CN107417824A - The method and polyethylene of a kind of vinyl polymerization - Google Patents
The method and polyethylene of a kind of vinyl polymerization Download PDFInfo
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- CN107417824A CN107417824A CN201610347732.7A CN201610347732A CN107417824A CN 107417824 A CN107417824 A CN 107417824A CN 201610347732 A CN201610347732 A CN 201610347732A CN 107417824 A CN107417824 A CN 107417824A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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Abstract
The present invention relates to vinyl polymerization field, in particular it relates to a kind of method of vinyl polymerization and the polyethylene being prepared by this method.The invention discloses a kind of method of vinyl polymerization, this method includes：Under the polymerization conditions, in the presence of a catalyst, ethene is set to carry out polymerisation, wherein, the catalyst contains spherical composite and the magnesium salts and/or titanium salt that are supported on the spherical composite, and the spherical composite contains meso-porous molecular sieve material and silica gel with hollow ball-shape structure.The invention also discloses the polyethylene being prepared by the above method.There is high catalytic activity when support type polyethylene catalysts provided by the invention are used for into ethylene polymerization, while the polyethylene product of function admirable can be obtained.
Description
Technical field
The present invention relates to polymerisation field, in particular it relates to a kind of method of vinyl polymerization and be prepared into by this method
The polyethylene arrived.
Background technology
Polyethylene is a kind of polymer generated using ethene as monomer by polymerisation.Due to polyethylene have it is excellent
Resistance to low temperature, the advantages that chemical stability is good, it is widely used in chemical field.During polyethylene is prepared, gather
The use of catalyst for ethylene is to influence one of key factor of yield and quality of polyethylene product.
The development and application of polyethylene catalysts are the olefin polymerization catalysis after traditional Ziegler-Natta catalyst
The another important breakthrough in field, this causes the research of polyethylene catalysts to enter the stage of a fast development.Due to equal
Phase polyethylene catalyst reach needed for high activity catalyst amount is big, production cost is high, and obtained polymer is without particle shape,
It can not be used on widely used slurry process or gas phase polymerization technique.The effective way for overcoming above mentioned problem is exactly solvable
Property polyethylene catalysts carry out supported processing.At present, the supported research report of relevant polyethylene catalysts is very more.It is deep
Study new support/catalyst/co-catalyst system, it is necessary to different carriers is studied, to promote carried catalyst and polyene
The further development of hydrocarbon industry.
Since the regular mesoporous material of Mobile companies synthesis duct high-sequential in 1992, because it has high ratio table
Face, regular pore passage structure and narrow pore-size distribution so that mesoporous material is applied in catalysis, separation, medicine and other fields
Very big concern is arrived.Zhao east member in 1998 et al. synthesizes a kind of new material-mesoporous material SBA-15, and the material has height
Spend orderly aperture (6-30nm), big pore volume (1.0cm3/ g), thicker hole wall (4-6nm), keep high mechanical properties
And good catalytic adsorption performance is (see D.Y.Zhao, J.L.Feng, Q.S.Huo, et al Science 279 (1998)
548-550).CN1341553A discloses a kind of preparation method of mesonic pore molecular sieve carrier material, mesoporous material made from this method
Material is used as heterogeneous reaction catalyst carrier, easily realizes the separation of catalyst and product.But conventional ordered mesoporous material
For SBA-15 microscopic appearances to be bar-shaped, itself mobility is poor, and its big specific surface area and high pore volume cause to make it have stronger
Water suction, moisture absorption ability, this has been further exacerbated by the reunion of ordered mesoporous material, limits storing, being defeated for ordered mesoporous material
Fortune, post-processing and application.
The mesoporous material for the load polyethylene catalysts reported at present on document is MCM-41, with MAO (MAO)
Catalytic activity is 10 after loading the MCM-41 progress vinyl polymerizations of polyethylene catalysts after processing again6gPE/(mol Zr h).It is situated between
The reason for progress ethylene polymerization activity is relatively low after Porous materials MCM-41 supported catalysts is mainly that MCM-41 hole wall structure heat is steady
Qualitative and hydrothermal stability is poor, just has part to cave in loading process hole wall, have impact on load effect, urged so that have impact on
Change activity.Therefore, it is necessary to seek a kind of stable mesoporous material of meso-hole structure, it can still keep orderly mesoporous after load
Material.
The content of the invention
The purpose of the present invention is the defects of overcoming prior art, there is provided a kind of method of vinyl polymerization, be the method use
A kind of stable loaded catalyst of meso-hole structure, the catalyst has higher catalytic efficiency, while obtains function admirable
Polyethylene product.
In order to realize foregoing invention purpose, the invention provides a kind of method of vinyl polymerization, this method includes：It is polymerizeing
Under reaction condition, in the presence of a catalyst, ethene is set to carry out polymerisation, wherein, the catalyst contains spherical composite
With the magnesium elements and/or titanium elements being supported on the spherical composite, wherein, the spherical composite contain with sky
The meso-porous molecular sieve material and silica gel of heart chondritic, the pore volume of the spherical composite is 0.5-1.8mL/g, compares surface
Product is 100-650m2/ g, average grain diameter are 20-60 μm, and aperture be in bimodal distribution, and bimodal the first most probable pore size corresponding respectively
With the second most probable pore size, first most probable pore size is less than second most probable pore size, and the first most probable hole
Footpath is 1-10nm, and second most probable pore size is 10-50nm.
Present invention also offers the polyethylene being prepared by the above method.
In the method for vinyl polymerization provided by the invention, the meso-hole structure of used spherical composite is stable,
Orderly meso-hole structure is maintained to after carrying active ingredients, and the support type polyethylene being prepared by it is catalyzed
Agent is used for having high catalytic activity during ethylene polymerization, while can obtain heap density and melt index is relatively low and non-breakable
Polyethylene product, specifically, the heap density of the polyethylene product of preparation is below 0.41g/mL, melt index 0.5g/
Below 10min, break powder rate and be less than 3%.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the X-ray diffracting spectrum of the spherical composite C1 described in the embodiment of the present invention 1；
Fig. 2 is the SEM scanning electron microscope (SEM) photographs of the microscopic appearance of the spherical composite C1 described in the embodiment of the present invention 1；
Fig. 3 is the graph of pore diameter distribution of the spherical composite C1 described in the embodiment of the present invention 1.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The invention provides a kind of method of vinyl polymerization, this method includes：Under the polymerization conditions, deposited in catalyst
Under, ethene is set to carry out polymerisation, it is characterised in that the catalyst contains spherical composite and is supported on described spherical
Magnesium salts and/or titanium salt on composite, wherein, the spherical composite contains the mesoporous molecular with hollow ball-shape structure
Material and silica gel are sieved, the pore volume of the spherical composite is 0.5-1.8mL/g, specific surface area 100-650m2/ g, it is average
Particle diameter is 20-60 μm, and aperture be in bimodal distribution, and bimodal the first most probable pore size corresponding respectively and the second most probable pore size, institute
State the first most probable pore size and be less than second most probable pore size, and first most probable pore size is 1-10nm, described second
Most probable pore size is 10-50nm.
In the present invention, the average grain diameter of the spherical composite is measured using laser fineness gage, specific surface area,
Pore volume and most probable pore size measure according to nitrogen adsorption methods, and the surface topography of the spherical composite passes through ESEM instrument
(SEM) measure.In the present invention, the average grain diameter is average particulate diameter.
In the present invention, by the way that the particle size of spherical composite is controlled within above range, it can be ensured that institute
State spherical composite to be not susceptible to reunite, and be used as loaded catalyst made of carrier to improve vinyl polymerization
Reaction raw materials conversion ratio in course of reaction.When the specific surface area of the spherical composite is less than 100m2/ g and/or pore volume
During less than 0.5mL/g, being used as the catalytic activity of loaded catalyst made of carrier can significantly reduce；When described spherical multiple
The specific surface area of condensation material is more than 650m2When/g and/or pore volume are more than 1.8mL/g, support type made of carrier is used as
Catalyst is easily reunited during ethylene polymerization, so as to influence the conversion of monomer during ethylene polymerization
Rate.
In the preferred case, the pore volume of the spherical composite is 0.6-1.6mL/g, specific surface area 200-
450m2/ g, average grain diameter are 30-55 μm, and the first most probable pore size is 3-8nm, and the second most probable pore size is 30-45nm.
It is further preferred that the pore volume of the spherical composite is 1.0-1.2mL/g, specific surface area 200-
300m2/ g, average grain diameter are 48-52 μm, and the first most probable pore size is 5-7nm, and the second most probable pore size is 40-43nm.
According to the present invention, in the loaded catalyst, the present invention is to the content of the magnesium salts and/or titanium salt without spy
Other restriction, can suitably it be determined according to the conventional loaded catalyst in this area, for example, with the total of the catalyst
On the basis of weight, the content of the carrier is 90-99 weight %, and the magnesium salts and titanium salt are respectively in terms of magnesium elements and titanium elements
Content sum is 1-10 weight %；Preferably, the content of the carrier is 92-96 weight %, the magnesium salts and titanium salt respectively with
The content sum of magnesium elements and titanium elements meter is 4-8 weight %；It is further preferred that the content of the carrier is 94-95.5 weights
% is measured, the magnesium salts and titanium salt are respectively using the content sum that magnesium elements and titanium elements are counted as 4.5-6 weight %.
In the present invention, the catalyst can be prepared according to various methods commonly used in the art, as long as described
Magnesium salts and/or titanium salt are loaded on spherical composite.
In situations where it is preferred, the preparation method of the catalyst can include：In the presence of an inert gas, carrier is existed
Impregnated in mother liquor containing magnesium salts and/or titanium salt, then filtered and dried successively；Wherein, the carrier is this hair
The spherical composite of bright offer.
In the present invention, the condition of the dipping can include：Temperature is 25-100 DEG C, time 0.1-5h；Preferably,
The condition of the dipping includes：Temperature is 40-60 DEG C, time 1-3h.
In the present invention, to the dosage of the magnesium salts and titanium salt, there is no particular limitation, in the preferred case, the load
The dosage of body, magnesium salts and titanium salt causes in the support type polyethylene catalysts being prepared, with the gross weight of the catalyst
On the basis of, the content of the carrier is 90-99 weight %, the magnesium salts and the titanium salt content in terms of magnesium elements and titanium elements respectively
Sum is 1-10 weight %；It is highly preferred that the content of the carrier is 92-96 weight %, the magnesium salts and titanium salt are respectively with magnesium
The content sum of element and titanium elements meter is 4-8 weight %；It is further preferred that the content of the carrier is 94-95.5 weights
% is measured, the magnesium salts and titanium salt are respectively using the content sum that magnesium elements and titanium elements are counted as 4.5-6 weight %.
In a kind of preferred embodiment of the present invention, the dosage weight ratio of the magnesium salts and titanium salt is 1：0.1-2, it is excellent
Elect 1 as：0.5-2.
In the present invention, the magnesium salts can be various magnesium salts commonly used in the art, for example, can be magnesium chloride,
One or more in magnesium sulfate, magnesium nitrate and magnesium bromide, preferably magnesium chloride.
In the present invention, the titanium salt can be various titanium salts commonly used in the art, for example, can be titanium tetrachloride
And/or titanium trichloride.
In the present invention, the content of element can be measured using X-ray fluorescence spectra analytic approach in the catalyst.
In situations where it is preferred, the mother liquor can also contain the organic solvent of dissolving magnesium salts and titanium salt, the present invention is to institute
State organic solvent to have no particular limits, as long as magnesium salts and titanium salt can be dissolved, such as can be isopropanol and tetrahydrochysene furan
Mutter, the volume ratio of isopropanol and tetrahydrofuran can be 1：1-3, preferably 1：1-1.5.
In the present invention, the drying condition of preparation of the present invention to the catalyst has no particular limits, and can be this
The conventional various conditions in field；The preparation of preferred catalyst is additionally included in after filtering and washing process before the drying, and/
Or process of lapping after drying.Those skilled in the art can enter according to practice situation to the condition of the washing and grinding
Row selection, will not be repeated here.
In the present invention, the inert gas is the gas not reacted with raw material and product, such as can be ability
At least one of group 0 element gas, preferably nitrogen in domain conventional nitrogen or the periodic table of elements.
According to the present invention, the preparation method of the spherical composite may comprise steps of：
(1) meso-porous molecular sieve material with hollow ball-shape structure is provided or prepared with the mesoporous of hollow ball-shape structure
The filter cake of molecular screen material, as component a；
(2) provide silica gel or prepare the filter cake of silica gel, as component b；
(3) by the component a, the component b and binding agent is mixed and ball milling, and the solid powder that will be obtained after ball milling
Water slurrying is used at end, is then spray-dried obtained slurry；
Wherein, above-mentioned steps make it that the pore volume of the spherical composite is 0.5-1.8mL/g, specific surface area 100-
650m2/ g, average grain diameter are 20-60 μm, and aperture is in bimodal distribution, and bimodal the first most probable pore size and second corresponding respectively is most
Can several apertures, first most probable pore size is less than second most probable pore size, and first most probable pore size is 1-
10nm, second most probable pore size are 10-50nm.
In the preferred case, the pore volume of the spherical composite is 0.6-1.6mL/g, specific surface area 200-
450m2/ g, average grain diameter are 30-55 μm, and the first most probable pore size is 3-8nm, and the second most probable pore size is 15-45nm.
It is further preferred that the pore volume of the spherical composite is 1.0-1.2mL/g, specific surface area 200-
300m2/ g, average grain diameter are 45-55 μm, and the first most probable pore size is 4-6nm, and the second most probable pore size is 20-45nm.
In step (1), preparing the process of the filter cake of the meso-porous molecular sieve material with hollow ball-shape structure can include：
In acidic aqueous solution, in the presence of trimethylpentane and ethanol, template is contacted with silicon source, and will be obtained after contact
The mixture arrived carries out crystallization and filtering.
In step (1), template, ethanol, the mol ratio of trimethylpentane and silicon source are 1：100-500：200-500：
50-200, preferably 1：180-400：250-400：70-150.
In the present invention, the template can be various templates commonly used in the art.Preferably, the template
Agent is triblock copolymer polyethylene glycol glycerine-polyethylene glycol, and the template can be commercially available (for example, can be with
Purchased from Aldrich, trade name P123, molecular formula EO20PO70EO202, molecular weight Mn, can also be by existing for 5800)
The various methods having are prepared.When the template is polyethylene glycol glycerine-polyethylene glycol, the template
Molal quantity calculates to obtain according to the mean molecule quantity of polyethylene glycol glycerine-polyethylene glycol.
In the present invention, the silicon source can be various silicon sources commonly used in the art, and preferably described silicon source is tetramethyl
TMOS.
In the present invention, the acidic aqueous solution can be various acidic aqueous solutions commonly used in the art, it is preferable that
The acidic aqueous solution is the acetic acid and sodium acetate buffer solution that pH value is 1-6.
In the present invention, the condition that template contacts with silicon source can include：Temperature is 10-60 DEG C, time 10-72h,
PH value is 1-7；Preferably, the condition that template contacts with silicon source can include：Temperature is 10-20 DEG C, time 10-30h.For
The uniform mixing being more beneficial between each material, the template contacts with silicon source is preferably carried out under agitation.The acid
The dosage of the property aqueous solution is preferably so that the pH value of the haptoreaction system of template and silicon source is 1-7.
In the present invention, the condition of the crystallization can include：Temperature is 30-150 DEG C, time 10-40h；Preferably,
Temperature is 40-80 DEG C, time 20-30h.It is further preferred that the crystallization is implemented by hydrothermal crystallization method.
In the present invention, during the filter cake of meso-porous molecular sieve material in above-mentioned preparation with hollow ball-shape structure,
It can be included with obtaining the process of filter cake by filtering：After filtration, wash that (washing times can be repeatedly with deionized water
2-10), then filtered.
In step (1), " providing the meso-porous molecular sieve material with hollow ball-shape structure " can directly be weighed or select
Take the product of the meso-porous molecular sieve material with hollow ball-shape structure or prepare mesoporous point with hollow ball-shape structure
Son sieve material.The preparation method of the meso-porous molecular sieve material with hollow ball-shape structure can be real according to the conventional method
Apply, for example, its preparation method can include：Meso-porous molecular sieve material with hollow ball-shape structure is prepared according to the above method
Filter cake, then by gained filtration cakes torrefaction.
In step (2), preparing the process of the filter cake of silica gel can include：In the presence of a mineral acid, by waterglass with it is more
First alcohol is contacted, and the mixture obtained after contact is filtered.
According to the present invention, there is no particular limitation to the polyalcohol by the present invention, and preferably described polyalcohol is ethylene glycol, third
At least one of glycol and glycerine, preferably ethylene glycol and/or glycerine, more preferably glycerine.
According to the present invention, there is no particular limitation for the condition that the present invention contacts to waterglass with polyalcohol, can be according to system
Suitably determined in the common process of standby silica gel.Under preferable case, the condition of the contact includes：Temperature is 10-60 DEG C, preferably
For 30-45 DEG C；Time is 1-5h, preferably 1-3h；PH value is 2-4, preferably 2.5-3.5.
In order to be more beneficial for the uniform mixing between each material, waterglass is preferably stirring with the catalytic process of polyalcohol
Under the conditions of carry out.
Preferably, the weight ratio of the waterglass, inorganic acid and polyalcohol is 3-6：2-3：1；More preferably 3-5：1：1.
The waterglass is the aqueous solution of sodium metasilicate, and its concentration can be 3-20 weight %, preferably 10-20 weight %.
The inorganic acid can be various inorganic acids commonly used in the art, for example, can be sulfuric acid, nitric acid and hydrochloric acid
At least one of.The inorganic acid can use in pure form, can also be used in the form of its aqueous solution.The nothing
The dosage of machine acid is preferably so that the pH value of the haptoreaction system of waterglass and polyalcohol is 2-4.
In step (2), " offer silica gel " can directly be weighed or choose silica gel product or prepare silica gel.
Preparing the method for silica gel can implement according to the conventional method, such as can include：The filter cake of silica gel is prepared according to the above method,
Then by gained filtration cakes torrefaction.
According to the present invention, in step (3), the present invention has no particular limits to the dosage and species of the binding agent,
In order to improve the intensity of spherical composite, and then the performance of polyethylene product is improved, relative to the component of 100 parts by weight
A, the component b dosage can be 1-200 parts by weight, and the dosage of the binding agent can be 1-10 parts by weight；Preferably, institute
The dosage for stating component b is 50-200 parts by weight, and the dosage of the binding agent is 2-8 parts by weight.It is highly preferred that the binding agent is
Polyvinyl alcohol and/or polyethylene glycol, most preferably polyvinyl alcohol.
In step (3), the ball milling can be carried out in ball mill, and the inwall of ball grinder is preferably in the ball mill
Agate liner, the diameter of the abrading-ball in ball mill can be 2-3mm；The quantity of abrading-ball can be closed according to the size of ball grinder
The selection of reason ground, for the ball grinder that size is 50-150mL, it can generally use 1 abrading-ball；The material of the abrading-ball can be
Agate, polytetrafluoroethylene (PTFE) etc., preferably agate.The condition of the ball milling can include：The rotating speed of abrading-ball is 200-800r/min,
Temperature in ball grinder is 15-100 DEG C, and the time of ball milling is 0.1-100h；Preferably, the rotating speed of abrading-ball is 300-500r/
Min, the temperature in ball grinder is 25-50 DEG C, and the time of ball milling is 5-20h.
In step (3), the process of the solid powder water slurrying obtained after ball milling can be entered at 25-60 DEG C
OK.In pulping process, the weight ratio of the dosage of solid powder and water can be 1:0.1-5, preferably 1：0.5-3.5.
In step (3), the spray drying can be implemented according to the mode of routine, such as can enter in atomizer
OK.The condition of the spray drying can include：Temperature is 150-600 DEG C, and the rotating speed of rotation can be 10000-15000r/
min；Under preferable case, the condition of the spray drying includes：Temperature is 150-250 DEG C, and the rotating speed of rotation is 11000-
13000r/min。
It is described when the filter cake that the component a is the meso-porous molecular sieve material with hollow ball-shape structure in step (3)
When component b is the filter cake of silica gel, namely when step (1) is the filter cake of meso-porous molecular sieve material of the preparation with hollow ball-shape structure
Process, step (2) be prepare silica gel filter cake process when, the preparation method of the spherical composite can also include：
After the spray-drying process of step (3), removed template method in the product obtained from spray drying.Preferably, the removing
The condition of template includes：Temperature is 90-600 DEG C, more preferably 400-600 DEG C；Time is 10-80 hours, more preferably 10-
24h。
According to the present invention, the condition of the polymerisation can be the conventional condition in this area.For example, the polymerisation
Carry out in the presence of an inert gas, the condition of the polymerisation includes：Temperature is 10-100 DEG C, time 0.5-5h, pressure
For 0.1-2MPa；Preferably, temperature is 20-95 DEG C, time 1-4h, pressure 0.5-1.5MPa；It is further preferred that temperature
For 70-85 DEG C, time 1-2h, pressure 1-1.5MPa.
Pressure of the present invention refers to gauge pressure.
In the present invention, the inert gas is the gas not reacted with raw material and product, such as can be ability
At least one of group 0 element gas in domain conventional nitrogen or the periodic table of elements；Preferably nitrogen.
In the present invention, the polymerisation can be carried out in the presence of solvent, used in the polymerisation
Solvent is not particularly limited, for example, can be hexane.
According to the present invention, in situations where it is preferred, the method for vinyl polymerization includes：Under the polymerization conditions, it is being catalyzed
In the presence of agent and auxiliary agent, ethene is set to carry out polymerisation；Preferably, the auxiliary agent is alkyl aluminum compound.
In the present invention, the structure of the alkyl aluminum compound is shown in formula I：
AlRnX5 (3-n)Formulas I
In Formulas I, R can be respectively C1-C5Alkyl；X5The one kind that can be respectively in halogen group, it is preferably-Cl；n
For 0,1,2 or 3.
Preferably, the C1-C5Alkyl can be methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl
One or more in base, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl and neopentyl.
In the present invention, the instantiation of the alkyl aluminum compound includes but is not limited to：Trimethyl aluminium, dimethylammonium chloride
Aluminium, triethyl aluminum, diethyl aluminum chloride, tri-n-n-propyl aluminum, diη-propyl aluminium chloride, three n-butylaluminums, three sec-butyl aluminium, three uncles
Butyl aluminium, di-n-butyl aluminium chloride and diisobutyl aluminum chloride.Most preferably, the alkyl aluminum compound is triethyl aluminum.
In the present invention, the dosage of the alkyl aluminum compound can also be the conventional selection in this area, usually, described
The mass ratio of alkyl aluminum compound and the catalyst amount can be 1：0.1-10；Under preferable case, the alkyl aluminum chemical combination
The mass ratio of thing and the catalyst amount is 1：0.2-8；More preferably 1：0.4-4.
In the present invention, the method for the vinyl polymerization can also include, after polymerisation terminates, to final reaction
Mixture carries out suction filtration separation, so as to which polyethylene particle powder be made.
Present invention also offers the polyethylene being prepared by the above method.
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples, polyethylene glycol glycerine-polyethylene glycol is purchased from Aldrich, commodity
Entitled P123, molecular formula EO20PO70EO202, molecular weight Mn is 5800.
In following examples and comparative example, X-ray diffraction analysis are in the model purchased from German Bruker AXS companies
Carried out on D8Advance X-ray diffractometer；Scanning of the scanning electron microscope analysis in the model XL-30 purchased from FEI Co. of the U.S.
Carried out on electron microscope；Pore structure parameter analysis is inhaled de- in the nitrogen of the model Autosorb-1 purchased from Kang Ta companies of the U.S.
Carried out on attached instrument, wherein, before being tested, sample is deaerated 4 hours at 200 DEG C；X-ray fluorescence analysis is in dutch company
Carried out on model Axios-Advanced x-ray fluorescence analyzer.
The heap density of polyolefine powder is measured using method as defined in GB/T 1636-2008.
Melt index：Determined according to ASTM D1238-99.
Polyethylene flour rate：Sieved and determined by 800 eye mesh screens.
Embodiment 1
The present embodiment is used to illustrate ethene polymerization method provided by the invention.
(1) spherical composite is prepared
1g (0.00017mol) template P123 and 1.69g (0.037mol) ethanol is added to 28mL pH=4.4's
In acetic acid and sodium acetate buffer solution, stirring to template is completely dissolved at 15 DEG C, and 6g (0.05mol) trimethylpentane is added
Into above-mentioned solution, after stirring 8h at 15 DEG C, then 2.13g (0.014mol) tetramethoxy-silicane is added in above-mentioned solution,
After stirring 20h at 15 DEG C, transfer the solution into the reactor of agate liner, after 60 DEG C of baking oven crystallization 24h, then filtered
And be washed with deionized 4 times, then filter the filter cake A1 for the meso-porous molecular sieve material for obtaining having hollow ball-shape structure.
By the waterglass that concentration is 15 weight % and the sulfuric acid solution that concentration is 12 weight % and glycerine using weight ratio as
5：1：1 is mixed and the haptoreaction 1.5h at 30 DEG C, then adjusts pH value to 3 with the sulfuric acid that concentration is 98 weight %, so
Obtained reaction mass is filtered afterwards, and it is 0.02 weight % to be washed with distilled water to sodium ions content, obtains silica gel
Filter cake B1.
10g filter cake A1,10g filter cake B1 and 0.5g polyvinyl alcohol of above-mentioned preparation is put into 100mL ball grinder together,
Wherein, the material of ball grinder is agate, and Material quality of grinding balls is agate, and a diameter of 3mm of abrading-ball, quantity is 1, rotating speed 400r/
min.Ball grinder is closed, temperature is ball milling 5h at 25 DEG C in ball grinder, obtains solid powder；The solid powder is dissolved in
In 25g deionized waters, at 200 DEG C in rotating speed be 12000r/min under be spray-dried；The product obtained after spray drying is existed
10h is calcined in Muffle furnace at 550 DEG C, removing P123 (template), obtains spherical composite C1.
Spherical composite C1 is characterized with XRD, ESEM and nitrogen adsorption instrument.
Fig. 1 is X-ray diffracting spectrum, and as seen from the figure, spherical composite C1 has hollow ball specific to mesoporous material
Shape structure.
Fig. 2 is spherical composite C1 microscopic appearance SEM figures, as seen from the figure, spherical composite C1 microscopic appearance
The microballoon for being 20-60 μm for particle diameter, and its good dispersion property.
Fig. 3 is spherical composite C1 graph of pore diameter distribution, and as seen from the figure, spherical composite C1 has diplopore knot
Structure is distributed, and duct is uniform.
Spherical composite C1 pore structure parameter is as shown in table 1 below.
Table 1
*：First most probable pore size and the second most probable pore size are separated with comma：It is the first most probable pore size before comma,
It is the second most probable pore size after comma.
(2) catalyst is prepared
0.1g magnesium chlorides and 0.1g titanium tetrachlorides are dissolved in (four in 10mL tetrahydrofuran and the double solvents of isopropanol
The volume ratio of hydrogen furans and isopropanol is 1：1.2) catalyst mother liquor, is formed.The spherical composite C1 of 1g are added at 45 DEG C
1h is impregnated into mother liquor, is then filtered, and washing 4 times is carried out with n-hexane, in 75 DEG C of dryings, and is ground, is catalyzed
Agent D1.
Drawn by x-ray fluorescence analysis, in the catalyst D1 described in the present embodiment, in terms of element, magnesium elements contain
Measure as 3.93 weight %, the content of titanium elements is 1.89 weight %.
(3) vinyl polymerization
In 2L stainless steel polymerization autoclave, with nitrogen and ethene, respectively displacement three times, then adds 200mL hexanes, will
Kettle temperature rises to 80 DEG C, adds 800mL hexanes, and with the addition of hexane, the concentration for adding 2mL is 1mol/L triethyl aluminum
(TEA) hexane solution, 0.5g catalytic component D1 is subsequently added into, is passed through ethylene gas, pressure is risen into 1MPa and maintained
For 1MPa, separation is filtered after being reacted 1 hour at 70 DEG C, obtains polyethylene particle powder.Polyethylene particle powder is measured,
The heap density (BD) of polyethylene particle powder is 0.38g/mL, melt index MI2.16=0.45g/10min, flour rate are less than
2%.It is computed determining, the efficiency of catalyst is 2195gPE/gcath.
Comparative example 1
Commercially available ES955 silica gel (GRACE companies) is calcined into 10h for 400 DEG C under nitrogen protection, with eliminating hydroxide and remaining
Moisture, so as to obtain the ES955 silica gel through thermal activation.
Method according to the step of embodiment 1 (2) prepares catalyst, except that, using the above-mentioned work of identical weight part
The ES955 silica gel of change replaces spherical composite C1, so as to which comparative catalyst DD1 be made.Drawn by x-ray fluorescence analysis,
In comparative catalyst DD1, in terms of element, the content of magnesium elements is 3.0 weight %, and the content of titanium elements is 1.2 weight %.
Vinyl polymerization is carried out according to the method for the step of embodiment 1 (3), except that, using the contrast of identical weight part
Catalyst DD1 replaces the catalyst D1 being prepared by embodiment 1.The heap density (BD) of gained polyethylene particle powder is
0.4g/mL, melt index MI2.16=0.87g/10min, flour rate are more than 8%.It is computed determining, the efficiency of catalyst is
1767g PE/gcat·h。
Comparative example 2
Spherical composite and catalyst are prepared according to method same as Example 1, wherein except that, in step
(1) prepare in spherical composite material, 10g filter cake A1 and 10g filter cakes B1 is put into 100mL ball grinder together, i.e., not
Add binding agent polyvinyl alcohol.So as to which comparative catalyst DD2 be made.Drawn by x-ray fluorescence analysis, in comparative catalyst
In DD2, in terms of element, the content of magnesium elements is 2.9 weight %, and the content of titanium elements is 0.77 weight %.
Vinyl polymerization is carried out according to the method for the step of embodiment 1 (3), except that, using the contrast of identical weight part
Catalyst DD2 replaces the catalyst D1 being prepared by embodiment 1.The heap density (BD) of gained polyethylene particle powder is
0.43g/mL, melt index MI2.16=0.55g/10min, flour rate are more than 8%.It is computed determining, the efficiency of catalyst is
1106g PE/gcat·h。
Embodiment 2
The present embodiment is used to illustrate ethene polymerization method provided by the invention.
(1) spherical composite is prepared
1g (0.00017mol) template P123 and 1.4g (0.03mol) ethanol is added to 28mL pH=4.4 second
Stir in acid and sodium acetate buffer solution, at 10 DEG C and be completely dissolved to template, 4.56g (0.04mol) trimethylpentane is added
Enter into above-mentioned solution, after stirring 8h at 10 DEG C, then 1.83g (0.012mol) tetramethoxy-silicane is added to above-mentioned solution
In, after stirring 30h at 10 DEG C, transfer the solution into the reactor of agate liner, after 80 DEG C of baking oven crystallization 20h, then carry out
Filter and be washed with deionized 6 times, then filter the filter cake A2 for the meso-porous molecular sieve material for obtaining having hollow ball-shape structure.
By the waterglass that concentration is 20 weight % and the sulfuric acid solution that concentration is 12 weight % and propane diols using weight ratio as
4：1：1 is mixed and the haptoreaction 3h at 40 DEG C, then adjusts pH value to 4 with the sulfuric acid that concentration is 98 weight %, then
Obtained reaction mass is filtered, and it is 0.02 weight % to be washed with distilled water to sodium ions content, obtains the filter of silica gel
Cake B2.
10g filter cake A2,5g filter cake B2 and 0.2g polyvinyl alcohol of above-mentioned preparation is put into 100mL ball grinder together,
Wherein, the material of ball grinder is agate, and Material quality of grinding balls is agate, and a diameter of 3mm of abrading-ball, quantity is 1, rotating speed 500r/
min.Ball grinder is closed, temperature is ball milling 10h at 30 DEG C in ball grinder, obtains solid powder；The solid powder is dissolved in
In 100g deionized waters, at 150 DEG C in rotating speed be 13000r/min under be spray-dried；The product obtained after spray drying is existed
15h is calcined in Muffle furnace at 600 DEG C, removing P123 (template), obtains spherical composite C2.
Spherical composite C2 pore structure parameter is as shown in table 2 below.
Table 2
*：First most probable pore size and the second most probable pore size are separated with comma：It is the first most probable pore size before comma,
It is the second most probable pore size after comma.
(2) catalyst is prepared
0.1g magnesium chlorides and 0.2g titanium tetrachlorides are dissolved in (four in 10mL tetrahydrofuran and the double solvents of isopropanol
The volume ratio of hydrogen furans and isopropanol is 1：1.5) catalyst mother liquor, is formed.At 60 DEG C, the spherical composite C2 of 1g are added
1h is impregnated into mother liquor, is then filtered, and washing 4 times is carried out with n-hexane, in 75 DEG C of dryings, and is ground, is catalyzed
Agent D2.
Drawn by xrf analysis, in the catalyst D2 described in the present embodiment, in terms of element, the content of magnesium elements is 4.0
Weight %, the content of titanium elements is 1.2 weight %.
(3) vinyl polymerization
In 2L stainless steel polymerization autoclave, with nitrogen and ethene, respectively displacement three times, then adds 200mL hexanes, will
Kettle temperature rises to 75 DEG C, adds 900mL hexanes, and with the addition of hexane, the concentration for adding 2mL is 1mol/L triethyl aluminum
(TEA) hexane solution, 0.1g catalytic component D2 is subsequently added into, is passed through ethylene gas, pressure is risen into 1MPa and maintained
For 1MPa, separation is filtered after being reacted 1.5 hours at 75 DEG C, obtains polyethylene particle powder.The heap of gained polyethylene particle powder
Density (BD) is 0.38g/mL, melt index MI2.16=0.45g/10min, flour rate are less than 3%.It is computed determining, catalyst
Efficiency be 2100g PE/gcath.
Embodiment 3
The present embodiment is used to illustrate ethene polymerization method provided by the invention.
(1) spherical composite is prepared
1g (0.00017mol) template P123 and 3.13g (0.068mol) ethanol is added to 28mL pH=4.4's
In acetic acid and sodium acetate buffer solution, stirring to template is completely dissolved at 20 DEG C, by 7.75g (0.068mol) trimethylpentane
It is added in above-mentioned solution, after stirring 8h at 20 DEG C, then 3.8g (0.025mol) tetramethoxy-silicane is added to above-mentioned solution
In, after stirring 10h at 20 DEG C, transfer the solution into the reactor of agate liner, after 40 DEG C of baking oven crystallization 30h, then carry out
Filter and be washed with deionized 6 times, then filter the filter cake A3 for the meso-porous molecular sieve material for obtaining having hollow ball-shape structure.
By the waterglass that concentration is 10 weight % and the sulfuric acid solution that concentration is 12 weight % and ethylene glycol using weight ratio as
3：1：1 is mixed and the haptoreaction 1h at 45 DEG C, then adjusts pH value to 2 with the sulfuric acid that concentration is 98 weight %, then
Obtained reaction mass is filtered, and it is 0.02 weight % to be washed with distilled water to sodium ions content, obtains the filter of silica gel
Cake B3.
10g filter cake A3,20g filter cake B3 and 0.8g polyethylene glycol of above-mentioned preparation is put into 100mL ball grinder together,
Wherein, the material of ball grinder is agate, and Material quality of grinding balls is agate, and a diameter of 3mm of abrading-ball, quantity is 1, rotating speed 300r/
min.Ball grinder is closed, temperature is ball milling 20h at 50 DEG C in ball grinder, obtains solid powder；The solid powder is dissolved in
In 50g deionized waters, at 250 DEG C in rotating speed be 11000r/min under be spray-dried；The product obtained after spray drying is existed
24h is calcined in Muffle furnace at 400 DEG C, removing P123 (template), obtains spherical composite C3.
Spherical composite C3 pore structure parameter is as shown in table 3 below.
Table 3
*：First most probable pore size and the second most probable pore size are separated with comma：It is the first most probable pore size before comma,
It is the second most probable pore size after comma.
(2) catalyst is prepared
0.2g magnesium chlorides and 0.1g titanium tetrachlorides are dissolved in (four in 10mL tetrahydrofuran and the double solvents of isopropanol
The volume ratio of hydrogen furans and isopropanol is 1：1) catalyst mother liquor, is formed.The spherical composite C3 of 1g are added at 40 DEG C
3h is impregnated in mother liquor, is then filtered, and washing 4 times is carried out with n-hexane, in 75 DEG C of dryings, and is ground, obtains catalyst
D3。
Drawn by xrf analysis, in the catalyst D3 described in the present embodiment, in terms of element, the content of magnesium elements is 3.6
Weight %, the content of titanium elements is 1.2 weight %.
(3) vinyl polymerization
In 2L stainless steel polymerization autoclave, with nitrogen and ethene, respectively displacement three times, then adds 200mL hexanes, will
Kettle temperature rises to 85 DEG C, adds 700mL hexanes, and with the addition of hexane, the concentration for adding 2mL is 1mol/L triethyl aluminum
(TEA) hexane solution, 1g catalytic component D3 is subsequently added into, is passed through ethylene gas, pressure is risen into 1MPa and is maintained
1MPa, separation is filtered after being reacted 2 hours at 85 DEG C, obtains polyethylene particle powder.The heap density of gained polyethylene particle powder
(BD) it is 0.4g/mL, melt index MI2.16=0.5g/10min, flour rate are less than 3%.It is computed determining, the efficiency of catalyst
For 2200g PE/gcath.
Embodiment 4
The present embodiment is used to illustrate ethene polymerization method provided by the invention.
Spherical composite and catalyst are prepared according to method same as Example 1, wherein except that, in step
(1) prepare in spherical composite material, during the filter cake of silica gel is prepared, do not add glycerine, obtain spherical compound
Material C 4 and catalyst D4.
Spherical composite C4 pore structure parameter is as shown in table 4 below.
Table 4
*：First most probable pore size and the second most probable pore size are separated with comma：It is the first most probable pore size before comma,
It is the second most probable pore size after comma.
Drawn by xrf analysis, in the catalyst D4 described in the present embodiment, in terms of element, the content of magnesium elements is 3.7
Weight %, the content of titanium elements is 1.0 weight %.
Vinyl polymerization is carried out according to the method for the step of embodiment 1 (3), except that, using the catalysis of identical weight part
Agent D4 replaces the catalyst D1 being prepared by embodiment 1.The heap density (BD) of gained polyethylene particle powder is 0.41g/mL,
Melt index MI2.16=0.44g/10min, flour rate are less than 3%.It is computed determining, the efficiency of catalyst is 1889g PE/
gcat·h。
It is can be seen that from the result of above example 1-4 and comparative example 1-2 contrasts by spherical composite wood provided by the invention
When material and loaded catalyst are used for ethylene polymerization, catalyst has higher catalytic activity, and it is close to obtain heap
Degree and the relatively low and non-breakable polyethylene product of melt index, specifically, the heap density of the polyethylene product of preparation is
Below 0.41g/mL, melt index are below 0.5g/10min, break powder rate and are less than 3%.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (16)
1. a kind of method of vinyl polymerization, this method include：Under the polymerization conditions, in the presence of a catalyst, enter ethene
Row polymerisation, it is characterised in that the catalyst contains spherical composite and is supported on the spherical composite
Magnesium salts and/or titanium salt, wherein, the spherical composite contains meso-porous molecular sieve material and silicon with hollow ball-shape structure
Glue, the pore volume of the spherical composite is 0.5-1.8mL/g, specific surface area 100-650m2/ g, average grain diameter 20-
60 μm, aperture is in bimodal distribution, and it is bimodal correspond to the first most probable pore size and the second most probable pore size respectively, described first most may be used
Several apertures are less than second most probable pore size, and first most probable pore size is 1-10nm, second most probable pore size
For 10-50nm.
2. the method according to claim 11, wherein, on the basis of the gross weight of the catalyst, the spherical composite wood
The content of material is 90-99 weight %, and the magnesium salts and titanium salt are respectively using the content sum that magnesium elements and titanium elements are counted as 1-10 weights
Measure %.
3. according to the method for claim 1, wherein, the preparation method of the catalyst includes：In the presence of an inert gas,
Spherical composite is impregnated in the mother liquor containing magnesium salts and/or titanium salt, is then filtered and is spray-dried successively；
Preferably, the condition of the dipping includes：Temperature is 25-100 DEG C, time 0.1-5h.
4. the method according to claim 11, wherein, relative to Jie described in 100 parts by weight with hollow ball-shape structure
Porous molecular sieve material, the content of the silica gel is 1-200 parts by weight；Preferably, the content of the silica gel is 50-200 parts by weight.
5. according to the method for claim 1, wherein, the preparation method of the spherical composite comprises the following steps：
(1) meso-porous molecular sieve material with hollow ball-shape structure is provided or prepares the mesoporous molecular with hollow ball-shape structure
The filter cake of material is sieved, as component a；
(2) provide silica gel or prepare the filter cake of silica gel, as component b；
(3) by the component a, the component b and binding agent is mixed and ball milling, and the solid powder obtained after ball milling is used
Water slurrying, then obtained slurry is spray-dried.
6. the method according to claim 11, wherein, relative to the component a of 100 parts by weight, the dosage of the component b
For 1-200 parts by weight, the dosage of the binding agent is 1-10 parts by weight；Preferably, the dosage of the component b is 50-200 weight
Part, the dosage of the binding agent is 2-8 parts by weight；
It is highly preferred that the binding agent is polyvinyl alcohol and/or polyethylene glycol, most preferably polyvinyl alcohol.
7. according to the method for claim 5, wherein, in step (1), prepare the mesoporous molecular with hollow ball-shape structure
Sieving the process of the filter cake of material includes：In acidic aqueous solution, in the presence of trimethylpentane and ethanol, by template and silicon
Source is contacted, and the mixture obtained after contact is carried out into crystallization and filtering.
8. according to the method for claim 7, wherein, template, ethanol, the mol ratio of trimethylpentane and silicon source are 1：
100-500：200-500：50-200, preferably 1：180-400：250-400：70-150；
Preferably, the template is triblock copolymer polyethylene glycol glycerine-polyethylene glycol；The silicon source is tetramethyl
TMOS；The acidic aqueous solution is the acetic acid and sodium acetate buffer solution that pH value is 1-6；
Preferably, the condition of the contact includes：Temperature is 10-60 DEG C, and the time is 10-72 hours, pH value 1-7；The crystalline substance
The condition of change includes：Temperature is 30-150 DEG C, and the time is 10-72 hours.
9. according to the method for claim 5, wherein, in step (2), preparing the process of the filter cake of silica gel includes：In nothing
In the presence of machine acid, waterglass is contacted with polyalcohol, and the mixture obtained after contact is filtered.
10. according to the method for claim 9, wherein, in step (2), the polyalcohol is ethylene glycol, propane diols and third
At least one of triol, preferably ethylene glycol and/or glycerine；It is highly preferred that the waterglass, inorganic acid and polyalcohol
Weight ratio is 3-6：2-3：1.
11. according to the method for claim 9, wherein, in step (2), the condition of the contact includes：Temperature is 10-
60 DEG C, the time is 1-5 hours, pH value 2-4；The inorganic acid is at least one of sulfuric acid, nitric acid and hydrochloric acid.
12. according to the method for claim 5, wherein, in step (3), the condition of the ball milling includes：The rotating speed of abrading-ball
For 300-500r/min, the temperature in ball grinder is 15-100 DEG C, and the time of ball milling is 0.1-100 hours；The spray drying
Condition include：150-600 DEG C of temperature, rotating speed 10000-15000r/min.
13. according to the method for claim 5, wherein, the component a is the mesopore molecular sieve material with hollow ball-shape structure
The filter cake of material, the component b are the filter cake of silica gel, and methods described also includes：After the spray-drying process of step (3), from
It is spray-dried removed template method in obtained product；Preferably, the condition of the removed template method includes：Temperature is 90-600
DEG C, the time is 10-80 hours.
14. according to the method for claim 1, wherein, the polymerisation is carried out in the presence of an inert gas, the polymerization
The condition of reaction includes：Temperature is 10-100 DEG C, time 0.5-5h, pressure 0.1-2MPa；Preferably, temperature 20-95
DEG C, time 1-4h, pressure 0.5-1.5MPa.
15. according to the method for claim 1, wherein, this method includes：Under the polymerization conditions, catalyst and helping
In the presence of agent, ethene is set to carry out polymerisation；Preferably, the auxiliary agent is alkyl aluminum compound；It is highly preferred that the auxiliary agent with
The mass ratio of catalyst amount is 1：0.1-10.
16. the polyethylene being prepared as the method described in any one in claim 1-15.
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| US7691773B2 (en) * | 2004-03-23 | 2010-04-06 | Samsung Sdi Co., Ltd. | Supported catalyst and method for preparing the same |
| CN105175586A (en) * | 2014-06-13 | 2015-12-23 | 中国石油化工股份有限公司 | Meso-porous composite material, preparation method thereof, catalyst ingredient preparation method, and polyethylene preparation method |
| CN105330768A (en) * | 2014-06-13 | 2016-02-17 | 中国石油化工股份有限公司 | Supported polyethylene catalyst ingredient and preparation method thereof, and supported polyethylene catalyst and application thereof |
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|---|---|---|---|---|
| US7691773B2 (en) * | 2004-03-23 | 2010-04-06 | Samsung Sdi Co., Ltd. | Supported catalyst and method for preparing the same |
| CN105175586A (en) * | 2014-06-13 | 2015-12-23 | 中国石油化工股份有限公司 | Meso-porous composite material, preparation method thereof, catalyst ingredient preparation method, and polyethylene preparation method |
| CN105330768A (en) * | 2014-06-13 | 2016-02-17 | 中国石油化工股份有限公司 | Supported polyethylene catalyst ingredient and preparation method thereof, and supported polyethylene catalyst and application thereof |
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| WO2020083386A1 (en) * | 2018-10-26 | 2020-04-30 | 中国石油化工股份有限公司 | Polyolefin catalyst component containing mesoporous material, preparation method therefor and use thereof |
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