74 results about "Aluminoxane" patented technology

Disclosed in the present invention is a composition for preparing a vinyl block copolymer, the composition comprising: a first monomer ethylene, a second monomer a C3-C20 α-olefin and at least one regulation monomer, the regulation monomer being an olefin or a substituted olefin with the C atom number greater than 3, or styrene / a styrene derivative, and in the same composition, the second monomer being different from the regulation monomer. The composition is catalyzed by a main catalyst and a co-catalyst to obtain the vinyl block copolymer, wherein the main catalyst is a complex L-MR1R2R3 that contains three substituents and that is formed by an IVB-group metal and a monoanionic ligand, and the co-catalyst includes alkyl aluminum, polymerized or oligomerized aluminoxane, a neutral Lewis acid, a non-polymer, a non-coordinated ionic compound, or a mixture of two or more described above. Provided in the present invention is a composition capable of obtaining a lower-olefin block copolymer, the composition can obtain a lower-olefin block copolymer without the need of replenishing monomers or adding a chain transfer reagent for polymerization during polymerization processes, so that a production process is simple and involves low cost.

The present application provides a kind of Ziegler-Natta catalyst for preparing high molecular weight polyethylene with narrow molecular weight distribution, porous polymer microspheres are used as carrier, load the Ziegler-Natta catalyst doped with trace metallocene, the doping amount of metallocene is 0.01-2wt% of the amount of Ziegler-Natta catalyst.The preparation method includes the reaction of porous polymer microspheres with alkyl magnesium chloride, then with aluminoxane compound, then the product is reacted with titanium tetrachloride, finally, add metallocene to the product to obtain Ziegler-Natta catalyst.The present application uses porous polymer microspheres as carrier, dopes trace metallocene in Ziegler-Natta catalyst, and the composite catalyst prepared is used for the synthesis of high molecular weight polyethylene, and high molecular weight polyethylene with narrow molecular weight distribution can be obtained, which can meet the application needs of lithium ion battery separator materials.

The invention relates to ethylene homopolymerized wax and a polymerization preparation method thereof. The invention relates to a polymerization preparation method of ethylene homopolymerized wax. The method comprises the following steps: under a catalytic system comprising one or more of a non-metallocene catalyst and a metallocene catalyst as a main catalyst and one or more of aluminoxane, boride, aluminum alkyl and aluminum alkyl chloride as a co-catalyst, carrying out a reaction on the main catalyst and the co-catalyst, ethylene is subjected to a polymerization reaction in the presence of hydrogen in an alkane solvent having a boiling point of 0-90 DEG C or a mixed alkane solvent having a saturated vapor pressure of 4-200 KPa at 20 DEG C as a polymerization solvent (preferably an alkane solvent having a boiling point of 25-82 DEG C or a mixed alkane solvent having a saturated vapor pressure of 30-160 KPa at 20 DEG C as a polymerization solvent). The ethylene homopolymer is narrow in molecular weight distribution, high in crystallinity, low in needle penetration, high in devolatilization efficiency and low in ash content, and the ethylene homopolymer wax shows excellent dispersity in the application of the color master batch and is excellent in processing performance.

The invention provides a preparation method of an antistatic metallocene catalyst. The method comprises the following steps: carrying out thermal activation treatment on a silica gel carrier; loading alkyl tin chloride on the silica gel carrier to obtain an alkyl tin chloride modified silica gel carrier; adding methylaluminoxane into the alkyl tin chloride modified silica gel carrier to obtain a methylaluminoxane / alkyl tin chloride modified silica gel carrier; adding a metallocene compound into the methylaluminoxane / alkyl tin chloride modified silica gel carrier for heating reaction, and then adding an antistatic agent to obtain the antistatic metallocene catalyst. Alkyl tin chloride is used for modifying a silica gel carrier and reacts with hydroxyl to greatly eliminate the hydroxyl; the loading capacity can be improved by combining with MAO, and metallocene combination sites can be increased; after the antistatic agent is added, static electricity generated in the reaction process is reduced, the flaking phenomenon is reduced, and the static electricity range can be controlled to be + / -0.02 KV.

The application discloses a method for selectively oligomerizing ethylene. The method comprises the following steps: filling ethylene into a reaction kettle which is replaced by nitrogen, adjusting temperature and pressure to reaction temperature and reaction pressure; adding a main catalyst and a cocatalyst composition into the reaction kettle to carry out an ethylene oligomerization reaction; after the reaction is completed, temperature and pressure are reduced, and a termination agent is used to terminate the reaction; the molar ratio of total boron and aluminum in the main catalyst and the cocatalyst composition is 1:0.1-7000; the main catalyst is formed by a ligand and a transition metal compound, and the molar ratio of the ligand and the transition metal compound is 0.5-1.5:1. The cocatalyst composition comprises an organic boron compound, an alkyl aluminum compound and an alkyl aluminum oxide compound.

The invention provides a supported metallocene catalyst, a preparation method of the supported metallocene catalyst, an ethylene homopolymerization reaction method and an ethylene and alpha-olefin copolymerization reaction method. The supported metallocene catalyst comprises a carrier, and a metallocene compound and a cocatalyst which are supported on the carrier, the carrier is selected from silicon dioxide and / or aluminum oxide; the metallocene compound has a structure as shown in a formula I. Formula I. The polymer particles are regular, and the phenomenon that the reactor adheres to the kettle is relieved; in addition, when the supported metallocene catalyst is used for copolymerization of ethylene and alpha-olefin by adopting a slurry polymerization process, the polymerization activity can be improved, the cost is reduced, and the dosage of methylaluminoxane is reduced.

The invention relates to modified aluminoxane and a preparation method and application thereof.The preparation method of the modified aluminoxane comprises the following steps that S1, an oxygen-containing compound containing carbonyl and trimethyl aluminum are dispersed in an organic solvent and heated, a transparent solution without gel is formed, and an MAO solution is obtained; and S2, dropwise adding the MAO solution obtained in the step S1 into a trifluoroaryl boron compound solution, mixing, heating for reaction, and washing and drying an obtained precipitated solid to obtain the modified aluminoxane. Compared with the prior art, the method has the advantages that silicon dioxide and the like are not used as carriers, the alkylaluminoxane solution is prepared only through the non-hydrolysis reaction, and near-particulate solid alkylaluminoxane with the median diameter of 1-80 microns is separated out from the alkylaluminoxane solution, so that when the alkylaluminoxane is applied to a polyolefin catalytic system, the high activity of a catalyst can be maintained; the content of inorganic components in polyolefin is reduced, and the processability of a polymer is improved.

The invention discloses a preparation method of an alkylaluminoxane solution, and belongs to the field of alkylaluminoxane preparation. The method comprises the following steps: firstly, performing vacuum drying on an aluminum hydroxide solid at high temperature to remove moisture adsorbed by the aluminum hydroxide solid; then dispersing aluminum hydroxide in an anhydrous hydrocarbon solvent under anhydrous and anaerobic conditions, adding a hydrocarbon solution of trimethylaluminum, and preparing alkylaluminoxo alkyl substrate through double decomposition reaction of the aluminum hydroxide and the trimethylaluminum; and respectively adding aluminum alkyl and inorganic salt hydrate into the alkyl aluminoxane base, reacting at a set temperature, and filtering to remove inorganic salt by-products after the reaction is completed, thereby obtaining the alkyl aluminoxane solution. The method disclosed by the invention is mild in reaction, high in yield and few in byproducts.

The application discloses a preparation method of a single-center catalyst system and application thereof, and the preparation method comprises the following steps: (1) performing vacuum distillation on a modified methylaluminoxane solution, separating out a solvent and aluminum alkyl to obtain a solid product; (2) dissolving the solid product obtained in step (1) with a pentane solution to obtain a homogeneous solution with different aluminum contents; and (3) combining the homogeneous solution obtained in step (2) with a single-active-center catalyst to form a catalyst system. When the single-active-center catalyst system is used for preparing polyethylene wax, different solvents can be avoided from being introduced into a polymerization system, a process flow of the polyethylene wax is simplified, and energy consumption for solvent separation is reduced; reduction of active aluminum helps to improve polymerization activity, the obtained polyethylene wax has lower metal content and narrower molecular weight distribution, the devolatilization efficiency of the polyethylene wax is improved, and the obtained polymer has a VOCs content lower than 20 ppm.

The invention provides an antistatic metallocene catalyst and application thereof. The antistatic metallocene catalyst comprises an antistatic agent / methylaluminoxane / alkyl tin chloride / silica gel carrier and a metallocene compound loaded on the carrier; the antistatic agent / methylaluminoxane / alkyl tin chloride / silica gel carrier is a silica gel carrier modified by an antistatic agent, methylaluminoxane and alkyl tin chloride. Alkyl tin chloride is used for modifying a silica gel carrier and reacts with hydroxyl to greatly eliminate the hydroxyl; the loading capacity can be improved by combining with MAO, and metallocene combination sites can be increased; after the antistatic agent is added, static electricity generated in the reaction process is reduced, the flaking phenomenon is reduced, and the static electricity range can be controlled to be + / -0.02 KV.

The invention provides a method and a system for treating methylaluminoxane gel. The method comprises the following steps: mixing cyclohexane of which the water content is not less than 100ppm and methylaluminoxane gel, and cleaning; the temperature of the cleaning treatment is not higher than 50 DEG C, and the cleaning treatment is carried out at the stirring rotating speed of 50-500rpm. According to the method, gel gathered on the olefin oligomerization cocatalyst storage tank can be removed, and the activity of the catalyst is not influenced.

Forming a catalyst system in the absence of aromatic solvents may be desirable. Catalyst systems effective for olefin polymerization may comprise a support material, an aluminum oxane formed in situ on the support material from a trialkylaluminum compound and water in the absence of aromatic solvents such as toluene, and a metallocene with C1 symmetry and containing a Group 4 metal. To form the catalyst system, the support material can be slurried in an aliphatic hydrocarbon solvent in the presence of water and contacted with a trialkylaluminum compound to form a supported activator, and the supported activator can be contacted with a metallocene with C1 symmetry and containing a Group 4 metal.

The invention relates to the technical field of cocatalyst preparation, and particularly provides alkylaluminoxane and a preparation method thereof. The preparation method of the alkylaluminoxane comprises the following steps: mixing metal salt containing crystal water with anhydrous alkali metal halide, grinding to form mixed crystals, and under the protection of inert atmosphere and inert solution, enabling the mixed crystals to be in contact and react with alkylaluminoxane to obtain the alkylaluminoxane. The alkylaluminoxane and the preparation method provided by the invention are used for realizing synthesis of alkylaluminoxane with high yield, high safety and high storage stability.

The invention provides a preparation method and application of modified alkyl aluminoxane. Comprising the following steps: carrying out first reaction on paraformaldehyde and trialkyl aluminum in a solvent to obtain a precursor solution; performing pyrolysis treatment on the precursor solution to obtain a solution containing alkylaluminoxane; and adding acetone into the solution containing alkylaluminoxane, and carrying out a second reaction at 0-100 DEG C to obtain the modified alkylaluminoxane. The method is beneficial to reducing the content of free alkyl aluminum in the modified alkyl aluminoxane.

This invention relates to catalyst compositions for the selective oligomerization of ethylene, particularly for the tetramerization of ethylene into 1-octene, comprising: - a chromium-based metal precursor; - a heteroatom ligand; - a supported methylaluminoxane on an inorganic support; - an additive in the form of an aluminum-based compound; wherein the composition has a molar ratio of aluminum in the supported methylaluminoxane on the inorganic support to chromium in the metal precursor greater than 250, and a molar ratio of aluminum in the additive to chromium in the metal precursor greater than 200.

The invention discloses a synthesis method of oligomerized methylaluminoxane. According to the method, alkyl aluminum of C2 or above is used as a starting raw material, n value distribution of generated MAO can be effectively controlled, high-oligomerization-degree MAO small in molecular weight distribution range and narrow in n value distribution is obtained, the MAO product catalytic activity is relatively concentrated, the method is especially suitable for a process for preparing high-carbon alpha-olefin through ethylene oligomerization, and the selectivity of target alpha-olefin can be remarkably improved.

This invention discloses a method for preparing low-entanglement ultra-high molecular weight polyethylene using an ONN-type Group IV metal catalyst at high temperature. Using methylaluminoxane (MAO) as a co-catalyst, homopolymerization of ethylene is carried out at a polymerization temperature of 50-110 °C and an ethylene pressure of 10-40 atm to obtain a weight-average molecular weight polyethylene (MAH). M w (Greater than 2.5 × 10) 6 g·mol ‑1 Ultra-high molecular weight polyethylene (UHMWPE) was obtained. The resulting virgin particles exhibited a low-entanglement structure, specifically characterized by: a ≥90% decrease or disappearance of the high-temperature melting peak area after DSC annealing; a storage modulus that increased to more than twice its initial value over time during rheological testing at 160 °C; a lamellar or petal-like crystal morphology as shown by scanning electron microscopy; and the ability to be directly pressed into transparent self-supporting films at room temperature. The Ti1 / MAO system, at 110 °C and 40 atm, still yielded a molecular weight of approximately 2.0 × 10⁻⁶. 6 g·mol ‑1 The polyethylene produced exhibits a tensile strength of 40 MPa and an elongation at break of 576% after hot pressing. This invention enables the direct preparation of low-entanglement UHMWPE under industrial-grade high-temperature and high-pressure conditions, resulting in significantly superior processing performance compared to traditional highly entangled products.

A method for polymerizing olefin monomers. The method comprises reacting ethylene and optionally one or more olefin monomers in the presence of a catalytic system, wherein the catalytic system comprises: AlR having a content of less than 50 mol% based on the total molar amount of aluminum. A1 R B1 R C1 Modified hydrocarbon methylaluminoxane, wherein R A1 R B1 and R C1 Independently for straight chains (C1-C) 40 Alkyl groups, branched (C1-C) 40 )alkyl or (C6-C 40 ) aryl; and one or more metal-ligand complexes according to formula (I).

The present disclosure provides for a supported bis(phenoxy-phenyl) (Sup-BPP) catalysts for production of polyethylene in a slurry-phase polymerization process. The Sup-BPP catalysts of the present disclosure include an inert support in the presence of an aluminoxane compound, where the aluminoxane compound functions as a binding agent. The Sup-BPP can be mixed with the support and the binder in an inert hydrocarbon. The Sup-BPP catalyst can be used for ethylene / alpha-olefin co-polymerizations in a slurry-phase reactor.

Provided are: a method for producing 1,2-polybutadiene, the method capable of producing 1,2-polybutadiene by polymerization without impairing the catalytic activity of a catalyst composition; and a catalyst composition for use in the method.　A method for producing 1,2-polybutadiene according to the present invention has a step for polymerizing 1,3-butadiene in the presence of a catalyst system, the catalyst system containing component (a) that is a salt of a transition metal, component (b) that is an aluminoxane compound, component (c) that is a phosphine compound represented by general formula (1), and component (d) that is a compound containing at least one element selected from the group consisting of nitrogen, oxygen, and sulfur. In general formula (1): R1 and R2 each represent a substituted or unsubstituted hydrocarbyl group having 6 to 30 carbon atoms; and R3 represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted branched alkyl group having 3 to 20 carbon atoms, or a substituted cycloalkyl group having 6 to 30 carbon atoms.

The application discloses an isocyanate polymerization catalyst and a preparation method thereof, and an isocyanate tar purification method. The polymerization catalyst comprises a main catalyst quaternary ammonium base, a first additive methylaluminoxane and / or trimethyl gallium, and a second additive sodium fatty acid. A mixed solution containing isocyanate polymers, urea, and isocyanate monomers in the system is removed of the monomers by catalytic polymerization in a reactor and by adding the catalyst to obtain isocyanate polymers, which are applied to downstream fields such as boards and adhesives. The application can convert waste tar liquid into by-products for sale, has significant economic benefits, and reduces the waste liquid treatment capacity of the running device and the operation cost of the device.

The present application relates to the field of catalysis and olefin polymerization, and discloses a reaction system for preparing polar ethylene copolymer, characterized in that the reaction system comprises: a) at least one metallocene compound; b) at least one alkyl aluminoxane; c) ethylene; d) a monomer represented by formula I; and e) at least one organic aluminum compound; the metallocene compound has a structure represented by formula II and / or formula III; the reaction system has high polymerization activity, can prepare copolymer with high molecular weight and comonomer content, and the prepared copolymer has the performance structure characteristics of both cyclic olefin copolymer and polar monomer copolymer, and has good heat resistance, surface wettability and barrier property.

This invention belongs to the field of petrochemical catalysis technology and relates to a controlled hydrolysis method for trimethylaluminum and its application. The technical features of this invention are as follows: First, hydrated aluminum sulfate is recrystallized in an aqueous solution containing the antisolvent ethanol to prepare small-crystal, plate-like recrystallized hydrated aluminum sulfate. Second, the recrystallized hydrated aluminum sulfate is subjected to low-temperature drying to adjust its water of crystallization content, obtaining a small-crystal, plate-like aluminum sulfate hydrolysant with a specific water of crystallization content. Third, trimethylaluminum is hydrolyzed using the aluminum sulfate hydrolysant with a specific water of crystallization content, controlling the rate and extent of hydrolysis to obtain a methylaluminoxane co-catalyst solution containing aluminum sulfate. The methylaluminoxane co-catalyst solution containing aluminum sulfate prepared by the method of this invention does not require desalting treatment and can be directly used to construct a PNP-Cr ethylene selective tetramerization catalytic system, providing an option for reducing the manufacturing cost of methylaluminoxane and enabling on-site production and use of methylaluminoxane.

Under the load of 2.16 kg and at the temperature of 190 DEG C, the melt index is 600-2500 g / 10 min, the molecular mass distribution is 1.2-1.8, the melting point is 90-135 DEG C, the crystallinity is 50-90%, the true density is 0.930-0.970 g / cm < 3 >, the branching degree is 0-1.0 mol%, the bulk density is 0.30-0.55 g / cm < 3 >, and the average particle size is 200-1000 mm. An alkane solvent with the boiling point being 5-55 DEG C or a mixed alkane solvent with the saturated vapor pressure being 20-150 KPa at the temperature of 20 DEG C is used as a polymerization solvent, a single-active-center catalyst is used as a main catalyst, aluminoxane, modified aluminoxane, alkyl aluminum or halogenated alkyl aluminum is used as a cocatalyst, the polymerization temperature is 70-100 DEG C, the temperature difference in a kettle is smaller than 2.0 DEG C, the polymerization pressure is 1.0-4.2 MPa, and the reaction time is 1-2 hours. A process for the preparation of a reactor slurry polymerization of a feedstock comprising ethylene, hydrogen, and / or a comonomer. The preparation method is simple and easy to control, and the obtained powdery polyethylene is high in melt index, adjustable and controllable in average particle size, true density, melting point, crystallinity and the like, and narrow in particle size distribution.

This invention belongs to the field of catalytic materials technology, specifically relating to a pyridinediimide cobalt complex and its preparation method, as well as a method for preparing 1-hexene. A pyridinediimide cobalt complex has the structural formula: ; wherein, R... 1 Selected from fluorine, chlorine, bromine, ester, cyano, benzyl, and hydrogen; R 2 Selected from methyl, ethyl, isopropyl, fluorine, hydrogen, trifluoromethyl, methoxy, R 2 The positions are ortho, para, and meta of aniline; R 3 Selected from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and hydrogen. This cobalt pyridine diimine complex, under the co-catalysis of methylaluminoxane (MAO), can catalyze the selective oligomerization of propylene to prepare 1-hexene. The oligomerization reaction conditions are mild, and the resulting polyethylene significantly reduces the symmetry and regularity of the polymer chain segments, thereby weakening its crystallinity. While maintaining mechanical strength, it also exhibits excellent flexibility, resistance to environmental stress cracking, and low-temperature impact resistance.

The present disclosure relates to aluminoxane compositions having a substantially or completely non-detectable alkyl aluminum content, methods of of forming such aluminoxane compositions, catalyst systems having the aluminoxane compositions, and methods of of polymerizing olefins using catalyst systems having the aluminoxane compositions. In some embodiments, the present disclosure relates to an unsupported or supported MAO composition, process of forming MAO, catalyst system with MAO, and process of polymerizing olefins using catalyst system with MAO. In some embodiments, the method of making an unsupported or supported MAO having an undetectable or low free trihydrocarbyl aluminum includes introducing an electron withdrawing compound to the unsupported or supported MAO with an electron withdrawing compound to form an unsupported or supported MAO composition having an undetectable or low free trihydrocarbyl aluminum.

The invention relates to the technical field of chemical materials, in particular to a supported metallocene catalyst for polyethylene wax synthesis and a preparation method and application thereof. The supported metallocene catalyst comprises a carrier, a main catalyst and a cocatalyst, the main catalyst comprises a metallocene compound with a structure shown in a general formula (I), R1, R3 and R4 are independently selected from C1-C6 alkyl groups, R2 and R5 are independently selected from C6-C13 aryl groups, Ln is selected from rare earth metal, and X is selected from halogen; the cocatalyst is alkyl aluminum of C1-C12 or alkyl aluminoxane; the carrier is selected from silica gel. The metallocene compound with the specific structure is used as a main catalyst and then is cooperated with a cocatalyst to be loaded on a silica gel carrier, and the formed loaded metallocene catalyst has good stability to hydrogen, high ethylene absorption rate, high polymerization activity and good catalytic activity. And the low molecular weight polyethylene wax with narrow molecular weight distribution can be prepared at low hydrogen partial pressure.

The application belongs to the technical field of conjugated diene polymerization, and particularly relates to a phosphine quinoline ligand, a phosphine quinoline iron complex, a preparation method thereof and application thereof in catalyzing conjugated diene polymerization. The phosphine quinoline ligand and the iron complex are respectively shown as formula I and formula II. The iron complex is a bidentate N, P-coordination catalyst, has a single catalytic active center, and can realize high-activity and high-selectivity polymerization of conjugated dienes by regulating ligand electronic effects, space effects and polymerization conditions. The iron complex only needs 5 equivalents of dry methylaluminoxane to be activated, and still maintains high activity at high temperature (100 DEG C). The obtained polyconjugated diene has narrow molecular weight distribution, and microstructure (cis-1, 4, trans-1, 4, 3, 4 or 1, 2) can be accurately regulated. The reaction system is green, environmentally friendly, low in cost and excellent in thermal stability, and is suitable for industrialized production of high-performance elastomer materials.

The application provides a supported metallocene catalyst and a preparation method, an ethylene homopolymerization method and an ethylene and alpha-olefin copolymerization method. The supported metallocene catalyst comprises a carrier and a metallocene compound and a cocatalyst supported on the carrier; the carrier is selected from silica and / or alumina; the metallocene compound has a structure as shown in formula I. Formula I. The polymer particles of the application are regular, and the reactor sticking phenomenon is reduced; in addition, when the supported metallocene catalyst is used for ethylene and alpha-olefin copolymerization by using a slurry polymerization process, the polymerization activity can be improved, the cost is reduced, and the amount of methylaluminoxane is reduced.