CN108017741A - 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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- CN108017741A CN108017741A CN201610944818.8A CN201610944818A CN108017741A CN 108017741 A CN108017741 A CN 108017741A CN 201610944818 A CN201610944818 A CN 201610944818A CN 108017741 A CN108017741 A CN 108017741A
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- ball milling
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- spherical mesoporous
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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
- C08F110/02—Ethene
Abstract
The present invention relates to polymerisation field, disclose a kind of method of vinyl polymerization, under the polymerization conditions, in the presence of a catalyst, ethene is set to carry out polymerisation, wherein, the catalyst contains spherical mesoporous composite material and the magnesium salts and/or titanium salt that are supported on the spherical mesoporous composite material, wherein, the spherical mesoporous composite material contains the meso-porous molecular sieve material with one-dimensional hollow ball-shape pore passage structure.The loaded catalyst that a kind of meso-hole structure is stablized is the method use, heap density and the relatively low and non-breakable polyethylene product of melt index can be obtained.
Description
Technical field
The present invention relates to polymerisation field, and in particular, to a kind of method of vinyl polymerization and is prepared into by this method
The polyethylene arrived.
Background technology
Since the regular mesoporous material of Mobile companies synthesis duct high-sequential in 1992, since it is with 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, which 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, the separation of catalyst and product easy to implement.
But conventional ordered mesoporous material SBA-15 microscopic appearances are bar-shaped, itself mobility is poor, its big ratio
Surface area and high pore volume cause to make it have stronger water suction, moisture absorption ability, this has been further exacerbated by the group of ordered mesoporous material
It is poly-, limit the storage of ordered mesoporous material, transport, post-processing and application.
The development and application of polyethylene catalysts are the olefinic polymerization catalysis after traditional Ziegler-Natta catalyst
The another important breakthrough in agent field, this causes the research of polyethylene catalysts to enter the stage of a fast development.Due to
Homogeneous polyethylene catalyst reach needed for high activity catalyst amount is big, production cost is high, and obtained polymer is without grain
Shape, can not use on widely used slurry process or gas phase polymerization technique.The effective way for overcoming the above problem is exactly handle
Soluble poly catalyst for ethylene carries out supported processing.At present, the supported research report of related polyethylene catalysts is very more.For
Further investigate new support/catalyst/co-catalyst system, it is necessary to study different carriers, with promote carried catalyst and
The further development of polyolefin industry.
The mesoporous material for the load polyethylene catalysts reported at present on document is MCM-41, is loaded again after being handled with MAO
Catalytic activity is 10 after the MCM-41 of polyethylene catalysts carries out vinyl polymerization6gPE/(mol Zr h).Mesoporous silica MCM 41
Hole wall structure heat endurance and the hydro-thermal that the reason for ethylene polymerization activity is relatively low mainly MCM-41 is carried out after supported catalyst are steady
It is qualitative poor, just there is part to cave in loading process hole wall, load effect is have impact on, so that have impact on catalytic activity.
Therefore, it is necessary to seek the mesoporous material that a kind of meso-hole structure is stablized, can still be kept after load active component
Orderly meso-hole structure and the loaded catalyst with higher catalytic activity, improve the performance of polyethylene product.
The content of the invention
The defects of the purpose of the present invention is overcoming the prior art, there is provided the method and polyethylene of a kind of vinyl polymerization, the party
Method has used the loaded catalyst that a kind of meso-hole structure is stablized, and can obtain heap density and melt index is relatively low and non-breakable
Polyethylene product.
In order to realize foregoing invention purpose, the present invention provides a kind of method of vinyl polymerization, under the polymerization conditions,
In the presence of a catalyst, ethene is made to carry out polymerisation, wherein, the catalyst contains spherical mesoporous composite material and is supported on
Magnesium salts and/or titanium salt on the spherical mesoporous composite material, wherein, the spherical mesoporous composite material contains with one-dimensional sky
The meso-porous molecular sieve material of bulbus cordis shape pore passage structure, the average grain diameter of the spherical mesoporous composite material is 21-29 microns, compares table
Area is 100-650 meters squared per grams, and pore volume is 0.5-1.8 mls/g, and aperture be in tri-modal distribution, and three peaks respectively corresponding the
One most probable pore size, the second most probable pore size and the 3rd most probable pore size, and first most probable pore size is 1-10 nanometers, institute
The second most probable pore size is stated as 20-50 nanometers, the 3rd most probable pore size is 55-65 nanometers.
Present invention also offers the polyethylene being prepared by the above method.
Present invention employs the Cyclone Separation Technology in secondary ball milling technology and spray drying technology, secondary ball milling technology makes
Obtained slurry is finer and smoother, the spheroidal particle stable structure obtained after being spray-dried, can be with as catalyst carrier
To recycle, intensity height is non-breakable, and the preparation of the spherical mesoporous composite material of the present invention need not use binding agent, this
Sample can be destroyed to avoid the structure of the sample during high temperature removal binding agent.Using Cyclone Separation Technology, obtain
Spherical mesoporous composite material particle diameter it is small, particle diameter distribution is uniform and grading curve is narrow, can be to avoid in use
The reunion of ordered mesoporous material, improves its mobility, storage to ordered mesoporous material, transport, post-processing and application are brought
It is convenient.
In addition, the meso-hole structure of spherical mesoporous composite material provided by the invention is stablized, after load active component still
Orderly meso-hole structure can be kept, the loaded catalyst good fluidity that will be prepared by it.By the loaded catalyst
During for ethylene polymerization, heap density and the relatively low and non-breakable polyethylene product of melt index can be obtained, specifically,
The heap density of the polyethylene product of preparation is below 0.5g/mL, and melt index is below 0.5g/10min, and flour rate is less than 3 weights
Measure %.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Attached 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 diffraction pattern (XRD spectra) of the spherical mesoporous composite material in embodiment 1, and abscissa is 2 θ, is indulged
Coordinate is intensity；
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of the spherical mesoporous composite material microscopic appearance in embodiment 1；
Fig. 3 is the size distribution curve of the spherical mesoporous composite material in embodiment 1；
Fig. 4 is the graph of pore diameter distribution of the spherical mesoporous composite material in embodiment 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 endpoint 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 a 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 present 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, wherein, the catalyst contains spherical mesoporous composite material and is supported on spherical Jie
Magnesium salts and/or titanium salt on hole composite material, wherein, the spherical mesoporous composite material contains with one-dimensional hollow ball-shape duct
The meso-porous molecular sieve material of structure, the average grain diameter of the spherical mesoporous composite material is 21-29 microns, specific surface area 100-
650 meters squared per grams, pore volume are 0.5-1.8 mls/g, and aperture is in tri-modal distribution, and three peaks correspond to the first most probable hole respectively
Footpath, the second most probable pore size and the 3rd most probable pore size, and first most probable pore size is 1-10 nanometers, described second most may be used
Several apertures are 20-50 nanometers, and the 3rd most probable pore size is 55-65 nanometers.
A kind of preferred embodiment according to the present invention, the average grain diameter of the spherical mesoporous composite material is 22-28
Micron, specific surface area are 250-350 meters squared per grams, and pore volume is 1-1.5 mls/g, and aperture is in tri-modal distribution, and three peaks divide
Dui Ying not 56-64 nanometers of 2-9 nanometers of the first most probable pore size, 30-50 nanometers of the second most probable pore size and the 3rd most probable pore size.
A kind of preferred embodiment according to the present invention, the average grain diameter of the spherical mesoporous composite material is 23-
27 microns, specific surface area is 275-300 meters squared per grams, and pore volume is 1.1-1.4 mls/g, and aperture is in tri-modal distribution, and three
Peak corresponds to 3-7 nanometers of the first most probable pore size, 35-45 nanometers of the second most probable pore size and the 3rd most probable pore size 57-63 respectively
Nanometer.
In the present invention, the average grain diameter of the spherical mesoporous composite material is measured using laser fineness gage, compares table
Area, pore volume and most probable pore size are measured according to nitrogen adsorption methods, and the surface topography of the spherical mesoporous composite material passes through
Scanning electron microscope instrument (SEM) measures.In the present invention, the average grain diameter is average particulate diameter.
According to the present invention, in the catalyst, the spherical mesoporous composite material and it is supported on the spherical mesoporous and answers
There is no particular limitation for the content of magnesium salts and/or titanium salt on condensation material, can be according to the loaded catalyst of this area routine
It is determined.For example, on the basis of the gross weight of the catalyst, the content of the spherical mesoporous composite material can be 90-
99 weight %, the sum of content in terms of magnesium elements and titanium elements can be 1-10 weight % respectively for the magnesium salts and titanium salt.It is preferred that
Ground, the content of the spherical mesoporous composite material is 90.5-98.5 weight %, and the magnesium salts and titanium salt are respectively with magnesium elements and titanium
The sum of content of element meter can be 1.5-9.5 weight %.It is highly preferred that the content of the spherical mesoporous composite material is 91-
96 weight %, the sum of content in terms of magnesium elements and titanium elements is 4-9 weight % respectively for the magnesium salts and titanium salt.
In the present invention, there is no particular limitation for the species of the magnesium salts and titanium salt, can be the conventional selection of this area.
For example, the magnesium salts can be the one or more in magnesium chloride, magnesium sulfate, magnesium nitrate and magnesium bromide, it is preferably magnesium chloride；Institute
It can be titanium tetrachloride and/or titanium trichloride to state titanium salt.
In the present invention, the content of each element can use X-ray fluorescence spectra analytic approach to survey in the catalytic component
.
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 mesoporous composite material.
In situations where it is preferred, the preparation method of the catalyst can include：In the presence of an inert gas, by spherical Jie
Hole composite material is contacted with the mother liquor containing magnesium salts and/or titanium salt.
Preferably, the condition of the contact includes：Temperature is 25-100 DEG C, is preferably 40-60 DEG C；Time is 0.1-5h,
Preferably 1-3h.
The mother liquor containing magnesium salts and/or titanium salt can be the organic solvent containing magnesium salts and/or titanium salt, described organic
Solvent can be isopropanol and tetrahydrofuran, and the volume ratio of tetrahydrofuran and isopropanol can be 1：1-3, is preferably 1：1-
1.5。
In the preparation process of the catalyst, the dosage of the magnesium salts and/or the titanium salt is preferably relative to spherical
Mesoporous composite material is excessive.It is highly preferred that the magnesium salts, the titanium salt and the dosage of the spherical mesoporous composite material to make
In standby obtained loaded catalyst, on the basis of the gross weight of the catalyst, the magnesium salts and titanium salt are respectively with magnesium elements
Can be 1-10 weight % with the sum of the content of titanium elements meter, the content of the spherical mesoporous composite material can be 90-99 weights
Measure %.Preferably, the sum of content in terms of magnesium elements and titanium elements is 1.5-9.5 weight % respectively for the magnesium salts and titanium salt, institute
The content for stating spherical mesoporous composite material is 90.5-98.5 weight %.It is highly preferred that the magnesium salts and titanium salt are respectively with magnesium elements
It is 4-9 weight % with the sum of the content of titanium elements meter, the content of the spherical mesoporous composite material is 91-96 weight %.
In a kind of preferred embodiment of the present invention, the dosage weight ratio of the magnesium salts and titanium salt can be 1：0.1-
2, it is preferably 1：0.5-2.
In the present invention, the preparation method of the catalyst further includes：Spherical mesoporous composite material with containing magnesium salts and/
Or after the mother liquor contact of titanium salt, the composite material for being loaded with magnesium salts and/or titanium salt is filtered and dried.The drying
Condition has no particular limits, and can be the conventional drying mode and condition of this area.It is preferred that the preparation of the catalyst is also
Including washing process after filtration and before the drying, and/or process of lapping after drying.Those skilled in the art
The condition of the washing and grinding can be made choice according to practice situation, details are not described herein.
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 the nitrogen or the periodic table of elements of domain routine, is preferably nitrogen.
In the present invention, the spherical mesoporous composite material does not contain binding agent such as polyvinyl alcohol or polyethylene glycol etc..
In the present invention, the spherical mesoporous composite material can also contain the silica introduced by silica gel." pass through
The silica that silica gel is introduced into " refers in the preparation process of the spherical mesoporous composite material, by silica gel as preparing raw material
Bring the silica component in the spherical mesoporous composite material finally prepared into.In the spherical mesoporous composite material, relatively
In described in 100 parts by weight have one-dimensional hollow ball-shape pore passage structure meso-porous molecular sieve material, it is described by silica gel introduce
The content of silica can be 1-200 parts by weight, be preferably 20-180 parts by weight, more preferably 50-150 parts by weight.
According to the present invention, the spherical mesoporous composite material can be prepared by method comprising the following steps：
(1) meso-porous molecular sieve material with one-dimensional hollow ball-shape pore passage structure is provided or is prepared with one-dimensional hollow ball
The filter cake of the meso-porous molecular sieve material of shape pore passage structure, as component a；
(2) provide silica gel or prepare the filter cake of silica gel, as component b；
(3) the component a and the component b are subjected to mixing and the first ball milling, the first ball milling slurry and water that will be obtained
Mixed pulp, then carries out the second ball milling and obtains the second ball milling slurry, used after the second ball milling slurry is spray-dried
Cyclone Separation Technology is screened；
Wherein, above-mentioned steps make it that the average grain diameter of the spherical mesoporous composite material is 21-29 microns, and specific surface area is
100-650 meters squared per grams, pore volume are 0.5-1.8 mls/g, and aperture is in tri-modal distribution, and three peaks correspond to first and most may be used respectively
Several apertures, the second most probable pore size and the 3rd most probable pore size, and first most probable pore size be 1-10 nanometers, described second
Most probable pore size is 20-50 nanometers, and the 3rd most probable pore size is 55-65 nanometers.
A kind of preferred embodiment according to the present invention, the average grain diameter of the spherical mesoporous composite material is 22-28
Micron, specific surface area are 250-350 meters squared per grams, and pore volume is 1-1.5 mls/g, and aperture is in tri-modal distribution, and three peaks divide
Dui Ying not 56-64 nanometers of 2-9 nanometers of the first most probable pore size, 30-50 nanometers of the second most probable pore size and the 3rd most probable pore size.
A kind of preferred embodiment according to the present invention, the average grain diameter of the spherical mesoporous composite material is 23-
27 microns, specific surface area is 275-300 meters squared per grams, and pore volume is 1.1-1.4 mls/g, and aperture is in tri-modal distribution, and three
Peak corresponds to 3-7 nanometers of the first most probable pore size, 35-45 nanometers of the second most probable pore size and the 3rd most probable pore size 57-63 respectively
Nanometer.
In the present invention, by the way that the particle size of spherical mesoporous composite material is controlled within the above range, it can be ensured that
The spherical mesoporous composite material is not susceptible to reunite, and is used as loaded catalyst made of carrier and can improve second
Reaction raw materials conversion ratio in alkene polymerization process.
In the preparation process of above-mentioned spherical mesoporous composite material, mainly by control mesoporous material filter cake (component a's)
Composition, is tri-modal distribution by the pore-size distribution control of the spherical mesoporous composite material, and mainly by controlling forming method
(that is, the component a and the component b are first subjected to mixing and the first ball milling, the first obtained ball milling slurry is mixed into system with water
Slurry, then carries out the second ball milling and obtains the second ball milling slurry, the second ball milling slurry is spray-dried) by spherical Jie
The microscopic appearance control of hole composite material is spherical.
According to the present invention, in step (1), the meso-porous molecular sieve material with one-dimensional hollow ball-shape pore passage structure is prepared
The process of filter cake can include：Template, silicon source, ethanol, trimethylpentane and sour agent are carried out first to be mixed, and will
The mixture arrived carries out crystallization and filtering.There is no particular limitation for first order being mixed, can first by template,
Silicon source, ethanol, trimethylpentane and sour agent are carried out at the same time mixing, can also be mixed any two or three, add other
Component is uniformly mixed.Template, ethanol and sour agent, are first uniformly mixed, so by a kind of preferred embodiment according to the present invention
Trimethylpentane is added afterwards to be uniformly mixed, and is then added silicon source (preferably tetramethoxy-silicane) and is uniformly mixed.
In the present invention, the dosage of the template, ethanol, trimethylpentane and silicon source can be in interior change in a big way
It is dynamic, for example, template, ethanol, the molar ratio of trimethylpentane and silicon source can be 1：100-500：200-500：50-200, more
Preferably 1：180-400：250-400：70-150.
In the present invention, the template can be the various templates of this area routine, as long as the ball enabled to
The pore structure of shape mesoporous composite material meets the requirements.For example, the template can be triblock copolymer polyoxyethylene-
Polyoxypropylene polyoxyethylene.Wherein, which can be commercially available (for example, Aldrich, commodity can be purchased from
Entitled P123, molecular formula EO20PO70EO20, molecular weight Mn is that 5800), can also be prepared by existing various methods.
When the template is polyoxyethylene-poly-oxypropylene polyoxyethylene, the molal quantity of the template is according to polyoxyethylene-poly-
Oxypropylene-polyoxyethylated number-average molecular weight is calculated.
In the present invention, the silicon source can be various silicon sources commonly used in the art.For example, the silicon source can be
At least one in ethyl orthosilicate, methyl orthosilicate (also known as tetramethoxy-silicane), positive silicic acid propyl ester, sodium metasilicate and Ludox
Kind, it is preferably tetramethoxy-silicane.
In the present invention, the sour agent can be various acidic aqueous solutions commonly used in the art, it is preferable that the acid
Agent is the acetic acid and sodium acetate buffer solution that pH value is 1-6.There is no particular limitation for the dosage of the acid agent, can be in larger model
Enclose interior variation, it is preferable that the first pH value being mixed is 1-7.
To first condition being mixed there is no particular limitation by the present invention, for example, described first is mixed
Condition generally includes：Temperature can be 10-60 DEG C, be preferably 10-20 DEG C；It is preferably 10-30 when time can be 10-72 small
Hour；PH value can be 1-7, be preferably 3-6.It is a kind of excellent according to the present invention in order to be more advantageous to the uniform mixing between each material
The embodiment of choosing, described first is mixed and carries out under agitation.
In the present invention, the condition of the crystallization includes：Temperature can be 30-150 DEG C, be preferably 40-80 DEG C；Time can
When thinking that 10-72 is small, when being preferably 20-30 small.According to a kind of preferred embodiment, the crystallization by hydrothermal crystallization method come
Implement.
In step (1), there is the filter cake of the meso-porous molecular sieve material of one-dimensional hollow ball-shape pore passage structure in above-mentioned preparation
During, it can be included with the process for obtaining filter cake by filtering：After filtration, (washing is washed repeatedly with deionized water
Number can be 2-10), then filtered.
In step (1), " providing the meso-porous molecular sieve material with one-dimensional hollow ball-shape pore passage structure " can be direct
Weigh or choose the product of the meso-porous molecular sieve material with one-dimensional hollow ball-shape pore passage structure or prepare with one-dimensional
The meso-porous molecular sieve material of hollow ball-shape pore passage structure.The meso-porous molecular sieve material with one-dimensional hollow ball-shape pore passage structure
Preparation method can implement according to the conventional method, for example, its preparation method can include：Being prepared according to the above method has
The filter cake of the meso-porous molecular sieve material of one-dimensional hollow ball-shape pore passage structure, then by gained filtration cakes torrefaction.
According to the present invention, in step (2), preparing the process of the filter cake of silica gel can include：By waterglass, polyalcohol and
Inorganic acid carries out second and is mixed, and obtained mixture is filtered.
In the present invention, there is no particular limitation for second condition being mixed, can be according to preparing the normal of silica gel
Rule technique suitably determines.For example, second condition being mixed includes：Temperature can be 10-60 DEG C, be preferably 20-
40℃；When time can be 1-5 small, when being preferably 1-3 small；PH value is 2-4.It is uniformly mixed between each material in order to be more advantageous to
Close, second process being mixed preferably carries out under agitation.
In the present invention, the dosage of the waterglass, inorganic acid and polyalcohol can be in interior variation in a big way.For example,
The weight ratio of the waterglass, inorganic acid and polyalcohol can be 1-8：0.1-5：1, it is preferably 3-6：0.5-4：1, more preferably
3-6：1-3：1.
In the present invention, the waterglass is the aqueous solution of sodium metasilicate, its concentration can be 3-20 weight %, is 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
One or more in hydrochloric acid.The inorganic acid can use in pure form, can also be used in the form of its aqueous solution,
It is preferred that used in the form of the aqueous solution of 3-20 weight %.The dosage of the inorganic acid is preferably so that contact of the waterglass with inorganic acid
The pH value of reaction system is 2-4.
In the present invention, there is no particular limitation for the species of the polyalcohol, such as can be glycerine and/or second two
Alcohol, is preferably glycerine.
According to the present invention, in step (2), " offer silica gel " can directly weigh or choose silica gel product, can also
It is to prepare silica gel.Preparing the method for silica gel can implement according to the conventional method, such as can include：Prepared according to the above method
The filter cake of silica gel, then by gained filtration cakes torrefaction.
It is above-mentioned prepare the filter cake of silica gel during, can be included with the process for obtaining filter cake by filtering：Filtering
Afterwards, it is below 0.2 weight % to wash to the content of sodium ion, is preferably 0.01-0.03 weight %, is then filtered.Wash
The mode washed is the conventional selection of this area, can be that washing and/or alcohol are washed, actual conditions is ripe for those skilled in the art
Know, details are not described herein.
According to the present invention, in step (3), the dosage of the component a and component b can be in interior variations in a big way.Example
Such as, relative to 100 parts by weight the component a dosage, the dosage of the component b can be 1-200 parts by weight, be preferably
20-180 parts by weight, more preferably 50-150 parts by weight.
The present invention improves prepared polyethylene product to improve the intensity of the spherical mesoporous composite material
Performance, is realized using to the secondary ball milling method of slurry.
According to the present invention, in step (3), first ball milling and the second ball milling can carry out in the ball mill, described
The inner wall of ball grinder is preferably agate liner in ball mill, and the diameter of the abrading-ball in ball mill can be 2-3mm；The quantity of abrading-ball
It can reasonably be selected according to the size of ball grinder, for the ball grinder that size is 50-150mL, can usually use 1
Abrading-ball；The material of the abrading-ball can be agate, polytetrafluoroethylene (PTFE) etc., be preferably agate.First ball milling and the second ball milling
Condition can be identical or different, the condition of first ball milling and the second ball milling includes independently of one another：The rotating speed of abrading-ball can
Think 200-800r/min, the temperature in ball grinder can be 15-100 DEG C, and the time of ball milling can be 0.1-100h；It is preferred that
Ground, the rotating speed of abrading-ball are 300-500r/min, and the temperature in ball grinder is 25-50 DEG C, and the time of ball milling is 5-20h.
According to the present invention, in step (3), the temperature by obtained the first ball milling slurry and water mixed pulp can be
25-60 DEG C, the weight ratio of the dosage of the first ball milling slurry and water can be 1：0.1-5, is preferably 1：0.5-3.5.
According to the present invention, in step (3), the spray drying can be implemented according to conventional mode, can be selected from pressure
At least one of gentle flow type spray seasoning of power spray drying process, centrifugal spray drying method.It is a kind of preferred according to the present invention
Embodiment, the spray drying uses centrifugal spray drying method.The spray drying can carry out in atomizer.It is described
The condition of spray drying can include：Temperature is 150-600 DEG C, rotating speed 10000-15000r/min；It is described under preferable case
The condition of spray drying includes：Temperature is 150-250 DEG C, and rotating rotating speed is 11000-13000r/min.
According to the present invention, the step of being screened after the second ball milling slurry is spray-dried using Cyclone Separation Technology
Including：The second ball milling slurry is spray-dried, the gas containing powder of discharge is subjected to cyclonic separation to collect
The powder.Specifically, powder contained in discharge gas is separated using Cyclone Separation Technology, the powder of recycling falls into collection powder
Cylinder, for exhaust gas by separator outlet to centrifugal blower, cyclone separator lower part is provided with butterfly valve, and when work opens butterfly valve, obtains
Sample has the particle diameter being evenly distributed.
According to the present invention, in step (3), when the component a is mesoporous point with one-dimensional hollow ball-shape pore passage structure
The filter cake of son sieve material, when the component b is the filter cake of silica gel, namely when step (1) has one-dimensional hollow ball-shape hole to prepare
The process of the filter cake of the meso-porous molecular sieve material of road structure, when step (2) is the process for the filter cake for preparing silica gel, spherical Jie
The preparation method of hole composite material can also include：After the spray-drying process of step (3), collected from by cyclonic separation
Powder in removed template method.The condition of the removed template method includes：Temperature can be 90-600 DEG C, be preferably 300-600
℃；It is preferably 10-24h when time can be 10-80 small.
According to the present invention, the condition of the polymerisation can be the condition of this area routine.For example, the polymerisation
Carry out in the presence of an inert gas, the condition of the polymerisation includes：Temperature can be 10-100 DEG C, and the time can be 0.5-
5h, pressure can be 0.1-2MPa；Preferably, temperature is 20-95 DEG C, time 1-4h, pressure 0.5-1.5MPa；Further
Preferably, temperature is 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 polymerisation can carry 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, 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 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 selection of this area routine, 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, to final reaction
Mixture carries out suction filtration separation, so that 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, polyoxyethylene-poly-oxypropylene polyoxyethylene is purchased from Fuka companies, trade name
For Synperonic F108, molecular formula PEO132-PPO50-PEO132, average molecular weight Mn=14600.
In following embodiments and comparative example, X-ray diffraction analysis are in the model purchased from German Bruker AXS companies
Carried out on the X-ray diffractometer of D8Advance；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, by sample when 200 DEG C of degassings 4 are small；X-ray fluorescence analysis is in dutch company
Carried out on the x-ray fluorescence analyzer of model Axios-Advanced；Size distribution curve is surveyed by Malvern laser particle analyzer
.
The heap density of polyolefine powder is measured using method as defined in GB/T 1636-2008.
Melt index：Measured according to ASTM D1238-99.
The flour rate of polyethylene particle powder：By 800 mesh sieve mesh screen point measure, specifically, by the polyethylene particle
For powder by 800 mesh sieves, flour rate is the weight and the polyethylene tested through the polyethylene particle powder of 800 mesh sieves
The percentage of the weight of grain powder.
Embodiment 1
The present embodiment is used for the polyethylene for illustrating the ethene polymerization method of the present invention and obtaining
(1) spherical mesoporous composite material is prepared
1g (0.00017mol) template P123 and 1.69g (0.037mol) ethanol is added to the pH=4.4's of 28mL
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 reaction kettle 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 for the meso-porous molecular sieve material for obtaining having one-dimensional hollow ball-shape pore passage structure
Cake A1.
By the waterglass that concentration is 15 weight % and the sulfuric acid solution that concentration is 12 weight % and glycerine using weight ratio as
4：1：1 is mixed and when haptoreaction 1 is small at 40 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.
The 20g filter cake A1 and 10g filter cakes B1 of above-mentioned preparation is put into togerther in the ball grinder of 100mL, wherein, ball grinder
Material 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.Close ball milling
Tank, carries out the first ball milling in ball grinder, and temperature is 25 DEG C, when the time is 5 small.By the first obtained ball milling slurry and 15g water
The mixed pulp at 25 DEG C, then carries out the second ball milling, and temperature is 25 DEG C, when the time is 5 small.The the second ball milling slurry that will be obtained
Then screened using Cyclone Separation Technology to be spray-dried under 12000r/min in rotating speed at 200 DEG C, screening is obtained
Product calcine 10h at 600 DEG C in Muffle furnace, removing P123 (template), obtains spherical mesoporous composite material C1.
Spherical mesoporous composite material C1 is characterized with XRD, scanning electron microscope and nitrogen adsorption instrument.
Fig. 1 is X-ray diffracting spectrum, and as seen from the figure, spherical mesoporous composite material C1 has one specific to mesoporous material
Tie up hollow ball-shape pore passage structure.
Fig. 2 is the microscopic appearance SEM figures of spherical mesoporous composite material C1, it can be seen from the figure that spherical mesoporous composite wood
The microscopic appearance of material C1 is microballoon that particle diameter is 21-29 μm, and its good dispersion property.
Fig. 3 is the size distribution curve of spherical mesoporous composite material C1, it can be seen from the figure that spherical mesoporous composite material
C1 has uniform size distribution.
Fig. 4 is the graph of pore diameter distribution of spherical mesoporous composite material C1, it can be seen from the figure that spherical mesoporous composite material C1
With three pore size distribution$s, and duct is uniform.
The pore structure parameter of spherical mesoporous composite material C1 is as shown in table 1 below.
Table 1
*：First most probable pore size, the second most probable pore size and the 3rd most probable pore size are separated with comma：According to by it is left extremely
Right order is the first most probable pore size, the second most probable pore size and the 3rd most probable pore size successively.
(2) catalyst is prepared
0.1g magnesium chlorides and 0.1g titanium tetrachlorides are dissolved in (four in the tetrahydrofuran of 10mL and the double solvents of isopropanol
The volume ratio of hydrogen furans and isopropanol is 1：1.2) catalyst mother liquor, is formed.By 1g spherical mesoporous composite materials C1 at 45 DEG C
It is added in mother liquor and impregnates 1h, then filter, and washing 4 times is carried out with n-hexane, in 75 DEG C of dryings, and is ground, obtains
Catalyst D1.
Drawn by x-ray fluorescence analysis, in the obtained catalyst D1 of the present embodiment, based on the element, magnesium elements
Content is 4 weight %, and the content of titanium elements is 1.0 weight %.
(3) vinyl polymerization
In the stainless steel polymerization autoclave of 2L, 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 the triethyl aluminum of 1mol/L
(TEA) hexane solution, is subsequently added into the catalytic component D1 of 0.5g, is passed through ethylene gas, pressure is risen to 1.0MPa and is tieed up
Hold as 1.0MPa, when 70 DEG C of reactions 1 are small after filter separation, obtain polyethylene particle powder.Gained polyethylene particle powder
Heap density (BD), melt index MI2.16, flour rate and catalyst efficiency be listed in Table 8 below.
Embodiment 2
The present embodiment is used for the polyethylene for illustrating the ethene polymerization method of the present invention and obtaining
(1) spherical mesoporous composite material is prepared
1g (0.00017mol) template P123 and 1.4g (0.03mol) ethanol is added to the second of the pH=4.4 of 28mL
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 reaction kettle 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 and obtain the meso-porous molecular sieve material with one-dimensional hollow ball-shape pore passage structure
Filter cake A2.
By the waterglass that concentration is 20 weight % and the sulfuric acid solution that concentration is 12 weight % and glycerine using weight ratio as
3：2：1 is mixed and the haptoreaction 3h at 20 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.
The 10g filter cake A2 and 15g filter cakes B2 of above-mentioned preparation is put into togerther in the ball grinder of 100mL, wherein, ball grinder
Material 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.Close ball milling
Tank, carries out the first ball milling in ball grinder, and temperature is 35 DEG C, when the time is 20 small.The the first ball milling slurry and 87.5g that will be obtained
Water mixed pulp at 35 DEG C, then carries out the second ball milling, and temperature is 25 DEG C, when the time is 10 small.The second ball milling that will be obtained
Slurry is to be spray-dried under 13000r/min in rotating speed at 150 DEG C, is then screened, will screened using Cyclone Separation Technology
Obtained product calcines 15h in Muffle furnace at 500 DEG C, and removing P123 (template), obtains spherical mesoporous composite material C2.
The pore structure parameter of spherical mesoporous composite material C2 is as shown in table 2 below.
Table 2
*：Separated between first most probable pore size, the second most probable pore size and the 3rd most probable pore size with comma.
(2) catalyst is prepared
0.1g magnesium chlorides and 0.2g titanium tetrachlorides are dissolved in (four in the tetrahydrofuran of 10mL 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, by 1g spherical mesoporous composite materials C2
It is added in mother liquor and impregnates 1h, then filter, and washing 4 times is carried out with n-hexane, in 75 DEG C of dryings, and is ground, obtains
Catalyst D2.
Drawn by xrf analysis, in the catalyst D2 described in the present embodiment, based on the element, the content of magnesium elements is 6.3
Weight %, the content of titanium elements is 0.7 weight %.
(3) vinyl polymerization
In the stainless steel polymerization autoclave of 2L, 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 the triethyl aluminum of 1mol/L
(TEA) hexane solution, is subsequently added into the catalytic component D2 of 0.1g, is passed through ethylene gas, pressure is risen to 1MPa and is maintained
For 1MPa, when 75 DEG C of reactions 1.5 are small after filter separation, obtain polyethylene particle powder.The heap of gained polyethylene particle powder
Density (BD), melt index MI2.16, flour rate and catalyst efficiency be listed in Table 8 below.
Embodiment 3
The present embodiment is used for the polyethylene for illustrating the ethene polymerization method of the present invention and obtaining
(1) spherical mesoporous composite material is prepared
1g (0.00017mol) template P123 and 3.13g (0.068mol) ethanol is added to the pH=4.4's of 28mL
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 reaction kettle 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 and obtain the meso-porous molecular sieve material with one-dimensional hollow ball-shape pore passage structure
Filter cake A3.
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
6：3：1 is mixed and the haptoreaction 1.5h at 30 DEG C, then adjusts pH value to 2 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 B3.
The 10g filter cake A3 and 10g filter cakes B3 of above-mentioned preparation is put into togerther in the ball grinder of 100mL, wherein, ball grinder
Material 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.Close ball milling
Tank, carries out the first ball milling in ball grinder, and temperature is 50 DEG C, when the time is 10 small.By the first obtained ball milling slurry and 40g water
The mixed pulp at 50 DEG C, then carries out the second ball milling, and temperature is 40 DEG C, when the time is 5 small.The the second ball milling slurry that will be obtained
Then screened using Cyclone Separation Technology to be spray-dried under 11000r/min in rotating speed at 250 DEG C, screening is obtained
Product calcine 24h at 300 DEG C in Muffle furnace, removing P123 (template), obtains spherical mesoporous composite material C3.
The pore structure parameter of obtained spherical mesoporous composite material C3 is as shown in table 3 below.
Table 3
*：Separated between first most probable pore size, the second most probable pore size and the 3rd most probable pore size with comma.
(2) catalyst is prepared
0.2g magnesium chlorides and 0.1g titanium tetrachlorides are dissolved in (four in the tetrahydrofuran of 10mL and the double solvents of isopropanol
The volume ratio of hydrogen furans and isopropanol is 1：1) catalyst mother liquor, is formed.1g spherical mesoporous composite materials C3 is added at 40 DEG C
Enter and 3h is impregnated into mother liquor, then filter, and washing 4 times is carried out with n-hexane, in 75 DEG C of dryings, and be ground, urged
Agent D3.
Drawn by xrf analysis, in the catalyst D3 described in the present embodiment, based on the element, the content of magnesium elements is 6.1
Weight %, the content of titanium elements is 0.8 weight %.
(3) vinyl polymerization
In the stainless steel polymerization autoclave of 2L, 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 the triethyl aluminum of 1mol/L
(TEA) hexane solution, is subsequently added into the catalytic component D3 of 1g, is passed through ethylene gas, pressure is risen to 1MPa and is maintained
1MPa, 85 DEG C reaction 2 it is small when after filter separation, obtain polyethylene particle powder.The heap density of gained polyethylene particle powder
(BD), melt index MI2.16, flour rate and catalyst efficiency be listed in Table 8 below.
Comparative example 1
This comparative example is used for the ethene polymerization method and polyethylene for illustrating reference
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 1 step of embodiment (2) prepares catalyst, the difference is that the above-mentioned work using identical weight part
The ES955 silica gel of change replaces spherical mesoporous composite material C1, so that comparative catalyst DD1 be made.
(3) vinyl polymerization
The polymerization of ethene is carried out according to the method for EXPERIMENTAL EXAMPLE 1, unlike, the contrast of identical weight part is respectively adopted
Catalyst DD1 replaces the catalyst D1 being prepared by embodiment 1.The heap density (BD) of gained polyethylene particle powder, melting
Index M I2.16, flour rate and catalyst efficiency be listed in Table 8 below.
Comparative example 2
This comparative example is used for the ethene polymerization method and polyethylene for illustrating reference
Method according to embodiment 1 prepares spherical mesoporous composite material and loaded catalyst.Unlike, only carry out the
One ball milling, without the second ball milling.Specifically, the 20g filter cake A1 and 10g filter cakes B1 of above-mentioned preparation is put into togerther 100mL's
In ball grinder.Ball grinder is closed, the first ball milling is carried out in ball grinder, temperature is 25 DEG C, when the time is 5 small.To obtain
One ball milling slurry and 87.5g water mixed pulp at 25 DEG C, by obtained slurry at 200 DEG C in rotating speed be under 12000r/min
Spray drying.Spherical mesoporous composite material DC2 and loaded catalyst DD2 is made.
The pore structure parameter of spherical mesoporous composite material DC2 is as shown in table 5 below.
Table 5
*：Separated between first most probable pore size, the second most probable pore size and the 3rd most probable pore size with comma.
Drawn by xrf analysis, in the catalyst DD2 described in this comparative example, based on the element, the content of magnesium elements is
5.6 weight %, the content of titanium elements is 0.7 weight %.
(3) vinyl polymerization
The polymerization of ethene is carried out according to the method for EXPERIMENTAL EXAMPLE 1, unlike, the catalysis of identical weight part is respectively adopted
Agent DD2 replaces the catalyst D1 being prepared by embodiment 1.Heap density (BD), the melt index of gained polyethylene particle powder
The efficiency of MI2.16, flour rate and catalyst are listed in Table 8 below.
Comparative example 3
This comparative example is used for the ethene polymerization method and polyethylene for illustrating reference
Method according to embodiment 1 prepares spherical mesoporous composite material and loaded catalyst.Unlike, rotation is not used
Wind isolation technics is screened, specifically, by the second obtained ball milling slurry at 200 DEG C in rotating speed be 12000r/min under spray
Mist is dried, and the product obtained after spray drying is then calcined 10h, removing P123 (template) in Muffle furnace at 600 DEG C,
Obtain spherical mesoporous composite material DC3 and loaded catalyst DD3.
The pore structure parameter of spherical mesoporous composite material DC3 is as shown in table 6 below.
Table 6
*：Separated between first most probable pore size, the second most probable pore size and the 3rd most probable pore size with comma.
Drawn by xrf analysis, in the catalyst DD3 described in this comparative example, based on the element, the content of magnesium elements is
4.8 weight %, the content of titanium elements is 0.9 weight %.
(3) vinyl polymerization
The polymerization of ethene is carried out according to the method for EXPERIMENTAL EXAMPLE 1, unlike, the catalysis of identical weight part is respectively adopted
Agent DD3 replaces the catalyst D1 being prepared by embodiment 1.Heap density (BD), the melt index of gained polyethylene particle powder
MI2.16, flour rate and catalyst efficiency be listed in Table 8 below.
Comparative example 4
This comparative example is used for the ethene polymerization method and polyethylene for illustrating reference
Method according to embodiment 1 prepares spherical mesoporous composite material and loaded catalyst.Unlike, only carry out the
One ball milling, without the second ball milling, does not also use Cyclone Separation Technology to be screened.Specifically, by the 20g filter cakes of above-mentioned preparation
A1 and 10g filter cakes B1 is put into togerther in the ball grinder of 100mL.Ball grinder is closed, the first ball milling is carried out in ball grinder, temperature is
25 DEG C, when the time is 5 small.By the first obtained ball milling slurry and 87.5g water mixed pulp at 25 DEG C, obtained slurry is existed
At 200 DEG C in rotating speed be 12000r/min under be spray-dried, then by the product obtained after spray drying in Muffle furnace in 600
10h is calcined at DEG C, removing P123 (template), obtains spherical mesoporous composite material DC4 and loaded catalyst DD4.
The pore structure parameter of spherical mesoporous composite material DC4 is as shown in table 7 below.
Table 7
*：Separated between first most probable pore size, the second most probable pore size and the 3rd most probable pore size with comma.
Drawn by xrf analysis, in the catalyst DD4 described in this comparative example, based on the element, the content of magnesium elements is
5.1 weight %, the content of titanium elements is 0.6 weight %.
(3) vinyl polymerization
The polymerization of ethene is carried out according to the method for EXPERIMENTAL EXAMPLE 1, unlike, the catalysis of identical weight part is respectively adopted
Agent DD4 replaces the catalyst D1 being prepared by embodiment 1.Heap density (BD), the melt index of gained polyethylene particle powder
MI2.16, flour rate and catalyst efficiency be listed in Table 8 below.
Table 8
It can be seen that from the result of above EXPERIMENTAL EXAMPLE 1-4 and Experimental comparison's example 1-4 contrasts by ball provided by the invention
When shape mesoporous composite material and loaded catalyst are used for ethylene polymerization, catalyst has higher catalytic activity, and
It can obtain heap density and the relatively low and non-breakable polyethylene product of melt index, specifically, the polyethylene product of preparation
Heap density is below 0.5g/mL, and melt index is below 0.5g/10min, and flour rate is less than 3 weight %.And not using the present invention
The obtained polyethylene product of method, flour rate is more than 5 weight %.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
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 (10)
1. a kind of method of vinyl polymerization, this method include：Under the polymerization conditions, in the presence of a catalyst, make ethene into
Row polymerisation, it is characterised in that the catalyst contains spherical mesoporous composite material and to be supported on the spherical mesoporous compound
Magnesium salts and/or titanium salt on material, wherein, the spherical mesoporous composite material contains with one-dimensional hollow ball-shape pore passage structure
Meso-porous molecular sieve material, the average grain diameter of the spherical mesoporous composite material is 21-29 microns, and specific surface area is put down for 100-650
Square rice/gram, pore volume is 0.5-1.8 mls/g, and aperture be in tri-modal distribution, and three peaks corresponding first most probable pore size, the respectively
Two most probable pore sizes and the 3rd most probable pore size, and first most probable pore size is 1-10 nanometers, the second most probable hole
Footpath is 20-50 nanometers, and the 3rd most probable pore size is 55-65 nanometers.
2. according to the method described in claim 1, wherein, on the basis of the gross weight of the catalyst, the spherical mesoporous is answered
The content of condensation material is 90-99 weight %, and the sum of content in terms of magnesium elements and titanium elements is 1- respectively for the magnesium salts and titanium salt
10 weight %.
3. according to the method described in claim 1, wherein, the preparation method of the catalyst includes, in the presence of an inert gas,
Spherical mesoporous composite material is contacted with the mother liquor containing magnesium salts and/or titanium salt；
Preferably, the condition of the contact includes：Temperature is 25-100 DEG C, time 0.1-5h.
4. according to the method described in claim 1, wherein, the spherical mesoporous composite material is by method comprising the following steps
It is prepared：
(1) meso-porous molecular sieve material with one-dimensional hollow ball-shape pore passage structure is provided or is prepared with one-dimensional hollow ball-shape hole
The filter cake of the meso-porous molecular sieve material of road structure, as component a；
(2) provide silica gel or prepare the filter cake of silica gel, as component b；
(3) the component a and the component b are subjected to mixing and the first ball milling, the first obtained ball milling slurry is mixed with water
Slurrying, then carries out the second ball milling and obtains the second ball milling slurry, whirlwind is used after the second ball milling slurry is spray-dried
Isolation technics is screened；
Wherein, above-mentioned steps make it that the average grain diameter of the spherical mesoporous composite material is 21-29 microns, specific surface area 100-
650 meters squared per grams, pore volume are 0.5-1.8 mls/g, and aperture is in tri-modal distribution, and three peaks correspond to the first most probable hole respectively
Footpath, the second most probable pore size and the 3rd most probable pore size, and first most probable pore size is 1-10 nanometers, described second most may be used
Several apertures are 20-50 nanometers, and the 3rd most probable pore size is 55-65 nanometers.
5. according to the method described in claim 4, wherein, in step (3), relative to the use of the component a of 100 parts by weight
Amount, the dosage of the component b is 1-200 parts by weight, is preferably 20-180 parts by weight, more preferably 50-150 parts by weight.
6. according to the method described in claim 4, wherein, in step (1), prepare with one-dimensional hollow ball-shape pore passage structure
The process of the filter cake of meso-porous molecular sieve material includes：Template, silicon source, ethanol, trimethylpentane and sour agent are carried out first to mix
Splice grafting touches, and obtained mixture is carried out crystallization and filtering；
Preferably, the template is triblock copolymer polyethylene glycol glycerine-polyethylene glycol；The silicon source is tetramethyl
Oxysilane；The acid agent is the acetic acid and sodium acetate buffer solution that pH value is 1-6；
Preferably, the molar ratio of template, ethanol, trimethylpentane and silicon source is 1：100-500：200-500：50-200, more
Preferably 1：180-400：250-400：70-150；
Preferably, first condition being mixed includes：Temperature is 10-60 DEG C, when the time is 10-72 small, pH value 1-
7；The condition of the crystallization includes：Temperature is 30-150 DEG C, when the time is 10-72 small；
Preferably, in step (2), preparing the process of the filter cake of silica gel includes：Waterglass, polyalcohol and inorganic acid are carried out the
Two are mixed, and obtained mixture is filtered；
Preferably, second condition being mixed includes：Temperature is 10-60 DEG C, when the time is 1-5 small, pH value 2-4；
Preferably, the weight ratio of the waterglass, inorganic acid and polyalcohol is 1-8：0.1-5：1；The inorganic acid is sulfuric acid, nitre
One or more in acid and hydrochloric acid；The polyalcohol is glycerine and/or ethylene glycol.
7. according to the method described in any one in claim 4-6, wherein, in step (3), first ball milling and second
The condition of ball milling is identical or different, and the condition of first ball milling and the second ball milling includes independently of one another：The rotating speed of abrading-ball is
200-800r/min, the temperature in ball grinder are 15-100 DEG C, time of ball milling for 0.1-100 it is small when；
Preferably, the weight ratio of the dosage of the first ball milling slurry and water is 1：0.1-5, the first ball milling slurry and water mixed pulp
Temperature is 25-60 DEG C；
Preferably, the condition of the spray drying includes：Temperature is 150-600 DEG C, rotating speed 10000-15000r/min.
8. method according to claim 4 or 5, wherein, using whirlwind point after the second ball milling slurry is spray-dried
The step of being screened from technology includes：The second ball milling slurry is spray-dried, by the gas containing powder of discharge
Body carries out cyclonic separation to collect the powder；
Preferably, the component a be the meso-porous molecular sieve material with one-dimensional hollow ball-shape pore passage structure filter cake, the component
B is the filter cake of silica gel；The method further includes：After the spray-drying process of step (3), from what is collected by cyclonic separation
Removed template method in powder；
Preferably, the condition of the removed template method includes：Temperature is 90-600 DEG C, when the time is 10-80 small.
9. according to the method described in claim 1, wherein, the polymerisation carries 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.
10. the polyethylene being prepared as the method described in any one in claim 1-9.
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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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| CN108017741B (en) | 2020-04-07 |
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