CN114315905B - Preparation of PCPN ligand, ethylene oligomerization catalyst and application thereof - Google Patents
Preparation of PCPN ligand, ethylene oligomerization catalyst and application thereof Download PDFInfo
- Publication number
- CN114315905B CN114315905B CN202111620520.9A CN202111620520A CN114315905B CN 114315905 B CN114315905 B CN 114315905B CN 202111620520 A CN202111620520 A CN 202111620520A CN 114315905 B CN114315905 B CN 114315905B
- Authority
- CN
- China
- Prior art keywords
- ligand
- reaction
- group
- catalyst
- pcpn
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a PCPN ligand, an ethylene oligomerization catalyst and application thereof, wherein the catalyst comprises the PCPN ligand shown in a structure of a formula I, a transition metal compound and an alkyl aluminum cocatalyst. The catalyst system can catalyze ethylene oligomerization with high activity, has high catalytic activity, high selectivity and low polymer content, and can effectively prevent reactor blockage.
Description
Technical Field
The invention belongs to the technical field of ethylene oligomerization, and particularly relates to preparation of a PCPN ligand, an ethylene oligomerization catalyst and application thereof.
Background
The linear alpha-olefin is an important chemical raw material and can be used in various fields such as polyolefin comonomer, PVC plasticizer, surfactant, lubricating oil additive and the like. Wherein the comonomer accounts for more than half of the consumption of alpha-olefin, the polyolefin products of 1-octene and 1-hexene have good mechanical property and excellent processability, and have great demands in industrial production.
The process of alpha-olefin mainly comprises a selective oligomerization process and a non-selective oligomerization process. The selectivity of 1-hexene of 1-octene in ethylene nonselective oligomerization process is between 10% and 20%, the conversion rate of the process for preparing 1-octene and 1-hexene is very low, and tens of various byproducts are existed, so that the process is difficult to use.
The selectivity of the selective oligomerization process 1-octene and 1-hexene accounts for more than 90% of the total products, and the selectivity is good, the conversion rate is high, and the method is suitable for industrial production. The common catalysts for selective oligomerization are chromium-based catalyst systems, respectively PCCP systems and PNP systems. The PCCP system has polymerization activity after complexing metal chromium, so that the preparation process is complex, and after complexing, the PCCP-Cr metal complex is insoluble in conventional polymerization solvents, such as saturated alkane, isoper-E, toluene and the like, and the problems of complex feeding system, difficult quantification, difficult guarantee of catalyst uniformity and the like exist.
Thus, after the first PNP framework was proposed by Sasol corporation in 2004, this framework has been the focus of research for the selective oligomerization of ethylene. The system has the advantages that the total selectivity of 1-octene and 1-hexene is more than 90%, and the prior complexation is not needed before use.
Although studied for more than ten years, the selectivity of 1-octene and 1-hexene has not been greatly improved, and especially the problem of polymers has not been solved properly. One of the main problems faced by the selective oligomerization industrialization is the problem of blockage caused by hanging wall hanging kettles of the byproduct polymer. Once the reaction kettle is blocked, continuous reaction is affected, shutdown cleaning is carried out, product quality and economy of the device are affected, and even the pipeline is blocked, so that larger device risks are caused.
Patent CN104961618A discloses a method of adding phenols as polyethylene inhibitors to reduce the formation of polymers, but other problems with the purification of the later products are also caused by the addition of phenols affecting the activity of the catalyst. Patent CN102850168A describes a method for coating polytetrafluoroethylene inside a kettle, which reduces the wall built-up phenomenon of polyethylene and reduces the problem of polymer blockage. However, the method does not substantially reduce the generation of polymer, and the problems of polymer wall built-up blocking and the like still exist at the corner or other positions of the pipeline.
Therefore, from various technical documents disclosed at present, no proposal is made for reducing the generation of polymer in the aspect of catalyst design without affecting the activity of the catalyst, and solving the problems of polymer wall built-up and reactor blockage.
Disclosure of Invention
The invention aims to provide a preparation method of a PCPN ligand, an ethylene oligomerization catalyst and application thereof in ethylene oligomerization reaction. The catalyst of the invention improves the selectivity of 1-hexene and 1-octene in the oligomerization reaction process of ethylene, has lower polymer yield and good catalytic activity, and is not easy to block equipment.
The invention provides a PCPN ligand, the structure of which is shown as a formula I:
wherein R is 2 Independently selected from aryl and derivatives thereof, preferably R 2 Selected from phenyl, benzyl, biphenyl, naphthyl, anthracenyl, 2-methylphenyl, 4-methylphenyl, 2, 4-dimethylphenyl, 2, 6-dimethylphenyl, 2-ethylphenyl, 4-ethylphenyl, 2, 4-diethylphenyl, 2, 6-diethylphenyl, 2-isopropylphenyl, 4-isopropylphenyl, 2, 4-diisopropylphenyl, 2, 6-diisopropylphenyl, 2-butylphenyl, 4-butylphenyl, 2, 4-dibutylphenyl, 2, 6-dibutylphenyl, 4-methoxyphenyl, o-methoxyphenyl, 4-ethoxyphenyl, o-ethoxyphenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2- (trimethylsilyl) phenyl, 3- (trimethylsilyl) phenyl, 4- (trimethylsilyl) phenyl, 2- (tri-n-butylsilyl) phenyl, 3- (tri-n-butylsilyl) phenyl, 4- (tri-n-butylsilyl) phenyl.
R 1 Independently selected from alkyl, aryl, and derivatives thereof; preferably methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, ethenyl, propenyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, anthracenyl or biphenyl, more preferablyFrom methyl, ethyl, isopropyl, n-butyl, cyclohexyl.
The invention also provides a preparation method of the ligand, which comprises the following steps:
(1) Dissolving a proper amount of compound phenylphosphine shown in formula II and methylene dichloride in a solvent A, stirring in an ice water bath, adding an alkaline solution, dropwise adding for 1-5h, reacting for 3-10h in the ice water bath after dropwise adding, adding water for quenching reaction, and purifying the reaction solution to obtain a product I, namely the hydrogen phosphine bridge ligand; the structure is shown in formula III:
(2) Dissolving a compound III and hexachloroethane in a solvent B, heating and refluxing for 24-48h, and purifying the reaction liquid to obtain a product II, namely the chlorophosphine bridge ligand, wherein the structure of the chlorophosphine bridge ligand is shown as a formula IV:
(3) Under the anhydrous and anaerobic condition, dissolving a substituted amine compound shown in a formula V in a solvent A to obtain a reaction liquid I;
(4) Under the anhydrous and anaerobic condition, dissolving a chlorophosphine bridge ligand shown in a formula IV in a solvent A to obtain a reaction liquid II;
(5) And (3) dropwise adding the second reaction liquid into the first reaction liquid under stirring at the temperature of minus 78 ℃, slowly heating to room temperature after adding the catalyst, continuing to react for 36-72h under stirring, and purifying the reaction liquid to obtain a product, namely the PCPN ligand.
The compounds of the formulae II to V described in steps 1) to 5) have the following structure
Wherein R is 1 、R 2 The definition is the same as formula I.
Preferably, in the step (1), the molar ratio of the substituted phenylphosphine to the dichloromethane is 1:0.3-0.7.
Preferably, the alkaline solution is sodium hydroxide or potassium hydroxide aqueous solution, and the mass concentration of the solution is 20% -80%.
The solvent A is one or more of toluene, methylcyclohexane, acetonitrile, cyclohexane, N-hexane, dichloromethane, N-dimethylformamide and N, N-dimethylacetamide.
Preferably, in the step (2), the solvent B is selected from one or more of toluene, methylcyclohexane, acetonitrile, cyclohexane, n-hexane, diethyl ether, dioxane;
preferably, the molar ratio of the hydrogen phosphine bridge ligand to hexachloroethane is 1:1-1:5.
Preferably, in the step (5), the molar ratio of the substituted amine in the first reaction solution to the chlorophosphine bridge ligand in the second reaction solution is 1:0.7-2.
Preferably, in the step (5), the catalyst is selected from triethylamine, N, N-dimethylaniline, diisopropylethylamine and 4-dimethylaminopyridine. The molar ratio of the catalyst to the chlorophosphine bridge ligand shown in the formula IV is 1:5-1:20.
The purification treatment comprises the steps of carrying out column chromatography purification on the reaction liquid to obtain a target product and carrying out recrystallization on the target product, wherein the height-diameter ratio of a chromatographic column used in the column chromatography purification is 5-10, the residence time is 10-60min, and the solvent used in the recrystallization is a mixed solvent of ethanol and ethyl acetate.
In another aspect, the invention also provides an ethylene oligomerization catalyst comprising a transition metal compound, a PCPN ligand of the invention, and an aluminum alkyl cocatalyst.
The transition metal compound is selected from one or more of chromium, molybdenum, cobalt, titanium, vanadium, zirconium, nickel and palladium, preferably chromium, zirconium and nickel compounds, and comprises organic salts, inorganic salts, coordination complexes or organic metal complexes of transition metals, such as one or more of chromium acetylacetonate, chromium chloride, chromium tri (tetrahydrofuran) trichloride, chromium (III) 2-ethylhexanoate, chromium (III) octoate, chromium hexacarbonyl and chromium (benzene) tricarbonyl.
The alkyl aluminum cocatalyst is one or more selected from trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, diethyl aluminum ethoxide, diethyl aluminum chloride, sesquiethyl aluminum chloride, trioctyl aluminum, methyl Aluminoxane (MAO), modified Methyl Aluminoxane (MMAO) or ethyl aluminoxane.
In the catalyst of the present invention, the molar ratio of the transition metal compound to PCPN ligand is 1:1-3, preferably 1:1-2; the molar ratio of the aluminum alkyl promoter to the transition metal compound is 50-2000:1, preferably 90-800:1.
The invention also provides application of the catalyst, which is used for ethylene oligomerization.
In some preferred embodiments of the invention, the ethylene oligomerization process is: before the reaction, the reaction kettle is heated to 110-160 ℃, vacuumized for 1-4 hours, replaced by nitrogen, cooled to room temperature, replaced by ethylene, firstly added with a solvent C and an alkyl aluminum cocatalyst, then added with a transition metal compound and a PCPN ligand, and after the temperature reaches the reaction temperature, 0-0.8Mpa hydrogen and 2-7 Mpa ethylene are sequentially introduced to start the reaction, the reaction temperature is 35-90 ℃, preferably 40-70 ℃, and the reaction time is 10-240 min, preferably 20-100 min.
The ethylene oligomerization solvent C is one or more than two selected from n-butane, isobutane, n-pentane, cyclopentane, methylcyclopentane, methylenecyclopentane, n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, n-nonane, benzene, toluene and xylene.
In a more specific embodiment, the polymerization process of the catalyst composition of the present invention is as follows: polymerization was carried out in a 300mL autoclave, and the purified alkane was used as solvent C. Before the reaction, the reaction kettle is heated to 130 ℃, vacuumized for 1-3h and replaced by nitrogen for three times. And cooling to room temperature, replacing ethylene twice, adding dehydrated and deoxidized solvent C and quantitative alkyl aluminum cocatalyst, adding transition metal compound and PCPN ligand, and introducing 0.2-0.7MPa hydrogen and 2-7 MPa ethylene in sequence to start reaction when the temperature is constant at the reaction temperature. The reaction temperature is 35-90 ℃, preferably 40-70 ℃ and the reaction time is 10-240 min, preferably 20-100 min. After the reaction is finished, closing an ethylene inlet valve, rapidly cooling by using ice water bath or liquid nitrogen, slowly decompressing, and discharging the kettle to obtain an ethylene oligomerization product.
The catalyst is added in an amount of 10 to 25. Mu. Mol/L (solvent), preferably 15 to 20. Mu. Mol/L (solvent) in the molar concentration of the transition metal compound in the ethylene oligomerization reaction system.
The effect on PNP skeleton activity is mainly focused on two aspects, namely an electronic effect on phosphine and a steric effect of substituent on N. The bond angle of PNP ligand is generally that the opening and closing of bond angle is indirectly regulated by the steric hindrance of the substituent on N, when the steric hindrance of the substituent on N is large, P on two sides is extruded to two sides, so that the bond angle of PNP is smaller, and the catalytic activity is changed.
The invention can prepare PCPN with small PNP bond angle and high catalyst activity by bridging carbon atoms and two phosphorus atoms, and experiments show that the metal catalyst prepared by the PCPN ligand can obviously reduce the generation amount of polymer in the reaction, prolong the service time of the catalyst, reduce equipment blockage and has very important significance for industrial production.
Compared with the prior art, the ethylene oligomerization catalyst system has the activity of over 1500000 g/(gCr.h) for ethylene oligomerization, the total selectivity of 1-hexene and 1-octene is 91.5%, PE selectivity is lower than 0.05wt%, compared with classical isopropyl PNP, 50% activity is improved, polymer is obviously reduced, and the total selectivity of 1-hexene and 1-octene is obviously improved.
FIG. 1 is a graph showing the polymer plugging in a reactor after 24 hours of operation in an ethylene oligomerization reaction using the method of comparative example 1.
FIG. 2 is a graph of polymer plugging in a reactor after 24 hours of operation in an ethylene oligomerization reaction using the method of example 1.
Detailed Description
The following specific examples are only illustrative of the present invention, but are merely a partial content of the present invention and are not intended to limit the application of the present invention to other fields.
The starting materials used in the examples were all conventional in the art and the purity specifications used were analytically or chemically pure.
Raw material source information:
isopropyl PNP ligand: shanghai medicine Mingkang Co Ltd
Alkoxyphosphine PCNP ligand: shanghai medicine Mingkang Co Ltd
Phenyl phosphine: 98%, carbofuran science and technology Co., ltd
Dichloromethane: 98%, shanghai Yi En chemical technology Co.Ltd
N, N-dimethylformamide: 99%, shanghai Michel chemical Co., ltd
N, N-dimethylacetamide: 99%, shanghai Michel chemical Co., ltd
Potassium hydroxide: 99.5% (GC) or more, shanghai Ala Ding Shenghua technology Co., ltd
Hexachloroethane: 99%, beijing Enoka technology Co., ltd
Diethyl ether: 99%, shanghai Ala Biochemical technology Co.Ltd
Dioxane: 99%, shanghai Ala Biochemical technology Co.Ltd
Cyclohexylmethylamine: 95%, shanghai Ala Biochemical technology Co.Ltd
1-adamantanemethylamine: 97%, shanghai Ala Biochemical technology Co.Ltd
Para-methylaniline: 98%, carbofuran science and technology Co., ltd
Phenyl phosphine: 97%, alfa Elisa (China) chemical Co., ltd
(2-methyl) phenylphosphine: 97%, shaanxi company of pharmaceutical and chemical industry Co., ltd
(2, 4, 6-tri-tert-butyl) phenylphosphine: 97%, shaanxi company of pharmaceutical and chemical industry Co., ltd
(4-methoxy) phenylphosphine: 97%, shaanxi company of pharmaceutical and chemical industry Co., ltd
(4-fluoro) phenylphosphine: 97%, shaanxi company of pharmaceutical and chemical industry Co., ltd
(2, 5-dimethyl) phenylphosphine: 97%, shaanxi company of pharmaceutical and chemical industry Co., ltd
Ethyl acetate: 99.9% >, of the technical Co.Ltd
Ethanol: analytically pure, national medicine group chemical reagent Co., ltd
The catalyst activity of oligomerization is determined qualitatively and quantitatively by analyzing each component in the reaction solution, and the GC analysis instrument is used under the following conditions:
instrument model: shimadzu GC2010
Chromatographic column: DB-5 (30 m 0.25mm 0.25 μm)
Column temperature procedure: first at 35℃for 10min, then at a rate of 10℃per minute, to 250℃for 10min.
Detector temperature: 300 DEG C
Carrier gas: 1bar
Air: 0.3bar
Gas (H2): 0.3bar
Sample mass analysis was performed using an internal standard method. Should:
wherein m1 is the mass of a certain product, m is the mass of an internal standard substance, a1 is the peak area of the product detected in the meteorological chromatograph, and a is the peak area of the internal standard substance. k is a correction factor related to the substance being tested and the detection conditions.
Example 1
Preparation of PCPN ligands: the relevant solvents were deoxygenated prior to use.
Preparation of a chlorophosphine bridge ligand: a proper amount of 150mmol of phenylphosphine and 75mmol of dichloromethane are taken and dissolved in 250ml of DMF, 520mol of potassium hydroxide aqueous solution (60 wt%) is added under stirring of ice water bath, 1.5h of dropwise addition is carried out, and after the dropwise addition is completed, the reaction is carried out under the ice water bath for 6h. Adding a proper amount of water for quenching reaction, extracting the reaction liquid by normal hexane, and obtaining the hydrogen phosphine bridge ligand through reduced pressure distillation. 100mmol of hydrogen phosphine bridge ligand and 200mmol of hexachloroethane are dissolved in 240ml of diethyl ether, reflux is carried out for 24-48h, insoluble substances are removed by filtration, and the extracted filtrate is the chlorine phosphine bridge ligand A, and the compound structure is shown as follows:
preparation of PCPN ligands: 50mmol of n-butylamine and 500mmol of triethylamine were dissolved in 180ml of dichloromethane under anhydrous and anaerobic conditions to obtain a reaction liquid I. Dropwise adding 50mmol of the chlorophosphine bridge ligand A into the reaction liquid I at the temperature of 0 ℃; after the completion of the dropwise addition, the reaction mixture was slowly warmed to room temperature and reacted under stirring for 36 hours. After the reaction is finished, filtering out a reaction clear liquid, removing a solvent under vacuum, and performing column chromatography treatment to obtain a PCPN pure product 1a, wherein the structure of the PCPN pure product is shown as the following formula:
the nuclear magnetic data of the ligand (1 a) are as follows: 1H NMR (400 MHz, CDCl 3): 7.36 to 7.48 (m, 10H), 2.65 (t, 2H), 1.55 to 1.31 (m, 8H), 0.91 (t, 3H)
Oligomerization of ethylene:
before the reaction, a 300ml reaction kettle is heated to 150 ℃, vacuumized for 3 hours and replaced by nitrogen for three times. After cooling to room temperature and two ethylene substitutions, 100ml of dehydrated and deoxygenated solvent methylcyclohexane and 1ml of MMAO-3a (7 wt% Al, n-heptane) were added, then 4.2. Mu. Mol of PCPN ligand 1a and 3.5. Mu. Mol of chromium acetylacetonate were added, and after the temperature was kept constant at 45 ℃, 0.5MPa hydrogen and 5MPa ethylene were sequentially introduced to start the reaction. The reaction temperature is 45 ℃ and the reaction time is 60min. After the reaction is finished, closing an ethylene inlet valve, slowly decompressing by using an ice water bath or rapidly cooling to below 5 ℃, and discharging the kettle to obtain an ethylene oligomerization product.
The product was analyzed by GC, activity 1623kg/gCr.h, (1-hexene+1-octene) selectivity 88.6wt% and polymer selectivity 0.09wt%.
Example 2
Preparation of PCPN ligands: the relevant solvents were deoxygenated prior to use.
Preparation of a chlorophosphine bridge ligand: a proper amount of 150mmol of the temporary fluorophosphine and 50mmol of dichloromethane are taken and dissolved in 250ml of DMF, 520mol of potassium hydroxide aqueous solution (60 wt%) is added under stirring in an ice water bath, 1.5h is added dropwise, and after the dropwise addition is finished, the reaction is carried out in the ice water bath for 6h. Adding a proper amount of water for quenching reaction, extracting the reaction liquid by normal hexane, and obtaining the hydrogen phosphine bridge ligand through reduced pressure distillation. 100mmol of hydrogen phosphine bridge ligand and 100mmol of hexachloroethane are dissolved in 240ml of diethyl ether, reflux is carried out for 24-48h, insoluble substances are removed by filtration, and the extracted filtrate is the chlorophosphine bridge ligand B, and the compound structure is shown as follows:
preparation of PCPN ligands: 35mmol of isopropylamine and 500mmol of diisopropylethylamine were dissolved in 180ml of methylene chloride under anhydrous and anaerobic conditions to obtain a second reaction solution. Dropwise adding 50mmol of the chlorophosphine bridge ligand B into the reaction liquid II at the temperature of 0 ℃; after the completion of the dropwise addition, the reaction mixture was slowly warmed to room temperature and reacted under stirring for 36 hours. After the reaction is finished, filtering out a reaction clear liquid, removing a solvent under vacuum, and performing column chromatography treatment to obtain a PCPN pure product 1a, wherein the structure of the PCPN pure product is shown as the following formula:
the nuclear magnetic data of the ligand (1 b) are as follows: 1H NMR (400 MHz, CDCl 3): 7.75 to 7.22 (m, 8H), 2.97 (m, 1H), 1.4 (t, 2H), 1.07 (d, 6H)
Oligomerization of ethylene:
before the reaction, the 500ml reaction kettle is heated to 160 ℃, vacuumized for 1.5 hours and replaced by nitrogen for three times. After cooling to room temperature and two ethylene substitutions, 200ml of dehydrated and deoxygenated solvent methylcyclohexane and 1.4ml (Al/cr=600) MMAO-3a (7 wt% Al, n-heptane) were added, then 4.8 μmol PCPN ligand 1b and 3 μmol chromium acetylacetonate were added, and after the temperature was constant at 55 ℃, 0.4Mpa hydrogen and 4.5Mpa ethylene were sequentially introduced to start the reaction. The reaction temperature is 55 ℃ and the reaction time is 40min. After the reaction is finished, closing an ethylene inlet valve, slowly decompressing by using an ice water bath or rapidly cooling to below 5 ℃, and discharging the kettle to obtain an ethylene oligomerization product.
The product was analyzed by GC, activity 2278kg/gCr.h, (1-hexene+1-octene) selectivity 90.2wt% and polymer selectivity 0.07wt%.
Example 3
Preparation of PCPN ligands: the relevant solvents were deoxygenated prior to use.
Preparation of a chlorophosphine bridge ligand: a proper amount of 150mmol of p-methoxyphenylphosphine and 105mmol of dichloromethane are taken and dissolved in 250ml of DMF, and under stirring in an ice water bath, 520mol of potassium hydroxide aqueous solution (60 wt%) is added, dropwise added for 1.5h, and after the dropwise addition is completed, the mixture is reacted for 6h in the ice water bath. Adding a proper amount of water for quenching reaction, extracting the reaction liquid by normal hexane, and obtaining the hydrogen phosphine bridge ligand through reduced pressure distillation. 100mmol of hydrogen phosphine bridge ligand and 300mmol of hexachloroethane are dissolved in 240ml of diethyl ether, reflux is carried out for 24-48h, insoluble substances are removed by filtration, and the extracted filtrate is the chlorine phosphine bridge ligand C, and the compound structure is shown as follows:
preparation of PCPN ligands: 50mmol of methylcyclohexylamine and 250mmol of triethylamine were dissolved in 180ml of methylene chloride under anhydrous and anaerobic conditions to obtain a second reaction solution. Dropwise adding 50mmol of the chlorophosphine bridge ligand C into the reaction liquid II at the temperature of 0 ℃; after the completion of the dropwise addition, the reaction mixture was slowly warmed to room temperature and reacted under stirring for 36 hours. After the reaction is finished, filtering out a reaction clear liquid, removing a solvent under vacuum, and performing column chromatography treatment to obtain a PCPN pure product 1c, wherein the structure of the PCPN pure product is shown as the following formula:
the nuclear magnetic data of the ligand (1 c) are as follows: 1H NMR (400 MHz, CDCl 3): 7.27-6.99 (m, 4H), 3.83 (s, 6H), 2.61 (d, 2H), 1.4 (t, 2H), 1.67-1.27 (m, 15H), ethylene oligomerization:
before the reaction, 500ml of the reaction kettle is heated to 120 ℃, vacuumized for 2 hours and replaced by nitrogen for three times. After cooling to room temperature, the ethylene was displaced twice, 200ml of dehydrated and deoxygenated solvent toluene and 0.93ml of (Al/cr=400) MAO (10 wt% toluene) were added, then 4.2. Mu. Mol of PCPN ligand 1c and 3.5. Mu. Mol of chromium acetylacetonate were added, and after the temperature was constant at 60 ℃, 0.3Mpa of hydrogen and 4.5Mpa of ethylene were sequentially introduced to start the reaction. The reaction temperature is 60 ℃ and the reaction time is 45min. After the reaction is finished, closing an ethylene inlet valve, slowly decompressing by using an ice water bath or rapidly cooling to below 5 ℃, and discharging the kettle to obtain an ethylene oligomerization product.
The product was analyzed by GC and had an activity of 1551kg/gCr.h, (1-hexene+1-octene) selectivity 91.5wt% and polymer selectivity 0.05wt%.
Example 4
Preparation of PCPN ligands: the relevant solvents were deoxygenated prior to use.
Preparation of a chlorophosphine bridge ligand: a proper amount of 150mmol of phenylphosphine and 75mmol of dichloromethane are taken and dissolved in 250ml of N, N-dimethylacetamide, 520mol of potassium hydroxide aqueous solution (60 wt%) is added under stirring in an ice water bath, 1.5h is added dropwise, and after the dropwise addition is finished, the reaction is carried out in the ice water bath for 6h. Adding a proper amount of water for quenching reaction, extracting the reaction liquid by normal hexane, and obtaining the hydrogen phosphine bridge ligand through reduced pressure distillation. 100mmol of hydrogen phosphine bridge ligand and 100mmol of hexachloroethane are dissolved in 240ml of dioxane, reflux is carried out for 24-48h, insoluble substances are removed by filtration, and the extracted filtrate is the chlorophosphine bridge ligand A, and the compound structure is shown as follows:
preparation of PCPN ligands: 100mmol of p-methylaniline and 500mmol of 4-dimethylaminopyridine were dissolved in 180ml of methylene chloride under anhydrous and anaerobic conditions to obtain a second reaction solution. Dropwise adding 50mmol of the chlorophosphine bridge ligand A into the reaction liquid II at the temperature of 0 ℃; after the completion of the dropwise addition, the reaction mixture was slowly warmed to room temperature and reacted under stirring for 36 hours. After the reaction is finished, filtering out a reaction clear liquid, removing a solvent under vacuum, and performing column chromatography treatment to obtain a PCPN pure product 1d, wherein the structure of the PCPN pure product is shown as the following formula:
the nuclear magnetic data of the ligand (1 d) are as follows: 1H NMR (400 MHz, CDCl 3): 7.45-7.38 (m, 10H), 6.98 (d, 2H), 6.51 (d, 2H), 2.34 (s, 3H), 1.4 (t, 2H)
Oligomerization of ethylene:
before the reaction, the 500ml reaction kettle is heated to 160 ℃, vacuumized for 2.5 hours and replaced by nitrogen three times. After cooling to room temperature and two ethylene substitutions, 200ml of dehydrated and deoxygenated solvent toluene and 1.2ml (Al/cr=600) of MMAO (7 wt% Al, n-heptane) were added, then 4.2 μmol of PCPN ligand L4 and 4 μmol of chromium acetylacetonate were added, and after the temperature was constant at 45 ℃, 0.5Mpa hydrogen and 4.5Mpa ethylene were sequentially introduced to start the reaction. The reaction temperature is 45 ℃ and the reaction time is 25min. After the reaction is finished, closing an ethylene inlet valve, slowly decompressing by using an ice water bath or rapidly cooling to below 5 ℃, and discharging the kettle to obtain an ethylene oligomerization product.
The product was analyzed by GC and had an activity of 1977kg/gCr.h, (1-hexene+1-octene) selectivity 89.8wt% and a polymer selectivity 0.08wt%.
Example 5
Preparation of PCPN ligands: the relevant solvents were deoxygenated prior to use.
The PCPN ligand was prepared in the same manner as in example 1.
Oligomerization of ethylene:
before the reaction, 500ml of the reaction kettle is heated to 120 ℃, vacuumized for 4 hours and replaced by nitrogen for three times. After cooling to room temperature and two ethylene substitutions, 200ml of dehydrated and deoxygenated solvent cyclohexane and 0.18ml of MMAO (7 wt% Al, n-heptane) (Al/Cr=90) were added, 3.5. Mu. Mol of the PCPN ligand prepared in this example and 3.5. Mu. Mol of chromium acetylacetonate were then added, and the reaction was started by introducing 0.5MPa of hydrogen and 4.5MPa of ethylene in this order until the temperature was constant at 55 ℃. The reaction temperature is 55 ℃ and the reaction time is 50min. After the reaction is finished, closing an ethylene inlet valve, slowly decompressing by using an ice water bath or rapidly cooling to below 5 ℃, and discharging the kettle to obtain an ethylene oligomerization product.
The product was analyzed by GC and had an activity of 1152kg/gCr.h, a (1-hexene+1-octene) selectivity of 88.8wt% and a polymer selectivity of 0.07wt%.
Example 6
Preparation of PCPN ligands: the relevant solvents were deoxygenated prior to use.
Preparation of a chlorophosphine bridge ligand: a proper amount of 150mmol of m-methylphenyl phosphine and 90mmol of dichloromethane are taken and dissolved in 250ml of acetonitrile, 520mol of potassium hydroxide aqueous solution (60 wt%) is added under stirring of an ice water bath, 1.5h of dropwise addition is carried out, and after the dropwise addition is finished, the reaction is carried out under the ice water bath for 6h. Adding a proper amount of water for quenching reaction, extracting the reaction liquid by normal hexane, and obtaining the hydrogen phosphine bridge ligand through reduced pressure distillation. 100mmol of hydrogen phosphine bridge ligand and 100mmol of hexachloroethane are dissolved in 240ml of n-hexane, the mixture is refluxed for 24 to 48 hours, insoluble matters are removed by filtration, and the filtrate is pumped to obtain the chlorophosphine bridge ligand D, and the compound structure is shown as follows:
preparation of PCPN ligands: 65mmol of isopropylamine and 500mmol of triethylamine were dissolved in 180ml of methylene chloride under anhydrous and anaerobic conditions to obtain a second reaction solution. Dropwise adding 50mmol of the chlorophosphine bridge ligand D into the reaction liquid II at the temperature of 0 ℃; after the completion of the dropwise addition, the reaction mixture was slowly warmed to room temperature and reacted under stirring for 36 hours. After the reaction is finished, filtering out a reaction clear liquid, removing a solvent under vacuum, and performing column chromatography treatment to obtain a PCPN pure product 1f, wherein the structure of the PCPN pure product is shown as the following formula:
the nuclear magnetic data of the ligand (1 f) are as follows: 1H NMR (400 MHz, CDCl 3): 1H NMR (400 MHz, CDCl 3): 7.33 to 7.26 (m, 8H), 2.97 (m, 1H), 2.34 (s, 6H) 1.41 (m, 2H), 1.07 (d, 6H)
Oligomerization of ethylene:
before the reaction, 500ml of the reaction kettle is heated to 120 ℃, vacuumized for 5 hours and replaced by nitrogen for three times. After cooling to room temperature and two ethylene substitutions, 200ml of dehydrated and deoxygenated solvent methylcyclohexane and 1.8ml of MMAO (7 wt% Al, n-heptane) (Al/Cr=900) were added, then 4.2. Mu. Mol of phosphine bridge ligand 1f and 3.5. Mu. Mol of chromium acetylacetonate were added, and after the temperature was kept constant at 60 ℃, 0.5MPa hydrogen and 4.5MPa ethylene were introduced in sequence to start the reaction. The reaction temperature is 60 ℃ and the reaction time is 20min. After the reaction is finished, closing an ethylene inlet valve, slowly decompressing by using an ice water bath or rapidly cooling to below 5 ℃, and discharging the kettle to obtain an ethylene oligomerization product.
The product was analyzed by GC and had an activity of 1833kg/gCr.h, (1-hexene+1-octene) selectivity of 89.7wt% and a polymer selectivity of 0.11wt%.
Example 7
Preparation of PCPN ligands: the relevant solvents were deoxygenated prior to use.
Preparation of a chlorophosphine bridge ligand: a proper amount of 150mmol of the temporary fluorophosphine and 50mmol of dichloromethane are taken and dissolved in 250ml of DMF, 520mol of potassium hydroxide aqueous solution (60 wt%) is added under stirring in an ice water bath, 1.5h is added dropwise, and after the dropwise addition is finished, the reaction is carried out in the ice water bath for 6h. Adding a proper amount of water for quenching reaction, extracting the reaction liquid by normal hexane, and obtaining the hydrogen phosphine bridge ligand through reduced pressure distillation. 100mmol of hydrogen phosphine bridge ligand and 100mmol of hexachloroethane are dissolved in 240ml of methylcyclohexane, reflux is carried out for 24-48h, insoluble substances are removed by filtration, and the extracted filtrate is the chlorophosphine bridge ligand B, and the compound structure is shown as follows:
preparation of PCPN ligands: 50mmol of n-butylamine and 500mmol of diisopropylethylamine were dissolved in 180ml of dichloromethane under anhydrous and anaerobic conditions to obtain a second reaction liquid. Dropwise adding 50mmol of the chlorophosphine bridge ligand B into the reaction liquid II at the temperature of 0 ℃; after the completion of the dropwise addition, the reaction mixture was slowly warmed to room temperature and reacted under stirring for 36 hours. After the reaction is finished, filtering out a reaction clear liquid, removing a solvent under vacuum, and carrying out column chromatography treatment to obtain 1g of PCPN pure product, wherein the structure of the PCPN pure product is shown as the following formula:
the nuclear magnetic data of the ligand (1 g) are as follows: 1H NMR (400 MHz, CDCl 3): :7.76-7.22 (m, 8H), 2.65 (t, 2H), 1.55-1.31 (m, 6H), 0.90 (t, 3H)
Oligomerization of ethylene:
before the reaction, the 500ml reaction kettle is heated to 125 ℃, vacuumized for 3.5 hours and replaced by nitrogen three times. After cooling to room temperature and two ethylene substitutions, 200ml of dehydrated and deoxygenated solvent methylcyclohexane and 1.2ml of (Al/cr=600) MMAO (7 wt% Al, n-heptane) were added, then 7 μmol of phosphine bridge ligand 1g and 3.5 μmol of chromium acetylacetonate were added, and after the temperature was constant at 55 ℃, 0.5Mpa hydrogen and 4.5Mpa ethylene were sequentially introduced to start the reaction. The reaction temperature is 55 ℃ and the reaction time is 60min. After the reaction is finished, closing an ethylene inlet valve, slowly decompressing by using an ice water bath or rapidly cooling to below 5 ℃, and discharging the kettle to obtain an ethylene oligomerization product.
The product was analyzed by GC and had an activity of 2170kg/gCr.h, a (1-hexene+1-octene) selectivity of 88.9wt% and a polymer selectivity of 0.13wt%.
Example 8
Preparation of PCPN ligands: the relevant solvents were deoxygenated prior to use.
Preparation of a chlorophosphine bridge ligand: a proper amount of 150mmol of p-methoxyphenylphosphine and 105mmol of dichloromethane are taken and dissolved in 250ml of methylcyclohexane, 520mol of potassium hydroxide aqueous solution (60 wt%) is added under stirring in an ice water bath, 1.5h of dropwise addition is carried out, and after the dropwise addition is completed, the reaction is carried out in the ice water bath for 6h. Adding a proper amount of water for quenching reaction, extracting the reaction liquid by normal hexane, and obtaining the hydrogen phosphine bridge ligand through reduced pressure distillation. 100mmol of hydrogen phosphine bridge ligand and 500mmol of hexachloroethane are dissolved in 240ml of diethyl ether, reflux is carried out for 24-48h, insoluble substances are removed by filtration, and the extracted filtrate is the chlorine phosphine bridge ligand C, and the compound structure is shown as follows:
preparation of PCPN ligands: 75mmol of n-butylamine and 750mmol of N, N-dimethylaniline were dissolved in 180ml of methylene chloride under anhydrous and anaerobic conditions to obtain a second reaction liquid. Dropwise adding 50mmol of the chlorophosphine bridge ligand C into the reaction liquid II at the temperature of 0 ℃; after the completion of the dropwise addition, the reaction mixture was slowly warmed to room temperature and reacted under stirring for 36 hours. After the reaction is finished, filtering out a reaction clear liquid, removing a solvent under vacuum, and performing column chromatography treatment to obtain a PCPN pure product for 1h, wherein the structure of the PCPN pure product is shown as the following formula:
the nuclear magnetic data of the ligand (1 h) are as follows: 1H NMR (400 MHz, CDCl 3): 7.27 (d, 2H), 6.99 (d, 2H), 2.65 (t, 2H), 1.55 to 1.31 (m, 6H), 0.90 (t, 3H)
Oligomerization of ethylene:
before the reaction, 500ml of the reaction kettle is heated to 155 ℃, vacuumized for 2 hours and replaced by nitrogen for three times. After cooling to room temperature and two ethylene substitutions, 200ml of dehydrated and deoxygenated solvent methylcyclohexane and 1.2ml of MMAO (7 wt% Al, n-heptane) (Al/Cr=500) were added, then 5.3. Mu. Mol of phosphine bridge ligand 1h and 3.5. Mu. Mol of chromium acetylacetonate were added, and after the temperature was constant at 50 ℃, 0.5MPa hydrogen and 4.5MPa ethylene were introduced in sequence to start the reaction. The reaction temperature is 50 ℃ and the reaction time is 60min. After the reaction is finished, closing an ethylene inlet valve, slowly decompressing by using an ice water bath or rapidly cooling to below 5 ℃, and discharging the kettle to obtain an ethylene oligomerization product.
The product was analyzed by GC and had an activity of 1933kg/gCr.h, (1-hexene+1-octene) selectivity of 89.1wt% and a polymer selectivity of 0.09wt%.
Example 9
Preparation of PCPN ligands: the relevant solvents were deoxygenated prior to use.
Preparation of a chlorophosphine bridge ligand: a proper amount of 150mmol of the temporary fluorophosphine and 75mmol of dichloromethane are taken and dissolved in 250ml of DMF, 520mol of potassium hydroxide aqueous solution (60 wt%) is added under stirring in an ice water bath, 1.5h is added dropwise, and after the dropwise addition is finished, the reaction is carried out in the ice water bath for 6h. Adding a proper amount of water for quenching reaction, extracting the reaction liquid by normal hexane, and obtaining the hydrogen phosphine bridge ligand through reduced pressure distillation. 100mmol of hydrogen phosphine bridge ligand and 100mmol of hexachloroethane are dissolved in 240ml of acetonitrile, reflux is carried out for 24-48h, insoluble substances are removed by filtration, and the extracted filtrate is the chlorophosphine bridge ligand B, and the compound structure is shown as follows:
preparation of PCPN ligands: 50mmol of isopropylamine and 500mmol of triethylamine were dissolved in 180ml of methylene chloride under anhydrous and anaerobic conditions to obtain a second reaction solution. Dropwise adding 50mmol of the chlorophosphine bridge ligand B into the reaction liquid II at the temperature of 0 ℃; after the completion of the dropwise addition, the reaction mixture was slowly warmed to room temperature and reacted under stirring for 36 hours. After the reaction is finished, filtering out a reaction clear liquid, removing a solvent under vacuum, and performing column chromatography treatment to obtain a PCPN pure product 1i, wherein the structure of the PCPN pure product is shown as the following formula:
the nuclear magnetic data of the ligand (1 i) are as follows: 1H NMR (400 MHz, CDCl 3): 7.75-7.22 (m, 8H), 2.97 (m, 1H), 1.41 (t, 2H), 1.07 (d, 6H)
Oligomerization of ethylene:
before the reaction, the 500ml reaction kettle is heated to 160 ℃, vacuumized for 2 hours and replaced by nitrogen for three times. After cooling to room temperature and two ethylene substitutions, 200ml of dehydrated and deoxygenated solvent methylcyclohexane and 1.4ml of (Al/cr=600) MMAO (7 wt% Al, n-heptane) were added, then 4.2 μmol of phosphine bridge ligand 1i and 3.5 μmol of chromium acetylacetonate were added, and after the temperature was kept at 53 ℃, 0.5Mpa hydrogen and 4.5Mpa ethylene were introduced in sequence to start the reaction. The reaction temperature was 53℃and the reaction time was 60min. After the reaction is finished, closing an ethylene inlet valve, slowly decompressing by using an ice water bath or rapidly cooling to below 5 ℃, and discharging the kettle to obtain an ethylene oligomerization product.
The product was analyzed by GC and had an activity of 1362kg/gCr.h, a (1-hexene+1-octene) selectivity of 88.5wt% and a polymer selectivity of 0.06wt%.
Comparative example 1
Preparation of isopropyl PNP ligand: purity from Shanghai Mingkang Co., ltd.): LC >98%
Oligomerization of ethylene:
before the reaction, the 500ml reaction kettle is heated to 160 ℃, vacuumized for 2 hours and replaced by nitrogen for three times. After cooling to room temperature and two ethylene substitutions, 200ml of dehydrated and deoxygenated solvent methylcyclohexane and 1.4ml of (Al/cr=600) MMAO (7 wt% Al, n-heptane) were added, then 4.2 μmol of phosphine bridge ligand 1j and 3.5 μmol of chromium acetylacetonate were added, and after the temperature was kept at 53 ℃, 0.5Mpa hydrogen and 4.5Mpa ethylene were introduced in sequence to start the reaction. The reaction temperature was 53℃and the reaction time was 60min. After the reaction is finished, closing an ethylene inlet valve, slowly decompressing by using an ice water bath or rapidly cooling to below 5 ℃, and discharging the kettle to obtain an ethylene oligomerization product.
The product was analyzed by GC for activity 732kg/gCr.h, (1-hexene+1-octene) selectivity 71.2wt% and polymer selectivity 2.16wt%.
Comparative example 2
Preparation of alkoxyphosphine PCNP ligand: purity from Shanghai Mingkang Co., ltd.): LC >98%
Oligomerization of ethylene:
before the reaction, the 500ml reaction kettle is heated to 160 ℃, vacuumized for 2 hours and replaced by nitrogen for three times. After cooling to room temperature and two ethylene substitutions, 200ml of dehydrated and deoxygenated solvent methylcyclohexane and 1.4ml of (Al/cr=600) MMAO (7 wt% Al, n-heptane) were added, then 4.2 μmol of phosphine bridge ligand 1k and 3.5 μmol of chromium acetylacetonate were added, and after the temperature was kept at 53 ℃, 0.5Mpa hydrogen and 4.5Mpa ethylene were introduced in sequence to start the reaction. The reaction temperature was 53℃and the reaction time was 60min. After the reaction is finished, closing an ethylene inlet valve, using an ice water bath or rapidly cooling to below 5 ℃, slowly decompressing, and discharging the kettle to obtain the product.
The product was analyzed by GC, activity 0.3kg/gCr.h, (1-hexene+1-octene) selectivity 0.02wt% and polymer selectivity 0.1wt%. No ethylene oligomerization activity.
Claims (19)
1. A PCPN ligand, having the structure of formula I:
wherein R is 2 Selected from phenyl, benzyl, biphenyl, naphthyl, anthracenyl, 2-methylphenyl, 4-methylphenyl, 2, 4-dimethylphenyl, 2, 6-dimethylphenyl, 2-ethylbenzeneA group, 4-ethylphenyl group, 2, 4-diethylphenyl group, 2, 6-diethylphenyl group, 2-isopropylphenyl group, 4-isopropylphenyl group, 2, 4-diisopropylphenyl group, 2, 6-diisopropylphenyl group, 2-butylphenyl group, 4-butylphenyl group, 2, 4-dibutylphenyl group, 2, 6-dibutylphenyl group, 4-methoxyphenyl group, o-methoxyphenyl group, 4-ethoxyphenyl group, o-ethoxyphenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group;
R 1 selected from methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, ethenyl, propenyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, anthracenyl or biphenyl.
2. The ligand of claim 1, wherein R 1 Selected from methyl, ethyl, isopropyl, n-butyl, and cyclohexyl.
3. A method of preparing a ligand according to claim 1, comprising the steps of:
(1) Dissolving a proper amount of compound phenylphosphine shown in formula II and methylene dichloride in a solvent A, stirring in an ice water bath, adding an alkaline solution, dropwise adding for 1-5h, reacting for 3-10h in the ice water bath after dropwise adding, adding water for quenching reaction, and purifying the reaction solution to obtain a product I, namely the hydrogen phosphine bridge ligand; the structure is shown in formula III:
(2) Dissolving a compound III and hexachloroethane in a solvent B, heating and refluxing for 24-48h, and purifying the reaction liquid to obtain a product II, namely the chlorophosphine bridge ligand, wherein the structure of the chlorophosphine bridge ligand is shown as a formula IV:
(3) Under the anhydrous and anaerobic condition, dissolving a substituted amine compound shown in a formula V in a solvent A to obtain a reaction liquid I;
(4) Under the anhydrous and anaerobic condition, dissolving a chlorophosphine bridge ligand shown in a formula IV in a solvent A to obtain a reaction liquid II;
(5) Dropwise adding a second reaction solution into the first reaction solution under stirring at the temperature of minus 78 ℃, slowly heating to room temperature after adding a catalyst, continuing to react for 36-72h under stirring, and purifying the reaction solution to obtain a product, namely the PCPN ligand;
the compounds of the formulae II to V described in steps 1) to 5) have the following structure
Wherein R is 1 、R 2 The definition is the same as that of formula I;
the solvent A is one or more of toluene, methylcyclohexane, acetonitrile, cyclohexane, N-hexane, dichloromethane, N-dimethylformamide and N, N-dimethylacetamide;
in the step (2), the solvent B is selected from one or more of toluene, methylcyclohexane, acetonitrile, cyclohexane, n-hexane, diethyl ether and dioxane.
4. The process according to claim 3, wherein in the step (1), the molar ratio of the substituted phenylphosphine to the dichloromethane is 1:0.3-0.7.
5. A method according to claim 3, wherein the alkaline solution is an aqueous solution of sodium hydroxide or potassium hydroxide, and the mass concentration of the solution is 20% -80%.
6. A process according to claim 3, wherein the molar ratio of hydrogen phosphine bridge ligand to hexachloroethane is from 1:1 to 1:5.
7. The process according to claim 3, wherein in the step (5), the molar ratio of the substituted amine in the first reaction solution to the chlorophosphine bridge ligand in the second reaction solution is 1:0.7-2.
8. The process according to claim 3, wherein in the step (5), the catalyst is selected from the group consisting of triethylamine, N, N-dimethylaniline, diisopropylethylamine and 4-dimethylaminopyridine.
9. The process according to claim 8, wherein the molar ratio of catalyst to chlorophosphine bridge ligand of formula IV is from 1:5 to 1:20.
10. An ethylene oligomerization catalyst comprising a transition metal compound and a ligand according to claim 1 or 2 or a PCPN ligand prepared by the method of any one of claims 3-9 and an aluminum alkyl cocatalyst;
the transition metal compound is one or more than two of chromium, molybdenum, cobalt, titanium, vanadium, zirconium, nickel and palladium compounds.
11. The catalyst of claim 10 wherein the transition metal compound is selected from the group consisting of chromium, zirconium and nickel compounds.
12. The catalyst according to claim 10, wherein the alkyl aluminum cocatalyst is selected from one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum ethoxide, diethylaluminum chloride, diethylaluminum dichloride, aluminum sesquioxide, trioctylaluminum, methylaluminoxane, modified methylaluminoxane, and ethylaluminoxane.
13. The catalyst of claim 10, wherein the molar ratio of transition metal compound to PCPN ligand is 1:1-3.
14. The catalyst of claim 13, wherein the molar ratio of transition metal compound to PCPN ligand is 1:1-2.
15. The catalyst of claim 10 wherein the molar ratio of alkyl aluminum cocatalyst to transition metal compound is from 50 to 2000:1.
16. The catalyst of claim 15 wherein the molar ratio of alkyl aluminum cocatalyst to transition metal compound is from 90 to 800:1.
17. Use of a catalyst according to any one of claims 10 to 16 for the oligomerization of ethylene.
18. The use according to claim 17, wherein the catalyst is added in a molar concentration of 10 to 25 μmol/L in the oligomerization system as a transition metal compound.
19. The use according to claim 18, wherein the catalyst is added in a molar concentration of 15 to 20 μmol/L in the oligomerization system as a transition metal compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111620520.9A CN114315905B (en) | 2021-12-28 | 2021-12-28 | Preparation of PCPN ligand, ethylene oligomerization catalyst and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111620520.9A CN114315905B (en) | 2021-12-28 | 2021-12-28 | Preparation of PCPN ligand, ethylene oligomerization catalyst and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114315905A CN114315905A (en) | 2022-04-12 |
| CN114315905B true CN114315905B (en) | 2023-10-20 |
Family
ID=81015746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111620520.9A Active CN114315905B (en) | 2021-12-28 | 2021-12-28 | Preparation of PCPN ligand, ethylene oligomerization catalyst and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114315905B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114933613B (en) * | 2022-05-23 | 2024-02-27 | 万华化学集团股份有限公司 | Preparation of PNNP ligand, ethylene oligomerization catalyst and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103100420A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Catalyst composition for ethylene tetramerization and preparation method of ligand thereof |
| KR20180008269A (en) * | 2016-07-14 | 2018-01-24 | 에스케이이노베이션 주식회사 | Oligomerisation of ethylene |
| CN108031493A (en) * | 2017-12-11 | 2018-05-15 | 天津科技大学 | Catalyst system and ethylene oligomerization reaction method for ethylene selectivity oligomerisation |
| CN108097322A (en) * | 2017-12-11 | 2018-06-01 | 天津科技大学 | It is a kind of for the catalyst system of ethylene selectivity oligomerisation and ethylene oligomerization reaction method |
| 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 |
| CN113372389A (en) * | 2021-06-29 | 2021-09-10 | 万华化学集团股份有限公司 | Phosphine-nitrogen ligand, preparation method thereof, ethylene oligomerization ternary catalyst system and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101757835B1 (en) * | 2015-06-12 | 2017-07-13 | 주식회사 엘지화학 | Ligand compound, organic chromium compound, catalyst system for oligomerization of olefins and method for oligomerization of olefins using the catalyst system |
| KR102058142B1 (en) * | 2015-09-02 | 2019-12-20 | 주식회사 엘지화학 | Ligand compound, catalyst system for olefin oligomerization, and method for olefin oligomerization using the same |
-
2021
- 2021-12-28 CN CN202111620520.9A patent/CN114315905B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103100420A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Catalyst composition for ethylene tetramerization and preparation method of ligand thereof |
| KR20180008269A (en) * | 2016-07-14 | 2018-01-24 | 에스케이이노베이션 주식회사 | Oligomerisation of ethylene |
| CN108031493A (en) * | 2017-12-11 | 2018-05-15 | 天津科技大学 | Catalyst system and ethylene oligomerization reaction method for ethylene selectivity oligomerisation |
| CN108097322A (en) * | 2017-12-11 | 2018-06-01 | 天津科技大学 | It is a kind of for the catalyst system of ethylene selectivity oligomerisation and ethylene oligomerization reaction method |
| 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 |
| CN113372389A (en) * | 2021-06-29 | 2021-09-10 | 万华化学集团股份有限公司 | Phosphine-nitrogen ligand, preparation method thereof, ethylene oligomerization ternary catalyst system and application |
Non-Patent Citations (3)
| Title |
|---|
| Alkali phosphorus compounds and their reactive behavior. LXXII. 2-Organoelement 1,3-diphospholanes and -phosphorinanes. Part II;Issleib, K. 等;《Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry》;第6卷(第3期);第179-190页 * |
| Synthesis and some properties of 1,2,4-azadiphosphetidines;Novikova, Z. S. 等;《Zhurnal Obshchei Khimii》;第55卷(第2期);第331-340页 * |
| 带有PNP配体的铬系催化剂在乙烯选择性齐聚中的研究进展;刘振华 等;能源化工;第37卷(第04期);第1-10页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114315905A (en) | 2022-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111774098B (en) | Ethylene oligomerization catalyst system, preparation method and application thereof | |
| CN102432414B (en) | Low temperature ethylene oligomerization method | |
| CN114192192B (en) | Catalyst composition for ethylene oligomerization and preparation method and application thereof | |
| CN113372389B (en) | Phosphine-nitrogen ligand, preparation method thereof, ethylene oligomerization ternary catalyst system and application | |
| CN101906009A (en) | Method for preparing linear alpha-olefin | |
| CN101391979B (en) | Unsymmetrical bis(imino)pyridines iron and cobalt complexes containing halogen, preparation method and use | |
| CN114315905B (en) | Preparation of PCPN ligand, ethylene oligomerization catalyst and application thereof | |
| EP1417213B1 (en) | Method for making late transition metal catalysts for olefin polymerization | |
| CN113402554B (en) | PNSiNP ligand and preparation method thereof, ethylene oligomerization catalyst and application thereof | |
| CN114789067A (en) | Ethylene selective oligomerization catalyst composition and preparation method thereof | |
| CN111349115B (en) | PNNP structural ligand, preparation method thereof, ethylene oligomerization catalyst system and application thereof | |
| CN112916046B (en) | Three-way catalyst system and application thereof in ethylene oligomerization reaction | |
| KR20190063840A (en) | Process for preparing oligomer using olefin | |
| CN114057558A (en) | Synthetic method, catalytic system and application of 3,5, 5-trimethylhexanal | |
| CN112473738B (en) | Ethylene oligomerization catalyst system and preparation method and application thereof | |
| CN103566973A (en) | Catalyst composition for ethylene oligomerization | |
| CN111715299B (en) | Boron salt complex catalyst, preparation method and application thereof in ethylene oligomerization | |
| CN114478873B (en) | N, O-type nickel catalyst containing fluorine effect and application thereof in olefin coordination copolymerization | |
| Diether et al. | Rare-earth metal-promoted (double) C–H-bond activation of a lutidinyl-functionalized alkoxy ligand: formation of [ONC] pincer-type ligands and implications for isoprene polymerization | |
| CA2726532C (en) | Sterically encumbered bidentate and tridentate naphthoxy-imine metallic complexes | |
| CN116284125A (en) | Norbornene PCNP ligand, preparation method and application thereof | |
| CN114933613B (en) | Preparation of PNNP ligand, ethylene oligomerization catalyst and application thereof | |
| CN113101975B (en) | Multi-phosphine ligand catalyst system and application thereof in ethylene oligomerization reaction | |
| CN115672406B (en) | High-temperature-resistant ethylene tetramerization catalyst and application thereof | |
| CN118307593A (en) | Tri-dentate phosphinopyrrolimine ligand, preparation method thereof, ethylene oligomerization catalyst and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |