An organic polymer carrier, Z-N catalyst and preparation method and application thereof

Abstract

The application provides an organic polymer carrier, a Z-N catalyst and a preparation method and application thereof. The organic polymer carrier is obtained by copolymerization of monomers including divinylbenzene and unsaturated di-ester-based silane monomers; wherein the unsaturated di-ester-based silane monomer has a structure shown in formula I: the catalyst has good polymerization activity and can catalyze polymerization to obtain ultrahigh molecular weight polyethylene with a viscosity average molecular weight of more than 7 million.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of catalysts, and particularly relates to an organic polymer carrier, a Z-N catalyst and a preparation method and application thereof, and particularly relates to an organic carrier loaded Z-N type ultrahigh molecular weight polyethylene catalyst system and a preparation method thereof. BACKGROUND

[0002] Ultrahigh molecular weight polyethylene (UHMWPE) generally refers to linear long-chain polyethylene material with a relative molecular weight of 1.5 million (or a viscosity average molecular weight of 1 million) or above. The ultrahigh molecular weight polyethylene has excellent properties such as high strength, impact resistance, wear resistance, self-lubrication, chemical corrosion resistance, low temperature resistance, etc. Main products include fibers, films, pipes, plates, rods, porous materials and profiled materials, etc., and are widely used in aerospace, ocean engineering, petrochemical industry, new energy materials and other fields.

[0003] The catalysts for preparing UHMWPE at present mainly include Ziegler-Natta catalyst, metallocene catalyst and non-metallocene catalyst such as phenoxy imine (FI) catalyst. The first UHMWPE was prepared by using Ziegler-Natta catalyst (hereinafter referred to as "Z-N catalyst"). There are many published methods for preparing Z-N type UHMWPE catalyst. Generally, TiCl4 is loaded on compounds such as Mg(OR)2, MgCl2 or MgR2, and then various processes are used to prepare UHMWPE catalyst by using alkyl aluminum reduction. In the process, internal electron donors can be added to control the electrophilicity of Ti active center to control the performance of the catalyst, such as patents US4,447,587, US4,933,393 and US6,114,271. The molecular weight of the polymer can be adjusted by the amount of alcohol added, such as US4,138,540. In addition, US4,962,167 prepared UHMWPE catalyst by the reaction of MgCl2 with titanium alkoxide compound, and then with aluminum trihalide and tetraalkoxysilane; CN106220768A added organosilicon compound electron donor to the UHMWPE catalyst in the Ti / Mg system; CN103509140A disclosed a method for preparing a UHMWPE catalyst. The catalyst was prepared by adding alcoholate to the solution of the reaction product of halogenated magnesium compound carrier and hydrocarbon solvent to form magnesium alcoholate with magnesium halide, then adding halogenated alkyl aluminum compound, and the halogenated alkyl aluminum compound and magnesium alcoholate formed an intermediate product, which was emulsified and then titanium compound was added for titanium loading reaction, and the catalyst was obtained by washing and drying. The invention can greatly improve the catalyst activity through emulsification technology, and the polymer obtained by polymerization has a high viscosity average molecular weight, which can reach more than 4 million. CN114181334A disclosed a UHMWPE catalyst system and its preparation method. The catalyst components include magnesium complex, acetic acid ester compound, titanium-containing compound, at least one 1,3-diether electron donor and or o-dimethyl ether electron donor, and olefin polymerization can obtain UHMWPE with a viscosity average molecular weight of more than 7 million.

[0004] Metallocene catalysts and non-metallocene catalysts are single-site catalysts, which can produce polymers with narrower molecular weight distribution compared to Z-N catalysts, thus improving product performance. Subsequently, many research teams and companies have studied metallocene catalysts. For example, Teknor Applied Catalysts uses a bridged metallocene catalyst to produce ultra-high molecular weight polyethylene with a viscosity average molecular weight of more than 1 million. In Angew Chem Int Ed. "Donor-acceptor metallocene catalysts for the production of UHMWPE: Pushing the selectivity for chain growth to its limits" (2006; 45 volume, pages 1799-1803), a metallocene compound [(Flu)Et2PB(Ph)2(Cp)]ZrCl2 is used to prepare ultra-high molecular weight polyethylene, and the viscosity average molecular weight reaches 3.9 million. CN101356199A discloses a double indenyl substituted bridged metallocene catalyst for ultra-high molecular weight polymer. The bridged metallocene catalyst can be dimethylsilyl-[2-isopropyl-4-(p-isopropyl-phenyl) indenyl][2-methyl-4-(p-isopropylphenyl) indenyl] zirconium dichloride, dimethylsilyl-bis(2-isopropyl indenyl) zirconium dichloride, etc. The metallocene catalysts reported so far for ultra-high molecular weight polyethylene have lower molecular weight than Z-N catalysts, and the synthesis of catalyst compounds is complex, and the catalyst and cocatalyst are expensive, which limits their industrial application.

[0005] At the same time, non-metallocene catalysts are also developing, CN102030844B discloses a supported non-metallocene polyolefin catalyst, which can be used to prepare ultra-low branching degree ultra-high molecular weight polyethylene, and the catalyst is a non-metallocene compound containing [ONX] tridentate ligand. Typical non-metallocene catalysts such as phenoxy imine (FI) catalysts can generally control the molecular weight of ultra-high molecular weight polyethylene through substituents on the compound. CN107936164A discloses a copolymerization type UHMWPE, which has a molecular weight comparable to that of homopolymerization products, and also has a comparable comonomer content, and the comonomer content is adjustable and controllable, the particle morphology is good, the bulk density is high, the activity decay is not obvious, and the α-olefin homopolymerization can be catalyzed without adding internal and external electron donors. The loss of wear resistance and impact strength performance of UHMWPE is low. However, the supported non-metallocene catalysts are easy to detach during polymerization, which leads to uneven distribution of polymer particles and the problem of sticking kettle.

[0006] The organic polymer support is different from the reported inorganic support, the POP support itself does not introduce impurities, thereby affecting the performance of the polymer. In addition, the organic support has the characteristics of controllable pore structure, high specific surface area, stable thermal performance, and easy functionalization. The high-performance or characteristic polyolefin catalyst can be prepared by designing and functionalizing the support. There are reports on porous organic support loaded Z-N catalyst, usually using organic support containing carboxylic acid group, hydroxyl group, cyano group, amino group and other functional groups to prepare Z-N catalyst, and the molecular weight of the polyethylene product obtained by polymerization is usually less than 300,000. For example, in the polymer "Porous polyethylene spheres with nanofiber structure from Ziegler-Natta catalyst supported on porous polymer particles" (2011; 52: 602-605), a cyano-functionalized organic support was used to prepare a POP support-loaded Z-N polyethylene catalyst, and the weight average molecular weight was between 100,000-200,000 g / mol. In J. Polym. Res. "Ethylene polymerization on polymer supported Ziegler-Natta catalyst" (2012; 19:9892, 1-13), a methyl methacrylate-functionalized POP support was used to prepare a Z-N polyethylene catalyst, and the weight average molecular weight was between 200,000-300,000 g / mol. In addition, metallocene catalysts prepared using organic supports, such as US 5,587,439, which uses an organic support containing a carboxylate group to prepare a metallocene catalyst, the molecular weight of the polyethylene product obtained by ethylene polymerization is less than 300,000. In addition, in the Journal of Polymer Science: Part A: Polymer Chemistry "Ultrahigh Molecular Weight Polyethylene Produced by a Bis(phenoxy-imine) Titanium Complex Supported on Latex Particles" (2006; 3103-3113), a porous organic support containing pyridine function and polyethylene oxide group was prepared by microemulsion polymerization, and a bisphenol amine titanium (FI-Ti) catalyst compound was used to prepare an ultrahigh molecular weight polyethylene catalyst. The weight average molecular weight of the prepared polyethylene is between 2,000,000-7,000,000, and the active center of the ultrahigh molecular weight polyethylene catalyst belongs to the FI-titanium series, not the Z-N catalyst.Patent US4,623,707 uses organic support prepared from chloromethylated styrene monomer to prepare Z-N catalyst; "Immobilization of Titanium Tetrachloride on Mixed Support of MgCl2xEB / Poly(methyl acrylate-co-1-octene):Catalyst for Synthesis of Broad MWD Polyethylene" (2009; 132; 87-93) in Catalyst Letter uses methyl acrylate and 1-octene copolymer as support to prepare Z-N catalyst for preparing broad molecular weight distribution polyethylene. SUMMARY

[0007] In order to solve the above problems, the present application aims to provide an organic polymer support, a Z-N catalyst and a preparation method and application thereof, the catalyst having good polymerization activity and being capable of catalyzing polymerization to obtain ultrahigh molecular weight polyethylene with viscosity average molecular weight of 7 million or more.

[0008] In order to achieve the above-mentioned purpose, the present application provides an organic polymer support, which is prepared by copolymerization of monomers including divinylbenzene and unsaturated di-ester-based silane monomers; wherein the unsaturated di-ester-based silane monomers have the structure shown in Formula I:

[0009]

[0010] In Formula I, R1, R2, R3 are each independently selected from hydrogen, chlorine, bromine, C1-C6 linear alkyl and derivatives thereof, C1-C6 branched alkyl and derivatives thereof, cycloalkyl and derivatives thereof, aryl and derivatives thereof; x is 0-6; R4 is selected from hydrogen, C1-C8 linear alkyl and derivatives thereof, C1-C8 branched alkyl and derivatives thereof, cycloalkyl and derivatives thereof, aryl and derivatives thereof; R5, R6 are each independently selected from hydrogen, C1-C8 linear alkyl and derivatives thereof, C1-C8 branched alkyl and derivatives thereof, cycloalkyl and derivatives thereof, aryl and derivatives thereof.

[0011] According to a specific embodiment of the present application, preferably, in Formula I, R1, R2, R3 are each independently selected from hydrogen, ethyl, chlorine, bromine, methyl; R4 is selected from methyl, ethyl, isopropyl, n-butyl, isobutyl, phenyl, phenoxy, methoxy, ethoxy; R5, R6 are each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-heptyl, phenyl, cyclohexyl, isohexyl, 2-ethylpentyl, 2-ethylbutyl; x is 0, 1.

[0012] According to a specific embodiment of the present application, preferably, the unsaturated di- ester silane monomer is selected from one or more than two combinations of vinylmethyl bis(methyl formate) silane, vinylmethyl bis(methyl acetate) silane (or vinylmethyl bis(acetyloxymethyl) silane), vinylmethyl bis(methyl propionate) silane, vinylmethyl bis(methyl n-butyrate) silane, vinylmethyl bis(methyl isobutyrate) silane, vinylmethyl bis(methyl n-pentanoate) silane, vinylmethyl bis(methyl n-hexanoate) silane, vinylmethyl bis(methyl n-octanoate) silane, vinylmethyl bis(methyl 2-methylhexanoate) silane, vinylmethyl bis(methyl 2- ethylhexanoate) silane, vinylmethyl bis(methyl 2-ethylpentanoate) silane, vinylmethyl bis(methyl benzoate) silane, vinylmethyl bis(methyl cyclohexanecarboxylate) silane, vinyl ethyl bis(methyl acetate) silane, vinyl phenyl bis(methyl acetate) silane, vinyl n-butyl bis(methyl acetate) silane, vinyl isobutyl bis(methyl acetate) silane, vinyl isopropyl bis(methyl acetate) silane, vinyl ethoxyl bis(methyl acetate) silane, allyl methyl bis(methyl acetate) silane, allyl methyl bis(methyl propionate) silane, allyl methyl bis(methyl n-butyrate) silane, allyl methyl bis(methyl isobutyrate) silane, allyl methyl bis(methyl n-pentanoate) silane, allyl methyl bis(methyl n-hexanoate) silane, allyl methyl bis(methyl n-octanoate) silane, allyl methyl bis(methyl 2-methylhexanoate) silane, allyl methyl bis(methyl 2- ethylhexanoate) silane, allyl methyl bis(methyl 2-ethylpentanoate) silane, allyl methyl bis(methyl benzoate) silane, allyl methyl bis(methyl cyclohexanecarboxylate) silane, allyl ethyl bis(methyl acetate) silane, allyl phenyl bis(methyl acetate) silane, allyl n-butyl bis(methyl acetate) silane, allyl isobutyl bis(methyl acetate) silane, allyl isopropyl bis(methyl acetate) silane, allyl methoxyl bis(methyl acetate) silane, allyl ethoxyl bis(methyl acetate) silane, allyl ethoxyl bis(methyl benzoate) silane, 1-butenyl ethoxyl bis(methyl acetate) silane, 1-buten-4-yl isopropyl bis(methyl benzoate) silane, allyl phenoxy bis(methyl acetate) silane, 1-chloroallyl ethoxyl bis(methyl acetate) silane.

[0013] According to a specific embodiment of the present application, preferably, the mass fraction of the unsaturated di-ester silane monomer is 10-60% calculated based on 100% of the mass of the organic polymer carrier; the content of the functional monomer in the carrier is determined by the amount of divinylbenzene and the unsaturated di-ester silane functional monomer added.

[0014] The application also provides a preparation method of the organic polymer carrier, comprising the following steps: using monomers including the divinylbenzene, the unsaturated di-ester-silane monomer and additional monomers as raw materials, and preparing the organic polymer carrier through copolymerization; the mass ratio of the additional monomers to the divinylbenzene is 0-1:1; and the mass ratio of the unsaturated di-ester-silane monomer to the divinylbenzene is 0.2-2:1.

[0015] According to a specific embodiment of the application, preferably, the organic polymer carrier is prepared by using a dispersion polymerization method, a suspension polymerization method or an emulsion polymerization method.

[0016] According to a specific embodiment of the application, preferably, the organic polymer carrier is prepared by using the dispersion polymerization method, which comprises the following steps: adding the divinylbenzene, the unsaturated di-ester-silane monomer and additional monomers into a dispersion solvent, then adding a stabilizer and an initiator, stirring and dispersing, and then reacting at 50-80°C for 5-12 hours to obtain the organic polymer carrier, which is denoted as POP-Si(CH2O2C)2; more preferably, the obtained organic polymer carrier can be further washed with a dispersion solvent to remove impurities and dried; the obtained organic carrier has a narrow dispersion and good fluidity.

[0017] According to a specific embodiment of the application, preferably, in the preparation method, the additional monomers include one or more than two combinations of styrene, alkyl-substituted styrene, chloromethyl-substituted styrene, methacrylic acid, methacrylic acid ester and hydroxyalkyl methacrylate, for example, hydroxyethyl methacrylate.

[0018] According to a specific embodiment of the application, preferably, in the preparation method, the dispersion solvent includes a fatty acid ester solvent.

[0019] According to a specific embodiment of the application, preferably, the fatty acid ester solvent includes ethyl acetate and / or butyl acetate.

[0020] According to a specific embodiment of the application, preferably, in the preparation method, the mass ratio of the total amount of monomers to the dispersion solvent is 1:5-20, so that the system is uniformly dispersed.

[0021] According to a specific embodiment of the application, preferably, in the preparation method, the stabilizer is polyvinyl alcohol and / or polypropylene oxide-polyethylene oxide copolymer.

[0022] According to a specific embodiment of the application, preferably, the weight average molecular weight of the stabilizer is 1000-100000.

[0023] According to a specific embodiment of the application, preferably, the mass ratio of the amount of the stabilizer to the total amount of monomers is 0.5-5:100.

[0024] According to the specific embodiment of the present application, preferably, in the above preparation method, the initiator is azobisisobutyronitrile (AIBN) and / or dibenzoyl peroxide (BPO).

[0025] According to the specific embodiment of the present application, preferably, the mass ratio of the amount of the initiator added to the total amount of monomers added is 0.5-5:100.

[0026] According to the specific embodiment of the present application, preferably, in the above preparation method, the divinylbenzene is pretreated divinylbenzene, and the pretreatment is removal of polymerization inhibitor.

[0027] The present application also provides a Z-N catalyst, the raw material composition of which comprises 60-85wt% organic polymer carrier, 1-6wt% magnesium compound calculated as magnesium element, 1-6wt% titanium compound calculated as titanium element and 0-5wt% internal electron donor, based on 100% of the mass of the Z-N catalyst.

[0028] According to the specific embodiment of the present application, preferably, the content of the organic polymer carrier is 65-80wt%, the content of magnesium element is 2-5wt%, and the content of titanium element is 2-5wt%.

[0029] According to the specific embodiment of the present application, preferably, the magnesium compound is R n MgX (2 -n), n is 0, 1 or 2; R is selected from C1-C8 alkyl and derivatives thereof, aryl and derivatives thereof, alkoxy and derivatives thereof, and X is fluorine, chlorine, bromine or iodine.

[0030] According to the specific embodiment of the present application, preferably, R is selected from methyl, ethyl, propyl, butyl, alkoxy, phenyl and substituted phenyl.

[0031] According to the specific embodiment of the present application, preferably, the magnesium compound is one or a combination of two or more of alkyl halogenated magnesium compound, alkyl magnesium compound and alkoxy halogenated magnesium compound, and more preferably is alkyl chlorinated magnesium compound.

[0032] According to a specific embodiment of the present application, preferably, the magnesium compound comprises one or a combination of two or more of methylmagnesium chloride, n-butylmagnesium chloride, isobutylmagnesium chloride, t-butylmagnesium chloride, benzylmagnesium chloride, ethylmagnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, n-butylmagnesium bromide, benzylmagnesium bromide, methylmagnesium iodide, t-butylmagnesium iodide, benzylmagnesium iodide, n-butylmagnesium iodide, methylmagnesium fluoride, t-butylmagnesium fluoride, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, ethoxymagnesium chloride; after the magnesium compound is contacted with the organic polymer support, a magnesium compound-treated porous organic support, denoted as POP-Si(CH2O2C)2...MgX, is prepared.

[0033] According to a specific embodiment of the present application, preferably, the titanium compound is titanium tetrachloride; the magnesium compound-treated porous organic support (POP-Si(CH2O2C)2...MgX) is further reacted with titanium tetrachloride to obtain the Z-N catalyst, denoted as POP-Si(CH2O2C)2...MgX / TiCl4.

[0034] The Z-N catalyst of the present application can be optionally added with an additional internal donor (ID) to obtain an ultra-high molecular weight polyethylene catalyst solid component, denoted as POP-Si(CH2O2C)2...MgX / TiCl4 / ID; according to a specific embodiment of the present application, preferably, the internal donor is one or a combination of two or more of diester compounds, diphenate compounds, diol ester compounds, succinate compounds, diether compounds. The organic polymer support-loaded Z-N type UHMWPE catalyst solid catalyst component of the present application, through the POP-Si(CH2O2C)2 group on its organic support and the additional (optionally added) internal donor, enables the prepared solid catalyst to have a good ethylene chain growth rate.

[0035] According to a specific embodiment of the present application, preferably, the internal donor comprises one or a combination of two or more of diisobutyl phthalate (DIBP), di-n-butyl phthalate (DNBP), 9,9-dimethoxyfluorene, 2,3-diisopropyl succinic acid diisobutyl ester, 3-methyl-5-t-butyl-1,2-benzenediol dibenzoyl ester, 2-isopropyl-2-isopentyl-1,3-propanediol dibenzoyl ester (IAIPPDB), 2-isopropyl-2-isopentyl-1,3-propanedimethyl ether (IAIPDMP).

[0036] The present application also provides a preparation method of the above-mentioned Z-N catalyst, comprising the following steps:

[0037] The organic polymer carrier is added into an inert solvent under anhydrous and anaerobic conditions, the magnesium compound is added, and the reaction is carried out at 0-50°C for 15-120 minutes. Then, the unreacted magnesium compound is filtered, and the inert solvent and titanium tetrachloride are added, and the reaction is carried out at 0-80°C for 15-180 minutes. Then, the internal electron donor is added at 20-120°C, and the reaction is carried out for 15-180 minutes. Then, the filter is washed, and the Z-N catalyst is obtained.

[0038] In the Z-N catalyst of the present application, the functional monomer content of the organic polymer carrier is generally 0.5 mmol / g carrier to 5 mmol / g carrier, preferably 1 mmol / g carrier to 4 mmol / g carrier. The functional monomer content is generally controlled by the ratio of the functional monomer to the amount of divinylbenzene (DVB) monomer added during the preparation of the carrier. The ratio of the amount of magnesium compound reagent (in terms of the number of moles of magnesium Mg) to the amount of carrier is 1 mmol / g carrier to 30 mmol / g carrier, preferably 3 mmol / g carrier to 20 mmol / g carrier. Generally, an excess amount of Ti metal compound, such as TiCl4, is added for the loading of the catalyst. The amount of Ti metal compound added (in terms of the number of moles of titanium Ti) is generally 5 mmol / g carrier to 200 mmol / g carrier, preferably 50 mmol / g carrier to 150 mmol / g carrier. The ratio of the amount of internal electron donor to the amount of carrier is 0 to 0.3 g internal electron donor / g carrier.

[0039] The present application also provides a Z-N catalyst system, which comprises the Z-N catalyst and a cocatalyst.

[0040] According to a specific embodiment of the present application, preferably, the cocatalyst comprises an aluminum alkyl compound.

[0041] According to a specific embodiment of the present application, preferably, the cocatalyst is triethylaluminum and / or triisobutylaluminum (TIBA); in addition, the aluminum alkyl compound can also be used as a scavenger in the polymerization system.

[0042] According to a specific embodiment of the present application, preferably, the molar ratio of aluminum in the aluminum alkyl compound to titanium in the Z-N catalyst is 10-500.

[0043] The present application also provides the use of the above-mentioned Z-N catalyst or the above-mentioned Z-N catalyst system in the polymerization of olefins.

[0044] According to a specific embodiment of the present application, preferably, the polymerization of olefins is the homopolymerization of ethylene.

[0045] According to a specific embodiment of the present application, preferably, the polymerization of olefins is gas phase polymerization, bulk polymerization, or slurry polymerization.

[0046] According to the specific embodiment of the present application, preferably, the reaction temperature of the slurry polymerization is 30-80℃, and the reaction pressure is 0.1-2.0Mpa.

[0047] According to the specific embodiment of the present application, preferably, the solvent of the slurry polymerization is C5-C 10 alkane, more preferably hexane.

[0048] The organic polymer carrier loaded Z-N type UHMWPE catalyst of the present application is prepared by screening the radical-polymerizable unsaturated di-ester-silane type functional monomer, adjusting the pore structure and morphology of the prepared carrier, relying on the di-ester-silane functional groups on the carrier to regulate the micro-chemical environment of the metal active center, preparing the POP-Si(CH2O2C)2 carrier, and integrating and designing the organic carrier loaded POP-Si(CH2O2C)2 / RMgX / TiCl4 ultra-high molecular weight polyethylene catalyst solid component by loading magnesium and titanium metals. The di-ester-silane functional groups on the carrier and the optional post-added internal electron donors can regulate the metal active center of the catalyst, reduce the chain transfer ability of the active center, and make the catalyst have good ethylene insertion ability, good polymerization activity, and the catalyst can be used to catalyze ethylene polymerization to obtain an ultra-high molecular weight polyethylene product with a relative molecular weight Mw of 10 million or a viscosity average molecular weight of more than 7 million. DETAILED DESCRIPTION

[0049] In order to have a clearer understanding of the technical features, objectives and beneficial effects of the present application, the technical solutions of the present application are described in detail as follows, but it should not be understood as a limitation on the implementable scope of the present application.

[0050] The co-monomer divinylbenzene (DVB) used in the present application can use commercially available monomers with 55% or 80% DVB content, which all need to be pretreated before use, i.e., removing the polymerization inhibitor before use. There are many methods for removing the polymerization inhibitor in the prior art, such as using NaOH solution and distilled water to wash divinylbenzene and styrene; the third monomer (additional monomer) such as hydroxyethyl methacrylate can use a neutral alumina column to remove the polymerization inhibitor before use.

[0051] The unsaturated di-ester-silane monomer in the present application can be prepared by reacting unsaturated di(chloromethyl)silane with the corresponding anhydride or acid under alkaline conditions, or directly used by outsourcing method.

[0052] In the present application, the specific surface area of the prepared organic polymer carrier is tested by using BET nitrogen adsorption method with Nova 2000e, and the specific surface area of the carrier prepared in the present application is controlled to be greater than 100m 2 / g, and the specific surface area of the carrier prepared in the present application is controlled to be 100-600m 2between 0.1 and 0.3 ml / g, and a pore volume of greater than 0.2 ml / g.

[0053] The ultra-high molecular weight polyethylene prepared in the present application has a viscosity average molecular weight determined by the method in ASTM D4020. The polymer viscosity is tested by Ubbelohde viscometer, the solvent is decalin, and the testing temperature is 135°C. The viscosity average molecular weight Mηof the polymer can be calculated by the intrinsic viscosity ηof the polymer through the formula Mη= 5.37 x 10 4 The weight average molecular weight Mwof the polymer can be calculated by the Margolis formula Mw= 5.37 x 10 4 [η]1.49.

[0054] The internal electron donor content can be determined by extraction and gas chromatography.

[0055] Treatment of the comonomer: The divinylbenzene is first treated with 10% NaOH solution to remove the polymerization inhibitor, then washed with deionized water for 3 times, dried with anhydrous magnesium sulfate, and then used.

[0056] Preparation of unsaturated di-esteryl silane monomers

[0057] Preparation Example 1

[0058] This preparation example provides a vinylmethylbis(methylacetate)silane (or vinylmethylbis(acetoxymethyl)silane) monomer, which is prepared by the following steps:

[0059] The vinylmethylbis(methylacetate)silane compound can be prepared by esterification of vinylmethylbis(chloromethyl)silane with acetic anhydride at 40-60°C under normal pressure to obtain a crude product, and then distilling the vinylmethylbis(methylacetate)silane under reduced pressure. Specifically, 6.0 g of acetic anhydride, 12 g of vinylmethylbis(chloromethyl)silane, and 80 g of N,N-dimethylformamide (DMF) solvent are added to a 250 ml reaction kettle, followed by the addition of 12 g of anhydrous K2CO3. The esterification is carried out at 60°C under normal pressure to obtain a crude product. After filtration and distillation under reduced pressure, the vinylmethylbis(methylacetate)silane is obtained with a yield of 89%. This preparation method is only for illustration and is not used to limit the preparation method of the unsaturated diester-based silane. Other monomers can be prepared by a similar method or directly purchased.

[0060] Preparation Example 2

[0061] This preparation example provides an allylmethylbis(methylisobutyrate)silane monomer, which is prepared by the following steps:

[0062] The allylmethyldi(methyl isobutyrate) silane compound can be prepared by reacting allylmethyldi(chloromethyl) silane with isobutyric acid at 40-60 °C under normal pressure to obtain a crude product, and then distilling the crude product under reduced pressure to obtain the allylmethyldi(methyl isobutyrate) silane. Specifically, 6.0 g of isobutyric acid, 11.2 g of vinylmethyldi(chloromethyl) silane, and 80 g of N,N-dimethylformamide (DMF) solvent are added to a 250 ml reaction kettle, and then 12 g of anhydrous K2CO3 is added. The mixture is esterified at 60 °C under normal pressure to obtain a crude product. The crude product is filtered and distilled under reduced pressure to obtain the allylmethyldi(methyl isobutyrate) silane with a yield of 85%.

[0063] Preparation Example 3

[0064] The present preparation example provides a preparation method of an allyl ethyloxydi(methyl benzoate) silane monomer, which is prepared by the following steps:

[0065] The allyl ethyloxydi(methyl benzoate) silane compound can be prepared by reacting allyl ethyloxydi(chloromethyl) silane with benzoic anhydride at 40-60 °C under normal pressure to obtain a crude product, and then distilling the crude product under reduced pressure to obtain the allyl ethyloxydi(methyl benzoate) silane. Specifically, 6.0 g of benzoic anhydride, 11.2 g of vinylmethyldi(chloromethyl) silane, and 80 g of N,N-dimethylformamide (DMF) solvent are added to a 250 ml reaction kettle, and then 12 g of anhydrous K2CO3 is added. The mixture is esterified at 60 °C under normal pressure to obtain a crude product. The crude product is filtered and distilled under reduced pressure to obtain the allyl ethyloxydi(methyl benzoate) silane with a yield of 91%.

[0066] Preparation Example 4

[0067] The present preparation example provides a preparation method of a 1-buten-4-yl isopropyldi(methyl benzoate) silane monomer, which is prepared by the following steps:

[0068] The 1-buten-4-yl isopropyldi(methyl benzoate) silane compound can be prepared by reacting 1-buten-4-yl isopropyldi(chloromethyl) silane with benzoic anhydride at 40-60 °C under normal pressure to obtain a crude product, and then distilling the crude product under reduced pressure to obtain the 1-buten-4-yl isopropyldi(methyl benzoate) silane. Specifically, 6.0 g of benzoic anhydride, 11.5 g of 1-buten-4-yl isopropyldi(chloromethyl) silane, and 80 g of N,N-dimethylformamide (DMF) solvent are added to a 250 ml reaction kettle, and then 12 g of anhydrous K2CO3 is added. The mixture is esterified at 60 °C under normal pressure to obtain a crude product. The crude product is filtered and distilled under reduced pressure to obtain the 1-buten-4-yl isopropyldi(methyl benzoate) silane with a yield of 83%.

[0069] Example 1

[0070] The present example provides a Z-N catalyst prepared by the following steps:

[0071] (1) Preparation of porous organic polymer support:

[0072] In a 250 ml glass reactor, 130 ml of ethyl acetate was added, followed by 5.0 g of divinylbenzene (Aldrin reagent, 55%) and 2.0 g of vinylmethylbis(acetoxymethyl)silane, stirred at room temperature for 5 min, then 3% of monomer mass of polyvinyl alcohol PVA (PVA, degree of polymerization 1750) was added, stirred at 45°C for 1 h, the stabilizer was completely dissolved, 2.0% of monomer mass of azobisisobutyronitrile (AIBN) was added, the temperature was raised to 70°C, and reacted for 3 hours, then the temperature was raised to 80°C, and reacted for 7 hours, the stirring speed was 350 rpm, after filtration, washed with 100 ml of ethyl acetate for 3 times, filtered and dried to obtain 3.8 g of free-flowing porous organic polymer support POP-1. The specific surface area of the support was 238 m 2 / g;

[0073] (2) Catalyst preparation:

[0074] In a 250 ml glass reactor, 2.0 g of the above-mentioned support POP-1 prepared by using vinylmethylbis(acetoxymethyl)silane functional monomer was added, 100 ml of toluene was added and stirred, then 15 ml of 3M methyl magnesium chloride reagent was added at room temperature (25°C, same below), stirred for 2 hours, filtered and washed with toluene for 2 times, then 50 ml of toluene was added, 50 ml of TiCl4 was added dropwise at room temperature, the temperature was raised to 80°C and reacted for 2 hours, after filtration, washed with toluene and hexane for 3 times each, and dried to obtain free-flowing catalyst particles, recorded as Cat-1. The Mg content of the catalyst Cat-1 was 4.2%, the titanium content was 3.2%, and the organic polymer support content was 71%.

[0075] Example 2

[0076] The present example provides a Z-N catalyst prepared by the following steps:

[0077] Catalyst preparation: In a 250 ml glass reactor, 2.0 g of the above prepared support POP-1 using vinyl methyl bis(methyl acetate) silane functional monomer was taken, 100 ml of toluene was added, stirred and then 10 ml of 3M methyl magnesium chloride Grignard reagent was added at room temperature, stirred for 2 hours, filtered and washed twice with toluene, then 50 ml of toluene was added, 30 ml of TiCl4was added drop wise at room temperature, temperature was raised to 60 °C for 2 hours, filtered and washed three times each with toluene and hexane, dried to get free flowing catalyst particles, noted as Cat-2, Mg content of the catalyst Cat-2 was 2.8%, Ti content was 2.5% and organic polymer support content was 81%.

[0078] Example 3

[0079] The present example provides a Z-N catalyst prepared by the following steps:

[0080] (1) Preparation of porous organic polymer support:

[0081] In a 250 ml glass reactor, 130 ml of butyl acetate was taken, then 6.0 g of divinyl benzene (Aldrich reagent, 50%) and 3.0 g of vinyl methyl bis(methyl acetate) silane was added, stirred for 5 min at room temperature, then 3% of monomer mass of block copolymer of polyethylene oxide and polypropylene oxide F127 was added, stirred for 1 h at 45 °C to completely dissolve the stabilizer, 2.0% of monomer mass of dibenzoyl peroxide BPO was added, temperature was raised to 70 °C and stirred for 3 hours, then temperature was raised to 80 °C and stirred for 8 hours, stirring speed was 450 rpm, after filtration, it was washed three times with 100 ml of ethyl acetate, filtered and dried to get 6.3 g of free flowing porous organic polymer support POP-2. The specific surface area of the support was 378 m 2 / g;

[0082] (2) Catalyst preparation:

[0083] In a 250 ml glass reactor, 2.0 g of the above prepared support POP-2 using vinyl methyl bis(methyl acetate) silane functional monomer was taken, 100 ml of toluene was added, stirred and then 12 ml of 3M methyl magnesium chloride Grignard reagent was added at room temperature, stirred for 2 hours, filtered and washed twice with toluene, then 50 ml of toluene was added, 35 ml of TiCl4was added drop wise at room temperature, temperature was raised to 80 °C for 2 hours, filtered and washed three times each with toluene and hexane, dried to get free flowing catalyst particles, noted as Cat-3, Mg content of the catalyst Cat-3 was 3.2%, Ti content was 2.8% and organic polymer support content was 73%.

[0084] Example 4

[0085] The present example provides a Z-N catalyst prepared by the following steps:

[0086] (1) Preparation of porous organic polymer support: In a 250 ml glass reactor, 120 ml of ethyl acetate was added, then 5.0 g of divinylbenzene (Aldrin reagent, 55%) and 2.0 g of allylmethyl di(isobutyrate) silane were added, stirred at room temperature for 5 min, then 2% of monomer mass of polyvinyl alcohol PVA (PVA, degree of polymerization 1750) was added, stirred at 45°C for 1 h, the stabilizer was completely dissolved, 2.0% of monomer mass of AIBN was added, the temperature was raised to 70°C, and reacted for 3 hours, then the temperature was raised to 80°C, and reacted for 7 hours, the stirring speed was 450 rpm, after filtration, washed with 100 ml of ethyl acetate for 3 times, filtered and dried to obtain 3.8 g of free-flowing porous organic polymer support POP-3. The specific surface area of the support was 245 m 2 / g;

[0087] (2) Preparation of Z-N catalyst:

[0088] In a 250 ml glass reactor, 2 g of the above-mentioned support POP-3 prepared from allylmethyl di(isobutyrate) silane functional monomer was added, 100 ml of toluene was added, stirred, then 10 ml of 3M methyl magnesium chloride Grignard reagent was added at room temperature, stirred for 2 hours, after filtration, washed with toluene for 2 times, then 50 ml of toluene was added, 30 ml of TiCl4 was added dropwise at room temperature, the temperature was raised to 60°C and reacted for 2 hours, after the reaction was completed, filtration was performed, then 50 ml of toluene was added, 30 ml of TiCl4 was added dropwise at room temperature, and reacted at 80°C for 1 hour, after filtration, washed with toluene and hexane for 3 times, and dried to obtain free-flowing catalyst particles, which were recorded as Cat-4. The Mg content of the catalyst Cat-4 was 2.7%, the Ti content was 2.4%, and the organic polymer support content was 78%.

[0089] Example 5

[0090] The present example provides a Z-N catalyst prepared by the following steps:

[0091] Z-N catalyst preparation: In a 250 ml glass reactor, 2 g of the above prepared support POP-3 from allylmethyl bis(methyl isobutyrate) silane functional monomer was taken, 100 ml of toluene was added, stirred and then 15 ml of 3M methyl magnesium chloride Grignard reagent was added at 5°C, stirred for 2 hours, filtered and washed twice with toluene, then 50 ml of toluene was added, 40 ml of TiCl4was added drop wise at room temperature, stirred for 1 hour, temperature was raised to 80°C and stirred for 2 hours, after completion of the reaction, filtered, washed with toluene and hexane each for 3 times, dried to get free flowing catalyst particles, noted as Cat-5, Mg content of the catalyst Cat-5 was 4.0%, Ti content was 4.2% and organic polymer support content was 68%.

[0092] Example 6

[0093] The present example provides a Z-N catalyst prepared by the following steps:

[0094] Z-N catalyst preparation: In a 250 ml glass reactor, 2 g of the above prepared support POP-3 from allylmethyl bis(methyl isobutyrate) silane functional monomer was taken, 100 ml of toluene was added, stirred and then 15 ml of 3M methyl magnesium chloride Grignard reagent was added at 5°C, stirred for 2 hours, filtered and washed twice with toluene, then 50 ml of toluene was added, 40 ml of TiCl4was added drop wise at room temperature, stirred for 1 hour, temperature was raised to 80°C and stirred for 2 hours, after completion of the reaction, filtered, washed with toluene and hexane each for 3 times, dried to get free flowing catalyst particles, noted as Cat-5, Mg content of the catalyst Cat-5 was 4.0%, Ti content was 4.2% and organic polymer support content was 68%.

[0095] Example 7

[0096] The present example provides a Z-N catalyst prepared by the following steps:

[0097] Z-N catalyst preparation: In a 250 ml glass reactor, 2 g of the above prepared support POP-3 from allyl methyl di(isobutyrate) silane functional monomer was added, 100 ml of toluene was added, stirred, then 10 ml of 3M benzyl magnesium chloride Grignard reagent was added at 35 °C, stirred for 2 hours, after filtration, washed with toluene twice, then heated to 50 °C, 40 ml of TiCl4was added dropwise, reacted for 2 hours, then heated to 80 °C, 0.15 g of 3-methyl-5-tert-butyl-1,2-hydroquinone benzoate was added, reacted for 3 hours, after the reaction was completed, filtered, then 50 ml of toluene and 30 ml of TiCl4was added at 80 °C for 2 hours, after the reaction was completed, filtered, washed with toluene and hexane each for 3 times, dried to obtain free-flowing catalyst particles, recorded as Cat-7, the Mg content of the catalyst Cat-7 was 2.8%, the titanium content was 3.2%, the internal electron donor content was 2.8%, and the organic polymer support content was 69%.

[0098] Example 8

[0099] The present embodiment provides a Z-N catalyst prepared by the following steps:

[0100] (1) Preparation of a porous organic polymer support:

[0101] In a 250 ml glass reactor, 120 ml of butyl acetate was added, then 5.0 g of divinylbenzene (Aldrin reagent, 55%) and 2.5 g of allyl ethoxy di(benzoate) silane were added, stirred at room temperature for 5 min, then 5% of the mass of the monomer of a block copolymer of polyethylene oxide and polypropylene oxide F127 was added, stirred at 45 °C for 1 h to completely dissolve the stabilizer, 2.0% of the mass of the monomer of AIBN was added, heated to 70 °C, reacted for 3 hours, then the temperature was raised to 80 °C, reacted for 7 hours, the stirring speed was 550 rpm, after filtration, washed with 100 ml of ethyl acetate for 3 times, filtered and dried to obtain 4.5 g of free-flowing porous organic polymer support POP-4. The specific surface area of the support was 378 m 2 / g;

[0102] (2) Z-N catalyst preparation:

[0103] In a 250 ml glass reactor, 2 g of the support POP-4 prepared from allyl ethoxy di(methyl benzoate) silane functional monomer was taken, 100 ml of toluene was added, stirred and then 12 ml of 3M methyl magnesium chloride Grignard reagent was added at room temperature, stirred for 2 hours, filtered and washed twice with toluene, then 50 ml of toluene was added, 50 ml of TiCl4was added drop wise at room temperature, heated to 60 °C for 2 hours, after completion of the reaction, filtered, then 50 ml of toluene was added, 30 ml of TiCl4was added drop wise at room temperature, heated to 80 °C for 1 hour, filtered and washed with toluene and hexane each for 3 times, dried to get free flowing catalyst particles, noted as Cat-8, the Mg content of the catalyst Cat-8 was 3.2%, the Ti content was 3.4% and the organic polymer support content was 72%.

[0104] Example 9

[0105] This example provides a Z-N catalyst prepared by the following steps:

[0106] Z-N catalyst preparation: In a 250 ml glass reactor, 2.0 g of the support POP-4 prepared from allyl ethoxy di(methyl benzoate) silane functional monomer was taken, 80 ml of toluene was added, stirred and then 8 ml of 3M methyl magnesium chloride Grignard reagent was added at 35 °C, stirred for 2 hours, filtered and washed twice with toluene, then heated to 50 °C, 30 ml of TiCl4was added drop wise, reacted for 2 hours, then heated to 80 °C, after completion of the reaction, filtered, washed with toluene, hexane each for 3 times, dried to get free flowing catalyst particles, noted as Cat-9, the Mg content of the catalyst Cat-9 was 2.1%, the Ti content was 2.2% and the organic polymer support content was 82%.

[0107] Example 10

[0108] This example provides a Z-N catalyst prepared by the following steps:

[0109] Z-N catalyst preparation: in a 250 ml glass reactor, 2.0 g of the above-mentioned carrier POP-4 prepared from allyl ethoxy di(methyl benzoate) silane functional monomer was added, 80 ml of toluene was added, stirred, then 15 ml of 3M di-n-butyl magnesium was added at room temperature, stirred for 3 hours, after filtration, washed twice with toluene, then heated to 50°C, 40 ml of TiCl4 was added dropwise, reacted for 2 hours, then heated to 80°C, 0.25 g of DIBP internal electron donor was added, reacted for 3 hours, after the reaction was completed, filtered, washed with toluene and hexane each for 3 times, dried to obtain free-flowing catalyst particles, marked as Cat-10, the Mg content of the catalyst Cat-10 was 2.7%, the titanium content was 2.5%, the internal electron donor content was 3.2%, and the organic polymer carrier content was 77%.

[0110] Example 11

[0111] The present embodiment provides a Z-N catalyst prepared by the following steps:

[0112] (1) Preparation of a porous organic polymer carrier:

[0113] In a 250 ml glass reactor, 130 ml of butyl acetate was added, then 5.0 g of divinylbenzene (Aldrin reagent, 55%) and 3.0 g of allyl ethoxy di(methyl benzoate) silane, and 2.0 g of 4-chloromethyl styrene were added, stirred at room temperature for 5 min, then 5% of the mass of the monomer of a block copolymer of polyethylene oxide and polypropylene oxide F127 was added, stirred at 45°C for 1 h to completely dissolve the stabilizer, 2.0% of the mass of the monomer of AIBN was added, heated to 70°C, reacted for 3 hours, then the temperature was raised to 80°C, reacted for 10 hours, the stirring speed was 450 rpm, after filtration, washed with 100 ml of ethyl acetate for 3 times, filtered and dried to obtain 7.6 g of a free-flowing porous organic polymer carrier POP-5. The specific surface area of the carrier was 325 m 2 / g;

[0114] (2) Z-N catalyst preparation:

[0115] In a 250 ml glass reactor, 3 g of the above prepared support POP-5 from 3.0 g of allyl ethoxy di(methyl benzoate) silane and third monomer 4-chloromethyl styrene was taken, 100 ml of toluene was added, stirred, then 15 ml of 3M methyl magnesium chloride Grignard reagent was added at 20 °C, stirred for 2 hours, after filtration, washed twice with toluene, then heated to 50 °C, 50 ml of TiCl4was added dropwise, then heated to 80 °C, reacted for 2 hours, after completion of the reaction, filtered, washed with toluene, hexane each 3 times, after drying, free flowing catalyst particles were obtained, noted as Cat-11, the Mg content of the catalyst Cat-11 was 2.7%, the titanium content was 2.8%, the organic polymer support content was 76%.

[0116] Example 12

[0117] This example provides a Z-N catalyst prepared by the following steps:

[0118] Preparation of Z-N catalyst: In a 250 ml glass reactor, 3 g of the above prepared support POP-5 from 3.0 g of allyl ethoxy di(methyl benzoate) silane and third monomer 4-chloromethyl styrene was taken, 100 ml of toluene was added, stirred, then 15 ml of 3M methyl magnesium chloride Grignard reagent was added at 0 °C, stirred for 2 hours, after filtration, washed twice with toluene, then heated to 50 °C, 50 ml of TiCl4was added dropwise, reacted for 2 hours, then heated to 80 °C, 0.25 g of 9,9-dimethoxyfluorene electron donor was added, reacted for 3 hours, after completion of the reaction, filtered, washed with toluene, hexane each 3 times, after drying, free flowing catalyst particles were obtained, noted as Cat-12, the Mg content of the catalyst Cat-12 was 2.4%, the titanium content was 2.4%, the electron donor content was 2.1%, the organic polymer support content was 73%.

[0119] Example 13

[0120] This example provides a Z-N catalyst prepared by the following steps:

[0121] (1) Preparation of porous organic polymer support:

[0122] In a 250 ml glass reactor, 120 ml of butyl acetate was added, then 5.0 g of divinylbenzene (Aldrin reagent, 55%) and 1.8 g of 1-buten-4-yl isopropyl bis(methyl benzoate) silane were added, stirred at room temperature for 5 min, then 3% of monomer mass of block copolymer F127 of polyethylene oxide and polypropylene oxide was added, stirred at 45°C for 1 h, the stabilizer was completely dissolved, 2.0% of monomer mass of AIBN was added, the temperature was raised to 70°C, and reacted for 3 h, then the temperature was raised to 80°C, and reacted for 10 h, the stirring speed was 550 r / min, after filtration, 100 ml of ethyl acetate was used for washing 3 times, after filtration and drying, 4.1 g of free-flowing porous organic polymer support POP-6 was obtained. The specific surface area of the support was 248 m 2 / g;

[0123] (2) Preparation of Z-N catalyst:

[0124] In a 250 ml glass reactor, 2.0 g of the above-mentioned support POP-6 prepared from 1-buten-4-yl isopropyl bis(methyl benzoate) silane functional monomer was added, 100 ml of toluene was added and stirred, then 12 ml of 3M methyl magnesium chloride Grignard reagent was added at room temperature, stirred for 2 h, after filtration, 2 times of toluene washing was performed, then 50 ml of toluene was added, 30 ml of TiCl4 was added dropwise at room temperature, the temperature was raised to 60°C and reacted for 2 h, after the reaction was completed, filtration was performed, then 50 ml of toluene was added, 30 ml of TiCl4 was added dropwise at room temperature, and reacted at 80°C for 1 h, after filtration, 3 times of toluene and hexane washing was performed, and after drying, free-flowing catalyst particles were obtained, which were recorded as Cat-13. The Mg content of the catalyst Cat-13 was 2.8%, the titanium content was 2.1%, and the organic polymer support content was 79%.

[0125] Example 14

[0126] The present example provides a Z-N catalyst prepared by the following steps:

[0127] Z-N catalyst preparation: In a 250 ml glass reactor, 3 g of the above prepared POP-6 support from 1 -buten-4-yl isopropyl bis(methyl benzoate) silane functional monomer was taken, 100 ml of toluene was added, stirred and then 15 ml of 3M methyl magnesium chloride Grignard reagent was added at room temperature, stirred for 2 hours, filtered and washed twice with toluene, then 50 ml of toluene was added, 30 ml of TiCl4was added drop wise at room temperature and stirred for 1 hour at 80 °C, filtered and washed with toluene and hexane each for 3 times, dried to get free flowing catalyst particles, noted as Cat- 15, the Mg content of the catalyst Cat-15 was 2.8%, Ti content was 3.2%, electron donor content was 2.9% and the organic polymer support content was 71%.

[0128] Example 15

[0129] The present example provides a Z-N catalyst prepared by the following steps:

[0130] Z-N catalyst preparation: In a 250 ml glass reactor, 3 g of the above prepared POP-6 support from 1 -buten-4-yl isopropyl bis(methyl benzoate) silane functional monomer was taken, 100 ml of toluene was added, stirred and then 15 ml of 3M methyl magnesium chloride Grignard reagent was added at room temperature, stirred for 2 hours, filtered and washed twice with toluene, then 50 ml of toluene was added, 30 ml of TiCl4was added drop wise at room temperature and stirred for 1 hour at 80 °C, filtered and washed with toluene and hexane each for 3 times, dried to get free flowing catalyst particles, noted as Cat- 15, the Mg content of the catalyst Cat-15 was 2.8%, Ti content was 3.2%, electron donor content was 2.9% and the organic polymer support content was 71%.

[0131] Ethylene polymerization

[0132] In a polymerization reactor, the above prepared catalyst was used to carry out ethylene slurry polymerization to prepare UHMWPE.

[0133] Ethylene homopolymerization: 2.0 liter of dry hexane was added to a 5 liter stainless steel autoclave which was purged with nitrogen and dried, then a certain amount of triethylaluminum TEA (1.0 mole / liter) was added, stirred, then 50 milligrams of the above catalyst was added, ethylene was introduced to keep the internal pressure of the reactor at 0.6-1.0 MPa, and the reaction was carried out at a certain polymerization temperature (60-80°C) for 1 hour under stirring at 600 rpm, the reaction was terminated, cooled to room temperature, and dried to obtain a polyethylene product.

[0134] Test Example 1

[0135] 2.0 liter of dry hexane was added to a 5 liter stainless steel autoclave which was purged with nitrogen and dried, then 5 milliliters of triethylaluminum TEA (1.0 mole / liter) was added, the stirring speed was 450 rpm, then 150 milligrams of the catalyst Cat-1 was added, ethylene was introduced to keep the internal pressure of the reactor at 1.0 MPa (10 bar), the temperature was raised to 70°C, and the reaction was carried out at 600 rpm for 1 hour, after the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 528 grams of UHMWPE-1 product, the catalyst activity was 10560 gPE / gcat.h, or 1580 kgPE / molTi.bar.h, and the results are shown in Table 1.

[0136] Test Examples 2-15

[0137] The ethylene polymerization conditions in Test Examples 2-15 were the same as in Test Example 1, except that different catalysts were added, and the catalysts used in Test Examples 2-15 were Cat-2 to Cat-15, respectively. The polymerization results are shown in Table 1.

[0138] Test Example 16

[0139] 2.0 liter of dry hexane was added to a 5 liter stainless steel autoclave which was purged with nitrogen and dried, then 5 milliliters of triethylaluminum TEA (1.0 mole / liter) was added, the stirring speed was 450 rpm, then 850 milligrams of the catalyst Cat-8 was added, ethylene was introduced to keep the internal pressure of the reactor at 1.0 MPa, the temperature was raised to 60°C, and the reaction was carried out at 600 rpm for 1 hour, after the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain a UHMWPE-1 product, and the results are shown in Table 1.

[0140] Test Example 17

[0141] Into a 5 liter stainless steel autoclave, which was replaced with nitrogen and dried, 2.0 liters of dried hexane was added, then 8 ml of triethylaluminum TEA (1.0 mole / liter) was added, the stirring speed was 450 rpm, then 850 mg of catalyst Cat-1 was added, ethylene was introduced to keep the internal pressure of the reactor at 0.8 MPa, 0.20 g of hydrogen was added, the temperature was raised to 70°C, and the polymerization was carried out at a stirring speed of 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain UHMWPE particles. The results are shown in Table 1.

[0142] Test Example 18

[0143] Into a 5 liter stainless steel autoclave, which was replaced with nitrogen and dried, 2.0 liters of dried hexane was added, then 8 ml of triethylaluminum TEA (1.0 mole / liter) was added, the stirring speed was 450 rpm, then 1350 mg of catalyst Cat-1 was added, ethylene was introduced to keep the internal pressure of the reactor at 1.0 MPa, the temperature was raised to 80°C, and the polymerization was carried out at a stirring speed of 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain UHMWPE particles. The results are shown in Table 1.

[0144] Test Example 19

[0145] Into a 5 liter stainless steel autoclave, which was replaced with nitrogen and dried, 2.0 liters of dried hexane was added, then 5 ml of triethylaluminum TEA (1.0 mole / liter) was added, the stirring speed was 450 rpm, then 1350 mg of catalyst Cat-1 was added, ethylene was introduced to keep the internal pressure of the reactor at 0.6 MPa, the temperature was raised to 60°C, and the polymerization was carried out at a stirring speed of 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain UHMWPE particles. The results are shown in Table 1.

[0146] Test Example 20

[0147] Into a 5 liter stainless steel autoclave, which was replaced with nitrogen and dried, 2.0 liters of dried hexane was added, then 10 ml of triethylaluminum TEA (1.0 mole / liter) was added, the stirring speed was 450 rpm, then 1350 mg of catalyst Cat-1 was added, ethylene was introduced to keep the internal pressure of the reactor at 1.0 MPa, the temperature was raised to 80°C, and the polymerization was carried out at a stirring speed of 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain UHMWPE particles. The results are shown in Table 1.

[0148] Table 1 Polymerization Results

[0149]

[0150]

[0151] Polymerization conditions in Comparative Test Example 1 : 1 L polymerization reactor, 500 ml hexane, cat: 43 mg, Al / Ti = 300 (molar ratio), polymerization pressure 5 bar, polymerization time 2 hours. Catalyst titanium content estimated at 1.64 mmol / g.

[0152] Polymerization conditions in Comparative Test Example 2: 100 ml heptane, cat: 50 mg, Al / Ti = 300 (molar ratio), polymerization pressure 1 bar, polymerization time 1 hour. Titanium content in ZN3 catalyst 2.5%.

[0153] Polymerization conditions in Comparative Test Example 3: 1 L polymerization reactor, 400 ml isobutane, cat: 18 mg, Al / Ti = 190 (molar ratio), polymerization pressure 40 bar, polymerization time 3 hours. Catalyst titanium content 45 pmol Ti / g cat.

[0154] Data in Comparative Test Examples are all from corresponding literature 1, 2, 3, wherein:

[0155] Literature 1 : "Porous polyethylene spheres with nanofiber structure from Ziegler-Natta catalyst supported on porous polymer particles" in polymer (2011 ; 52, pp. 602-605);

[0156] Literature 2: "Ethylene polymerization on polymer supported Ziegler-Natta catalyst" in J. Polym. Res. (2012; 19:9892, pp. 1-13);

[0157] Literature 3: "Ultrahigh Molecular Weight Polyethylene Produced by a Bis(phenoxy-imine) Titanium Complex Supported on Latex Particles" in Journal of Polymer Science: Part A: Polymer Chemistry (2006, pp. 3103-3113).

[0158] As shown in Table 1, the Z-N catalyst supported by the porous organic polymer carrier containing di-ester-silane functional monomers of the present application is used for ethylene homopolymerization, and the weight average molecular weight of the obtained product polyethylene is between 500,000 and 12,000,000, and the viscosity average molecular weight can reach more than 7,000,000, which is higher than the organic carrier supported FI-Ti catalyst system reported in the document 3. The Z-N catalyst supported by the organic carrier containing di-ester-silane functional monomers of the present application has good polymerization activity and good hydrogen regulation sensitivity, and the polymerization activity is between 1,200 and 6,300 kgPE / molTi.bar.h, reaching the activity level of commercialized inorganic carrier supported Z-N ultra-high molecular weight polyethylene catalyst.

Claims

1. A ZN catalyst, wherein the raw material composition, calculated as 100% by mass of the ZN catalyst, comprises 60-85 wt% organic polymer support, 1-6 wt% magnesium compound calculated as magnesium element, 1-6 wt% titanium compound calculated as titanium element, and 0-5 wt% internal electron donor; The organic polymer carrier is obtained by copolymerization of monomers including divinylbenzene and unsaturated diester silane monomers; in, The unsaturated diester-based silane monomer has the structure shown in Formula I: Formula I, In Formula I, R1, R2, and R3 are each independently selected from hydrogen, chlorine, bromine, C1-C6 straight-chain alkyl, C1-C6 branched alkyl, cycloalkyl, and aromatic groups; x is 0-6; R4 is selected from C1-C8 straight-chain alkyl, C1-C8 branched alkyl, cycloalkyl, and aromatic groups; R5 and R6 are each independently selected from C1-C8 straight-chain hydrocarbon, C1-C8 branched hydrocarbon, cycloalkyl, and aromatic groups. Based on the organic polymer carrier having a mass of 100%, the mass fraction of the unsaturated diester-based silane monomer is 10-60%. The specific surface area of ​​the organic polymer carrier is 100-600 m². 2 / g, pore volume > 0.2 ml / g.

2. The ZN catalyst according to claim 1, wherein, In Formula I, R1, R2, and R3 are each independently selected from hydrogen, chlorine, bromine, methyl, and ethyl. R4 is selected from methyl, ethyl, isopropyl, n-butyl, isobutyl, phenyl, phenoxy, methoxy, and ethoxy. R5 and R6 are each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-heptyl, phenyl, cyclohexyl, isohexyl, 2-ethylpentyl, and 2-ethylbutyl; x is 0 or 1.

3. The ZN catalyst according to claim 1, wherein, The unsaturated diester silane monomers are selected from vinylmethyl di(methyl acetate)silane, vinylmethyl di(methyl propionate)silane, vinylmethyl di(methyl butyrate)silane, vinylmethyl di(methyl isobutyrate)silane, vinylmethyl di(methyl valerate)silane, vinylmethyl di(methyl hexanoate)silane, vinylmethyl di(methyl octanoate)silane, vinylmethyl di(methyl 2-methylhexanoate)silane, vinylmethyl di(methyl 2-ethylhexanoate)silane, and vinylmethyl di(methyl 2-ethylvalerate)silane. Vinylmethyl di(methyl benzoate)silane, vinylmethyl di(methyl cyclohexylcarboxylate)silane, vinylethyl di(methyl acetate)silane, vinylphenyl di(methyl acetate)silane, vinyl-n-butyl di(methyl acetate)silane, vinyl isobutyl di(methyl acetate)silane, vinyl isopropyl di(methyl acetate)silane, vinyl ethoxy di(methyl acetate)silane, allylmethyl di(methyl acetate)silane, allylmethyl di(methyl propionate)silane, allylmethyl di(methyl butyrate ... (Methyl isobutyrate)silane, allylmethyl di(methyl valerate)silane, allylmethyl di(methyl hexanoate)silane, allylmethyl di(methyl octanoate)silane, allylmethyl di(methyl 2-methylhexanoate)silane, allylmethyl di(methyl 2-ethylhexanoate)silane, allylmethyl di(methyl 2-ethylvalerate)silane, allylmethyl di(methyl benzoate)silane, allylmethyl di(methyl cyclohexanoate)silane, allylethyl di(methyl acetate)silane, allylphenyl di(methyl acetate)silane, allyl... The first one or a combination of two or more of the following: methyl butyl di(acetate)silane, allyl isobutyl di(acetate)silane, allyl isopropyl di(acetate)silane, allyl methoxy di(acetate)silane, allyl ethoxy di(acetate)silane, allyl ethoxy di(acetate)silane, 1-butenylethoxy di(acetate)silane, 1-buten-4-ylisopropyl di(acetate)silane, allyl phenoxy di(acetate)silane, and 1-chloroallylethoxy di(acetate)silane.

4. The ZN catalyst according to claim 1, wherein, The method for preparing the organic polymer carrier includes the following steps: The organic polymer carrier is prepared by copolymerization using monomers including the divinylbenzene, the unsaturated diester silane monomer, and additional monomers as raw materials; The mass ratio of the additional monomer to divinylbenzene is 0-1:1; the mass ratio of the unsaturated diester silane monomer to divinylbenzene is 0.2-2:

1.

5. The ZN catalyst according to claim 4, wherein, The organic polymer carrier is prepared by dispersion polymerization, suspension polymerization or emulsion polymerization. The dispersion polymerization method includes the following steps: adding divinylbenzene, unsaturated diester silane monomers and additional monomers to a dispersion solvent, then adding a stabilizer and an initiator, stirring and dispersing, and reacting at 50-80℃ for 5-12 hours to obtain the organic polymer carrier.

6. The ZN catalyst according to claim 4, wherein, The additional monomers include one or more of styrene, alkyl-substituted styrene, chloromethyl-substituted styrene, methacrylic acid, methacrylate, and hydroxyalkyl methacrylate.

7. The ZN catalyst according to claim 5, wherein, The dispersing solvent includes fatty acid ester solvents.

8. The ZN catalyst according to claim 7, wherein, The fatty acid ester solvents include ethyl acetate and / or butyl acetate.

9. The ZN catalyst according to claim 5, wherein, The mass ratio of the total amount of monomer added to the dispersing solvent is 1:5-20.

10. The ZN catalyst according to claim 5, wherein, The stabilizer is polyvinyl alcohol and / or polypropylene oxide-ethylene oxide copolymer.

11. The ZN catalyst according to claim 5, wherein, The weight-average molecular weight of the stabilizer is 1,000-100,000.

12. The ZN catalyst according to claim 5, wherein, The mass ratio of the amount of stabilizer added to the total amount of monomer added is 0.5-5:

100.

13. The ZN catalyst according to claim 5, wherein, The initiator is azobisisobutyronitrile and / or benzoyl peroxide.

14. The ZN catalyst according to claim 5, wherein, The mass ratio of the initiator to the total amount of monomers added is 0.5-5:

100.

15. The ZN catalyst according to claim 4, wherein, The divinylbenzene is a pretreated divinylbenzene, wherein the pretreatment is to remove the polymerization inhibitor.

16. The ZN catalyst according to claim 1, wherein, The organic polymer carrier contains 65-80 wt%, magnesium 2-5 wt%, and titanium 2-5 wt%.

17. The ZN catalyst according to claim 1, wherein, The magnesium compound is R n MgX (2-n) n is 0, 1 or 2; R is selected from C1-C8 alkyl, aryl or alkoxy groups, and X is fluorine, chlorine, bromine or iodine.

18. The ZN catalyst according to claim 17, wherein, R is selected from methyl, ethyl, propyl, butyl, alkoxy, phenyl, or substituted phenyl.

19. The ZN catalyst according to claim 17, wherein, The magnesium compound is one or a combination of two or more of alkyl halide magnesium compounds, alkyl magnesium compounds, and alkoxy halide magnesium compounds.

20. The ZN catalyst according to claim 19, wherein, The magnesium compound includes one or more of the following: methyl magnesium chloride, n-butyl magnesium chloride, isobutyl magnesium chloride, tert-butyl magnesium chloride, benzyl magnesium chloride, ethyl magnesium chloride, methyl magnesium bromide, ethyl magnesium bromide, n-butyl magnesium bromide, benzyl magnesium bromide, methyl magnesium iodide, tert-butyl magnesium iodide, benzyl magnesium iodide, n-butyl magnesium iodide, methyl magnesium fluoride, tert-butyl magnesium fluoride, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, and ethoxy magnesium chloride.

21. The ZN catalyst according to claim 1, wherein, The titanium compound is titanium tetrachloride.

22. The ZN catalyst according to claim 1, wherein, The internal electron donor is one or a combination of two or more of the following: diester compounds, diphenol ester compounds, diol ester compounds, succinate compounds, and diether compounds.

23. The ZN catalyst according to claim 22, wherein, The internal electron donor includes one or more of the following: diisobutyl phthalate, di-n-butyl phthalate, 9,9-dimethoxyfluorene, diisobutyl 2,3-diisopropylsuccinate, 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol diphenyl methyl ester, and 2-isopropyl-2-isopentyl-1,3-propanedimethyl ether.

24. A method for preparing the ZN catalyst according to any one of claims 1-23, comprising the following steps: Under anhydrous and oxygen-free conditions, the organic polymer support is added to an inert solvent, followed by the magnesium compound. After reacting at 0℃-50℃ for 15-120 minutes, the unreacted magnesium compound is filtered out. Then, an inert solvent and titanium tetrachloride are added, and the reaction is carried out at 0℃-80℃ for 15-180 minutes. Finally, an internal electron donor is added at 20℃-120℃, and the reaction is carried out for 15-180 minutes. The mixture is then filtered, and finally washed with an inert solvent to obtain the ZN catalyst.

25. A ZN catalyst system comprising a ZN catalyst and a co-catalyst; in, The ZN catalyst is the ZN catalyst according to any one of claims 1-23.

26. The ZN catalyst system according to claim 25, wherein, The cocatalyst includes alkylaluminum compounds.

27. The ZN catalyst system according to claim 26, wherein, The co-catalyst is triethylaluminum and / or triisobutylaluminum.

28. The ZN catalyst system according to claim 26, wherein, The molar ratio of aluminum in the alkylaluminum compound to titanium in the ZN catalyst is 10-500.

29. The use of the ZN catalyst according to any one of claims 1-23 or the ZN catalyst system according to claims 25-28 in olefin polymerization.

30. The application according to claim 29, wherein, The olefin polymerization is ethylene homopolymerization.

31. The application according to claim 29, wherein, The olefin polymerization is gas-phase polymerization, bulk polymerization, or slurry polymerization.

32. The application according to claim 31, wherein, The reaction temperature for slurry polymerization is 30-80℃, and the reaction pressure is 0.1-2.0 MPa.

33. The application according to claim 31, wherein, The solvent for the slurry polymerization is C5-C. 10 Alkanes.

34. The application according to claim 31, wherein, The solvent used for slurry polymerization is hexane.

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