CN109265586B - FI catalyst for preparing low-entanglement high-molecular-weight polyethylene and preparation method and application thereof - Google Patents

FI catalyst for preparing low-entanglement high-molecular-weight polyethylene and preparation method and application thereof Download PDF

Info

Publication number
CN109265586B
CN109265586B CN201810994241.0A CN201810994241A CN109265586B CN 109265586 B CN109265586 B CN 109265586B CN 201810994241 A CN201810994241 A CN 201810994241A CN 109265586 B CN109265586 B CN 109265586B
Authority
CN
China
Prior art keywords
catalyst
group
substituted
reaction
molecular weight
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
Application number
CN201810994241.0A
Other languages
Chinese (zh)
Other versions
CN109265586A (en
Inventor
郭建双
杨超
王新威
孙勇飞
李济祥
郑晗
茆汉军
李建龙
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Research Institute of Chemical Industry SRICI
Original Assignee
Shanghai Research Institute of Chemical Industry SRICI
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shanghai Research Institute of Chemical Industry SRICI filed Critical Shanghai Research Institute of Chemical Industry SRICI
Priority to CN201810994241.0A priority Critical patent/CN109265586B/en
Publication of CN109265586A publication Critical patent/CN109265586A/en
Application granted granted Critical
Publication of CN109265586B publication Critical patent/CN109265586B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic System
    • C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic System compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00—Metallocene catalysts
    • C08F2420/02—Cp or analog bridged to a non-Cp X anionic donor

Abstract

The invention relates to an FI catalyst for preparing low-entanglement high-molecular-weight polyethylene, a preparation method and application thereof, wherein a phenol derivative, paraformaldehyde, an inorganic catalyst and triethylamine are added into a reaction bottle, an organic solvent is added, and heating reflux reaction is carried out to prepare a salicylaldehyde derivative; adding the salicylaldehyde derivative and the substituted primary amine into a reaction bottle, adding an organic solvent, performing an aldehyde-amine condensation dehydration reaction, and purifying after the reaction to obtain a phenoxyimine ligand; reacting the phenoxyimine ligand with alkyl lithium, then carrying out complex reaction with chlorinated metal, filtering, concentrating and crystallizing to obtain the FI catalyst. Compared with the prior art, when the catalyst is used for catalyzing ethylene polymerization, high molecular weight polyethylene with the molecular weight of 20-800 ten thousand can be obtained, and the crystallinity reaches 60-70%.

Description

FI catalyst for preparing low-entanglement high-molecular-weight polyethylene and preparation method and application thereof
Technical Field
The invention relates to the field of polymerization catalysts, and particularly relates to an FI catalyst for preparing low-entanglement high-molecular-weight polyethylene.
Background
The polyolefin material has the advantages of high strength, low density, strong chemical corrosion resistance, low manufacturing cost and the like, can replace common materials such as paper, wood, glass, metal, concrete and the like to a certain extent, has wide application, and becomes one of the most widely applied polymer materials in the world today. Among them, polyethylene is a variety of general-purpose synthetic resins with the highest yield, and is a thermoplastic plastic with the widest use, and is mainly used for manufacturing films, containers, pipes, fibers, electric wires and cables, daily necessities, and the like, and also can be used as a high-frequency insulating material for manufacturing televisions, radars, and the like.
In the industry, high molecular weight polyethylene is produced in slurry polymerization mostly by using a Ziegler-Natta catalyst, a Z-N catalyst is a multi-active site catalyst, and a catalyst system has multiple types of active sites, so that polyethylene molecular chains growing at active sites in the polymerization process are intertwined, and polyethylene products of unit mass have more entangled sites. And at a relatively high polymerization temperature, the crystallization rate of the molecular chain of the generated polymer is slow and is far lower than the growth rate of the molecular chain, the molecular chain does not have enough time to be arranged in a crystal lattice, but tends to be mixed and cross-linked together to grow, and finally the prepared polymer has high entanglement. Because of the high molecular weight and high entanglement of the polymer, the movement of the polymer molecular chain is greatly restricted, the mobility of the high molecular weight polyethylene molecular chain is very low, the movement capability of the chain segment is very poor, and the polymer has very high melt viscosity even in a molten state, so that the processing is extremely difficult. In summary, the polymer structure resulting from the Z-N catalyzed polymerization mechanism makes processing difficult and performance degrades to a large extent.
Patent CN106543301A discloses a method for preparing a Ziegler-Natta catalyst for efficiently preparing low-entanglement polyethylene, which comprises the steps of stirring and filtering an alcohol-adsorbed porous carrier and a polyhedral oligomeric silsesquioxane molecule/Mg mixture in tetrahydrofuran, reacting with aluminum alkyl to obtain a POSS carrier, stirring, reacting with titanium tetrachloride, and drying to obtain the Ziegler-Natta catalyst for efficiently preparing low-entanglement polyethylene. However, due to the limitation of POSS molecular size (3-8nm), most of the catalyst loaded on the carrier enters into the macropores of the porous carrier and is difficult to enter into the micropores of the porous carrier, so that the active centers are unevenly distributed in the carrier, the activity of the catalyst is unstable, and the particle morphology of the obtained polyethylene is poor in catalyzing the polymerization activity of ethylene. And the Z-N catalyst is a multi-active-site catalyst, the molecular weight of the obtained polyethylene is wide, and various elements in the carrier can cause the ash content of the final polyethylene to be high, so that impurities can be introduced into the polyethylene.
Patent CN106084101A discloses a method for preparing low-entanglement polyethylene by styrene in-situ radical polymerization in a porous carrier, wherein styrene, a comonomer and an initiator are firstly diffused into the carrier, and then polymerization is initiated, so as to obtain a modified porous carrier with channels uniformly filled with styrene-based copolymer, and then the modified porous carrier is further used for loading a catalyst, so as to finally prepare the low-entanglement polyethylene; the process of the present invention is capable of producing low entanglement polyethylenes having molecular weights in the range of from 10,000g/mol to 10,000,000 g/mol. The ethylene polymerization reaction is a free radical polymerization mechanism which is not easy to control, the mass transfer resistance of the styrene-based copolymer to ethylene and the separation of an active center in the patent can reduce the growth rate of a polyethylene chain, so that the catalytic ethylene polymerization activity is reduced, and the vinyl end group of the styrene-based copolymer chain in a carrier pore channel can be copolymerized with ethylene, so that the obtained polyolefin contains a branched chain.
Patent CN104725536A discloses a preparation method of low-entanglement ultra-high molecular weight polyethylene powder, which comprises loading acetylacetone salt compound and pyridine diimine ligand main catalyst on mesoporous molecular sieve ZSM-41, and depositing a layer of polymer film on ZSM-41 to obtain the low-entanglement ultra-high molecular weight polyethylene heterogeneous catalyst. When the catalyst is polymerized, the growing polyethylene chain segment is not easy to be wound, so that the ultrahigh molecular weight polyethylene powder with low entanglement degree is obtained. However, the strength of the physically-coated polymer film is poor, the polyethylene growing from the inside of the carrier can quickly break the polymer film during polymerization, the control of chain entanglement by the ethylene mass transfer resistance environment created by the polymer film fails immediately, the polymerization reaction cannot be continued for a long time, and the processing performance and the mechanical property of the product are influenced.
Patent CN107501444A discloses a supported phenoxy imine polyolefin catalyst and a preparation method and application thereof, firstly, a phenol derivative, paraformaldehyde, an inorganic catalyst and triethylamine are mixed, acetonitrile is used as a solvent to prepare a salicylaldehyde derivative, the salicylaldehyde derivative and primary amine or imine are reacted in ethanol to obtain Schiff base, then a catalyst precursor is prepared, and the catalyst precursor is supported on a carrier to obtain the catalyst, wherein the catalyst can be used for catalyzing ethylene polymerization, propylene homopolymerization or copolymerization of ethylene and linear olefin with the carbon atom number of 3-8, and can also be used for catalyzing copolymerization of ethylene and norbornene. The yield of the phenoxyimine catalyst is lower and is less than 50 percent.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an FI catalyst which has high catalyst activity and high crystallinity of the obtained polyethylene and is used for preparing low-entanglement high-molecular-weight polyethylene, and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
an FI catalyst for use in the production of low entanglement high molecular weight polyethylene, said FI catalyst having the formula:
Figure BDA0001781508120000031
m is chromium, ruthenium, rhodium or palladium; the metals have more outer-layer electron orbitals, the phenoxyimine ligand is used as an electron donor, the metals can be better coordinated with the phenoxyimine ligand, and the catalyst has a stable structure.
R1、R2、R3、R4Independently hydrogen, C1-C6 straight chain alkyl, branched alkyl, cycloalkyl, halogen substituted alkyl, oxacyclyl, azacyclyl, phosphacycloyl, thiacyclyl, substituted amine, substituted alkoxy, substituted mercapto, substituted phenyl, substituted biphenyl, or substituted naphthyl;
R5、R6、R7、R8、R9independently hydrogen, linear alkanes of C1-C6A group, a branched alkyl group, a cycloalkyl group, a halogen-substituted alkyl group, an oxacyclyl group, an azacyclyl group, a phosphacyclic group, a thiacyclyl group, a substituted amine group, a substituted alkoxy group, a substituted mercapto group, a substituted phenyl group, a substituted biphenyl group, or a substituted naphthyl group.
Further, the air conditioner is provided with a fan,
m is chromium, ruthenium, rhodium or palladium;
R1、R2、R3、R4independently hydrogen, an oxacyclyl group, an azacyclyl group, a phosphacyclic group, a thiacyclyl group, a substituted amine group, a substituted alkoxy group, a substituted mercapto group, a substituted phenyl group, a substituted biphenyl group, or a substituted naphthyl group;
R5、R6、R7、R8、R9independently hydrogen, an oxacyclyl group, an azacyclyl group, a phosphacyclic group, a thiacyclyl group, a substituted amine group, a substituted alkoxy group, a substituted mercapto group, a substituted phenyl group, a substituted biphenyl group, or a substituted naphthyl group.
Further, the air conditioner is provided with a fan,
m is palladium;
R1、R2、R3、R4independently hydrogen, a phosphacyclic group, a thiacylation group, a substituted mercapto group, or a substituted phenyl group;
R5、R6、R7、R8、R9independently hydrogen, a phosphacyclic group, a thiacylation group, a substituted mercapto group, a substituted phenyl group, or a substituted biphenyl group.
A method for preparing a low-entanglement high molecular weight polyethylene, FI, catalyst, comprising the steps of:
(1) preparation of salicylaldehyde derivatives: adding a phenol derivative, paraformaldehyde, an inorganic catalyst and triethylamine into a reaction bottle, adding an organic solvent, heating for reflux reaction at the temperature of 70-150 ℃ to obtain a salicylaldehyde derivative;
(2) preparing a phenoxyimine ligand: adding a salicylaldehyde derivative and substituted primary amine into a reaction bottle, adding an organic solvent, performing an aldehyde-amine condensation dehydration reaction, and purifying after the reaction to obtain a phenoxyimine ligand;
(3) preparing an FI catalyst: reacting the phenoxyimine ligand with alkyl lithium at the low temperature of-78-0 ℃, then carrying out complex reaction with chlorinated metal, filtering, concentrating and crystallizing to obtain the FI catalyst.
Further, the molar ratio of the phenol derivative, the paraformaldehyde, the inorganic catalyst, the triethylamine and the organic solvent in the step (1) is 1.0-2.0: 5.0-15.0: 0.5-3.5: 3.0-10.0: 20.0-50.0.
Further, the structural formula of the salicylaldehyde derivative obtained in the step (1) is as follows:
Figure BDA0001781508120000041
R1、R2、R3、R4independently hydrogen, C1-C6 straight chain alkyl, branched alkyl, cycloalkyl, halogen substituted alkyl, oxacyclyl, azacyclyl, phosphacycloyl, thiacyclyl, substituted amine, substituted alkoxy, substituted mercapto, substituted phenyl, substituted biphenyl, or substituted naphthyl;
further, the inorganic catalyst in the step (1) is one of sodium hydroxide, boric acid, copper oxide, phosphorus oxychloride, magnesium methoxide and sodium cyanide. Sodium hydroxide is preferred. The sodium hydroxide has strong basicity and can catalyze the aldolization reaction of the substituted phenol, boric acid, copper oxide and magnesium chloride have weak basicity, and phosphorus oxychloride, magnesium methoxide and sodium cyanide have high danger in the reaction.
Further, the substituted primary amine in step (2) is: 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2, 6-difluoroaniline, 3, 5-difluoroaniline, 3,4, 5-trifluoroaniline, 2,3,4,5, 6-pentafluoroaniline.
Further, the organic solvent in the steps (1) and (2) is one or more of methanol, ethanol, ethyl acetate, dichloroethane, chloroform, toluene, N-dimethylformamide, pentane, isopentane, N-hexane, N-heptane and petroleum ether. Methanol is preferred. The polarity of the methanol is stronger than that of the acetonitrile, and the product phenoxyimine ligand is a nonpolar compound, so that the phenoxyimine ligand has poor solubility in polar solvent methanol, can be crystallized and separated out in a reaction system, and is convenient for post-treatment and purification.
The structural formula of the phenoxyimine ligand in the step (2) is as follows:
Figure BDA0001781508120000051
R5、R6、R7、R8、R9independently hydrogen, C1-C6 straight chain alkyl, branched chain alkyl, cycloalkyl, halogen substituted alkyl, oxacyclyl, azacyclyl, phosphacycloyl, thiacyclyl, substituted amine, substituted alkoxy, substituted mercapto, substituted phenyl, substituted biphenyl, or substituted naphthyl.
Further, the amount of the substituted primary amine substance in the step (2) is 1-3 times of that of the salicylaldehyde derivative.
Further, the alkyl lithium in the step (3) is one or more of isobutyl lithium, tert-butyl lithium or methyl lithium, and the alkyl lithium can be replaced by n-butyl lithium.
Further, the metal chloride in the step (3) is any one of chromium chloride, ruthenium chloride, rhodium chloride and palladium chloride, and the metal chloride can be replaced by tetrahydrofuran complex of the metal chloride.
Further, the molar ratio of the phenoxyimine ligand to the alkyl lithium to the chlorinated metal in the step (3) is 0.8-1.2: 0.9-1.5: 0.4-0.6.
The application of an FI catalyst for preparing low-entanglement high-molecular-weight polyethylene is characterized in that the FI catalyst is used for preparing the low-entanglement high-molecular-weight polyethylene and comprises the following specific steps: fully drying the polymerization reaction kettle to the required temperature and pressure, wherein the polymerization temperature is 20-70 ℃, the pressure is 1-50bar, introducing ethylene gas, adding a cocatalyst and a solvent, adding the FI catalyst, and polymerizing for 2-6 h to obtain the low-entanglement high-molecular-weight polyethylene.
Further, the cocatalyst is a mixture of one or more of alkyl metal compounds, trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum monochloride, methylaluminoxane and organic boride, and the polymerization temperature is 40-70 ℃;
the solvent comprises organic solvent with boiling point of 30-150 ℃ such as n-hexane, n-heptane, 120# solvent oil, 90# solvent oil, dichloromethane, toluene or xylene.
Furthermore, the addition amount of the cocatalyst is 0.05-5000mmol, the addition amount of the FI catalyst is 0.05-0.5umol, the dosage of the solvent is 100-450mL, and the catalytic activity of the FI catalyst reaches 7.5 x 107g/mol。
Further, the viscosity average molecular weight of the low-entanglement high-molecular-weight polyethylene is 20-800 ten thousand, the crystallinity is 60-70%, the viscosity average molecular weight of the polyethylene is measured by adopting a high-temperature Ubbelohde viscometer, the intrinsic viscosity of the polyethylene is measured at 135 ℃ by taking decalin as a solvent, and the viscosity average molecular weight is calculated according to a Mark-Hawink equation.
Compared with the prior art, the FI catalyst is prepared by reacting substituted phenol with paraformaldehyde to obtain a salicylaldehyde derivative, performing an aldehyde-amine condensation dehydration reaction on the salicylaldehyde derivative and primary amine to obtain a phenoxyimine ligand, reacting the phenoxyimine ligand with alkyl lithium, and then reacting with a metal chloride or a tetrahydrofuran complex of the metal chloride. The invention protects around the active center of the catalyst, polymer chain segments are not easy to tangle with each other in the chain growth process, the growth speed of the polyethylene chain is slowed down, and the polymerization is carried out in a lower polymerization environment (20-70 ℃) and a lower catalyst concentration condition, so the FI catalyst prepared by the invention can be used for preparing high molecular weight polyethylene with low entanglement degree in the polymerization environment. The catalyst has the advantages of convenient synthesis, high yield of more than 60 percent and good water and oxygen tolerance. The ethylene polymerization mechanism is a coordination polymerization mechanism, the polymerization is easy to control, the polymerization reaction condition is mild, the catalytic activity is high and reaches 7.5 x 107g/mol. The structure of the catalyst is adjusted by adjusting the structure of the ligand, the steric hindrance of the ligand is increased, the protection is built at the active center of the catalyst, the low-entanglement high-molecular-weight polyethylene is prepared, the crystallinity is higher,up to 70%. The catalyst does not use a carrier and thus does not introduce impurities into the resulting polyethylene.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
The embodiment of the invention meets the following conditions during the preparation of the catalyst and the test of polyethylene:
all air sensitive substances are operated by adopting a standard vacuum double-row-wire anhydrous and oxygen-free operation method. All reagents are used after refining treatment.
The viscosity average molecular weight of polyethylene was measured by a high temperature Ubbelohde viscometer. Measuring the intrinsic viscosity of polyethylene at 135 deg.C with decalin as solvent by high temperature Ubbelohde viscometer, calculating viscosity average molecular weight according to Mark-Hawink equation with K being 6.67 × 10-4,α＝0.67。
The low entanglement properties of the polymer were tested by differential scanning calorimetry. The polyethylene entanglement characteristics were characterized using crystallinity analysis. The higher the crystallinity, the more ordered the molecular chains of the polyethylene are arranged, with a lower entanglement density per unit mass and a lower degree of entanglement.
Sampling 5mg in the testing process of a differential scanning calorimeter, heating from 50 ℃ to 180 ℃, wherein the heating rate is 10 ℃/min, heating for the first time to eliminate the thermal history, keeping the temperature at 180 ℃ for 3min, then cooling to 50 ℃ at the rate of 10 ℃/min, keeping the temperature for 3min, then heating to 180 ℃ at the rate of 10 ℃/min for the second time, and recording a DSC curve. The crystallinity Xc of the polymer sample was calculated from the heat absorbed during the elevated temperature melting by the following equation: xc ═ Δ H/Δ Hm0X 100%. Where Δ H represents the amount of heat absorbed during melting, Δ Hm0Represents the melting enthalpy of 100 percent of the crystallized polyethylene and takes 289J/g.
Example 1
3-Synthesis of tert-butyl salicylaldehyde:
500mL eggplant-shaped bottle is added with 2-tert-butylphenol 50mAnd (3) heating, refluxing and stirring at 70 ℃ for reaction, wherein the mol is 250mmol of paraformaldehyde, 75mmol of sodium hydroxide, 50mmol of triethylamine and 100mL of methanol, tracking the reaction process by TLC, and cooling to room temperature after the reaction is finished. Hydrochloric acid is added into the reaction liquid, stirring is carried out until the reaction liquid is clear, layers are separated, the water phase is extracted by ethyl acetate, the organic phases are combined and washed by saturated saline solution, dried by anhydrous sodium sulfate, filtered, the solvent is removed by rotation, and the product is purified by column chromatography (normal hexane: ethyl acetate: 25:1) to obtain 7.81g of the product, wherein the yield is 87.65%. Elemental analysis (%) C11H14O2Measured (calculated): c, 74.42 (74.13); h, 7.96 (7.92). The structure of 3-tert-butylsalicylaldehyde is shown below:
Figure BDA0001781508120000071
example 2
3, 5-di-tert-butyl salicylaldehyde synthesis:
adding 50mmol of 2, 4-tert-butylphenol, 500mmol of paraformaldehyde, 150mmol of sodium hydroxide, 100mmol of triethylamine and 100mL of tetrahydrofuran into a 500mL eggplant-shaped bottle, heating at 90 ℃, refluxing, stirring and reacting, tracking the reaction process by TLC, and cooling to room temperature after the reaction is finished. Hydrochloric acid is added into the reaction liquid, stirring is carried out until the reaction liquid is clear, layers are separated, the water phase is extracted by ethyl acetate, the organic phases are combined and washed by saturated saline solution, dried by anhydrous sodium sulfate, filtered, the solvent is removed by rotation, and the product is purified by column chromatography (normal hexane: ethyl acetate: 30:1) to obtain 10.56g of the product, wherein the yield is 90.16%. Elemental analysis (%) C15H22O2Measured (calculated): c, 76.95 (76.88); h, 9.50 (9.46). The structure of 3, 5-di-tert-butyl salicylaldehyde is shown as follows:
Figure BDA0001781508120000081
example 3
Synthesis of 3, 5-dicumyl salicylaldehyde:
adding 50mmol of 2, 4-dicumylphenol and 300mmol of paraformaldehyde into a 500mL eggplant-shaped bottle,75mmol of boric acid, 150mmol of triethylamine and 100mL of dichloromethane, heating at 60 ℃, refluxing, stirring and reacting, tracking the reaction process by TLC, and cooling to room temperature after the reaction is finished. Hydrochloric acid was added to the reaction solution, and the mixture was stirred until the reaction solution was clear, the layers were separated, the aqueous phase was extracted with ethyl acetate, the organic phases were combined and washed with saturated brine, dried over anhydrous sodium sulfate, filtered, the solvent was removed by rotation, and purified by column chromatography (n-hexane: ethyl acetate: 40:1) to obtain 16.11g of a product, the yield of which was 89.86%. Elemental analysis (%) C25H26O2Measured (calculated): c, 83.85 (83.76); h, 7.36 (7.31). The structure of 3, 5-dicumylsalicylaldehyde is shown below:
Figure BDA0001781508120000082
example 4
Synthesis of 3, 5-ditrityl salicylaldehyde:
adding 50mmol of 2, 4-ditritylphenol, 400mmol of paraformaldehyde, 100mmol of sodium hydroxide, 200mmol of triethylamine and 100mL of N, N-dimethylformamide into a 500mL eggplant-shaped bottle, heating at 150 ℃, refluxing, stirring, reacting, tracking the reaction process by TLC, and cooling to room temperature after the reaction is finished. Hydrochloric acid is added into the reaction liquid, the mixture is stirred until the reaction liquid is clear, layers are separated, the water phase is extracted by ethyl acetate, organic phases are combined and washed by saturated saline solution, dried by anhydrous sodium sulfate, filtered, solvent is removed by rotation, and the mixture is purified by column chromatography (normal hexane: ethyl acetate: 50:1) to obtain 26.07g of a product, wherein the yield is 85.93%. Elemental analysis (%) C45H34O2Measured (calculated): c, 89.29 (89.08); h, 5.76 (5.65). The structure of 3, 5-ditritylsalicylaldehyde is shown below:
Figure BDA0001781508120000091
example 5
Synthesis of phenoxyimine ligand L1: adding 10mmol of 3-tert-butyl salicylaldehyde, 12mmol of pentafluoroaniline and 30mL of anhydrous methanol into a 100mL eggplant-shaped bottle, and heating and refluxing at 60 DEG CAnd (4) reacting. TLC tracks the progress of the reaction, and after the reaction is finished, recrystallization purification is carried out to obtain 1.76g of a product with 51.36% yield. Elemental analysis (%) C17H14F5NO, found (calculated): c, 59.68 (59.48); h, 4.02 (4.11); n,4.05 (4.08). The structure of ligand L1 is shown below:
Figure BDA0001781508120000092
example 6
Synthesis of phenoxyimine ligand L2: in a 100mL eggplant-shaped bottle, 10mmol of 3, 5-di-tert-butyl salicylaldehyde, 14mmol of pentafluoroaniline and 40mL of absolute ethyl alcohol are added, and the mixture is heated and refluxed at 80 ℃ for reaction. TLC tracks the reaction progress, after the reaction is finished, column chromatography (normal hexane) is carried out for purification, and 2.00g of product is obtained, and the yield is 50.12%. Elemental analysis (%) C21H22F5NO, found (calculated): c, 63.36 (63.15); h, 5.46 (5.55); n,3.42 (3.51). The structure of ligand L2 is shown below:
Figure BDA0001781508120000093
example 7
Synthesis of phenoxyimine ligand L3: in a 100mL eggplant-shaped bottle, 10mmol of 3, 5-dicumyl salicylaldehyde, 15mmol of pentafluoroaniline and 50mL of dichloromethane are added, and the mixture is heated and refluxed at 60 ℃ for reaction. The reaction progress was followed by TLC, and after completion of the reaction, column chromatography (n-hexane) was performed for purification to give 2.56g of a product in 50.70% yield. Elemental analysis (%) C31H26F5NO, found (calculated): c, 71.45 (71.12); h, 4.96 (5.01); n,2.54 (2.68). The structure of ligand L3 is shown below:
Figure BDA0001781508120000101
example 8
Synthesis of phenoxyimine ligand L4: in a 100mL eggplant-shaped bottle, 10mmol, penta-3, 5-ditrityl salicylaldehyde was added20mmol of fluoroaniline and 50mL of trichloromethane, and heating and refluxing at 70 ℃ for reaction. The reaction progress was followed by TLC, and after completion of the reaction, column chromatography (n-hexane) purification was carried out to obtain 3.96g of the product, with a yield of 51.25%. Elemental analysis (%) C51H34F5NO, found (calculated): c, 79.51 (79.36); h, 4.25 (4.44); n,1.72 (1.81). The structure of ligand L4 is shown below:
Figure BDA0001781508120000102
example 9
And (3) FI-1 catalyst synthesis:
a100 mL eggplant-shaped Schlenk flask was baked for 10 minutes under vacuum using a spray gun, the vacuum was turned off, and argon gas was introduced to normal pressure, and the process was repeated three times. Ligand L1(5mmol) was dissolved in anhydrous ether under argon protection, n-butyllithium (6mmol) was slowly added dropwise at-78 deg.C, and after completion of addition, stirring was resumed at room temperature for 2 hours. Chromium chloride (2.5mmol) was added slowly and stirring was resumed at room temperature for 24 hours. And (3) post-treatment: the solvent anhydrous ether was dried by suction, and anhydrous dichloromethane was added thereto, stirred and dissolved, and then settled, filtered, the obtained filtrate was concentrated, anhydrous dichloromethane and anhydrous n-hexane were added, and a solid was precipitated by crystallization, and filtered to obtain 1.31g of a green solid, with a yield of 65.23%. Elemental analysis (%) C34H26Cl2F10N2O2Cr, found (calculated): c, 50.54 (50.57); h, 3.15 (3.25); n, 3.37 (3.47). The FI-1 structure is as follows:
Figure BDA0001781508120000111
example 10
And (3) FI-2 catalyst synthesis:
a100 mL eggplant-shaped Schlenk flask was baked for 10 minutes under vacuum using a spray gun, the vacuum was turned off, and argon gas was introduced to normal pressure, and the process was repeated three times. Ligand L2(5mmol) was dissolved in anhydrous tetrahydrofuran under argon protection, n-butyllithium (7.5mmol) was slowly added dropwise at-30 deg.C, and after completion of addition, stirring was continued at room temperature for 2 hours. SlowChromium chloride (2.6mmol) was slowly added and stirring was resumed at room temperature for 24 hours. And (3) post-treatment: the solvent anhydrous tetrahydrofuran was dried by suction, and anhydrous dichloromethane was added thereto, stirred to dissolve, and then settled, and filtered, and the obtained filtrate was concentrated, and anhydrous dichloromethane and anhydrous n-hexane were added, to crystallize out a solid, and the green solid was obtained by filtration in a yield of 68.85%, 1.18 g. Elemental analysis (%) C42H42Cl2F10N2O2Cr, found (calculated): c, 55.01 (54.85); h, 4.58 (4.60); n, 3.01 (3.05). The FI-2 structure is as follows:
Figure BDA0001781508120000112
example 11
And (3) FI-3 catalyst synthesis:
a100 mL eggplant-shaped Schlenk flask was baked for 10 minutes under vacuum using a spray gun, the vacuum was turned off, and argon gas was introduced to normal pressure, and the process was repeated three times. Ligand L3(5mmol) was dissolved in anhydrous ether under argon protection, n-butyllithium (5.5mmol) was slowly added dropwise at-20 deg.C, and after completion of addition, stirring was resumed at room temperature for 2 hours. Chromium chloride (3.0mmol) was added slowly and stirring was resumed at room temperature for 24 hours. And (3) post-treatment: the solvent anhydrous ether was drained, anhydrous dichloromethane was added thereto, stirred to dissolve it, and then settled, filtered, the obtained filtrate was concentrated, anhydrous dichloromethane and anhydrous petroleum ether were added, the solid was precipitated by crystallization, and filtered to obtain 1.51g of a green solid with a yield of 65.13%. Elemental analysis (%) C62H50Cl2F10N2O2Cr, found (calculated): c, 63.79 (63.76); h, 4.14 (4.31); n, 2.25 (2.40). The FI-3 structure is as follows:
Figure BDA0001781508120000121
example 12
And (3) FI-4 catalyst synthesis:
under vacuum, 100mL eggplant-shaped Schlenk bottle was baked for 10 minutes using a spray gun, the vacuum was turned off, and argon gas was introduced to normal pressureThis was repeated three times. Ligand L4(5mmol) was dissolved in anhydrous tetrahydrofuran under argon protection, n-butyllithium (8mmol) was slowly added dropwise at 0 ℃ and the mixture was allowed to stir at room temperature for 2 hours after completion of addition. Chromium chloride (2.5mmol) was added slowly and stirring was resumed at room temperature for 24 hours. And (3) post-treatment: the solvent anhydrous tetrahydrofuran is drained, anhydrous dichloromethane is added into the solvent, the mixture is stirred and dissolved and then is settled, the obtained filtrate is filtered, the obtained filtrate is concentrated, the anhydrous dichloromethane and the anhydrous petroleum ether are added, solid is separated out through crystallization, and the green solid 2.21g is obtained through filtration, wherein the yield is 63.27%. Elemental analysis (%) C102H66Cl2F10N2O2Cr, found (calculated): c, 73.59 (73.60); h, 4.01 (4.00); n, 1.57 (1.68). The FI-4 structure is as follows:
Figure BDA0001781508120000122
example 13
Low entanglement high molecular weight polyethylene FI catalysts are used to catalyze ethylene polymerization:
the ethylene pressurized polymerization reaction device is a 0.5L stainless steel polymerization reaction kettle with water circulation temperature control, the reaction kettle is vacuumized at 90 ℃ for 2 hours, then argon is filled, a cocatalyst and a solvent are added into the dried polymerization reaction kettle under the protection of argon, then a solution in which the catalyst is dissolved is injected into the polymerization reaction kettle by a needle cylinder, the polymerization reaction kettle is added, the constant temperature water bath temperature is set, ethylene is filled, and the polymerization reaction is stirred. After the reaction is finished, adding 0.5 percent by volume of hydrochloric acid ethanol solution to terminate the reaction. Standing for 30min, filtering, washing with 0.5 vol% ethanol hydrochloride solution for 3 times, vacuum drying the polymer at 60 deg.C to constant weight to obtain polymer, weighing its mass, calculating catalytic activity of the catalyst, and testing molecular weight and crystallinity of polyethylene. The results are shown in Table 1.
TABLE 1
Figure BDA0001781508120000131
From aboveIt can be seen that the activity of the catalyst of the invention can reach up to 7.5 x 107g/mol M, 4.29X 10 of the highest activity of the catalysts of the same type of the prior art5g/mol M, the crystallinity of the polyethylene product produced by the catalyst of the invention can reach more than 60 percent, and the prior art generally has about 50 percent.

Claims (16)

1. An FI catalyst for use in the production of low entanglement high molecular weight polyethylene, said FI catalyst having the formula:
Figure FDA0002971356830000011
m is chromium;
R1、R2、R3、R4independently hydrogen, C1-C6 straight chain alkyl, branched alkyl, cycloalkyl, halogen substituent, oxacyclyl, azacyclyl, phosphacycloyl, thiacyclyl, substituted amine, substituted alkoxy, substituted mercapto, substituted phenyl, substituted biphenyl, or substituted naphthyl;
R5、R6、R7、R8、R9independently hydrogen, C1-C6 straight chain alkyl, branched alkyl, cycloalkyl, halogen substituent, oxacyclyl, azacyclyl, phosphacycloyl, thiacyclyl, substituted amine, substituted alkoxy, substituted mercapto, substituted phenyl, substituted biphenyl, or substituted naphthyl.
2. The FI catalyst for producing a low-entanglement high molecular weight polyethylene according to claim 1,
m is chromium;
R1、R2、R3、R4independently hydrogen, an oxacyclyl group, an azacyclyl group, a phosphacyclic group, a thiacyclyl group, a substituted amine group, a substituted alkoxy group, a substituted mercapto group, a substituted phenyl group, a substituted biphenyl group, or a substituted naphthyl group;
R5、R6、R7、R8、R9independently hydrogen, an oxacyclyl group, an azacyclyl group, a phosphacyclic group, a thiacyclyl group, a substituted amine group, a substituted alkoxy group, a substituted mercapto group, a substituted phenyl group, a substituted biphenyl group, or a substituted naphthyl group.
3. A method for preparing the FI catalyst of claim 1 or 2, comprising the steps of:
(1) preparation of salicylaldehyde derivatives: adding a phenol derivative, paraformaldehyde, an inorganic catalyst and triethylamine into a reaction bottle, adding an organic solvent, and carrying out heating reflux reaction to obtain a salicylaldehyde derivative;
(2) preparing a phenoxyimine ligand: adding a salicylaldehyde derivative and substituted primary amine into a reaction bottle, adding an organic solvent, performing an aldehyde-amine condensation dehydration reaction, and purifying after the reaction to obtain a phenoxyimine ligand;
(3) preparing an FI catalyst: reacting the phenoxyimine ligand with alkyl lithium at the low temperature of-78-0 ℃, then carrying out complex reaction with chlorinated metal at the temperature of 15-35 ℃, filtering, concentrating and crystallizing to obtain the FI catalyst.
4. The FI catalyst preparation method according to claim 3, wherein the phenol derivative, the paraformaldehyde, the inorganic catalyst, the triethylamine and the organic solvent are added in the step (1) at a molar ratio of 1.0-2.0: 5.0-15.0: 0.5-3.5: 3.0-10.0: 20.0-50.0.
5. The method for preparing FI catalyst as claimed in claim 3, wherein the salicylaldehyde derivative obtained in step (1) has the following structural formula:
Figure FDA0002971356830000021
R1、R2、R3、R4independently hydrogen, C1-C6An alkyl group, a branched alkyl group, a cycloalkyl group, a halogen substituent, an oxacyclyl group, an azacyclyl group, a phosphacyclic group, a thiacyclyl group, a substituted amine group, a substituted alkoxy group, a substituted mercapto group, a substituted phenyl group, a substituted biphenyl group, or a substituted naphthyl group.
6. The method for preparing FI catalyst according to claim 3, wherein the inorganic catalyst in step (1) is one of sodium hydroxide, boric acid, copper oxide, phosphorus oxychloride and sodium cyanide.
7. The FI catalyst preparation method of claim 3, wherein the organic solvent in steps (1) and (2) is one or more selected from methanol, ethanol, ethyl acetate, dichloroethane, chloroform, toluene, N-dimethylformamide, pentane, N-hexane, N-heptane, and petroleum ether.
8. The method for preparing an FI catalyst according to claim 3, wherein the phenoxyimine ligand in step (2) has the following structural formula:
Figure FDA0002971356830000022
R5、R6、R7、R8、R9independently hydrogen, C1-C6 straight chain alkyl, branched alkyl, cycloalkyl, halogen substituent, oxacyclyl, azacyclyl, phosphacycloyl, thiacyclyl, substituted amine, substituted alkoxy, substituted mercapto, substituted phenyl, substituted biphenyl, or substituted naphthyl.
9. The method for preparing FI catalyst as claimed in claim 3, wherein the amount of substituted primary amine substance in step (2) is 1-3 times that of salicylaldehyde derivative.
10. The FI catalyst preparation method according to claim 3, wherein the alkyl lithium in step (3) is one or more of isobutyl lithium, tert-butyl lithium or methyl lithium, and the alkyl lithium can be replaced by n-butyl lithium.
11. The method for preparing FI catalyst according to claim 3, wherein the metal chloride in step (3) is any one of chromium chloride, ruthenium chloride, rhodium chloride and palladium chloride, and the metal chloride can be replaced by tetrahydrofuran complex of the metal chloride.
12. The FI catalyst preparation method of claim 3, wherein the molar ratio of the phenoxyimine ligand to the alkyl lithium to the chlorinated metal in step (3) is 0.8-1.2: 0.9-1.5: 0.4-0.6.
13. Use of the FI catalyst of claim 1, wherein the FI catalyst is used to produce low entanglement high molecular weight polyethylene by the steps of: fully drying the polymerization reaction kettle to the required temperature and pressure, wherein the polymerization temperature is 20-70 ℃, the pressure is 1-50bar, introducing ethylene gas, adding a cocatalyst and a solvent, adding the FI catalyst, and polymerizing for 2-6 h to obtain the low-entanglement high-molecular-weight polyethylene.
14. The use of the FI catalyst of claim 13, wherein the co-catalyst is a mixture of one or more of a metal alkyl compound, trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum monochloride, methylaluminoxane and an organic boron compound, and the polymerization temperature is 40-70 ℃;
the solvent comprises organic solvent with boiling point of 30-150 ℃ such as n-hexane, n-heptane, 120# solvent oil, 90# solvent oil, dichloromethane, toluene or xylene.
15. The use of the FI catalyst as claimed in claim 13, wherein the co-catalyst is added in an amount of 0.05-5000mmol and the FI catalyst is added in an amount of 0.05-0.5umol, the dosage of the solvent is 100-450mL, and the catalytic activity of the FI catalyst reaches 7.5 x 107g/mol。
16. The use of the FI catalyst of claim 13, wherein the low entanglement high molecular weight polyethylene has a viscosity average molecular weight of 20 to 800 ten thousand, a crystallinity of 60 to 70%, and a viscosity average molecular weight of polyethylene measured using a high temperature uk viscometer, an intrinsic viscosity of polyethylene measured at 135 ℃ using decalin as a solvent, and a viscosity average molecular weight calculated according to the Mark-Hawink equation.
CN201810994241.0A 2018-08-29 2018-08-29 FI catalyst for preparing low-entanglement high-molecular-weight polyethylene and preparation method and application thereof Active CN109265586B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810994241.0A CN109265586B (en) 2018-08-29 2018-08-29 FI catalyst for preparing low-entanglement high-molecular-weight polyethylene and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810994241.0A CN109265586B (en) 2018-08-29 2018-08-29 FI catalyst for preparing low-entanglement high-molecular-weight polyethylene and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN109265586A CN109265586A (en) 2019-01-25
CN109265586B true CN109265586B (en) 2021-05-11

Family

ID=65154734

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810994241.0A Active CN109265586B (en) 2018-08-29 2018-08-29 FI catalyst for preparing low-entanglement high-molecular-weight polyethylene and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN109265586B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999019335A1 (en) * 1997-10-11 1999-04-22 Bp Chemicals Limited Novel polymerisation catalysts
CN1472230A (en) * 2000-07-04 2004-02-04 三井化学株式会社 Method for preparing polar olefin copolymer and polar olefin copolymer therefrom
CN104053684A (en) * 2011-10-10 2014-09-17 信实工业公司 Process for synthesis of ethylene polymers
CN107501444A (en) * 2017-09-28 2017-12-22 上海化工研究院有限公司 Support type benzene oxygen imines polyolefin catalyst and preparation method and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999019335A1 (en) * 1997-10-11 1999-04-22 Bp Chemicals Limited Novel polymerisation catalysts
CN1472230A (en) * 2000-07-04 2004-02-04 三井化学株式会社 Method for preparing polar olefin copolymer and polar olefin copolymer therefrom
CN104053684A (en) * 2011-10-10 2014-09-17 信实工业公司 Process for synthesis of ethylene polymers
CN107501444A (en) * 2017-09-28 2017-12-22 上海化工研究院有限公司 Support type benzene oxygen imines polyolefin catalyst and preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Salicylaldiminato-based cobalt(III)-, iron(III)-, and chromium(III)/methyl aluminoxane catalyst systems for polymerization of t-butyl acrylate";Adnan S. Abu-Surrah.Khalid A. Ibrahim .Hamzeh M. Abdel-Halim;《Transition Met Chem》;20090831;第803-808页 *

Also Published As

Publication number Publication date
CN109265586A (en) 2019-01-25

Similar Documents

Publication Publication Date Title
KR102209393B1 (en) Supported hybrid catalyst
Yang et al. Homo-and copolymerization of norbornene with tridentate nickel complexes bearing o-aryloxide-N-heterocyclic carbene ligands
KR101768193B1 (en) Metallocene supported catalyst and method for preparing polyolefin using the same
KR101492571B1 (en) Hybride supported metallocene catalysts and method for preparing the same
JP2009537573A (en) Applications for producing organometallic compounds containing heteroatoms and single active site Ziegler-Natta type catalysts
CN108602908B (en) Supported composite catalyst and method for preparing olefin polymer using the same
CN102336846A (en) Loaded alpha-palladium diimine and method for preparing hyperbranched polyethylene by catalyzing with same
CN109957049B (en) Asymmetric (alpha-diimine) nickel olefin catalyst and preparation method and application thereof
CN105153239B (en) A kind of two amido nickel complexes and its preparation method and application
Tian et al. Pd (II) complexes bearing di‐and monochelate fluorinated β‐ketonaphthyliminato ligand and their catalytic properties towards vinyl‐addition polymerization and copolymerization of norbornene and ester‐functionalized norbornene derivative
CN112552433B (en) Constrained geometry metallocene catalyst, preparation method and application thereof
CN109956979B (en) Heat-resistant asymmetric alpha-diimine nickel olefin catalyst and preparation method and application thereof
CN109956980B (en) Ethylidene acenaphthene asymmetric alpha-diimine nickel catalyst and preparation method and application thereof
CN109265586B (en) FI catalyst for preparing low-entanglement high-molecular-weight polyethylene and preparation method and application thereof
KR101262333B1 (en) Post-metallocene complexes based on bis(naphtoxy)pyridine and bis(naphtoxy)thiophene ligands for the polymerisation of ethylene and alpha-olefins
CN112745355A (en) Complex for preparing highly branched poly (4-methyl-1-pentene) material and preparation method thereof
CN108864327A (en) 5,6- dimethyl acenaphthene（Alpha-diimine）Nickel alkene catalyst and its preparation and application
CN109467625B (en) Aniline oxime catalyst and preparation method thereof
Li et al. The influences of electronic effect and isomerization of salalen titanium (iv) complexes on ethylene polymerization in the presence of methylaluminoxane
CN113527190B (en) Pyridine imine ligand, pyridine imine nickel palladium complex based on ligand and application of pyridine imine nickel palladium complex in catalyzing ethylene polymerization reaction
CN111471074B (en) Substituted indenyl metal complex, preparation method and application thereof
HOSSEIN et al. Synthesis of high molecular weight polyethylene using FI catalyst
CN112552436B (en) Metallocene catalyst, preparation method and application thereof
CN104277159B (en) A kind of catalyst for producing Narrow Molecular Weight Distribution polyethylene
CN112851715A (en) Complex for catalyzing polymerization of 4-methyl-1-pentene and preparation method 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