CN109438593B - Catalyst for producing ultrahigh molecular weight polyolefin and preparation method and application thereof - Google Patents
Catalyst for producing ultrahigh molecular weight polyolefin and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for producing ultrahigh molecular weight polyolefin, a preparation method and application thereof, wherein the catalyst comprises the following components: inorganic carrier loaded with surfactant, catalytic component loaded on inorganic carrier, transition metal halide MX as catalytic component4With an organometallic reagent M' R containing an R groupn(n-1-3) reaction to form catalytic component MR4. Compared with the prior art, the catalyst prepared by the invention has high bulk density, uniform particles and average particle size of less than 200 mu m, can be used for preparing and applying medium-high density ultrahigh molecular weight polyolefin, and is particularly suitable for products such as high-performance ultrahigh molecular weight polyethylene fiber and the like.
Description
Technical Field
The invention relates to a catalyst, in particular to a catalyst for producing ultrahigh molecular weight polyolefin and a preparation method and application thereof.
Background
China has rapid development of polyolefin industry, but can not meet the requirements of domestic markets, and particularly high-performance polyolefin materials mainly depend on import. The development of general-purpose polymer materials such as polyethylene with high performance has been a focus of research. Olefin polymerization catalysts are the core of polyolefin polymerization technology. The traditional Ziegler-Natta catalyst loaded on a carrier has obviously improved catalytic efficiency, is called as a high-efficiency Ziegler-Natta catalyst, and leads the polyolefin industry to be rapidly developed. The superfine polyethylene has wide application, and superfine polyolefin products such as superfine ultrahigh molecular weight polyethylene, superfine polyethylene wax, superfine high density polyethylene and the like are used for manufacturing products such as injection molding, extrusion molding, blow molding and the like by downstream customers.
In patent CN102002124, petroleum discloses a production method for preparing high-density ultrafine polyethylene powder by a slurry method, wherein a magnesium ethoxide/titanium tetrachloride catalyst with a particle size of 0.2-5.0 polyethylene is adopted, and the particle size of the prepared polyethylene powder reaches 30-80 microns after a monomer is subjected to polymerization reaction under the conditions of a reaction temperature of 75-85 ℃, a reaction pressure of 0.8-1.0 MPa and a stirring speed of 50-1500 RPM.
In patents CN106317562A and CN106319667A, a series of patents relating to the preparation method of ultra-high molecular weight ultra-fine polyethylene and its application in the fields of film and fiber are disclosed in chemistry. The solubilization type ultra-high molecular weight ultrafine grain diameter polyethylene is synthesized by controlling the polymerization temperature of ethylene, the purity of monomer ethylene, adjusting the preparation steps of a catalyst and introducing a dispersion medium into a polymerization system. The catalyst adopts the traditional preparation method that magnesium chloride alcoholate is dealcoholized by titanium tetrachloride. The patent claims and examples do not suggest the average particle size and properties of the prepared catalyst, the average particle size of the finally obtained polyethylene in the patent is 50-80 microns, and the polymer contains a certain amount of high-boiling point dispersion medium, the bulk density of the product is extremely low and is only 0.1-0.3g/mL, although the residual solvent in the polymer improves the performance of subsequent processing, and the catalyst can be used in the fields of membranes and fibers. However, the extremely low bulk density of polyethylene presents difficulties in the collection and transport of the product.
A polyethylene device of Liaoyang petrochemical company adopts an ethoxy magnesium/titanium tetrachloride catalytic system to produce high-density polyethylene, the particle size of a catalyst is about 5 microns, and the particle size of a produced polyethylene product is 100-180 microns, so that the polyethylene device is mainly used for manufacturing injection molding, extrusion molding and blow molding products by downstream users.
Another method for preparing ultra-fine polyethylene powder is cryogenic grinding, i.e. ordinary polyethylene powder is frozen and then ground, which is too high in production cost and increases user burden.
In patents CN101906179B andin CN101633703A, Beijing university of chemical industry previously disclosed a method for preparing (ultra-high molecular weight) polyolefin catalyst by mixing a carrier such as SiO2Dispersing in an organic solvent; adding organic lithium (such as butyl lithium) or Grignard reagent into the obtained dispersion at-40-30 deg.C, reacting at-20-30 deg.C for 0.5-3 hr, heating to 30-100 deg.C, and reacting for 0.5-5 hr to obtain mixture; filtering the mixture, and washing to remove the excess organic lithium or Grignard reagent; at-30-30 deg.C, adding organosilicon compound (such as dimethyl diethoxy silicon) and titanium tetrachloride compound, reacting at-30-30 deg.C for 0.5-3 hr, heating to 30-100 deg.C, and reacting for 1-5 hr; and filtering and washing to remove the excessive titanium halide, and drying to obtain the main catalyst. Then adding a main catalyst and a cocatalyst (such as triethyl aluminum) into the slurry reaction kettle, and introducing ethylene for reaction to prepare a polyethylene product. The method comprises the steps of reacting a Grignard reagent (butyl lithium) with silica gel, so as to improve the loading capacity of titanium tetrachloride; the reaction of the Grignard reagent and the silica gel is also beneficial to widening the range of the silica gel activation temperature (100-1000 ℃), and the catalyst obtained at lower silica gel activation temperature also has higher activity; the purpose of adding the organic silicon when preparing the main catalyst is to improve the copolymerization efficiency of ethylene and comonomer. According to the method, the Grignard reagent is added to modify the silica gel, so that the activation efficiency of the silica gel is improved, but the active component of the catalyst is still titanium tetrachloride, and the defects of titanium tetrachloride supported by the silica gel, such as low bulk density, wide distribution of product molecular weight, agglomeration growth in polymerization of a polymerization product, large particle size, uneven distribution and the like, are difficult to overcome, the difficulty in post-processing of the ultra-high molecular weight polyethylene is increased, the application field of the product is limited, and the product is difficult to use in high-end fields such as spinning and diaphragm fields.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, adopts a different preparation method of the catalyst compared with the prior art, and aims to solve one problem of providing the catalyst capable of producing the ultrafine ultrahigh molecular weight polyolefin. The catalyst is used for polymerization reaction, the catalytic activity is higher, the particle size of the obtained polymerization product is finer, the particle size is below 200 micrometers, and the average molecular weight is between 100 and 1000 ten thousand.
The second technical problem to be solved by the present invention is to provide a method for preparing the ultrafine supported catalyst.
The invention also provides the application of the supported catalyst in ethylene polymerization.
The purpose of the invention can be realized by the following technical scheme:
a catalyst for producing an ultrahigh molecular weight polyolefin, comprising:
an inorganic carrier loaded with a surfactant,
a catalytic component supported on an inorganic support,
the catalytic component is transition metal halide MX4With an organometallic reagent M' R containing an R groupn(n-1-3) reaction to form catalytic component MR4。
The transition metal halide MX4Wherein M is titanium, zirconium, vanadium or hafnium, X is halogen, fluorine, chlorine, bromine or iodine; organometallic reagent M' RnM' in the formula is Li, Mg, Zn or Al, and the R group is one or more of benzyl, alkyl silicon methyl, methylene naphthyl or neopentyl.
The content of the catalytic component is 0.1-10 wt% of the total amount of the catalyst calculated by metal.
The inorganic carrier is one or more selected from magnesia, silica, alumina, titania, silica-alumina, silica-magnesia, chain silicate, layered silicate, talc or magnesium hydroxide-magnesium sulfate, has an average particle diameter of 0.01-100 μm, and contains hydroxyl and/or carboxyl on the surface.
The inorganic carrier has an average particle size of 0.1 to 30 microns, preferably 0.5 to 10 microns.
The surfactant is a component with an amphiphilic molecular structure, one end of the surfactant is a hydrophilic group, the other end of the surfactant is a hydrophobic group, and the molar ratio of the surfactant to the inorganic carrier is 0.01-100: 1.
The surfactant is one or more selected from fatty acid methyl ester, alkyl olefine acid methyl ester or alkyl dienoic acid methyl ester, the number of the alkyl carbon chain is selected from 10-24, preferably 12-18, and in addition, the alkyl carbon chain can also have a side chain, and/or a hydroxyl group and/or other groups.
A method for preparing a catalyst for producing ultrahigh molecular weight polyolefin, comprising the steps of:
(1) ultrasonically dispersing at least one inorganic carrier without molecular water in an organic solvent, adding a surfactant, and reacting at a proper temperature to obtain a modified inorganic carrier;
(2) stirring in organic solvent at proper temperature to obtain transition metal halide MX4Dipping the modified inorganic carrier obtained in the step (1) to react with the surface of the carrier to ensure that the transition metal halide MX4The components are loaded on the modified inorganic carrier through in-situ reaction;
(3) adding the inorganic composite carrier obtained in the step (2) into an organic solvent to form a suspension, and then adding an organic metal compound M' RnCarrying out in-situ reaction at a proper temperature;
(4) and (4) filtering and washing the product obtained in the step (3) by using a solvent to remove excessive organic metal compounds, and drying to obtain the catalyst for producing the ultrahigh molecular weight polyolefin.
The organic solvent in the step (1) is selected from long-chain saturated alkane or halogenated aromatic hydrocarbon of C10-C20, or a mixed solvent thereof; the reaction temperature is 20-200 ℃; the reaction time is 0.1 to 10 hours; the weight ratio of the dosage of the surfactant to the dosage of the inorganic carrier is 0.01-100: 1;
the transition metal halide MX in the step (2)4The weight ratio of the modified inorganic carrier to the modified inorganic carrier is 0.01-50: 1; the reaction temperature is-40 to 200 ℃; the reaction time is 0.1 to 10 hours; the stirring speed is 20-800 rpm;
the organometallic compound M' R of the step (3)nWith transition metal halides MX4In a weight ratio of 0.01-50: 1; the reaction temperature is-120-80 ℃, and the reaction time is 0.1-10 hours.
As a more preferred embodiment of the present invention,
the reaction temperature of the step (1) is preferably 50 to 180 ℃, more preferably 80 to 160 ℃, the reaction time is 0.5 to 5 hours, more preferably 1 to 3 hours, and the weight ratio of the surfactant to the inorganic carrier is preferably 0.1 to 20: 1, more preferably 0.5 to 5:1, the organic solvent comprises one or more of decane, dodecane, kerosene, dichlorobenzene, trichlorobenzene, trimethylbenzene, xylene, toluene or benzyl chloride, and the preferred is kerosene or dichlorobenzene;
the transition metal halide MX in the step (2)4The weight ratio to the modified inorganic support is preferably 0.5 to 30: 1, more preferably 1 to 10: 1; the reaction temperature is preferably 60-160 ℃, and more preferably 100-140 ℃; the reaction time is preferably 1 hour to 6 hours, more preferably 2 to 4 hours; the stirring speed is 150-400 rpm; more preferably 200-300 rpm;
the organometallic compound M' R of the step (3)nWith transition metal halides MX4Preferably 0.1 to 20: 1, more preferably 0.5 to 5: 1; the reaction temperature is preferably-90 to 50 deg.C, more preferably-80 to 20 deg.C. The reaction time is preferably 0.5 to 5 hours, more preferably 1 to 3 hours.
The application of catalyst for producing ultrahigh molecular weight polyolefin is characterized by that in single reactor or series-connected reactors of 2 or more than 2 reactors, ethylene, alpha-olefin comonomer, catalyst and cocatalyst are added to make polymerization reaction so as to produce polyethylene, the mole ratio of alpha-olefin comonomer and ethylene is 0.01-1: 1, the addition amount of the catalyst is 0.01-100ppm, and the addition amount of the cocatalyst is 5-500 ppm.
The alpha-olefin comonomer is C1-C20 alpha-olefin, including propylene, 1-butene, 1-pentene, 1-hexene, 1-octene or 1-decene, and the molar ratio of the alpha-olefin comonomer to ethylene is 0.05-0.5: 1, the addition amount of the cocatalyst is controlled to make the concentration of the cocatalyst be 20-400 ppm.
The polymerization reaction is an olefin polymerization process and comprises slurry kettle type, slurry loop pipe or solution polymerization, wherein the reaction pressure is 0.1-5MPa, the reaction temperature is 0-120 ℃, preferably 40-90 ℃, and most preferably 60-80 ℃ during slurry kettle type polymerization; the slurry loop polymerization is carried out at a reaction pressure of 0.5 to 6MPa and a reaction temperature of 30 to 150 ℃, preferably 50 to 100 ℃, and most preferably 60 to 80 ℃.
The polyethylene produced has an average particle size of 10 to 500 microns, preferably 40 to 400 microns, most preferably 60 to 200 microns. The viscosity average molecular weight of the product is 30-1000 ten thousand, and the preferred average molecular weight is 100-900 ten thousand; the density is 0.918-0.950g/cm3Preferably, the density is 0.920-0.940g/cm3。
The present invention improves the useful support material over the prior art in that it comprises an inorganic support treated with a surface active agent. The invention selects fatty acid methyl ester, alkyl olefine acid methyl ester or alkyl dienoic acid methyl ester with 12-18 alkyl carbon chain number as the surfactant, and has two purposes and functions: one is to improve the dispersibility of the inorganic support and the uniformity of the reaction with the organomagnesium reagent. The surfactant can chemically react with the surface of the inorganic carrier at a higher temperature (the temperature is over 150 ℃), so that long-chain alkyl is generated on the surface of the inorganic carrier, the dispersion of the inorganic carrier is facilitated, and the modified inorganic carrier is favorably and uniformly reacted with an organic magnesium reagent; and secondly, the deactivation resistant temperature of the catalytic component is improved. When the reaction temperature is over 100 ℃, the catalytic component and the inorganic carrier are facilitated to fully react, the active center is not inactivated, and the catalytic active center obtained by the reaction is uniformly dispersed on the surface of the carrier. In the polymerization, the catalyst can be uniformly dispersed in the polymerization, the agglomeration of catalyst particles is reduced, and polyethylene particles with ultra-fine particle size are finally prepared. By loading different active centers, the ultra-high molecular weight polyethylene with ultra-fine particle size can be prepared, and can be used in high-end fields such as lithium battery diaphragms, fiber spinning and the like.
Compared with the prior art, the transition metal halide MX is utilized4The in-situ reaction is carried out on the surface of an inorganic carrier by adding an organic metal compound M' RnAnd MX4And in the reaction, a large functional group R is introduced into an active center ligand, so that the activity of the catalyst is improved, the polymer chain transfer can be reduced, and the molecular weight of the product polyethylene is improved. Because the surface active agent contained in the catalyst improves the dispersion degree of polyolefin particles in the polymerization process, the catalyst is beneficial to preparing ultra-high molecular weight polyethylene powder with the particle size of less than 200 microns.
Drawings
FIG. 1 is an electron micrograph of a polyethylene sample of example 1 a;
FIG. 2 is an electron micrograph of a polyethylene sample of comparative example 1;
FIG. 3 is a graph showing ethylene polymerization kinetics of catalysts of example 1a, example 1b and comparative example 1.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The performance index of each polymer in examples was measured in the following manner.
ASTM D1238 for testing melt index (MI2.16 at 2.16kg load, 190 ℃ C.), flow index (FI at 21.6kg load, 190 ℃ C.) of polyethylene resin
Determination of the bulk Density of the Polymer: measured according to ASTM-D1895.
Catalyst composition for producing superfine ultrahigh molecular weight polyolefin
The present invention provides a catalyst for producing ultra-fine ultra-high molecular weight polyolefin, which comprises the catalyst supported on a surface-modified inorganic carrier.
According to one embodiment, the catalyst of the invention comprises:
(1) an inorganic carrier obtained by surfactant treatment is used as a carrier;
(2) loading the transition metal halide and the carrier on the surface of the carrier through in-situ reaction;
(3) then adding an organometallic compound M' RnAnd MX4Reaction, in situ formation of MR4A catalytic component;
the catalyst suitable for producing polyolefin with superfine particle size synthesized by the invention is characterized in that the inorganic carrier used as the carrier comprises one or more of magnesia, silica, alumina, titanium dioxide, silica-alumina, silica-magnesia, chain silicate, layered silicate, talc, magnesium hydroxide-magnesium sulfate and the like; the average particle size of the functional inorganic carrier is 0.01-100 microns.
The surfactant refers to that the molecular structure has amphipathy: one end is a hydrophilic group and the other end is a hydrophobic group. Preferably one or more of fatty acid methyl ester, alkyl olefine acid methyl ester and alkyl dienoic acid methyl ester. The molar ratio of the dosage of the surfactant to the dosage of the functional inorganic carrier is (0.01-50): 1.
the transition metal halide MX4Wherein M is titanium, zirconium, vanadium or hafnium, and X is a halogen compound, preferably fluorine, chlorine, bromine, iodine, etc.
The organometallic reagent M' RnM' in (n ═ 1-3) is Li, Mg, Zn, Al or the like, and R is one or more of benzyl, alkylsilylmethyl, methylenenaphthyl, neopentyl or the like.
The catalytic component is formed by transition metal halide MX supported on the surface of an inorganic carrier4With an organometallic reagent M' R containing an R groupnReaction to form MR4. The content of the catalytic component is 0.1 to 10 weight percent of the total amount of the catalyst calculated by metal;
the average grain diameter of the functional inorganic material is 0.1-30 microns, preferably 0.5-10 microns;
according to a particular aspect of this embodiment, the following preparation method can be used:
(1) ultrasonically dispersing at least one micro-nano inorganic carrier without molecular water in an organic solvent, then adding a surfactant, and reacting at a proper temperature to obtain a modified inorganic carrier;
(2) in organic solvent, transition metal halide MX is reacted at proper temperature4Dipping the functional inorganic composite carrier obtained in the step (2) to react with the surface of the carrier so as to load the catalyst component on the inorganic composite carrier;
(3) in an organic solvent, adding an organometallic compound M' RnAdding the functional inorganic suspension obtained in the step (2) at a proper temperatureAnd (4) carrying out in-situ reaction.
(4) Filtering and washing the product obtained in the step (3) by a solvent to remove excessive organic metal compounds, and drying to obtain the catalytic component MR4The solid catalyst of (4).
The carrier is first dehydrated, and the carrier is selected from anhydrous magnesia, silica, alumina, silica-magnesia and alumina-magnesia, but not limited thereto. The program dehydration treatment method comprises the following steps: under the protection of inert gas (nitrogen or argon), fluidization treatment activation is carried out. Keeping the temperature of 100 ℃ to the maximum of 600 ℃ for 2 hours every 100 ℃, then gradually cooling to room temperature, and packaging the carrier with nitrogen for storage. Adding dehydrated activated inorganic carrier in organic solvent including but not limited to dichlorobenzene, ultrasonic dispersing, adding surfactant, and reacting at proper temperature to obtain modified functional inorganic carrier.
Adding transition metal halide including but not limited to titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride, vanadium tetrachloride and the like into the functional inorganic carrier suspension obtained in the step in an organic solvent including but not limited to dichlorobenzene, wherein the reaction temperature is-50-100 ℃, and the transition metal halide reacts with the surface of the carrier to react MX4The catalytic component is loaded on the inorganic composite carrier. And filtering and washing the obtained product with a solvent to remove excessive catalytic components, drying, and preserving under the protection of nitrogen.
Organometallic compounds M' R in organic solvents including, but not limited to, dichlorobenzenenAdding the functional inorganic suspension obtained in the step, and reacting in situ at a proper temperature. Filtering and washing the obtained product with solvent to remove excessive organic metal compound, and drying to obtain catalytic component MR4The solid catalyst of (4).
The cocatalyst used in the polymerization of ethylene according to the present invention is selected from the group consisting of alkylaluminum compounds, alkylaluminoxane compounds, haloalkylaluminum compounds, alkylmagnesium compounds, alkylzinc compounds, alkylboron compounds or combinations thereof, preferably triethylaluminum, diethylaluminum monochloride, ethylaluminum dichloride, triisobutylaluminum, most preferably triethylaluminum or diethylaluminum monochloride. The concentration of the cocatalyst is generally about 5 to 500ppm, preferably about 20 to 400ppm, and most preferably about 40 to 300ppm (based on the ethylene employed).
the present invention provides a process for preparing ultra-fine particle size polyolefin powders comprising polymerizing ethylene alone or in combination with other olefinic monomers, such as one or more higher α -olefins, under polymerization conditions in the presence of the catalyst of the present invention and a corresponding cocatalyst, an example of which is C3-C10such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene and 1-octene, preferably 1-butene, 1-pentene, 1-hexene or 4-methyl-1-pentene and most preferably 1-hexene.
The polymerization may be carried out using any suitable, conventional olefin polymerization process, such as slurry loop, tank, solution or gas phase polymerization, but is preferably carried out in a slurry loop reactor or in a tank reactor, especially a slurry loop reactor. The polymerization can be carried out batchwise, semicontinuously or continuously. The reaction is conducted with a catalytically effective amount of the catalyst (composition) at a temperature and pressure sufficient to initiate the polymerization reaction, while eliminating catalyst poisons such as moisture, oxygen, carbon monoxide and acetylene in the polymerization system. A particularly desirable method of producing the polymers of the present invention is in a slurry loop or tank reactor.
The polymerization reaction is a conventional olefin polymerization process and comprises slurry kettle type, slurry loop pipe or solution polymerization, wherein the reaction pressure of the slurry kettle type polymerization is 0.1-5MPa, and the reaction temperature is 0-120 ℃, preferably 40-90 ℃, and most preferably 60-80 ℃; the slurry loop polymerization has reaction pressure of 0.5-6MPa and reaction temperature of 30-150 deg.c, preferably 50-100 deg.c, and most preferably 60-80 deg.c.
In the polymerization process of the present invention, those polymerization conditions generally employed in the art can be employed. For example, in slurry loop polymerization, the reaction pressure is in the range of from 0.5 to 6MPa, preferably from 1 to 3 MPa; the reaction temperature is in the range of 30 to 150 deg.C, preferably 60 to 120 deg.C, more preferably 90 to 110 deg.C. The kettle polymerization process is generally operated at a pressure of from 0.1 to about 5.0MPa or greater, preferably from about 0.5MPa to about 2.0MPa, and a temperature of from 0 ℃ to about 120 ℃, preferably from about 30 ℃ to about 110 ℃, more preferably from about 60 ℃ to about 100 ℃.
With the catalyst according to the invention, the molecular weight of the polymer can be suitably controlled in a known manner, for example by using hydrogen. Hydrogen acts as a chain transfer agent, other reaction conditions being the same, with a greater amount of hydrogen resulting in a lower average molecular weight of the polymer. The hydrogen/ethylene molar ratio employed will vary depending on the desired average molecular weight of the polymer and can be determined by one skilled in the art on a case-by-case basis. Without limiting the invention, the amount of hydrogen is generally from about 0.001 to about 2.0 moles of hydrogen per mole of ethylene, preferably from 0.01 to 0.5 moles of hydrogen per mole of ethylene.
The polymerization temperature and time can be determined by one skilled in the art depending on many factors, such as the type of polymerization process to be used and the type of polymer to be prepared. Since chemical reactions are generally carried out at greater rates using higher temperatures, the polymerization temperature should be high enough to obtain an acceptable polymerization rate. Thus, in general, the polymerization temperature is above about 30 ℃ and more usually above about 65 ℃. On the other hand, the polymerization temperature should not be too high to cause, for example, deterioration of the catalyst or the polymer. Generally, the polymerization temperature is less than about 200 deg.C, preferably less than about 115 deg.C, and more preferably less than about 100 deg.C.
The polymerization temperature used in the process is determined in part by the density of the polyethylene resin to be produced. More particularly, the melting point of the resin depends on the resin density. The higher the density of the resin, the higher its melting point. By the ethylene polymerization process of the present invention, it is possible to produce a polymer having a density of 0.918 to 0.950g/cm3In the range of (1), preferably from 0.920 to 0.940g/cm3A range of (d); a powdered polymer having a viscosity average molecular weight in the range of 100 to 1000 ten thousand. The polymerization process of the present invention can be used for ultra-fine particle size polyethylene resins with a product molecular weight distribution MWD in the range of 3 to 20 and a product average particle size of 10 to 500. mu.m, preferably 40 to 400. mu.m, and most preferably 60 to 200. mu.m.
Example 1:
preparation of Ti (TMSM)4/MgCl2a/MgO catalyst system;
example 1a
Preparation of the catalyst:
preparation of support (activation): under the protection of nitrogen (nitrogen or argon), the magnesium oxide is fluidized and activated by a small fluidized bed. 100g of anhydrous nano magnesium oxide (average particle size of 10 microns) is added for temperature programmed activation treatment. The temperature program control step is as follows: keeping the temperature of 100-400 ℃ for 2 hours every 100 ℃, and then gradually cooling to room temperature to obtain the activated magnesium oxide carrier S0And packaging and storing in nitrogen. Then 10g of dehydrated and activated nano magnesium oxide S is taken0Adding into white oil, ultrasonic dispersing for 30 min, adding 20ml surfactant-methyl octadecanoate, reacting at 180 deg.C for 2 hr, washing with 100ml xylene for three times, and drying to obtain modified functional inorganic carrier S1。
2g of S are added to a stirred reaction flask under nitrogen1The support and 30ml of titanium tetrachloride were stirred at 140 ℃ for 2 hours at 250 rpm. After the reaction was completed, the reaction mixture was washed 6 times with 100ml of n-hexane and dried to obtain Cat0 as solid particles.
Under the protection of nitrogen, 100ml of toluene is added, 5g of solid particles Cat0 are added simultaneously, 10ml of 1.0M (trimethylsilyl) methyllithium Li (TMSM) is slowly dropped under stirring, the reaction temperature is-78 ℃, the reaction is stirred for 1 hour, the temperature is increased to 50 ℃, and the reaction is carried out for 1 hour. Finally, it was washed 3 times with 100ml of toluene and 100ml of n-hexane and dried to obtain a solid catalyst Ti (TMSM)4/MgCl2/MgO。
Slurry polymerization: the reaction device is a 2L steel pressure-resistant water circulation temperature-control reaction kettle, the reaction kettle is firstly subjected to vacuum-nitrogen replacement treatment at 95 ℃ for 2-4 hours, and is finally filled with nitrogen, 1L of n-hexane, 50mg of catalyst and 2ml of diethyl aluminum chloride are respectively added under the protection of nitrogen, then ethylene is replaced for 4 times, nitrogen is removed, ethylene with the pressure of 1.0MPa is supplemented, and polymerization reaction is carried out at 70 ℃. When the reaction temperature rises, the jacket of the heat exchanger is adjusted to heat steam or cooling water, and the temperature of the reactor is controlled to be about 70 ℃. After 2 hours of reaction, the reaction was terminated, cooled to room temperature, discharged, dried to obtain a polyethylene product, which was finally weighed, measured for bulk density, tested for particle size distribution, calculated for catalyst activity and tested for the properties of the polyethylene resin according to the above test methods, as shown in table 1.
Example 1 b:
a composite catalyst was prepared using the same procedure as in example 1a, except that the surfactant was changed to cis-9-octadecenoic acid methyl ester. Slurry polymerization was carried out according to the same procedure as in example 1 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 1.
Example 1 c:
a composite catalyst was prepared using the same method as in example 1a except that the surfactant was changed to 13.16-cis-docosadienoic acid methyl ester. Slurry polymerization was carried out according to the same procedure as in example 1 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 1.
Example 1 d:
a composite catalyst was prepared using the same procedure as in example 1a except that the surfactant was changed to 18-methyl nonadecamethyl carbonate. Slurry polymerization was carried out according to the same procedure as in example 1 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 1.
Example 1 e:
a composite catalyst was prepared using the same method as example 1a, except that the organometallic reagent was changed to benzyllithium. Slurry polymerization was carried out according to the same procedure as in example 1 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 1.
Example 1 f:
a composite catalyst was prepared using the same method as in example 1a, except that the organometallic reagent was changed to 1-methyl-1-naphthyl lithium. Slurry polymerization was carried out according to the same procedure as in example 1 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 1.
Example 1 g:
a composite catalyst was prepared using the same method as example 1a, except that the organometallic reagent was changed to neopentyl lithium. Slurry polymerization was carried out according to the same procedure as in example 1 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 1.
Example 1 h:
a composite catalyst was prepared using the same method as example 1a except that the organometallic reagent was changed to lithium (trimethylsilyl) acetylene. Slurry polymerization was carried out according to the same procedure as in example 1 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 1.
Example 1 i:
a composite catalyst was prepared using the same method as in example 1a, except that the organometallic reagent was changed to phenyllithium. Slurry polymerization was carried out according to the same procedure as in example 1 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 1.
Example 1 j:
a composite catalyst was prepared using the same method as example 1a, except that the organometallic reagent was changed to (trimethylsilyl) methylmagnesium. Slurry polymerization was carried out according to the same procedure as in example 1 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 1.
Example 1 k:
a composite catalyst was prepared using the same method as example 1a, except that the organometallic reagent was changed to benzylmagnesium. Slurry polymerization was carried out according to the same procedure as in example 1 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 1.
Example 1 l:
a composite catalyst was prepared using the same method as in example 1a, except that the organometallic reagent was changed to 1-methyl-1-naphthylzinc. Slurry polymerization was carried out according to the same procedure as in example 1 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 1.
Example 1 m:
a composite catalyst was prepared using the same method as example 1a, except that the organometallic reagent was changed to neopentyl zinc. Slurry polymerization was carried out according to the same procedure as in example 1 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 1.
Example 1 n:
a composite catalyst was prepared using the same method as example 1a, except that the organometallic reagent was changed to (trimethylsilyl) methylzinc. Slurry polymerization was carried out according to the same procedure as in example 1 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 1.
Example 1 o:
a composite catalyst was prepared using the same method as example 1a, except that the organometallic reagent was changed to benzylzinc. Slurry polymerization was carried out according to the same procedure as in example 1 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 1.
Example 1 p:
a composite catalyst was prepared using the same method as in example 1a, except that the organometallic reagent was changed to 1-methyl-1-naphthylaluminum. Slurry polymerization was carried out according to the same procedure as in example 1 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 1.
Example 1 q:
a composite catalyst was prepared using the same method as example 1a, except that the organometallic reagent was changed to tribenzylaluminum. Slurry polymerization was carried out according to the same procedure as in example 1 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 1.
Comparative example 1:
a catalyst was prepared using the same method as in example 1a except that the surfactant was changed to 0 ml. Slurry polymerization was carried out according to the same procedure as in example 1 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 1.
The electron micrographs of the polyethylene samples of example 1a and comparative example 1 are shown in fig. 1 and 2, fig. 1 shows the electron micrograph of the polyethylene sample of example 1a, fig. 2 shows the electron micrograph of the polyethylene sample of comparative example 1, and it can be seen from the electron micrographs that the polyethylene particles prepared by the process of this patent are smaller and more regular, which is helpful for application in post-processing, such as more uniform and finer particles due to the increased efficiency of the dissolution-swelling process before fiber spinning, and the quality of the fiber product. In table 1, it is also seen that the bulk density of example 1a is greater than that of comparative example 1, and the particles are more uniform.
The ethylene polymerization kinetics curves for the catalysts of examples 1a-1b and comparative example 1 are shown in FIG. 3: wherein curve a represents the ethylene polymerization kinetics plot for the catalyst of example 1a, curve b represents the ethylene polymerization kinetics plot for the catalyst of example 1b, and curve c represents the ethylene polymerization kinetics plot for the catalyst of comparative example 1. As can be seen from the kinetic curve, because the fatty acid methyl ester and the (trimethylsilyl) methyllithium are added, the polymerization kinetics shows a more stable trend, which is beneficial to the growth uniformity of the polymerization product, the uniform growth of the molecular weight of the product, the chain entanglement of the molecular chain is reduced, and the processing performance of the product is improved.
TABLE 1
As can be seen from the table, the use of the surfactant helps to increase the bulk density of the granules and reduce the average particle size of the resulting polyethylene.
Example 2:
preparing a V (TMSM) 4/inorganic carrier catalyst system;
example 2a
Preparation of the catalyst:
preparation of support (activation): under the protection of nitrogen, the magnesium oxide is fluidized and activated by a small fluidized bed. 100g of sheet silicate (preferably but not limited to montmorillonite with an average particle size of 10.0 microns) is added and temperature programmed activation is carried out. The temperature program control step is as follows: at a temperature ofThe temperature is between 100 ℃ and 500 ℃, the temperature is kept for 2 hours every 100 ℃, and then the temperature is gradually reduced to the room temperature to obtain the activated montmorillonite carrier S0And packaging and storing in nitrogen. Then 10g of the dehydrated activated montmorillonite S was taken0Adding into kerosene, ultrasonic dispersing for 30 min, adding 20ml surfactant methyl octadecanoate, reacting at 140 deg.C for 2 hr, washing with 100ml xylene for three times, drying to obtain modified functional inorganic carrier S1。
2g of S are added to a stirred reaction flask under nitrogen1The support and 30ml of V (VCl4) tetrachloride are stirred at 130 ℃ for 2 hours at 250 rpm. After the reaction was completed, the reaction mixture was washed 6 times with 100ml of n-hexane and dried to obtain Cat1 as solid particles.
Under the protection of nitrogen, 100ml of n-heptane is added, 5g of solid particles Cat1 are added simultaneously, 10ml of 1.0M (trimethylsilyl) methyllithium Li (TMSM) is slowly dropped under stirring, the reaction temperature is-78 ℃, the reaction is stirred for 1 hour, the temperature is increased to 50 ℃, and the reaction is carried out for 1 hour. Finally, it was washed 3 times with 100ml of toluene and 100ml of n-hexane and dried to obtain solid catalyst V (TMSM) 4/MMT.
Slurry polymerization: the reaction device is a 2L steel pressure-resistant water circulation temperature-control reaction kettle, the reaction kettle is firstly subjected to vacuum-nitrogen replacement treatment at 95 ℃ for 2-4 hours, and is finally filled with nitrogen, 1L of n-hexane, 50mg of catalyst and 2ml of diethyl aluminum chloride are respectively added under the protection of nitrogen, then ethylene is replaced for 4 times, nitrogen is removed, ethylene with the pressure of 1.0MPa is supplemented, and polymerization reaction is carried out at 90 ℃. When the reaction temperature rises, the jacket of the heat exchanger is adjusted to heat steam or cooling water, and the temperature of the reactor is controlled to be about 90 ℃. After 2 hours of reaction, the reaction was terminated, cooled to room temperature, discharged, dried to obtain a polyethylene product, which was finally weighed, measured for bulk density, tested for particle size distribution, calculated for catalyst activity and tested for the properties of the polyethylene resin according to the above test methods, are shown in table 2.
Example 2 b:
a composite catalyst was prepared by the same method as in example 2a, except that the inorganic carrier was changed to talc (average particle diameter: 5 μm). Slurry polymerization was carried out according to the same procedure as in example 1 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 1.
Example 2 c:
a composite catalyst was prepared using the same method as example 2a, except that the inorganic carrier was changed to a inosilicate (preferably, but not limited to, attapulgite, average silica gel particle size 2 μm). Slurry polymerization was carried out following the same procedure as example 2 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 1.
Example 2 d:
a composite catalyst was prepared using the same method as in example 2a, except that the inorganic support was changed to nano alumina (average particle size of 0.1. mu.m). Slurry polymerization was carried out following the same procedure as example 2 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 1.
Example 2 e:
a composite catalyst was prepared using the same method as in example 2a, except that the inorganic carrier was changed to magnesium hydroxide-magnesium sulfate (average particle size 3 μm). Slurry polymerization was carried out following the same procedure as example 2 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 1.
Example 2 f:
a composite catalyst was prepared using the same method as in example 2a, except that the inorganic support was changed to a silica-alumina composition (SiO)2：Al2O3Weight ratio 1:4, average particle size 4 μm). Slurry polymerization was carried out following the same procedure as example 2 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 1.
Example 2 g:
a composite catalyst was prepared using the same method as in example 2a, except that the inorganic support was changed to a silica-magnesia composition (SiO)2: MgO weight ratio of 1:3, average particle size of 0.5 μm). Slurry polymerization was carried out following the same procedure as example 2 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 1.
Example 2 h:
a composite catalyst was prepared using the same method as in example 2a, except that the inorganic support was changed to silica (average particle size 30 μm). Slurry polymerization was carried out following the same procedure as example 2 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 1.
Example 2 i:
a composite catalyst was prepared by the same method as in example 2a, except that the inorganic carrier was changed to titanium dioxide (average particle diameter 1.0. mu.m). Slurry polymerization was carried out following the same procedure as example 2 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 2.
TABLE 2
As can be seen from Table 2, the activity of the obtained catalyst is also relatively high by changing the types of different inorganic carriers, and under the action of the surfactant and the organometallic reagent, the particle size of the obtained polyethylene particles is very fine and is less than 150 μm, so that the industrial requirements are met.
Example 3:
a catalyst was prepared using the same method as in example 1a, except that the catalytic component was changed to zirconium chloride. Slurry polymerization was carried out according to the same procedure as in example 1 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 3.
Example 4:
a catalyst was prepared using the same procedure as in example 1a, except that the catalytic component was changed to hafnium chloride. Slurry polymerization was carried out according to the same procedure as in example 1 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 3.
Example 5:
a catalyst was prepared using the same procedure as in example 1a, except that the catalytic component was changed to titanium tetrabromide. Slurry polymerization was carried out according to the same procedure as in example 1 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 3.
Example 6:
a catalyst was prepared using the same method as in example 1a, except that the catalytic component was titanium tetrafluoride. Slurry polymerization was carried out according to the same procedure as in example 1 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 3.
Example 7:
a catalyst was prepared by the same method as in example 1a, except that the catalytic component was changed to titanium tetraiodide. Slurry polymerization was carried out according to the same procedure as in example 1 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 3.
Example 8:
a catalyst was prepared by the same method as in example 1a, except that the catalytic component was changed to titanium methoxytrichloride. Slurry polymerization was carried out according to the same procedure as in example 1 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 3.
Example 9:
a catalyst was prepared by the same method as in example 1a, except that the catalytic component was changed to phenoxytitanium chloride. Slurry polymerization was carried out according to the same procedure as in example 1 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 3.
Example 10:
a catalyst was prepared using the same procedure as in example 1a, except that the catalytic component was changed to methyl titanate. Slurry polymerization was carried out according to the same procedure as in example 1 a. The calculated catalytic activity and the properties of the polyethylene resin tested according to the above test method are shown in table 3.
Example 11:
a catalyst was prepared by the same procedure as in example 1a, except that the catalytic component was changed to pentamethylcyclopentadienyltitanium trichloride. Slurry polymerization was carried out according to the same procedure as in example 1 a.
TABLE 3
It can be seen from table 3 that by changing different catalytic components, under the action of surfactant and organometallic reagent, polyethylene particles with very fine particle size, all less than 150 μm, can be obtained, meeting the industrial requirements.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (12)
1. A catalyst for producing ultrahigh molecular weight polyolefin, comprising:
inorganic carrier loaded with surfactant, wherein the inorganic carrier is magnesium oxide, and the surfactant is fatty acid methyl ester; the volume mass ratio of the surfactant to the inorganic carrier is 15:1 (ml/g);
a catalytic component supported on an inorganic support,
the catalytic component is transition metal halide MX4With an organometallic reagent M' R containing an R groupn(n-1-3) reaction to form catalytic component MR4(ii) a Wherein, the transition metal halide MX4Is titanium tetrachloride and the organometallic reagent is (trimethylsilyl) methyllithium; (trimethylsilyl) methylmagnesium, benzylmagnesium, 1-methyl-1-naphthylzinc, neopentylzinc, (trimethylsilyl) methylzinc, benzylzinc, 1-methyl-1-naphthylaluminum, tribenzylaluminum.
2. The catalyst for producing ultrahigh molecular weight polyolefin as claimed in claim 1, wherein the content of said catalytic component is 0.1 to 10% by weight in terms of metal based on the total amount of the catalyst.
3. The catalyst for producing ultrahigh molecular weight polyolefin according to claim 1 wherein said inorganic carrier has an average particle diameter of 0.01 to 100 μm and contains hydroxyl groups and/or carboxyl groups on the surface.
4. The catalyst for producing ultrahigh molecular weight polyolefin according to claim 1 wherein said inorganic carrier has an average particle diameter of 0.1 to 30 μm.
5. The method of preparing a catalyst for ultrahigh molecular weight polyolefin according to claim 1, comprising the steps of:
(1) ultrasonically dispersing the nano magnesium oxide without molecular water in an organic solvent, then adding fatty acid methyl ester, and reacting at a proper temperature to obtain a modified inorganic carrier;
(2) stirring at a proper temperature in an organic solvent, dipping titanium tetrachloride on the modified inorganic carrier obtained in the step (1), and reacting with the surface of the carrier to enable the titanium tetrachloride component to react in situ and be loaded on the modified inorganic carrier;
(3) adding the inorganic composite carrier obtained in the step (2) into an organic solvent to form a suspension, and then adding an organic metal compound M' RnCarrying out in-situ reaction at a proper temperature;
(4) and (4) filtering and washing the product obtained in the step (3) by using a solvent to remove excessive organic metal compounds, and drying to obtain the catalyst for producing the ultrahigh molecular weight polyolefin.
6. The process for producing a catalyst for ultrahigh molecular weight polyolefin according to claim 5,
the organic solvent in the step (1) is selected from long-chain saturated alkane or halogenated aromatic hydrocarbon of C10-C20, or a mixed solvent thereof; the reaction temperature is 20-200 ℃; the reaction time is 0.1 to 10 hours;
the weight ratio of the titanium tetrachloride to the modified inorganic carrier in the step (2) is 0.01-50: 1; the reaction temperature is-40 to 200 ℃; the reaction time is 0.1 to 10 hours; the stirring speed is 20-800 rpm;
the organometallic compound M' R of the step (3)nThe weight ratio of the titanium tetrachloride to the titanium tetrachloride is 0.01-50: 1; the reaction temperature is-120-80 ℃, and the reaction time is 0.1-10 hours.
7. The process for producing a catalyst for ultrahigh molecular weight polyolefin according to claim 6,
the reaction temperature in the step (1) is 50-180 ℃, the reaction time is 0.5-5 hours, and the organic solvent comprises one or more of decane, dodecane, kerosene, dichlorobenzene, trichlorobenzene, trimethylbenzene, xylene, toluene or benzyl chloride;
the weight ratio of the titanium tetrachloride to the modified inorganic carrier in the step (2) is 0.5-30: 1, the reaction temperature is 60-160 ℃, the reaction time is 1-6 hours, and the stirring speed is 150-400 rpm;
the organometallic compound M' R of the step (3)nThe weight ratio of the titanium tetrachloride to the titanium tetrachloride is 0.1-20: 1, the reaction temperature is-90-50 ℃, and the reaction time is 0.5-5 hours.
8. Use of a catalyst for the production of ultra high molecular weight polyolefin according to claim 1, wherein ethylene, an α -olefin comonomer, a catalyst and a cocatalyst are polymerized to produce polyethylene, the α -olefin comonomer to ethylene molar ratio being from 0.01 to 1: 1, the addition amount of the catalyst is 0.01-100ppm, and the addition amount of the cocatalyst is 5-500 ppm.
9. The use of the catalyst of claim 8, wherein the alpha-olefin comonomer is a C1-C20 alpha-olefin comprising propylene, 1-butene, 1-pentene, 1-hexene, 1-octene or 1-decene, and the molar ratio of the alpha-olefin comonomer to ethylene is 0.05-0.5: 1, the addition amount of the cocatalyst is controlled to make the concentration of the cocatalyst be 20-400 ppm.
10. The use of the catalyst according to claim 8, wherein the polymerization is an olefin polymerization process comprising slurry tank, slurry loop or solution polymerization, wherein the slurry tank polymerization is carried out at a reaction pressure of 0.1-5MPa, a reaction temperature of 0-120 ℃, and the slurry loop polymerization is carried out at a reaction pressure of 0.5-6MPa and a reaction temperature of 30-150 ℃.
11. The use of a catalyst for the production of ultra high molecular weight polyolefin according to claim 8, wherein the polyethylene has an average particle size of 10 to 500 μm.
12. The use of a catalyst for the production of ultra high molecular weight polyolefin according to claim 8, wherein the polyethylene has a viscosity average molecular weight of 30 to 1000 ten thousand; the density is 0.918-0.950g/cm3。
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| CN111172607B (en) * | 2020-01-19 | 2022-11-25 | 上海化工研究院有限公司 | Preparation method of creep-resistant ultra-high molecular weight polyethylene fiber |
| CN115636893A (en) * | 2021-07-20 | 2023-01-24 | 中国石油天然气股份有限公司 | High-density polyethylene resin and preparation method thereof |
| EP4155324A3 (en) * | 2021-09-22 | 2023-05-03 | Sumitomo Chemical Company, Limited | Method for producing solid catalyst component for olefin polymerization, method for producing catalyst for olefin polymerization, and method for producing olefin polymer |
| CN115160458A (en) * | 2022-08-02 | 2022-10-11 | 上海欣鑫化工有限公司 | Catalyst suitable for producing polyolefin with superfine grain diameter and preparation method thereof |
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