CN114315905A - Preparation of PCPN ligand, ethylene oligomerization catalyst and application thereof - Google Patents
Preparation of PCPN ligand, ethylene oligomerization catalyst and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a PCPN ligand, an ethylene oligomerization catalyst and an application thereof. The catalytic system can catalyze the ethylene oligomerization reaction with high activity, has high catalytic activity, high selectivity and low polymer content, and can effectively prevent the reactor from being blocked.
Description
Technical Field
The invention belongs to the technical field of ethylene oligomerization, and particularly relates to a preparation method of a PCPN ligand, an ethylene oligomerization catalyst and application thereof.
Background
Linear alpha-olefin is an important chemical raw material and can be used as polyolefin comonomer, PVC plasticizer, surfactant, lubricating oil additive and other fields. The consumption of the comonomer accounts for more than half of the consumption of the alpha-olefin, and the polyolefin product prepared from the 1-octene and the 1-hexene has good mechanical property and excellent processability, and has a large amount of demands in industrial production.
The alpha-olefin process mainly comprises a selective oligomerization process and a non-selective oligomerization process. The selectivity of 1-hexene of 1-octene in the 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 dozens of byproducts are difficult to utilize.
The selectivity of the 1-octene and 1-hexene in the selective oligomerization process accounts for more than 90 percent of the total product, and the selective oligomerization process has good selectivity and high conversion rate and is suitable for industrial production. Common catalysts for selective oligomerization are chromium-based catalyst systems, PCCP systems and PNP systems, respectively. The PCCP system has polymerization activity only after metal chromium is complexed, so that the problem of complex preparation process exists, and after the complexation, 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 also exist.
Therefore, since the first proposal of PNP framework by Sasol company in 2004, the framework has been the hot point of research on selective oligomerization of ethylene. The system has the advantages that the total selectivity of the 1-octene and the 1-hexene is more than 90 percent, and the prior complexation is not needed before use.
Although the research has been carried out for more than ten years, the selectivity of 1-octene and 1-hexene is not greatly improved, and particularly, the problem of polymer is not solved properly. One of the main problems faced by the industrialization of selective oligomerization is the blockage problem caused by hanging a wall-hung kettle with a byproduct polymer. Once the reaction kettle is blocked, the continuous reaction is influenced, the shutdown and the cleaning are carried out, the product quality and the economy of the device are influenced, and even a pipeline is blocked to cause greater risk of the device.
Patent CN104961618A discloses a method of adding phenols as polyethylene inhibitor to reduce the formation of polymer, but the addition of phenols affects the activity of the catalyst and also causes other problems in the purification of the product in the later period. Patent CN102850168A describes a method for coating polytetrafluoroethylene in a tank, which reduces the wall build-up of polyethylene and thus the polymer clogging problem. However, this method does not substantially reduce the generation of polymer, and still has the problems of polymer wall build-up and clogging at the corner of the line or other locations.
Therefore, there is no suggestion in the various technical documents disclosed so far that the problems of polymer wall-hanging and reactor clogging can be solved by reducing the polymer generation from the aspect of catalyst design without affecting the catalyst activity.
Disclosure of Invention
The invention aims to provide a preparation method of a PCPN ligand, an ethylene oligomerization catalyst and an application of the catalyst in an ethylene oligomerization reaction. The catalyst of the invention improves the selectivity of 1-hexene and 1-octene in the ethylene oligomerization reaction process, and has the advantages of lower polymer generation amount, good catalytic activity and difficult equipment blockage.
The invention provides a PCPN ligand, which has a structure shown in a formula I:
wherein R is2Independently selected from aryl and derivatives thereof, preferably, R2Selected from the group consisting of 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 group, 4- (trimethylsilyl) phenyl group, 2- (tri-n-butylsilyl) phenyl group, 3- (tri-n-butylsilyl) group) Phenyl, 4- (tri-n-butylsilyl) phenyl.
R1Independently selected from alkyl, aryl and derivatives thereof; preferably methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, vinyl, propenyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, anthracenyl or biphenyl, more preferably from 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 phenyl phosphine shown as a formula II and dichloromethane in a solvent A, adding an alkaline solution under the stirring of an ice water bath, dropwise adding for 1-5h, reacting for 3-10h under the stirring of the ice water bath, adding water to quench the reaction, and purifying the reaction solution to obtain a product I, namely the hydrogen phosphine bridge ligand; the structure is shown as formula III:
(2) dissolving a compound III and hexachloroethane in a solvent B, heating and refluxing for 24-48h, and purifying reaction liquid to obtain a product II, namely a chlorophosphine bridge ligand, wherein the structure of the product II is shown as a formula IV:
(3) dissolving a substituted amine compound shown as a formula V in a solvent A under anhydrous and anaerobic conditions to obtain a reaction solution I;
(4) dissolving a chlorophosphine bridge ligand shown in a formula IV in a solvent A under anhydrous and anaerobic conditions to obtain a reaction solution II;
(5) and (3) dropwise adding a second reaction solution into the first reaction solution under stirring at-78 ℃, slowly heating to room temperature after adding a catalyst, continuously reacting for 36-72 hours under stirring, and purifying the reaction solution to obtain a product, namely the PCPN ligand.
The structures of the compounds of formula II-formula V described in the steps 1) -5) are as follows
Wherein R is1、R2The 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 a 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 and dioxane;
preferably, the molar ratio of the hydrogen phosphine bridge ligand to hexachloroethane is from 1:1 to 1: 5.
Preferably, in the step (5), the molar ratio of the substituted amine in the first reaction solution to the chlorophosphine-bridged 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 added catalyst to the chlorophosphine bridge ligand shown in 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 for the column chromatography purification is 5-10, the retention time is 10-60min, and a solvent used for the recrystallization is a mixed solvent of ethanol and ethyl acetate.
In another aspect, the invention also provides an ethylene oligomerization catalyst, which comprises a transition metal compound, the PCPN ligand and an aluminum alkyl cocatalyst.
The transition metal compound of the present invention is one or more compounds selected from chromium, molybdenum, cobalt, titanium, vanadium, zirconium, nickel and palladium, preferably chromium, zirconium and nickel, and the transition metal compound includes organic salt, inorganic salt, coordination complex or organometallic complex of transition metal, such as one or more compounds selected from chromium acetylacetonate, chromium chloride, chromium tris (tetrahydrofuran) trichloride, chromium (III) 2-ethylhexanoate, chromium (III) octanoate, chromium hexacarbonyl and chromium (benzene) tricarbonyl.
The alkyl aluminum cocatalyst disclosed by the invention is selected from one or more than two of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethyl aluminum ethoxide, diethyl aluminum monochloride, ethyl aluminum dichloride, aluminum sesquiethyl chloride, trioctylaluminum, Methylaluminoxane (MAO), Modified Methylaluminoxane (MMAO) or ethylaluminoxane.
In the catalyst of the present invention, the molar ratio of the transition metal compound to the PCPN ligand is 1: 1-3, preferably 1: 1-2; the molar ratio of aluminum alkyl cocatalyst to transition metal compound is from 50 to 2000:1, preferably from 90 to 800: 1.
The invention also provides the application of the catalyst, which is used for ethylene oligomerization.
In some preferred embodiments of the present invention, the ethylene oligomerization process comprises: heating the reaction kettle to 160 ℃ for 110-160 ℃ before reaction, vacuumizing for 1-4h, replacing by nitrogen, cooling to room temperature, replacing ethylene, adding a solvent C and an alkyl aluminum cocatalyst, then adding a transition metal compound and a PCPN ligand, introducing 0-0.8MPa hydrogen and 2MPa-7MPa ethylene in sequence to start reaction after the temperature reaches the reaction temperature, wherein the reaction temperature is 35-90 ℃, preferably 40-70 ℃, and the reaction time is 10-240 min, preferably 20-100 min.
The ethylene oligomerization reaction solvent C is one or more than two of n-butane, isobutane, n-pentane, cyclopentane, methylcyclopentane, methylene cyclopentane, 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. Cooling to room temperature, replacing ethylene twice, adding dehydrated and deoxidized solvent C and quantitative alkyl aluminum cocatalyst, then adding transition metal compound and PCPN ligand, and introducing hydrogen of 0.2-0.7MPa and ethylene of 2MPa-7MPa sequentially 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 10min-240min, preferably 20min-100 min. After the reaction is finished, closing the ethylene inlet valve, rapidly cooling by using ice water bath or liquid nitrogen, slowly releasing pressure, and discharging the kettle to obtain an ethylene oligomerization product.
The addition amount of the catalyst is 10-25 mu mol/L (solvent) of the molar concentration of the transition metal compound in the ethylene oligomerization reaction system, and preferably 15-20 mu mol/L (solvent).
The current impact on the activity of the PNP backbone is mainly focused on two aspects, one is the electronic effect on the phosphine and the other is the steric effect of the substituent on the N. The bond angle of the PNP ligand is generally adjusted and controlled indirectly through the steric hindrance of the substituent on the N, and when the steric hindrance of the substituent on the N is large, the P on the two sides is squeezed towards the two sides, so that the PNP bond angle is reduced, and the catalytic activity is changed.
According to the invention, the carbon atom and the two phosphorus atoms are bridged, so that the PCPN with small bonding angle of PNP and high catalyst activity can be prepared, and experiments show that the metal catalyst prepared by the PCPN ligand can obviously reduce the generation amount of polymers in the reaction, prolong the service time of the catalyst and reduce the equipment blockage, and has very important significance corresponding to industrial production.
Moreover, compared with the prior art, the ethylene oligomerization catalyst system has the activity of ethylene oligomerization of more than 1500000 g/(gCr.h), most obviously, the total selectivity of 1-hexene and 1-octene can reach 91.5%, the PE selectivity is lower than 0.05 wt%, compared with the classical isopropyl PNP, the activity is improved by 50%, the polymer is obviously reduced, and the total selectivity of 1-hexene and 1-octene is obviously improved.
Description of the drawings fig. 1 is a diagram showing the polymer blockage in the reactor after 24 hours of operation in the ethylene oligomerization process carried out according to the method of comparative example 1.
FIG. 2 is a graph showing the clogging of the polymer in the reactor after 24 hours of operation in the ethylene oligomerization reaction carried out by the method of example 1.
Detailed Description
The following specific examples are merely illustrative of the present invention, but these examples are only part of the present invention and do not limit the application of the present invention in other fields.
The starting materials used in the examples are conventional in the art and the purity specifications used are either analytically or chemically pure.
Raw material source information:
isopropyl PNP ligand: shanghai drug Mingkude Ltd
Alkoxy phosphine PCNP ligand: shanghai drug Mingkude Ltd
Phenyl phosphine: 98%, Bailingwei Tech Co Ltd
Dichloromethane: 98% of Shanghai Yien chemical technology Limited
N, N-dimethylformamide: 99%, Shanghai Mirui chemical science and technology Limited
N, N-dimethylacetamide: 99%, Shanghai Mirui chemical science and technology Limited
Potassium hydroxide: not less than 99.5% (GC), Shanghai Aladdin Biotechnology Ltd
Hexachloroethane: 99%, Beijing YinuoKai science and technology Co., Ltd
Diethyl ether: 99%, Shanghai Aladdin Biotechnology Ltd
Dioxane: 99%, Shanghai Aladdin Biotechnology Ltd
Cyclohexylmethylamine: 95% Shanghai Aladdin Biotechnology Ltd
1-adamantanemethylamine: 97% Shanghai Aladdin Biotechnology Ltd
P-methylaniline: 98%, Bailingwei Tech Co Ltd
Phenyl phosphine: 97% of Alfa Angsa chemical Co Ltd
(2-methyl) phenylphosphine: 97% Shanxi Dadu pharmaceutical chemical Co Ltd
(2,4, 6-tri-tert-butyl) phenylphosphine: 97% Shanxi Dadu pharmaceutical chemical Co Ltd
(4-methoxy) phenylphosphine: 97% Shanxi Dadu pharmaceutical chemical Co Ltd
(4-fluoro) phenylphosphine: 97% Shanxi Dadu pharmaceutical chemical Co Ltd
(2, 5-dimethyl) phenylphosphine: 97% Shanxi Dadu pharmaceutical chemical Co Ltd
Ethyl acetate: 99.9%%, Bailingwei science & technology Limited
Ethanol: chemical reagent of analytical pure, national drug group Co Ltd
The activity of the catalyst for oligomerization is qualitatively and quantitatively analyzed by components in the reaction solution, and the conditions of a GC analyzer are as follows:
the instrument model is as follows: shimadzu GC2010
A chromatographic column: DB-5(30m 0.25mm 0.25 μm)
Column temperature procedure: the temperature was first maintained at 35 ℃ for 10min and then raised to 250 ℃ at a rate of 10 ℃/min, and maintained at this temperature for 10 min.
Detector temperature: 300 deg.C
Carrier gas: 1bar
Air: 0.3bar
Fuel gas (H2): 0.3bar
The sample quality analysis was performed using an internal standard method. The following should be mentioned:
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 a gas chromatogram, and a is the peak area of the internal standard substance. k is a correction factor associated with the substance to be measured and the detection condition.
Example 1
Preparation of PCPN ligand: the relevant solvent is treated with water and oxygen before use.
Preparation of a chlorophosphine bridge ligand: taking a proper amount of 150mmol of phenylphosphine and 75mmol of dichloromethane, dissolving in 250ml of DMF, adding 520mol of potassium hydroxide aqueous solution (60 wt%) while stirring in an ice-water bath, dropwise adding for 1.5h, and reacting for 6h in the ice-water bath after dropwise adding. Adding a proper amount of water to quench the reaction, extracting the reaction solution by using normal hexane, and distilling under reduced pressure to obtain the hydrogen phosphine bridge ligand. Dissolving 100mmol of hydrogen phosphine bridge ligand and 200mmol of hexachloroethane in 240ml of ether, refluxing for 24-48h, filtering to remove insoluble substances, and draining the filtrate to obtain the chlorophosphine bridge ligand A, wherein the compound structure is shown as follows:
preparation of PCPN ligand: 50mmol of n-butylamine and 500mmol of triethylamine are dissolved in 180ml of dichloromethane under anhydrous and oxygen-free conditions to obtain a reaction solution I. At 0 ℃, 50mmol of chlorophosphine bridge ligand A is dripped into the first reaction solution; after the dropwise addition, the reaction solution was slowly warmed to room temperature and stirred for reaction for 36 hours. After the reaction is finished, filtering out the reaction clear solution, removing the solvent in vacuum, and carrying out 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 above ligand (1a) are as follows: 1H NMR (400MHz, 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 reaction, a 300ml reaction kettle is heated to 150 ℃, vacuumized for 3 hours and replaced by nitrogen for three times. After the temperature is cooled to room temperature, ethylene is replaced twice, 100ml of dehydrated and deoxidized solvent methylcyclohexane and 1ml of (Al/Cr ═ 500) MMAO-3a (7 wt% Al, n-heptane) are added, then 4.2 mu mol of PCPN ligand 1a and 3.5 mu mol of chromium acetylacetonate are added, and after the temperature is kept constant at 45 ℃, 0.5Mpa hydrogen and 5MPa ethylene are sequentially introduced to start the reaction. The reaction temperature is 45 ℃ and the reaction time is 60 min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product.
The product was analyzed by GC, for an activity of 1623kg/gCr.h, a selectivity of (1-hexene + 1-octene) of 88.6 wt% and a polymer selectivity of 0.09 wt%.
Example 2
Preparation of PCPN ligand: the relevant solvent is treated with water and oxygen before use.
Preparation of a chlorophosphine bridge ligand: taking a proper amount of 150mmol of the pentafluorophenyl phosphine and 50mmol of dichloromethane, dissolving the mixture in 250ml of DMF, adding 520mol of potassium hydroxide aqueous solution (60 wt%) while stirring in an ice water bath, dropwise adding the mixture for 1.5h, and reacting for 6h in the ice water bath after the dropwise adding is finished. Adding a proper amount of water to quench the reaction, extracting the reaction solution by using normal hexane, and distilling under reduced pressure to obtain the hydrogen phosphine bridge ligand. Dissolving 100mmol of hydrogen phosphine bridge ligand and 100mmol of hexachloroethane in 240ml of ether, refluxing for 24-48h, filtering to remove insoluble substances, and draining the filtrate to obtain the chlorophosphine bridge ligand B, wherein the compound structure is shown as follows:
preparation of PCPN ligand: 35mmol of isopropylamine and 500mmol of diisopropylethylamine are dissolved in 180ml of dichloromethane under anhydrous and oxygen-free conditions to obtain reaction liquid II. At 0 ℃, 50mmol of chlorophosphine bridge ligand B is dripped into the reaction liquid II; after the dropwise addition, the reaction solution was slowly warmed to room temperature and stirred for reaction for 36 hours. After the reaction is finished, filtering out the reaction clear solution, removing the solvent in vacuum, and carrying out 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 above ligand (1b) are as follows: 1H NMR (400MHz, 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, a 500ml reaction kettle is heated to 160 ℃, vacuumized for 1.5h and replaced by nitrogen for three times. After the temperature is cooled to room temperature, ethylene is replaced twice, 200ml of dehydrated and deoxidized solvent methylcyclohexane and 1.4ml (Al/Cr ═ 600) of MMAO-3a (7 wt% Al, n-heptane) are added, then 4.8 mu mol of PCPN ligand 1b and 3 mu mol of chromium acetylacetonate are added, and after the temperature is kept constant at 55 ℃, 0.4MPa of hydrogen and 4.5MPa of ethylene are sequentially introduced to start the reaction. The reaction temperature is 55 ℃, and the reaction time is 40 min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product.
The product was analyzed by GC with an activity of 2278kg/gCr. h, a selectivity for (1-hexene + 1-octene) of 90.2 wt% and a polymer selectivity of 0.07 wt%.
Example 3
Preparation of PCPN ligand: the relevant solvent is treated with water and oxygen before use.
Preparation of a chlorophosphine bridge ligand: taking a proper amount of 150mmol of p-methoxyphenyl phosphine and 105mmol of dichloromethane, dissolving the p-methoxyphenyl phosphine and the 105mmol of dichloromethane in 250ml of DMF, adding 520mol of potassium hydroxide aqueous solution (60 wt%) while stirring in an ice water bath, dropwise adding for 1.5h, and reacting for 6h in the ice water bath after the dropwise adding is finished. Adding a proper amount of water to quench the reaction, extracting the reaction solution by using normal hexane, and distilling under reduced pressure to obtain the hydrogen phosphine bridge ligand. Dissolving 100mmol of hydrogen phosphine bridge ligand and 300mmol of hexachloroethane in 240ml of ether, refluxing for 24-48h, filtering to remove insoluble substances, and draining the filtrate to obtain the chlorophosphine bridge ligand C, wherein the compound structure is shown as follows:
preparation of PCPN ligand: and under the anhydrous and oxygen-free conditions, dissolving 50mmol of methylcyclohexylamine and 250mmol of triethylamine in 180ml of dichloromethane to obtain a reaction solution II. At 0 ℃, 50mmol of chlorophosphine bridge ligand C is dripped into the reaction liquid II; after the dropwise addition, the reaction solution was slowly warmed to room temperature and stirred for reaction for 36 hours. After the reaction is finished, filtering out the reaction clear solution, removing the solvent in 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 above ligand (1c) are as follows: 1H NMR (400MHz, 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 reaction, a 500ml 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 replaced twice, 200ml of toluene as a dehydrated deoxygenated solvent 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 the reaction was started by passing 0.3MPa of hydrogen and 4.5MPa of ethylene in succession at a constant temperature of 60 ℃. The reaction temperature is 60 ℃, and the reaction time is 45 min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product.
The product was analyzed by GC, activity 1551kg/gCr. h, (1-hexene + 1-octene) selectivity 91.5 wt%, polymer selectivity 0.05 wt%.
Example 4
Preparation of PCPN ligand: the relevant solvent is treated with water and oxygen before use.
Preparation of a chlorophosphine bridge ligand: taking a proper amount of 150mmol of phenylphosphine and 75mmol of dichloromethane, dissolving the phenylphosphine and the dichloromethane in 250ml of N, N-dimethylacetamide, adding 520mol of potassium hydroxide aqueous solution (60 wt%) while stirring in an ice-water bath, dropwise adding the mixture for 1.5h, and reacting for 6h in the ice-water bath after the dropwise adding is finished. Adding a proper amount of water to quench the reaction, extracting the reaction solution by using normal hexane, and distilling under reduced pressure to obtain the hydrogen phosphine bridge ligand. Dissolving 100mmol of hydrogen phosphine bridge ligand and 100mmol of hexachloroethane in 240ml of dioxane, refluxing for 24-48h, filtering to remove insoluble substances, and draining the filtrate to obtain the chlorophosphine bridge ligand A, wherein the compound structure is shown as follows:
preparation of PCPN ligand: 100mmol of p-methylaniline and 500mmol of 4-dimethylaminopyridine are dissolved in 180ml of dichloromethane under anhydrous and oxygen-free conditions to obtain a reaction solution II. At 0 ℃, 50mmol of chlorophosphine bridge ligand A is dripped into the reaction liquid II; after the dropwise addition, the reaction solution was slowly warmed to room temperature and stirred for reaction for 36 hours. After the reaction is finished, filtering out the reaction clear liquid, removing the solvent in vacuum, and obtaining a PCPN pure product 1d after column chromatography treatment, wherein the structure of the PCPN pure product is shown as the following formula:
the nuclear magnetic data of the above ligand (1d) are as follows: 1H NMR (400MHz, 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, a 500ml reaction kettle is heated to 160 ℃, vacuumized for 2.5 hours and replaced by nitrogen for three times. After the temperature is cooled to room temperature, the ethylene is replaced twice, 200ml of dehydrated and deoxidized solvent toluene and 1.2ml of (Al/Cr ═ 600) MMAO (7 wt% Al, n-heptane) are added, then 4.2 mu mol of PCPN ligand L4 and 4 mu mol of chromium acetylacetonate are added, and after the temperature is kept constant at 45 ℃, 0.5MPa of hydrogen and 4.5MPa of ethylene are sequentially introduced to start the reaction. The reaction temperature is 45 ℃ and the reaction time is 25 min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product.
The product was analyzed by GC, the activity was 1977kg/gCr. h, the (1-hexene + 1-octene) selectivity was 89.8 wt%, the polymer selectivity was 0.08 wt%.
Example 5
Preparation of PCPN ligand: the relevant solvent is treated with water and oxygen before use.
The PCPN ligand was prepared by the same method as in example 1.
Oligomerization of ethylene:
before reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 4 hours and replaced by nitrogen for three times. After the temperature is cooled to room temperature, the ethylene is replaced twice, 200ml of dehydrated and deoxidized solvent cyclohexane and 0.18ml of (Al/Cr ═ 90) MMAO (7 wt% Al, n-heptane) are added, then 3.5. mu. mol of the PCPN ligand prepared in the example and 3.5. mu. mol of chromium acetylacetonate are added, and the reaction is started by introducing 0.5MPa hydrogen and 4.5MPa ethylene in sequence when the temperature is constant at 55 ℃. The reaction temperature is 55 ℃, and the reaction time is 50 min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product.
The product was analyzed by GC with an activity of 1152kg/gCr. h and a selectivity for (1-hexene + 1-octene) of 88.8 wt% and a polymer selectivity of 0.07 wt%.
Example 6
Preparation of PCPN ligand: the relevant solvent is treated with water and oxygen before use.
Preparation of a chlorophosphine bridge ligand: taking a proper amount of 150mmol of o-methylphenyl phosphine and 90mmol of dichloromethane, dissolving the mixture in 250ml of acetonitrile, adding 520mol of potassium hydroxide aqueous solution (60 wt%) while stirring in an ice-water bath, dropwise adding for 1.5h, and reacting for 6h in the ice-water bath after the dropwise adding is finished. Adding a proper amount of water to quench the reaction, extracting the reaction solution by using normal hexane, and distilling under reduced pressure to obtain the hydrogen phosphine bridge ligand. Dissolving 100mmol of hydrogen phosphine bridge ligand and 100mmol of hexachloroethane in 240ml of n-hexane, refluxing for 24-48h, filtering to remove insoluble substances, and draining the filtrate to obtain the chlorophosphine bridge ligand D, wherein the compound structure is shown as follows:
preparation of PCPN ligand: and dissolving 65mmol of isopropylamine and 500mmol of triethylamine in 180ml of dichloromethane under anhydrous and oxygen-free conditions to obtain a reaction solution II. At 0 ℃, 50mmol of chlorophosphine bridge ligand D is dripped into the reaction liquid II; after the dropwise addition, the reaction solution was slowly warmed to room temperature and stirred for reaction for 36 hours. After the reaction is finished, filtering out the reaction clear solution, removing the solvent in 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 above ligand (1f) are as follows: 1H NMR (400MHz, CDCl 3): 1H NMR (400MHz, 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 reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 5 hours and replaced by nitrogen for three times. After the temperature is cooled to room temperature, ethylene is replaced twice, 200ml of dehydrated and deoxidized solvent methylcyclohexane and 1.8ml of (Al/Cr ═ 900) MMAO (7 wt% Al, n-heptane) are added, then 4.2 mu mol of phosphine bridge ligand 1f and 3.5 mu mol of chromium acetylacetonate are added, and after the temperature is constant at 60 ℃, 0.5MPa of hydrogen and 4.5MPa of ethylene are sequentially introduced to start the reaction. The reaction temperature is 60 ℃, and the reaction time is 20 min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product.
The product was analyzed by GC for an activity of 1833kg/gCr. h, a selectivity for (1-hexene + 1-octene) of 89.7 wt% and a polymer selectivity of 0.11 wt%.
Example 7
Preparation of PCPN ligand: the relevant solvent is treated with water and oxygen before use.
Preparation of a chlorophosphine bridge ligand: taking a proper amount of 150mmol of the pentafluorophenyl phosphine and 50mmol of dichloromethane, dissolving the mixture in 250ml of DMF, adding 520mol of potassium hydroxide aqueous solution (60 wt%) while stirring in an ice water bath, dropwise adding the mixture for 1.5h, and reacting for 6h in the ice water bath after the dropwise adding is finished. Adding a proper amount of water to quench the reaction, extracting the reaction solution by using normal hexane, and distilling under reduced pressure to obtain the hydrogen phosphine bridge ligand. 100mmol of hydrogen phosphine bridge ligand and 100mmol of hexachloroethane are dissolved in 240ml of methylcyclohexane, the mixture is refluxed for 24 to 48 hours, insoluble substances are removed by filtration, and the filtrate is taken out to be the chlorine phosphine bridge ligand B, and the compound structure is shown as follows:
preparation of PCPN ligand: 50mmol of n-butylamine and 500mmol of diisopropylethylamine are dissolved in 180ml of dichloromethane under anhydrous and oxygen-free conditions to obtain reaction liquid II. At 0 ℃, 50mmol of chlorophosphine bridge ligand B is dripped into the reaction liquid II; after the dropwise addition, the reaction solution was slowly warmed to room temperature and stirred for reaction for 36 hours. After the reaction is finished, filtering out the reaction clear liquid, removing the solvent in 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 for the above ligand (1g) are as follows: 1H NMR (400MHz, 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, a 500ml reaction kettle is heated to 125 ℃, vacuumized for 3.5 hours and replaced by nitrogen for three times. After the temperature is cooled to room temperature, the ethylene is replaced twice, 200ml of dehydrated and deoxidized solvent methylcyclohexane and 1.2ml of (Al/Cr ═ 600) MMAO (7 wt% Al, n-heptane) are added, then 7 mu mol of phosphine bridge ligand 1g and 3.5 mu mol of chromium acetylacetonate are added, and when the temperature is constant at 55 ℃, 0.5Mpa of hydrogen and 4.5MPa of ethylene are sequentially introduced to start the reaction. The reaction temperature is 55 ℃, and the reaction time is 60 min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product.
The product was analyzed by GC and had an activity of 2170kg/gCr. h, a selectivity for (1-hexene + 1-octene) of 88.9 wt% and a polymer selectivity of 0.13 wt%.
Example 8
Preparation of PCPN ligand: the relevant solvent is treated with water and oxygen before use.
Preparation of a chlorophosphine bridge ligand: taking a proper amount of 150mmol of p-methoxyphenyl phosphine and 105mmol of dichloromethane, dissolving the p-methoxyphenyl phosphine and the 105mmol of dichloromethane in 250ml of methylcyclohexane, adding 520mol of potassium hydroxide aqueous solution (60 wt%) while stirring in an ice water bath, dropwise adding for 1.5h, and reacting for 6h in the ice water bath after the dropwise adding is finished. Adding a proper amount of water to quench the reaction, extracting the reaction solution by using normal hexane, and distilling under reduced pressure to obtain the hydrogen phosphine bridge ligand. Dissolving 100mmol of hydrogen phosphine bridge ligand and 500mmol of hexachloroethane in 240ml of ether, refluxing for 24-48h, filtering to remove insoluble substances, and draining the filtrate to obtain the chlorophosphine bridge ligand C, wherein the compound structure is shown as follows:
preparation of PCPN ligand: 75mmol of N-butylamine and 750mmol of N, N-dimethylaniline are dissolved in 180ml of dichloromethane under anhydrous and oxygen-free conditions to obtain reaction liquid II. At 0 ℃, 50mmol of chlorophosphine bridge ligand C is dripped into the reaction liquid II; after the dropwise addition, the reaction solution was slowly warmed to room temperature and stirred for reaction for 36 hours. After the reaction is finished, filtering out the reaction clear liquid, removing the solvent in vacuum, and obtaining a PCPN pure product for 1h after column chromatography treatment, wherein the structure of the PCPN pure product is shown as the following formula:
the nuclear magnetic data for the above ligand (1h) are as follows: 1H NMR (400MHz, CDCl 3): 7.27(d, 2H), 6.99(d, 2H), 2.65(t, 2H), 1.55 ~ 1.31(m, 6H), 0.90(t, 3H)
Oligomerization of ethylene:
before the reaction, a 500ml reaction kettle is heated to 155 ℃, vacuumized for 2 hours and replaced by nitrogen for three times. After the temperature is cooled to room temperature, ethylene is replaced twice, 200ml of dehydrated and deoxidized solvent methylcyclohexane and 1.2ml of (Al/Cr ═ 500) MMAO (7 wt% Al, n-heptane) are added, then 5.3 mu mol of phosphine bridge ligand 1h and 3.5 mu mol of chromium acetylacetonate are added, and after the temperature is kept constant at 50 ℃, 0.5MPa of hydrogen and 4.5MPa of ethylene are sequentially introduced to start the reaction. The reaction temperature is 50 ℃, and the reaction time is 60 min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product.
The product was analyzed by GC for an activity of 1933kg/gCr. h, a selectivity for (1-hexene + 1-octene) of 89.1 wt% and a polymer selectivity of 0.09 wt%.
Example 9
Preparation of PCPN ligand: the relevant solvent is treated with water and oxygen before use.
Preparation of a chlorophosphine bridge ligand: taking a proper amount of 150mmol of the pentafluorophenyl phosphine and 75mmol of dichloromethane, dissolving the mixture in 250ml of DMF, adding 520mol of potassium hydroxide aqueous solution (60 wt%) while stirring in an ice water bath, dropwise adding the mixture for 1.5h, and reacting for 6h in the ice water bath after the dropwise adding is finished. Adding a proper amount of water to quench the reaction, extracting the reaction solution by using normal hexane, and distilling under reduced pressure to obtain the hydrogen phosphine bridge ligand. 100mmol of hydrogen phosphine bridge ligand and 100mmol of hexachloroethane are dissolved in 240ml of acetonitrile, the mixture is refluxed for 24 to 48 hours, insoluble substances are removed by filtration, and the filtrate is taken out to be the chlorine phosphine bridge ligand B, and the compound structure is shown as follows:
preparation of PCPN ligand: and dissolving 50mmol of isopropylamine and 500mmol of triethylamine in 180ml of dichloromethane under anhydrous and oxygen-free conditions to obtain a reaction solution II. At 0 ℃, 50mmol of chlorophosphine bridge ligand B is dripped into the reaction liquid II; after the dropwise addition, the reaction solution was slowly warmed to room temperature and stirred for reaction for 36 hours. After the reaction is finished, filtering out the reaction clear liquid, removing the solvent in 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 above ligand (1i) are as follows: 1H NMR (400MHz, 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, a 500ml reaction kettle is heated to 160 ℃, vacuumized for 2 hours and replaced by nitrogen for three times. After the temperature is cooled to room temperature, ethylene is replaced twice, 200ml of dehydrated and deoxidized solvent methylcyclohexane and 1.4ml of (Al/Cr ═ 600) MMAO (7 wt% Al, n-heptane) are added, then 4.2 mu mol of phosphine bridge ligand 1i and 3.5 mu mol of chromium acetylacetonate are added, and when the temperature is constant at 53 ℃, 0.5Mpa of hydrogen and 4.5MPa of ethylene are sequentially introduced to start the reaction. The reaction temperature is 53 ℃, and the reaction time is 60 min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product.
The product was analyzed by GC for activity 1362kg/gCr. h, (1-hexene + 1-octene) selectivity 88.5 wt%, polymer selectivity 0.06 wt%.
Comparative example 1
Preparation of isopropyl PNP ligand: purchased from shanghai pharmaceutical minkangdi ltd, purity: LC is more than 98%
Oligomerization of ethylene:
before the reaction, a 500ml reaction kettle is heated to 160 ℃, vacuumized for 2 hours and replaced by nitrogen for three times. After the temperature is cooled to room temperature, ethylene is replaced twice, 200ml of dehydrated and deoxidized solvent methylcyclohexane and 1.4ml of (Al/Cr ═ 600) MMAO (7 wt% Al, n-heptane) are added, then 4.2 mu mol of phosphine bridge ligand 1j and 3.5 mu mol of chromium acetylacetonate are added, and when the temperature is constant at 53 ℃, 0.5Mpa of hydrogen and 4.5MPa of ethylene are sequentially introduced to start the reaction. The reaction temperature is 53 ℃, and the reaction time is 60 min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product.
The product was analyzed by GC, the activity was 732kg/gCr. h, the selectivity (1-hexene + 1-octene) was 71.2 wt%, the polymer selectivity was 2.16 wt%.
Comparative example 2
Preparation of alkoxyphosphine PCNP ligand: purchased from shanghai pharmaceutical minkangdi ltd, purity: LC is more than 98%
Oligomerization of ethylene:
before the reaction, a 500ml reaction kettle is heated to 160 ℃, vacuumized for 2 hours and replaced by nitrogen for three times. After the temperature is cooled to room temperature, ethylene is replaced twice, 200ml of dehydrated and deoxidized solvent methylcyclohexane and 1.4ml of (Al/Cr ═ 600) MMAO (7 wt% Al, n-heptane) are added, then 4.2 mu mol of phosphine bridge ligand 1k and 3.5 mu mol of chromium acetylacetonate are added, and when the temperature is constant at 53 ℃, 0.5Mpa of hydrogen and 4.5MPa of ethylene are sequentially introduced to start the reaction. The reaction temperature is 53 ℃, and the reaction time is 60 min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the kettle to obtain no product.
The product was analyzed by GC, the activity was 0.3kg/gCr.h, the (1-hexene + 1-octene) selectivity was 0.02 wt%, the polymer selectivity was 0.1 wt%. No ethylene oligomerization activity.
Claims (10)
1. A PCPN ligand is characterized in that the structure is shown as formula I:
wherein R is2Independently selected from aryl and derivatives thereof, preferably, R2Selected from the group consisting of 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;
R1selected from alkyl, aryl and derivatives thereof; preferably methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, vinyl, propenyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, anthracenyl or biphenyl, more preferably from methyl, ethyl, isopropyl, n-butyl, cyclohexyl.
2. A method for preparing the ligand of claim 1, comprising the steps of:
(1) dissolving a proper amount of phenyl phosphine shown as a formula II and dichloromethane in a solvent A, adding an alkaline solution under the stirring of an ice water bath, dropwise adding for 1-5h, reacting for 3-10h under the stirring of the ice water bath, adding water to quench the reaction, and purifying the reaction solution to obtain a product I, namely the hydrogen phosphine bridge ligand; the structure is shown as formula III:
(2) dissolving a compound III and hexachloroethane in a solvent B, heating and refluxing for 24-48h, and purifying reaction liquid to obtain a product II, namely a chlorophosphine bridge ligand, wherein the structure of the product II is shown as a formula IV:
(3) dissolving a substituted amine compound shown as a formula V in a solvent A under anhydrous and anaerobic conditions to obtain a reaction solution I;
(4) dissolving a chlorophosphine bridge ligand shown in a formula IV in a solvent A under anhydrous and anaerobic conditions to obtain a reaction solution II;
(5) dropwise adding a second reaction solution into the first reaction solution under stirring at-78 ℃, slowly heating to room temperature after adding a catalyst, continuously reacting for 36-72 hours under stirring, and purifying the reaction solution to obtain a product, namely a PCPN ligand;
the structures of the compounds of formula II-formula V described in the steps 1) -5) are as follows
Wherein R is1、R2The definition is the same as formula I.
3. The method according to claim 2, wherein in the step (1), the molar ratio of the substituted phenylphosphine to dichloromethane is 1: 0.3-0.7;
preferably, the alkaline solution is a sodium hydroxide or potassium hydroxide aqueous solution, and the mass concentration of the solution is 20-80%;
preferably, the solvent A is one or more of toluene, methylcyclohexane, acetonitrile, cyclohexane, N-hexane, dichloromethane, N-dimethylformamide and N, N-dimethylacetamide.
4. The method according to claim 2 or 3, wherein in the step (2), the solvent B is one or more selected from toluene, methylcyclohexane, acetonitrile, cyclohexane, n-hexane, diethyl ether, dioxane;
preferably, the molar ratio of the hydrogen phosphine bridge ligand to hexachloroethane is from 1:1 to 1: 5.
5. The production method according to any one of claims 2 to 4, 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;
preferably, in the step (5), the catalyst is selected from triethylamine, N, N-dimethylaniline, diisopropylethylamine and 4-dimethylaminopyridine;
preferably, the molar ratio of the catalyst to the chlorophosphine bridge ligand of formula IV is from 1:5 to 1: 20.
6. An ethylene oligomerization catalyst comprising a transition metal compound and the ligand of claim 1 or prepared by the process of any one of claims 2 to 5 and an aluminum alkyl cocatalyst;
preferably, the transition metal compound is one or more compounds selected from chromium, molybdenum, cobalt, titanium, vanadium, zirconium, nickel and palladium, preferably a compound of chromium, zirconium and nickel.
7. The catalyst of claim 6 wherein the alkylaluminum cocatalyst is selected from one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylethoxyaluminum, diethylaluminum monochloride, ethylaluminum dichloride, ethylaluminum sesquichloride, trioctylaluminum, methylaluminoxane, modified methylaluminoxane and ethylaluminoxane.
8. The catalyst according to claim 6 or 7, wherein the molar ratio of transition metal compound to PCPN ligand is 1: 1-3, preferably 1: 1-2;
preferably, the molar ratio of aluminum alkyl co-catalyst to transition metal compound is from 50 to 2000:1, preferably from 90 to 800: 1.
9. Use of a catalyst according to any one of claims 6 to 8 for the oligomerization of ethylene.
10. The use according to claim 9, wherein the catalyst is added in an amount such that the molar concentration of the transition metal compound in the oligomerization system is 10 to 25 μmol/L, preferably 15 to 20 μmol/L.
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