CN104558281B - It is a kind of for ball type carrier of olefin polymerization catalysis and preparation method thereof - Google Patents
It is a kind of for ball type carrier of olefin polymerization catalysis and preparation method thereof Download PDFInfo
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- CN104558281B CN104558281B CN201310491393.6A CN201310491393A CN104558281B CN 104558281 B CN104558281 B CN 104558281B CN 201310491393 A CN201310491393 A CN 201310491393A CN 104558281 B CN104558281 B CN 104558281B
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- NLOCCOZBLHQKRI-UHFFFAOYSA-N CCCC(CC)C[ClH]C Chemical compound CCCC(CC)C[ClH]C NLOCCOZBLHQKRI-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to a kind of for ball type carrier of olefin polymerization catalysis and preparation method thereof.It the described method comprises the following steps：（1）In the presence of at least one macromolecular dispersion stabilizer, by magnesium halide and the organic compound reaction containing active hydrogen to form complex solution；（2）The complex solution and alkylene oxides compound are reacted, solid particle is separated out；（3）Reclaim the solid particle and obtain ball type carrier.When being used for propylene polymerization by catalyst prepared by ball type carrier of the present invention, with compared with high polymerization activity and higher stereotaxis ability.
Description
Technical field
Prepared the present invention relates to a kind of preparation method of the ball type carrier for olefin polymerization catalysis, and by this method
Ball type carrier.
Background technology
Catalyst for olefinic polymerization is obtained by the way that halogenated titanium is loaded on inactive anhydrous magnesium chloride mostly.Its
In, it is by anhydrous MgCl for a kind of common method for preparing active magnesium chloride2React to form formula for MgCl with alcohol2·
mROH·nH2O magnesium dichloride-alcohol adducts, then prepare olefin polymerization catalysis with this adduct load halogenated titanium again and consolidate
Body component.Such alcohol adduct can be prepared by methods such as spray drying, misting cooling, high pressure extrusion or high-speed stirreds.Such as：
US4421674、US4469648、WO8707620、WO9311166、US5100849、US6020279、US4399054、
Chlorination magnesium alcoholate disclosed in EP0395383, US6127304 and US6323152.The preparation of above-mentioned chlorination magnesium alcoholate carrier
Process is typically both needed to after high-temperature fusion carry out sub-cooled shaping again, and process power consumption is big, and gained alcohol adduct carrier also needs to carry out
Dealcoholation treatment, technique is complex.
Activated magnesium chloride carrier can also alkoxyl magnesium be raw material prepared.For example, CN1033385A discloses one kind
The preparation method of Ziegler-Natta type solid catalyst, it is in the presence of transition metal alkoxide, to make soluble dialkyl magnesium
Reacted with transition metal halide, reusable liquid hydrocarbon is settled out solid constituent and is made.Alkane in the dialkoxy magnesium wherein used
Epoxide is the branched alkoxy of the linear alkoxide groups containing 6-12 carbon atom or 5-12 carbon atom, and liquid is dissolved in be formed
The alcohol magnesium solution of state hydrocarbon, but this alkoxyl magnesium is difficult to obtain.
CN1177868C discloses a kind of preparation method for olefin polymerization catalysis precursor, and the precursor is in truncated agent
In the presence of make alkoxyl magnesium and alkoxytitanium react to form solid complexes and be made.Wherein alkoxyl magnesium is diethoxy
Magnesium, alkoxytitanium is purity titanium tetraethoxide.
CN101056894A discloses a kind of catalyst for propylene polymerization, and it is by by dialkoxy magnesium and halogenation
Titanium compound or silane halide compound and internal electron donor react obtained in presence of organic solvent.Wherein dialkoxy
The formula of base magnesium is Mg (OR)2, wherein R is C1-C6 alkyl, and reacts obtained by magnesium metal and alcohol.
US4727051 discloses a kind of compound that can be used as carrier for olefin polymerization catalyst, and its structural formula is XnMg
(OR)2-n, X is halogen in formula, and R is C1-C10 alkyl, and n values are 0.2-1.9.Described compound is by being MgX by formula2
Magnesium halide and formula reacted for ROH alcohol after, then with made from metal reactive magnesium.
CN1255436C discloses a kind of preparation method of olefin polymerization catalysis, and its preparation process is as follows：Use halogenating agent
It is Mg (OR ") with formula2The contact of soluble dialkoxy magnesium, the halogenating agent can use one alkoxy of a halogen displacement, shape
Contacted into reaction product A, then with the first halogenation/titanizing agent with reaction product A, reaction product B is formed, with the second halogenation/titanizing
Agent is contacted with reaction product B, forms catalyst component.Wherein in dialkoxy magnesium R " be the alkyl containing 1-20 carbon atom or
Substituted hydrocarbon radical, and it by formula is that MgRR ' alkyl magnesium and formula are R " OH alcohol that the soluble magnesium diaikoxide compound, which is,
React obtained reaction product.The R and R ' of wherein alkyl magnesium are the alkyl containing 1-10 carbon atom, can be with identical or different.
Described alcohol is straight or branched alcohol, and wherein R " is the alkyl containing 4-20 carbon atom.
CN101190953A discloses a kind of preparation method of catalyst solid component of olefin polymerization, including is by formula
ClMg (OR) n's (ROH) contains magnesium complex, is reacted respectively with electron donor compound and titanium tetrahalide in the presence of unreactive hydrocarbons
It is made.This contains magnesium complex and reacts obtained by metal magnesium powder and alcohol, and R is selected from C1-C5 alkyl in its formula of, and n is 0.1-
1.0。
Above-mentioned alkoxyl magnesium compound uses magnesium powder or alkyl magnesium to be prepared for raw material mostly, compared with magnesium chloride, raw material valency
Lattice are high, and preparation technology is complicated.
In order to solve the above problems, CN102040681A discloses a kind of chemical combination that can be used as carrier for olefin polymerization catalyst
Thing, it has following structure：Wherein R1For C1-C12Straight or branched alkane
Base；R2And R3It is identical or differ, it is hydrogen or C1-C5Hydrogen in straight or branched alkyl, wherein alkyl is optionally by halogen atom
Substitution；X is chlorine or bromine, also can one of X by C1-C14Alkyl or alkoxy, C6-C14Aryl or aryloxy group substitution；M is 0.1-
1.9, n be 0.1-1.9, p+m+n=2.The preparation process of the compound is as follows：In the presence of inert dispersion medium, by MgX2、
General formula R1Alcohol compound shown in OH, is heated to 30-160 DEG C of reaction, forms magnesium halide alcohol adduct solution；Afterwards by itself and ring
Oxidative ethane class compound is reacted at 30-160 DEG C, forms carrier；Wherein X is chlorine or bromine, R1For C1-C12Straight or branched
Alkyl.
Although technical scheme disclosed in above-mentioned patent application reduces the cost of material of carrier preparation, simplifies carrier system
Standby technique, but due to needing to use a large amount of inert dispersion mediums in carrier preparation process, so that the single-autoclave yield rate of carrier is reduced,
And the recovery of inert dispersion medium adds solvent recovery cost；In addition, the olefinic polymerization of the carrier using the patent application
The stereoregularity for the polymer that catalyst is obtained in olefin polymerization process need further raising.
The content of the invention
The invention aims to overcome the above-mentioned of existing carrier for olefin polymerization catalyst and preparation method thereof presence
Defect there is provided a kind of preparation method of new ball type carrier for olefin polymerization catalysis and by this method prepare it is spherical
Carrier.
The invention provides a kind of preparation method of the ball type carrier for olefin polymerization catalysis, this method includes：
In the presence of at least one macromolecular dispersion stabilizer, it will be reacted by least following component and directly precipitation obtains solid product：
（a）Magnesium halide；（b）Organic compound containing active hydrogen；And（c）Alkylene oxides compound.
Present invention also offers the ball type carrier prepared by the above method.
By above technical scheme, the present invention has advantages below：
（1）Need not be added in the preparation process of the ball type carrier inert dispersion medium can obtain particle shape it is good,
The narrower solid particle of particle diameter distribution, so as to improve the single-autoclave yield rate of ball type carrier；
（2）The macromolecular dispersion stabilizer used in the preparation process of the ball type carrier is relative to inert dispersion medium more
It is easily recycled, so that the relative reduction cost recovery of solvent；
（3）The olefin polymerization catalysis prepared using ball type carrier of the present invention as carrier is in olefinic polymerization（It is special
It is not propylene polymerization or copolymerization）When resulting polymers have higher stereoregularity.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute a part for specification, 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 ball type carrier prepared by embodiment 11H-NMR spectrum；
Fig. 2 is ball type carrier prepared by embodiment 21H-NMR spectrum；
Fig. 3 is ball type carrier prepared by embodiment 131H-NMR spectrum；
Fig. 4 is ball type carrier prepared by embodiment 161H-NMR spectrum；
Fig. 5 is the optical microscope photograph of ball type carrier prepared by embodiment 1；
Fig. 6 is the optical microscope photograph of block carrier prepared by comparative example 3.
Embodiment
The embodiment of the present invention is described in detail below in conjunction with accompanying drawing.It should be appreciated that this place is retouched
The embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
Term " ball type carrier " used herein refers to that the carrier has spherical particle shape, without requiring
Stating carrier has perfect spherical morphology.
" carrier " specifically described herein refers to the material without olefin polymerizating activity, i.e., not containing in the carrier to form
Active component with olefin polymerizating activity, such as titanium compound.
Heretofore described " directly separate out and obtain solid product " has following implication：
（1）Gained solid product in the present invention（That is ball type carrier）Separated out and obtained by chemically reacting, i.e., solid is produced
Directly separated out and shaped in original system by chemically reacting in thing preparation process, without passing through solvent flashing or change system
Temperature（Such as spray drying, reduction system temperature）Reactant precipitation is set to obtain spherical solid particle etc. means.
（2）The shape of solid product in the present invention（It is spherical）Acquisition without in preparation process add have good particle
The inert carrier compound of form（Such as SiO2, metal oxide etc.）It can just realize.
The invention provides a kind of preparation method of the ball type carrier for olefin polymerization catalysis, this method includes：
In the presence of at least one macromolecular dispersion stabilizer, it will be reacted by least following component and directly precipitation obtains solid product：
（a）Magnesium halide；（b）Organic compound containing active hydrogen；And（c）Alkylene oxides compound.
In the preferred case, the process of the component reaction is included：
（1）In the presence of at least one macromolecular dispersion stabilizer, by magnesium halide and the organic compound containing active hydrogen
Thing reacts to form complex solution；
（2）The complex solution and alkylene oxides compound are reacted, solid particle is separated out.
In step（1）In, relative to the consumption of every mole of magnesium halide, the consumption of the organic compound containing active hydrogen
It can be 3-30 moles, preferably 4-20 moles.
In the present invention, the consumption of the macromolecular dispersion stabilizer for the magnesium halide and described can contain active hydrogen
Organic compound total consumption 0.1-10 weight %, preferably 0.2-5 weight %.
Step（1）In reaction condition can include：Reaction temperature is 30-160 DEG C, preferably 40-120 DEG C；Reaction time
For 0.1-5 hours, preferably 0.5-2 hours.Step（1）In reaction can be carried out in conventional reactor or container, it is excellent
Selection of land, step（1）In reaction carried out in closed container, can for example carry out in a kettle..
In the present invention, the formula of magnesium halide is MgX2, wherein, X is preferably bromine, chlorine or iodine.It is highly preferred that the halogenation
Magnesium is selected from least one of magnesium dichloride, dibrominated magnesium and magnesium diiodide, most preferably magnesium dichloride.
In the present invention, the organic compound containing active hydrogen is preferably Organic Alcohol R1OH, wherein, R1Preferably C1-
C8Straight or branched alkyl, more preferably C2-C5Straight or branched alkyl, such as ethyl, propyl group, butyl or amyl group.Specifically
Ground, the Organic Alcohol for example can selected from methanol, ethanol, propyl alcohol, isopropanol, n-butanol, isobutanol, amylalcohol, isoamyl alcohol, just oneself
Alcohol, n-octyl alcohol and 2- ethyls -1- at least one of alcohol.
In invention, " macromolecule " in macromolecular dispersion stabilizer is not particularly limited to molecular weight, but uses IUPAC
（International Union of Pure and Applied Chemistry, international purely chemistry is combined with applied chemistry
Meeting）In to macromolecule（Or macromolecular）Definition be that " with respect to the molecule of high molecule mass, its structure is mainly by low relative molecular
The molecule of quality, which is pressed actually, or conceptive derivative unit is multiple repeats what is constituted ".In the present invention, step（1）In high score
The weight average molecular weight of sub- dispersion stabilizer is preferably greater than 1000, more preferably greater than 3000, more preferably 6,000-2,000,
000.Specifically, the macromolecular dispersion stabilizer can be selected from polyacrylate, styrene-maleic anhydride copolymer, polyphenyl
Vinyl sulfonate, naphthalene sulfonic acid-formaldehyde condensation product, condensation alkyl phenyl ether sulfuric ester, condensation polyoxyethylene alkylphenol ether phosphoric acid
Ester, epoxide alkyl acrylate copolymer are modified poly- Ethylenimine, the polymer of 1- 12-4-vinylpyridine bromides, poly- second
Alkenyl benzyl front three amine salt, polyvinyl alcohol, polyacrylamide, ethylene oxide propylene oxide block copolymer, polyvinylpyrrolidine
Ketone（PVP）, polyvinylpyrrolidone vinylacetate copolymers, polyethylene glycol（PEG）, alkyl phenyl polyethylene oxides ether and poly- first
At least one of base alkyl-acrylates compound, preferably polyvinylpyrrolidone, polyvinylpyrrolidone acetic acid second
At least one of enoate copolymer and polyethylene glycol.
In the present invention, the magnesium halide, the organic compound containing active hydrogen and the macromolecule stably dispersing
During agent can participate in forming magnesium halide alcohol adduct solution in the form of containing minor amount of water.These minor amount of water refer to industrial life
The water inevitably introduced in production or in storage or transportation, rather than the water artificially added.
In step（1）In, the magnesium halide, the organic compound containing active hydrogen and the macromolecule stably dispersing
Charging sequence between agent, three in no particular order, can be added with arbitrary charging sequence.
In the present invention, relative to the consumption of magnesium halide every mole described, the consumption of the alkylene oxides compound can be with
For 1-10 moles, preferably 2-6 moles.
Step（2）In reaction condition can include：Reaction temperature is 30-160 DEG C, preferably 40-120 DEG C；Reaction time
For 0.1-5 hours, preferably 0.2-1 hours.
In the present invention, the alkylene oxides compound is preferably structural formula such as formula（1）Shown compound,
Formula（1）
Wherein, R2And R3It is identical or different, and it is each independently hydrogen or C1-C5Straight or branched alkyl, wherein alkane
Hydrogen on base is optionally optionally substituted by halogen, specifically, R2And R3It is preferably hydrogen, methyl, ethyl, propyl group, chloro first independently of one another
Base, Chloroethyl, chloro propyl group, bromomethyl, bromoethyl or Bromopropyl.Specifically, the alkylene oxides compound can
With selected from oxirane, expoxy propane, epoxy butane, epoxychloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy NBB
At least one of.
In the methods described that the present invention is provided, in step（1）In can add or be added without inert dispersion medium.It is described
Inert dispersion medium is inert dispersion medium commonly used in the art, for example, can be selected from aliphatic series, aromatics or the ring grease of liquid
At least one of race's hydro carbons and silicone oil, specifically, for example, can be more than the straight or branched liquid of 6 carbon for carbon chain lengths
Alkane, aromatic hydrocarbons（Such as toluene）, kerosene, paraffin oil, vaseline oil, at least one of white oil and methyl-silicone oil.When in step（1）
During the middle addition inert dispersion medium, the consumption of the inert dispersion medium and the organic compound containing active hydrogen
The volume ratio of consumption can be 1：0.2-20, preferably 1：0.5-10.In more preferably embodiment, in step（1）With（2）
In be added without inert dispersion medium.
In the methods described that the present invention is provided, it will at least include component（a）, component（b）And component（c）Raw material enter
During row reaction, except component（a）, component（b）And component（c）, conventional additive component can also be added, such as to electricity
Daughter.The electron donor can be electron donor compound commonly used in the art, such as ether, ester, ketone, aldehyde, amine, ammonification
At least one of thing, alkoxy silane etc., preferably ether, ester and alkoxy silane.
In the methods described that the present invention is provided, it is preferable that will at least include component（a）, component（b）And component（c）
Raw material reacted during, be added without titanium tetrachloride.
In a preferred embodiment, the preparation method of the ball type carrier includes：
（1）In closed container, in the presence of at least one macromolecular dispersion stabilizer, by magnesium halide MgX2And have
Machine alcohol R1OH mixture is at 30-160 DEG C（It is preferred that 40-120 DEG C）Lower reaction 0.1-5 hours（It is preferred that 0.5-2 hours）, form halogen
Change magnesium alcoholate solution, i.e. complex solution；
（2）By the magnesium halide alcohol adduct solution and above-mentioned formula（1）Shown alkylene oxides compound is at 30-160 DEG C（It is excellent
Select 40-120 DEG C）Lower reaction 0.1-5 hours（It is preferred that 0.2-1 hours）, separate out solid particle；
（3）The solid particle is reclaimed by solid-liquid separation technique and obtains ball type carrier.
In a kind of preferred embodiment, the preparation method of the ball type carrier includes：
（1）In closed container, under agitation by magnesium halide, Organic Alcohol and at least one macromolecular dispersion stabilizer
Mixture heats to 30-160 DEG C, preferably 40-120 DEG C, reacts 0.1-5 hours, preferably 0.5-2 hours, forms magnesium halide
Alcohol adduct solution, wherein, in terms of every mole of magnesium, the consumption of the Organic Alcohol is 3-30 moles, preferably 4-25 moles；The height
The consumption of molecule dispersion stabilizer is 0.1-10 weight %, preferably the 0.2-5 weights of the magnesium halide and the total consumption of the Organic Alcohol
Measure %.
（2）Under agitation, above-mentioned formula is added into above-mentioned magnesium halide alcohol adduct solution（1）Shown alkylene oxides chemical combination
Thing, at 30-160 DEG C（It is preferred that 40-120 DEG C）Lower reaction 0.1-5 hours, preferably 0.2-1 hours, forms solid particle, wherein, with
Every mole of magnesium meter, the consumption of the alkylene oxides compound is 1-10 moles, preferably 2-6 moles；
（3）The solid particle is reclaimed by solid-liquid separation technique and obtains ball type carrier.
In above-mentioned preferred embodiment, skill can be separated according to the conventional solid-liquid of this area by reclaiming the process of solid particle
Art is implemented, and the mode such as can use filtering, decantation, centrifuge is implemented.Moreover, step（3）It can also include obtaining
Spherical carrier particle washed and dried with inert hydrocarbon solvent.The inert hydrocarbon solvent is preferably that carbon chain lengths are more than
The straight chain or straight chain liquid alkane, aromatic hydrocarbons of 4 carbon, specifically, such as can be hexane, heptane, octane, decane, toluene.
Present invention also offers the ball type carrier prepared by the above method.
In the preferred case, main constitute of the ball type carrier prepared by the above method be：Formula（2）Shown magnesium compound
And formula（1）Shown alkylene oxides compound,
Formula（1）Formula（2）
Wherein, R1For C1-C12Straight or branched alkyl；R2And R3It is identical or different, and be each independently hydrogen or
C1-C5Straight or branched alkyl, the wherein hydrogen on alkyl is optionally optionally substituted by halogen；X is halogen；M is 0.1-1.9, and n is
0.1-1.9, and m+n=2；
Wherein, relative to every mole formula（2）Shown magnesium compound, formula（1）The content of shown alkylene oxides compound
For 0.01-0.8 moles, preferably 0.02-0.5 moles, more preferably 0.02-0.3 moles.
Preferably, X is bromine, chlorine or iodine, more preferably chlorine.
Preferably, m is 0.5-1.5, and n is 0.5-1.5, and m+n=2.Most preferably, m is that 1, n is 1.
The average grain diameter of the ball type carrier（D50）Preferably 30-125 μm, more preferably 40-85 μm.The spherical load
The particle size distribution values of body（SPAN=(D90-D10)/D50）Preferably 0.6-2.5, more preferably 0.6-0.85.In the present invention,
The average grain diameter and particle size distribution values of ball type carrier use the particle size analyzers of Masters Sizer 2000（By Malvern
Instruments Ltd are manufactured）Determine.
The invention will be further described by the following examples.
（1）The composition of ball type carrier：Ball type carrier is dissolved with TRI N BUTYL PHOSPHATE and deuterated toluene, and uses nuclear magnetic resonance ripple
Spectrometer is tested1H-NMR spectrum.
（2）Melt index：Determined according to ASTM D1238-99 method.
（3）Polymer isotactic index：Determined using heptane extraction process（Heptane boiling extracting 6 hours）, that is, take what 2g was dried
Polymer samples, are placed in extractor and are extracted 6 hours with boiling heptane, afterwards, by residue drying to constant weight, resulting polymers
Weight（g）Ratio with 2 is isotactic index.
（4）Particle diameter distribution is tested：Average grain diameter and size distribution the Masters Sizer 2000 of spherical carrier particle
Particle size analyzer（Manufactured by Malvern Instruments Ltd）Determine, wherein, particle size distribution values SPAN=(D90-D10)/D50.
Embodiment 1-22
These embodiments are used to illustrate the ball type carrier of the present invention for olefin polymerization catalysis and its preparation side
Method.
In 500mL closed reactor, magnesium chloride, Organic Alcohol are sequentially added（R1OH）And macromolecular dispersion stabilizer,
And the extra toluene that adds is used as inert dispersion medium respectively in embodiment 19-22（Wherein, for toluene and Organic Alcohol plus
Enter the volume ratio of amount, embodiment 19 is 1:10, embodiment 20 is 1:3, embodiment 21 is 1:1, embodiment 22 is 1:2）, in stirring
Under be warming up to reaction temperature (T), after isothermal reaction 1 hour, add alkylene oxides compound (E), maintain thermotonus 0.5 small
When, liquid is filtered off, is washed with hexane 5 times, is dried in vacuo, spherical carrier particle is obtained, specific preparation condition is as shown in table 1, from
And ball type carrier A1-A22 is made respectively, wherein, the respective average grain diameter of these ball type carriers（D50）And particle size distribution values
（SPAN）As shown in table 1, ball type carrier A11H-NMR spectrum is as shown in figure 1, ball type carrier A21H-NMR spectrum such as Fig. 2 institutes
Show, ball type carrier A13's1H-NMR spectrum is as shown in figure 3, ball type carrier A161H-NMR spectrum is as shown in figure 4, ball type carrier
A1 optical microscope photograph is as shown in Figure 5.
Table 1
The form of spherical carrier particle prepared according to the methods of the invention is substantially it can be seen from table 1 and Fig. 5
It is spherical, and particle size distribution is narrow.
The ball type carrier A1's prepared in embodiment 11In H-NMR spectrum, Spectra peak recognition and integral area such as table 2 below institute
Show.
Table 2
| Belonging to group | Chemical shift ppm | Integral area |
| CH3（Ⅴ） | 1.40 | 3.01 |
| CH2（Ⅴ） | 3.93 | 7.10-5.10=2 |
| CH（Ⅴ） | 4.29 | 1.00 |
| CH2Cl（Ⅴ） | 3.79 | 4.00 |
| CH2Cl（Ⅵ） | 2.87 | 0.08 |
| C-CH-C（Ⅵ） | 2.60 | 0.04 |
| C-CH-O（Ⅵ） | 2.16 | 0.04 |
| C-CH-O（Ⅵ） | 1.95 | 0.04 |
Note：Peak position person is not marked in Fig. 1 for solvent peak
It follows that ball type carrier A1 prepared by embodiment 1 is main by formula（V）And formula（VI）Shown compound group into,
And formula（V）And formula（VI）The mol ratio of the content of shown compound is 1:0.04.
Formula（V）Formula（VI）
The ball type carrier A2's prepared in embodiment 21In H-NMR spectrum, Spectra peak recognition and integral area such as table 3 below institute
Show.
Table 3
| Belonging to group | Chemical shift ppm | Integral area |
| CH3（Ⅴ） | 1.41 | 3.03 |
| CH2（Ⅴ） | 3.94 | 7.26-5.23=2.03 |
| CH（Ⅴ） | 4.31 | 1.00 |
| CH2Cl（Ⅴ） | 3.81 | 3.99 |
| CH2Cl（Ⅵ） | 2.88 | 0.13 |
| C-CH-C（Ⅵ） | 2.61 | 0.06 |
| C-CH-O（Ⅵ） | 2.17 | 0.07 |
| C-CH-O（Ⅵ） | 1.95 | 0.07 |
Note：Peak position person is not marked in Fig. 2 for solvent peak
It follows that ball type carrier A2 prepared by embodiment 2 is main by formula（V）And formula（VI）Shown compound group into,
And formula（V）And formula（VI）The mol ratio of the content of shown compound is 1:0.07.
The ball type carrier A13's prepared in embodiment 131In H-NMR spectrum, Spectra peak recognition and integral area such as table 4 below institute
Show.
Table 4
| Belonging to group | Chemical shift ppm | Integral area |
| CH3（Ⅶ） | 1.09 | 3.00 |
| CH2（Ⅶ） | 3.87 | 2.00 |
| CH2（Ⅶ） | 1.76 | 2.00 |
| CH2（Ⅶ） | 1.48 | 8.60-6.60=2.00 |
| CH（Ⅶ） | 4.28 | 1.00 |
| CH2Cl（Ⅶ） | 3.78 | 6.00-2.00=4.00 |
| CH2Cl（Ⅵ） | 2.87 | 0.04 |
| C-CH-C（Ⅵ） | 2.60 | 0.02 |
| C-CH-O（Ⅵ） | 2.14 | 0.02 |
| C-CH-O（Ⅵ） | 1.94 | 0.02 |
Note：Peak position person is not marked in Fig. 3 for solvent peak
It follows that ball type carrier A13 prepared by embodiment 13 is main by formula（VII）And formula（VI）Shown compound group
Into, and formula（VII）And formula（VI）The mol ratio of the content of shown compound is 1:0.02.
Formula（VII）Formula（VI）
The ball type carrier A16's prepared in embodiment 161In H-NMR spectrum, Spectra peak recognition and integral area such as table 5 below institute
Show.
Table 5
| Belonging to group | Chemical shift ppm | Integral area |
| CH3（Ⅴ） | 1.40 | 9.08-6.88-1.18=1.02 |
| CH2（Ⅴ） | 3.95 | 5.86-4-1.18=0.68 |
| CH3（Ⅶ） | 1.06 | 1.77 |
| CH2（Ⅶ） | 3.86 | 1.18 |
| CH2（Ⅶ） | 1.74 | 1.18 |
| CH2（Ⅶ） | 1.51 | 1.18 |
| CH（Ⅶ） | 4.34 | 1.00 |
| CH2Cl（Ⅶ） | 3.84 | 4.00 |
| CH2Cl（Ⅵ） | 2.86 | 0.49 |
| C-CH-C（Ⅵ） | 2.60 | 0.23 |
| C-CH-O（Ⅵ） | 2.15 | 0.24 |
| C-CH-O（Ⅵ） | 1.94 | 0.24 |
Note：Peak position person is not marked in Fig. 4 for solvent peak
It follows that ball type carrier A16 prepared by embodiment 16 is main by formula（V）, formula（VI）And formula（VII）Shown change
Compound is constituted, and formula（VI）The content and formula of shown compound（V）And formula（VII）The content sum of shown compound is rubbed
You are than being 0.24:1, formula（VI）Shown compound and formula（VII）The mol ratio of the content of shown compound is 1:1.74.
Comparative example 1
In 500mL reactor, 7.2g magnesium chlorides, 180ml white oils and 82ml ethanol are sequentially added, and content is existed
It is warming up to 90 DEG C under stirring, and after reacting 1 hour at such a temperature, 24ml epoxychloropropane is added into reactor, and make anti-
It should at such a temperature proceed 0.5 hour, liquid is filtered off afterwards, residual solid be washed 5 times with hexane, then vacuum is dry
It is dry, obtain ball type carrier D1.
Comparative example 2
Ball type carrier is prepared according to the method for comparative example 1, except that, inert dispersion medium white oil is added without, as a result
Solid particle is not obtained.
Comparative example 3
Carrier is prepared according to the method for embodiment 1, except that, with the nonionic surface active agent department of identical weight
Disk 80 replaces the PVP added in embodiment 1, so that block carrier D3, optical microscope photograph such as Fig. 6 of the block carrier is made
It is shown.
Comparative example 4
Carrier is prepared according to the method for embodiment 1, except that, macromolecular dispersion stabilizer PVP is added without, so as to make
Obtain block carrier D4.
Comparative example 5
In 500mL closed reactor, magnesium chloride 22g, ethanol 188ml, PVP2.7g (Mw=10000) are sequentially added,
It is warming up to 80 DEG C under agitation, after isothermal reaction 1 hour, 4ml TiCl is slowly added dropwise into solution4, after maintaining 0.5 hour, to
Epoxychloropropane 57ml is added in above-mentioned solution, thermotonus is maintained 0.5 hour, liquid is filtered off, a small amount of amorphous powder is only obtained
Last shape solid.
Test example 1
（1）Prepare solid catalyst
In 300mL glass reaction bottle, 100ml titanium tetrachlorides are sequentially added, -20 DEG C are cooled to, the above-mentioned realities of 8g are added
The ball type carrier A1 of the preparation of example 1 is applied, 110 DEG C are warming up to.Diisobutyl phthalate 1.5ml, filter are added in temperature-rise period
Liquid is removed, washs secondary with titanium tetrachloride, is washed with hexane three times, solid catalyst Cat-1 is obtained after vacuum drying.
（2）Liquid phase bulk propylene polymerization
Liquid phase bulk propylene polymerization is carried out in 5L stainless steel autoclave.Under nitrogen protection into reactor
Sequentially add the hexane solution of 5ml triethyl aluminums（Concentration is 0.5mmol/ml）, 1ml Cyclohexyl Methyl Dimethoxysilanes
（CHMMS）Hexane solution（Concentration is 0.1mmol/ml）With the above-mentioned solid catalyst Cat-1 of 9mg.Autoclave is closed, one is added
Quantitative hydrogen（Normal volume）With 2.3L liquid propene.70 DEG C are warming up to, after reacting 1 hour, cooling, release, discharging, by institute
Obtain and weigh and analyze after Noblen is dried, as a result as shown in table 6.
Test example 2-10
Solid catalyst is prepared according to the method for test example 1 and implements liquid phase bulk propylene polymerization, except that, respectively
With the ball type carrier A2 of the preparation of embodiment 2, the ball type carrier A3 of the preparation of embodiment 3, the ball type carrier A6 of the preparation of embodiment 6, reality
Apply ball type carrier A11, implementation prepared by the ball type carrier A8 of the preparation of example 8, ball type carrier A9 prepared by embodiment 9, embodiment 11
The ball type carrier A20 of ball type carrier A13, ball type carrier A16 prepared by embodiment 16 and the preparation of embodiment 20 prepared by example 13
Instead of the ball type carrier A1.As a result it is as shown in table 6.
Comparative experimental example 1
According to the method for test example 1 prepare solid catalyst and implement liquid phase bulk propylene polymerization, except that, with pair
Ball type carrier D1 prepared by ratio 1 replaces the ball type carrier A1.As a result it is as shown in table 6.
Table 6
The catalyst prepared by ball type carrier of the present invention is can be seen that from the data in table 6 is used for propylene polymerization
When, with compared with high polymerization activity and higher stereotaxis ability；Meanwhile, the hydrogen response of the catalyst preferably, is particularly
Under high melt index (MI), polymer still has higher isotactic index.
Claims (23)
1. a kind of preparation method of ball type carrier for olefin polymerization catalysis, this method includes：In at least one macromolecule
In the presence of dispersion stabilizer, it will be reacted by least following component and directly precipitation obtains solid product：(a) magnesium halide；(b) contain
There is the organic compound of active hydrogen；And (c) alkylene oxides compound, wherein, inertia point is added without during this method
Dispersion media.
2. according to the method described in claim 1, wherein, the process of the reaction includes：
(1) it is in the presence of at least one macromolecular dispersion stabilizer, magnesium halide and the organic compound containing active hydrogen is anti-
Should be to form complex solution；
(2) complex solution and alkylene oxides compound are reacted；
Wherein, it is added without inert dispersion medium in step (1) and (2).
3. method according to claim 2, wherein, it is described relative to the consumption of every mole of magnesium halide in step (1)
The consumption of organic compound containing active hydrogen is 3-30 moles；The consumption of the macromolecular dispersion stabilizer is the magnesium halide
With the 0.1-10 weight % of total consumption of the organic compound containing active hydrogen.
4. method according to claim 3, wherein, it is described relative to the consumption of every mole of magnesium halide in step (1)
The consumption of organic compound containing active hydrogen is 4-20 moles；The consumption of the macromolecular dispersion stabilizer is the magnesium halide
With the 0.2-5 weight % of total consumption of the organic compound containing active hydrogen.
5. method according to claim 2, wherein, the reaction condition in step (1) includes：Reaction temperature is 30-160
℃；Reaction time is 0.1-5 hours.
6. method according to claim 5, wherein, the reaction condition in step (1) includes：Reaction temperature is 40-120
℃；Reaction time is 0.5-2 hours.
7. the method according to any one in claim 1-3, wherein, the Weight-average molecular of the macromolecular dispersion stabilizer
Amount is more than 1000.
8. method according to claim 7, wherein, the weight average molecular weight of the macromolecular dispersion stabilizer is more than 3000.
9. method according to claim 8, wherein, the weight average molecular weight of the macromolecular dispersion stabilizer is 6,000-2,
000,000。
10. the method according to any one in claim 1-3 and 8-9, wherein, the macromolecular dispersion stabilizer is selected from
Polyacrylate, styrene-maleic anhydride copolymer, poly styrene sulfonate, naphthalene sulfonic acid-formaldehyde condensation product, condensation alkyl phenyl
Ether sulfuric ester, condensation polyoxyethylene alkylphenol ether phosphate, epoxide alkyl acrylate copolymer are modified poly- Ethylenimine, 1-
The polymer of 12-4-vinylpyridine bromide, polyvinyl benzyl front three amine salt, polyvinyl alcohol, polyacrylamide, epoxy second
Alkane propylene oxide block copolymer, polyvinylpyrrolidone, polyvinylpyrrolidone vinylacetate copolymers, polyethylene glycol,
At least one of alkyl phenyl polyethylene oxides ether and polyalkyl methacrylate class compound.
11. method according to claim 10, wherein, the macromolecular dispersion stabilizer be selected from polyvinylpyrrolidone,
At least one of polyvinylpyrrolidone vinylacetate copolymers and polyethylene glycol.
12. the method according to any one in claim 1-3, wherein, the magnesium halide is selected from magnesium dichloride, dibrominated
At least one of magnesium and magnesium diiodide.
13. the method according to any one in claim 1-3, wherein, the organic compound containing active hydrogen is
Organic Alcohol R1OH, wherein, R1For C1-C12Straight or branched alkyl.
14. method according to claim 13, wherein, the Organic Alcohol is selected from methanol, ethanol, normal propyl alcohol, isopropanol, just
At least one of butanol, isobutanol, n-amyl alcohol, isoamyl alcohol, n-hexyl alcohol, n-octyl alcohol and 2- ethyl -1- hexanols.
15. method according to claim 2, wherein, in step (2), relative to the consumption of magnesium halide every mole described,
The consumption of the alkylene oxides compound is 1-10 moles.
16. method according to claim 15, wherein, in step (2), relative to the use of magnesium halide every mole described
Amount, the consumption of the alkylene oxides compound is 2-6 moles.
17. the method according to any one in claim 2 and 15-16, wherein, the reaction condition in step (2) includes：
Reaction temperature is 30-160 DEG C；Reaction time is 0.1-5 hours.
18. method according to claim 17, wherein, the reaction condition in step (2) includes：Reaction temperature is 40-120
℃；Reaction time is 0.2-1 hours.
19. the method according to any one in claim 1-3, wherein, the structural formula of the alkylene oxides compound is such as
Shown in formula (1),
Wherein, R2And R3It is identical or different, and it is each independently hydrogen or C1-C5Straight or branched alkyl, wherein on alkyl
Hydrogen be optionally optionally substituted by halogen.
20. method according to claim 19, wherein, the alkylene oxides compound be selected from oxirane, expoxy propane,
At least one of epoxy butane, epoxychloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy NBB.
21. method according to claim 2, wherein, the inert dispersion medium is selected from aliphatic series, aromatics or the ring grease of liquid
At least one of race's hydro carbons and silicone oil.
22. method according to claim 1 or 2, wherein, four chlorinations are added without during by the component reaction
Titanium.
23. the ball type carrier prepared as the method described in any one in claim 1-22.
Priority Applications (13)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310491393.6A CN104558281B (en) | 2013-10-18 | 2013-10-18 | It is a kind of for ball type carrier of olefin polymerization catalysis and preparation method thereof |
| EP14854726.8A EP3059263B1 (en) | 2013-10-18 | 2014-10-17 | Spherical carriers for olefin polymerization catalyst, catalyst components, catalyst, and preparation methods therefor |
| JP2016524132A JP6397908B2 (en) | 2013-10-18 | 2014-10-17 | Spherical support for olefin polymerization catalyst, catalyst component, catalyst, and preparation method thereof |
| PCT/CN2014/088806 WO2015055136A1 (en) | 2013-10-18 | 2014-10-17 | Spherical carriers for olefin polymerization catalyst, catalyst components, catalyst, and preparation methods therefor |
| US15/030,000 US9951157B2 (en) | 2013-10-18 | 2014-10-17 | Spherical carriers for olefin polymerization catalyst, catalyst components, catalyst, and preparation methods therefor |
| SG11201603004RA SG11201603004RA (en) | 2013-10-18 | 2014-10-17 | Spherical carriers for olefin polymerization catalyst, catalyst components, catalyst, and preparation methods therefor |
| MYPI2016701399A MY172451A (en) | 2013-10-18 | 2014-10-17 | Spherical carriers for olefin polymerization catalyst, catalyst components, catalyst, and preparation methods therefor |
| KR1020167012712A KR102019727B1 (en) | 2013-10-18 | 2014-10-17 | Spherical carriers for olefin polymerization catalyst, catalyst components, catalyst, and preparation methods therefor |
| RU2016118406A RU2668082C2 (en) | 2013-10-18 | 2014-10-17 | Spherical carriers for olefin polymerisation catalyst, catalyst components, catalyst and preparation methods therefor |
| BR112016008605-8A BR112016008605B1 (en) | 2013-10-18 | 2014-10-17 | METHOD FOR PREPARING A SPHERICAL CONVEYOR OF A POLYMERIZATION DEOLEFINS, SPHERICAL CONVEYOR, PROCESS FOR PREPARING A SOLID COMPOSITION, COMPOSITION OF SOLID, CATALYST COMPONENT FOR POLYMERIZATION OF OLEFINES, METHODS OF PREPARATION OF OLEFINS AND METHOD FOR POLYMERIZING OLEFINS |
| TW103136036A TWI650335B (en) | 2013-10-18 | 2014-10-17 | Spherical carrier for olefin polymerization catalyst, catalyst component, catalyst and preparation method thereof |
| SA516370961A SA516370961B1 (en) | 2013-10-18 | 2016-04-17 | Spherical carriers for olefin polymerization catalyst, catalyst components, catalyst, and preparation methods therefor |
| CL2016000919A CL2016000919A1 (en) | 2013-10-18 | 2016-04-18 | Method for preparing a spherical carrier of a catalyst for the polymerization of olefins; spherical carrier; process to prepare a solid composition; solid composition; catalyst component; method for preparing a catalyst component; catalyst for the polymerization of olefins; use of the catalyst; and method for the polymerization of olefin (s). |
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| CN109400778B (en) * | 2017-08-18 | 2021-02-05 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method thereof, catalyst for olefin polymerization and olefin polymerization method |
| CN109694423B (en) * | 2017-10-24 | 2021-07-30 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, preparation method thereof and catalyst for ethylene polymerization |
| CN111072797B (en) * | 2018-10-19 | 2021-07-02 | 中国石油化工股份有限公司 | Olefin polymerization catalyst spherical carrier and preparation method thereof, catalyst component, catalyst and application |
| CN111072808B (en) * | 2018-10-19 | 2022-09-20 | 中国石油化工股份有限公司 | Catalyst component, catalyst, application thereof and olefin polymerization method |
| CN110498871B (en) * | 2019-08-23 | 2022-03-18 | 上海化工研究院有限公司 | Alkoxy magnesium carrier particle and application thereof |
| CN112759687B (en) * | 2019-10-21 | 2023-05-12 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation method thereof, catalyst and olefin polymerization method |
| CN114478858B (en) * | 2020-10-26 | 2023-05-30 | 中国石油化工股份有限公司 | Olefin polymerization catalyst carrier, preparation method thereof and olefin polymerization catalyst component |
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