Ethylene polymerization method and polyethylene

Mode of execution

. Should be understood in the following detailed description of specific embodiments of the present invention; is intended to illustrate and explain that the invention, is not intended to limit the invention.

The endpoints and any values of the ranges disclosed herein are not limited to this exact range or value, and these ranges or values should be understood to include values, close to these ranges or values that may be combined with each other for a range, individual point values to obtain one or more new numerical ranges, that are to be considered specifically disclosed . and herein.

The method comprises, under the polymerization reaction condition: polymerizing ethylene in the presence of a catalyst, in the presence of a catalyst, wherein, g, of the mesoporous molecular sieve material/and, of the spherical mesoporous composite material have a pore size, nm, a pore size of 21-29 nm, and a pore size of the spherical mesoporous composite material are 100-650 sq m/nm or more, nm 0.5-1.8. The method/has a pore size of, nm or more, nm or 1st. The method comprises the step of polymerizing ethylene in the presence of a catalyst in the presence of a catalyst in an amount of, second in the presence of a catalyst in the presence of a catalyst in the presence of a catalyst in the presence of a catalyst in the range of, from third nm to about, μm first respectively third 1-10 in diameter, 55-65 nm 2nd. in diameter 20-50.

To a preferred embodiment, of the present invention, the spherical mesoporous composite material has an average particle diameter of 22-28 μm, and a pore volume 250-350 sq m/g, pore volume of 1-1.5 g/g, pore size distribution, and three peaks respectively corresponding first most possible pore diameter 2-9 nm, second and 30-50 nm pore diameter third nm 56-64.

To a more preferred embodiment, of the present invention, the spherical mesoporous composite has an average particle diameter of 23-27 μm, and a pore volume 275-300 sq m/g, pore volume of 1.1-1.4 g/g, pore size distribution, and three peaks respectively corresponding first most possible pore diameter 3-7 nm, second and 35-45 nm pore diameter third nm 57-63.

In the present invention, the average particle size of the spherical mesoporous composite material is, than the surface topography, pore volume and the most probable pore diameter of, of the spherical mesoporous composite material measured by the nitrogen adsorption method according to nitrogen adsorption. (SEM). The average particle size, in the present invention is the average particle diameter.

In the catalyst according to, of the present invention, the content of the spherical mesoporous composite material and/or the titanium salt contained in the spherical mesoporous composite material may be, wt . and the content of the magnesium salt and the titanium salt may be, wt, more preferably 90-99 wt %, respectively, and 1-10 wt.% of the spherical mesoporous composite material. %. wt.% of the magnesium salt and the titanium salt, respectively, may be contained in an amount, wt.% based on the total weight of each of the magnesium and titanium. 90.5-98.5.% %, respectively 1.5-9.5, wt.% based on the total weight of the supported catalyst can be determined %, 91-96%. wt.% based on the total weight of the catalyst 4-9%.

In the present invention, the magnesium salt and the titanium salt are not particularly limited, and for example . the magnesium salt may be magnesium chloride, magnesium sulfate, magnesium nitrate and magnesium bromide, preferably magnesium chloride, and the titanium salt may be titanium tetrachloride and; or titanium trichloride .

In the present invention, the content of each element in the catalyst component can be measured. X by-ray fluorescence spectrometry.

In the present invention, the catalyst may be prepared, by various methods conventionally used in the art as long as magnesium salt and/or titanium salt is supported on the spherical mesoporous composite material.

In a preferred case, the process for preparing the catalyst may comprise contacting: the spherical mesoporous composite with a mother liquor containing a magnesium salt and, or a titanium salt in the presence of an inert gas .

, The condition of contact of, includes: temperature is 25-100 °C, preferably 40-60 °C; and 0.1-5h, is preferably 1-3h.

The mother liquor containing the magnesium salt and/or the titanium salt may be an organic solvent/containing a magnesium salt and, or a titanium salt, which may be isopropanol and tetrahydrofuran, and a volume ratio of tetrahydrofuran and isopropanol may be 1:1-3, preferably 1:1-1.5.

In the preparation of the catalyst, the content of the magnesium salt and/or the titanium salt is preferably. wt, more preferably, wt, and the content of the magnesium salt and the titanium salt in, wt 1-10 of the spherical mesoporous composite material is %, wt %, respectively, of 90-99 wt. %. %. wt.% of the spherical mesoporous composite material is preferably 1.5-9.5 wt.% of the magnesium salt and the titanium salt, respectively, contained in an amount of %, wt. % based on the total weight of the titanium element and the titanium element, respectively 90.5-98.5 wt.% of the spherical mesoporous composite material. %. 4-9. The catalyst is prepared. %, The magnesium salt and the titanium salt, respectively 91-96%.

In a preferred embodiment of the present invention, the magnesium salt and the titanium salt are used in an amount of 1:0.1-2, wt % to 1:0.5-2. wt %.

The preparation method of the catalyst, of the present invention further comprises: after contacting the spherical mesoporous composite with the magnesium salt and/or the titanium salt thereof, preferably drying/the dried conditions. The drying conditions are not particularly limited and may be preferably selected, by those skilled in the art after filtration and prior to drying or by a person skilled in the art in accordance with practical conditions of the washing and polishing conditions, and the conditions, are not particularly limited herein .

In the present invention, the inert gas is a gas, that does not react with the raw material and the product, and may be, for example, at least one, preferably nitrogen, in a nitrogen gas or a zero group element gas in the periodic table of the element.

In the present invention, the spherical mesoporous composite material does not contain a binder such as polyvinyl alcohol or polyethylene glycol.

In the present invention, the spherical mesoporous composite material may further include silica ." introduced by silica gel ", and, parts by weight . more preferably, parts by weight 100, of the silica included, parts by weight of the mesoporous molecular sieve material having one-dimensional hollow spherical pore structure in the spherical mesoporous composite material is introduced into the spherical mesoporous composite material. 1-200 parts by weight of the mesoporous molecular sieve material having a one-dimensional hollow spherical pore structure in the, spherical mesoporous 20-180 composite material, in the preparation 50-150 process of, the spherical mesoporous composite material.

The spherical mesoporous composite material, according to the present invention may be obtained: by a method comprising the following steps.

(1) Provides a mesoporous molecular sieve material having a one-dimensional hollow spherical pore structure or a filter cake, of a mesoporous molecular sieve material having a one-dimensional hollow spherical pore structure as component a.

(2) Provides silica gel or a filter cake, made of silica gel as component b.

(3) The components a and b were mixed and first ball milled, to mix the resulting first ball mill slurry with water to prepare slurry, and second ball mill and obtain second ball mill slurry, for spray drying second ball mill slurry.

Wherein, the steps make the spherical mesoporous composite material have an average particle diameter 21-29 microns, pore volume of 100-650 sq m/g, pore volume of 0.5-1.8 g / g, pore size distribution, and three peaks respectively corresponding first with a minimum pore diameter, second of third nm, and first nm 1-10 Å diameter, pore diameter. 2nd. The pore size of 20-50 nm is in the range, nanometers to third nm. The pore size is 55-65. nanometers or less.

To a preferred embodiment, of the present invention, the spherical mesoporous composite material has an average particle diameter of 22-28 μm, and a pore volume 250-350 sq m/g, pore volume of 1-1.5 g/g, pore size distribution, and three peaks respectively corresponding first most possible pore diameter 2-9 nm, second and 30-50 nm pore diameter third nm 56-64.

To a more preferred embodiment, of the present invention, the spherical mesoporous composite has an average particle diameter of 23-27 μm, and a pore volume 275-300 sq m/g, pore volume of 1.1-1.4 g/g, pore size distribution, and three peaks respectively corresponding first most possible pore diameter 3-7 nm, second and 35-45 nm pore diameter third nm 57-63.

In the present invention, by controlling the particle size of the spherical mesoporous composite in the above range, it is ensured that the spherical mesoporous composite material is less likely to agglomerate, and the supported catalyst used as a carrier can improve the reaction raw material conversion, in the ethylene polymerization reaction.

In the preparation process, of the spherical mesoporous composite material, the pore size distribution of the spherical mesoporous composite material is controlled to be a three-peak distribution (mainly by controlling the molding method a), i.e. ball milling and, ball milling (, and then, first ball milling is performed, second a ball mill second slurry b is used for) second spray drying first to control the microtopography, of the spherical, mesoporous composite material to be spherical.

[, ] In step (1), the process of preparing a filter cake of a mesoporous molecular sieve material having a one-dimensional hollow spherical pore structure may include: mixing the template agent, silicon source, ethanol, trimethylpentane and the acid agent uniformly first and then adding trimethylpentane to mix the mixture uniformly, and then adding the silicon source, preferably tetramethoxysilane first to mix the mixture uniformly, and then uniformly mixing the mixture, with the acid agent to obtain a mixture of, g of the template agent, and then mixing, the mixture of, the mixture, with the acid agent in) a preferred embodiment, of the present invention, (.

In the present invention, the template agent, ethanol, trimethylpentane and the silicon source may be used in an amount ranging from, for example, moldants, ethanol, trimethylpentane and a silicon source in a molar ratio 1:100-500:200-500:50-200, more preferably 1:180-400:250-400:70-150.

In the present invention, as long as the pore structure of the spherical mesoporous composite material can meet the requirements, for example . the template may be a triblock copolymer polyoxyethylene, polyoxypropylene - polyoxyethylene - of which is commercially available, for example (under the trade name, from Aldrich . for example P123, EO.₂₀ PO₇₀ EO₂₀ , Molecular weight Mn is 5800), and . the mole number - of the template agent when the template is polyoxyethylene - polyoxypropylene, polyoxyethylene is calculated - according to the number average molecular weight of polyoxyethylene - polyoxypropylene. polyoxyethylene.

In the present invention, the silicon source may be various silicon sources, conventionally used in the art, for example, the silicon source may be orthosilicate, orthosilicate (, also tetramethoxysilane), n-propyl silicate, n-propyl silicate, and at least one, of silicon sol is preferably tetramethoxysilane.

In the present invention, the acid agent may be any acidic aqueous solution, conventionally used in the art, preferably, having pH pH of 1-6 acetic acid and sodium acetate buffer solution . and the acid dose not particularly limited, may be varied, within a wide range such that first of the mixed contact pH is 1-7 may.

The conditions for the first mixture contact are not particularly limited, for example, and first preferably: may be 10-60 °C, hours 10-20 °C; preferably 10-72 hours, may be, hours and 10-30 hours, preferably ;pH hours, and even more advantageous in accordance with a preferred embodiment 1-7, of the present invention. 3-6. C. The mixture contact is carried out, in first a stirred condition in accordance with a, preferred embodiment of the present invention.

The conditions for the crystallization, in the present invention include: ° C. may be 30-150 °C, preferably 40-80 °C; hours 10-72, preferably, hours 20-30, and the crystallization according to a preferred embodiment, is carried out by a water heat crystallization method for, hours.

In step (1), the process, of preparing a filter cake of a mesoporous molecular sieve material having a one-dimensional hollow spherical pore structure described above may include: by filtering to obtain a filter cake after filtration, times the washing (times may be 2-10), and suction filtration.

In step (1), ", the mesoporous molecular sieve material " with one-dimensional hollow spherical pore structure can be prepared by directly weighing or selecting the mesoporous molecular sieve material, with a one-dimensional hollow spherical pore canal structure. The preparation method of the mesoporous molecular sieve material with the one-dimensional hollow spherical pore structure can also be carried out according to a conventional method . The method can include: according to a conventional method, for preparing a mesoporous molecular sieve material, having a one-dimensional. hollow spherical pore structure.

The process according to, in step (2), for preparing a filter cake of silica gel may comprise: mixing water glass, polyol and inorganic acid second into contact, and filtering the resulting mixture.

The conditions for the mixed contact, of the second are not particularly limited, may suitably be determined . for example, by second hours: preferably 10-60 °C, hours at 20-40 °C; hours, preferably 1-5 hours to, hours 1-3 in order to more facilitate uniform mixing ;pH of the materials between the various materials, for example, in the range 2-4. ° C. in second the conventional process for preparing the silica gel, respectively .

In the present invention, the amount of the water glass, inorganic acid and the polyhydric alcohol may vary . for example, and the weight ratio of the water glass, inorganic acid and the polyol may be 1-8:0.1-5:1, preferably 3-6:0.5-4:1, and more preferably 3-6:1-3:1.

In the present invention, the aqueous solution, of water glass as sodium silicate may be 3-20 wt %, preferably 10-20 wt %. inorganic acid, which may be used, for example, in the form of an aqueous solution of sulfuric, and hydrochloric acid. The inorganic acid may be used in pure form . The inorganic acid may be used in pure form, for example, in an aqueous solution in, wt 3-20 or more % wt.% of the inorganic pH acid may be used in a pure form. 2-4.

In the present invention, the kind of the polyol is not particularly limited, and for example, glycerin and/or ethylene glycol, are preferably glycerin.

To the invention, (2) in step, " providing silica gel " may be a direct weighing or selection of the silica gel product, or the preparation of silica gel, can also be carried out according to a conventional method embodiment, for example comprising: preparation of a filter cake, of silica gel according to the above method and drying, the obtained filter cake.

The process, of washing the filter cake of silica gel to obtain a filter cake may include: washing the filter cake, by filtration to a sodium ion content 0.2 wt % or less, and preferably 0.01-0.03 wt %, and then suction filtration. washing, specific conditions are well known/to those skilled in the art and will not be described in further detail herein.

[, ] In step (3), the amount of component a and component b can vary . for example, parts 100, preferably a parts, more preferably b parts by weight, per 1-200 parts by weight of component, in an amount 20-180 parts by weight, for example, in an amount of, 50-150 parts by weight.

In order to improve the strength, of the spherical mesoporous composite material, the performance, of the prepared polyethylene product is improved by the secondary ball milling method for the slurry.

[, ] In step (3), the first ball milling and second ball milling may be performed, ball mill in an agate liner, preferably 2-3mm; ball mill and, ball mill conditions may each independently include 50-150mL ball milling and the conditions of, ball milling may be 1 ball milling in; ball mill for a time, preferably, ball mill in a, ball mill, respectively first ball mill may be used in a ball mill having second grit, ball mill conditions, independently of the size of the ball milling tank, or different first ball mills may be used in a ball mill for an agate liner ball second ball mill at a temperature in the range of from about .times.10.sup.sup.15-100 °C, 300-500r/min,times.10 .times.10.sup.0.1-100h; 25-50 °C, 200-800r/min, ball-milling 5-20h.

To the present invention, in step (3), the temperature of first ball mill slurry and water mixed slurry obtained may be 25-60 °C, and the weight ratio of the first ball mill slurry to water used may be 1:0.1-5, preferably 1:0.5-3.5.

The spray drying, according to the invention (3) in step, may be performed in accordance with a conventional manner, by at least one, selected from a pressure spray drying method . a centrifugal spray drying method and a gas flow spray drying method, the spray drying may include, ° C. preferably. ° C. and: ° C. The spray drying conditions include 150-600 °C, ° C. and 10000-15000r/min; ° C. The spray drying conditions may be 11000-13000r/min. 150-250 °C.

After spray drying,ball mill slurry second the :ball mill slurry is subjected to spray-drying second to separate the discharged powder-containing gas from the separator outlet to the cyclone separator lower portion of the centrifugal fan, to collect the powder particles, to obtain a sample having a uniform distribution . The collected powder particles, are separated into a cyclone separator by a cyclone separation technique, to collect the, powder particles from the, separator outlet to the lower portion of the, cyclone separator of the centrifugal fan.

[, ] In step (3), when said component a is a cake, of a mesoporous molecular sieve material having a one-dimensional hollow spherical pore structure b, the process of removing the template agent, from the particles collected by the cyclone separation in step (1) may further include, ˜ (2) hours, preferably: hours, of (3) hours after the spray-drying process of the silica gel is prepared in the step, of the spray-drying step of the silica gel filtration cake of the silica gel filtration, cake of the silica gel filtration cake: the silica 90-600 °C, gel filtration 300-600 °C; cake of the 10-80 one,dimensional 10-24h. hollow spherical pore canal structure.

The conditions for the polymerization reaction according to, of the present invention may be conditions . for example, which may be, ° C. and: in the presence of an inert gas, may be 10-100 °C, preferably 0.5-5h, and 0.1-2MPa; preferably, at a temperature 20-95 °C, time of 1-4h, degree. C. of 0.5-1.5MPa; degree 70-85 °C, C. 1-2h, is preferably at a pressure of 1-1.5MPa. from.

The pressure of the present invention refers to a gauge pressure.

In the present invention, the polymerization reaction may be performed, in the presence of a solvent, and the solvent used in the polymerization reaction is not particularly limited, for example, may be hexane.

To the invention, in the preferred case, ethylene polymerization comprises: polymerising ethylene in the presence of a catalyst and an auxiliary, in the presence of a catalyst and an auxiliary under polymerization conditions, preferably; the auxiliary being an alkyl aluminum compound.

In the present invention, the structure of the alkylaluminum compound is I as shown in Formula :

AlR_n X⁵_(3-n) Formula I

I In Formula, R may each be C.₁ -C₅ Alkyl ;X⁵ One, which may each be a halogen group, is preferably -Cl;n or 0, 1, 2 3.

, Is said C.₁ -C₅ The alkyl groups may be methyl, ethyl, n-propyl, isopropyl, n-butyl, n-butyl- isobutyl,butyl, n-pentyl,pentyl-tert-pentyl and neopentyl.

Specific examples of,alkylaluminum compounds in the present invention include, but are not limited to: trimethyl aluminum,dimethyl aluminum chloride,ethyl aluminum,n-propyl aluminum, tri-n-butylaluminum, tri-n-butylaluminum, di-n-butylaluminum chloride and diisobutylaluminum chloride,most preferably,alkyl aluminum compound is triethyl. aluminum.

In the present invention, the molar ratio of the alkylaluminum compound to the amount of the catalyst employed, in general, may be 1:0.1-10; and the mass ratio, of the alkyl aluminum compound to the amount of the catalyst in the present invention may be 1:0.2-8; more preferably 1:0.4-4.

In the present invention, the method for polymerizing ethylene may further include, subjecting the final reaction mixture to suction filtration separation, at the end of the polymerization reaction to obtain a polyethylene particle powder.

The invention further provides the polyethylene, prepared by the method.

. The present invention will be described in detail by way of examples.

In the following examples and comparative examples, polyoxyethylene - polyoxypropylene - polyoxyethylene was purchased from Fuka Company, under the tradename Synperonic F108, of molecular formula PEO.₁₃₂ -PPO₅₀ -PEO₁₃₂ , Average molecular weight M_n ＝14600.

, X-ray diffraction analysis of Bruker AXS-ray diffraction on a D8Advance-ray diffractometer from Model X of Germany; was followed FEI with XL-30-ray fluorescence analysis on ;ray fluorescence analyser of Model Autosorb-1 from USA, for,particle size distribution curves measured, by a Markov laser granulometer on a Model No. 200 °C from American Controde Company under 4; X-ray diffractometry for ;X. hours Axios-Advanced.

The bulk density of the polyolefin powder was measured GB/T 1636-2008 using a method specified.

The polymer melt index: is determined ASTM D1238-99 according to.

The crushed powder rate: the polyethylene particle powder is determined 800 by, mesh sieve screening, in particular, by 800 mesh sieve, the weight of the polyethylene particle powder through 800 mesh sieve and the weight percentage, of the polyethylene particle powder to be tested.

Embodiment 1

This example is used to illustrate the ethylene polymerization process and the resulting polyethylene of the present invention

(1)-prepared spherical mesoporous composite material

1g(0.00017mol) And P123 ethanol were added to 1.69g(0.037mol) ml of acetic acid and sodium acetate buffer solution 28mL and stirred pH＝4.4 to complete dissolution, 15 °C of, ml pentane into an agate lined reaction kettle 6g(0.05mol) and stirred at, 15 °C and then filtered and washed 8h times, with deionized water and then suction filtered to obtain a filter cake 2.13g(0.014mol) of a mesoporous molecular sieve material having a one-dimensional hollow spherical pore canal 24h structure, respectively, 15 °C. Next 4 20h hours of stirring A1. was performed, 60 °C.

A sulfuric acid solution having a concentration of 15%% and a sulfuric acid solution having a concentration 12%% are mixed at a weight ratio 4:1:1 and contacted for 40 °C h 1 at, degree. 98 and then filtered with distilled water to %, weight 0.02 pH to obtain a silica gel-containing filter B1. cake 3, %.

Ball mill slurry 20g prepared A1 by 10g mixing B1 the 100mL balls and, into ball milling pots, and for, hours and then 3mm, subjecting the resulting 1, ball 400r/min. mill slurry to, a ball mill first temperature, of about 25 °C, and 5 hours at a speed of hours to a ball milling tank is, hours at ° 15g C. first for a, 25 °C second hour period and a 25 °C, period ranging from 5 about. 2nd. hour to 12000r/min 200 °C about hours to, stir the obtained product, at. degree. C. for a period of time of sup. times.10 .sup.times.10 .sup.), C1. 600 °C 10h, P123(.

A XRD, scanning electron microscope and a nitrogen adsorption instrument are used to characterize the spherical mesoporous composite material C1.

1 Is X-ray diffraction spectrum, of a one-dimensional hollow spherical pore structure, which is specific to a mesoporous material C1 in.ray diffraction pattern.

2 Shows the microstructure C1 of the spherical mesoporous composite SEM, and FIG. shows that the microtopography of, spherical mesoporous composite material C1 is microsphere 21-29 μ m with a particle diameter, and the dispersion property is good.

3 Is a particle size distribution curve C1 of the spherical mesoporous composite material, and the,spherical mesoporous composite material C1 has a uniform particle size distribution.

4 Is an aperture distribution diagram C1 of the spherical mesoporous composite material, and the,spherical mesoporous composite material C1 has a three-pore structure distribution, and uniform pore channels.

The pore structure parameters of the spherical mesoporous composite material C1 are 1 as shown, in Table below.

Table 1

* first Most probable pore diameter, second may be at most a few pore diameters and third mm diameter comma spacing: in the order of from left to right, the first most probable pore diameter, second being most preferably a few pore diameters and third most probable pore diameters.

(2) Preparation catalyst

: 0.1g G of magnesium chloride and 0.1g titanium tetrachloride dissolved in 10mL mixture of tetrahydrofuran and isopropanol were added to the mother liquor at (by volume ratio 1:1.2), to form a catalyst mother liquor, which was then filtered 45 °C and washed 1g times C1 at 1h, with n-hexane to give catalyst, 75 °C, 4. The, catalyst was D1. obtained.

X In the catalyst, obtained in this example by D1-ray fluorescence analysis, the content of the elemental, magnesium element was 4% %, by weight and the content of the titanium element was 1.0% %. by weight.

(3) Ethylene polymerization

In 2L stainless steel autoclave, three times, were replaced with nitrogen and ethylene and then 200mL ml, of hexanes 80 °C, were added to 800mL and, ml of ethyl aluminum, were added 2mL to add 1mol/L of catalyst component (TEA) to the ethylene gas, and then suction with 0.5g hour suction filtration to obtain a polyethylene particle powder D1, obtained by filtration through suction filtration at, ° F. for 1.0MPa hour, respectively 1.0MPa, and then stirred for a period of 70 °C hour (BD), and then filtered by suction filtration. 1. The resulting polyethylene particle powder was obtained MI ._2.16 , Powder Rate and efficiency of the catalyst are shown in Table 8.

Embodiment 2

This example is used to illustrate the ethylene polymerization process and the resulting polyethylene of the present invention

(1)-prepared spherical mesoporous composite material

1g(0.00017mol) And P123 ethanol were added to 1.4g(0.03mol) ml of acetic acid and sodium acetate buffer solution 28mL and stirred pH＝4.4 to complete dissolution, 10 °C of, ml pentane into an agate lined reaction kettle 4.56g(0.04mol) and stirred at, 10 °C and then filtered and washed 8h times, with deionized water and then suction filtered to obtain a filter cake 1.83g(0.012mol) of a mesoporous molecular sieve material having a one-dimensional hollow spherical pore canal 20h structure, respectively, 10 °C. Next 6 30h hours of stirring A2. was performed, 80 °C.

A sulfuric acid solution having a concentration of 20%% and a sulfuric acid solution having a concentration 12%% are mixed at a weight ratio 3:2:1 and contacted with the reaction 20 °C at 3h, degree. 98 to % and then filtered and washed with distilled water to pH weight 4, 0.02 silica gel-containing filter cake B2. %.

Ball mill slurry 10g prepared A2 by 15g mixing B2 the 100mL balls and, into ball milling pots, and for, hours and then 3mm, subjecting the resulting 1, ball 500r/min. mill slurry to, a ball mill first temperature, of about 35 °C, and 20 hours at a speed of hours to a ball milling tank is, hours at ° 87.5g C. first for a, 35 °C second hour period and a 25 °C, period ranging from 10 about. 2nd. hour to 13000r/min 150 °C about hours to, stir the obtained product, at. degree. C. for a period of time of sup. times.10 .sup.times.10 .sup.), C2. 500 °C 15h, P123(.

The pore structure parameters of the spherical mesoporous composite material C2 are 2 as shown, in Table below.

Table 2

* first Most probable aperture, second may be spaced, third between the most probable aperture diameter and most probable aperture diameter by comma.

(2) Preparation catalyst

: 0.1g G of magnesium chloride and 0.2g tetrachloride of titanium tetrachloride in 10mL mixture of tetrahydrofuran and isopropanol are added to the mother liquor at (. degree. 1:1.5), to form catalyst mother liquor, and 60 °C g of mesoporous composite material, were added to the mother solution 1g and then filtered C2 and milled 1h, at, 75 °C, with n-hexane to give, catalyst D2. 4 .

To X fluorescence analysis, of the catalyst D2 according to the present embodiment shows, wt, of the titanium element in an amount 6.3 wt % of the element, %. %, and 0.7 wt % of the titanium element.

(3) Ethylene polymerization

In 2L stainless steel autoclave, three times, were replaced with nitrogen and ethylene and then 200mL ml, of hexanes 75 °C, were added to 900mL and, ml of ethyl aluminum, were added 2mL to add 1mol/L of catalyst component (TEA) to the ethylene gas, and then suction with 0.1g hour suction filtration to obtain a polyethylene particle powder D2, obtained by filtration through suction filtration at, ° F. for 1MPa hour, respectively 1MPa, and then stirred for a period of 75 °C hour (BD), and then filtered by suction filtration. 1.5. The resulting polyethylene particle powder was obtained MI ._2.16 , Powder Rate and efficiency of the catalyst are shown in Table 8.

Embodiment 3

This example is used to illustrate the ethylene polymerization process and the resulting polyethylene of the present invention

(1)-prepared spherical mesoporous composite material

1g(0.00017mol) And P123 ethanol were added to 3.13g(0.068mol) ml of acetic acid and sodium acetate buffer solution 28mL and stirred pH＝4.4 to complete dissolution, 20 °C of, ml pentane into an agate lined reaction kettle 7.75g(0.068mol) and stirred at, 20 °C and then filtered and washed 8h times, with deionized water and then suction filtered to obtain a filter cake 3.8g(0.025mol) of a mesoporous molecular sieve material having a one-dimensional hollow spherical pore canal 30h structure, respectively, 20 °C. Next 6 10h hours of stirring A3. was performed, 40 °C.

A sulfuric acid solution having a concentration of 10 wt % and a sulfuric acid solution having a concentration 12 wt % are mixed at a weight ratio 6:3:1 and contacted with a reaction 30 °C at 1.5h, weight 98 to % and then a filtered cake pH of silica gel is obtained by suction filtration 2, with a concentration of, wt % and washing with distilled water to 0.02 wt %, B3.

Ball mill slurry 10g prepared A3 by 10g mixing B3 the 100mL balls and, into ball milling pots, and for, hours and then 3mm, subjecting the resulting 1, ball 300r/min. mill slurry to, a ball mill first temperature, of about 50 °C, and 10 hours at a speed of hours to a ball milling tank is, hours at ° 40g C. first for a, 50 °C second hour period and a 40 °C, period ranging from 5 about. 2nd. hour to 11000r/min 250 °C about hours to, stir the obtained product, at. degree. C. for a period of time of sup. times.10 .sup.times.10 .sup.), C3. 300 °C 24h, P123(.

The pore structure parameters of the obtained spherical mesoporous composite material C3 are 3 as shown in Table. below.

Table 3

* first Most probable aperture, second may be spaced, third between the most probable aperture diameter and most probable aperture diameter by comma.

(2) Preparation catalyst

: 0.2g G of magnesium chloride and 0.1g titanium tetrachloride dissolved in 10mL mixture of tetrahydrofuran and isopropanol were added to the mother liquor at (by volume ratio 1:1), to form a catalyst mother liquor, which was then filtered 40 °C and washed 1g times C3 at 3h, with n-hexane to give catalyst, 75 °C, 4. The, catalyst was D3. obtained.

To X fluorescence analysis, of the catalyst D3 according to the present embodiment shows, wt, of the titanium element in an amount 6.1 wt % of the element, %. %, and 0.8 wt % of the titanium element.

(3) Ethylene polymerization

In 2L stainless steel autoclave, three times, were replaced with nitrogen and ethylene and then 200mL ml, of hexanes 85 °C, were added to 700mL and, ml of ethyl aluminum, were added 2mL to add 1mol/L of catalyst component (TEA) to the ethylene gas, and then suction with 1g hour suction filtration to obtain a polyethylene particle powder D3, obtained by filtration through suction filtration at, ° F. for 1MPa hour, respectively 1MPa, and then stirred for a period of 85 °C hour (BD), and then filtered by suction filtration. 2. The resulting polyethylene particle powder was obtained MI ._2.16 , Powder Rate and efficiency of the catalyst are shown in Table 8.

Comparative Example 1

Process for the polymerization of ethylene and polyethylene according to the invention for the purpose of describing the parameters

ES955 Silica-(GRACE company) commercially available under nitrogen protection 400 °C was calcined 10h, to remove hydroxyl and residual moisture, to give a thermally activated ES955 silica gel.

To the method of Example 1 and Step (2), the catalyst, was prepared by, parts by weight of the activated ES955 silica gel, instead of the spherical mesoporous composite material C1, to prepare a comparative catalyst DD1.

(3) Ethylene polymerization

Polymerization 1 of ethylene according to the method of Experimental Example, differs from, using the same weight parts of the comparative catalyst DD1 in place of the bulk density 1 melt index D1. of the polyethylene particle powder obtained from the catalyst (BD), prepared in Example MI, respectively._2.16 , Powder Rate and efficiency of the catalyst are shown in Table 8.

Comparative Example 2

Process for the polymerization of ethylene and polyethylene according to the invention for the purpose of describing the parameters

To Example 1, the spherical mesoporous composite material and the supported catalyst, were prepared, except, ball mill first of, ball mill (2nd ball mill.) at, ° C. for 20g hours A1 and 10g ball mill B1 at 100mL ° C. in, hours to prepare the obtained, pellets first and, ball milled slurry at 25 °C, ° C. for 5 hours to prepare spherical mesoporous composite material, and supported catalyst first respectively 87.5g in a ball mill tank 25 °C at a rotating speed of, 12000r/min The obtained slurry was DC2 dried 200 °C by spray drying DD2.

The pore structure parameters of the spherical mesoporous composite material DC2 are 5 as shown, in Table below.

Table 5

* first Most probable aperture, second may be spaced, third between the most probable aperture diameter and most probable aperture diameter by comma.

By X fluorescence analysis, % DD2 weight, of titanium element is contained in the catalyst, according to the ratio 5.6, and the content of the element %, magnesium element %. is 0.7% by weight.

(3) Ethylene polymerization

Polymerization 1 of ethylene according to method, of Experiment Experiment The same was, except that catalyst DD2 was used in place of catalyst 1 obtained in Example D1. in place of the bulk density (BD), melt index MI2.16, of the obtained polyethylene pellet powder and the catalyst efficiency is shown in Table 8.

Comparative Example 3

Process for the polymerization of ethylene and polyethylene according to the invention for the purpose of describing the parameters

To the method of Example 1, the spherical mesoporous composite material and the supported catalyst, were prepared by spray-drying, without using a cyclone separation technique, and spray-drying the obtained,ball mill slurry at, rpm for second and then calcining 200 °C at 12000r/min in a muffle furnace to obtain spherical mesoporous composite, and a supported catalyst 600 °C), 10h, by spraying the dried DC3 product. P123( DD3. The obtained product was subjected to spray drying in a muffle furnace.

The pore structure parameters of the spherical mesoporous composite material DC3 are 6 as shown, in Table below.

Table 6

* first Most probable aperture, second may be spaced, third between the most probable aperture diameter and most probable aperture diameter by comma.

By X fluorescence analysis, % DD3 weight, of titanium element is contained in the catalyst, according to the ratio 4.8, and the content of the element %, magnesium element %. is 0.9% by weight.

(3) Ethylene polymerization

Polymerization 1 of ethylene according to the method of Experimental Example, differs from, by using the same weight parts of catalyst DD3 in place of the bulk density 1 melt index D1. of the polyethylene particle powder obtained from the catalyst (BD), prepared in Example MI, respectively._2.16 , Powder Rate and efficiency of the catalyst are shown in Table 8.

Comparative Example 4

Process for the polymerization of ethylene and polyethylene according to the invention for the purpose of describing the parameters

The 1-ball mill slurry obtained by mixing the, ball mill slurry with, water at first for, hours second and, hours, and then subjecting the obtained slurry to, ball mill, at 20g ° C. in a ball milling tank A1 for 10g hours to a ball milling tank B1 of 100mL hours, and then subjecting the resulting slurry to a calcination. at, ° C. in a muffle furnace at a speed first to obtain a spherical mesoporous composite material, and a supported catalyst 25 °C, respectively 200 °C 5 hours, and the 12000r/min slurry, is stirred in a ball, mill. 1st. The obtained 600 °C slurry was 10h, sieved 87.5g and dried 25 °C P123( in a), ball milling tank for a DC4 period of time DD4. at a temperature of about.

The pore structure parameters of the spherical mesoporous composite material DC4 are 7 as shown, in Table below.

Table 7

* first Most probable aperture, second may be spaced, third between the most probable aperture diameter and most probable aperture diameter by comma.

By X fluorescence analysis, % DD4 weight, of titanium element is contained in the catalyst, according to the ratio 5.1, and the content of the element %, magnesium element %. is 0.6% by weight.

(3) Ethylene polymerization

Polymerization 1 of ethylene according to the method of Experimental Example, differs from, by using the same weight parts of catalyst DD4 in place of the bulk density 1 melt index D1. of the polyethylene particle powder obtained from the catalyst (BD), prepared in Example MI, respectively._2.16 , Powder Rate and efficiency of the catalyst are shown in Table 8.

Table 8

As a result of Comparative Example 1-4 and Experimental Example 1-4 above, Catalyst The spherical mesoporous composite material and the supported catalyst provided by the present invention were used for the ethylene polymerization reaction, catalyst had higher catalytic activity, and can obtain a polyethylene product, having a bulk density and a lower melt index of, or less 0.5g/mL and a powder yield of, or more and not less than 0.5g/10min % by weight of the polyethylene product obtained by the method of the present invention, in particular, hours 3 minutes %. %, % weight. percent. 5 of the polyethylene product obtained by the method of the present invention.

Although a preferred embodiment, of the present invention has been described above in detail, the present invention is not limited to the specific details, in the above-described embodiments, may perform various simple modifications, to the technical solution of the present invention, all of which fall within the protection scope, of the present invention.

It should be noted that the specific technical features, described, in the above-described embodiments may be combined, in any suitable manner in order to avoid unnecessary repetition . and the present invention will not be described otherwise,for various possible combinations.

Further, any combination, may be made between various embodiments of the present invention as long as it does not depart from the concept, of the present invention, and it should also be considered as the content, disclosed in the present invention.