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WO2018187945A1 - Fi supported catalyst, preparation method therefor and use thereof - Google Patents

Fi supported catalyst, preparation method therefor and use thereof Download PDF

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Publication number
WO2018187945A1
WO2018187945A1 PCT/CN2017/080138 CN2017080138W WO2018187945A1 WO 2018187945 A1 WO2018187945 A1 WO 2018187945A1 CN 2017080138 W CN2017080138 W CN 2017080138W WO 2018187945 A1 WO2018187945 A1 WO 2018187945A1
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nanospheres
supported catalyst
polyethylene
aralkyl
ligand
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Chinese (zh)
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陈忠仁
余锋
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Southwest University of Science and Technology
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    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/02—Carriers therefor
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound

Definitions

  • This invention relates to the field of chemistry, and in particular to FI supported catalysts and methods for their preparation and use, and more particularly to FI supported catalysts, methods of making the FI supported catalysts, and methods of making polyethylene.
  • Polyethylene is a commonly used polymer in the industry. There are many catalysts for synthesizing polyethylene.
  • the FI catalyst system is a high performance catalyst for olefin polymerization developed in recent years. Its extremely high activity, controllability of polymer molecular structure, and activity polymerization have attracted people's interest.
  • the molecular weight dispersion of the polyethylene catalyzed by the existing FI catalyst is narrow, and the molecular weight range of the catalytically synthesized polyethylene is adjusted by changing the structure of the FI catalyst, and it is difficult to adjust the molecular weight range of the polyethylene by changing the reaction conditions.
  • an object of the present invention is to provide a FI-supported catalyst which is a pressure-sensitive catalyst which simply adjusts the molecular weight of different polyethylenes by changing the pressure of the polymerization reaction, and the synthetic polyethylene
  • the molecular weight has a high dispersion index.
  • the inventors have found that polystyrene nanospheres having a large steric hindrance are introduced through the catalyst.
  • the process of the ⁇ -hydrogen elimination/reduction elimination reaction sharply increases, and the molecular weight of the polyethylene is lowered by chain transfer.
  • the invention provides a FI supported catalyst.
  • the FI supported catalyst comprises:
  • ligand being covalently linked to said body, said ligand being a polystyrene nanosphere,
  • R 1 is hydrogen, alkyl, heteroalkyl, aralkyl, cycloalkyl, heterocyclyl, heteroaryl or aralkyl;
  • R 2 is hydrogen, alkyl, heteroalkyl, cycloalkyl or aralkyl.
  • the FI-supported catalyst is a pressure-sensitive catalyst
  • the molecular weight of the synthesized polyethylene can be adjusted by merely changing the pressure of the polymerization reaction, and the high molecular weight can be obtained by catalytic polymerization of the FI-supported catalyst at a low pressure.
  • Polyethylene which is catalyzed by high pressure, can obtain low molecular weight polyethylene.
  • low pressure polymerization and high pressure polymerization can be carried out to catalyze the preparation of polyethylene with different molecular weight distribution. Further, the dispersibility of the molecular weight of the synthesized polyethylene can be adjusted.
  • FI-supported catalyst according to the above embodiment of the present invention may further have the following additional technical features:
  • R 1 is alkyl, aralkyl or cycloalkyl; and R 2 is oxo or thioheteroalkyl.
  • the ligand has a particle size of from 10 to 100 nm.
  • the molar ratio of titanium atoms to ligand of the body is (0.1-1):1.
  • the method comprises:
  • the polystyrene nanospheres are subjected to nitrification treatment to obtain nanospheres after nitrification;
  • the nitrified nanospheres are subjected to amination treatment to obtain aminated nanospheres;
  • the compound of formula II is supported on the aminated nanosphere to obtain a loaded nanosphere;
  • R 3 is hydrogen, alkyl, heteroalkyl, aralkyl, cycloalkyl, heterocyclyl, heteroaryl or aralkyl;
  • R 4 is hydrogen, alkyl, heteroalkyl, cycloalkyl or aralkyl.
  • the FI-supported catalyst obtained by supporting the bulk on the nanosphere can adjust the molecular weight of the synthesized polyethylene by merely changing the pressure of the polymerization reaction.
  • the synthetic polyethylene has a high molecular weight dispersibility index.
  • the steps of the method are simple and easy to operate.
  • the FI-supported catalyst prepared by the method has all the technical features and advantages of the above FI-supported catalyst, and will not be described herein.
  • the method comprises: emulsion-polymerizing an emulsifier and an initiator to obtain the polystyrene nanosphere; and dispersing the polystyrene nanosphere in a nitric acid solution after stirring Under the condition, sulfuric acid is added dropwise and reacted for 6-8 hours to obtain the nanosphere after the nitrification; the nanosphere after the nitrification is mixed with glacial acetic acid, hydrochloric acid and SnCl 2 ⁇ 2H 2 O, and stirred under reflux to obtain a solution.
  • Said aminated nanosphere mixing said aminated nanosphere and compound of formula II to obtain said supported nanosphere; and said loaded nanosphere and n-butyllithium TiCl 4 was mixed to obtain the FI supported catalyst.
  • the heteroalkyl group is oxaalkyl, thiaalkyl and azaalkyl.
  • the cycloalkyl group is a C 3-7 cycloalkyl group.
  • the molar ratio of the emulsifier to the initiator is (0.5-1.5):1.
  • the temperature of the emulsion polymerization treatment is from 65 to 80 °C.
  • the emulsion polymerization treatment is carried out under agitation at a speed of from 100 to 300 rpm.
  • the nitrified nanosphere and glacial acetic acid, the hydrochloric acid and the SnCl 2 ⁇ 2H 2 O are nanospheres after nitrification according to 1 g: 1-2 ml of glacial acetic acid: 0.05-0.1 mol of hydrochloric acid The proportions are mixed.
  • the phenolic hydroxyl group of the loaded nanosphere is mixed with the n-butyllithium and the TiCl 4 in a molar ratio of 1:1:1.
  • the present invention provides a method of preparing polyethylene.
  • the polyethylene is catalytically synthesized using the aforementioned FI supported catalyst.
  • the molecular weight of the synthesized polyethylene can be adjusted simply by changing the pressure of the polymerization reaction, and the method can obtain high molecular weight polyethylene by catalytic polymerization at a low pressure by using the aforementioned FI-supported catalyst. Catalytic polymerization under high pressure can obtain low molecular weight polyethylene. In the process of repolymerization, low pressure polymerization and high pressure polymerization can be used to catalyze the preparation of polyethylene with different molecular weight distribution, and it is easy to regulate the molecular weight distribution of polyethylene. Further, the polyethylene synthesized by this method has a high molecular weight dispersibility index.
  • the molecular weight of the polyethylene is inversely related to the pressure of the polymerization reaction.
  • methylaluminoxane is used as a cocatalyst.
  • FIG. 1 shows a schematic structural view of a FI-supported catalyst according to an embodiment of the present invention
  • FIG. 2 shows a schematic flow chart of a method of preparing a FI-supported catalyst according to an embodiment of the present invention
  • FIG. 3 is a flow chart showing a method of preparing a FI-supported catalyst according to an embodiment of the present invention
  • FIG. 4 is a schematic view showing the molecular weight distribution of polyethylene prepared by heating to 30 degrees Celsius according to an embodiment of the present invention
  • Figure 5 is a schematic view showing the molecular weight distribution of polyethylene prepared by heating to 50 degrees Celsius according to an embodiment of the present invention
  • Figure 6 shows a schematic diagram of the molecular weight distribution of bimodal polyethylene according to one embodiment of the present invention
  • Figure 7 shows a photomicrograph of a bimodal polyethylene in accordance with one embodiment of the present invention.
  • the invention provides a FI supported catalyst.
  • the FI supported catalyst is illustrated in accordance with an embodiment of the present invention, the FI supported catalyst comprising: a body 100 and a ligand 200.
  • the body 100 has the structure shown in Formula I; the ligand 200 is covalently attached to the body 100, which is a polystyrene nanosphere.
  • the FI-supported catalyst is a pressure-sensitive catalyst
  • the molecular weight of the synthesized polyethylene can be adjusted by merely changing the pressure of the polymerization reaction, and the high molecular weight can be obtained by catalytic polymerization of the FI-supported catalyst at a low pressure.
  • Polyethylene which is catalyzed by high pressure, can obtain low molecular weight polyethylene.
  • low pressure polymerization and high pressure polymerization can be used to catalyze the preparation of polyethylene with different molecular weight distribution.
  • the synthesized polyethylene has a high molecular weight dispersion index.
  • the pressure-sensitive catalyst catalyzes the synthesis of polyethylene having a molecular weight ranging from 10 3 to 10 6 .
  • R 1 may be hydrogen, alkyl, heteroalkyl, aralkyl, cycloalkyl, heterocyclyl, heteroaryl or aralkyl.
  • R 1 is an alkyl group, an aralkyl group or a cycloalkyl group.
  • R 2 may be hydrogen, alkyl, heteroalkyl, cycloalkyl or aralkyl.
  • R 2 may be oxo or thioheteroalkyl.
  • the R 2 group has a strong electron-donating ability, a small steric hindrance, and a high activity of the catalyst.
  • the ligand may have a particle diameter of 10 to 100 nm.
  • the carrier prepared by the nanoparticles of the particle size range has a high specific surface area, and the prepared polyethylene has good dispersibility.
  • the molar ratio of the titanium atom to the ligand of the bulk may be (0.1-1):1.
  • the amount of the supported catalyst can be adjusted to control the distribution density of the active center on the nano surface, thereby adjusting the morphology of the synthesized polyethylene.
  • a process for the preparation of the aforementioned FI supported catalyst Referring to Figure 2, a method of preparing a FI supported catalyst is illustrated in accordance with an embodiment of the present invention, the method comprising:
  • polystyrene nanospheres are formed.
  • the inventors screened nanospheres of various materials and found that the catalysts using polystyrene nanospheres as ligands have good pressure sensitivity and high catalytic activity.
  • polystyrene nanospheres can be formed by emulsion polymerization using styrene.
  • the size of the polystyrene nanospheres can be controlled by adjusting the ratio of the emulsion-polymerized emulsifier to the initiator, the temperature of the polymerization, the speed of stirring, and the like.
  • the emulsifier may be Sodium dodecyl sulfonate.
  • the initiator may be azobisisobutyronitrile.
  • the ratio of emulsifier to initiator may range from 0.5 to 1.5:1.
  • the temperature of the polymerization may be from 65 to 80 °C.
  • the speed of agitation may be from 100 to 300 revolutions.
  • polystyrene nanospheres having a particle diameter of 10 to 100 nm can be polymerized and synthesized.
  • the polystyrene nanospheres are subjected to a nitrification treatment to obtain nanospheres after nitrification.
  • the nitrated polystyrene is obtained by the nitrification treatment.
  • the method for nitrification treatment may include: mixing polystyrene nanospheres with concentrated nitric acid, then ultrasonically dispersing, slowly adding concentrated sulfuric acid at 0 ° C under stirring, mixing uniformly, and controlling the reaction temperature.
  • the reaction was carried out at 40-45 ° C for 6-8 hours, the reaction was completed, filtered, and washed with deionized water until neutral, and then vacuum dried at 60 ° C for 5 hours to obtain a nanosphere after nitrification.
  • the ratio of polystyrene nanospheres, concentrated nitric acid, and concentrated sulfuric acid is 1 g of polystyrene nanospheres: 2-8 ml of concentrated nitric acid (mass fraction 69%): 0.5-3 ml of concentrated sulfuric acid (mass fraction 98%) ).
  • 1 g of polystyrene nanospheres correspond to 2-8 ml of concentrated nitric acid (69% by mass) and 0.5-3 ml of concentrated sulfuric acid (98% by mass).
  • the nitrated nanospheres are subjected to amination treatment to obtain aminated nanospheres.
  • the nitrated polystyrene is reduced to the aminopolystyrene by amination treatment, facilitating the reaction of the amine group with the compound of the formula II in the subsequent loading treatment.
  • the method of amination treatment comprises: mixing the nitrated polystyrene nanospheres with glacial acetic acid, hydrochloric acid, and SnCl 2 ⁇ 2H 2 O uniformly and refluxing at 80-100 ° C for 7-12 hours. After completion of the reaction, the reaction solution was filtered to obtain a solid product, which was washed with 0.1 mol/L hydrochloric acid, and then dried under vacuum at 40 ° C for 24 hours to obtain an aminated nanosphere.
  • the nitrated nanospheres are mixed with glacial acetic acid, hydrochloric acid, and SnCl 2 ⁇ 2H 2 O in a ratio of 1 g of nitrated nanospheres: 1-2 ml of glacial acetic acid: 0.05 to 0.1 mol of hydrochloric acid.
  • the volume fraction of glacial acetic acid is 99.8%.
  • the compound of the formula II is supported on the aminated nanosphere to obtain a loaded nanosphere.
  • the body is loaded on the nanospheres.
  • the compound of formula II is as follows:
  • R 3 is hydrogen, alkyl, heteroalkyl, aralkyl, cycloalkyl, heterocyclyl, heteroaryl or aralkyl;
  • R 4 is hydrogen, alkyl, heteroalkyl, cycloalkyl or aralkyl.
  • the heteroalkyl group is oxaalkyl, thiaalkyl and azaalkyl.
  • the cycloalkyl group is a C 3-7 cycloalkyl group.
  • the method of loading a compound of formula II on an aminated nanosphere may comprise: mixing the aminated nanosphere with a compound of formula II, adding a catalytic amount of p-methyl The benzenesulfonic acid was refluxed in n-hexane for 4-6 hours and filtered to give a bright yellow powder which was the loaded nanosphere.
  • the aminated nanospheres and the compound of formula II are mixed in a ratio of 1:1.
  • the proportion of the body supported on the nanosphere is suitable.
  • the loaded nanospheres are subjected to a synthesis treatment to obtain a FI-supported catalyst.
  • the FI-supported catalyst was obtained by subjecting the compound of the bulk to organic synthesis treatment.
  • the method of the synthetic treatment comprises: mixing the supported nanospheres and n-butyllithium in a solution of n-hexane and tetrahydrofuran at -78 ° C, and then adding TiCl 4 to the mixed solution, the reaction After 18-24 hours, it was filtered and washed with anhydrous n-hexane to give a FI supported catalyst. Thereby, the reaction efficiency is high and the effect is good.
  • the molar ratio of the phenolic hydroxyl group, n-butyllithium and TiCl 4 of the loaded nanospheres is 1:1:1.
  • Emulsifying agent and initiator are subjected to emulsion polymerization treatment to obtain the polystyrene nanospheres;
  • the FI-supported catalyst obtained by supporting the bulk on the nanosphere can adjust the molecular weight of the synthesized polyethylene by merely changing the pressure of the polymerization reaction.
  • the synthetic polyethylene has a high molecular weight dispersibility index.
  • the steps of the method are simple and easy to operate.
  • the FI-supported catalyst prepared by the method has all the technical features and advantages of the above FI-supported catalyst, and will not be described herein.
  • the present invention provides a method of preparing polyethylene.
  • the polyethylene is catalytically synthesized using the aforementioned FI supported catalyst.
  • the molecular weight of the synthesized polyethylene can be adjusted simply by changing the pressure of the polymerization reaction, and the method can obtain high molecular weight polyethylene by catalytic polymerization at a low pressure by using the aforementioned FI-supported catalyst. Catalytic polymerization under high pressure can obtain low molecular weight polyethylene.
  • low pressure polymerization and high pressure polymerization can be carried out to catalyze the preparation of different distribution of polyethylene, and it is easy to regulate the molecular weight distribution of polyethylene.
  • the party The polyethylene synthesized by the method has a high molecular weight dispersibility index.
  • the molecular weight of the polyethylene is inversely related to the pressure of the polymerization reaction.
  • the high-molecular-weight polyethylene can be obtained by catalytic polymerization at a low pressure by using the FI-supported catalyst, and low-molecular-weight polyethylene can be obtained by catalytic polymerization under high pressure, and low-pressure polymerization and high-pressure polymerization in the repolymerization process can be used to catalyze different preparations.
  • Distributed polyethylene can be used to catalyze different preparations.
  • methylaluminoxane (MAO) is used as a cocatalyst, thereby activating the FI supported catalyst to catalyze the polymerization of ethylene.
  • the supported catalyst is prepared by the method for preparing a FI-supported catalyst according to an embodiment of the present invention. Referring to FIG. 3, the specific steps are as follows:
  • styrene as raw material, sodium dodecyl sulfate as emulsifier and azobisisobutyronitrile as initiator to synthesize PS nanospheres by emulsion polymerization, among which sodium dodecyl sulfate and azobisisobutylene
  • the mass ratio of the nitrile was 1:1, the polymerization temperature was 65-80 ° C, and the stirring speed was 200 rpm, and PS nanospheres having an average particle diameter of 60 nm were obtained.
  • the PS nanospheres and concentrated nitric acid are mixed, then ultrasonically dispersed, and concentrated sulfuric acid is slowly added dropwise at 0 ° C under stirring. After mixing uniformly, the reaction temperature is controlled at 40-45 ° C for 7 hours, and the mixing ratio of the reactants is 1 g PS corresponds to 5 ml concentrated nitric acid (mass fraction 69%) and 2 ml concentrated sulfuric acid (mass fraction 98%). After completion of the reaction, filtration was carried out to obtain a solid powder, which was washed with deionized water until neutral, and then vacuum-dried at 60 ° C for 5 hours until use.
  • the step (2) aminated PS nanospheres and glacial acetic acid, hydrochloric acid, SnCl 2 ⁇ 2H 2 O are uniformly mixed and stirred under reflux at 80-100 ° C for 10 hours, and the ratio of materials used is 1 g PS nanospheres corresponding to 1.5 ml of glacial acetic acid. (volume fraction 99.8%), 4 ml 6 mol/L hydrochloric acid, 2 g SnCl 2 ⁇ 2H 2 O. After the reaction was completed, it was filtered and washed with 0.1 mol/L hydrochloric acid. It was then vacuum dried at 40 ° C for 24 hours until use.
  • the aminated amino group and the 3,5-substituted salicylaldehyde are charged at a ratio of the amine group to the aldehyde group of 1: (0.5-1), and a catalytic amount of p-toluenesulfonic acid is added in n-hexane. After refluxing for 5 hours, filtration gave a bright yellow powder, i.e., supported ligand.
  • 0.1 mol of the supported ligand and 0.1 mol of n-butyllithium were mixed in a solution of n-hexane and tetrahydrofuran at -78 ° C, and then 0.1 mol of TiCl 4 was added, and then reacted for 22 hours, followed by filtration, using anhydrous The alkane is washed to obtain a FI supported catalyst.
  • Example 2 The catalyst prepared in Example 1 was injected into the reaction vessel through a pressure lock under an argon atmosphere, and when the polymerization reaction was completed, ethylene was released to obtain polyethylene.
  • the polyethylene was prepared by the method of Example 2, except that the pressure dependence of the molecular weight on the pressure of the stainless steel reaction vessel was switched from a low pressure of 2 bar to a high pressure of 10 bar to prepare a bimodal polyethylene.
  • the pressure change was polymerization.
  • the reaction was carried out at 2 bar for 30 min and then switched to 10 bar for 60 min.
  • GPC analysis showed a bimodal molecular weight distribution as shown in Figure 6, with two peaks (Mp) of 1,000 and 870,000, respectively.
  • An SEM image of the bimodal molecular weight polyethylene showed uniform particle size and a particle size of about 500 nm, as shown in FIG.

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Abstract

An FI supported catalyst, a preparation method therefor and use thereof. The FI supported catalyst comprises: a body; and a ligand covalently linked to the body, the ligand being a polystyrene nanosphere. Polyethylenes having different molecular weights are synthesized by using the catalyst and changing pressure regulation during a polymerization reaction.

Description

FI负载催化剂及其制备方法和应用FI supported catalyst and preparation method and application thereof 技术领域Technical field

本发明涉及化学领域，具体地，涉及FI负载催化剂及其制备方法和应用，更具体地，涉及FI负载催化剂、制备该FI负载催化剂的方法和制备聚乙烯的方法。This invention relates to the field of chemistry, and in particular to FI supported catalysts and methods for their preparation and use, and more particularly to FI supported catalysts, methods of making the FI supported catalysts, and methods of making polyethylene.

背景技术Background technique

聚乙烯是工业上一种常用的聚合物，合成聚乙烯的催化剂有很多，FI催化剂系是近几年发展起来的烯烃聚合高性能催化剂。它的极高的活性、聚合物分子结构的可控性、活性聚合等特性引起人们的兴趣。但现有的FI催化剂催化合成的聚乙烯的分子量的分散性较窄，多通过改变FI催化剂的结构调节催化合成的聚乙烯的分子量范围，难以通过改变反应条件来调节聚乙烯的分子量范围。Polyethylene is a commonly used polymer in the industry. There are many catalysts for synthesizing polyethylene. The FI catalyst system is a high performance catalyst for olefin polymerization developed in recent years. Its extremely high activity, controllability of polymer molecular structure, and activity polymerization have attracted people's interest. However, the molecular weight dispersion of the polyethylene catalyzed by the existing FI catalyst is narrow, and the molecular weight range of the catalytically synthesized polyethylene is adjusted by changing the structure of the FI catalyst, and it is difficult to adjust the molecular weight range of the polyethylene by changing the reaction conditions.

由此，现有的FI催化剂有待改进。Thus, the existing FI catalyst needs to be improved.

发明内容Summary of the invention

本发明旨在至少解决现有技术中存在的技术问题之一。为此，本发明的一个目的在于提出一种FI负载催化剂，该催化剂是一种压敏性催化剂，只需通过改变聚合反应的压力调节合成不同的聚乙烯的分子量，并且，合成的聚乙烯的分子量的分散性指数高。The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, an object of the present invention is to provide a FI-supported catalyst which is a pressure-sensitive catalyst which simply adjusts the molecular weight of different polyethylenes by changing the pressure of the polymerization reaction, and the synthetic polyethylene The molecular weight has a high dispersion index.

需要说明的是，本发明是基于发明人的下列工作而完成的：It should be noted that the present invention has been completed based on the following work of the inventors:

发明人发现，通过在催化剂引入了空间位阻大的聚苯乙烯纳米球。在聚合压力升高到5bar或更高的时，β-氢消除/还原消除反应的过程急剧增加，通过链转移导致聚乙烯分子量的降低。The inventors have found that polystyrene nanospheres having a large steric hindrance are introduced through the catalyst. When the polymerization pressure is raised to 5 bar or more, the process of the β-hydrogen elimination/reduction elimination reaction sharply increases, and the molecular weight of the polyethylene is lowered by chain transfer.

因而，根据本发明的一个方面，本发明提供了一种FI负载催化剂。根据本发明的实施例，该FI负载催化剂包括：Thus, in accordance with one aspect of the invention, the invention provides a FI supported catalyst. According to an embodiment of the invention, the FI supported catalyst comprises:

本体，所述本体具有式I所示的结构；a body having a structure of Formula I;

配体，所述配体与所述本体共价相连，所述配体为聚苯乙烯纳米球，a ligand, said ligand being covalently linked to said body, said ligand being a polystyrene nanosphere,

Figure PCTCN2017080138-appb-000001
Figure PCTCN2017080138-appb-000001

其中，among them,

R1为氢、烷基、杂烷基、芳烷基、环烷基、杂环基、杂芳基或芳烷基； R 1 is hydrogen, alkyl, heteroalkyl, aralkyl, cycloalkyl, heterocyclyl, heteroaryl or aralkyl;

R2为氢、烷基、杂烷基、环烷基或芳烷基。R 2 is hydrogen, alkyl, heteroalkyl, cycloalkyl or aralkyl.

发明人惊奇地发现，该FI负载催化剂是一种压敏性催化剂，只需通过改变聚合反应的压力即可调节合成的聚乙烯的分子量，利用该FI负载催化剂在低压下催化聚合可以得到高分子量的聚乙烯，在高压下催化聚合可以得到低分子量的聚乙烯，在聚合过程中先低压聚合再高压聚合，可以催化制备不同分子量分布的聚乙烯。并且，合成的聚乙烯的分子量的分散性可调节。The inventors have surprisingly found that the FI-supported catalyst is a pressure-sensitive catalyst, and the molecular weight of the synthesized polyethylene can be adjusted by merely changing the pressure of the polymerization reaction, and the high molecular weight can be obtained by catalytic polymerization of the FI-supported catalyst at a low pressure. Polyethylene, which is catalyzed by high pressure, can obtain low molecular weight polyethylene. In the polymerization process, low pressure polymerization and high pressure polymerization can be carried out to catalyze the preparation of polyethylene with different molecular weight distribution. Further, the dispersibility of the molecular weight of the synthesized polyethylene can be adjusted.

另外，根据本发明上述实施例的FI负载催化剂还可以具有如下附加的技术特征：Further, the FI-supported catalyst according to the above embodiment of the present invention may further have the following additional technical features:

根据本发明的实施例，R1为烷基、芳烷基或环烷基；R2为氧代或硫代杂烷基。According to an embodiment of the invention, R 1 is alkyl, aralkyl or cycloalkyl; and R 2 is oxo or thioheteroalkyl.

根据本发明的实施例，配体的粒径为10-100nm。According to an embodiment of the invention, the ligand has a particle size of from 10 to 100 nm.

根据本发明的实施例，本体的钛原子与配体的摩尔比为(0.1-1)：1。According to an embodiment of the invention, the molar ratio of titanium atoms to ligand of the body is (0.1-1):1.

根据本发明的另一方面，本发明提供了一种制备前述FI负载催化剂的方法。根据本发明的实施例，该方法包括：According to another aspect of the invention, there is provided a process for the preparation of the aforementioned FI supported catalyst. According to an embodiment of the invention, the method comprises:

形成聚苯乙烯纳米球；Forming polystyrene nanospheres;

将所述聚苯乙烯纳米球进行硝化处理，以便得到硝化后的纳米球；The polystyrene nanospheres are subjected to nitrification treatment to obtain nanospheres after nitrification;

将所述硝化后的纳米球进行胺化处理，以便得到胺化后的纳米球；The nitrified nanospheres are subjected to amination treatment to obtain aminated nanospheres;

将式II所示化合物负载在所述胺化后的纳米球上，以便得到负载后的纳米球；以及The compound of formula II is supported on the aminated nanosphere to obtain a loaded nanosphere;

将所述负载后的纳米球进行合成处理，以便获得所述FI负载催化剂，Performing a synthetic treatment on the loaded nanospheres to obtain the FI supported catalyst,

其中，所述式II所示化合物如下：Wherein the compound of formula II is as follows:

Figure PCTCN2017080138-appb-000002
Figure PCTCN2017080138-appb-000002

R3为氢、烷基、杂烷基、芳烷基、环烷基、杂环基、杂芳基或芳烷基；R 3 is hydrogen, alkyl, heteroalkyl, aralkyl, cycloalkyl, heterocyclyl, heteroaryl or aralkyl;

R4为氢、烷基、杂烷基、环烷基或芳烷基。R 4 is hydrogen, alkyl, heteroalkyl, cycloalkyl or aralkyl.

发明人惊奇地发现，利用本发明实施例的制备前述FI负载催化剂的方法，将本体负载在纳米球上得到的FI负载催化剂，只需通过改变聚合反应的压力即可调节合成的聚乙烯的分子量，并且，合成的聚乙烯的分子量的分散性指数高。并且，该方法的步骤简单，易于操作。此外，需要说明的是，该方法制备的FI负载催化剂具有上述FI负载催化剂的全部技术特征和优点，在此不再赘述。The inventors have surprisingly found that by using the method for preparing the aforementioned FI-supported catalyst of the present invention, the FI-supported catalyst obtained by supporting the bulk on the nanosphere can adjust the molecular weight of the synthesized polyethylene by merely changing the pressure of the polymerization reaction. Moreover, the synthetic polyethylene has a high molecular weight dispersibility index. Moreover, the steps of the method are simple and easy to operate. In addition, it should be noted that the FI-supported catalyst prepared by the method has all the technical features and advantages of the above FI-supported catalyst, and will not be described herein.

根据本发明的实施例，该方法包括：将乳化剂和引发剂进行乳液聚合处理，以便得到所述聚苯乙烯纳米球；将所述聚苯乙烯纳米球在硝酸溶液中超声分散后，在搅拌条件下滴加硫酸并反应6-8小时，以便得到所述硝化后的纳米球；将所述硝化后的纳米球与冰醋酸、盐酸和SnCl2·2H2O混合后搅拌回流，以便得到所述胺化后的纳米球；将所述胺化后的纳米球和式II所示化合物混合，以便得到所述负载后的纳米球；以及将所述负载后的纳米球与 正丁基锂和TiCl4混合，以便获得所述FI负载催化剂。According to an embodiment of the present invention, the method comprises: emulsion-polymerizing an emulsifier and an initiator to obtain the polystyrene nanosphere; and dispersing the polystyrene nanosphere in a nitric acid solution after stirring Under the condition, sulfuric acid is added dropwise and reacted for 6-8 hours to obtain the nanosphere after the nitrification; the nanosphere after the nitrification is mixed with glacial acetic acid, hydrochloric acid and SnCl 2 · 2H 2 O, and stirred under reflux to obtain a solution. Said aminated nanosphere; mixing said aminated nanosphere and compound of formula II to obtain said supported nanosphere; and said loaded nanosphere and n-butyllithium TiCl 4 was mixed to obtain the FI supported catalyst.

根据本发明的实施例，所述杂烷基为氧杂烷基、硫杂烷基和氮杂烷基。According to an embodiment of the invention, the heteroalkyl group is oxaalkyl, thiaalkyl and azaalkyl.

根据本发明的实施例，所述环烷基为C3-7环烷基。According to an embodiment of the invention, the cycloalkyl group is a C 3-7 cycloalkyl group.

根据本发明的实施例，所述乳化剂和所述引发剂的摩尔比为(0.5-1.5)：1。According to an embodiment of the invention, the molar ratio of the emulsifier to the initiator is (0.5-1.5):1.

根据本发明的实施例，所述乳液聚合处理的温度为65-80℃。According to an embodiment of the invention, the temperature of the emulsion polymerization treatment is from 65 to 80 °C.

根据本发明的实施例，所述乳液聚合处理是在搅拌条件下进行的，所述搅拌的速度为100-300转。According to an embodiment of the invention, the emulsion polymerization treatment is carried out under agitation at a speed of from 100 to 300 rpm.

根据本发明的实施例，所述硝化后的纳米球与冰醋酸、所述盐酸和所述SnCl2·2H2O是按照1g硝化后的纳米球：1-2ml冰醋酸：0.05-0.1mol盐酸的比例进行混合的。According to an embodiment of the present invention, the nitrified nanosphere and glacial acetic acid, the hydrochloric acid and the SnCl 2 ·2H 2 O are nanospheres after nitrification according to 1 g: 1-2 ml of glacial acetic acid: 0.05-0.1 mol of hydrochloric acid The proportions are mixed.

根据本发明的实施例，所述负载后的纳米球的酚羟基与所述正丁基锂和所述TiCl4按照摩尔比1：1：1进行混合。According to an embodiment of the present invention, the phenolic hydroxyl group of the loaded nanosphere is mixed with the n-butyllithium and the TiCl 4 in a molar ratio of 1:1:1.

根据本发明的又一方面，本发明提供了一种制备聚乙烯的方法。根据本发明的实施例，采用前述的FI负载催化剂催化合成聚乙烯。According to still another aspect of the present invention, the present invention provides a method of preparing polyethylene. According to an embodiment of the invention, the polyethylene is catalytically synthesized using the aforementioned FI supported catalyst.

根据本发明实施例的制备聚乙烯的方法，只需通过改变聚合反应的压力即可调节合成的聚乙烯的分子量，该方法利用前述的FI负载催化剂在低压下催化聚合可以得到高分子量的聚乙烯，在高压下催化聚合可以得到低分子量的聚乙烯，在再聚合过程中先低压聚合再高压聚合，可以催化制备不同分子量分布的聚乙烯，易于调控聚乙烯的分子量的分布。并且，该方法合成的聚乙烯的分子量的分散性指数高。According to the method for producing polyethylene according to the embodiment of the present invention, the molecular weight of the synthesized polyethylene can be adjusted simply by changing the pressure of the polymerization reaction, and the method can obtain high molecular weight polyethylene by catalytic polymerization at a low pressure by using the aforementioned FI-supported catalyst. Catalytic polymerization under high pressure can obtain low molecular weight polyethylene. In the process of repolymerization, low pressure polymerization and high pressure polymerization can be used to catalyze the preparation of polyethylene with different molecular weight distribution, and it is easy to regulate the molecular weight distribution of polyethylene. Further, the polyethylene synthesized by this method has a high molecular weight dispersibility index.

根据本发明的实施例，所述聚乙烯的分子量与聚合反应的压力呈负相关。According to an embodiment of the invention, the molecular weight of the polyethylene is inversely related to the pressure of the polymerization reaction.

根据本发明的实施例，采用甲基铝氧烷为助催化剂。According to an embodiment of the invention, methylaluminoxane is used as a cocatalyst.

本发明的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本发明的实践了解到。The additional aspects and advantages of the invention will be set forth in part in the description which follows.

附图说明DRAWINGS

本发明的上述和/或附加的方面和优点从结合下面附图对实施例的描述中将变得明显和容易理解，其中：The above and/or additional aspects and advantages of the present invention will become apparent and readily understood from

图1显示了根据本发明一个实施例的FI负载催化剂的结构示意图；1 shows a schematic structural view of a FI-supported catalyst according to an embodiment of the present invention;

图2显示了根据本发明一个实施例的制备FI负载催化剂的方法的流程示意图；2 shows a schematic flow chart of a method of preparing a FI-supported catalyst according to an embodiment of the present invention;

图3显示了根据本发明一个实施例的制备FI负载催化剂的方法的流程示意图；3 is a flow chart showing a method of preparing a FI-supported catalyst according to an embodiment of the present invention;

图4显示了根据本发明一个实施例的加热至30摄氏度制备的聚乙烯的分子量分布示意图；4 is a schematic view showing the molecular weight distribution of polyethylene prepared by heating to 30 degrees Celsius according to an embodiment of the present invention;

图5显示了根据本发明一个实施例的加热至50摄氏度制备的聚乙烯的分子量分布示意图；Figure 5 is a schematic view showing the molecular weight distribution of polyethylene prepared by heating to 50 degrees Celsius according to an embodiment of the present invention;

图6显示了根据本发明一个实施例的双峰聚乙烯的分子量分布示意图；Figure 6 shows a schematic diagram of the molecular weight distribution of bimodal polyethylene according to one embodiment of the present invention;

图7显示了根据本发明一个实施例的双峰聚乙烯的显微图片示意图。 Figure 7 shows a photomicrograph of a bimodal polyethylene in accordance with one embodiment of the present invention.

发明详细描述Detailed description of the invention

下面详细描述本发明的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，仅用于解释本发明，而不能理解为对本发明的限制。The embodiments of the present invention are described in detail below, and the examples of the embodiments are illustrated in the drawings, wherein the same or similar reference numerals are used to refer to the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are intended to be illustrative of the invention and are not to be construed as limiting.

根据本发明的一个方面，本发明提供了一种FI负载催化剂。参考图1，根据本发明的实施例，对该FI负载催化剂进行解释说明，该FI负载催化剂包括：本体100和配体200。根据本发明的实施例，本体100具有式I所示的结构；配体200与本体100共价相连，该配体200为聚苯乙烯纳米球。According to one aspect of the invention, the invention provides a FI supported catalyst. Referring to Figure 1, the FI supported catalyst is illustrated in accordance with an embodiment of the present invention, the FI supported catalyst comprising: a body 100 and a ligand 200. According to an embodiment of the invention, the body 100 has the structure shown in Formula I; the ligand 200 is covalently attached to the body 100, which is a polystyrene nanosphere.

发明人惊奇地发现，该FI负载催化剂是一种压敏性催化剂，只需通过改变聚合反应的压力即可调节合成的聚乙烯的分子量，利用该FI负载催化剂在低压下催化聚合可以得到高分子量的聚乙烯，在高压下催化聚合可以得到低分子量的聚乙烯，在再聚合过程中先低压聚合再高压聚合，可以催化制备不同分子量分布的聚乙烯。并且，合成的聚乙烯的分子量的分散指数高。The inventors have surprisingly found that the FI-supported catalyst is a pressure-sensitive catalyst, and the molecular weight of the synthesized polyethylene can be adjusted by merely changing the pressure of the polymerization reaction, and the high molecular weight can be obtained by catalytic polymerization of the FI-supported catalyst at a low pressure. Polyethylene, which is catalyzed by high pressure, can obtain low molecular weight polyethylene. In the process of repolymerization, low pressure polymerization and high pressure polymerization can be used to catalyze the preparation of polyethylene with different molecular weight distribution. Further, the synthesized polyethylene has a high molecular weight dispersion index.

根据本发明的实施例，该压敏性催化剂催化合成的聚乙烯的分子量的范围大，达到103-106。According to an embodiment of the present invention, the pressure-sensitive catalyst catalyzes the synthesis of polyethylene having a molecular weight ranging from 10 3 to 10 6 .

发明人研究发现，R1基团越大聚合的活性越高。根据本发明的实施例，R1可以为氢、烷基、杂烷基、芳烷基、环烷基、杂环基、杂芳基或芳烷基。根据本发明的优选实施例，R1为烷基、芳烷基或环烷基。由此，R1基团的空间位阻大，催化剂的活性高。The inventors have found that the larger the R 1 group, the higher the activity of polymerization. According to an embodiment of the invention, R 1 may be hydrogen, alkyl, heteroalkyl, aralkyl, cycloalkyl, heterocyclyl, heteroaryl or aralkyl. According to a preferred embodiment of the invention, R 1 is an alkyl group, an aralkyl group or a cycloalkyl group. Thereby, the steric hindrance of the R 1 group is large and the activity of the catalyst is high.

同时，发明人还发现，R2基团给电子能力越强聚合活性越高，并且空间位阻越大活性反而降低。根据本发明的实施例，R2可以为氢、烷基、杂烷基、环烷基或芳烷基。根据本发明的优选实施例，R2可以为氧代或硫代杂烷基。由此，R2基团给电子能力强，空间位阻小，催化剂的活性高。At the same time, the inventors have also found that the stronger the electron donating ability of the R 2 group, the higher the polymerization activity, and the greater the steric hindrance, the lower the activity. According to an embodiment of the invention, R 2 may be hydrogen, alkyl, heteroalkyl, cycloalkyl or aralkyl. According to a preferred embodiment of the invention, R 2 may be oxo or thioheteroalkyl. Thus, the R 2 group has a strong electron-donating ability, a small steric hindrance, and a high activity of the catalyst.

根据本发明的实施例，配体的粒径可以为10-100nm。由此，该粒径范围的纳米粒子制备的载体比表面积高，且制备的聚乙烯分散性好。According to an embodiment of the present invention, the ligand may have a particle diameter of 10 to 100 nm. Thus, the carrier prepared by the nanoparticles of the particle size range has a high specific surface area, and the prepared polyethylene has good dispersibility.

根据本发明的实施例，本体的钛原子与配体的摩尔比可以为(0.1-1)：1。由此可以调节负载催化剂的量，从而控制活性中心在纳米表面的分布密度，从而调节合成的聚乙烯的形貌。According to an embodiment of the present invention, the molar ratio of the titanium atom to the ligand of the bulk may be (0.1-1):1. Thereby, the amount of the supported catalyst can be adjusted to control the distribution density of the active center on the nano surface, thereby adjusting the morphology of the synthesized polyethylene.

根据本发明的另一方面，本发明提供了一种制备前述FI负载催化剂的方法。参考图2，根据本发明的实施例，对该制备FI负载催化剂的方法进行解释说明，该方法包括：According to another aspect of the invention, there is provided a process for the preparation of the aforementioned FI supported catalyst. Referring to Figure 2, a method of preparing a FI supported catalyst is illustrated in accordance with an embodiment of the present invention, the method comprising:

S100形成纳米球S100 forms nanospheres

根据本发明的实施例，形成聚苯乙烯纳米球。发明人对多种材料的纳米球进行筛选，发现以聚苯乙烯纳米球为配体的催化剂的压力敏感性好，催化活性高。According to an embodiment of the invention, polystyrene nanospheres are formed. The inventors screened nanospheres of various materials and found that the catalysts using polystyrene nanospheres as ligands have good pressure sensitivity and high catalytic activity.

根据本发明的具体实施例，利用苯乙烯通过乳液聚合可以形成聚苯乙烯纳米球(PS纳米球)。According to a specific embodiment of the present invention, polystyrene nanospheres (PS nanospheres) can be formed by emulsion polymerization using styrene.

根据本发明的实施例，通过调整乳液聚合的乳化剂和引发剂的比例、聚合的温度、搅拌的速度等均可以控制聚苯乙烯纳米球的尺寸。根据本发明的一些实施例，乳化剂可以为 十二烷基磺酸钠。根据本发明的一些实施例，引发剂可以为偶氮二异丁腈。根据本发明的一些实施例，乳化剂和引发剂的比例可以为0.5-1.5：1。根据本发明的一些实施例，聚合的温度可以为65-80℃。根据本发明的一些实施例，搅拌的速度可以为100-300转。由此，通过对上述实验条件的调节，可以聚合合成粒径为10-100nm的聚苯乙烯纳米球。According to an embodiment of the present invention, the size of the polystyrene nanospheres can be controlled by adjusting the ratio of the emulsion-polymerized emulsifier to the initiator, the temperature of the polymerization, the speed of stirring, and the like. According to some embodiments of the invention, the emulsifier may be Sodium dodecyl sulfonate. According to some embodiments of the invention, the initiator may be azobisisobutyronitrile. According to some embodiments of the invention, the ratio of emulsifier to initiator may range from 0.5 to 1.5:1. According to some embodiments of the invention, the temperature of the polymerization may be from 65 to 80 °C. According to some embodiments of the invention, the speed of agitation may be from 100 to 300 revolutions. Thus, by adjusting the above experimental conditions, polystyrene nanospheres having a particle diameter of 10 to 100 nm can be polymerized and synthesized.

S200硝化处理S200 nitrification

根据本发明的实施例，将聚苯乙烯纳米球进行硝化处理，得到硝化后的纳米球。由此，通过硝化处理得到硝化聚苯乙烯。According to an embodiment of the present invention, the polystyrene nanospheres are subjected to a nitrification treatment to obtain nanospheres after nitrification. Thereby, the nitrated polystyrene is obtained by the nitrification treatment.

根据本发明的实施例，该硝化处理的方法可以包括：把聚苯乙烯纳米球和浓硝酸混合，然后超声分散，在0℃、搅拌条件下缓慢滴加浓硫酸，混合均匀后，反应温度控制在40-45℃，反应6-8小时，反应完成后过滤，并用去离子水洗涤至中性，然后60℃下真空烘干5小时，得到硝化后的纳米球。According to an embodiment of the present invention, the method for nitrification treatment may include: mixing polystyrene nanospheres with concentrated nitric acid, then ultrasonically dispersing, slowly adding concentrated sulfuric acid at 0 ° C under stirring, mixing uniformly, and controlling the reaction temperature. The reaction was carried out at 40-45 ° C for 6-8 hours, the reaction was completed, filtered, and washed with deionized water until neutral, and then vacuum dried at 60 ° C for 5 hours to obtain a nanosphere after nitrification.

根据本发明的实施例，聚苯乙烯纳米球、浓硝酸和浓硫酸的比例为1g聚苯乙烯纳米球：2-8ml浓硝酸(质量分数69％)：0.5-3ml浓硫酸(质量分数98％)。换句话说，也就是1g聚苯乙烯纳米球对应2-8ml浓硝酸(质量分数69％)和0.5-3ml浓硫酸(质量分数98％)。According to an embodiment of the present invention, the ratio of polystyrene nanospheres, concentrated nitric acid, and concentrated sulfuric acid is 1 g of polystyrene nanospheres: 2-8 ml of concentrated nitric acid (mass fraction 69%): 0.5-3 ml of concentrated sulfuric acid (mass fraction 98%) ). In other words, 1 g of polystyrene nanospheres correspond to 2-8 ml of concentrated nitric acid (69% by mass) and 0.5-3 ml of concentrated sulfuric acid (98% by mass).

S300胺化处理S300 amination treatment

根据本发明的实施例，将硝化后的纳米球进行胺化处理，得到胺化后的纳米球。由此，通过胺化处理使硝化的聚苯乙烯还原为胺基聚苯乙烯，便于在后续的负载处理中，胺基与式II所示化合物的反应。According to an embodiment of the present invention, the nitrated nanospheres are subjected to amination treatment to obtain aminated nanospheres. Thereby, the nitrated polystyrene is reduced to the aminopolystyrene by amination treatment, facilitating the reaction of the amine group with the compound of the formula II in the subsequent loading treatment.

根据本发明的实施例，胺化处理的方法包括：把硝化后的聚苯乙烯纳米球和冰醋酸、盐酸、SnCl2·2H2O混合均匀在80-100℃下搅拌回流7-12小时，反应结束后，将反应溶液过滤，得到固体产物，并用0.1mol/L的盐酸洗涤，然后40℃下真空烘干24小时，得到胺化后的纳米球。According to an embodiment of the present invention, the method of amination treatment comprises: mixing the nitrated polystyrene nanospheres with glacial acetic acid, hydrochloric acid, and SnCl 2· 2H 2 O uniformly and refluxing at 80-100 ° C for 7-12 hours. After completion of the reaction, the reaction solution was filtered to obtain a solid product, which was washed with 0.1 mol/L hydrochloric acid, and then dried under vacuum at 40 ° C for 24 hours to obtain an aminated nanosphere.

根据本发明的实施例，硝化后的纳米球与冰醋酸、盐酸和SnCl2·2H2O是按照1g硝化后的纳米球：1-2ml冰醋酸：0.05-0.1mol盐酸的比例进行混合的。根据本发明的实施例，冰醋酸的体积分数为99.8％。由此，使硝化后的聚苯乙烯纳米球的硝基充分还原为胺基。According to an embodiment of the present invention, the nitrated nanospheres are mixed with glacial acetic acid, hydrochloric acid, and SnCl 2 · 2H 2 O in a ratio of 1 g of nitrated nanospheres: 1-2 ml of glacial acetic acid: 0.05 to 0.1 mol of hydrochloric acid. According to an embodiment of the invention, the volume fraction of glacial acetic acid is 99.8%. Thereby, the nitro group of the nitrated polystyrene nanospheres is sufficiently reduced to an amine group.

S400负载处理S400 load processing

根据本发明的实施例，将式II所示化合物负载在胺化后的纳米球上，得到负载后的纳米球。由此，将本体负载在纳米球上。According to an embodiment of the present invention, the compound of the formula II is supported on the aminated nanosphere to obtain a loaded nanosphere. Thereby, the body is loaded on the nanospheres.

根据本发明的实施例，式II所示化合物如下：According to an embodiment of the invention, the compound of formula II is as follows:

Figure PCTCN2017080138-appb-000003
Figure PCTCN2017080138-appb-000003

R3为氢、烷基、杂烷基、芳烷基、环烷基、杂环基、杂芳基或芳烷基； R 3 is hydrogen, alkyl, heteroalkyl, aralkyl, cycloalkyl, heterocyclyl, heteroaryl or aralkyl;

R4为氢、烷基、杂烷基、环烷基或芳烷基。R 4 is hydrogen, alkyl, heteroalkyl, cycloalkyl or aralkyl.

根据本发明的实施例，杂烷基为氧杂烷基、硫杂烷基和氮杂烷基。According to an embodiment of the invention, the heteroalkyl group is oxaalkyl, thiaalkyl and azaalkyl.

根据本发明的实施例，环烷基为C3-7环烷基。由此，R3的位阻越大催化剂的活性越高，R4的给电子的能力越强催化剂越稳定，且活性会提高。According to an embodiment of the invention, the cycloalkyl group is a C 3-7 cycloalkyl group. Thus, the higher the steric hindrance of R 3 is , the higher the activity of the catalyst is, and the stronger the electron donating ability of R 4 is , the more stable the catalyst is, and the activity is improved.

根据本发明的具体实施例，将式II所示化合物负载在胺化后的纳米球上的方法可以包括：把胺化后的纳米球和式II所示化合物混合，加入催化量的对甲基苯磺酸，在正己烷中，回流4-6小时，过滤得到亮黄色粉末，该亮黄色粉末即负载后的纳米球。According to a particular embodiment of the invention, the method of loading a compound of formula II on an aminated nanosphere may comprise: mixing the aminated nanosphere with a compound of formula II, adding a catalytic amount of p-methyl The benzenesulfonic acid was refluxed in n-hexane for 4-6 hours and filtered to give a bright yellow powder which was the loaded nanosphere.

根据本发明的实施例，胺化后的纳米球和式II所示化合物按1：1的比例进行混合。由此，纳米球上负载的本体的比例适宜。According to an embodiment of the invention, the aminated nanospheres and the compound of formula II are mixed in a ratio of 1:1. Thereby, the proportion of the body supported on the nanosphere is suitable.

S500合成处理S500 synthesis processing

根据本发明的实施例，将负载后的纳米球进行合成处理，获得FI负载催化剂。由此，通过对本体的化合物进行有机合成处理，得到FI负载催化剂。According to an embodiment of the present invention, the loaded nanospheres are subjected to a synthesis treatment to obtain a FI-supported catalyst. Thus, the FI-supported catalyst was obtained by subjecting the compound of the bulk to organic synthesis treatment.

根据本发明的实施例，合成处理的方法包括：在-78℃条件下，把负载的纳米球和正丁基锂在正己烷和四氢呋喃的溶液中混合，然后再向混合溶液中加入TiCl4，反应18-24小时之后过滤，用无水正己烷洗涤，得FI负载催化剂。由此，反应效率高，效果好。According to an embodiment of the present invention, the method of the synthetic treatment comprises: mixing the supported nanospheres and n-butyllithium in a solution of n-hexane and tetrahydrofuran at -78 ° C, and then adding TiCl 4 to the mixed solution, the reaction After 18-24 hours, it was filtered and washed with anhydrous n-hexane to give a FI supported catalyst. Thereby, the reaction efficiency is high and the effect is good.

根据本发明的具体实施例，该合成处理中，负载后的纳米球的酚羟基、正丁基锂与TiCl4的摩尔比为1：1：1。由此，避免反应物浪费，并为产物的纯化带来影响。According to a specific embodiment of the present invention, in the synthesis treatment, the molar ratio of the phenolic hydroxyl group, n-butyllithium and TiCl 4 of the loaded nanospheres is 1:1:1. Thereby, waste of reactants is avoided and the purification of the product is affected.

进一步地，在此提供一种制备FI负载催化剂的一般方法，该方法包括：Further, there is provided a general method of preparing a FI supported catalyst, the method comprising:

将乳化剂和引发剂进行乳液聚合处理，以便得到所述聚苯乙烯纳米球；Emulsifying agent and initiator are subjected to emulsion polymerization treatment to obtain the polystyrene nanospheres;

将所述聚苯乙烯纳米球在硝酸溶液中超声分散后，在搅拌条件下滴加硫酸并反应6-8小时，以便得到所述硝化后的纳米球；After the polystyrene nanospheres are ultrasonically dispersed in a nitric acid solution, sulfuric acid is added dropwise under stirring for 6-8 hours to obtain the nanospheres after the nitrification;

将所述硝化后的纳米球与冰醋酸、盐酸和SnCl2·2H2O混合后搅拌回流，以便得到所述胺化后的纳米球；Mixing the nitrated nanospheres with glacial acetic acid, hydrochloric acid and SnCl 2 · 2H 2 O, and stirring and refluxing to obtain the aminated nanospheres;

将所述胺化后的纳米球和式II所示化合物混合，以便得到所述负载后的纳米球；Mixing the aminated nanosphere and the compound of formula II to obtain the loaded nanosphere;

将所述负载后的纳米球与正丁基锂和TiCl4混合，以便获得所述FI负载催化剂。The nanospheres after the load with n-butyllithium and mixing TiCl 4, so as to obtain the supported catalyst FI.

发明人惊奇地发现，利用本发明实施例的制备前述FI负载催化剂的方法，将本体负载在纳米球上得到的FI负载催化剂，只需通过改变聚合反应的压力即可调节合成的聚乙烯的分子量，并且，合成的聚乙烯的分子量的分散性指数高。并且，该方法的步骤简单，易于操作。此外，需要说明的是，该方法制备的FI负载催化剂具有上述FI负载催化剂的全部技术特征和优点，在此不再赘述。The inventors have surprisingly found that by using the method for preparing the aforementioned FI-supported catalyst of the present invention, the FI-supported catalyst obtained by supporting the bulk on the nanosphere can adjust the molecular weight of the synthesized polyethylene by merely changing the pressure of the polymerization reaction. Moreover, the synthetic polyethylene has a high molecular weight dispersibility index. Moreover, the steps of the method are simple and easy to operate. In addition, it should be noted that the FI-supported catalyst prepared by the method has all the technical features and advantages of the above FI-supported catalyst, and will not be described herein.

根据本发明的又一方面，本发明提供了一种制备聚乙烯的方法。根据本发明的实施例，采用前述的FI负载催化剂催化合成聚乙烯。According to still another aspect of the present invention, the present invention provides a method of preparing polyethylene. According to an embodiment of the invention, the polyethylene is catalytically synthesized using the aforementioned FI supported catalyst.

根据本发明实施例的制备聚乙烯的方法，只需通过改变聚合反应的压力即可调节合成的聚乙烯的分子量，该方法利用前述的FI负载催化剂在低压下催化聚合可以得到高分子量的聚乙烯，在高压下催化聚合可以得到低分子量的聚乙烯，在聚合过程中先低压聚合再高压聚合，可以催化制备不同分布的聚乙烯，易于调控聚乙烯的分子量的分布。并且，该方 法合成的聚乙烯的分子量的分散性指数高。According to the method for producing polyethylene according to the embodiment of the present invention, the molecular weight of the synthesized polyethylene can be adjusted simply by changing the pressure of the polymerization reaction, and the method can obtain high molecular weight polyethylene by catalytic polymerization at a low pressure by using the aforementioned FI-supported catalyst. Catalytic polymerization under high pressure can obtain low molecular weight polyethylene. In the polymerization process, low pressure polymerization and high pressure polymerization can be carried out to catalyze the preparation of different distribution of polyethylene, and it is easy to regulate the molecular weight distribution of polyethylene. And the party The polyethylene synthesized by the method has a high molecular weight dispersibility index.

根据本发明的实施例，聚乙烯的分子量与聚合反应的压力呈负相关。具体地，利用该FI负载催化剂在低压下催化聚合可以得到高分子量的聚乙烯，在高压下催化聚合可以得到低分子量的聚乙烯，在再聚合过程中先低压聚合再高压聚合，可以催化制备不同分布的聚乙烯。According to an embodiment of the invention, the molecular weight of the polyethylene is inversely related to the pressure of the polymerization reaction. Specifically, the high-molecular-weight polyethylene can be obtained by catalytic polymerization at a low pressure by using the FI-supported catalyst, and low-molecular-weight polyethylene can be obtained by catalytic polymerization under high pressure, and low-pressure polymerization and high-pressure polymerization in the repolymerization process can be used to catalyze different preparations. Distributed polyethylene.

根据本发明的实施例，采用甲基铝氧烷(MAO)为助催化剂，从而，激活FI负载催化剂催化乙烯的聚合。According to an embodiment of the invention, methylaluminoxane (MAO) is used as a cocatalyst, thereby activating the FI supported catalyst to catalyze the polymerization of ethylene.

下面参考具体实施例，对本发明进行说明，需要说明的是，这些实施例仅仅是说明性的，而不能理解为对本发明的限制。The invention is described below with reference to the specific embodiments, which are intended to be illustrative, and are not to be construed as limiting.

下面将结合实施例对本发明的方案进行解释。本领域技术人员将会理解，下面的实施例仅用于说明本发明，而不应视为限定本发明的范围。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品，例如可以采购自Sigma公司。The solution of the present invention will be explained below in conjunction with the embodiments. Those skilled in the art will appreciate that the following examples are merely illustrative of the invention and are not to be considered as limiting the scope of the invention. Where specific techniques or conditions are not indicated in the examples, they are carried out according to the techniques or conditions described in the literature in the art or in accordance with the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are conventional products that can be obtained commercially, for example, can be purchased from Sigma.

实施例1Example 1

利用本发明实施例的制备FI负载催化剂方法制备负载催化剂，参考图3，具体步骤如下：The supported catalyst is prepared by the method for preparing a FI-supported catalyst according to an embodiment of the present invention. Referring to FIG. 3, the specific steps are as follows:

(1)PS纳米球的合成(1) Synthesis of PS nanospheres

以苯乙烯为原料，以十二烷基磺酸钠为乳化剂，偶氮二异丁腈为引发剂利用乳液聚合合成PS纳米球，其中，十二烷基磺酸钠和偶氮二异丁腈的质量比为1：1、聚合的温度为65-80℃、搅拌的速度为200转，得到平均粒径为60nm的PS纳米球。Using styrene as raw material, sodium dodecyl sulfate as emulsifier and azobisisobutyronitrile as initiator to synthesize PS nanospheres by emulsion polymerization, among which sodium dodecyl sulfate and azobisisobutylene The mass ratio of the nitrile was 1:1, the polymerization temperature was 65-80 ° C, and the stirring speed was 200 rpm, and PS nanospheres having an average particle diameter of 60 nm were obtained.

(2)PS纳米球的硝化(2) Nitrification of PS nanospheres

先把PS纳米球和浓硝酸混合，然后超声分散，在0℃、搅拌条件下缓慢滴加浓硫酸，混合均匀后，反应温度控制在40-45℃，反应7小时，反应物的混合比例为1g PS对应5ml浓硝酸(质量分数69％)和2ml浓硫酸(质量分数98％)。反应完成后过滤，得到固体粉末，并用去离子水洗涤至中性，然后60℃下真空烘干5小时，待用。First, the PS nanospheres and concentrated nitric acid are mixed, then ultrasonically dispersed, and concentrated sulfuric acid is slowly added dropwise at 0 ° C under stirring. After mixing uniformly, the reaction temperature is controlled at 40-45 ° C for 7 hours, and the mixing ratio of the reactants is 1 g PS corresponds to 5 ml concentrated nitric acid (mass fraction 69%) and 2 ml concentrated sulfuric acid (mass fraction 98%). After completion of the reaction, filtration was carried out to obtain a solid powder, which was washed with deionized water until neutral, and then vacuum-dried at 60 ° C for 5 hours until use.

(3)PS纳米球的胺化(3) Amination of PS nanospheres

把步骤(2)胺基化的PS纳米球和冰醋酸、盐酸、SnCl2·2H2O混合均匀在80-100℃下搅拌回流10小时，用料比例为1g PS纳米球对应1.5ml冰醋酸(体积分数99.8％)、4ml 6mol/L的盐酸、2g SnCl2·2H2O.。反应完成后过滤，并用0.1mol/L的盐酸洗涤。然后40℃下真空烘干24小时，待用。The step (2) aminated PS nanospheres and glacial acetic acid, hydrochloric acid, SnCl 2 · 2H 2 O are uniformly mixed and stirred under reflux at 80-100 ° C for 10 hours, and the ratio of materials used is 1 g PS nanospheres corresponding to 1.5 ml of glacial acetic acid. (volume fraction 99.8%), 4 ml 6 mol/L hydrochloric acid, 2 g SnCl 2 · 2H 2 O. After the reaction was completed, it was filtered and washed with 0.1 mol/L hydrochloric acid. It was then vacuum dried at 40 ° C for 24 hours until use.

(4)配体负载(4) ligand loading

把胺基化的PS和3，5取代的水杨醛按照胺基和醛基的比例为1：(0.5-1)进行投料，加入催化量的对甲基苯磺酸，在正己烷中，回流5小时，过滤得到亮黄色粉末，即负载的配体。The aminated amino group and the 3,5-substituted salicylaldehyde are charged at a ratio of the amine group to the aldehyde group of 1: (0.5-1), and a catalytic amount of p-toluenesulfonic acid is added in n-hexane. After refluxing for 5 hours, filtration gave a bright yellow powder, i.e., supported ligand.

(5)催化剂的合成 (5) Synthesis of catalyst

把0.1mol负载的配体和0.1mol正丁基锂，在-78℃条件下正己烷和四氢呋喃的溶液中混合，然后再加入0.1mol TiCl4，然后反应22个小时之后过滤，用无水正己烷洗涤，得FI负载催化剂。0.1 mol of the supported ligand and 0.1 mol of n-butyllithium were mixed in a solution of n-hexane and tetrahydrofuran at -78 ° C, and then 0.1 mol of TiCl 4 was added, and then reacted for 22 hours, followed by filtration, using anhydrous The alkane is washed to obtain a FI supported catalyst.

实施例2Example 2

利用实施例1的催化剂在不同的温度和压力条件下分别合成8组聚乙烯，方法如下：Eight groups of polyethylene were synthesized by using the catalyst of Example 1 under different temperature and pressure conditions, as follows:

(1)向配有U型搅拌器的不锈钢反应釜中加入甲苯(500mL)。恒温器在150rpm的搅拌速度下将反应器加热到30或50℃。乙烯的压力在1-10bar，具体反应条件详见表1。(1) Toluene (500 mL) was placed in a stainless steel reactor equipped with a U-type stirrer. The thermostat was heated to 30 or 50 ° C at a stirring speed of 150 rpm. The pressure of ethylene is 1-10 bar, and the specific reaction conditions are shown in Table 1.

(2)在氩气氛下通过一个压力锁把实施例1制备的催化剂注入到反应釜中，当聚合反应完成后，释放乙烯，得到聚乙烯。(2) The catalyst prepared in Example 1 was injected into the reaction vessel through a pressure lock under an argon atmosphere, and when the polymerization reaction was completed, ethylene was released to obtain polyethylene.

(3)将聚乙烯在400mL酸化的甲醇溶液中搅拌，然后过滤，并在70℃真空烘箱中干燥5h，得到聚乙烯产品，各组聚乙烯产品的参数如表1和图4和5所示。(3) The polyethylene was stirred in 400 mL of acidified methanol solution, then filtered, and dried in a vacuum oven at 70 ° C for 5 h to obtain a polyethylene product. The parameters of each group of polyethylene products are shown in Table 1 and Figures 4 and 5. .

表1聚合反应条件和结果Table 1 polymerization conditions and results

Figure PCTCN2017080138-appb-000004
Figure PCTCN2017080138-appb-000004

实验结果表明，在30℃聚合条件下压力增高，分子量降低，50℃条件下有同样的规律，温度增高活性会有所增高，但分散指数并没有明显的变化规律。The experimental results show that under the polymerization condition of 30 °C, the pressure increases and the molecular weight decreases. Under the condition of 50 °C, the same law occurs, and the temperature increase activity will increase, but the dispersion index has no obvious change rule.

实施例3Example 3

利用实施例2的方法制备聚乙烯，其不同在于，本实施例利用分子量对压力的依赖性，将不锈钢反应釜的压力从低压2bar切换到高压10bar制备双峰聚乙烯，压力的变化情况为聚合反应在2bar下进行30min，再切换到10bar下进行60min。GPC分析展示双峰分子量分布如图6所示，两个峰(Mp)分别为1,000和870,000。双峰分子量的聚乙烯的SEM图像显示粒子尺寸均一，粒径大约500nm，如图7所示。The polyethylene was prepared by the method of Example 2, except that the pressure dependence of the molecular weight on the pressure of the stainless steel reaction vessel was switched from a low pressure of 2 bar to a high pressure of 10 bar to prepare a bimodal polyethylene. The pressure change was polymerization. The reaction was carried out at 2 bar for 30 min and then switched to 10 bar for 60 min. GPC analysis showed a bimodal molecular weight distribution as shown in Figure 6, with two peaks (Mp) of 1,000 and 870,000, respectively. An SEM image of the bimodal molecular weight polyethylene showed uniform particle size and a particle size of about 500 nm, as shown in FIG.

尽管本发明的具体实施方式已经得到详细的描述，本领域技术人员将会理解。根据已经公开的所有教导，可以对那些细节进行各种修改和替换，这些改变均在本发明的保护范围之内。本发明的全部范围由所附权利要求及其任何等同物给出。Although specific embodiments of the invention have been described in detail, those skilled in the art will understand. Various modifications and alterations of the details are possible in light of the teachings of the invention. The full scope of the invention is given by the appended claims and any equivalents thereof.

在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示意性实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结 构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不一定指的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。 In the description of the present specification, the description with reference to the terms "one embodiment", "some embodiments", "illustrative embodiment", "example", "specific example", or "some examples", etc. Specific features and knots described in the examples or examples A structure, material or feature is included in at least one embodiment or example of the invention. In the present specification, the schematic representation of the above terms does not necessarily mean the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in a suitable manner in any one or more embodiments or examples.

Claims (16)

一种FI负载催化剂，其特征在于，包括：A FI supported catalyst characterized by comprising: 本体，所述本体具有式I所示的结构；a body having a structure of Formula I; 配体，所述配体与所述本体共价相连，所述配体为聚苯乙烯纳米球，a ligand, said ligand being covalently linked to said body, said ligand being a polystyrene nanosphere,
Figure PCTCN2017080138-appb-100001
Figure PCTCN2017080138-appb-100001
 其中，among them, R1为氢、烷基、杂烷基、芳烷基、环烷基、杂环基、杂芳基或芳烷基；R 1 is hydrogen, alkyl, heteroalkyl, aralkyl, cycloalkyl, heterocyclyl, heteroaryl or aralkyl; R2为氢、烷基、杂烷基、环烷基或芳烷基。R 2 is hydrogen, alkyl, heteroalkyl, cycloalkyl or aralkyl. 根据权利要求1所述的FI负载催化剂，其特征在于，The FI supported catalyst according to claim 1, wherein R1为烷基、芳烷基或环烷基；R 1 is an alkyl group, an aralkyl group or a cycloalkyl group; R2为氧代或硫代杂烷基。R 2 is oxo or thioheteroalkyl. 根据权利要求1所述的FI负载催化剂，其特征在于，所述配体的粒径为10-100nm。The FI-supported catalyst according to claim 1, wherein the ligand has a particle diameter of from 10 to 100 nm. 根据权利要求1所述的FI负载催化剂，其特征在于，所述本体的钛原子与所述配体的摩尔比为(0.1-1)：1。The FI-supported catalyst according to claim 1, wherein a molar ratio of titanium atoms to said ligand of said body is (0.1-1):1. 一种制备权利要求1-4任一项所述FI负载催化剂的方法，其特征在于，包括：A method of preparing the FI-supported catalyst according to any one of claims 1 to 4, comprising: 形成聚苯乙烯纳米球；Forming polystyrene nanospheres; 将所述聚苯乙烯纳米球进行硝化处理，以便得到硝化后的纳米球；The polystyrene nanospheres are subjected to nitrification treatment to obtain nanospheres after nitrification; 将所述硝化后的纳米球进行胺化处理，以便得到胺化后的纳米球；The nitrified nanospheres are subjected to amination treatment to obtain aminated nanospheres; 将式II所示化合物负载在所述胺化后的纳米球上，以便得到负载后的纳米球；以及The compound of formula II is supported on the aminated nanosphere to obtain a loaded nanosphere; 将所述负载后的纳米球进行合成处理，以便获得所述FI负载催化剂，Performing a synthetic treatment on the loaded nanospheres to obtain the FI supported catalyst, 其中，所述式II所示化合物如下： Wherein the compound of formula II is as follows:
Figure PCTCN2017080138-appb-100002
Figure PCTCN2017080138-appb-100002
 R3为氢、烷基、杂烷基、芳烷基、环烷基、杂环基、杂芳基或芳烷基；R 3 is hydrogen, alkyl, heteroalkyl, aralkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl or aralkyl; R4为氢、烷基、杂烷基、环烷基或芳烷基。R 4 is hydrogen, alkyl, heteroalkyl, cycloalkyl or aralkyl. 根据权利要求5所述的方法，其特征在于，所述杂烷基为氧杂烷基、硫杂烷基和氮杂烷基。The method of claim 5 wherein said heteroalkyl group is oxaalkyl, thiaalkyl and azaalkyl. 根据权利要求5所述的方法，其特征在于，所述环烷基为C3-7环烷基。The method of claim 5 wherein the cycloalkyl group is a C 3-7 cycloalkyl group. 根据权利要求5所述的方法，其特征在于，包括：The method of claim 5, comprising: 将乳化剂和引发剂进行乳液聚合处理，以便得到所述聚苯乙烯纳米球；Emulsifying agent and initiator are subjected to emulsion polymerization treatment to obtain the polystyrene nanospheres; 将所述聚苯乙烯纳米球在硝酸溶液中超声分散后，在搅拌条件下滴加硫酸并反应6-8小时，以便得到所述硝化后的纳米球；After the polystyrene nanospheres are ultrasonically dispersed in a nitric acid solution, sulfuric acid is added dropwise under stirring for 6-8 hours to obtain the nanospheres after the nitrification; 将所述硝化后的纳米球与冰醋酸、盐酸和SnCl2·2H2O混合后搅拌回流，以便得到所述胺化后的纳米球；Mixing the nitrated nanospheres with glacial acetic acid, hydrochloric acid and SnCl 2 · 2H 2 O, and stirring and refluxing to obtain the aminated nanospheres; 将所述胺化后的纳米球和式II所示化合物混合，以便得到所述负载后的纳米球；以及Mixing the aminated nanospheres with a compound of formula II to obtain the loaded nanospheres; 将所述负载后的纳米球与正丁基锂和TiCl4混合，以便获得所述FI负载催化剂。The nanospheres after the load with n-butyllithium and mixing TiCl 4, so as to obtain the supported catalyst FI. 根据权利要求8所述的方法，其特征在于，所述乳化剂和所述引发剂的摩尔比为(0.5-1.5)：1。The method according to claim 8, wherein the molar ratio of the emulsifier to the initiator is (0.5 - 1.5): 1. 根据权利要求8所述的方法，其特征在于，所述乳液聚合处理的温度为65-80℃。The method according to claim 8, wherein the emulsion polymerization treatment has a temperature of from 65 to 80 °C. 根据权利要求8所述的方法，其特征在于，所述乳液聚合处理是在搅拌条件下进行的，所述搅拌的速度为100-300转。The method according to claim 8, wherein the emulsion polymerization treatment is carried out under agitation at a speed of from 100 to 300 rpm. 根据权利要求8所述的方法，其特征在于，所述硝化后的纳米球与冰醋酸、所述盐酸和所述SnCl2·2H2O是按照1g硝化后的纳米球：1-2ml冰醋酸：0.05-0.1mol盐酸的比例进行混合的。The method according to claim 8, wherein the nitrified nanospheres and glacial acetic acid, the hydrochloric acid and the SnCl 2 ·2H 2 O are nanospheres after nitrification according to 1 g: 1-2 ml of glacial acetic acid : A ratio of 0.05-0.1 mol of hydrochloric acid was mixed. 根据权利要求8所述的方法，其特征在于，所述负载后的纳米球的酚羟基与所述正丁基锂和所述TiCl4按照摩尔比1：1：1进行混合。The method according to claim 8, wherein the phenolic hydroxyl group of the loaded nanospheres is mixed with the n-butyllithium and the TiCl 4 in a molar ratio of 1:1:1. 一种制备聚乙烯的方法，其特征在于，采用权利要求1-4任一项所述的FI负载催化剂催化合成聚乙烯。A process for the preparation of polyethylene, characterized in that the polyethylene is catalytically synthesized by the FI supported catalyst according to any one of claims 1 to 4. 根据权利要求14所述的方法，其特征在于，所述聚乙烯的分子量与聚合反应的压力呈负相关。The method of claim 14 wherein the molecular weight of the polyethylene is inversely related to the pressure of the polymerization reaction. 根据权利要求14所述的方法，其特征在于，采用甲基铝氧烷为助催化剂。 The method of claim 14 wherein methylaluminoxane is used as a cocatalyst.
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