CN110922424A - [ P, P ] type full heterocyclic non-metallocene catalyst, preparation method and application thereof - Google Patents

[ P, P ] type full heterocyclic non-metallocene catalyst, preparation method and application thereof Download PDF

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CN110922424A
CN110922424A CN201811098375.0A CN201811098375A CN110922424A CN 110922424 A CN110922424 A CN 110922424A CN 201811098375 A CN201811098375 A CN 201811098375A CN 110922424 A CN110922424 A CN 110922424A
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义建军
黄启谷
王科峰
许蔷
李荣波
李志飞
王静
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Petrochina Co Ltd
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Abstract

The invention provides [ P, P ]]A full heterocyclic non-metallocene catalyst, a preparation method and application thereof. The invention firstly provides compounds of the general formula (1),
Figure DDA0001806086830000011
in the general formula (1), R1、R2Is selected from C1-C20 alkyl, C3-C20 cycloalkyl and C6-C20 aryl; r3Or R4The same or different, are respectively and independently selected from hydrogen atoms, alkyl groups of C1-C20, cycloalkyl groups of C3-C20 and aryl groups of C6-C20; x is selected from F, Cl, Br, I or C1-C20 alkyl; m represents a transition metal atom selected from one of the elements of groups IIIB, IV B, VB or VIII. The compound of the general formula (1) is a full heterocyclic non-metallocene catalyst compound and can be used as a main catalyst of an olefin polymerization catalyst. The invention also provides an olefin polymerization catalyst comprising the compound of the general formula (1), a preparation method and application thereof.

Description

[ P, P ] type full heterocyclic non-metallocene catalyst, preparation method and application thereof
Technical Field
The invention belongs to the field of olefin polymerization catalysts and olefin coordination polymerization, and particularly relates to a [ P, P ] type full-heterocyclic non-metallocene catalyst for ethylene or propylene homopolymerization, ethylene/α -olefin copolymerization or propylene/α -olefin copolymerization and application thereof.
Background
The non-metallocene catalyst has the characteristics that the activity of the catalyst, the stereoregularity of a polymer, the molecular weight and the molecular weight distribution can be controlled by changing the ligand structure and the like due to the single active center of the non-metallocene catalyst; and the excellent properties of polymers synthesized with non-metallocene catalysts have been consistently recognized.
However, if a certain amount of high-grade α -olefin (such as 1-octene and the like) is inserted into a polyolefin molecular chain to prepare a block copolymer, the structure and the performance of the polyolefin are obviously changed, so that the density of the polymer is lower than that of the common polyolefin, and the density is 0.85-0.92g/cm3To (c) to (d); low glass transition temperature, good low temperature resistance, and good dispersibility, weather resistance, flexibility and processability. The ethylene/1-octene copolymer is superior in performance to the ethylene/propylene copolymer and the ethylene/1-butene copolymer, and an era of replacement of the ethylene/propylene copolymer and the ethylene/1-butene copolymer with the ethylene/1-octene copolymer is coming.
Non-metallocene catalysts appear in the nineties of the twentieth century, coordination atoms of the catalysts are nitrogen, phosphorus, oxygen, sulfur and the like, and oxygen affinity of central metal atoms of the catalysts is weaker, so that copolymerization of olefin and polar monomers is easily realized, and 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 has developed 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.
Marifa [ Ma L F, et al. journal Polymer Science: Part A: Polymer Chemistry,2008,46: 33; ma L F, et al, journal Polymer Science, Part A, Polymer Chemistry,2010,48:417, prepares a series of [ N, N ] heterocyclic non-metallocene compounds, and after MAO activation, ethylene polymerization and ethylene/1-hexene copolymerization can be efficiently catalyzed to obtain the broad/bimodal polyethylene.
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 ] class 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 [ Zhang W J, et al J of organometallic Chem.2006,691: 4759-.
CN1544485A reports a compound 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 105gPE/molTi.h。
CN102030843A discloses a non-metallocene catalyst containing [ N, N, O, O ] structural ligand for olefin polymerization, which has better catalytic activity for ethylene homopolymerization, ethylene/α -olefin and ethylene/polar monomer copolymerization during olefin polymerization.
The main ring structures of the non-metallocene catalysts disclosed above all contain carbon atoms, heteroatoms and transition metal atoms.
Disclosure of Invention
It is an object of the present invention to provide a fully heterocyclic non-metallocene catalyst compound as a procatalyst for an olefin polymerization catalyst.
Another object of the present invention is to provide a process for preparing the compound.
Another object of the present invention is to provide the use of said compounds.
It is another object of the present invention to provide an olefin polymerization non-metallocene catalyst comprising the compound.
Another object of the present invention is to provide the use of said catalyst for the catalytic homopolymerization or copolymerization of olefins.
In one aspect of the present invention, the present invention provides a compound of formula (1):
Figure BDA0001806086820000031
in the general formula (1), R1、R2Are respectively and independently selected from C1-C20 alkyl, C3-C20 cycloalkyl or C6-C20 aryl; r3、R4Are respectively and independently selected from a hydrogen atom, an alkyl group of C1-C20, a cycloalkyl group of C3-C20 or an aryl group of C6-C20; x is selected from F, Cl, Br, I or C1-C20 alkyl; m represents a transition metal atom selected from one of the elements of groups IIIB, IV B, VB or VIII.
According to some embodiments of the present invention, in the compound of the above general formula (1), R1、R2May be the same or different substituents; r3、R4May be the same or different substituents.
According to some embodiments of the present invention, in the compound of formula (1) above, M is titanium, zirconium, hafnium, vanadium, rhodium, iron, nickel, cobalt, neodymium, palladium or yttrium.
According to some embodiments of the present invention, in the compound of formula (1) above, M is vanadium, zirconium, rhodium, nickel, neodymium, palladium, titanium or yttrium.
According to some embodiments of the invention, in the compound of formula (1) above, according to the invention, X is selected from Cl, Br, Me or Et.
According to some embodiments of the present invention, there is provided specific compounds 1-21 according to formula (1), wherein M, X, R1、R2、R3And R4Each having the following respective group definitions (table 1):
table 1 Compounds corresponding to general formula (1)
Figure BDA0001806086820000032
Figure BDA0001806086820000041
The compound of the general formula (1) is a novel [ P, P ] type full-heterocyclic non-metallocene catalyst, the main ring of the catalyst does not contain carbon atoms and consists of three heteroatoms (P, Si and P) and transition metal atoms, the [ P, P ] type full-heterocyclic non-metallocene catalyst can effectively catalyze ethylene homopolymerization, propylene homopolymerization, ethylene and α -olefin copolymerization, propylene and α -olefin copolymerization, ethylene and polar olefin monomer copolymerization or propylene and polar olefin monomer copolymerization, the catalyst activity is high, the [ P, P ] type heterocyclic non-metallocene catalyst can be loaded on a carrier to prepare a loaded catalyst, the catalyst can effectively catalyze ethylene homopolymerization, propylene homopolymerization, ethylene and α -olefin copolymerization, propylene and α -olefin copolymerization, ethylene and polar olefin monomer copolymerization and propylene and polar olefin monomer copolymerization, and the catalyst activity is high.
Thus, in another aspect, the invention also provides the use of the compound as a procatalyst for olefin polymerization catalysts.
In another aspect, the present invention also provides an olefin polymerization catalyst comprising a procatalyst and a cocatalyst, wherein the procatalyst comprises the compound of the general formula (1) according to the present invention (a full heterocyclic non-metallocene catalyst compound):
Figure BDA0001806086820000051
in the general formula (1), R1、R2Are respectively and independently selected from C1-C20 alkyl, C3-C20 cycloalkyl or C6-C20 aryl; r3、R4Each independently selected from hydrogen atom, C1-C20 alkaneA C3-C20 cycloalkyl group or a C6-C20 aryl group; x is selected from F, Cl, Br, I or C1-C20 alkyl; m represents a transition metal atom selected from one of the elements of groups IIIB, IV B, VB or VIII.
According to some embodiments of the invention, in the olefin polymerization catalyst of the invention, the cocatalyst comprises an organometallic aluminium compound. More specifically, the organometallic aluminium compound preferably comprises an aluminium alkyl and/or a hydrolysate of an aluminium alkyl alkylaluminium, such as trimethylaluminium, triethylaluminium, triisobutylaluminium, tri-n-hexylaluminium, Methylaluminoxane (MAO). In yet another aspect of the invention, the molar ratio of cocatalyst to procatalyst is: (100-5000): 1, preferably (150- > 1000): 1.
in another aspect, the present invention also provides a method for preparing the compound of formula (1), which comprises: reacting a ligand compound corresponding to the general formula (2) with a transition metal compound in an organic solvent, removing the solvent after the reaction is finished, washing with the organic solvent to obtain a compound of the general formula (1),
Figure BDA0001806086820000052
wherein, R is1、R2Are respectively and independently selected from C1-C20 alkyl, C3-C20 cycloalkyl and C6-C20 aryl; r3、R4Are respectively and independently selected from a hydrogen atom, an alkyl group of C1-C20, a cycloalkyl group of C3-C20 and an aryl group of C6-C20.
In some embodiments of the invention, specific ligand compounds 2-1 to 2-21 correspond to general formula (2), wherein R1、R2、R3And R4Each having the following respective group definitions (table 2):
table 2 Compounds corresponding to general formula (2)
Figure BDA0001806086820000061
According to some embodiments of the invention, in the method of preparing the compound of formula (1), the transition gold isThe generic compound corresponds to the general formula (3): MXnWherein X is selected from F, Cl, Br, I or C1-C20 alkyl; m represents a transition metal atom selected from one of elements in groups IIIB, IV B, VB or VIII, and n is a positive integer less than or equal to 4.
According to some embodiments of the present invention, in the method for preparing the compound of formula (1) of the present invention, the molar ratio of the ligand compound of formula (2) to the transition metal compound of formula (3) is 1: (1-2.5); preferably 1: (1-2).
According to some embodiments of the present invention, in the method for preparing the compound of the general formula (1), the reaction temperature is-30 to 100 ℃, preferably 10 to 100 ℃, and more preferably 30 to 70 ℃; the reaction time is 1 to 10 hours, preferably 3 to 5 hours.
According to some embodiments of the present invention, in the method for preparing the compound of formula (1), the organic solvent is selected from a saturated hydrocarbon of C5-C15, an alicyclic hydrocarbon of C5-C10, an aromatic hydrocarbon of C6-C15, a saturated heterocyclic hydrocarbon of C2-C10, or a mixed solvent of the above solvents.
In another aspect of the invention, the invention also provides a process for preparing said ligand compound corresponding to general formula (2), comprising the steps of:
a certain amount of compound corresponding to the general formula R1R2Si(H)2The biomimetic compound of (a) is dissolved in an organic solvent, and two molar amounts of a compound corresponding to formula R are added3POX2Or R4POX2An organic phosphorus compound, reacting at 0-70 ℃ for 1-5 hours, preferably at 10-50 ℃ for 2-4 hours; then adding HNa with the molar weight of 1-2.5, and reacting at 20-80 ℃ for 1-8 hours, preferably at 30-60 ℃ for 3-6 hours to obtain the ligand compound corresponding to the general formula (2).
In the above process for preparing the ligand compound (2), the organic solvents may be the same or different and are each selected from the group consisting of saturated hydrocarbons of C5-C15, alicyclic hydrocarbons of C5-C10, aromatic hydrocarbons of C6-C15, saturated heterocyclic hydrocarbons of C2-C10, and mixtures thereof.
Among the aforementioned methods for preparing the compound corresponding to general formula (1), the aforementioned methods for preparing the compound of general formula (2) may be included.
The main catalyst provided by the invention can be directly matched with a cocatalyst to catalyze olefin polymerization, and can also be matched with the cocatalyst for use after being loaded. With reference to the method provided by patent CN200910092169.3 to load main catalyst, the main catalyst loading process: dissolving a main catalyst which accords with the general formula (1) in an organic solvent, reacting with a carrier for 1-8 hours at the temperature of 10-90 ℃, wherein the molar ratio of the carrier to the main catalyst is 1 (0.5-20), and washing for 4-6 times by using an inert organic solvent after the reaction is finished to obtain the supported main catalyst. The reaction temperature is preferably 40-80 ℃, the reaction time is preferably 2-5 hours, and the molar ratio of the carrier to the main catalyst is preferably 1 (0.5-10); in the process of loading the main catalyst, the inert organic solvent is selected from C5～C15Saturated hydrocarbon of (C)5～C10Alicyclic hydrocarbon of (2), C6～C15Aromatic hydrocarbon of (2), C2～C10The saturated heterocyclic hydrocarbon or a mixed solvent composed of the above solvents; in the process of loading the main catalyst, the carrier is inorganic oxide and inorganic halide, wherein the inorganic oxide is preferably SiO2 or Al2O 3; among them, the inorganic halide is preferably magnesium chloride; the olefin polymerization cocatalyst is an organic metal aluminum compound, preferably alkyl aluminum, alkyl aluminoxane which is a hydrolysis product of alkyl aluminum, such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, and Methyl Aluminoxane (MAO). The molar ratio of the cocatalyst to the main catalyst is as follows: (50-5000):1, preferably (100- > 1000): 1.
The invention provides the application of the compound or the olefin polymerization catalyst in catalyzing olefin homopolymerization or olefin copolymerization, wherein the polymerization monomer for olefin homopolymerization or olefin copolymerization can be any one or more of ethylene, α -olefin of C3-C20 or polar vinyl monomer of C3-C20, specifically, the olefin polymerization catalyst provided by the invention can effectively catalyze ethylene homopolymerization, propylene homopolymerization, ethylene and α -olefin copolymerization, propylene and α -olefin copolymerization, ethylene and polar vinyl monomer copolymerization or propylene and polar vinyl monomer copolymerization, and the catalytic activity of the catalyst is high, wherein the α -olefin is C3-C20 olefin, preferably propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 3-methyl-1-butene, 4-methyl-1-pentene, styrene, α -methyl styrene and norbornene, the polar vinyl monomer is a compound containing carbon-carbon double bond and simultaneously carrying polar groups, preferably propylene, 4-cyano methyl styrene, butyl methacrylate or acrylic acid.
When the olefin polymerization catalyst provided by the invention is used for catalyzing olefin polymerization, the polymerization temperature is 20-90 ℃, the polymerization time is 5min-3h, the pressure of ethylene or propylene is 0.1-5MPa, and the used solvent is n-hexane, heptane or toluene and the like.
In conclusion, the compound of the general formula (1) is a novel [ P, P ] type full-heterocyclic non-metallocene catalyst, the main ring of the catalyst does not contain carbon atoms and consists of three heteroatoms (P, Si and P) and a transition metal atom, the [ P, P ] type full-heterocyclic non-metallocene catalyst can effectively catalyze ethylene homopolymerization, propylene homopolymerization, ethylene and α -olefin copolymerization, propylene and α -olefin copolymerization, ethylene and polar olefin monomer copolymerization or propylene and polar olefin monomer copolymerization, the catalyst activity is high, the [ P, P ] type heterocyclic non-metallocene catalyst can be further loaded on a carrier to prepare a loaded catalyst, the catalyst can effectively catalyze ethylene homopolymerization, propylene homopolymerization, ethylene and α -olefin copolymerization, propylene and α -olefin copolymerization, ethylene and polar olefin monomer copolymerization and propylene and polar olefin monomer copolymerization, and the catalyst activity is high.
Detailed Description
The following examples are intended to illustrate the practice and advantageous effects of the present invention, but are not to be construed as limiting the scope of the present invention.
Example 1
(1) Synthesis of catalyst Compound 1 corresponding to general formula (1)
30ml of toluene and 12ml (0.1314mol) of a diphenyldihydrosilane solution are taken and put into a 300ml schlenk bottle, 12ml (0.0657mol) of phenyl phosphine dichloride is added into an intermediate system 1, after reaction for 4 hours at 35 ℃, 0.0657mol of HNa is added, after reaction for 5 hours at 45 ℃, the mixture is drained, 100ml of n-hexane is added into the residual solid, dissolution and filtration are carried out, and the filtrate is recrystallized to obtain 11.4g of diphenylsilanediphenyldiphenylphosphine hydrogenphosphoric acid, wherein the yield is as follows: 56 percent.
(2) Preparation of procatalyst Compound 1
Under the protection of nitrogen, 0.43g of compound 2-1 corresponding to general formula (2) was dissolved in 30mL of toluene, 0.11mL (1mmol) of titanium tetrachloride was added, the temperature was raised to 50 ℃ and the reaction was carried out for 4 hours. The solvent was removed in vacuo and the residue was washed 3 times with n-hexane and dried to give 0.53g of catalyst 1(Cat. 1).1H NMR(600MHz,CDCl3):δ7.45(4H,m),δ7.40(2H,t),δ7.02-7.143(10H,m),δ6.63-6.88(4H,m),δ6.63(2H,t),δ6.51(2H,d),δ0.63(6H,s)；Anal.Calcd.(％)for C24H20P2SiO2TiCl2:C,52.49；H,3.67；found:C,52.51；H,3.70。
(3) Ethylene polymerization:
in a 300ml reaction flask, 5mg of the main catalyst, 100ml of toluene and 18ml of MAO solution (10 wt%) were added in this order under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 50 deg.C, ethylene pressure of 0.7MPa, and polymerizing for 120 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then air-dried at 50 ℃ for 24 hours.
(4) Ethylene copolymerization:
5mg of main catalyst, 80ml of toluene, 18ml of MAO solution (10 wt%) and 5ml of 1-butene were sequentially added to a 300ml reaction flask under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 50 deg.C, maintaining ethylene pressure of 0.7MPa, and polymerizing for 30 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
Example 2
(1) Preparation of procatalyst compound 2:
according to the method of example 1, 0.43g of compound 2-2 corresponding to general formula (2) was reacted with 0.23g (1mmol) of zirconium tetrachloride to obtain 0.45g of compound 2(Cat.2) corresponding to general formula (1).1H NMR(600MHz,CDCl3)：1H NMR(600MHz,CDCl3)：δ7.44(4H，m)，δ7.35(2H，t)，δ7.05-7.11(10H，m)，δ6.67-6.92(4H，m)，δ6.64(2H,t)，δ6.53(2H,d)，δ0.68(6H,s)；Anal.Calcd.(％)for C22H24P2SiO2ZrCl2：C:46.15,H:4.22；found:C:46.21,H:4.27。
(2) Polymerization of propylene:
in a 300ml reaction flask, 9mg of main catalyst, 100ml of toluene and 3ml of triethylaluminum solution (1M) were sequentially added under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 40 deg.C, propylene pressure of 2.5MPa, and polymerizing for 100 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
(3) And (2) propylene copolymerization:
in a 300ml reaction flask, 7mg of main catalyst, 80ml of toluene, 4ml of triethylaluminum solution (1M) and 5ml of 1-butene were sequentially added under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 40 deg.C, maintaining propylene pressure of 2.5MPa, and polymerizing for 50 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
Example 3
(1) Preparation of procatalyst compound 3:
according to the method of example 1, 0.43g of compound 2-3 corresponding to general formula (2) was reacted with 0.20g (1mmol) of yttrium trichloride to obtain 0.39g of compound 3(Cat.3) corresponding to general formula (1).1H NMR(600MHz,CDCl3):δ3.41(4H，m),δ2.31(2H，t),δ2.05-2.16(10H，m),δ2.68-2.95(4H，m),δ2.63(10H，t),δ2.56(3H，d),δ0.95(3H，s)；Anal.Calcd.(％)for C19H36P2SiO2YCl(585):C,41.77；H,6.64；found:C,41.57；H,6.41。
(2) Ethylene polymerization:
6mg of procatalyst, 100ml of toluene, and 7ml of MAO solution (10 wt%) were added sequentially in a 300ml reaction flask in the absence of water and oxygen. Ventilating for three times, heating to 90 deg.C, ethylene pressure of 0.8MPa, and polymerizing for 90 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
(3) Ethylene copolymerization:
6mg of procatalyst, 100ml of toluene, 7ml of MAO solution (10 wt%), and 5ml of 1-hexene were added in this order to a 300ml reaction flask in the absence of water and oxygen. Ventilating for three times, increasing the temperature to 20 ℃, keeping the ethylene pressure of 0.8MPa and the propylene pressure of 0.6MPa, and polymerizing for 30 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
Example 4
(1) Preparation of procatalyst Compound 4:
according to the method of example 1, 0.43g of compound 2-4 corresponding to general formula (2) was reacted with 0.25g (1mmol) of neodymium trichloride to obtain 0.51g of compound 4(Cat.4) corresponding to general formula (1).1H NMR(600MHz,CDCl3):1H NMR(600MHz,CDCl3):δ7.02-7.12(6H，m),δ6.65-6.97(5H，m),δ6.63(2H，t),δ6.51(2H，d),δ1.30-2.5(9H,s)；Anal.Calcd.(％)for C23H24P2SiO2NdCl:C,43.32；H,3.79；found:C,43.49；H,3.81。
(2) Ethylene polymerization:
in a 300ml reaction flask, 8mg of main catalyst, 100ml of toluene and 7ml of MAO solution (10 wt%) were added in this order under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 65 deg.C, ethylene pressure of 0.6MPa, and polymerizing for 120 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
(3) Ethylene copolymerization:
in a 300ml reaction flask, 7mg of main catalyst, 100ml of toluene, 7ml of MAO solution (10 wt%), and 5ml of 1-octene were sequentially added under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 65 deg.C, maintaining ethylene pressure of 0.6MPa, and polymerizing for 10 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
Example 5
(1) Preparation of procatalyst compound 5:
method according to example 10.43g of compound 2-5 corresponding to formula (2) is reacted with 0.21g (1mmol) of rhodium trichloride to give 0.35g of compound 5 corresponding to formula (1) (Cat.5).1H NMR(600MHz,CDCl3):1H NMR(600MHz,CDCl3):δ7.41(4H，m),δ7.36(2H，t),δ7.01-7.14(4H，m),δ2.66-2.92(5H，m),δ2.64(2H，t),δ2.58(2H，d),δ0.82(3H，s)；Anal.Calcd.(％)for C18H22P2SiO2RhCl:C,43.35；H,4.45；found:C,43.46；H,4.53。
(2) Ethylene polymerization:
in a 300ml reaction flask, 5mg of the main catalyst, 100ml of toluene and 3ml of MAO solution (10 wt%) were added in this order under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 50 deg.C, ethylene pressure of 0.5MPa, and polymerizing for 120 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
(3) Ethylene copolymerization:
5mg of main catalyst, 100ml of toluene, 6ml of MAO solution (10 wt%) and 4ml of 1-decene were sequentially added to a 300ml reaction flask under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 70 deg.C, maintaining ethylene pressure of 0.5MPa, and polymerizing for 10 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
Example 6
(1) Preparation of procatalyst Compound 6:
following the procedure of example 1, 0.43g of compounds 2-6 according to formula (2) were reacted with 0.29g (1mmol) of vanadium tribromide to afford 0.37g of compound 6 according to formula (1) (Cat.6).
1H NMR(600MHz,CDCl3):δ7.50(4H，m),δ7.35(2H，t),δ7.08-7.18(4H，m),δ0.71-1.49(10H,s)；Anal.Calcd.(％)for C16H20P2SiO2VBr:C,41.31；H,4.33；found:C,41.40；H,4.25。
(2) Polymerization of propylene:
7mg of a main catalyst, 100ml of n-hexane and 5ml of a triisobutylaluminum solution (1M) were added in this order to a 300ml reaction flask under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 35 deg.C, propylene pressure of 2.8MPa, and polymerizing for 80 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
(3) And (2) propylene copolymerization:
6mg of a main catalyst, 100ml of toluene, 4ml of a triisobutylaluminum solution (1M), and 6ml of styrene were sequentially added to a 300ml reaction flask under anhydrous and oxygen-free conditions. Ventilating for three times, increasing the temperature to 35 ℃, maintaining the propylene pressure of 2.8MPa and the ethylene pressure of 2.4MPa, and polymerizing for 30 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
Example 7
(1) Preparation of procatalyst compound 7:
following the procedure of example 1, 0.43g of compounds 2 to 7 corresponding to general formula (2) were reacted with 0.24g (1mmol) of nickel dichloride to give 0.49g of compound 7 corresponding to general formula (1) (Cat.7).
Anal.Calcd.(％)for C13H22P2SiO2Ni:C,43.49；H,6.18；found:C,43.51；H,6.68。
(2) Ethylene polymerization:
6mg of procatalyst, 100ml of toluene, and 4ml of MAO solution (10 wt%) were added sequentially in a 300ml reaction flask in the absence of water and oxygen. Ventilating for three times, heating to 55 deg.C, ethylene pressure of 0.8MPa, and polymerizing for 120 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
(3) Ethylene copolymerization:
in a 300ml reaction flask, 6mg of main catalyst, 100ml of toluene, 6ml of MAO solution (10 wt%), and 6ml of acrylonitrile were sequentially added under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 55 deg.C, maintaining ethylene pressure of 0.8MPa, and polymerizing for 10 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
Example 8
(1) Preparation of procatalyst Compound 8:
according to the method of example 1, 0.45g of the compound 2-8 corresponding to the general formula (2) was dissolved in 30mL of toluene under nitrogen protection, 0.19mL (1.7mmol) of titanium tetrachloride was added, the temperature was raised to 50 ℃ and the reaction was carried out for 8 hours. The solvent was removed in vacuo and the residue was washed 3 times with n-hexane and dried by suction to give 0.52g of compound 8(Cat.8) according to formula (1).1H NMR(600MHz,CDCl3):δ7.46(4H，m),δ7.38(4H，t),δ7.23(4H，m),δ7.06(1H，t),δ6.81-6.93(4H，t),δ6.62(1H,m),δ2.46(6H,s)；δ0.89(6H,s)；Anal.Calcd.(％)for C28H28P2SiO2TiCl2:C,55.56；H,4.66；found:C,55.46；H,4.58。
(2) Polymerization of propylene:
in a 300ml reaction flask, 7mg of the procatalyst, 100ml of toluene, and 9ml of MAO solution (10 wt%) were added in this order under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 50 deg.C, propylene pressure of 3.1MPa, and polymerizing for 120 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
(3) And (2) propylene copolymerization:
6mg of main catalyst, 100ml of toluene, 5ml of MAO solution (10 wt%) and 5ml of 3-methyl-1-butene were sequentially added to a 300ml reaction flask in the absence of water and oxygen. Ventilating for three times, heating to 50 deg.C, maintaining propylene pressure of 3.1MPa, and polymerizing for 10 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
Example 9
(1) Preparation of procatalyst compound 9:
according to the method of example 1, 0.45g of compounds 2 to 9 corresponding to general formula (2) was reacted with 0.23g (1mmol) of zirconium tetrachloride to obtain 0.44g of compound 9(Cat.9) corresponding to general formula (1).1H NMR(600MHz,CDCl):δ7.43(4H，m),δ7.45(4H，t),δ7.17(4H，m),δ7.00(1H，t),δ6.83-6.78(4H，t),δ6.53(1H,m),δ2.42(6H,s),δ0.98(6H,s)；Anal.Calcd.(％)for C25H30P2SiO2ZrCl2:C,48.85；H,4.92found:C,48.77；H,4.82。
(2) Ethylene polymerization:
in a 300ml reaction flask, 10mg of main catalyst, 100ml of toluene and 10ml of MAO solution (10 wt%) were added in this order under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 40 deg.C, ethylene pressure of 0.8MPa, and polymerizing for 100 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
(3) Ethylene copolymerization:
6mg of main catalyst, 100ml of toluene, 6ml of MAO solution (10 wt%), and 6ml of 4-methyl-1-pentene were sequentially added to a 300ml reaction flask under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 40 deg.C, maintaining ethylene pressure of 0.8MPa, and polymerizing for 30 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
Example 10
(1) Preparation of procatalyst compound 10:
according to the method of example 1, 0.45g of compounds 2 to 10 corresponding to general formula (2) was reacted with 0.20g (1mmol) of yttrium trichloride to obtain 0.46g of compound 10(Cat.10) corresponding to general formula (1).1H NMR(600MHz,CDCl3):δ7.41(2H，m),δ7.15(2H，m),δ7.01(2H，t),δ2.45(4H,s),δ1.22(3H，s),δ1.26(3H，m),δ1.02(18H，s)；Anal.Calcd.(％)for C27H34P2SiO2YCl:C,53.61；H,5.66；found:C,53.72；H,5.77。
(2) Ethylene polymerization:
6mg of main catalyst, 100ml of toluene and 8ml of triethylaluminum solution (1M) were added in this order in a 300ml reaction flask under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 40 deg.C, ethylene pressure of 0.6MPa, and polymerizing for 120 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
(3) Ethylene copolymerization:
6mg of main catalyst, 100ml of toluene, 7ml of triethylaluminum solution (1M) and 5ml of acrylonitrile are sequentially added into a 300ml reaction flask under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 40 deg.C, maintaining ethylene pressure of 0.6MPa, and polymerizing for 10 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
Example 11
(1) Preparation of procatalyst Compound 11:
by following the procedure of example 1, 0.45g of compounds 2 to 11 according to formula (2) were reacted with 0.25g (1mmol) of neodymium trichloride to give 0.43g of compound 11 according to formula (1) (Cat.11).
1H NMR(600MHz,CDCl3):δ7.34(4H，t),δ7.28(5H，m),δ6.83-7.03(4H，t),δ1.16(3H，m),δ0.98(6H，s)；Anal.Calcd.(％)for C21H22P2SiNdCl:C,43.78；H,3.85；found:C,43.71；H,3.75。
(2) Ethylene polymerization:
6mg of procatalyst, 100ml of toluene, and 7ml of MAO solution (10 wt%) were added sequentially in a 300ml reaction flask in the absence of water and oxygen. Ventilating for three times, heating to 80 deg.C, ethylene pressure of 0.8MPa, and polymerizing for 90 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
(3) Ethylene copolymerization:
6mg of the procatalyst, 100ml of toluene, 7ml of MAO solution (10 wt%), 6ml of acrylonitrile and 10ml of 1-octene were added in succession to a 300ml reaction flask in the absence of water and oxygen. Ventilating for three times, heating to 80 deg.C, maintaining ethylene pressure of 0.8MPa, and polymerizing for 20 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
Example 12
(1) Preparation of procatalyst Compound 12:
according to the method of example 1, 0.45g of the compound 2-12 corresponding to formula (2) and 0.21g (1mmol) of rhodium trichlorideReaction to give 0.37g of Compound 12(Cat.12) according to formula (1).1H NMR(600MHz,CDCl3):δ7.34(2H，t),δ7.03(1H，t),δ2.41(2H,s),δ1.72-2.11(16H，s),δ0.79-1.21(9H，s)；Anal.Calcd.(％)forC19H30P2SiO2RhCl:C,43.98；H,5.83；found:C,43.85；H,5.79。
(2) Polymerization of propylene:
in a 300ml reaction flask, 9mg of main catalyst, 100ml of toluene and 7ml of MAO solution (10 wt%) were added in this order under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 50 deg.C, propylene pressure of 2.7MPa, and polymerizing for 120 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
(3) And (2) propylene copolymerization:
6mg of procatalyst, 100ml of toluene, 6ml of MAO solution (10 wt%), 5ml of acrylonitrile and 10ml of 1-hexene were added in succession to a 300ml reaction flask in the absence of water and oxygen. Ventilating for three times, heating to 45 deg.C, maintaining propylene pressure of 2.7MPa, and polymerizing for 10 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
Example 13
(1) Preparation of procatalyst Compound 13:
following the procedure of example 1, 0.45g of compounds 2 to 13 corresponding to general formula (2) were reacted with 0.18g (1mmol) of cobalt dichloride to give 0.35g of compound 13 corresponding to general formula (1) (Cat.13). anal.Calcd. (%) for C25H46P2SiO2Co:C,56.91；H,8.79；found:C,56.88；H,8.71。
(2) Ethylene polymerization:
in a 300ml reaction flask, 7mg of the main catalyst, 100ml of toluene and 7ml of MAO solution (10 wt%) were added in this order under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 50 deg.C, ethylene pressure of 0.6MPa, and polymerizing for 120 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
(3) Ethylene copolymerization:
in a 300ml reaction flask, 6mg of procatalyst, 100ml of toluene, 8ml of MAO solution (10 wt%), and 7ml of methyl methacrylate were sequentially added under anhydrous and oxygen-free conditions. Ventilating for three times, increasing the temperature to 45 ℃, maintaining the ethylene pressure of 0.6MPa and the propylene pressure of 0.7MPa, and polymerizing for 10 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
Example 14
(1) Preparation of procatalyst Compound 14:
according to the method of example 1, 0.45g (1mmol) of the compounds 2 to 14 corresponding to the general formula (2) are reacted with 0.24g of hafnium tetrachloride to give 0.39g of the compound 14 corresponding to the general formula (1) (Cat.14).1H NMR(600MHz,CDCl3):δ7.33(2H，t),δ7.02(1H，t),δ2.25(4H,m),δ1.23-1.46(16H,m),δ1.31(3H,s),δ1.15(6H,s),δ0.96(6H,s)；Anal.Calcd.(％)for C21H38P2SiO2HfCl2:C,38.10；H,5.79；found:C,38.15；H,5.71。
(2) Ethylene polymerization:
in a 300ml reaction flask, 5mg of the main catalyst, 100ml of toluene and 7ml of MAO solution (10 wt%) were added in this order under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 30 deg.C, ethylene pressure of 0.7MPa, and polymerizing for 130 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
(3) Ethylene copolymerization:
5mg of procatalyst, 100ml of toluene, 7ml of MAO solution (10 wt%), and 6ml of methyl acrylate were sequentially added in a 300ml reaction flask under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 30 deg.C, maintaining ethylene pressure of 0.7MPa, and polymerizing for 40 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
Example 15
(1) Preparation of procatalyst compound 15:
according toThe procedure of example 1 was followed by dissolving 0.48g of the compound 2-15 corresponding to formula (2) in 30mL of toluene under nitrogen, adding 0.22mL (2mmol) of titanium tetrachloride, heating to 50 ℃ and reacting for 4 h. The solvent was removed in vacuo and the residue was washed 3 times with n-hexane and dried by suction to give 0.51g of compound 15(Cat.15) according to formula (1).1H NMR(600MHz,DMSO-d6):δ7.55-7.73(8H，m),δ7.23-7.34(4H，m),δ7.01(2H，m),Anal.Calcd.(％)forC24H14F6P2SiO2TiCl2:C,43.86；H,2.15；found:C,43.76；H,2.19。
(2) Ethylene polymerization:
5mg of main catalyst, 100ml of heptane and 7ml of tri-n-hexylaluminum solution (1M) are sequentially added into a 300ml reaction flask under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 65 deg.C, ethylene pressure of 0.9MPa, and polymerizing for 120 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
(3) Ethylene copolymerization:
in a 300ml reaction flask, 5mg of main catalyst, 100ml of toluene, 7ml of tri-n-hexylaluminum solution (1M) and 5ml of ethyl acrylate are sequentially added under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 65 deg.C, maintaining ethylene pressure of 0.9MPa, and polymerizing for 10 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
Example 16
(1) Preparation of the procatalyst compound 16:
according to the method of example 1, 0.48g of the compounds 2 to 16 corresponding to the general formula (2) was reacted with 0.23g of zirconium tetrachloride to obtain 0.53g of the compound 16(Cat.16) corresponding to the general formula (1).1H NMR(600MHz,DMSO-d6):δ7.38-7.66(4H,m),δ7.16-7.33(4H,m),δ7.02(2H,m),δ7.1-7.2(2H,m),δ6.74(2H,d),δ6.86(2H,d),Anal.Calcd.(％)for C24H16F4P2SiO4ZrCl2：C,41.38；H,2.32；found:C,41.27；H,2.23。
(2) Polymerization of propylene:
in a 300ml reaction flask, 5mg of the main catalyst, 100ml of toluene and 7ml of MAO solution (10 wt%) were added in this order under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 55 deg.C, propylene pressure of 3.2MPa, and polymerizing for 120 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
(3) And (2) propylene copolymerization:
in a 300ml reaction flask, 9mg of main catalyst, 100ml of toluene, 11ml of MAO solution (10 wt%) and 6ml of 1-decene were sequentially added under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 55 deg.C, maintaining propylene pressure of 3.2MPa, and polymerizing for 30 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
Example 17
(1) Preparation of procatalyst compound 17:
according to the method of example 1, 0.48g of the compounds 2 to 17 corresponding to the general formula (2) was reacted with 0.20g of aluminum trichloride to obtain 0.56g of the compound 17(Cat.17) corresponding to the general formula (1).1H NMR(600MHz,DMSO-d6):δ7.74-7.69(2H,m),δ7.26-7.45(2H,m),δ7.01(1H,m),δ7.11-7.28(2H,m),δ6.78(2H,d),δ1.33(2H,t),δ0.93(3H,tr)；Anal.Calcd.(％)for C20H14F6P2SiO4AlCl:C,41.08；H,2.41；found:C,41.13；H,2.42。
(2) Ethylene polymerization:
in a 300ml reaction flask, 8mg of main catalyst, 100ml of toluene and 5ml of MAO solution (10 wt%) were added in this order under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 50 deg.C, ethylene pressure of 0.6MPa, and polymerizing for 120 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
(3) Ethylene copolymerization:
in a 300ml reaction flask, 8mg of main catalyst, 100ml of toluene, 8ml of MAO solution (10 wt%), and 6ml of styrene were sequentially added under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 45 deg.C, maintaining ethylene pressure of 0.6MPa, and polymerizing for 10 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
Example 18
(1) Preparation of procatalyst compound 18:
according to the method of example 1, 0.48g of the compounds 2 to 18 corresponding to the general formula (2) was reacted with 0.25g of samarium trichloride to obtain 0.49g of the compound 18(Cat.18) corresponding to the general formula (1).1H NMR(600MHz,DMSO-d6):δ7.54-7.76(2H,m),δ7.26-7.36(2H,m),δ7.01(1H,m),δ7.1-7.2(2H,m),δ6.77(2H,d),δ1.03(3H,tr)；Anal.Calcd.(％)for C19H12F6P2SiO2SmCl:C,34.46；H,1.83；found:C,34.55；H,1.91。
(2) Ethylene polymerization:
in a 300ml reaction flask, 5mg of the main catalyst, 100ml of toluene and 5ml of MAO solution (10 wt%) were added in this order under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 45 deg.C, ethylene pressure of 0.7MPa, and polymerizing for 120 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
(3) Ethylene copolymerization:
in a 300ml reaction flask, 5mg of procatalyst, 100ml of toluene, 8ml of MAO solution (10 wt%), and 5ml of 1-butenyl-N-acetyl-L-tyrosine-ethyl ester were sequentially added under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 45 deg.C, maintaining ethylene pressure of 0.7MPa, and polymerizing for 10 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
Example 19
(1) Preparation of procatalyst Compound 19:
following the procedure of example 1, 2.9g of compounds 2-19 according to formula (2) were reacted with 1g of chloromethylpalladium to give 3.4g of compound 19 according to formula (1) (Cat.19).1H NMR(600MHz,DMSO-d6):δ7.47-7.67(2H,m),δ7.24-7.38(2H,m),δ7.02(1H,m),δ6.84(4H,d),δ6.62(4H,d),δ3.42(3H,s)；Anal.Calcd.(％)for C19H16F2P2SiO3Pd:C,43.32；H,3.06；found:C,43.42；H,3.11。
(2) Ethylene polymerization:
in a 300ml reaction flask, 14mg of the main catalyst, 100ml of toluene and 5ml of MAO solution (10 wt%) were added in this order under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 50 deg.C, ethylene pressure of 0.5MPa, and polymerizing for 120 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
(3) Ethylene copolymerization:
in a 300ml reaction flask, 9mg of main catalyst, 100ml of toluene, 8ml of MAO solution (10 wt%), and 6ml of 1-hexenyl-N-acetyl-L-tyrosine-ethyl ester were sequentially added under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 50 deg.C, maintaining ethylene pressure of 0.5MPa, and polymerizing for 10 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
Example 20
(1) Preparation of the procatalyst compound 20:
following the procedure of example 1, 4.4g of compounds 2-20 according to formula (2) were reacted with 1.6g of chloromethylpalladium to give 4.8g of compound 20 according to formula (1) (Cat.20).1H NMR(600MHz,DMSO)：δ7.64-7.76(4H,m),δ7.25-7.33(4H,m),δ7.02(2H,m),δ6.86(1H,d),δ6.73(4H,d)；Anal.Calcd.(％)forC24H14F6P2SiO4Pd:C,42.59；H,2.08；found:C,42.49；H,2.13。
(2) Ethylene polymerization:
in a 300ml reaction flask, 14mg of the main catalyst, 80ml of toluene and 10ml of MAO solution (10 wt%) were added in this order under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 45 deg.C, ethylene pressure of 0.5MPa, and polymerizing for 100 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
(3) Ethylene copolymerization:
in a 300ml reaction flask, 10mg of main catalyst, 100ml of toluene, 6ml of MAO solution (10 wt%), and 6ml of 4-methyl-1-pentene were sequentially added under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 45 deg.C, maintaining ethylene pressure of 0.5MPa, and polymerizing for 30 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
Example 21
(1) Preparation of the procatalyst compound 21:
following the procedure of example 1, 3.9g of compounds 2 to 21 corresponding to general formula (2) were reacted with 1.9g of ferrous dichloride to give 5.1g of compound 21(Cat.21) corresponding to general formula (1). anal.Calcd. (%) for C19H12F6P2SiO2Fe:C,42.88；H,2.27；found:C,42.79；H,2.18。
(2) Polymerization of propylene:
in a 300ml reaction flask, 7mg of the procatalyst, 80ml of toluene, and 3ml of MAO solution (10 wt%) were added in this order under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 50 deg.C, propylene pressure of 2.3MPa, and polymerizing for 120 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
(3) And (2) propylene copolymerization:
in a 300ml reaction flask, 9mg of main catalyst, 100ml of toluene, 2ml of MAO solution (10 wt%), and 5ml of styrene were sequentially added under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 50 deg.C, maintaining propylene pressure of 2.3MPa, and polymerizing for 10 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
Example 22
(1) Preparation of a supported main catalyst:
3g of the procatalyst from example 8 were dissolved in 45ml of toluene, reacted with 0.02g (0.34mmol) of silica at 65 ℃ for 5 hours, the solvent was removed, and washed four times with toluene to give a supported catalyst. The titanium content of the resulting catalyst was determined to be 3.4 wt% by ICP method.
(2) Ethylene polymerization:
in a 300ml reaction flask, 7mg of the procatalyst, 100ml of toluene, and 5ml of MAO solution (10 wt%) were added in this order under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 50 deg.C, ethylene pressure of 0.5MPa, and polymerizing for 120 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
(3) Ethylene copolymerization:
in a 300ml reaction flask, 7mg of main catalyst, 100ml of toluene, 5ml of MAO solution (10 wt%), and 6ml of 1-hexenyl-N-acetyl-L-tyrosine-ethyl ester were sequentially added under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 50 deg.C, maintaining ethylene pressure of 0.5MPa, and polymerizing for 30 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
Example 23
(1) Preparation of a supported main catalyst:
4.2g (6mmol) of the procatalyst from example 19 were dissolved in 40ml of toluene, reacted with 0.03g (0.5mmol) of silica at 70 ℃ for 6 hours, the solvent was removed, and washed five times with toluene to give a supported catalyst. The palladium content of the resulting catalyst was 2.3% by weight as determined by ICP method.
(2) Ethylene polymerization:
in a 300ml reaction flask, 10mg of main catalyst, 80ml of toluene and 2ml of MAO solution (10 wt%) were added in this order under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 45 deg.C, ethylene pressure of 0.5MPa, and polymerizing for 100 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
(3) Ethylene copolymerization:
in a 300ml reaction flask, 10mg of main catalyst, 100ml of toluene, 2ml of MAO solution (10 wt%), and 6ml of 4-methyl-1-pentene were sequentially added under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 45 deg.C, maintaining ethylene pressure of 0.5MPa, and polymerizing for 30 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
Example 24
(1) Preparation of a supported main catalyst:
2.3g (4mmol) of the procatalyst from example 7 were dissolved in 30ml ethanol and reacted with 0.38g (4mmol) of magnesium chloride at 70 ℃ for 3 hours, the solvent was removed and washed six times with toluene to give a supported catalyst. The nickel content of the resulting catalyst was 3.1 wt% as determined by ICP method.
(2) Polymerization of propylene:
in a 300ml reaction flask, 7mg of the procatalyst, 80ml of toluene, and 2ml of MAO solution (10 wt%) were added in this order under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 50 deg.C, propylene pressure of 2.3MPa, and polymerizing for 120 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
(3) And (2) propylene copolymerization:
in a 300ml reaction flask, 7mg of main catalyst, 100ml of toluene, 2ml of MAO solution (10 wt%), and 5ml of styrene were sequentially added under anhydrous and oxygen-free conditions. Ventilating for three times, heating to 50 deg.C, maintaining propylene pressure of 2.3MPa, and polymerizing for 30 min. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times and then vacuum-dried at 50 ℃ for 24 hours.
The results of the catalytic polymerization for each example are shown in Table 3.
TABLE 3
Figure BDA0001806086820000231
Figure BDA0001806086820000241
It can be seen that the catalyst of the present invention has a higher catalytic activity.

Claims (10)

1. A compound of the general formula (1):
Figure FDA0001806086810000011
in the general formula (1), R1、R2Are respectively and independently selected from C1-C20 alkyl, C3-C20 cycloalkyl or C6-C20 aryl; r3、R4Are respectively and independently selected from a hydrogen atom, an alkyl group of C1-C20, a cycloalkyl group of C3-C20 or an aryl group of C6-C20; x is selected from F, Cl, Br, I or C1-C20 alkyl; m represents a transition metal atom selected from one of the elements of groups IIIB, IV B, VB or VIII.
2. A compound according to claim 1, wherein X is selected from Cl, Br, Me or Et.
3. A compound according to claim 1 or 2, wherein M is titanium, zirconium, hafnium, vanadium, rhodium, iron, nickel, cobalt, neodymium, palladium or yttrium.
4. Use of a compound according to any one of claims 1 to 3 as a procatalyst for an olefin polymerization catalyst.
5. An olefin polymerization catalyst comprising a procatalyst and a cocatalyst, wherein the procatalyst comprises a compound of any of claims 1-3.
6. The olefin polymerization catalyst according to claim 5, wherein the cocatalyst comprises an organometallic aluminum compound.
7. The olefin polymerization catalyst according to claim 6, wherein the organometallic aluminium compound comprises an aluminium alkyl and/or a hydrolysate of an aluminium alkyl aluminoxane.
8. The olefin polymerization catalyst according to any one of claims 5 to 7, wherein the molar ratio of cocatalyst to procatalyst is: (100-5000): 1.
9. a process for the preparation of a compound of general formula (1) according to any one of claims 1 to 3, which comprises: reacting a ligand compound corresponding to the general formula (2) with a transition metal compound in an organic solvent, removing the solvent after the reaction is finished, washing with the organic solvent to obtain a compound of the general formula (1),
Figure FDA0001806086810000021
wherein, R is1、R2Are respectively and independently selected from C1-C20 alkyl, C3-C20 cycloalkyl and C6-C20 aryl; r3、R4Are respectively and independently selected from hydrogen atoms, alkyl groups of C1-C20, cycloalkyl groups of C3-C20 and aryl groups of C6-C20;
wherein the transition metal compound corresponds to the general formula (3): MXnWherein X is selected from F, Cl, Br, I or C1-C20 alkyl; m represents a transition metal atom and is selected from one of IIIB, IV B, VB or VIII group elements, and n is a positive integer less than or equal to 4;
wherein the molar ratio of the ligand compound of the general formula (2) to the transition metal compound of the general formula (3) in the process is 1: (1-2.5);
wherein the reaction temperature is-30-100 ℃, and the reaction time is 1-10 hours.
10. Use of the catalyst of any one of claims 5-8 for catalyzing homopolymerization or copolymerization of olefins, wherein the polymerizable monomer for homopolymerization or copolymerization of olefins is any one or more of ethylene, α -olefin of C3-C20, or polar olefinic monomer of C3-C20.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020115560A1 (en) * 2001-01-18 2002-08-22 Gracia Pascual Royo Olefin polymerization catalysts
CN103159803A (en) * 2013-03-31 2013-06-19 北京化工大学 All-heterocyclic non-metallocene catalyst, and preparation method and application thereof
CN108264588A (en) * 2016-12-30 2018-07-10 中国石油天然气股份有限公司 Main catalyst of olefin polymerization catalyst, preparation method of main catalyst and olefin polymerization catalyst

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020115560A1 (en) * 2001-01-18 2002-08-22 Gracia Pascual Royo Olefin polymerization catalysts
CN103159803A (en) * 2013-03-31 2013-06-19 北京化工大学 All-heterocyclic non-metallocene catalyst, and preparation method and application thereof
CN108264588A (en) * 2016-12-30 2018-07-10 中国石油天然气股份有限公司 Main catalyst of olefin polymerization catalyst, preparation method of main catalyst and olefin polymerization catalyst

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