CN111234055A - Supported titanium catalyst and preparation method and application thereof - Google Patents

Supported titanium catalyst and preparation method and application thereof Download PDF

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CN111234055A
CN111234055A CN202010061212.6A CN202010061212A CN111234055A CN 111234055 A CN111234055 A CN 111234055A CN 202010061212 A CN202010061212 A CN 202010061212A CN 111234055 A CN111234055 A CN 111234055A
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silica gel
titanium catalyst
gel carrier
supported titanium
catalyst
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CN111234055B (en
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郑浩
王原
郭建双
王新威
李建龙
徐绍魁
赵志成
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Shanghai Research Institute of Chemical Industry SRICI
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    • 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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene

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Abstract

The invention relates to a supported titanium catalyst and a preparation method and application thereof, which comprises the following steps of carrying out heat activation treatment on a silica gel carrier, reacting the heat-activated silica gel carrier with an organic aluminum compound at a certain temperature to obtain a modified silica gel carrier, reacting the titanium catalyst with the modified silica gel carrier, and washing for several times to obtain the supported titanium catalyst, wherein alkylphenol aluminum is used as an auxiliary agent, and the supported titanium catalyst can be used for ethylene homopolymerization or copolymerization of ethylene and other α -olefin.

Description

Supported titanium catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of olefin coordination polymerization, in particular to a supported titanium catalyst and a preparation method and application thereof.
Background
Polyethylene (PE) is a typical thermoplastic. Polyethylene generally has a molecular weight of between 1 million and 100 million and can be classified according to density into Low Density Polyethylene (LDPE), Medium Density Polyethylene (MDPE), and High Density Polyethylene (HDPE). When the molecular weight is more than 100 ten thousand, the ultrahigh molecular weight polyethylene (UHMWPE) is called, the UHMWPE has unique properties, such as impact resistance, abrasion resistance, low friction coefficient, chemical corrosion resistance, biocompatibility and the like which are incomparable with other engineering plastics, has very wide application prospect in the fields of chemical industry, machinery, textile, medical treatment, military and the like, and has the potential to become the most widely applied polymer material in the world at present.
The catalyst is the core technology of resin products, directly determines the key performance of resin materials and influences the subsequent processing technology and application field. Therefore, designing and developing a high-efficiency catalyst system and perfecting the corresponding loading technology are the technical sources of improving the microstructure of resin, increasing the molecular weight of polyethylene and developing special materials such as novel ultrahigh molecular weight polyethylene. The improvement of the molecular weight of the polyethylene is beneficial to obviously improving the impact resistance and the abrasion resistance. The existing catalyst has certain difficulty in preparing high molecular weight polyethylene, and a bottleneck exists in increasing the molecular weight of the polyethylene. The research and the supporting technology development of the catalyst are always the focus and hot spots of the international academia and the industrial community. In 1953, Ziegler discovered that TiCl was used4And AlEt3The system is a representative IVB group titanium series, vanadium series and other transition metal catalysts, realizes the industrial production of polyethylene, lays the foundation of olefin polymerization industry, and promotes the industrial revolution of olefin polymerization. In 1958, the ultra-high molecular weight polyethylene was successfully developed by Hoechst (Hoechst) in Germany and the industrial production was realized. The Hercules (Hercules) company, Mitsui petrochemical industries, Japan, and Distman Netherlands, all of which were followed by industrial production on a larger scaleAnd (4) producing. Kakugo et al, EP 0721954A 1, disclose a titanium complex of a bis-phenolic derivative, MAO activated (TBP) TiCl2Wasseenaar et al, in patent US 9617362, disclose several naphthoxy imine titanium complexes, which use metal titanium as the active center, introduce trimethylsilyl to the ortho-position of naphthoxy, introduce cyclohexyl, fluoro-substituted phenyl and other groups to the imine moiety2The support of the titanyl imine titanium group metal complex to obtain high molecular weight polyethylene shows extremely high activity, which represents an example of the first borate-free, Methylaluminoxane (MAO) -free high activity unit catalyst system (J.mol.Catal.A.,2004,213, 141-150.).
In summary, although research on ultra-high molecular weight polyethylene catalysts has made a major breakthrough, it is difficult to prepare polyethylene with higher molecular weight, and the increase of molecular weight still has a bottleneck, and further breakthrough cannot be made.
Disclosure of Invention
The invention aims to overcome the defect that the molecular weight needs to be further improved in the prior art, and provides a supported titanium catalyst, and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a supported titanium catalyst comprises the following steps:
(1) carrying out thermal activation treatment on the silica gel carrier;
(2) placing the thermally activated silica gel carrier in a sealed container, adding an organic medium, fully stirring under an inert atmosphere, then dropwise adding an organic aluminum compound to obtain a mixed solution, reacting under the stirring condition, and carrying out solid-liquid separation, washing and drying on the mixed solution after reaction to obtain a modified silica gel carrier;
(3) dissolving a titanium catalyst in an organic medium to obtain a titanium catalyst solution; and dropwise adding the titanium catalyst solution into the modified silica gel carrier under the protection of inert atmosphere to obtain a solid-liquid mixture, continuously stirring to enable the modified silica gel carrier and the titanium catalyst to react, and carrying out solid-liquid separation, washing and drying on the solid-liquid mixture after reaction to obtain the supported titanium catalyst.
The thermal activation treatment in the step (1) is specifically drying or roasting the silica gel carrier for 1-36 hours at the temperature of 120-800 ℃ under the inert atmosphere or reduced pressure condition;
the proportion of the thermally activated silica gel carrier to the organoaluminum compound in the step (2) is 5-10 g: 5.0-10.0 mL; in the reaction process of the mixed solution, the stirring speed is 200-3000 RPM, the reaction temperature is 0-120 ℃, and the reaction time is 2-96 hours;
the weight ratio of the titanium catalyst to the modified silica gel carrier in the step (3) is 1: 1-10000; the reaction temperature in the reaction process of the solid-liquid mixture is 0-120 ℃; the reaction time is 2-96 h.
The organic aluminum compound is one or a mixture of more of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane or isopropylaluminoxane; preferably methylaluminoxane or ethylaluminoxane.
The particle size of the silica gel carrier is 1.0-80 mu m, and the pore volume is 1.0-3.5 cm3A pore diameter of 10 to 30nm and a specific surface area of 150 to 850m2/g。
In the preparation process, the organic medium is selected from one or more of tetrahydrofuran, diethyl ether, toluene, benzene, chloroform, dichloromethane, petroleum ether or n-hexane.
In the whole preparation process, the most key steps are the activation of the silica gel carrier, the loading process of the titanium catalyst and the silica gel carrier and the use of an auxiliary agent in the polymerization process.
Since silica gel surface contains a large amount of adsorbed water and hydroxyl groups, which leads to deactivation of the catalyst, it is very important to reduce the concentration of hydroxyl groups on the silica gel surface by thermal activation. If the thermal activation temperature is too low, the residual hydroxyl on the surface of the silica gel is too much; if the thermal activation temperature is too high, local sintering can be caused to affect the performance of the catalyst. The silica gel carrier is dried or roasted for 1 to 36 hours, preferably for 4 to 6 hours, at the temperature of 120 to 800 ℃, preferably 400 to 600 ℃ and under the inert atmosphere or reduced pressure condition.
After thermal activation, residual hydroxyl on the surface of the silica gel needs to be further removed by chemical reaction. The method uses an organic aluminum compound such as methyl aluminoxane or ethyl aluminoxane to react and remove surface hydroxyl, so that a barrier is formed on the surface of silica gel to prevent the titanium catalyst from contacting with the surface hydroxyl in the subsequent loading process, and the titanium catalyst can be alkylated to form a catalyst active center.
The invention also provides a supported titanium catalyst obtained by the preparation method, and the supported titanium catalyst has the following structure:
Figure BDA0002374556700000031
wherein R is1、R2Is a hydrogen atom, an alkyl group or an aryl group; r3～R7Is a hydrogen atom, an alkyl group, an alkoxy group, a silane group, a heteroatom-containing group or a halogen-substituted group; r8～R9Is alkyl, benzyl or halogen substituent group; m is a group IVB element, preferably titanium, zirconium or hafnium.
The heteroatom-containing group is a hydrocarbyl group (e.g., alkyl, aryl, aralkyl, etc.) having 1 to 20C atoms in the group, wherein at least one C atom is substituted with a heteroatom selected from groups 14 or 15 of the periodic Table of the elements, and the heteroatoms may be the same or different if more than one heteroatom is present in the group.
The group in the halogen substituent group is not required as long as it is substituted with a halogen atom.
The invention also provides an application of the supported titanium catalyst obtained by the preparation method, the supported titanium catalyst catalyzes ethylene homopolymerization or ethylene and α -olefin copolymerization to obtain a polymer under the auxiliary action of an auxiliary agent, and the auxiliary agent is alkylphenol aluminum oxide.
The general formula of the alkyl phenol-oxygen-group aluminum is Al (ArO)nR8 3-nWherein ArO is derived from a hindered phenolic compound ArOH, said hindered phenolic compoundThe phenolic compound ArOH has the structural formula:
Figure BDA0002374556700000041
wherein R is8Is C1～C8A linear or branched alkyl group, preferably methyl, ethyl or isobutyl; r9、R10、R11And R13Hydrogen, alkyl with a C1-C10 linear chain, branched chain or cyclic structure, cumyl, alkoxy, silane group, C6-C10 mono-or multi-alkyl, halogen substituted or unsubstituted benzyl, C7-C20 mono-or multi-aryl substituted alkyl or halogen; the hindered phenol compound ArOH is preferably 2, 6-di-tert-butyl-p-cresol (BHT) or 2,4, 6-tris (dimethylaminomethyl) phenol (TAP).
Further preferably, the aluminum alkyl phenoxide is MeAl (BHT)2Or EtAl (TAP)2。
The selection of an auxiliary agent in the polymerization process is also critical, the auxiliary agent and the supported titanium catalyst play a role in synergy to improve the polymerization reaction effect, and the patent uses alkylphenol aluminum oxide with a general formula of Al (ArO)nR8 3-nThe catalyst can effectively remove impurities in a system, improve the activity of the catalyst, effectively inhibit chain transfer reaction, promote chain growth and improve the viscosity-average molecular weight of a polymer.
The supported titanium catalyst is used for catalyzing ethylene and/or α -olefin to perform slurry polymerization, gas phase polymerization or solution polymerization in an organic medium, the organic medium in the polymerization reaction process is selected from one or more of n-heptane, n-hexane, petroleum ether, toluene, benzene, tetrahydrofuran and dichloromethane, and the α -olefin is selected from one or more of propylene, 1-butene, 1-hexene, 1-octene or norbornene.
The viscosity average molecular weight of the polymer is 100-3000 ten thousand.
Compared with the prior art, the invention has the following advantages:
(1) the catalyst-supported titanium catalyst has high loading efficiency, stable property and high catalytic activity, can be used for preparing the ultra-high molecular weight polyethylene with the molecular weight of 100-3000 ten thousand, and has good shape, better impact resistance and wear resistance and wide application range;
(2) the polymer obtained by the catalyst of the invention has uniform particles and good fluidity, and can meet the requirements of industrial production;
(3) the catalyst of the invention has convenient preparation and stable property, and is easy for industrial implementation and production application.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
A preparation method of a supported titanium catalyst comprises the following steps:
(1) drying or roasting the silica gel carrier for 1-36 h at 120-800 ℃ under an inert atmosphere or a reduced pressure condition for thermal activation to adjust the surface hydroxyl concentration of the silica gel carrier;
(2) placing 5-10 g of thermally activated silica gel carrier in a sealed flask, adding an organic medium, fully stirring under an inert atmosphere, dropwise adding 5.0-10.0 mL of an organic aluminum compound to react with the silica gel carrier at the reaction temperature of 0-120 ℃, fully stirring at the rotating speed of 200-3000 RPM for 2-96 h, and filtering, washing and drying to obtain the required carrier;
(3) placing 5-100 mg of titanium catalyst into a sealed flask, adding 50ml of organic medium for dissolving, then dropwise adding the mixture into a silica gel carrier, continuously stirring, wherein the weight ratio of the titanium catalyst to the silica gel carrier is 1: 1-10000, the reaction temperature is 0-120 ℃, fully contacting the catalyst with the carrier for 2-96 hours, washing, filtering, drying and draining to obtain the supported titanium catalyst.
Wherein, in the step (1), the specification of the silica gel carrier is that the grain diameter is 1.0-80 μm, and the pore volume is 1.0-3.5 cm3A pore diameter of 10 to 30nm, and a specific surface area of 150-850 m2/g；
In the step (2), modifying the silica gel carrier by using an organic aluminum compound, wherein the organic aluminum compound can be selected from methyl aluminoxane, modified methyl aluminoxane, ethyl aluminoxane or isopropyl aluminoxane;
in the step (3), the titanium-based catalyst may be any one of the existing or commercially available titanium-based catalysts applicable to polymerization reaction, and examples thereof include:
Figure BDA0002374556700000061
Figure BDA0002374556700000071
throughout the preparation, the organic medium may be exemplified by tetrahydrofuran, diethyl ether, toluene, benzene, chloroform, methylene chloride, petroleum ether and n-hexane.
The catalyst prepared by the preparation method has the following structure:
Figure BDA0002374556700000081
wherein R is1、R2Is a hydrogen atom, an alkyl group or an aryl group; r3～R7Is a hydrogen atom, an alkyl group, an alkoxy group, a silane group, a heteroatom-containing group or a halogen-substituted group; r8～R9Is alkyl, benzyl or halogen substituent group; m is a group IVB element, preferably titanium, zirconium or hafnium.
The prepared supported titanium catalyst can be used for olefin polymerization process, and specifically, the supported titanium catalyst takes alkyl phenol aluminum oxide with large steric hindrance as an auxiliary agent to catalyze ethylene homopolymerization and ethylene and α -olefin copolymerization.
For the highly sterically hindered aluminum alkylphenyloxys, the general formula is Al (ArO)nR8 3-nArOH is a hindered phenolic compound having the following structural formula:
Figure BDA0002374556700000082
wherein: al (ArO)nR8 3-nIn R8Represents C1-C8 straight-chain and branched-chain alkyl; r9～R13Respectively represent hydrogen, alkyl with a C1-C10 linear chain, branched chain or cyclic structure, cumyl, alkoxy, silane group, C6-C10 mono-or multi-alkyl, halogen substituted or unsubstituted benzyl, C7-C20 mono-or multi-aryl substituted alkyl and halogen.
The catalyst of the embodiment is adopted to carry out slurry polymerization, gas phase polymerization or solution polymerization on ethylene and α -olefin in an organic medium, the organic medium is required to be adopted in the polymerization process, the organic medium can be enumerated by n-heptane, n-hexane, petroleum ether, toluene, benzene, tetrahydrofuran and dichloromethane, α -olefin is propylene, 1-butene, 1-hexene, 1-octene or norbornene, the molecular weight of the polymer obtained after polymerization can reach 100-3000 ten thousand, meanwhile, the polymer particles are uniform, the flowability is good, and the requirement of industrial production can be met.
The following detailed description is given using specific examples:
example 1
The preparation method of the supported titanium catalyst a1 comprises the following steps: under the protection of argon, placing the silica gel carrier in an atmosphere furnace, and roasting at 600 ℃ for 12 hours to obtain the thermally activated silica gel carrier; under the inert gas atmosphere, 5ml of methyl aluminoxane toluene solution is slowly dripped into 10g of thermally activated silica gel carrier, the temperature is raised to 100 ℃, and the stirring reaction is carried out for 12 hours. After cooling to room temperature, filtration was carried out, washing was carried out 3 times with n-heptane, and the remaining solid was dried under vacuum for 4 hours to obtain a chemically treated silica gel carrier. 20mmol of the titanium catalyst a1 was dissolved in 20mL of toluene and added dropwise to 10g of the organoaluminum compound-modified silica gel carrier under the protection of argon. The resulting mixture was stirred at 50 ℃ for 4 hours, allowed to stand for a while, filtered, and the remaining solid was washed once with toluene (5mL) and n-hexane (5mL) in this order, and dried under vacuum for 2 hours to obtain 10.3g of supported titanium catalyst a 1.
Example 2
The preparation method of the supported titanium catalyst a2 comprises the following steps: under the protection of argon, placing the silica gel carrier in an atmosphere furnace, and roasting for 8 hours at 450 ℃ to obtain the thermally activated silica gel carrier; under the inert gas atmosphere, 5ml of methyl aluminoxane toluene solution is slowly dripped into 10g of thermally activated silica gel carrier, the temperature is raised to 85 ℃, and the stirring reaction is carried out for 12 hours. After cooling to room temperature, filtration was carried out, washing was carried out 3 times with n-heptane, and the remaining solid was dried under vacuum for 4 hours to obtain a chemically treated silica gel carrier. 20mmol of the titanium catalyst a2 was dissolved in 20mL of toluene and added dropwise to 10g of the organoaluminum compound-modified silica gel carrier under the protection of argon. The resulting mixture was stirred at 80 ℃ for 4h, allowed to stand for a while, filtered, and the remaining solid was washed once with toluene (5mL) and n-hexane (5mL) in this order, and dried under vacuum for 2h to give 10.2g of supported titanium catalyst a 2.
Example 3
The preparation method of the supported titanium catalyst a3 comprises the following steps: under the protection of argon, placing the silica gel carrier in an atmosphere furnace, and roasting for 4 hours at 600 ℃ to obtain the thermally activated silica gel carrier; under the inert gas atmosphere, 5ml of methyl aluminoxane toluene solution is slowly dripped into 10g of thermally activated silica gel carrier, the temperature is raised to 85 ℃, and the stirring reaction is carried out for 12 hours. After cooling to room temperature, filtration was carried out, washing was carried out 3 times with n-heptane, and the remaining solid was dried under vacuum for 4 hours to obtain a chemically treated silica gel carrier. 20mmol of the titanium catalyst a3 was dissolved in 20mL of toluene and added dropwise to 10g of the organoaluminum compound-modified silica gel carrier under the protection of argon. The resulting mixture was stirred at 60 ℃ for 12 hours, allowed to stand for a while, filtered, and the remaining solid was washed once with toluene (5mL) and n-hexane (5mL) in this order, and dried under vacuum for 2 hours to obtain 10.4g of supported titanium catalyst a 3.
Example 4
The preparation method of the supported titanium catalyst a4 comprises the following steps: under the protection of argon, placing the silica gel carrier in an atmosphere furnace, and roasting for 4 hours at 800 ℃ to obtain the thermally activated silica gel carrier; under the inert gas atmosphere, 5ml of methyl aluminoxane toluene solution is slowly dripped into 10g of thermally activated silica gel carrier, the temperature is raised to 60 ℃, and the stirring reaction is carried out for 12 hours. After cooling to room temperature, filtration was carried out, washing was carried out 3 times with n-heptane, and the remaining solid was dried under vacuum for 4 hours to obtain a chemically treated silica gel carrier. 20mmol of the titanium catalyst was dissolved in 20mL of toluene and added dropwise to 10g of the organoaluminum compound-modified silica gel carrier under the protection of argon. The mixture is stirred and reacted for 4h at the temperature of 80 ℃, kept stand for a while and filtered, and the residual solid is washed once by toluene (5mL) and n-hexane (5mL) in turn and dried for 2h under vacuum, thus obtaining the 10.3 type titanium catalyst a 4.
Example 5
The preparation method of the supported titanium catalyst a5 comprises the following steps: under the protection of argon, placing the silica gel carrier in an atmosphere furnace, and roasting for 12 hours at 500 ℃ to obtain the thermally activated silica gel carrier; under the inert gas atmosphere, 5ml of methyl aluminoxane toluene solution is slowly dripped into 10g of thermally activated silica gel carrier, the temperature is raised to 60 ℃, and the stirring reaction is carried out for 10 hours. After cooling to room temperature, filtration was carried out, washing was carried out 3 times with n-heptane, and the remaining solid was dried under vacuum for 4 hours to obtain a chemically treated silica gel carrier. 20mmol of the titanium catalyst a5 was dissolved in 20mL of toluene and added dropwise to 10g of the organoaluminum compound-modified silica gel carrier under the protection of argon. The obtained mixture is stirred and reacted for 12h at the temperature of 60 ℃, is kept stand for a while, is filtered, the residual solid is washed once by toluene (5mL) and n-hexane (5mL) in turn, and is dried for 2h under vacuum, thus obtaining the 10.2 supported titanium catalyst a 5.
Example 6
The preparation method of the supported titanium catalyst a6 comprises the following steps: under the protection of argon, placing the silica gel carrier in an atmosphere furnace, and roasting for 8 hours at 150 ℃ to obtain the thermally activated silica gel carrier; under the inert gas atmosphere, 5ml of methyl aluminoxane toluene solution is slowly dripped into 10g of thermally activated silica gel carrier, the temperature is raised to 105 ℃, and the reaction is stirred for 2 h. After cooling to room temperature, filtration was carried out, washing was carried out 3 times with n-heptane, and the remaining solid was dried under vacuum for 4 hours to obtain a chemically treated silica gel carrier. 20mmol of the titanium catalyst a6 was dissolved in 20mL of toluene and added dropwise to 10g of the organoaluminum compound-modified silica gel carrier under the protection of argon. The resulting mixture was stirred at 25 ℃ for 6 hours, allowed to stand for a while, filtered, and the remaining solid was washed once with toluene (5mL) and n-hexane (5mL) in this order, and dried under vacuum for 2 hours to obtain 10.4g of supported titanium catalyst a 6.
Example 7
The preparation method of the supported titanium catalyst b1 comprises the following steps: under the protection of argon, placing the silica gel carrier in an atmosphere furnace, and roasting for 6 hours at 750 ℃ to obtain the thermally activated silica gel carrier; under the inert gas atmosphere, 5ml of methyl aluminoxane toluene solution is slowly dripped into 10g of thermally activated silica gel carrier, the temperature is raised to 65 ℃, and the stirring reaction is carried out for 4 hours. After cooling to room temperature, filtration was carried out, washing was carried out 3 times with n-heptane, and the remaining solid was dried under vacuum for 4 hours to obtain a chemically treated silica gel carrier. 20mmol of the titanium-based catalyst b1 was dissolved in 20mL of toluene, and the solution was added dropwise to 10g of the organoaluminum compound-modified silica gel carrier under the protection of argon. The resulting mixture was stirred at 60 ℃ for 6 hours, allowed to stand for a while, filtered, and the remaining solid was washed once with toluene (5mL) and n-hexane (5mL) in this order, and dried under vacuum for 2 hours to obtain 10.5g of supported titanium catalyst b 1.
Example 8
The preparation method of the supported titanium catalyst b2 comprises the following steps: under the protection of argon, placing the silica gel carrier in an atmosphere furnace, and roasting at 750 ℃ for 12 hours to obtain the thermally activated silica gel carrier; under the inert gas atmosphere, 5ml of methyl aluminoxane toluene solution is slowly dripped into 10g of thermally activated silica gel carrier, the temperature is raised to 65 ℃, and the stirring reaction is carried out for 4 hours. After cooling to room temperature, filtration was carried out, washing was carried out 3 times with n-heptane, and the remaining solid was dried under vacuum for 4 hours to obtain a chemically treated silica gel carrier. 20mmol of the titanium-based catalyst b2 was dissolved in 20mL of toluene, and the solution was added dropwise to 10g of the organoaluminum compound-modified silica gel carrier under the protection of argon. The resulting mixture was stirred at 60 ℃ for 8h, allowed to stand for a while, filtered, and the remaining solid was washed once with toluene (5mL) and n-hexane (5mL) in that order, and dried under vacuum for 2h to give 10.4g of supported titanium catalyst b 2.
Example 9
The preparation method of the supported titanium catalyst b3 comprises the following steps: under the protection of argon, placing the silica gel carrier in an atmosphere furnace, and roasting for 2 hours at 250 ℃ to obtain the thermally activated silica gel carrier; under the inert gas atmosphere, 5ml of methyl aluminoxane toluene solution is slowly dripped into 10g of thermally activated silica gel carrier, the temperature is raised to 115 ℃, and the stirring reaction is carried out for 1 h. After cooling to room temperature, filtration was carried out, washing was carried out 3 times with n-heptane, and the remaining solid was dried under vacuum for 4 hours to obtain a chemically treated silica gel carrier. 20mmol of the titanium-based catalyst b3 was dissolved in 20mL of toluene, and the solution was added dropwise to 10g of the organoaluminum compound-modified silica gel carrier under the protection of argon. The resulting mixture was stirred at 90 ℃ for 4h, allowed to stand for a while, filtered, and the remaining solid was washed once with toluene (5mL) and n-hexane (5mL) in that order, and dried under vacuum for 2h to give 10.5g of supported titanium catalyst b 3.
Example 10
The preparation method of the supported titanium catalyst b4 comprises the following steps: under the protection of argon, placing the silica gel carrier in an atmosphere furnace, and roasting for 6 hours at 350 ℃ to obtain the thermally activated silica gel carrier; under the inert gas atmosphere, 5ml of methyl aluminoxane toluene solution is slowly dripped into 10g of thermally activated silica gel carrier, the temperature is raised to 105 ℃, and the reaction is stirred for 2 h. After cooling to room temperature, filtration was carried out, washing was carried out 3 times with n-heptane, and the remaining solid was dried under vacuum for 4 hours to obtain a chemically treated silica gel carrier. 20mmol of the titanium-based catalyst b4 was dissolved in 20mL of toluene, and the solution was added dropwise to 10g of the organoaluminum compound-modified silica gel carrier under the protection of argon. The resulting mixture was stirred at 100 ℃ for 6 hours, allowed to stand for a while, filtered, and the remaining solid was washed once with toluene (5mL) and n-hexane (5mL) in this order, and dried under vacuum for 2 hours to obtain 10.8g of supported titanium catalyst b 4.
Example 11
The preparation method of the supported titanium catalyst c1 comprises the following steps: under the protection of argon, placing the silica gel carrier in an atmosphere furnace, and roasting for 4 hours at 650 ℃ to obtain the thermally activated silica gel carrier; under the inert gas atmosphere, 5ml of methyl aluminoxane toluene solution is slowly dripped into 10g of thermally activated silica gel carrier, the temperature is raised to 95 ℃, and the stirring reaction is carried out for 4 hours. After cooling to room temperature, filtration was carried out, washing was carried out 3 times with n-heptane, and the remaining solid was dried under vacuum for 4 hours to obtain a chemically treated silica gel carrier. 20mmol of the titanium catalyst c1 was dissolved in 20mL of toluene and added dropwise to 10g of the organoaluminum compound-modified silica gel carrier under the protection of argon. The resulting mixture was stirred at 90 ℃ for 6 hours, allowed to stand for a while, filtered, and the remaining solid was washed once with toluene (5mL) and n-hexane (5mL) in this order, and dried under vacuum for 2 hours to obtain 10.9g of supported titanium catalyst c 1.
Example 12
The preparation method of the supported titanium catalyst c2 comprises the following steps: under the protection of argon, placing the silica gel carrier in an atmosphere furnace, and roasting for 2 hours at 650 ℃ to obtain the thermally activated silica gel carrier; under the inert gas atmosphere, 5ml of methyl aluminoxane toluene solution is slowly dripped into 10g of thermally activated silica gel carrier, the temperature is raised to 75 ℃, and the stirring reaction is carried out for 4 hours. After cooling to room temperature, filtration was carried out, washing was carried out 3 times with n-heptane, and the remaining solid was dried under vacuum for 4 hours to obtain a chemically treated silica gel carrier. 20mmol of the titanium catalyst c2 was dissolved in 20mL of toluene and added dropwise to 10g of the organoaluminum compound-modified silica gel carrier under the protection of argon. The resulting mixture was stirred at 120 ℃ for 4h, allowed to stand for a while, filtered, and the remaining solid was washed once with toluene (5mL) and n-hexane (5mL) in this order, and dried under vacuum for 2h to give 10.6g of supported titanium catalyst c 2.
Example 13
The supported titanium catalyst obtained in example 1 is used for preparing ultra-high molecular weight polyethylene, and the specific process is as follows: under nitrogen, 350mL of n-heptane and 1g of MeAl (BHT) were charged into a stainless steel polymerizer2The temperature of the pot liquid was adjusted to 50 ℃ and kept stable, and 10mg of the supported catalyst was weighed and dissolved in n-heptane and added to the reaction pot. The ethylene pressure was rapidly adjusted to 1.0MPa and a timer was started, and the ethylene pressure was kept constant during the polymerization. After reacting for 4h, stopping introducing the ethylene gas, slowly releasing the ethylene gas in the polymerization kettle, adding a 5% hydrochloric acid-ethanol solution to terminate polymerization, and filtering to obtain white solid polyethylene. Vacuum drying until constant weight. Yield: 40.6g, Mη＝1.35×107g/mol. Infrared spectrum at 1471cm-1And 719cm-1Strong absorption signals are respectively shear vibration and plane sway vibration of long-chain methylene, and the polyethylene is shown to have linear structural characteristics. DSC test shows that the polymer has higher melting point (T)m140 c) in combination with its molecular weight, further proved to be linear ultra high molecular weight polyethylene.
Example 14: preparation of ultra-high molecular weight polyethylene
The supported titanium catalyst obtained in example 2 is used for preparing ultra-high molecular weight polyethylene, and the specific process is as follows: under nitrogen, 350mL of toluene and 1g of EtAl (BHT) were added to a stainless steel polymerizer2Regulating the temperature of the kettle liquidTo 50 ℃ and kept stable, 10mg of the supported catalyst was weighed out and dissolved in n-heptane and added to the reaction vessel. The ethylene pressure was rapidly adjusted to 1.0MPa and a timer was started, and the ethylene pressure was kept constant during the polymerization. After reacting for 8h, stopping introducing the ethylene gas, slowly releasing the ethylene gas in the polymerization kettle, adding a 5% hydrochloric acid-ethanol solution to terminate polymerization, and filtering to obtain white solid polyethylene. Vacuum drying until constant weight. Yield: 70.6g, Mη＝1.51×107g/mol. Infrared spectrum at 1471cm-1And 719cm-1Strong absorption signals are respectively shear vibration and plane sway vibration of long-chain methylene, and the polyethylene is shown to have linear structural characteristics. DSC test shows that the polymer has higher melting point (T)mTogether with its molecular weight, 138 ℃) further proves to be linear ultrahigh molecular weight polyethylene.
Example 15: preparation of ultra-high molecular weight polyethylene
The supported titanium catalyst obtained in example 3 is used for preparing ultra-high molecular weight polyethylene, and the specific process is as follows: under nitrogen protection, 350mL of n-hexane and 1g of MeAl (TAP) were added to a stainless steel polymerizer2The temperature of the pot liquid was adjusted to 70 ℃ and kept stable, and 10mg of the supported catalyst was weighed and dissolved in n-heptane and added to the reaction pot. The ethylene pressure was rapidly adjusted to 1.0MPa and a timer was started, and the ethylene pressure was kept constant during the polymerization. After reacting for 4h, stopping introducing the ethylene gas, slowly releasing the ethylene gas in the polymerization kettle, adding a 5% hydrochloric acid-ethanol solution to terminate polymerization, and filtering to obtain white solid polyethylene. Vacuum drying until constant weight. Yield: 40.9g, Mη＝2.15×107g/mol。
Example 16: preparation of ultra-high molecular weight polyethylene
The supported titanium catalyst obtained in example 4 is used for preparing ultra-high molecular weight polyethylene, and the specific process is as follows: under nitrogen, 350mL of n-heptane and 1g of EtAl (BHT) were charged into a stainless steel polymerizer2The temperature of the pot liquid was adjusted to 50 ℃ and kept stable, and 10mg of the supported catalyst was weighed and dissolved in n-heptane and added to the reaction pot. Rapidly adjusting the ethylene pressure to 1.0MPa and starting the timing, andthe ethylene pressure was kept constant during the polymerization. After reacting for 4h, stopping introducing the ethylene gas, slowly releasing the ethylene gas in the polymerization kettle, adding a 5% hydrochloric acid-ethanol solution to terminate polymerization, and filtering to obtain white solid polyethylene. Vacuum drying until constant weight. Yield: 76.2g, Mη＝1.53×107g/mol。
Example 17: preparation of ultra-high molecular weight polyethylene
The supported titanium catalyst obtained in example 5 is used for preparing ultra-high molecular weight polyethylene, and the specific process is as follows: under nitrogen, 350mL of n-heptane and 1g of MeAl (BHT) were charged into a stainless steel polymerizer2The temperature of the kettle liquid is adjusted to 5 ℃ and kept stable, and 10mg of the supported catalyst is weighed and dissolved in n-heptane to be added into the reaction kettle. The ethylene pressure was rapidly adjusted to 1.0MPa and a timer was started, and the ethylene pressure was kept constant during the polymerization. After reacting for 3h, stopping introducing the ethylene gas, slowly releasing the ethylene gas in the polymerization kettle, adding a 5% hydrochloric acid-ethanol solution to terminate polymerization, and filtering to obtain white solid polyethylene. Vacuum drying until constant weight. Yield: 46.5g, Mη＝1.36×107g/mol。
Example 18: preparation of ultra-high molecular weight polyethylene
The supported titanium catalyst obtained in example 6 is used for preparing ultra-high molecular weight polyethylene, and the specific process is as follows: under nitrogen, 350mL petroleum ether and 1g EtAl (BHT) were added to a stainless steel polymerizer2The temperature of the pot liquid was adjusted to 50 ℃ and kept stable, and 10mg of the supported catalyst was weighed and dissolved in n-heptane and added to the reaction pot. The ethylene pressure was rapidly adjusted to 1.0MPa and a timer was started, and the ethylene pressure was kept constant during the polymerization. After reacting for 4h, stopping introducing the ethylene gas, slowly releasing the ethylene gas in the polymerization kettle, adding a 5% hydrochloric acid-ethanol solution to terminate polymerization, and filtering to obtain white solid polyethylene. Vacuum drying until constant weight. Yield: 65.6g, Mη＝2.34×107g/mol。
Example 19: preparation of ultra-high molecular weight polyethylene
The supported titanium catalyst obtained in example 7 was used for preparing ultra-high molecular weight polyethyleneThe alkene comprises the following specific processes: under nitrogen, 350mL of toluene and 1g of MeAl (BHT) were added to a stainless steel polymerizer2The temperature of the pot liquid was adjusted to 50 ℃ and kept stable, and 10mg of the supported catalyst was weighed and dissolved in n-heptane and added to the reaction pot. The ethylene pressure was rapidly adjusted to 1.0MPa and a timer was started, and the ethylene pressure was kept constant during the polymerization. After reacting for 4h, stopping introducing the ethylene gas, slowly releasing the ethylene gas in the polymerization kettle, adding a 5% hydrochloric acid-ethanol solution to terminate polymerization, and filtering to obtain white solid polyethylene. Vacuum drying until constant weight. Yield: 49.6g, Mη＝8.9×106g/mol。
Example 20: preparation of ultra-high molecular weight polyethylene
The supported titanium catalyst obtained in example 8 is used for preparing ultra-high molecular weight polyethylene, and the specific process is as follows: under nitrogen protection, 350mL of toluene and 1g of EtAl (TAP) were added to a stainless steel polymerizer2The temperature of the kettle liquid is adjusted to 45 ℃ and kept stable, and 10mg of the supported catalyst is weighed and dissolved in n-heptane to be added into the reaction kettle. The ethylene pressure was rapidly adjusted to 1.0MPa and a timer was started, and the ethylene pressure was kept constant during the polymerization. After reacting for 4h, stopping introducing the ethylene gas, slowly releasing the ethylene gas in the polymerization kettle, adding a 5% hydrochloric acid-ethanol solution to terminate polymerization, and filtering to obtain white solid polyethylene. Vacuum drying until constant weight. Yield: 31.6g, Mη＝2.16×107g/mol。
Example 21: preparation of ultra-high molecular weight polyethylene
The supported titanium catalyst obtained in example 9 is used for preparing ultra-high molecular weight polyethylene, and the specific process is as follows: under nitrogen protection, 350mL of n-hexane and 1g of MeAl (BHT) were added to a stainless steel polymerizer2The temperature of the kettle liquid is adjusted to 65 ℃ and kept stable, and 10mg of the supported catalyst is weighed and dissolved in n-heptane to be added into the reaction kettle. The ethylene pressure was rapidly adjusted to 0.5MPa and a timer was started, and the ethylene pressure was kept constant during the polymerization. After reacting for 8h, stopping introducing the ethylene gas, slowly releasing the ethylene gas in the polymerization kettle, adding a 5% hydrochloric acid-ethanol solution to terminate polymerization, and filtering to obtain white solid polyethylene. VacuumDrying until constant weight. Yield: 58.7g, Mη＝1.63×107g/mol。
Example 22: preparation of ultra-high molecular weight polyethylene
The supported titanium catalyst obtained in example 10 is used for preparing ultra-high molecular weight polyethylene, and the specific process is as follows: under nitrogen protection, 350mL of toluene and 2g of EtAl (TAP) were added to a stainless steel polymerizer2The temperature of the kettle liquid is adjusted to 80 ℃ and kept stable, and 10mg of the supported catalyst is weighed and dissolved in n-heptane to be added into the reaction kettle. The ethylene pressure was rapidly adjusted to 1.0MPa and a timer was started, and the ethylene pressure was kept constant during the polymerization. After reacting for 6h, stopping introducing the ethylene gas, slowly releasing the ethylene gas in the polymerization kettle, adding a 5% hydrochloric acid-ethanol solution to terminate polymerization, and filtering to obtain white solid polyethylene. Vacuum drying until constant weight. Yield: 61.7g, Mη＝1.56×107g/mol。
The synthesized supported titanium catalyst in the embodiment has high loading efficiency, stable property and high catalytic activity, and the molecular weight of the obtained polymer can reach 100-3000 ten thousand. Meanwhile, the polymer particles are uniform and have good fluidity, and the requirements of industrial production can be met.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.

Claims (10)

1. A preparation method of a supported titanium catalyst is characterized by comprising the following steps:
(1) carrying out thermal activation treatment on the silica gel carrier;
(2) placing the thermally activated silica gel carrier in a sealed container, adding an organic medium, fully stirring under an inert atmosphere, then dropwise adding an organic aluminum compound to obtain a mixed solution, reacting under the stirring condition, and carrying out solid-liquid separation, washing and drying on the mixed solution after reaction to obtain a modified silica gel carrier;
(3) dissolving a titanium catalyst in an organic medium to obtain a titanium catalyst solution; and dropwise adding the titanium catalyst solution into the modified silica gel carrier under the protection of inert atmosphere to obtain a solid-liquid mixture, continuously stirring to enable the modified silica gel carrier and the titanium catalyst to react, and carrying out solid-liquid separation, washing and drying on the solid-liquid mixture after reaction to obtain the supported titanium catalyst.
2. The method of claim 1, wherein the supported titanium-based catalyst is prepared by the following steps,
the thermal activation treatment in the step (1) is specifically drying or roasting the silica gel carrier at 120-800 ℃ under a protective atmosphere or a reduced pressure condition for 1-36 h;
the proportion of the thermally activated silica gel carrier to the organoaluminum compound in the step (2) is 5-10 g: 5.0-10.0 mL; in the reaction process of the mixed solution, the stirring speed is 200-3000 RPM, the reaction temperature is 0-120 ℃, and the reaction time is 2-96 hours;
the weight ratio of the titanium catalyst to the modified silica gel carrier in the step (3) is 1: 1-10000; the reaction temperature in the reaction process of the solid-liquid mixture is 0-120 ℃; the reaction time is 2-96 h.
3. The method for preparing the supported titanium catalyst according to claim 1, wherein the organic aluminum compound is one or a mixture of several selected from methylaluminoxane, modified methylaluminoxane, ethylaluminoxane and isopropylaluminoxane; preferably methylaluminoxane or ethylaluminoxane.
4. The method according to claim 1, wherein the silica gel carrier has a particle size of 1.0 to 80 μm and a pore volume of 1.0 to 3.5cm3A pore diameter of 10 to 30nm and a specific surface area of 150 to 850m2/g。
5. The method for preparing the supported titanium catalyst according to claim 1, wherein in the preparation process, the organic medium is one or more selected from tetrahydrofuran, diethyl ether, toluene, benzene, chloroform, dichloromethane, petroleum ether and n-hexane.
6. A supported titanium-based catalyst obtained by the preparation method according to claim 1, wherein the supported titanium-based catalyst has the following structure:
Figure FDA0002374556690000021
wherein R is1、R2Is a hydrogen atom, an alkyl group or an aryl group; r3～R7Is a hydrogen atom, an alkyl group, an alkoxy group, a silane group, a heteroatom-containing group or a halogen-substituted group; r8～R9Is alkyl, benzyl or halogen substituent group; m is a group IVB element, preferably titanium, zirconium or hafnium.
7. The use of the supported titanium catalyst obtained by the preparation method according to claim 1, wherein the supported titanium catalyst is used for catalyzing homopolymerization of ethylene or copolymerization of ethylene and α -olefin to obtain a polymer under the auxiliary action of an auxiliary agent, wherein the auxiliary agent is aluminum alkyl phenolate.
8. The use of a supported titanium-based catalyst according to claim 7, wherein said aluminum alkyl phenoxide has the general formula Al (ArO)nR8 3-nWherein ArO is derived from a hindered phenolic compound ArOH having the formula:
Figure FDA0002374556690000022
wherein R is8Is C1～C8A linear or branched alkyl group, preferably methyl, ethyl or isobutyl; r9、R10、R11And R13Is hydrogen, C1～C10Alkanes of straight, branched or cyclic structureRadicals, cumyl, alkoxy, silyl radicals, C6～C10Mono-or polyalkyl, halogen-substituted or unsubstituted benzyl, C7～C20Mono-or polyaryl-substituted alkyl or halogen; the hindered phenol compound ArOH is preferably 2, 6-di-tert-butyl-p-cresol or 2,4, 6-tris (dimethylaminomethyl) phenol.
9. The use of the supported titanium catalyst as claimed in claim 7, wherein the supported titanium catalyst is used for catalyzing ethylene and/or α -olefin to perform slurry polymerization, gas phase polymerization or solution polymerization in an organic medium, the organic medium in the polymerization reaction process is selected from one or more of n-heptane, n-hexane, petroleum ether, toluene, benzene, tetrahydrofuran and dichloromethane, and the α -olefin is selected from one or more of propylene, 1-butene, 1-hexene, 1-octene and norbornene.
10. The use of a supported titanium-based catalyst according to claim 7, wherein said polymer has a viscosity average molecular weight of 100 to 3000 ten thousand.
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