CN114989341B - Modified PNP catalyst ligand, preparation method thereof and ethylene selective oligomerization catalyst - Google Patents

Modified PNP catalyst ligand, preparation method thereof and ethylene selective oligomerization catalyst Download PDF

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CN114989341B
CN114989341B CN202210467716.7A CN202210467716A CN114989341B CN 114989341 B CN114989341 B CN 114989341B CN 202210467716 A CN202210467716 A CN 202210467716A CN 114989341 B CN114989341 B CN 114989341B
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catalyst
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lithium
ligand
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CN114989341A (en
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冯其龙
徐英博
张蒙
刘鹏
吕希林
卫旭光
岳瑞英
杨洪业
袁卫杰
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Hainan Beiouyi Technology Co ltd
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    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
    • B01J31/188—Amide derivatives thereof
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    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention provides a modified PNP catalyst ligand with a structure shown in a formula (I). The ligand provided by the invention can be effectively complexed with chromium catalysts, has the activity of the ligand before modification, and can be applied to batch kettle type reaction and tubular fixed bed reaction devices. When in kettle reaction, the solid wax and the high polymer can well grow in the micro-channel of the spherical particles, which is helpful for solving the problem of solid wall hanging; when in fixed bed reaction, the catalyst is convenient to fill, the metal loss of the catalyst can be reduced, and the reaction period of the catalyst can be prolonged.

Description

Modified PNP catalyst ligand, preparation method thereof and ethylene selective oligomerization catalyst
Technical Field
The invention relates to the technical field of polyolefin catalysts, in particular to a modified PNP catalyst ligand, a preparation method thereof and an ethylene selective oligomerization catalyst.
Background
The linear alpha-olefin is an important chemical raw material with huge demand, wherein the linear alpha-olefin of C4-C24 has wide application in the fields of preparing low-density polyethylene, high-grade detergent, high-grade lubricating oil, surfactant, POE, high-grade linear alcohol and the like. The ethylene oligomerization method is the most promising industrialized method for the intensive research in China at present.
Since the first time the conversion of ethylene trimerization to tetramerization is realized by adopting a Cr/PNP/MAO catalytic system by Sasol company Bollmann, a great deal of research is carried out by scientific researchers at home and abroad on the chromium-based main catalyst ligand used for ethylene oligomerization. The ligand of F-PNP, PNCP, PNSiP, PCCP, PNNP and other types is developed successively, the catalyst activity is improved greatly, and a batch of catalytic systems are applied industrially.
The existing ethylene selective oligomerization catalyst mainly uses ligand researches such as PNP, PCCP and the like, the activity of the catalyst can meet the requirements, but the solid content is large, and macromolecule solid polyolefin is easy to wall in the industrialized process, so that equipment such as stirring and filtering and the like needs frequent maintenance, and the operation is complicated.
In order to solve the problem, the domestic and foreign groups also select a catalyst loaded by molecular sieve or silicon dioxide, and the catalyst can be used in a fixed bed reactor, so that the loss problem of a main catalyst is reduced, but the catalytic activity and the selectivity are not high, and the industrialization is not facilitated.
Therefore, it is necessary to provide a catalyst which has high activity and can solve the problems of long post-treatment time and solid wall build-up in a batch reaction solution.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a modified PNP catalyst ligand, wherein the ligand provided by the present invention has a plurality of active centers after being complexed with chromium, the produced oligoolefin can be separated from the catalyst, and the polymer grows in the styrene pore canal, so that the solid wall hanging and the metal catalyst loss can be reduced.
The invention provides a modified PNP catalyst ligand with a structure shown in a formula (I),
Wherein R 1、R2、R3 is independently selected from one or more of C1-C10 alkyl, C2-C10 terminal alkylene, C6-C20 aryl, C6-C20 heterocyclic group and C3-C15 cycloalkyl; r 4 is isopropyl or cyclopentyl; r 5 is one or more of C1-C10 alkyl, C6-C20 aryl, C6-C20 heterocycle and C3-C15 cycloalkyl, and n is 30-500.
Preferably, R 1、R2、R3 is independently selected from one or more of C1-C6 alkyl, C2-C8 terminal alkylene, C6-C10 aryl, C6-C10 heterocyclic and C4-C10 cycloalkyl; r 5 is one or more of C1-C6 alkyl, C6-C10 aryl, C6-C10 heterocycle and C3-C10 cycloalkyl.
Preferably, the modified PNP catalyst ligand of the structure of formula (I) is specifically of the structure:
wherein m, n, s, r is independently selected from 30 to 500.
The invention provides a preparation method of a modified PNP catalyst ligand with a structure shown in a formula (I), which comprises the following steps:
a) Mixing a compound with a structure of a formula (II), R 4NH2, triethylamine and a solvent, and reacting to obtain a monomer with a structure of a formula (III);
B) Mixing and reacting a monomer with a structure of a formula (III), styrene, an initiator and a solvent, and drying to obtain a modified PNP catalyst with a structure of a formula (I);
Wherein R 1、R2、R3 is independently selected from one or more of C1-C10 alkyl, C2-C10 terminal alkylene, C6-C20 aryl, C6-C20 heterocyclic group and C3-C15 cycloalkyl; r 4 is isopropyl or cyclopentyl; r 5 is one or more of C1-C10 alkyl, C6-C20 aryl, C6-C20 heterocycle and C3-C15 cycloalkyl, and n is 30-500.
Preferably, the molar ratio of the compound of the structure of formula (II) to R 4NH2 in step a) is 2-2.5, and the molar ratio of triethylamine to R 4NH2 is 3-3.5; the solvent is one of tetrahydrofuran, n-hexane, cyclohexane and toluene.
Preferably, the initiator in the step B) is one or more of azo and alkyl peroxides; the molar ratio of the styrene to the monomer with the structure of formula (III) is 10-1000; the solvent is one of toluene, xylene and ethylbenzene.
Preferably, the preparation method of the compound with the structure of the formula (II) comprises the following steps:
mixing halogenated olefin with a structure of a formula (IV), diethyl ether and magnesium powder, and carrying out reflux reaction to obtain a reactant;
Reacting the reactant with phosphorus trichloride in the presence of a solvent, and filtering to remove salt to obtain the catalyst;
Wherein X is Cl or Br; r 5 is one or more of C1-C10 alkyl, C6-C20 aryl, C6-C20 heterocycle and C3-C15 cycloalkyl.
The invention provides an ethylene selective oligomerization catalyst, which comprises a main catalyst and a cocatalyst; the main catalyst comprises a modified PNP catalyst ligand with the structure of formula (I) and an organic chromium compound.
Preferably, the organic chromium compound is chromium acetylacetonate or chromium tetrahydrofuran trichloride;
The cocatalyst is selected from one or more of MAO, MMAO, methyl lithium, ethyl lithium, propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, amyl lithium, hexyl lithium, cyclohexyl lithium, tert-octyl lithium or triethyl aluminum;
The molar ratio of the cocatalyst to the main catalyst was 500, and the molar concentration of the main catalyst (Cr) was 2. Mu. Mol/mL.
The invention provides an ethylene selective oligomerization method, which comprises the following steps:
in the presence of hydrogen, the catalyst for ethylene selective oligomerization and ethylene are subjected to oligomerization reaction, and the catalyst is obtained.
Compared with the prior art, the invention provides a modified PNP catalyst ligand with a structure shown in a formula (I). The ligand provided by the invention can be effectively complexed with chromium catalysts, has the activity of the ligand before modification, and can be applied to batch kettle type reaction and tubular fixed bed reaction devices. When in kettle reaction, the solid wax and the high polymer can well grow in the micro-channel of the spherical particles, which is helpful for solving the problem of solid wall hanging; when in fixed bed reaction, the catalyst is convenient to fill, the metal loss of the catalyst can be reduced, and the reaction period of the catalyst can be prolonged.
Detailed Description
The invention provides a modified PNP catalyst ligand, a preparation method thereof and an ethylene selective oligomerization catalyst, and the technical personnel in the field can properly improve the technological parameters by referring to the content of the invention. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and they are intended to be within the scope of the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that the invention can be practiced and practiced with modification and alteration and combination of the methods and applications herein without departing from the spirit and scope of the invention.
The invention provides a modified PNP catalyst ligand with a structure shown in a formula (I),
Wherein R 1、R2、R3 is independently selected from one or more of C1-C10 alkyl, C2-C10 terminal alkylene, C6-C20 aryl, C6-C20 heterocyclic group and C3-C15 cycloalkyl; preferably, R 1、R2、R3 is independently selected from one or more of C1-C6 alkyl, C2-C8 terminal alkylene, C6-C10 aryl, C6-C10 heterocyclic and C4-C10 cycloalkyl; wherein the alkyl is methyl, ethyl, isopropyl or isobutyl; the cycloalkyl is cyclopentyl or cyclohexyl; the aryl is phenyl.
R 4 is isopropyl or cyclopentyl;
R 5 is one or more of C1-C10 alkyl, C6-C20 aryl, C6-C20 heterocycle and C3-C15 cycloalkyl; preferably, R 5 is one or more of C1-C6 alkyl, C6-C10 aryl, C6-C10 heterocycle, C3-C10 cycloalkyl. Wherein the alkyl is methyl, ethyl, isopropyl or isobutyl; the cycloalkyl is cyclopentyl or cyclohexyl; the aryl is phenyl.
N is 30-500; preferably, n is 50 to 100.
In a preferred embodiment of a part of the present invention, the modified PNP catalyst ligand of the structure of formula (I) is specifically of the structure:
wherein m, n, s, r is independently selected from 30 to 500.
The invention provides a preparation method of a modified PNP catalyst ligand with a structure shown in a formula (I), which comprises the following steps:
a) Mixing a compound with a structure of a formula (II), R 4NH2, triethylamine and a solvent, and reacting to obtain a monomer with a structure of a formula (III);
B) Mixing and reacting a monomer with a structure of a formula (III), styrene, an initiator and a solvent, and drying to obtain a modified PNP catalyst with a structure of a formula (I);
Wherein R 1、R2、R3 is independently selected from one or more of C1-C10 alkyl, C2-C10 terminal alkylene, C6-C20 aryl, C6-C20 heterocyclic group and C3-C15 cycloalkyl; preferably, R 1、R2、R3 is independently selected from one or more of C1-C6 alkyl, C2-C8 terminal alkylene, C6-C10 aryl, C6-C10 heterocyclic and C4-C10 cycloalkyl; wherein the alkyl is methyl, ethyl, isopropyl or isobutyl; the cycloalkyl is cyclopentyl or cyclohexyl; the aryl is phenyl.
R 4 is isopropyl or cyclopentyl;
R 5 is one or more of C1-C10 alkyl, C6-C20 aryl, C6-C20 heterocycle and C3-C15 cycloalkyl; preferably, R 5 is one or more of C1-C6 alkyl, C6-C10 aryl, C6-C10 heterocycle, C3-C10 cycloalkyl. Wherein the alkyl is methyl, ethyl, isopropyl or isobutyl; the cycloalkyl is cyclopentyl or cyclohexyl; the aryl is phenyl.
N is 30-500; preferably, n is 50 to 100.
In a preferred embodiment of some of the present invention, the reaction scheme is as follows:
The preparation method of the modified PNP catalyst ligand with the structure shown in the formula (I) comprises the steps of firstly mixing a compound with the structure shown in the formula (II), R 4NH2, triethylamine and a solvent, and reacting to obtain a monomer with the structure shown in the formula (III).
The compounds of the structure of formula (II) are preferably prepared first.
The preparation method of the compound with the structure of the formula (II) is as follows:
mixing halogenated olefin with a structure of a formula (IV), diethyl ether and magnesium powder, and carrying out reflux reaction to obtain a reactant;
Reacting the reactant with phosphorus trichloride in the presence of a solvent, and filtering to remove salt to obtain the catalyst;
Wherein X is Cl or Br; r 5 is one or more of C1-C10 alkyl, C6-C20 aryl, C6-C20 heterocycle and C3-C15 cycloalkyl.
The mol ratio of the halogenated olefin to the magnesium powder is 1:1.
The preferred specific examples are: under the anhydrous and anaerobic condition, adding halogenated olefin and diethyl ether with the structure of formula (IV) into a reaction bottle, adding magnesium powder under stirring, slowly heating until violent reaction, refluxing for 30-120 min to complete preparation of the format reagent, and cooling to room temperature for standby.
Reacting the reactant with phosphorus trichloride in the presence of a solvent, and filtering to remove salt to obtain the catalyst;
Adding phosphorus trichloride into a new reaction bottle, adding a solvent, cooling to 30-40 ℃ below zero, then slowly dripping a format reagent into the reaction bottle, and continuing to perform heat preservation reaction for 30-120 min after dripping is finished, thus finishing the reaction. The salt is removed by filtration at low temperature. The molar ratio of the halogenated olefin of the structure of formula (IV) to phosphorus trichloride is preferably 2 to 2.5. The solvent includes, but is not limited to THF.
And (3) after the compound with the structure shown in the formula (II) is prepared, under the protection of nitrogen at room temperature, triethylamine, R 4NH2 and a solvent are taken and mixed in a reaction bottle, a crude product solution of the compound with the structure shown in the formula (II) is taken and put in a constant pressure low liquid funnel, and is slowly dripped into a reaction system, and after 1h of dripping is finished, stirring is continued for reacting for 1-5 h, and the reaction is finished. Removing salt by suction filtration, removing solvent and amine by rotary evaporation of filtrate to obtain a solid crude product, and then recrystallizing.
The recrystallization solvent of the present invention is preferably one or more of n-hexane, cyclohexane, vinyl acetate, methanol, ethanol, and n-propanol.
According to the invention, the molar ratio of the compound of formula (II) to R 4NH2 is 2 to 2.5 and the molar ratio of triethylamine to R 4NH2 is 3 to 3.5.
Mixing and reacting the monomer with the structure of the formula (III), styrene, an initiator and a solvent, and drying to obtain the modified PNP catalyst with the structure of the formula (I).
The reaction temperature is 40-70 ℃;
The time is 1-5 h;
The initiator is one or more of azo and alkyl peroxides; AIBN is preferred.
The molar ratio of styrene to the monomer of formula (III) is preferably between 10 and 1000; the solvent is one of toluene, xylene and ethylbenzene.
And (5) finishing the reaction. Filtering to obtain a solid crude product, and drying in a vacuum drying oven at 50-80 ℃ to obtain a powdery compound.
The particle size of the powder is spherical and the particle size is 1.0-3.0 mm.
The invention provides an ethylene selective oligomerization catalyst, which comprises a main catalyst and a cocatalyst; the main catalyst comprises a modified PNP catalyst ligand with the structure of formula (I) and an organic chromium compound.
The main catalyst comprises the modified PNP catalyst ligand with the structure of formula (I) and an organic chromium compound. The organic chromium compound is chromium acetylacetonate or chromium tetrahydrofuran trichloride; preferably tetrahydrofuran chromium trichloride.
The modified PNP catalyst ligand with the structure shown in the formula (I) and the organic chromium compound can undergo a complexation reaction.
The complexing ratio of the ligand and the organic chromium is 0.5-2.
The cocatalyst is one or more selected from MAO, MMAO, methyl lithium, ethyl lithium, propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, amyl lithium, hexyl lithium, cyclohexyl lithium, tert-octyl lithium or triethyl aluminum; preferably a mixture of MMAO and triethylaluminium.
The molar ratio of the cocatalyst to the main catalyst was 500, and the molar concentration of the main catalyst (Cr) was 2. Mu. Mol/mL.
The above-mentioned technical scheme is only one of many methods for synthesizing the modified ligand, and all methods capable of synthesizing the terminal olefin L and P (including but not limited to directly using the olefin group on the existing PNP ligand) are within the protection scope of the present invention.
The invention provides an ethylene selective oligomerization method, which comprises the following steps:
in the presence of hydrogen, the catalyst for ethylene selective oligomerization and ethylene are subjected to oligomerization reaction, and the catalyst is obtained.
The preferred specific examples are: the modified PNP catalyst with the structure shown in the formula (I) and the organic chromium compound are put in a closed autoclave, nitrogen is replaced for 2-3 times, solvent is pumped in under negative pressure, stirring is carried out for 2-8 hours at room temperature, then the introduced hydrogen is injected, an injector takes the auxiliary catalytic mixed solution under micro-positive pressure to be injected into the reaction kettle, then the hydrogen is pressurized, finally ethylene is introduced, and the reaction is carried out under heat preservation and pressure maintaining. And cooling and deflating after the reaction is finished, weighing the reaction liquid, and calculating the reaction activity according to the weight gain. The reaction solvent is one or more of n-hexane, cyclohexane, toluene, methylcyclohexane and n-heptane, preferably methylcyclohexane or cyclohexane. Preferably cyclohexane, and most preferably 0.4 times the volume of the solvent in the reaction vessel. The reaction temperature of the polymerization process is 60-75 ℃. The hydrogen partial pressure is 0.1-1.0 MPa, the ethylene pressure is 5.0MPa, and the reaction temperature is 40-70 ℃. The solvent drying mode is one of molecular sieve drying or sodium reflux distillation.
The invention provides a preparation method of an ethylene selective oligomerization catalyst ligand, which obtains a porous material with activity and pore channels through polymerization of a small amount of ligand and excessive styrene, reduces the occurrence of solid wall built-up phenomenon, and ensures that the material post-treatment processing is more convenient and feasible; compared with the catalyst load and the carbon nano tube load reported in the literature, the preparation method is simpler, more convenient and more various, and can design PNP ligand containing terminal olefin from the source, and can also modify (upper olefin group) on the basis of the existing PNP ligand; the polymerization process is simple and feasible, PNP monomer can be doped with different molar amounts according to experimental requirements, and the polymerization conditions are compared with the existing mature polystyrene process.
To further illustrate the present invention, the following is a detailed description of a modified PNP catalyst ligand, method of preparing the same, and an ethylene selective oligomerization catalyst provided by the present invention.
Example 1
(1) Synthesis of compound B1: the operation is carried out under anhydrous and anaerobic conditions. Firstly, 36.6g of bromostyrene and 100ml of diethyl ether are added into a reaction bottle together, 4.8g of magnesium powder is slowly added under strong stirring, the mixture is slowly heated until the violent reaction is carried out, the preparation of the reagent in a format of 30min of reflux is completed, and the reaction mixture is cooled to room temperature for standby. 13.75g of phosphorus trichloride is taken to be placed in a new reaction bottle, 50ml of THF is added, the temperature is reduced to minus 30-40 ℃, then the grignard reagent is slowly dropped into the reaction bottle, the reaction is continued to be carried out for 30min after the dropping is finished, and the reaction is finished. The salt is removed by rapid filtration at low temperature to give a crude solution of compound B1.
(2) Synthesis of monomer L1: under the protection of nitrogen at room temperature, 30.3g of triethylamine, 8.72g of isopropylamine and 100ml of THF are taken and stirred in a reaction bottle, a crude product solution of the compound B1 is taken and slowly dripped into a reaction system in a constant pressure low liquid funnel, and after the dripping is finished, the reflux reaction is carried out for 2 hours, and the reaction is finished. The salt was removed by suction filtration, and the solvent and amine were removed by rotary evaporation of the filtrate to give a crude solid, which was then recrystallized from n-hexane to give 19.11g of a white solid product. The monomer nuclear magnetic data are as follows:
1H-NMR(δ,ppm):7.10～7.34(16H,m,benzene-H);6.69～6.75(4H,m,benzene-C-H);5.23～5.77(8H,d,benzene-C-C-H);2.80～2.86(1H,m,N-C-H);1.03～1.08(6H,d,N-C-C-H).
(3) Synthesis of Polymer P1: 1.0g of L1, 50ml of toluene, 9.8g of styrene (50 equ) and 0.1g of AIBN are taken in a high-pressure reaction kettle, the reaction temperature is controlled to be 60-75 ℃, the reaction is kept at the temperature for 2 hours, and the reaction is finished. The crude solid product is obtained by filtration, 10.3g of P1 powder is obtained by drying in a vacuum drying oven at 50 ℃, and the concentration of ligand in the polymer is 172.8 mu mol/g.
(4) And (3) oligomerization activity verification: taking 5.8mgP1 and 3.8mg3THF.CrCl 3 in a closed autoclave, replacing nitrogen for three times, pumping 200ml of dry cyclohexane under negative pressure, stirring for 4 hours at room temperature, then introducing hydrogen, taking MMAO by a syringe under micro positive pressure, injecting the MMAO into the reaction kettle, pressurizing the hydrogen to 0.5Mpa, finally introducing ethylene to 5.0Mpa, controlling the reaction temperature to 55-65 ℃, and carrying out heat preservation and pressure maintaining reaction for 1 hour. After the reaction is finished, the temperature is reduced to 20 ℃ and the gas is discharged, the reaction liquid is weighed, the weight gain can reach 53.50g, and the calculated reaction activity is 514.42kg/g (Cr) h.
Example 2
(1) Synthesis of compound C2: the operation is carried out under anhydrous and anaerobic conditions. Firstly, 18.3g of bromostyrene and 100ml of diethyl ether are added into a reaction bottle together, 2.4g of magnesium powder is slowly added under strong stirring, the mixture is slowly heated until the violent reaction is carried out, the preparation of the reagent in a format of 30min of reflux is completed, and the reaction mixture is cooled to room temperature for standby. 13.75g of phosphorus trichloride is taken and placed in a new reaction bottle, 50ml of THF is added, the temperature is reduced to minus 30-40 ℃, then the grignard reagent is slowly dripped into the reaction bottle, the reaction is continued for 30min after the dripping is finished, and a crude product solution containing the compound B2 is obtained after the reaction is finished. Then 50ml of 2mol/L isopropyl magnesium chloride THF solution is taken and placed in a constant pressure dropping funnel, slowly added into the B2 crude product solution in a dropwise manner, the reaction is carried out for 30min after the dropwise addition is finished, and salt is removed by filtration after the reaction is finished, so as to obtain the crude product solution of the compound C2.
(2) Synthesis of monomer L2: under the protection of nitrogen at room temperature, 30.3g of triethylamine, 8.72g of isopropylamine and 100ml of THF are taken and stirred in a reaction bottle, a crude product solution of the compound C2 is taken and slowly dripped into a reaction system in a constant pressure low liquid funnel, and after the dripping is finished, the reaction is carried out for 2 hours under reflux. The salt was removed by suction filtration, and the solvent and amine were removed by rotary evaporation of the filtrate to give a crude solid, which was then recrystallized from n-hexane to give 15.53g of a white solid product. The monomer nuclear magnetic data are as follows:
1H-NMR(δ,ppm):7.09～7.32(8H,m,benzene-H);6.70～6.77(2H,m,benzene-C-H);5.23～5.77(4H,d,benzene-C-C-H);2.80～2.85(1H,m,N-C-H);1.58～1.61(1H,m,P-C-H);1.03～1.08(6H,d,N-C-C-H);0.90～0.94(12H,d,P-C-C-H).
(3) Synthesis of Polymer P2: 1.0g of L1, 50ml of toluene, 12.7g of styrene (50 equ) and 0.1g of AIBN are taken in a high-pressure reaction kettle, the reaction temperature is controlled to be 60-75 ℃, the reaction is kept at the temperature for 2 hours, and the reaction is finished. The crude solid product is obtained by filtration, 13.3g of P2 powder is obtained by drying in a vacuum drying oven at 50 ℃, and the concentration of ligand in the polymer is 177.6 mu mol/g.
(4) And (3) oligomerization activity verification: taking 5.6mgP2 and 3.8mg3THF.CrCl 3 in a closed autoclave, replacing nitrogen for three times, pumping 200ml of dry cyclohexane under negative pressure, stirring for 4 hours at room temperature, then introducing hydrogen, taking MMAO by a syringe under micro positive pressure, injecting the MMAO into the reaction kettle, pressurizing the hydrogen to 0.5Mpa, finally introducing ethylene to 5.0Mpa, controlling the reaction temperature to 55-65 ℃, and carrying out heat preservation and pressure maintaining reaction for 1 hour. After the reaction is finished, the temperature is reduced to 20 ℃ and the gas is discharged, the reaction liquid is weighed, the weight gain can reach 72.76g, and the calculated reaction activity is 699.61kg/g (Cr) h.
Example 3
(1) Synthesis of compound C3: the operation is carried out under anhydrous and anaerobic conditions. Firstly, 18.3g of bromostyrene and 100ml of diethyl ether are added into a reaction bottle together, 2.4g of magnesium powder is slowly added under strong stirring, the mixture is slowly heated until the violent reaction is carried out, the preparation of the reagent in a format of 30min of reflux is completed, and the reaction mixture is cooled to room temperature for standby. 13.75g of phosphorus trichloride is taken and placed in a new reaction bottle, 50ml of THF is added, the temperature is reduced to minus 30-40 ℃, then the grignard reagent is slowly dripped into the reaction bottle, the reaction is continued for 30min after the dripping is finished, and a crude product solution containing the compound B3 is obtained after the reaction is finished. Then 50ml of 2mol/L isopropyl magnesium chloride THF solution is taken and placed in a constant pressure dropping funnel, slowly added into the B3 crude product solution in a dropwise manner, the reaction is carried out for 30min after the dropwise addition is finished, and salt is removed by filtration after the reaction is finished, so as to obtain the crude product solution of the compound C3.
(2) Synthesis of compound F3: 30.3g of triethylamine, 8.72g of isopropylamine and 100ml of THF are taken in a reaction bottle, a solution containing C3 is dripped at the temperature of 0-20 ℃, and the reaction is stirred for 4 hours after the dripping is finished, and the reaction is finished. The salt was removed by suction filtration and the solvent was removed by rotary evaporation with excess amine to give 20.5g of crude D3. 6.88g of phosphorus trichloride and 50ml of THF are taken in a reaction bottle, stirred and cooled to-30 ℃, then 15.2g of triethylamine is taken in a constant drop, slowly added into the reaction system in a dropwise manner, and stirred for 30min after the dropwise addition. Then, 11.8g of D3 is weighed and dissolved in 50ml of THF, the reaction system is added dropwise in a constant drop, the dropwise addition is completed for 1 hour, the reaction is carried out for 1 hour at a constant temperature, and the reaction is completed. And (3) carrying out suction filtration rapidly at low temperature to obtain a crude solution containing F3.
(3) Synthesis of monomer L3: and (3) placing the crude product solution of F3 in a low-temperature tank, cooling to-30 ℃, placing 50ml of 2mol/L isopropyl magnesium chloride THF solution in a constant-pressure low-liquid funnel, slowly dripping the solution into a reaction system, and after dripping, heating to room temperature for continuous reaction for 1h, wherein the reaction is finished. The salt was removed by suction filtration, and the solvent and amine were removed by rotary evaporation of the filtrate to give a crude solid of L3, which was then recrystallized from n-hexane to give 4.15g of a white solid product. The monomer nuclear magnetic data are as follows:
1H-NMR(δ,ppm):7.09～7.32(4H,m,benzene-H);6.70～6.73(1H,m,benzene-C-H);5.23～5.77(2H,d,benzene-C-C-H);2.80～2.85(1H,m,N-C-H);1.58～1.61(3H,m,P-C-H);1.03～1.08(6H,d,N-C-C-H);0.90～0.94(18H,d,P-C-C-H).
(4) Synthesis of Polymer P3: 1.0g of L1, 50ml of toluene, 14.8g of styrene (50 equ) and 0.1g of AIBN are taken in a high-pressure reaction kettle, the reaction temperature is controlled to be 60-75 ℃, the reaction is kept at the temperature for 2 hours, and the reaction is finished. The crude solid product is obtained by filtration, and the powder 14.9g of P1 is obtained by drying in a vacuum drying oven at 50 ℃, and the ligand concentration in the polymer is 180.3 mu mol/g.
(5) And (3) oligomerization activity verification: 5.5mg of P3 and 3.8mg of 3THF CrCl 3 are taken in a closed autoclave, nitrogen is replaced for three times, 200ml of dry cyclohexane is pumped in under negative pressure, stirring is carried out for 4 hours at room temperature, then the introduced hydrogen is injected into the autoclave by a syringe under micro positive pressure, MMAO is injected into the autoclave, then the hydrogen is pressurized to 0.5Mpa, finally ethylene is introduced to 5.0Mpa, the reaction temperature is controlled to 55-65 ℃, and the reaction is carried out for 1 hour under heat preservation and pressure maintaining. After the reaction is finished, the temperature is reduced to 20 ℃ and the gas is discharged, the reaction liquid is weighed, the weight gain can reach 113.38g, and the calculated reaction activity is 1090.21kg/g (Cr) h.
Example 4
(1) F3 was synthesized in the same manner as in example 3.
(2) Synthesis of monomer L4: and (3) placing the crude product solution of F3 in a low-temperature tank to cool to-30 ℃, placing 25ml of 2mol/L isopropyl magnesium chloride THF solution in a constant-pressure low-liquid funnel, slowly dripping the solution into a reaction system, heating to room temperature after dripping, continuously reacting for 1h, slowly dripping 25ml of 2mol/L ethyl magnesium chloride THF solution into the reaction system after reacting, keeping the low temperature to-30 ℃ in the dripping process, and heating to room temperature after dripping, continuously reacting for 1h, and finishing the reaction. The salt is removed by suction filtration, the solvent and amine are removed by rotary evaporation of the filtrate, the crude solid of L4 is obtained, and then the crude solid is recrystallized by n-hexane, and finally the white solid product 3.81 is obtained. The monomer nuclear magnetic data are as follows:
1H-NMR(δ,ppm):7.10～7.35(4H,m,benzene-H);6.70～6.74(1H,m,benzene-C-H);5.23～5.77(2H,d,benzene-C-C-H);2.80～2.85(1H,m,N-C-H);1.58～1.61(2H,m,P-C-H);1.46～1.50(2H,m,P-C-H);1.03～1.08(6H,d,N-C-C-H);0.90～0.98(15H,m,P-C-C-H).
(3) Synthesis of Polymer P4: 1.0g of L1, 50ml of toluene, 15.4g of styrene (50 equ) and 0.1g of AIBN are taken in a high-pressure reaction kettle, the reaction temperature is controlled to be 60-75 ℃, the reaction is kept at the temperature for 2 hours, and the reaction is finished. The crude solid product is obtained by filtration, and the crude solid product is dried in a vacuum drying oven at 50 ℃ to obtain 14.4g of powder of P4, wherein the concentration of ligand in the polymer is 179.8 mu mol/g.
(4) And (3) oligomerization activity verification: 5.5mg of P4 and 3.8mg of 3THF CrCl 3 are taken in a closed autoclave, nitrogen is replaced for three times, 200ml of dry cyclohexane is pumped in under negative pressure, stirring is carried out for 4 hours at room temperature, then the introduced hydrogen is injected into the autoclave by a syringe under micro positive pressure, MMAO is injected into the autoclave, then the hydrogen is pressurized to 0.5Mpa, finally ethylene is introduced to 5.0Mpa, the reaction temperature is controlled to 55-65 ℃, and the reaction is carried out for 1 hour under heat preservation and pressure maintaining. After the reaction is finished, the temperature is reduced to 20 ℃ and the gas is discharged, the reaction liquid is weighed, the weight gain can reach 63.18g, and the calculated reaction activity is 607.52kg/g (Cr) h.
Example 5
The procedure of example 1 was repeated except that isopropylamine was changed to cyclopentylamine (R 4: cyclopentanyl).
The reaction solution is weighed, the weight gain can reach 75.03g, and the calculated reaction activity is 722.42kg/g (Cr) h.
Example 6
The procedure of example 2 was repeated except that isopropylamine was changed to cyclopentylamine (R 4: cyclopentanyl).
The reaction solution is weighed, the weight gain can reach 43.50g, and the calculated reaction activity is 418.84kg/g (Cr) h.
Example 7
The procedure of example 3 was repeated except that isopropylamine was changed to cyclopentylamine (R 4: cyclopentanyl).
The reaction solution is weighed, the weight gain can reach 65.61g, and the calculated reaction activity is 631.73kg/g (Cr) h.
Example 8
The procedure of example 4 was repeated except that isopropylamine was changed to cyclopentylamine (R 4: cyclopentanyl).
The reaction solution is weighed, the weight gain can reach 83.25g, and the calculated reaction activity is 800.86kg/g (Cr) h.
Example 9
The procedure of example 1 was repeated except that p-bromostyrene was changed to p-chlorostyrene (X: cl).
The reaction solution is weighed, the weight gain can reach 51.21g, and the calculated reaction activity is 492.64kg/g (Cr) h.
Example 10
The procedure of example 2 was repeated except that p-bromostyrene was changed to p-chlorostyrene (X: cl).
The reaction solution was weighed to give a weight gain of 60.64g and a calculated reactivity of 583.35kg/g (Cr). H.
Example 11
The procedure of example 3 was repeated except that p-bromostyrene was changed to p-chlorostyrene (X: cl).
The reaction solution is weighed, the weight gain can reach 68.27g, and the calculated reaction activity is 656.75kg/g (Cr) h.
Example 12
The procedure of example 4 was repeated except that p-bromostyrene was changed to p-chlorostyrene (X: cl).
The reaction solution is weighed, the weight gain can reach 73.34g, and the calculated reaction activity is 705.53kg/g (Cr) h.
Example 13
The procedure of example 1 was repeated except that p-bromostyrene was changed to chloropropene (X: cl, R 5: propenyl).
The reaction solution is weighed, the weight gain can reach 55.16g, and the calculated reaction activity is 530.64kg/g (Cr) h.
Example 14
The procedure of example 2 was repeated except that p-bromostyrene was changed to chloropropene (X: cl, R 5: propenyl).
The reaction solution is weighed, the weight gain can reach 65.0g, and the calculated reaction activity is 625.30kg/g (Cr) h.
Example 15
The procedure of example 3 was repeated except that p-bromostyrene was changed to chloropropene (X: cl, R 5: propenyl).
The reaction solution is weighed, the weight gain can reach 70.05g, and the calculated reaction activity is 673.88kg/g (Cr) h.
Example 16
The procedure of example 4 was repeated except that p-bromostyrene was changed to chloropropene (X: cl, R 5: propenyl).
The reaction solution is weighed, the weight gain can reach 86.42g, and the calculated reaction activity is 831.36kg/g (Cr) h.
Example 17
The amount of styrene in the polymerization process was increased from 50equ to 100equ, and the other steps were the same as in example 1.
After the treatment, 18.34g of P1 powder was obtained, and the ligand concentration in the polymer was 90.99. Mu. Mol/g.
Example 18
The amount of styrene in the polymerization process was increased from 50equ to 100equ, and the other steps were the same as in example 2.
After the treatment, 24.25g of P2 powder was obtained, and the ligand concentration in the polymer was 92.49. Mu. Mol/g.
Example 19
The amount of styrene in the polymerization process was increased from 50equ to 100equ, and the other steps were the same as in example 3.
After the treatment, 28.47g of P3 powder was obtained, and the ligand concentration in the polymer was 93.38. Mu. Mol/g.
Example 20
The amount of styrene in the polymerization process was increased from 50equ to 100equ, and the other steps were the same as in example 4.
After the treatment, 28.65g of P4 powder was obtained, and the ligand concentration in the polymer was 92.99. Mu. Mol/g.
Example 21
The oligomerization reactions of examples 1 to 20 were now followed and the data are summarized as follows:
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The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (7)

1. A method for preparing a modified PNP catalyst ligand comprising the steps of:
A) Mixing a compound with a structure of a formula (II), R 4NH2, triethylamine and a solvent, and reacting to obtain a monomer with a structure of a formula (III);
B) Mixing and reacting a monomer with a structure of a formula (III), styrene, an initiator and a solvent, and drying to obtain a modified PNP catalyst ligand; the reaction temperature is 40-70 ℃; the reaction time is 1-5 h; the initiator is one or more of azo and alkyl peroxides;
Formula (II); /(I) Formula (III);
Wherein R 1、R2、R3 is ; R 4 is isopropyl or cyclopentyl; r 5 is one or more of C1-C10 alkylene, C6-C20 arylene, C6-C20 heterocyclylene, and C3-C15 cycloalkylene.
2. The method according to claim 1, wherein the molar ratio of the compound of formula (II) to R 4NH2 in step a) is 2 to 2.5, and the molar ratio of triethylamine to R 4NH2 is 3 to 3.5; the solvent is one of tetrahydrofuran, n-hexane, cyclohexane and toluene.
3. The method according to claim 1, wherein the molar ratio of styrene to the monomer of formula (III) is 10 to 1000; the solvent is one of toluene, xylene and ethylbenzene.
4. The preparation method according to claim 1, wherein the preparation method of the compound of the structure of formula (II) is as follows:
Mixing halogenated olefin with a structure of a formula (IV), diethyl ether and magnesium powder, and carrying out reflux reaction to obtain a reactant;
Reacting the reactant with phosphorus trichloride in the presence of a solvent, and filtering to remove salt to obtain the catalyst;
Formula (IV);
Wherein X is Cl or Br; r 5 is one or more of C1-C10 alkylene, C6-C20 arylene, C6-C20 heterocyclylene, and C3-C15 cycloalkylene.
5. An ethylene selective oligomerization catalyst, which is characterized by comprising a main catalyst and a cocatalyst; the main catalyst comprises the modified PNP catalyst ligand and the organic chromium compound prepared by the preparation method of any one of claims 1-4.
6. The catalyst according to claim 5, wherein the organic chromium compound is chromium acetylacetonate or chromium tetrahydrofuran trichloride;
The cocatalyst is selected from one or more of MAO, MMAO, methyl lithium, ethyl lithium, propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, amyl lithium, hexyl lithium, cyclohexyl lithium, tert-octyl lithium or triethyl aluminum;
the molar ratio of the cocatalyst to the main catalyst was 500, and the molar concentration of Cr in the main catalyst was 2. Mu. Mol/mL.
7. A process for the selective oligomerization of ethylene comprising the steps of:
The ethylene selective oligomerization catalyst according to any one of claims 5 to 6 is obtained by oligomerization of ethylene in the presence of hydrogen.
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JP2006511625A (en) * 2002-12-20 2006-04-06 サソル テクノロジー （ピーティーワイ） リミテッド Tetramerization of olefins
CN112742480A (en) * 2020-12-07 2021-05-04 山东京博石油化工有限公司 Preparation method of catalyst for synthesizing 1-octene through ethylene selective oligomerization
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