimethylaniline is added at minus 30 ℃, the mixture is stirred and reacted for 8 hours, dicyclohexyl phosphonium chloride with the same mole as the dimethylaniline is added to react for 6 hours at minus 30 ℃, the solvent is removed in vacuum, the mixture is washed for 2 times by using normal hexane and dried in vacuum, and the product is obtained, wherein the yield is 85 percent.
Synthesis of catalyst (3)
20ml of toluene and 1g of ligand are taken and put into a 200ml schlenk bottle, n-butyllithium which is equimolar with the ligand is added at-40 ℃, the mixture is stirred and reacted for 4 hours, hfCl which is equimolar with the ligand is added 4 Reacting at-30 deg.C for 5 hr, removing solvent in vacuum, washing with n-hexane for 3 times, and vacuum drying to obtain catalyst (3) with yield of 82%.
After a 5-liter stainless steel autoclave is fully replaced by nitrogen, 2.5L of N-hexane is added into the reaction kettle, 6mg of [ N, P ] type non-metallocene catalyst (3) is added, 3.25mmol of MAO is added, 40 g of 1-octene is added, ethylene is filled until the pressure is 1.5MPa, the mixture is stirred, the temperature is raised to 55 ℃, the reaction is carried out for 1 hour, and 736 g of polymerization product is collected.
Example 4
Synthesis of ligands
50ml of toluene and 5g of difluoroaniline were put into a 300ml schlenk bottle, n-butyllithium twice as much as the difluoroaniline was added at-35 ℃ and stirred to react for 8 hours, bis (2, 4, 6-trifluorophenyl) -phosphine chloride equimolar to the difluoroaniline was added to react at-30 ℃ for 6 hours, the solvent was removed in vacuo, washed 3 times with n-pentane and dried in vacuo to obtain the product in 83% yield.
Synthesis of catalyst (4)
30ml of toluene and 1g of ligand are taken to be put into a 200ml schlenk bottle, n-butyllithium which is equal to the mole of the ligand is added at the temperature of minus 20 ℃, the mixture is stirred and reacted for 4 hours, and TiCl which is equal to the mole of the ligand is added 4 The reaction was carried out at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed with n-hexane 3 times, and dried in vacuo to obtain catalyst (4) with a yield of 91%.
After a 5L stainless steel autoclave is fully replaced by nitrogen, 2.5L of N-hexane is added into the reaction kettle, 3mg of [ N, P ] type non-metallocene catalyst (4) is added, 0.85mmol of MAO is added, 40 g of 1-octene is added, 20 g of styrene is added, ethylene is filled until the pressure is 1.0MPa, stirring is carried out, the temperature is raised to 70 ℃ for reaction for 1 hour, and 632 g of polymerization product is collected.
Example 5
Synthesis of ligands
50ml of toluene and 5g of trifluoroaniline are put into a 300ml schlenk bottle, n-butyllithium with 1.5 times mole of the trifluoroaniline is added at minus 35 ℃, the mixture is stirred and reacted for 8 hours, diphenyl phosphine chloride with 1.1 times mole of the trifluoroaniline is added and reacted for 6 hours at minus 30 ℃, the solvent is removed in vacuum, the mixture is washed with n-pentane for 3 times, and the product is dried in vacuum, so that the yield is 86%.
Synthesis of catalyst (5)
30ml of toluene and 1.5g of ligand are taken to be put into a 200ml schlenk bottle, n-butyllithium which is 1.1 times as much as the ligand is added at the temperature of-20 ℃, the mixture is stirred and reacted for 5 hours, and TiCl which is 3 times as much as the ligand is added 4 The reaction was carried out at-35 ℃ for 7 hours, the solvent was removed in vacuo, washed with n-hexane 3 times, and dried in vacuo to obtain catalyst (5) with a yield of 83%.
After a 5L stainless steel autoclave is fully replaced by nitrogen, 3L of N-hexane is added into the reaction kettle, 6mg of [ N, P ] type non-metallocene catalyst (5) is added, 0.85mmol of MAO is added, 500 g of propylene is added, the mixture is stirred, the temperature is raised to 75 ℃ for reaction for 2 hours, and 358 g of a polymerization product is collected.
Example 6
Synthesis of ligands
50ml of toluene and 2g of pentafluoroaniline are taken to be put into a 300ml schlenk bottle, n-butyllithium which is twice as molar as the pentafluoroaniline is added at minus 25 ℃, the mixture is stirred and reacted for 6 hours, bis (trimethylphenyl) -phosphine chloride which is equal to the pentafluoroaniline is added and reacted for 6 hours at minus 10 ℃, the solvent is removed in vacuum, the mixture is washed for 4 times by using n-pentane, and the product is dried in vacuum, so that the yield is 85 percent.
Synthesis of catalyst (6)
30ml of toluene and 1g of ligand are taken and put into a 200ml schlenk bottle, n-butyllithium which is 1.2 times of the ligand is added at the temperature of minus 20 ℃, the mixture is stirred and reacted for 4 hours, hfCl which is equimolar with the ligand is added 4 The reaction was carried out at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed with n-hexane 3 times, and dried in vacuo to obtain catalyst (6) with a yield of 88%.
After a 5L stainless steel autoclave is fully replaced by nitrogen, 2.5L of N-hexane is added into the reaction kettle, 10mg of [ N, P ] type non-metallocene catalyst (6) is added, 5.15mmol of MAO is added, 600 g of propylene and 100 g of 1-octene are added, the mixture is stirred, the temperature is raised to 70 ℃ for reaction for 2 hours, and 511 g of polymerization product is collected.
Example 7
Synthesis of ligands
Taking 40ml of xylene and 1g of 2, 6-trifluoromethylaniline into a 300ml schlenk bottle, adding n-butyllithium which is twice as much as the moles of the trifluoromethylaniline at-35 ℃, stirring, reacting for 8 hours, adding diphenyl phosphine chloride which is equal to the moles of the trifluoromethylaniline, reacting for 6 hours at-30 ℃, removing the solvent in vacuum, washing for 2 times by using n-pentane, and drying in vacuum to obtain the product with the yield of 82%.
Synthesis of catalyst (7)
30ml of toluene and 0.5g of ligand are taken to be put into a 200ml schlenk bottle, n-butyllithium with 1.2 times of the mole of the ligand is added at the temperature of minus 20 ℃, the mixture is stirred and reacted for 4 hours, and NiMe with the same mole of the ligand is added 2 Reacting at-30 deg.C for 5 hr, removing solvent in vacuum, washing with n-hexane for 3 times, and vacuum drying to obtain catalyst (7) with yield of 90%.
After a 5-liter stainless steel autoclave is fully replaced by nitrogen, 2.5L of N-hexane is added into the reaction kettle, 5mg of [ N, P ] type non-metallocene catalyst (7) is added, 2.75mmol of MAO is added, 400 g of propylene and 80 g of 1-octene are added, ethylene is filled until the pressure is 0.8MPa, the mixture is stirred, the temperature is increased to 80 ℃ for reaction for 2 hours, and 622 g of a polymerization product is collected.
Example 8
Synthesis of ligands
50ml of toluene and 5g of trifluoroaniline are put into a 300ml schlenk bottle, n-butyllithium which is twice as molar as the trifluoroaniline is added at the temperature of minus 35 ℃, the mixture is stirred and reacted for 8 hours, diphenyl phosphine chloride which is equal to the trifluoroaniline in molar is added, the mixture is reacted for 6 hours at the temperature of minus 30 ℃, the solvent is removed in vacuum, the mixture is washed for 2 times by using n-pentane, and the product is dried in vacuum, so that the yield is 85 percent.
Synthesis of catalyst (8)
30ml of toluene and 1g of ligand are taken to be put into a 200ml schlenk bottle, n-butyllithium which is equal to the ligand in mole is added at the temperature of minus 20 ℃, the mixture is stirred and reacted for 4 hours, fe (MePyrid) which is equal to the ligand in mole is added, the reaction is carried out for 5 hours at the temperature of minus 30 ℃, the solvent is removed in vacuum, the mixture is washed by n-hexane for 3 times, and the vacuum drying is carried out, so that the catalyst (8) is obtained, and the yield is 82%.
After a 2L stainless steel autoclave is fully replaced by nitrogen, 1L of N-hexane is added into the reaction kettle, 8mg of [ N, P ] type non-metallocene catalyst (8) is added, 3.01mmol of MAO is added, 40 g of 6-chloro-1-hexene is added, 60 g of 1-octene is added, ethylene is charged until the pressure is 0.7MPa, the mixture is stirred, the temperature is raised to 60 ℃ for reaction for 1 hour, and 126 g of polymerization product is collected.
Example 9
Synthesis of ligands
50ml of toluene and 1g of pentafluoroaniline were put into a 300ml schlenk flask, n-butyllithium twice as much as pentafluoroaniline in mol was added at-15 ℃ and stirred to react for 8 hours, bis (2, 4, 6-trimethylphenyl) -phosphine chloride in mol equivalent to pentafluoroaniline was added to react at-30 ℃ for 6 hours, the solvent was removed in vacuo, washed with n-pentane 3 times, and dried in vacuo to obtain the product in 86% yield.
Synthesis of catalyst (9)
Adding 30ml of toluene and 1g of ligand into a 200ml schlenk bottle, adding n-butyllithium with the same mole as the ligand at the temperature of-20 ℃, stirring, reacting for 4 hours, adding YCl with the same mole as the ligand 3 Reacting at-30 ℃ for 5 hours, removing the solvent in vacuum, washing with n-hexane for 3 times, and drying in vacuum to obtain the catalyst (9) with the yield of 83 percent.
After a 5-liter stainless steel autoclave is fully replaced by nitrogen, 2.5L of N-hexane is added into the reaction kettle, 15mg of [ N, P ] type non-metallocene catalyst (9) is added, 4.59mmol of MAO is added, 30 g of 10-bromo-1-decene is added, 50 g of 1-decene is added, 100 g of propylene is added, ethylene is charged until the pressure is 0.8MPa, stirring is carried out, the temperature is raised to 70 ℃ for reaction for 1.5 hours, and 163 g of polymerization product is collected.
Example 10
Synthesis of ligands
50ml of toluene and 0.5g of 2, 6-trifluoromethylaniline are put into a 300ml schlenk bottle, n-butyllithium with 1.1 times mole of the trifluoromethylaniline is added at-35 ℃, the mixture is stirred and reacted for 8 hours, diphenyl phosphine chloride with the same mole of the trifluoromethylaniline is added, the reaction is carried out for 6 hours at-20 ℃, the solvent is removed in vacuum, the mixture is washed 3 times with n-pentane, and the product is dried in vacuum, so that the yield is 87%.
Synthesis of catalyst (10)
30ml of toluene and 0.5g of ligand are taken to be put into a 200ml schlenk bottle, n-butyllithium which is equal to the ligand in mole is added at the temperature of minus 10 ℃, the mixture is stirred and reacted for 4 hours, and PdMe which is equal to the ligand in mole is added 2 The reaction was carried out at 10 ℃ for 5 hours, the solvent was removed in vacuo, washed with n-hexane 3 times, and dried in vacuo to obtain a catalyst (10) with a yield of 90%.
After a 5-liter stainless steel autoclave is fully replaced by nitrogen, 2.5L of N-hexane is added into the reaction kettle, 5mg of [ N, P ] type non-metallocene catalyst (10) is added, 9.38mmol of MAO is added, 30 g of 10-carboxyl-1-decene is added, 60 g of 1-octene is added, ethylene is filled until the pressure is 0.7MPa, the mixture is stirred, the temperature is raised to 70 ℃ for reaction for 1 hour, and 185 g of polymerization product is collected.
Example 11
Synthesis of ligands
50ml of toluene and 0.5g of 2,4, 6-tris (pentafluorothio) aniline were charged into a 300ml schlenk flask, n-butyllithium was added at-35 ℃ in an amount twice as much as the amount of tris (pentafluorothio) aniline, the mixture was stirred and reacted for 8 hours, bis (2, 6-difluorophenyl) phosphine chloride was added in an amount equimolar to the amount of tris (pentafluorothio) aniline and reacted at 20 ℃ for 6 hours, the solvent was removed in vacuo, the mixture was washed with n-pentane 3 times, and dried in vacuo to obtain the product in a yield of 85%.
Synthesis of catalyst (11)
30ml of toluene and 0.5g of ligand are taken and put into a 200ml schlenk bottle, n-butyllithium which is equimolar with the ligand is added at 0 ℃, the mixture is stirred and reacted for 4 hours, and C which is equimolar with the ligand is added O Cl (Pyrid) was reacted at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed 3 times with n-hexane, and dried in vacuo to obtain catalyst (11) in 88% yield.
After a 5L stainless steel autoclave was fully replaced with nitrogen, 2.5L of N-hexane was added to the reaction kettle, 25mg of [ N, P ] type non-metallocene catalyst (11) was added, 4.7mmol of MAO was added, 20 g of MMA was added, ethylene was charged to a pressure of 0.7MPa, stirring was carried out, the temperature was raised to 70 ℃ to react for 1 hour, and 119 g of a polymerization product was collected.
Example 12
Synthesis of ligands
50ml of toluene and 2g of pentafluoroaniline were put in a 300ml schlenk flask, n-butyllithium 1 times mole of which was added to pentafluoroaniline at-5 ℃ and stirred to react for 10 hours, bis (2, 4, 6-trifluorophenyl) phosphine chloride equivalent to pentafluoroaniline was added to react at 40 ℃ for 6 hours, the solvent was removed in vacuo, washed with n-pentane 3 times and dried in vacuo to obtain the product in a yield of 81%.
Synthesis of catalyst (12)
30ml of toluene and 1g of ligand are taken and put into a 200ml schlenk bottle, n-butyllithium with the same mole as the ligand is added at the temperature of minus 20 ℃, the mixture is stirred and reacted for 4 hours, and ScBr with the same mole as the ligand is added 3 The reaction was carried out at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed with n-hexane 3 times, and dried in vacuo to obtain catalyst (12) with a yield of 81%.
After a 5L stainless steel autoclave is fully replaced by nitrogen, 2.5L of N-hexane is added into the reaction kettle, 20mg of [ N, P ] type non-metallocene catalyst (12) is added, 5.85mmol of MAO is added, 20 g of ethylidene norbornene is added, 200 g of propylene is added, ethylene is filled until the pressure is 0.7MPa, the mixture is stirred, the temperature is increased to 90 ℃ for reaction for 2 hours, and 319 g of polymerization product is collected.
Example 13
Synthesis of ligands
Taking 50ml of toluene and 5g of tert-butylamine in a 300ml schlenk bottle, adding n-butyllithium which is twice molar to tert-butylamine at the temperature of-55 ℃, stirring, heating to 50 ℃ for reaction for 8 hours, adding diethylphosphonium chloride which is equal molar to tert-butylamine, reacting at the temperature of-30 ℃ for 6 hours, removing the solvent in vacuum, washing with n-pentane for 3 times, and drying in vacuum to obtain the product, wherein the yield is 75%.
Synthesis of catalyst (13)
30ml of toluene and 1g of ligand are taken and put into a 200ml schlenk bottle, n-butyllithium with the same mole as the ligand is added at the temperature of minus 20 ℃, the mixture is stirred and reacted for 4 hours, and RhCl with the same mole as the ligand is added 3 Reacting at-30 ℃ for 5 hours, removing the solvent in vacuum, washing with n-hexane for 3 times, and drying in vacuum to obtain the catalyst (13) with the yield of 89%.
After a 5L stainless steel autoclave is fully replaced by nitrogen, 2.5L of N-hexane is added into the reaction kettle, 3mg of [ N, P ] type non-metallocene catalyst (13) is added, 1.35mmol of MAO is added, 20 g of norbornene is added, 80 g of 1-hexene is added, ethylene is filled until the pressure is 0.7MPa, stirring is carried out, the temperature is raised to 100 ℃ for reaction for 2 hours, and 422 g of polymerization product is collected.
Example 14
Synthesis of ligands
Taking 50ml of toluene and 5g of aniline in a 300ml schlenk bottle, adding n-butyl lithium which is twice molar to the aniline at the temperature of-45 ℃, stirring, reacting for 8 hours, adding dicyclohexyl phosphonium chloride which is equal to the aniline, reacting for 6 hours at the temperature of-30 ℃, removing the solvent in vacuum, washing for 3 times by using n-pentane, and drying in vacuum to obtain the product with the yield of 87%.
Synthesis of catalyst (14)
30ml of toluene and 1g of ligand are taken to be put into a 200ml schlenk bottle, n-butyllithium with the same mole as the ligand is added at the temperature of minus 20 ℃, the mixture is stirred and reacted for 4 hours, and RuCl with the same mole as the ligand is added 4 The reaction was carried out at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed with n-hexane 3 times, and dried in vacuo to obtain catalyst (14) with a yield of 91%.
After a 5L stainless steel autoclave is fully replaced by nitrogen, 2.5L of N-hexane is added into the reaction kettle, 5mg of [ N, P ] type non-metallocene catalyst (14) is added, 2.02mmol of MAO is added, 80 g of 1-hexene is added, 30 g of acrylic acid is added, ethylene is charged until the pressure is 0.7MPa, the mixture is stirred, the temperature is raised to 70 ℃ for reaction for 2 hours, and 125 g of a polymerization product is collected.
Example 15
Synthesis of ligands
50ml of toluene and 5g of dimethylaniline are taken to be put into a 300ml schlenk bottle, n-butyllithium which is twice as much as the dimethylaniline is added at the temperature of minus 35 ℃, the mixture is stirred and reacted for 8 hours, dicyclohexyl phosphine chloride which is equal to the dimethylaniline is added and reacted for 6 hours at the temperature of minus 30 ℃, the solvent is removed in vacuum, the mixture is washed for 3 times by using n-pentane and dried in vacuum, and the product is obtained, wherein the yield is 85 percent.
Synthesis of catalyst (15)
30ml of toluene and 1g of ligand are taken to be put into a 200ml schlenk bottle, n-butyl lithium which is equal to the ligand in mol is added at the temperature of minus 20 ℃,stirring, reacting for 4 hours, adding VCl with equal mole of ligand 5 The reaction was carried out at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed with n-hexane 3 times, and dried in vacuo to obtain catalyst (15) with a yield of 83%.
After a 5-liter stainless steel autoclave is fully replaced by nitrogen, 2.5L of N-hexane is added into the reaction kettle, 15mg of [ N, P ] type non-metallocene catalyst (15) is added, 4.23mmol of MAO is added, 10 g of 1-hydroxy-9-decene and 80 g of 1-octene are added, 1L of hydrogen is filled, ethylene is filled until the pressure is 0.8MPa, the mixture is stirred, the temperature is raised to 75 ℃ for reaction for 2 hours, and 433 g of polymerization product is collected.
Example 16
Synthesis of ligands
Taking 50ml of toluene and 5g of difluoroaniline into a 300ml schlenk bottle, adding n-butyllithium which is twice molar to the difluoroaniline at-35 ℃, stirring, reacting for 8 hours, adding bis (2, 4, 6-trifluorophenyl) -phosphine chloride which is equimolar to the difluoroaniline, reacting for 8 hours at 30 ℃, removing the solvent in vacuum, washing with n-pentane for 3 times, and drying in vacuum to obtain the product, wherein the yield is 85%.
Synthesis of catalyst (16)
30ml of toluene and 1g of ligand were taken in a 200ml schlenk flask, n-butyllithium equimolar to the ligand was added at-20 ℃, stirred and reacted for 4 hours, and V (OEt) equimolar to the ligand was added 3 The reaction was carried out at 50 ℃ for 8 hours, the solvent was removed in vacuo, washed with n-hexane 3 times, and dried in vacuo to obtain catalyst (16) in 92% yield.
After a 5-liter stainless steel autoclave is fully replaced by nitrogen, 2.5L of normal hexane is added into the reaction kettle, 5mg of [ N, P ] type non-metallocene catalyst (16) is added, 2.68mmol of MAO is added, 180 g of propylene is added, ethylene is charged until the pressure is 0.8MPa, the mixture is stirred, the temperature is raised to 75 ℃ for reaction for 2 hours, and 562 g of polymerization product is collected.
Example 17
Synthesis of ligands
50ml of toluene and 5g of trifluoroaniline are put into a 300ml schlenk bottle, n-butyllithium which is twice as molar as the trifluoroaniline is added at-35 ℃, the mixture is stirred and reacted for 8 hours, diphenyl phosphine chloride which is equal to the trifluoroaniline is added, the mixture is reacted for 6 hours at 30 ℃, the solvent is removed in vacuum, the mixture is washed for 3 times by using n-pentane, and the product is dried in vacuum, so that the yield is 86%.
Synthesis of catalyst (17)
30ml of toluene and 1g of ligand were taken and put in a 200ml schlenk bottle, n-butyllithium in an amount equimolar to the ligand was added at-20 ℃, stirred and reacted for 4 hours, and Cr (Ac) in an amount equimolar to the ligand was added 3 The reaction was carried out at 40 ℃ for 5 hours, the solvent was removed in vacuo, washed with n-hexane 3 times, and dried in vacuo to obtain catalyst (17) with a yield of 90%.
After a 5L stainless steel autoclave is fully replaced by nitrogen, 2.5L of N-hexane is added into the reaction kettle, 5mg of [ N, P ] type non-metallocene catalyst (17) is added, 2.65mmol of MAO is added, 20 g of 10-methyl carboxylic ester-1-decene is added, 19 g of perfluoro-isobutyl methacrylate is added, 180 g of propylene is added, ethylene is charged until the pressure is 2.5MPa, the mixture is stirred, the temperature is raised to 70 ℃ for reaction for 2 hours, and 365 g of polymerization product is collected.
Example 18
Synthesis of ligands
50ml of toluene and 5g of tetrafluoroaniline are put into a 300ml schlenk bottle, n-butyllithium which is twice as molar as the tetrafluoroaniline is added at minus 35 ℃, the mixture is stirred and reacted for 8 hours, bis (2, 6-dimethylphenyl) phosphine chloride which is equal to the tetrafluoroaniline is added and reacted for 6 hours at minus 30 ℃, the solvent is removed in vacuum, the mixture is washed for 3 times by n-pentane, and the product is dried in vacuum, so that the yield is 83 percent.
Synthesis of catalyst (18)
30ml of toluene and 1g of ligand are taken and put into a 200ml schlenk bottle, n-butyllithium which is equal to the ligand in mol is added at the temperature of minus 20 ℃, the mixture is stirred and reacted for 4 hours, and NdCl which is equal to the ligand in mol is added 4 The reaction was carried out at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed with n-hexane 3 times, and dried in vacuo to obtain catalyst (18) with a yield of 91%.
After a 5L stainless steel autoclave is fully replaced by nitrogen, 2.5L of normal hexane is added into the reaction kettle, 5mg of [ N, P ] type non-metallocene catalyst (18) is added, 2.25mmol of MAO is added, 25 g of vinyl acetate is added, 30 g of ethylidene norbornene is added, 180 g of propylene is added, ethylene is filled until the pressure is 3.5MPa, the mixture is stirred, the temperature is raised to 60 ℃ for reaction for 2 hours, and 426 g of a polymerization product is collected.
Example 19
Synthesis of ligands
Taking 50ml of THF and 5g of difluoroaniline into a 300ml schlenk bottle, adding n-butyllithium which is twice as molar as the difluoroaniline at-35 ℃, stirring and reacting for 8 hours, adding diphenyl phosphine chloride which is equal to the difluoroaniline in molar quantity, heating to 60 ℃ for reacting for 6 hours, removing the solvent in vacuum, washing for 3 times by using n-pentane, and drying in vacuum to obtain the product, wherein the yield is 85%.
Synthesis of catalyst (19)
30ml of toluene and 1g of ligand were taken and put in a 200ml schlenk flask, n-butyllithium in an amount equimolar to the ligand was added at-20 ℃, stirred and reacted for 4 hours, and Ti (Me) in an amount equimolar to the ligand was added 4 Reacting at-30 ℃ for 5 hours, removing the solvent in vacuum, washing with n-hexane for 3 times, and drying in vacuum to obtain the catalyst (19) with the yield of 87%.
After a 5-liter stainless steel autoclave is fully replaced by nitrogen, 2.5L of normal hexane is added into the reaction kettle, 5mg of [ N, P ] type non-metallocene catalyst (19) is added, 2.55mmol of MAO is added, 25 g of acrylonitrile is added, 30 g of hydroxy ethylidene norbornene is added, 80 g of 1-octene is added, ethylene is filled until the pressure is 1.0MPa, stirring is carried out, the temperature is raised to 70 ℃ for reaction for 2 hours, and 362 g of polymerization product is collected.
Example 20
Synthesis of ligands
50ml of toluene and 5g of trifluoroaniline are put into a 300ml schlenk bottle, n-butyllithium which is twice as much as the trifluoroaniline in mol is added at the temperature of minus 5 ℃, the mixture is stirred and heated to 70 ℃ for reaction for 8 hours, diphenyl phosphine chloride which is equal to the trifluoroaniline in mol is added for reaction for 6 hours at the temperature of 50 ℃, the solvent is removed in vacuum, the mixture is washed by n-pentane for 3 times, and the product is dried in vacuum, so that the yield is 83 percent.
Synthesis of catalyst (20)
30ml of toluene and 1g of ligand were taken and put in a 200ml schlenk flask, n-butyllithium equimolar to the ligand was added at-20 ℃ and stirred to react for 4 hours, and Ti (Et) equimolar to the ligand was added 4 Reacting at-30 deg.C for 5 hr, and heating to 80 deg.C for 4 hr. Removing the solvent in vacuo withWashed 3 times with hexane and dried in vacuo to afford catalyst (20) in 83% yield.
After a 5L stainless steel autoclave is fully replaced by nitrogen, 2.5L of N-hexane is added into the reaction kettle, 8mg of [ N, P ] type non-metallocene catalyst (20) is added, 2.5mmol of MAO is added, 25 g of 4-chloromethyl styrene and 80 g of 1-hexene are added, ethylene is charged until the pressure is 1.5MPa, the mixture is stirred, the temperature is increased to 75 ℃ for reaction for 1 hour, and 291 g of polymerization product is collected.
Example 21
Synthesis of ligands
50ml of toluene and 2g of pentafluoroaniline were taken out and put into a 300ml schlenk bottle, n-butyllithium twice as much as pentafluoroaniline in mole was added at-35 ℃ and stirred for 10 hours, bis (2, 4, 6-trimethylphenyl) -phosphine chloride equal to pentafluoroaniline in mole was added and reacted at-30 ℃ for 6 hours, the solvent was removed in vacuo, washed with n-pentane for 3 times and dried in vacuo to obtain the product in a yield of 85%.
Synthesis of catalyst (21)
30ml of toluene and 1g of ligand were taken in a 200ml schlenk flask, n-butyllithium in an amount equimolar to the ligand was added at-20 ℃, stirred and reacted for 4 hours, and Ti (iBu) in an amount equimolar to the ligand was added 4 The reaction was carried out at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed with n-hexane 3 times, and dried in vacuo to obtain catalyst (21) with a yield of 91%.
After a 5L stainless steel autoclave is fully replaced by nitrogen, 2.5L of N-hexane is added into the reaction kettle, 15mg of [ N, P ] type non-metallocene catalyst (21) is added, 11.5mmol of MAO is added, 50 g of pentadiene is added, 120 g of propylene is added, 80 g of 1-hexene is added, ethylene is charged until the pressure is 1.5MPa, the mixture is stirred, the temperature is raised to 155 ℃ for reaction for 1 hour, and 283 g of polymerization product is collected.
Example 22
Synthesis of ligands
20ml of toluene and 0.5g of bis- (2, 4-trifluoromethyl) aniline were taken in a 300ml schlenk bottle, n-butyllithium which is twice as molar as much as trifluoromethylaniline was added at-35 ℃ and stirred for 8 hours, diphenyl phosphonium chloride which is equal molar as trifluoromethylaniline was added and reacted at-30 ℃ for 6 hours, the solvent was removed in vacuo, the mixture was washed with n-pentane 3 times and dried in vacuo to obtain a product with a yield of 88%.
Synthesis of catalyst (22)
30ml of toluene and 0.3g of ligand were taken in a 200ml schlenk flask, n-butyllithium in an amount equivalent to that of the ligand was added at-20 ℃ and the mixture was stirred and reacted for 4 hours, and Sm (Me) in an amount equivalent to that of the ligand was added 2 Reacting at-30 deg.C for 5 hr, removing solvent in vacuum, washing with n-hexane for 3 times, and vacuum drying to obtain catalyst (22) with yield of 90%.
After a 5L stainless steel autoclave is fully replaced by nitrogen, 2.5L of N-hexane is added into the reaction kettle, 10mg of [ N, P ] type non-metallocene catalyst (22) is added, 1.5mmol of MAO is added, 50 g of 1-butene is added, 120 g of propylene is added, ethylene is filled until the pressure is 1.5MPa, the mixture is stirred, the temperature is raised to 45 ℃ for reaction for 1 hour, and 675 g of a polymerization product is collected.
Example 23
Synthesis of ligands
30ml of toluene and 0.5g of tris- (2, 4, 6-pentafluorothio) aniline were put into a 200ml schlenk flask, n-butyllithium was added at-5 ℃ in an amount of twice the mole of pentafluorosulfanylaniline, the mixture was stirred and reacted for 8 hours, bis (2, 4, 6-trifluorophenyl) -phosphine chloride was added in an amount of equimolar to pentafluorosulfanylaniline and reacted at 0 ℃ for 6 hours, the solvent was removed in vacuo, the mixture was washed with n-pentane 3 times and dried in vacuo to obtain the product in a yield of 87%.
Synthesis of catalyst (23)
30ml of toluene and 0.5g of ligand were put in a 200ml schlenk bottle, n-butyllithium equimolar to the ligand was added at-20 ℃ and stirred to react for 4 hours, and Pd (Cy) equimolar to the ligand was added 2 The reaction was carried out at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed with n-hexane 3 times, and dried in vacuo to obtain catalyst (23) with a yield of 91%.
After a 5L stainless steel autoclave is fully replaced by nitrogen, 2.5L of N-hexane is added into the reaction kettle, 10mg of [ N, P ] type non-metallocene catalyst (23) is added, 5.3mmol of MAO is added, 50 g of vinyl acetate is added, ethylene is filled until the pressure is 15MPa, the mixture is stirred, the temperature is raised to 50 ℃ for reaction for 3 hours, and 281 g of polymerization product is collected.
Example 24
Synthesis of ligands
50ml of toluene and 2g of pentafluoroaniline are taken to be put into a 300ml schlenk bottle, n-butyllithium which is twice as molar as the pentafluoroaniline is added at the temperature of minus 35 ℃, stirred and reacted for 8 hours, diphenyl phosphine chloride which is equal to the molar of the pentafluoroaniline is added, the reaction is carried out for 6 hours at the temperature of minus 30 ℃, the solvent is removed in vacuum, the mixture is washed for 3 times by using n-pentane and dried in vacuum, and the product is obtained, wherein the yield is 82%.
Synthesis of catalyst (24)
30ml of toluene and 1g of ligand are taken and put into a 200ml schlenk bottle, n-butyllithium which is equal to the ligand in mol is added at the temperature of minus 20 ℃, the mixture is stirred and reacted for 4 hours, and NdBr which is equal to the ligand in mol is added 2 Reacting at-30 deg.C for 5 hr, removing solvent in vacuum, washing with n-hexane for 3 times, and vacuum drying to obtain catalyst (24) with yield of 90%.
After a 5L stainless steel autoclave is fully replaced by nitrogen, 2.5L of N-hexane is added into the reaction kettle, 10mg of [ N, P ] type non-metallocene catalyst (24) is added, 3.15mmol of MAO is added, 1000 g of propylene is added, the mixture is stirred, the temperature is increased to 75 ℃ for reaction for 2 hours, and 683 g of a polymerization product is collected.
Example 25
Synthesis of ligands
50ml of toluene and 0.5g of bis- (2.10-trifluoromethyl) benzidine were taken in a 300ml schlenk flask, n-butyllithium twice molar to trifluoromethyl benzidine was added at 10 ℃, stirred and reacted for 8 hours, diphenyl phosphonium chloride equal molar to trifluoromethyl benzidine was added, reacted for 8 hours at 30 ℃, the solvent was removed in vacuo, washed with n-hexane for 3 times, and dried in vacuo to obtain the product with a yield of 86%.
Synthesis of catalyst (25)
30ml of toluene and 0.3g of ligand are taken to be put into a 200ml schlenk bottle, n-butyllithium which is equal to the ligand in mole is added at the temperature of minus 20 ℃, the mixture is stirred and reacted for 4 hours, and PdMe which is equal to the ligand in mole is added 2 The reaction was carried out at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed with n-hexane 3 times, and dried in vacuo to obtain catalyst (25) with a yield of 91%.
After a 5-liter stainless steel autoclave is fully replaced by nitrogen, 2.5L of normal hexane is added into the reaction kettle, 10mg of [ N, P ] type non-metallocene catalyst (25) is added, 1000 g of propylene is added, 80 g of 1-octene is added, the mixture is stirred, the temperature is raised to 95 ℃ for reaction for 2 hours, and 535 g of polymerization product is collected.
Example 26
Synthesis of ligands
50ml of toluene and 2g of 2, 5-difluorobenzidine were taken in a 300ml schlenk flask, n-butyllithium twice as much as difluorobenzidine was added at 5 ℃ and stirred to react for 8 hours, bis (2, 4, 6-trifluorophenyl) -phosphine chloride equal to difluorobenzidine was added to react at 10 ℃ for 6 hours, the solvent was removed in vacuo, washed with n-hexane 3 times, and dried in vacuo to obtain the product in a yield of 86%.
Synthesis of catalyst (26)
30ml of toluene and 0.5g of ligand are taken to be put into a 200ml schlenk bottle, n-butyllithium which is equal to the mole of the ligand is added at the temperature of minus 20 ℃, the mixture is stirred and reacted for 4 hours, and TiCl which is equal to the mole of the ligand is added 4 Reacting at-30 ℃ for 5 hours, removing the solvent in vacuum, washing with n-hexane for 3 times, and drying in vacuum to obtain the catalyst (26) with the yield of 93 percent.
After a 5L stainless steel autoclave is fully replaced by nitrogen, 2.5L of N-hexane is added into the reaction kettle, 12mg of [ N, P ] type non-metallocene catalyst (26) is added, 4.0mmol of MAO is added, 100 g of 1-octene is added, ethylene is filled to 0.8MPa, stirring is carried out, the temperature is raised to 130 ℃ for reaction for 2 hours, and 410 g of polymerization product is collected.
Example 27
Synthesis of ligands
10ml of toluene and 0.5g of bis- (2, 10-pentafluorothio) naphthylamine were taken in a 200ml schlenk flask, n-butyllithium in an amount twice the mole of the naphthylamine was added at-35 ℃ and stirred and reacted for 8 hours, bis (phenylphosphonium chloride) in an amount equimolar to the naphthylamine was added and reacted at-30 ℃ for 6 hours, the solvent was removed in vacuo, washed 3 times with n-pentane and dried in vacuo to obtain the product in a yield of 85%.
Synthesis of catalyst (27)
30ml of toluene and 0.2g of ligand are taken to be put into a 200ml schlenk bottle, n-butyllithium which is equal to the mole of the ligand is added at the temperature of minus 20 ℃, the mixture is stirred and reacted for 4 hours, and TiCl which is equal to the mole of the ligand is added 4 Reacting at 10 ℃ for 5 hours, removing the solvent in vacuo, andwashed with n-hexane for 3 times and dried under vacuum to obtain the catalyst (27) with a yield of 91%.
After a 5L stainless steel autoclave was fully replaced with nitrogen, 2.5L N-hexane was added to the reactor, 20mg of [ N, P ] type non-metallocene catalyst (27) was added, 5.2mmol MAO was added, 80 g of 1-octene was added, ethylene was charged to 0.8MPa, stirring was carried out, the temperature was raised to 150 ℃ for 2 hours, and 462 g of the polymerization product was collected.
Example 28
After a 5L stainless steel autoclave is fully replaced by nitrogen, 2.5L of N-hexane is added into the reaction kettle, 10mg of [ N, P ] type non-metallocene catalyst (5) is added, 5.1mmol of M triethyl aluminum is added, 80 g of 1-octene is added, ethylene is charged to 0.8MPa, the mixture is stirred, the temperature is raised to 80 ℃ for reaction for 2 hours, and 667 g of polymerization product is collected.
Example 29
After a 5L stainless steel autoclave is fully replaced by nitrogen, 2.5L of N-hexane is added into the reaction kettle, 10mg of [ N, P ] type non-metallocene catalyst (5) is added, 5.1mmol of M trihexylaluminum is added, 50 g of 1-hexene is added, ethylene is charged to 0.8MPa, the mixture is stirred, the temperature is raised to 70 ℃ for reaction for 2 hours, and 673 g of a polymerization product is collected.
Example 30
After a 5-liter stainless steel autoclave is fully replaced by nitrogen, 2.5L of normal hexane is added into the reaction kettle, 10mg of [ N, P ] type non-metallocene catalyst (5) is added, 5.1mmol of M-chloroethyl aluminum is added, 100 g of 1-butene is added, ethylene is charged to 0.7MPa, the mixture is stirred, the temperature is raised to 80 ℃ for reaction for 2 hours, and 688 g of polymerization product is collected.
The results are shown in Table 1.
TABLE 1
Figure BDA0001991474540000251
Figure BDA0001991474540000261

Claims (8)

1. The non-metallocene catalyst is characterized in that the non-metallocene catalyst is a [ N, P ] type non-metallocene catalyst which accords with a general formula 1;
Figure FDA0003561989660000011
wherein, in the general formula 1, R 1 、R 2 Or R 3 Are identical or different substituents, R 1 、R 2 Or R 3 Are respectively selected from C 1 -C 20 Alkyl of (C) 3 -C 20 Cycloalkyl of, C 6 -C 40 Aryl of (C) 6 -C 40 Halogenated aryl of (2), C 1 -C 20 Alkoxy group of (C) 3 -C 20 Cycloalkoxy of (C) 6 -C 40 Aryloxy group of, or C 6 -C 40 The N heteroaryl group of (1); x is selected from halogen, or C 1 -C 15 Alkyl of (2), or C 3 -C 15 Cycloalkyl of, or C 5 -C 20 The heteroaryl group of (a); m represents transition metal and is selected from one of IIIB, IVB, VB, VIB or VIII; n is a positive integer greater than or equal to 1 and less than or equal to 3; m is a positive integer equal to or less than 5; and m is not less than n.
2. A method of preparing a non-metallocene catalyst according to claim 1, comprising the steps of:
(1) At the temperature of-70 ℃ to 100 ℃, adding an [ N, P ] type organic ligand which accords with a general formula 2 into a reaction bottle, adding an inert organic solvent, adding a hydrogen-withdrawing reagent, and reacting for 0.5 to 30 hours; wherein the molar ratio of the [ N, P ] type organic ligand corresponding to the general formula 2 to the hydrogen abstraction reagent is 1: (1-2); wherein the hydrogen abstraction reagent is a grignard reagent, butyl lithium;
(2) Adding a transition metal salt into the step (1) at the temperature of between 70 ℃ below zero and 200 ℃, reacting for 0.5 to 30 hours, removing the organic solvent, washing with an inert organic solvent, and drying to obtain the [ N, P ] type non-metallocene catalyst which accords with the general formula 1; wherein the molar ratio of the [ N, P ] type organic ligand corresponding to formula 2 to the transition metal salt is 1: (1.1-5); wherein the transition metal salt is a halide of a transition metal; wherein the transition metal is selected from one of IIIB, IVB, VB, VIB or VIII;
Figure FDA0003561989660000021
wherein, R in the general formula 2 1 、R 2 Or R 3 Are identical or different substituents, R 1 、R 2 Or R 3 Are respectively selected from C 1 -C 20 Alkyl of (C) 3 -C 20 Cycloalkyl of, C 6 -C 40 Aryl of (C) 6 -C 40 Halogenated aryl of (2), C 1 -C 20 Alkoxy group of (C) 3 -C 20 Cycloalkoxy of (A), C 6 -C 40 Aryloxy group of, or C 6 -C 40 The N heteroaryl group of (1);
wherein the inert organic solvent is selected from C 5 ～C 15 Saturated hydrocarbon of (C) 5 ～C 10 Alicyclic hydrocarbon of (2), C 6 ～C 15 Aromatic hydrocarbon of (C) 2 ～C 10 The saturated heterocyclic hydrocarbon or the mixed solvent composed of the above solvents.
3. The process according to claim 2, wherein the organic ligand of the type [ N, P ] corresponding to general formula 2 is prepared by the following steps:
(1) Reacting a primary amine R 1 NH 2 Adding the mixture into a reaction bottle, adding an inert organic solvent and a hydrogen-withdrawing reagent, and reacting at the temperature of between 70 ℃ below zero and 200 ℃ for 2 to 24 hours; primary amines R 1 NH 2 The molar ratio of the hydrogen extracting reagent to the hydrogen extracting reagent is 1: (1-1.5); wherein R is 1 Is selected from C 1 -C 20 Alkyl of (C) 3 -C 20 Cycloalkyl of, C 6 -C 40 Aryl of (C) 6 -C 40 Halogenated aryl of (2), C 1 -C 20 Alkoxy group of (1), C 3 -C 20 Cycloalkoxy of (A), C 6 -C 40 Aryloxy group of, or C 6 -C 40 The N heteroaryl group of (1); wherein the hydrogen is extractedThe reagent is Grignard reagent and butyl lithium;
(2) Adding dialkylphosphorus halides or diarylphosphorus halides R 2 R 3 PCl, the reaction temperature is-30 to 150 ℃, and the reaction time is 1 to 24 hours; removing the solvent, washing with an inert organic solvent, filtering and drying to obtain an organic ligand conforming to the general formula 2; wherein the primary amine R 1 NH 2 The molar ratio to dialkylphosphonium halide or diarylphosphonium halide is 1: (1-1.2); wherein, R is 2 Or R 3 Are identical or different substituents, R 2 Or R 3 Are respectively selected from C 1 -C 20 Alkyl of (C) 3 -C 20 Cycloalkyl of, C 6 -C 40 Aryl of, C 6 -C 40 Halogenated aryl of, C 1 -C 20 Alkoxy group of (1), C 3 -C 20 Cycloalkoxy of (C) 6 -C 40 Aryloxy group of (A), or C 6 -C 40 The N heteroaryl group of (1);
wherein the inert organic solvent is selected from C 5 ～C 15 Saturated hydrocarbon of (C) 5 ～C 10 Alicyclic hydrocarbon of (2), C 6 ～C 15 Aromatic hydrocarbon of (2), C 2 ～C 10 The saturated heterocyclic hydrocarbon or the mixed solvent composed of the above solvents.
4. The use of the non-metallocene catalyst of claim 1 to catalyze ethylene homopolymerization, propylene homopolymerization, ethylene and alpha-olefin copolymerization, propylene and alpha-olefin copolymerization, or nonpolar olefin monomer and polar olefin monomer multiple copolymerization, wherein the alpha-olefin is C 3 -C 2000 The olefin of (a); wherein the polar olefinic monomer is a compound containing carbon-carbon double bond and simultaneously carrying polar group, the polar olefinic monomer is selected from compounds corresponding to general formula 3, wherein Z is selected from an integer of 0 to 50, FG is selected from hydroxyl-OH and phenolic hydroxyl-C 6 H 4 OH, carboxyl-COOH, arylcarboxyl-C 6 H 4 COOH, ester group-COOR, aryl ester group-C 6 H 4 COOR, halogen, nitrile-CN, -N (H) R, amino acid or amino acid ester, wherein R is selected from C1 to C30 alkyl, C1 to C30 polyfluoroalkylC30 alkoxy, C1 to C30 siloxane, C1 to C30 silane, C3 to C30 cycloalkyl, C3 to C30 cycloalkoxy, C3 to C30 siloxycycloalkyl, C3 to C30 silacycloalkyl, C6 to C30 aryl, C6 to C30 silaaryl, C6 to C30 siloxyaryl, C6 to C30 aryloxy, C6 to C30 pyridyl or derivative, C1 to C30 sulfonyl or derivative, wherein the halogen is selected from F, cl or Br;
Figure FDA0003561989660000031
5. use of the non-metallocene catalyst of claim 1, comprising a solution polymerization process, a gas phase bulk polymerization process, a liquid phase bulk polymerization process, a loop polymerization process, a slurry polymerization process, or a combination polymerization process; wherein the solution polymerization process or the slurry polymerization process is carried out in the presence of a solvent selected from water and C 5 To C 20 Aliphatic alkanes or cycloalkanes of, or C 6 To C 20 Or a mixed solvent thereof.
6. Use of a non-metallocene catalyst according to claim 1 to catalyze ethylene homopolymerization, propylene homopolymerization, ethylene and alpha-olefin copolymerization, propylene and alpha-olefin copolymerization, or nonpolar olefin monomer and polar olefin monomer multiple copolymerization, the resulting polymer having a weight average molecular weight of 500 to 7000000g/mol, a polymerization temperature of 0 to 200 ℃, a polymerization time of 0.5 to 5 hours, and a polymerization pressure of 0.1mPa to 30mPa.
7. The use of a non-metallocene catalyst according to claim 1 to catalyze ethylene homopolymerization, propylene homopolymerization, ethylene and alpha-olefin copolymerization, propylene and alpha-olefin copolymerization, or non-polar olefin monomer and polar olefin monomer multiple copolymerization, with the addition of a co-catalyst, wherein the co-catalyst is an organometallic aluminum compound selected from alkylaluminums or alkylaluminoxanes that are hydrolysates of alkylaluminoxanes; the mol ratio of the cocatalyst to the [ N, P ] type non-metallocene catalyst is as follows: (50-5000): 1.
8. the use of the non-metallocene catalyst of claim 1 to catalyze ethylene homopolymerization, propylene homopolymerization, copolymerization of ethylene and α -olefin, copolymerization of propylene and α -olefin, or copolymerization of non-polar olefin monomer and polar olefin monomer, the weight average molecular weight of the obtained polymer is 500 to 7000000g/mol, the polymerization temperature is 0 to 200 ℃, the polymerization time is 0.5 to 5 hours, and the polymerization pressure is 0.1mPa to 25mPa.
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