Propylene polymer, catalyst carrier for preparing propylene polymer as well as preparation method and application of catalyst carrier

Abstract

The invention belongs to the field of polymers, and discloses a propylene polymer, a catalyst carrier for preparing the propylene polymer, and a preparation method and application of the propylene polymer. The propylene polymer comprises a silver element and a magnesium element, and the molar ratio of the silver element to the magnesium element in the propylene polymer is (0.001-100): 1; the elution resistance of the propylene polymer is greater than or equal to 79%; the melting point of the propylene polymer is less than or equal to 162.5 DEG C; the catalyst carrier for preparing the propylene polymer comprises a compound as shown in a structural formula (II) and a silver element, # imgabs0 # formula (II); in the catalyst carrier, the molar ratio of the silver element to the compound shown in the formula (II) is (0.10-0.30): 1; wherein the compound shown in the formula (II) is metered by the molar weight of Mg; the catalyst carrier prepared by the method provided by the invention is not easy to adhere and has good morphology, and when the catalyst carrier is used for olefin polymerization, antibacterial polypropylene microspheres with good fluidity, low melting point and good morphology can be obtained.

Description

Technical Field

[0001] The present invention relates to the technical field of polymers, and in particular to a propylene polymer, a catalyst carrier for preparing the propylene polymer and a preparation method thereof, and application of the catalyst carrier in preparing a catalyst for olefin polymerization. Background Art

[0002] Polymer microspheres generally refer to geometric bodies with diameters ranging from nanometers to micrometers and spherical shapes. Their applications involve almost all fields, from bulk products such as coatings, paper surface coatings, and cosmetics to high-value-added products such as microcapsules for sustained and controlled release of drugs and chromatography media for protein separation. Microsphere technology is used.

[0003] Polypropylene itself has many excellent characteristics such as light weight, non-toxicity, good electrical insulation performance and chemical resistance, and it is cheap and has a high cost performance. There are methods for preparing microspheres using single substances as raw materials, such as emulsion polymerization, soap-free emulsion polymerization, microemulsion polymerization, miniemulsion polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization and seed polymerization. There are also methods for preparing microspheres using polymers as raw materials, such as emulsification-solidification, single coagulation, complex coagulation, spray drying, self-emulsification-solidification and page unfolding. Due to the preparation and physical properties of polypropylene, there is no way to prepare it through the above two characteristics. It can only be crushed into micron-sized powder under low temperature conditions by utilizing the low-temperature brittleness of the material, but the crushing of polyolefins often requires the relatively high cost of liquid nitrogen deep cold treatment for crushing. The most inadequate thing is that the powder obtained by crushing is of poor morphology, irregular shape and poor fluidity.

[0004] As the public's requirements for hygiene and health are getting higher and higher, a variety of pathogens may remain on the surface of plastic products. The use of antibacterial materials can reduce the cross-contamination caused by the use of plastics, and various antibacterial agents and antibacterial plastics have also developed. Antibacterial polypropylene has great advantages in application because it has the advantages of polypropylene. The production of antibacterial polypropylene mainly includes melt blending, impregnation, coating and other methods. The melt blending method heats the antibacterial agent and other components such as resin to above the melting temperature in the mixing equipment to obtain a uniform eutectic, but this method cannot produce antibacterial polypropylene microspheres or micron-sized particles. The impregnation method is usually used for antibacterial polypropylene fibers. It is to put the prepared polypropylene material into a liquid or gas containing antibacterial active substances, and achieve the combination of antibacterial substances and materials through deposition and adsorption. The coating method is to coat the gel antibacterial substance on the polypropylene material substrate. The coating method is simple in process, but the antibacterial durability is poor. The melt blending method requires heating the plastic to the melting point, consumes a lot of energy, and there may be compatibility problems. The immersion method not only has low utilization efficiency, but also has the problem of antibacterial durability.

[0005] In practical applications, good fluidity and regular morphology are the key to improving the application performance of microspheres. Therefore, there is an urgent need for antibacterial polypropylene microspheres with good fluidity and morphology to meet practical needs.

[0006] Therefore, it is of great significance to develop an antibacterial polypropylene microsphere that can overcome the above-mentioned defects of the prior art. Summary of the invention

[0007] The technical problem to be solved by the present invention is that the method for preparing antibacterial propylene polymers in the prior art is complicated, the propylene polymers have poor fluidity, and the antibacterial property is not durable enough. A propylene polymer and a catalyst carrier for preparing the propylene polymer and a preparation method and application thereof are provided to prepare antibacterial polypropylene microspheres with good fluidity, low melting point and good morphology.

[0008] In order to solve the above technical problems, the first aspect of the present invention provides a propylene polymer, which is obtained by polymerizing propylene in the presence of a catalyst, wherein the catalyst is prepared from a catalyst carrier for preparing propylene polymers; the propylene polymer includes silver and magnesium, and the molar ratio of the silver element to the magnesium element in the propylene polymer is (0.001-100):1.

[0009] According to some embodiments of the present invention, the molar ratio of silver element to magnesium element in the propylene polymer is (0.1-20):1; the elution resistance of the propylene polymer is ≧79%; and the melting point of the propylene polymer is ≦162.5°C.

[0010] The second aspect of the present invention provides a method for preparing a catalyst support for preparing the above-mentioned propylene polymer, comprising the following steps:

[0011] (1) mixing a magnesium halide and an alcohol compound, and reacting the mixture with an ethylene oxide compound to obtain a first reactant;

[0012] (2) adding a silver carboxylate ethanol solution to the first reactant obtained in step (1) to obtain a mixture, and solidifying the mixture to obtain the catalyst support;

[0013] Optionally, the step (1) further comprises adding an inert liquid solvent.

[0014] According to some embodiments of the present invention, in step (1), the general formula of the magnesium halide is MgXY, the general formula of the alcohol compound is R1OH, and the structural formula of the ethylene oxide compound is as shown in formula (I).

[0015]

[0016] According to some embodiments of the present invention, in the general formula MgXY, X is a halogen, Y is a halogen, a C1-C14 Alkyl, C1-C 14 Alkoxy, C6-C 14 Aryl or C6-C 14 Further preferably, in the general formula MgXY, X is fluorine, chlorine or bromine, and Y is fluorine, chlorine, bromine, C1-C5 alkyl, C1-C5 alkoxy, C6-C 10 Aryl or C6-C 10 The C1-C5 alkyl group may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl or neopentyl; the C1-C5 alkoxy group may be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy; the C6-C 10 The aryl group may be, for example, phenyl, o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl or naphthyl. 10 The aryloxy group may be, for example, a phenoxy group or a naphthoxy group; the magnesium halide of the general formula MgXY may be a single magnesium halide or a mixture of multiple magnesium halides; further preferably, the magnesium halide of the general formula MgXY is selected from at least one of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride and n-butoxymagnesium chloride.

[0017] According to some embodiments of the present invention, in the general formula R1OH, R1 is a C1-C8 straight chain alkyl group, a C3-C8 branched chain alkyl group or a C3-C8 cycloalkyl group; preferably, in the general formula R1OH, R1 is a C1-C6 straight chain alkyl group, a C3-C6 branched chain alkyl group or a C3-C8 cycloalkyl group; more preferably, in the general formula R1OH, R1 is a C1-C5 straight chain alkyl group, a C3-C5 branched chain alkyl group or a C3-C6 cycloalkyl group. ; Further preferably, in the general formula R1OH, R1 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, cyclopropyl, cyclopentyl, methylcyclopropyl, dimethylcyclopropyl, cyclohexyl, methylcyclopentyl; Still further preferably, the alcohol compound of the general formula R1OH is selected from at least one of ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol and 2-ethylhexanol.

[0018] According to some embodiments of the present invention, in formula (I), R2 and R3 are the same or different, and are independently hydrogen, a C1-C5 straight-chain alkyl group or a C3-C5 branched alkyl group, wherein the hydrogen on the alkyl group is optionally substituted by a halogen atom; preferably, R2 and R3 are the same or different, and are independently hydrogen, a C1-C3 straight-chain alkyl group or a C1-C3 haloalkyl group; more preferably, R2 and R3 are the same or different, and are independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, chloromethyl, bromomethyl, chloroethyl, chloropropyl, bromopropyl; further preferably, the oxirane compound is selected from at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epichlorohydrin, epibromohydrin and epibromohydrin.

[0019] According to some embodiments of the present invention, the silver carboxylate in the ethanol solution is selected from at least one of silver acetate, silver propionate, silver butyrate and silver octanoate.

[0020] In the present invention, the phrase "optionally, the step (1) further comprises adding an inert liquid solvent" means that the inert liquid solvent may or may not be involved in the mixing. That is, the method of the present invention may or may not require an inert liquid solvent.

[0021] In the present invention, the halogen elements include fluorine, chlorine, bromine and iodine.

[0022] In the present invention, the C1-C 14 The alkyl group refers to an alkyl group having 1 to 14 carbon atoms, including branched alkyl groups and branched alkyl groups, including unsubstituted alkyl groups and substituted alkyl groups in which hydrogen atoms are selectively substituted by halogen elements or the like.

[0023] In the present invention, the C1-C 14 The alkoxy group refers to an alkoxy group having 1 to 14 carbon atoms, including branched alkoxy groups and branched alkoxy groups, including unsubstituted alkoxy groups and substituted alkoxy groups in which hydrogen atoms are selectively substituted by halogen elements or the like.

[0024] In the present invention, the C6-C 14 The aryl group refers to an aryl group having 6 to 14 carbon atoms, including phenyl, the C6-C 14 The aryl group may include an aryl group in which a hydrogen atom is substituted by a halogen element or the like.

[0025] In the present invention, the C6-C 14 The aryloxy group refers to an aryloxy group having 6 to 14 carbon atoms, including a phenoxy group, the C6-C 14 The aryloxy group may include an aryloxy group in which a hydrogen atom is substituted by a halogen element or the like.

[0026] In the present invention, the C1-C5 alkyl group includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl and isopentyl.

[0027] In the present invention, there is no particular limitation on the conditions for reacting the mixture of the magnesium halide of the general formula MgXY and the compound of the general formula R1OH with the ethylene oxide compound of the structure shown in formula (I) and the optional inert liquid solvent, as long as the mixing and reaction conditions allow the mixture of the magnesium halide of the general formula MgXY, the compound of the general formula R1OH and the ethylene oxide compound of the structure shown in formula (I) to form a solid substance (first reactant).

[0028] According to some embodiments of the present invention, in step (1), the mixing temperature is 70-90° C.; and the mixing time is 0.5-2 hours.

[0029] According to some embodiments of the present invention, in step (1), the reaction temperature is 70-90° C.; and the reaction time is 0.5-2 hours.

[0030] According to some embodiments of the present invention, in step (1), the inert liquid solvent is silicone oil and / or an inert liquid hydrocarbon solvent; preferably, the inert liquid solvent is selected from at least one of kerosene, paraffin oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methylethyl silicone oil, phenyl silicone oil and methylphenyl silicone oil.

[0031] In the present invention, the amount of components in the catalyst carrier can be selected and varied within a wide range.

[0032] According to some embodiments of the present invention, in step (1), based on 1 mol of magnesium halide of the general formula MgXY, the amount of the alcohol compound of the general formula R1OH is 4-30 mol, preferably 6-22 mol; the amount of the ethylene oxide compound represented by formula (I) is 1-10 mol, preferably 2-6 mol; and the amount of the inert liquid solvent is 0-10 L, preferably 2-8 L.

[0033] In the present invention, there is no particular limitation on the mixing conditions of the solid substance (first reactant) and the silver carboxylate ethanol solution, as long as the mixing conditions allow the solid substance (first reactant) and the silver carboxylate ethanol solution to be added to obtain a mixture, which can then solidify when entering the inert medium in the sprayer.

[0034] According to some embodiments of the present invention, in step (2), based on 1 mol of magnesium halide of the general formula MgXY, the amount of silver carboxylate used is 0.001-100 mol, preferably 0.001-10 mol.

[0035] According to some embodiments of the present invention, in step (2), the curing is carried out in a sprayer; preferably, the sprayer is provided with an atomizing nozzle, the atomizing nozzle comprises a material conduit and a nozzle head, the mixture is introduced into the nozzle head through the material conduit, and is sprayed into a tower body containing an inert medium of the sprayer through the nozzle head for curing; more preferably, the temperature of the mixture in the material conduit is 0-80°C, and the temperature in the nozzle head is 80-180°C, preferably 120-180°C.

[0036] According to some embodiments of the present invention, the sprayer includes an inert medium; preferably, the temperature of the inert medium is 60-200°C, preferably 90-150°C; more preferably, the amount of the inert medium can be selected according to the amount of magnesium halide with the general formula MgXY; generally, based on 1 mol of magnesium halide with the general formula MgXY, the amount of the inert medium is 0.8-10L, preferably 2-8L.

[0037] According to some embodiments of the present invention, the inert medium is an inert gas medium or an inert liquid medium, and there is no particular limitation on the type of the inert medium; preferably, the inert gas medium is selected from at least one of nitrogen, helium, and carbon dioxide; the inert liquid medium is silicone oil and / or an inert liquid hydrocarbon solvent; more preferably, the inert liquid medium can be various liquid media commonly used in the art that do not chemically interact with the reactants and reaction products, for example, at least one selected from kerosene, paraffin oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methylethyl silicone oil, phenyl silicone oil and methylphenyl silicone oil.

[0038] In the present invention, the conditions for solidifying the fluid mixed substance (mixture) by spraying can be various existing conditions that can form a catalyst carrier, for example, the fluid mixed substance (mixture) is sprayed into a sprayer so that the fluid mixed substance (mixture) contacts the inert medium in the sprayer.

[0039] In the present invention, the fluid mixed substance (mixture) can be emulsified by various methods known to those skilled in the art. For example, the fluid mixed substance (mixture) can be subjected to high-speed shearing to emulsify it. The high-speed shearing method is well known to those skilled in the art, for example, the fluid mixed substance (mixture) is stirred at a speed of 2000-5000 rpm. In addition, the fluid mixed substance can also be emulsified by referring to the following methods disclosed in the prior art: CN1267508C discloses that a solution containing a liquid magnesium halide adduct is rotated and dispersed in a supergravity bed (the rotation speed can be 100-3000 rpm); CN1463990A discloses that a solution containing a liquid magnesium halide adduct is output in an emulsifier at a speed of 1500-8000 rpm; US6020279 discloses that a solution containing a liquid magnesium halide adduct is emulsified by a spray method.

[0040] According to the present invention, the preparation method of the catalyst carrier may further include: separating the product obtained after spray solidification from the solid-liquid phase, washing the solid phase product and drying it. The solid-liquid separation may be any existing method capable of separating the solid phase from the liquid phase, such as suction filtration, filter pressing or centrifugal separation. Preferably, the method of solid-liquid separation is filter pressing. The present invention does not particularly limit the conditions for filter pressing, and the separation of the solid phase from the liquid phase is achieved as fully as possible. The washing may be performed by washing the obtained solid phase product using methods known to those skilled in the art, for example, an inert hydrocarbon solvent (for example, pentane, hexane, heptane, petroleum ether and gasoline) may be used to wash the obtained solid phase product. The present invention does not particularly limit the conditions for the drying, for example, the drying temperature may be 20-70°C, and the drying time may be 0.5-10 hours. According to the present invention, the drying may be performed under normal pressure or reduced pressure.

[0041] According to the preparation method of the present invention, trace amounts of water in the above-mentioned reactants can also participate in the reaction of forming the catalyst carrier.

[0042] According to the preparation method of the present invention, the possible water contained in the catalyst carrier comes from the trace water carried by the synthetic raw materials and the reaction medium.

[0043] The third aspect of the present invention provides a catalyst carrier prepared by the above-mentioned catalyst carrier preparation method, wherein the catalyst carrier comprises a compound as shown in structural formula (II) and silver element;

[0044]

[0045] In the compound represented by formula (II), R1 is a C1-C8 straight-chain alkyl, a C3-C8 branched-chain alkyl or a C3-C8 cycloalkyl; R2 and R3 are the same or different and are independently hydrogen, a C1-C5 straight-chain alkyl or a C3-C5 branched-chain alkyl, wherein the hydrogen on the R2 and R3 alkyl groups is optionally replaced by a halogen atom; X is a halogen, preferably chlorine or bromine; m is 0.1-1.9, n is 0.1-1.9, and m+n=2;

[0046] In the catalyst carrier, the molar ratio of silver element to the compound represented by formula (II) is (0.0010-100):1, preferably (0.0010-10):1; wherein the compound represented by formula (II) is calculated based on the molar amount of Mg.

[0047] According to some embodiments of the present invention, the average particle size of the catalyst support is 1-100 microns, preferably 1-80 microns; and / or the particle size distribution of the catalyst support is less than 1.5, preferably less than 1.2. In this preferred embodiment, the catalyst prepared from the catalyst support can obtain an olefin polymer with a lower melting point.

[0048] The inventors of the present invention unexpectedly discovered that in the process of preparing the catalyst carrier, after a magnesium halide of the general formula MgXY, an alcohol compound of the general formula R1OH and an ethylene oxide compound of the structural formula shown in formula (I) react to form a solid, the solid obtained by removing the mother liquor through solid-liquid separation is dissolved in ethanol to form a fluid material, and the addition of a silver carboxylate ethanol solution can affect the crystallization and accumulation of the carrier particles, thereby finally obtaining a carrier with good morphology.

[0049] A fourth aspect of the present invention provides the use of the above catalyst carrier or the catalyst carrier prepared by the above preparation method in the preparation of a catalyst for olefin polymerization or in olefin polymerization.

[0050] The present invention does not particularly limit the conditions for the application of the catalyst carrier in the preparation of the catalyst for olefin polymerization, and those skilled in the art can prepare the catalyst for olefin polymerization of the present invention by conventional technical means. In the embodiments of the present invention, the catalyst is prepared by contacting the carrier prepared by the present invention with a titanium source and an internal electron donor compound, and there is no particular limitation on the temperature and time of the contact reaction, which should not be understood by those skilled in the art as limiting the technical solution of the present invention.

[0051] Beneficial effects:

[0052] The catalyst carrier prepared by the method of the present invention is not prone to adhesion and has a good morphology. When used for olefin polymerization, an antibacterial polypropylene microsphere with good fluidity, low melting point and good morphology can be obtained. DETAILED DESCRIPTION

[0053] The present invention will be further described below in conjunction with the embodiments, but the present invention is not limited by these embodiments.

[0054] In the following examples and comparative examples of the present invention, unless otherwise specified, all raw materials used are commercially available.

[0055] In the Examples and Comparative Examples:

[0056] 1. The average particle size and particle size distribution of the catalyst carrier were measured using a Masters Sizer 2000 particle size analyzer (manufactured by Malvern Instruments Ltd);

[0057] 2. The surface morphology of the catalyst support was observed using an Eclipse E200 optical microscope purchased from Nikon Corporation;

[0058] 3. In each embodiment and comparative example of the present invention, DSC detection is carried out using the method specified in "GBT 19466 Plastics Differential Scanning Calorimetry (DSC)".

[0059] 4. Elution test of polyolefin powder: 10g sample was washed 10 times with anhydrous ethanol, 100ml / time, and frozen and sectioned. The silver content of the particles was analyzed by X-ray fluorescence spectroscopy. The ratio of the silver content after elution to the silver content before elution was defined as the elution resistance.

[0060] 5. Calculation of the activity of the catalyst used for olefin polymerization: Catalyst activity = (mass of polyolefin prepared) / (mass of catalyst solid component) g / g.

[0061] 6. Determination of melt index (MI) of polyolefin powder: According to ASTM D1238-99, measured at a load of 2.16 kg and 190°C.

[0062] Example 1

[0063] This example is used to illustrate the catalyst carrier and its preparation method of the present invention.

[0064] In a 0.6L reactor, add 0.08mol (8.0g) of magnesium chloride and 1.7mol of ethanol, raise the temperature to 90°C under stirring conditions, and react at a constant temperature of 90°C for 1 hour, then add 0.48mol (38ml) of epichlorohydrin, continue to react at 90°C for 30 minutes, and then filter, add silver acetate ethanol solution (silver acetate: ethanol = 0.2mol: 2.8mol) to the filter press product, stir to form a fluidized mixture, and use a sprayer containing a nozzle head and a material conduit to spray the fluidized mixture into the circulating nitrogen, and use the nozzle head heating temperature to 140°C to obtain the catalyst carrier Z1.

[0065] According to the characterization of gas chromatography-mass spectrometry, elemental analysis and nuclear magnetic resonance, the carrier Z1 contains the structural formula The compound and the silver element, wherein the molar ratio of the silver element to the compound (based on the molar amount of Mg) is 2.5:1.

[0066] Example 2

[0067] This example is used to illustrate the catalyst carrier and its preparation method of the present invention.

[0068] In a 0.6L reactor, add 0.08mol (8.0g) of magnesium chloride and 1.7mol of ethanol, raise the temperature to 90°C under stirring conditions, and react at a constant temperature of 90°C for 1 hour, then add 0.48mol (38mL) of epichlorohydrin, continue to react at 90°C for 30 minutes, and then filter, add silver acetate ethanol solution (silver acetate: ethanol = 0.006mol: 2mol; silver acetate 0.006mol) to the filter press product, stir to form a fluidized mixture, and use a sprayer containing a nozzle head and a material conduit to spray the fluidized mixture into the circulating nitrogen, and use the nozzle head heating temperature to 140°C to obtain the catalyst carrier Z2.

[0069] According to GC-MS, elemental analysis and NMR characterization, the carrier Z2 contains the structural formula The compound and silver, wherein the molar ratio of the silver element to the compound (based on the molar amount of Mg) is 0.072:1.

[0070] Example 3

[0071] This example is used to illustrate the catalyst carrier and its preparation method of the present invention.

[0072] In a 0.6L reactor, add 0.08mol (8.0g) of magnesium chloride and 1.7mol of ethanol, raise the temperature to 90°C under stirring conditions, and react at a constant temperature of 90°C for 1 hour, then add 0.48mol (38ml) of epichlorohydrin, continue to react at 90°C for 30 minutes, and then filter, add silver octanoate ethanol solution (silver octanoate: ethanol = 0.2mol: 2.8mol) to the filter press product, stir to form a fluidized mixture, and use a sprayer containing a nozzle head and a material conduit to spray the fluidized mixture into the circulating nitrogen, and use the nozzle head heating temperature to 140°C to obtain the catalyst carrier Z1.

[0073] According to the characterization of gas chromatography-mass spectrometry, elemental analysis and nuclear magnetic resonance, the carrier Z1 contains the structural formula The compound and the silver element, wherein the molar ratio of the silver element to the compound (based on the molar amount of Mg) is 2.4:1.

[0074] Example 4

[0075] This example is used to illustrate the catalyst carrier and its preparation method of the present invention.

[0076] In a 0.6L reactor, add 0.08mol (8.0g) of magnesium chloride and 1.7mol of ethanol, raise the temperature to 90°C under stirring conditions, and react at a constant temperature of 90°C for 1 hour, then add 0.48mol (38ml) of epichlorohydrin, continue to react at 90°C for 30 minutes, and then filter, add silver acetate ethanol solution (silver acetate: ethanol = 0.01mol: 2.8mol) to the filter press product, stir to form a fluidized mixture, and use a sprayer containing a nozzle head and a material conduit to spray the fluidized mixture into the circulating nitrogen, and use the nozzle head heating temperature to 140°C to obtain the catalyst carrier Z1.

[0077] According to the characterization of gas chromatography-mass spectrometry, elemental analysis and nuclear magnetic resonance, the carrier Z1 contains the structural formula The compound and the silver element, wherein the molar ratio of the silver element to the compound (based on the molar amount of Mg) is 0.12:1.

[0078] Comparative Example 1

[0079] This comparative example is used to illustrate the catalyst carrier and its preparation method described in the comparative example of the present invention.

[0080] In a 0.6L reactor, add 0.08mol magnesium chloride and 1.7mol ethanol, raise the temperature to 90°C under stirring conditions, and react at a constant temperature of 90°C for 1 hour, then add 0.48mol (38ml) of epichlorohydrin, react at 90°C for 30 minutes, and filter press, add 2.8mol ethanol to the filter press product, stir to form a fluid mixture, and use a sprayer containing a nozzle head and a material conduit to spray the emulsified fluid mixture into the circulating nitrogen, and the nozzle head heating temperature is 140°C to finally obtain the catalyst carrier DZ1.

[0081] According to GC-MS, elemental analysis and NMR characterization, the carrier DZ1 contains the structural formula compounds, without silver.

[0082] Comparative Example 2

[0083] This comparative example is used to illustrate the catalyst carrier and its preparation method described in the comparative example of the present invention.

[0084] The preparation method of Example 1 was adopted, except that the same molar amount of silver chloride was used instead of silver acetate, and eventually blockage occurred during the spraying process, and no carrier could be obtained.

[0085] The average particle size (D50) and particle size distribution ((D90-D10) / D50) of the catalyst carriers prepared in the above Examples 1-4 and Comparative Examples 1-2 were measured and their surface morphologies were observed. The results are shown in Table 1 below:

[0086] Table 1

[0087]

[0088] Example 5

[0089] This example is used to illustrate that the catalyst support of the present invention is used for the preparation of polyolefins.

[0090] (1) Preparation of catalyst components for olefin polymerization

[0091] In a 300mL reaction bottle, add 100mL of titanium tetrachloride, cool to -20°C, then add 8g of the catalyst carrier Z1 obtained in Example 1, and stir at -20°C for 30min. Then, slowly heat up to 110°C, add 1.5mL of diisobutyl phthalate during the heating process, maintain the temperature at 110°C for 30min, filter out the liquid, then add titanium tetrachloride and wash twice, finally wash three times with hexane, and obtain the catalyst component C1 for olefin polymerization after drying.

[0092] (2) Propylene polymerization

[0093] A 5L stainless steel autoclave was purged with a nitrogen gas flow, and then 1mmol of a hexane solution of triethylaluminum (the concentration of triethylaluminum was 0.5mmol / mL), 0.05mmol of methylcyclohexyldimethoxysilane, 10mL of anhydrous hexane and 10mg of the catalyst component C1 for olefin polymerization obtained in the above step (1), 1.5L (standard volume) of hydrogen and 2.5L of liquid propylene were introduced into the nitrogen gas flow. The temperature was raised to 70°C and polymerization reaction was carried out at this temperature for 1 hour. The temperature was then lowered, the pressure was released, and the discharged material was dried to obtain a polypropylene powder.

[0094] Example 6

[0095] This example is used to illustrate the use of the catalyst support of the present invention in the preparation of polyolefins.

[0096] Propylene polymerization was carried out according to the method of Example 5, except that the catalyst carrier Z1 was replaced by the catalyst carrier Z2 obtained in Example 2, to obtain catalyst components for olefin polymerization and polypropylene powder.

[0097] Example 7

[0098] This example is used to illustrate the use of the catalyst support of the present invention in the preparation of polyolefins.

[0099] Propylene polymerization was carried out according to the method of Example 5, except that the catalyst carrier Z1 was replaced by the catalyst carrier Z3 obtained in Example 3, to obtain catalyst components for olefin polymerization and polypropylene powder.

[0100] Example 8

[0101] This example is used to illustrate the use of the catalyst support of the present invention in the preparation of polyolefins.

[0102] Propylene polymerization was carried out according to the method of Example 5, except that the catalyst carrier Z1 was replaced by the catalyst carrier Z4 obtained in Example 4, to obtain catalyst components for olefin polymerization and polypropylene powder.

[0103] Comparative Example 3

[0104] This comparative example is used to illustrate that the catalyst support of the present invention is used for the preparation of polyolefins.

[0105] Propylene polymerization was carried out according to the method of Example 5, except that the catalyst support Z1 was replaced by the catalyst support DZ1 obtained in Comparative Example 1, to obtain a catalyst component for olefin polymerization and a polypropylene powder.

[0106] The catalyst components for olefin polymerization prepared in the above Examples 5-8 and Comparative Example 3 were used for propylene polymerization, and the catalytic activity of the catalysts for olefin polymerization in Examples 5-8 and Comparative Example 3 after 1 hour of polymerization was calculated, and the appearance of the prepared polypropylene powder was observed. The results are shown in Table 2 below:

[0107] Table 2

[0108]

[0109] Note: In Table 2, the molar ratio of silver / magnesium indicates the molar ratio of silver / magnesium in the polypropylene powder; * indicates that when testing the experimental data, the prepared polypropylene powder is first immersed in the same amount of silver acetate ethanol solution as in Example 1 for 1 hour, and then vacuum dried and subjected to a wash resistance test.

[0110] It can be seen from the results in Table 2 above that the present invention overcomes the above-mentioned defects of the prior art. By using the catalyst prepared by the catalyst carrier prepared by the preparation method of the present invention to polymerize propylene, an antibacterial polypropylene microsphere with good fluidity and good morphology is directly obtained; in this way, not only the antibacterial polypropylene microsphere with good compatibility that cannot be obtained by the current technology is obtained, but also the process and energy are saved; the obtained polypropylene microsphere also has a lower melting point, can be processed and applied at a lower temperature, saves energy, and has great industrial application prospects.

[0111] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. A propylene polymer, characterized in that The propylene polymer is obtained by polymerizing propylene in the presence of a catalyst, wherein the catalyst is prepared from a catalyst carrier used to prepare the propylene polymer; the propylene polymer includes silver and magnesium, and the molar ratio of the silver element to the magnesium element in the propylene polymer is (0.001-100):

1.

2. The propylene polymer according to claim 1, characterized in that The molar ratio of silver element to magnesium element in the propylene polymer is (0.1-20):1; the elution resistance of the propylene polymer is ≧79%; and the melting point of the propylene polymer is ≦162.5°C.

3. A method for preparing a catalyst carrier for preparing the propylene polymer according to claim 1 or 2, characterized in that: The steps include: (1) mixing a magnesium halide and an alcohol compound, and reacting the mixture with an ethylene oxide compound to obtain a first reactant; (2) adding a silver carboxylate ethanol solution to the first reactant obtained in step (1) to obtain a mixture, and solidifying the mixture to obtain the catalyst support; Optionally, the step (1) further comprises adding an inert liquid solvent.

4. The preparation method according to claim 3, characterized in that: In step (1), the general formula of the magnesium halide is MgXY, the general formula of the alcohol compound is R1OH, and the structural formula of the ethylene oxide compound is as shown in formula (I); Preferably, in the general formula MgXY, X is halogen, Y is halogen, C1-C 14 Alkyl, C1-C 14 Alkoxy, C6-C 14 Aryl or C6-C 14 Further preferably, in the general formula MgXY, X is fluorine, chlorine or bromine, and Y is fluorine, chlorine, bromine, C1-C5 alkyl, C1-C5 alkoxy, C6-C 10 Aryl or C6-C 10 More preferably, the magnesium halide of the general formula MgXY is selected from at least one of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride and n-butoxymagnesium chloride; and / or, in the general formula R1OH, R1 is a C1-C8 straight chain alkyl group, a C3-C8 branched chain alkyl group or a C3-C8 cycloalkyl group; preferably, in the general formula R1OH, R1 is a C1-C6 straight chain alkyl group, a C3-C6 branched chain alkyl group or a C3-C8 cycloalkyl group; more preferably, in the general formula R1OH, R1 is a C1-C5 straight chain alkyl group, a C3-C5 branched chain alkyl group or a C3-C6 cycloalkyl group; further Preferably, in the general formula R1OH, R1 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, cyclopropyl, cyclopentyl, methylcyclopropyl, dimethylcyclopropyl, cyclohexyl, methylcyclopentyl; further preferably, the alcohol compound of the general formula R1OH is at least one selected from ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol and 2-ethylhexanol; And / or, in formula (I), R2 and R3 are the same or different, and are independently hydrogen, a C1-C5 straight-chain alkyl group or a C3-C5 branched alkyl group, wherein the hydrogen on the alkyl group is optionally substituted by a halogen atom; preferably, R2 and R3 are the same or different, and are independently hydrogen, a C1-C3 straight-chain alkyl group or a C1-C3 haloalkyl group; more preferably, R2 and R3 are the same or different, and are independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, chloromethyl, bromomethyl, chloroethyl, chloropropyl, bromopropyl; further preferably, the oxirane compound is selected from at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epichlorohydrin, epibromohydrin and epibromohydrin; And / or, the silver carboxylate in the silver carboxylate ethanol solution is selected from at least one of silver acetate, silver propionate, silver butyrate and silver octanoate.

5. The preparation method according to claim 3 or 4, characterized in that: In step (1), the mixing temperature is 70-90° C. and the mixing time is 0.5-2 hours; And / or, the reaction temperature is 70-90°C; the reaction time is 0.5-2 hours; And / or, the inert liquid solvent is silicone oil and / or an inert liquid hydrocarbon solvent; preferably, the inert liquid medium is selected from at least one of kerosene, paraffin oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methylethyl silicone oil, phenyl silicone oil and methylphenyl silicone oil; And / or, based on 1 mol of magnesium halide with the general formula MgXY, the amount of the alcohol compound with the general formula R1OH is 4-30 mol, preferably 6-22 mol; the amount of the ethylene oxide compound shown in formula (I) is 1-10 mol, preferably 2-6 mol; the amount of the inert liquid solvent is 0-10 L, preferably 2-8 L.

6. The preparation method according to any one of claims 3 to 5, characterized in that: In step (2), the curing is carried out in a sprayer; preferably, the sprayer is provided with an atomizing nozzle, and the atomizing nozzle comprises a material conduit and a nozzle head; more preferably, the temperature of the mixture in the material conduit is 0-80°C, and the temperature in the nozzle head is 80-180°C, preferably 120-180°C.

7. The preparation method according to claim 6, characterized in that: The sprayer includes an inert medium; preferably, the temperature of the inert medium is 60-200°C, preferably 90-150°C; more preferably, based on 1 mol of magnesium halide with the general formula MgXY, the amount of silver carboxylate is 0.001-100 mol, preferably 0.001-10 mol; the amount of the inert medium is 0.8-10L, preferably 2-8L.

8. The preparation method according to claim 6, characterized in that: The inert medium is an inert gas medium or an inert liquid medium; preferably, the inert gas medium is selected from at least one of nitrogen, helium, and carbon dioxide; the inert liquid medium is silicone oil and / or an inert liquid hydrocarbon solvent; more preferably, the inert liquid medium is selected from at least one of kerosene, paraffin oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methylethyl silicone oil, phenyl silicone oil, and methylphenyl silicone oil.

9. A catalyst carrier prepared by the preparation method according to any one of claims 3 to 8, characterized in that: The catalyst carrier comprises a compound as shown in structural formula (II) and silver element; In the compound represented by formula (II), R1 is a C1-C8 straight-chain alkyl, a C3-C8 branched-chain alkyl or a C3-C8 cycloalkyl; R2 and R3 are the same or different and are independently hydrogen, a C1-C5 straight-chain alkyl or a C3-C5 branched-chain alkyl, wherein the hydrogen on the R2 and R3 alkyl groups is optionally replaced by a halogen atom; X is a halogen, preferably chlorine or bromine; m is 0.1-1.9, n is 0.1-1.9, and m+n=2; In the catalyst carrier, the molar ratio of silver element to the compound represented by formula (II) is (0.0010-100):1; wherein the compound represented by formula (II) is calculated based on the molar amount of Mg.

10. The catalyst carrier according to claim 9, characterized in that The average particle size of the catalyst carrier is 1-100 microns, preferably 1-80 microns; and / or the particle size distribution of the catalyst carrier is less than 1.2, preferably less than 0.

9.

11. Use of a catalyst carrier prepared by the preparation method according to any one of claims 3 to 8 or a catalyst carrier according to claim 9 or 10 in preparing a catalyst for olefin polymerization or in olefin polymerization.

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