CN105777951A - Alkoxy magnesium carrier for olefin polymerization catalyst and preparation method thereof - Google Patents
Alkoxy magnesium carrier for olefin polymerization catalyst and preparation method thereof Download PDFInfo
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- CN105777951A CN105777951A CN201410817455.2A CN201410817455A CN105777951A CN 105777951 A CN105777951 A CN 105777951A CN 201410817455 A CN201410817455 A CN 201410817455A CN 105777951 A CN105777951 A CN 105777951A
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Abstract
The invention discloses a method for preparing an alkoxy magnesium carrier for an olefin polymerization catalyst. Specifically, in the presence of a halogenating agent, one or several inert organic solvents are used as a dispersant to carry out a reaction between magnesium metal and alcohol. The invention is characterized in that magnesium metal, alcohol and one or several inert organic solvents are added continuously or repeatedly into a reaction system of alcohol reflux. The method has advantages as follows: reaction rate is controllable; and an alkoxy magnesium carrier with excellent particle morphology, average particle size being maintained at 10-15 microns, large specific surface area and high bulk density can be prepared.
Description
Technical field
The preparation method that the present invention relates to a kind of alkoxyl magnesium carrier for olefin polymerization catalysis, it is specifically included under halogenating agent existence, adopt one or more inert organic solvents as dispersant, make magnesium metal and alcohol reaction, it is characterised in that the reaction system under alcohol reflux is added magnesium metal, alcohol and one or more inert organic solvents continuously or repeatedly.The method response speed is controlled, the alkoxyl magnesium carrier granular form of preparation is good, mean diameter 10～15 μm, specific surface area is big and bulk density is high.
Background technology
Olefinic polyreaction usually completes when adding Ziegler-Natta catalyst, and Ziegler-Natta catalyst is made up of transition metal titanium compound and organic metal aluminium compound two parts.Conventionally used transition metals Ti load method on a solid support prepares carrier model transition metal titanium catalyst.Owing to supported olefin polymerization type catalyst is suitable for various polymerization technique, such as slurry polymerization, polymerisation in bulk and gas-phase polymerization etc., therefore, require that carrier meets various performance, namely suitable granularity and shape, uniform distribution of particles and high bulk density etc., and high catalyst activity and three-dimensional regularity.
Conventional catalyst solid supports has MgCl2、SiO2With Mg (OR)2(R be carbon number 1～10 alkyl) etc..And with loaded catalyst that alkoxyl magnesium is carrier, it is possible to there is more premium properties.As publication number be multiple patent disclosure such as CN101173015A, CN1359394A and CN1420130A be the method that carrier prepares premium properties catalyst with alkoxyl magnesium.
Japan Kokai patent 1991-74341,1992-368391 and 1996-73388 provide the method that magnesium metal and ethanol are synthesized spherical or oval diethoxy magnesium under elemental iodine exists.But, when this method prepares diethoxy magnesium, the more difficult control of reaction rate, react very fast, substantial amounts of reaction heat and hydrogen are released in reaction simultaneously, and the dialkoxy-magnesium support of gained contains substantial amounts of microgranule or the bulky grain formed by several particle aggregations.If the catalyst prepared by this carrier is used for olefinic polymerization, it will produce the excessive polymer of particle, or the problem of the shape of particle collapse caused due to the heat of polymerization in polymerization process etc, cause serious process cumbersome.
Summary of the invention
The preparation method that it is an object of the invention to provide a kind of alkoxyl magnesium carrier for olefin polymerization catalysis.This carrier has higher bulk density, good particle shape, suitable granular size and uniform particle size distribution.
The preparation method that the present invention provides a kind of alkoxyl magnesium carrier for olefin polymerization catalysis; comprising the steps: under inert gas shielding, employing inert organic solvents is dispersant, makes magnesium metal and alcohol reaction under halogenating agent exists; reaction temperature is 0～90 DEG C, until reaction does not produce H2After, then 50-80 DEG C of ripening 2-10 hour, wash, separate, dry, prepare alkoxyl magnesium carrier；It is characterized in that the reaction system under alcohol reflux adds magnesium metal, alcohol and inertia alkane organic solvent.
Wherein, in 1 mole metal magnesium, total consumption of described alcohol is 2～50 moles, and total consumption of described halogenating agent is 0.0025～0.03 mole, and total consumption of described inert organic solvents is 2～50 moles.
Described magnesium metal, alcohol and inert organic solvents are 50～100 minutes add continuously or 2～8 times be added separately to the addition manner of reaction system.
Described halogenating agent is iodine, carbon tetrachloride, magnesium iodide, magnesium chloride or Alkoxymagnesium halides.
Described inertia alkane organic solvent is at least one in the group of the free hexane of choosing, heptane, octane, decane.
Described alcohol is at least one in the unitary aliphatic alcohol of C2～C10 or the unitary aromatic alcohols of C2～C10.
Described alcohol is at least one in the group selecting free methanol, ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, n-amyl alcohol, isoamyl alcohol, hexanol, isohexyl alcohol, n-heptanol, iso-heptanol, n-octyl alcohol, isooctanol, n-nonyl alcohol, isononyl alcohol, Decanol, isodecanol, phenol, benzyl alcohol, phenethanol, phenylpropanol to form.
In 1 mole metal magnesium, total consumption of described alcohol is 5～20 moles, and total consumption of described halogenating agent is 0.0025～0.01 mole, and total consumption of described inert organic solvents is 2～20 moles.
Present invention simultaneously provides a kind of alkoxyl magnesium carrier for olefin polymerization catalysis, the bulk density of described alkoxyl carrier is more than or equal to 0.33g/cm3。
The mean diameter D50 of described alkoxyl magnesium carrier is 10～15 μm.
Particle size distribution Span=(the D90-D10)/D50 of described alkoxyl magnesium carrier is less than or equal to 1.5.
The present invention can be specified as follows:
According to the present invention, the preparation method that a kind of alkoxyl magnesium carrier for olefin polymerization catalysis is provided, under halogenating agent exists, adopt one or more inert organic solvents as dispersant, make magnesium metal and alcohol reaction, it is characterised in that the reaction system under alcohol reflux is added magnesium metal, alcohol and one or more inert organic solvents continuously or repeatedly.The total amount of the alcohol wherein used is by 1 mole metal magnesium, alcohol: magnesium is 2～50:1；The consumption of halogenating agent is by 1 mole metal magnesium, halogenating agent: magnesium is 0.0025～0.03:1；The total amount of inert organic solvents is by 1 mole metal magnesium, inert organic solvents: magnesium is 2～50:1.
The halogenating agent that the present invention uses has no particular limits, instantiation has: iodine, bromine, chlorine, magnesium iodide, magnesium bromide, magnesium chloride, calcium iodide, calcium bromide, calcium chloride, mercuric iodixde, mercuric bromide, mercuric chloride, carbon tetraiodide, carbon tetrabromide, carbon tetrachloride etc., one in preferred iodine, carbon tetrachloride, magnesium iodide, magnesium chloride and Alkoxymagnesium halides, more preferably iodine.Iodine can be applied in reaction with the form of pure state or solution.The ethanol solution of the preferred iodine of the present invention.
The addition (metal magnesium by 1 mole) of the halogenating agent that the present invention uses, it is preferred to 0.0025～0.03 mole, more preferably 0.0025～0.01 mole.
The present invention uses inert organic solvents to carry out dispersed material, inert organic solvents can diluted material, make feed liquid carry out under good stirring, it is beneficial to shedding of reaction heat, avoid reaction fierceness, it is also possible to eliminate partial electrostatic, make product keep good particle shape.Inert organic solvents may select one or more in hexane, heptane, octane, decane.Present invention preferably uses octane, decane etc..
Total addition (metal magnesium by 1 mole) of the inert organic solvents that the present invention uses, it is preferred to 2～50 moles, more preferably 2～20 moles.
The shape of the magnesium metal that the present invention uses is not particularly limited, when its reactivity worth is good, whatsoever the magnesium metal of shape can use, such as graininess, silk ribbon shape or Powdered, Average Particle Diameters in order to ensure the alkoxyl magnesium generated is maintained at 10～15 μm, and particle shape is excellent, it is preferable that mean diameter is the magnesium metal powder of 10～300 μm, or more preferably mean diameter is the magnesium metal powder of 50～200 μm.
The alcohol that the present invention uses has no particular limits, described alcohol be carbon number 1～10 unitary aliphatic alcohol or unitary aromatic alcohols in one or more, instantiation has: methanol, ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, n-amyl alcohol, isoamyl alcohol, hexanol, isohexyl alcohol, n-heptanol, iso-heptanol, n-octyl alcohol, isooctanol, n-nonyl alcohol, isononyl alcohol, Decanol, isodecanol, phenol, benzyl alcohol, phenethanol, phenylpropanol etc..Preferably one or more in methanol, ethanol, propanol and butanol.
Total addition (metal magnesium by 1 mole) of the alcohol that the present invention uses, it is preferred to 2～50 moles, more preferably 5～20 moles.
Magnesium metal, alcohol and inert organic solvents to the interpolation of reaction system are, it is preferable that 50～100 minutes add continuously or about 2～8 times be added separately.Improve the number of times being added separately the performance impact of granule is little, but the number of times being added separately can not be too low；Magnesium metal, alcohol every time can be identical to the feeding quantity of reaction system with inert organic solvents, it is also possible to gradually increase or gradually reduce.At the present invention it is preferable to so carry out the interpolation of raw material, wait until that the primary particle of dialkoxy magnesium generated in reaction system is attached on the dialkoxy magnesium particle in Already in system, then carry out next step synthetic reaction.The interval being added separately is that other conditions such as the size according to reaction unit and temperature are changed, it is preferred to use 10～60 minutes intervals.More preferably adopting following addition manner: after being added separately of previous stage, dialkoxy reactive magnesium generates, at H2Add raw material subsequently when producing close to the stage stopped.
Halogenating agent can react, to the interpolation of reaction system, the total amount being initially added into halogenating agent, it is also possible to be added separately with magnesium metal, alcohol and inert organic solvents simultaneously.Present invention preferably uses and be added separately halogenating agent
After last raw material adds, it is desirable at H2Generation terminate after under the reflux temperature of reaction system, carry out slaking reaction further, it is achieved generate particle stabilisation.
Reaction temperature of the present invention can carry out at the temperature of 0 DEG C～90 DEG C, and it is more high that reaction temperature selects, and it is more fast that reaction carries out.During reaction, reaction temperature can also change, and can be changed particle diameter and particle shape by selective response temperature.The reflux temperature of preferred reaction system of the present invention.
The all methods of the present invention are all at noble gas, for instance carry out under argon, nitrogen atmosphere, present invention preferably uses nitrogen.
After reaction terminates, product can wash with the alcohol preparing alkoxyl magnesium；Can also wash with the inert organic solvents used in course of reaction；Can also wash with other inert organic solvents.The mode of carrying out washing treatment and number of times not specially provided for.
The present invention compares with prior art, there is following evident characteristic: introduce one or more inertia alkane organic solvents and adopt the mode being continuously or intermittently added separately magnesium metal, alcohol and one or more inert organic solvents, make reaction be easier to control, prepare the more perfect carrier of particle shape；And carrier Average Particle Diameters prepared by the present invention is maintained at 10～15 μm, there is relatively high specific surface area.
The bulk density of alkoxyl magnesium, size and profile exponent (span) thereof are asked for as described below.
(1) bulk density:
A certain amount of alkoxyl magnesium is loosely joined in fixing container, get on container tare weight at balance, obtain the weight (with a gram note, recorded 2 significant digits) of alkoxyl magnesium.
The volume of the weight/mensuration of the numerical value=mensuration of bulk density
Unit is g/cm3, the arithmetic average of the value of twice mensuration is designated as measurement result
(2) particle size distribution:
Use MalvernMastersizerTMX measures the grain size of alkoxyl magnesium；
Particle mean size (D50): corresponding to the granularity of 50% accumulating weight
Span=(D90-D10)/D50 is used for characterizing even particle size distribution degree.
Accompanying drawing explanation
Fig. 1 is the grain size distribution of the alkoxyl magnesium that the present invention obtains.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is specifically described, but the present invention is not limited to following embodiment.
Embodiment 1: in the reactor with agitator, installs reflux condensing tube, thermometer and burette.Conduit is accessed in the top of reflux condensing tube, and the other end of conduit connects oil-sealing arrangement, conveniently observes H2Generation.After being sufficiently displaced from nitrogen, in reactor, add 0.2g magnesium powder, the ethanol solution (0.0266g/ml) of 10ml decane and 0.2ml iodine, priming reaction 15min, be subsequently adding 10ml dehydrated alcohol.Starting to warm up, until reaching the reaction temperature of reaction system, not being then exhausted from H in reaction system every time2After add the magnesium powder identical with previous feeding quantity, alcohol, the ethanol solution (0.0266g/ml) of iodine and decane again, add 5 times altogether, add last raw material and react and do not produce H2After, continue slaking reaction 2h.Product is washed, separates and dries after terminating by reaction.
Embodiment 2: in the reactor with agitator, installs reflux condensing tube, thermometer and burette.Conduit is accessed in the top of reflux condensing tube, and the other end of conduit connects oil-sealing arrangement, conveniently observes H2Generation.After being sufficiently displaced from nitrogen, in reactor, add 0.1g magnesium powder, the ethanol solution (0.0266g/ml) of 5ml decane and 0.1ml iodine, priming reaction 15min (system color is not in change), be subsequently adding 5ml dehydrated alcohol.Starting to warm up, until reaching the reaction temperature of reaction system, not being then exhausted from H in reaction system every time2After add the magnesium powder identical with previous feeding quantity, alcohol, the ethanol solution (0.0266g/ml) of iodine and decane again, add 10 times altogether, add last raw material and react and do not produce H2After, continue slaking reaction 2h.Product is washed, separates and dries after terminating by reaction.
Embodiment 3: in the reactor with agitator, installs reflux condensing tube, thermometer and burette.Conduit is accessed in the top of reflux condensing tube, and the other end of conduit connects oil-sealing arrangement, conveniently observes H2Generation.After being sufficiently displaced from nitrogen, in reactor, add 0.1g magnesium powder, the ethanol solution (0.0266g/ml) of 5ml decane and 0.1ml iodine, priming reaction 15min (system color is not in change), be subsequently adding 5ml dehydrated alcohol.Starting to warm up, until reaching the reaction temperature of reaction system, reaction system is not then exhausted from H2After, second time is reinforced, adds 0.2g magnesium powder, 10ml decane, the ethanol solution (0.0266g/ml) of 0.2ml iodine and 10ml dehydrated alcohol.The relatively previous feeding quantity of each feeding quantity all gradually increases, reinforced 4 times altogether, adds last raw material and reaction does not produce H2After, continue slaking reaction 2h.Product is washed, separates and dries after terminating by reaction.
Embodiment 4: in the reactor with agitator, installs reflux condensing tube, thermometer and burette.Conduit is accessed in the top of reflux condensing tube, and the other end of conduit connects oil-sealing arrangement, conveniently observes H2Generation.After being sufficiently displaced from nitrogen, in reactor, add 0.4g magnesium powder, the ethanol solution (0.0266g/ml) of 20ml decane and 0.4ml iodine, priming reaction 15min (system color is not in change), be subsequently adding 20ml dehydrated alcohol.Starting to warm up, until reaching the reaction temperature of reaction system, reaction system is not then exhausted from H2After, second time is reinforced, adds 0.3g magnesium powder, 15ml decane, the ethanol solution (0.0266g/ml) of 0.3ml iodine and 15ml dehydrated alcohol.The relatively previous feeding quantity of each feeding quantity all gradually reduces, reinforced 4 times altogether, adds last raw material and reaction does not produce H2After, continue slaking reaction 2h.Product is washed, separates and dries after terminating by reaction.
Embodiment 5: in the reactor with agitator, installs reflux condensing tube, thermometer and burette.Conduit is accessed in the top of reflux condensing tube, and the other end of conduit connects oil-sealing arrangement, conveniently observes H2Generation.After being sufficiently displaced from nitrogen, in reactor, add 0.2g magnesium powder, the ethanol solution (0.0266g/ml) of 10ml decane and 1.0ml iodine, priming reaction 15min, be subsequently adding 10ml dehydrated alcohol.Starting to warm up, until reaching the reaction temperature of reaction system, each reaction system is not then exhausted from H2The rear interpolation magnesium powder identical with previous feeding quantity, alcohol and decane, add 5 times altogether, adds last raw material and reaction does not produce H2After, continue slaking reaction 2h.Product is washed, separates and dries after terminating by reaction.
Embodiment 6: in the reactor with agitator, installs reflux condensing tube, thermometer and burette.Conduit is accessed in the top of reflux condensing tube, and the other end of conduit connects oil-sealing arrangement, conveniently observes H2Generation.After being sufficiently displaced from nitrogen, in reactor, add 0.2g magnesium powder, the ethanol solution (0.0266g/ml) of 10ml decane and 1.0ml iodine, priming reaction 15min, be subsequently adding 10ml mixed alcohol (ethanol 9ml+ butanol 1ml).Starting to warm up, until reaching the reaction temperature of reaction system, each reaction system is not then exhausted from H2The rear interpolation magnesium powder identical with previous feeding quantity, mixed alcohol and decane, add 5 times altogether, adds last raw material and reaction does not produce H2After, continue slaking reaction 2h.Product is washed, separates and dries after terminating by reaction.
Embodiment 7: in the reactor with agitator, installs reflux condensing tube, thermometer and burette.Conduit is accessed in the top of reflux condensing tube, and the other end of conduit connects oil-sealing arrangement, conveniently observes H2Generation.After being sufficiently displaced from nitrogen, in reactor, add 0.2g magnesium powder, the ethanol solution (0.0266g/ml) of 10ml decane and 1.0ml iodine, priming reaction 15min, be subsequently adding 10ml mixed alcohol (ethanol 9ml+ benzylalcohol 1ml).Starting to warm up, until reaching the reaction temperature of reaction system, each reaction system is not then exhausted from H2The rear interpolation magnesium powder identical with previous feeding quantity, mixed alcohol and decane, add 5 times altogether, adds last raw material and reaction does not produce H2After, continue slaking reaction 2h.Product is washed, separates and dries after terminating by reaction.
Embodiment 8: in the reactor with agitator, installs reflux condensing tube, thermometer and burette.Conduit is accessed in the top of reflux condensing tube, and the other end of conduit connects oil-sealing arrangement, conveniently observes H2Generation.After being sufficiently displaced from nitrogen, in reactor, add 0.2g magnesium powder, the ethanol solution (0.0266g/ml) of 10ml mixed organic solvents (decane 8ml+ octane 2ml) and 1.0ml iodine, priming reaction 10min, be subsequently adding 10ml ethanol.Starting to warm up, until reaching the reaction temperature of reaction system, each reaction system is not then exhausted from H2The rear interpolation magnesium powder identical with previous feeding quantity, alcohol and mixed organic solvents, add 5 times altogether, adds last raw material and reaction does not produce H2After, continue slaking reaction 2h.Product is washed, separates and dries after terminating by reaction.
Embodiment 9: in the reactor with agitator, installs reflux condensing tube, thermometer and burette.Conduit is accessed in the top of reflux condensing tube, and the other end of conduit connects oil-sealing arrangement, conveniently observes H2Generation.After being sufficiently displaced from nitrogen, in reactor, add 0.2g magnesium powder, the ethanol solution (0.0266g/ml) of 10ml mixed organic solvents (decane 7ml+ toluene 3ml) and 1.0ml iodine, priming reaction 20min, be subsequently adding 10ml ethanol.Starting to warm up, until reaching the reaction temperature of reaction system, each reaction system is not then exhausted from H2The rear interpolation magnesium powder identical with previous feeding quantity, alcohol and mixed organic solvents, add 5 times altogether, adds last raw material and reaction does not produce H2After, continue slaking reaction 2h.Product is washed, separates and dries after terminating by reaction.
Comparative example 1: in the reactor with agitator, installs reflux condensing tube, thermometer and burette.Conduit is accessed in the top of reflux condensing tube, and the other end of conduit connects oil-sealing arrangement, conveniently observes H2Generation.After being sufficiently displaced from nitrogen, in reactor, add 0.2g magnesium powder, the ethanol solution (0.0266g/ml) of 50ml decane and 1.0ml iodine, priming reaction 15min, be subsequently adding 50ml dehydrated alcohol.Starting to warm up, until reaching the reaction temperature of reaction system, not being then exhausted from H in reaction system every time2After add 0.2g magnesium powder again, add 5 times altogether, the final total feeding quantity of reaction is 1.0g magnesium powder.Add last raw material and reaction does not produce H2After, continue slaking reaction 2h.Product is washed, separates and dries after terminating by reaction.
Comparative example 2: in the reactor with agitator, installs reflux condensing tube, thermometer and burette.Conduit is accessed in the top of reflux condensing tube, and the other end of conduit connects oil-sealing arrangement, conveniently observes H2Generation.After being sufficiently displaced from nitrogen, in reactor, add 0.2g magnesium powder, the ethanol solution (0.0266g/ml) of 50ml decane and 1.0ml iodine, priming reaction 15min, be subsequently adding 10ml dehydrated alcohol.Starting to warm up, until reaching the reaction temperature of reaction system, not being then exhausted from H in reaction system every time2After add 0.2g magnesium powder and 10ml dehydrated alcohol again, add 5 times altogether, the final total feeding quantity of reaction is 1.0g magnesium powder, 50ml decane, the ethanol solution (0.0266g/ml) of 1.0ml iodine and 50ml dehydrated alcohol.Add last raw material and reaction does not produce H2After, continue slaking reaction 2h.Product is washed, separates and dries after terminating by reaction.
Comparative example 3: in the reactor with agitator, installs reflux condensing tube, thermometer and burette.Conduit is accessed in the top of reflux condensing tube, and the other end of conduit connects oil-sealing arrangement, conveniently observes H2Generation.After being sufficiently displaced from nitrogen, in reactor, add 0.2g magnesium powder, the ethanol solution (0.0266g/ml) of 1.0ml iodine and 10ml dehydrated alcohol.Starting to warm up, until reaching the reaction temperature of reaction system, each reaction system is not then exhausted from H2Rear interpolation 0.2g magnesium powder and 10ml dehydrated alcohol, adds 5 times altogether, and the final total feeding quantity of reaction is 1.0g magnesium powder, the ethanol solution (0.0266g/ml) of 1.0ml iodine and 50ml dehydrated alcohol.Add last raw material and reaction does not produce H2After, continue slaking reaction 2h.Product is washed, separates and dries after terminating by reaction.
Table 1
From table 1 it follows that manufacturing method according to the invention, it is possible to obtaining bulk density height, particle shape excellent, particle mean size is less, particle size distribution index is low and specific grain surface amasss relatively large alkoxyl magnesium granule.
Claims (12)
1. the preparation method for the alkoxyl magnesium carrier of olefin polymerization catalysis; comprise the steps: under inert gas shielding; employing inert organic solvents is dispersant; magnesium metal and alcohol reaction is made under halogenating agent exists; reaction temperature is 0～90 DEG C, until reaction do not produce H2 after, then 50-80 DEG C of ripening 2-10 hour; wash, separate, dry, prepare alkoxyl magnesium carrier；It is characterized in that the reaction system under alcohol reflux adds magnesium metal, alcohol and inertia alkane organic solvent.
2. the preparation method of the alkoxyl magnesium carrier for olefin polymerization catalysis according to claim 1, it is characterized in that in 1 mole metal magnesium, total consumption of described alcohol is 2～50 moles, total consumption of described halogenating agent is 0.0025～0.03 mole, and total consumption of described inert organic solvents is 2～50 moles.
3. the preparation method of the alkoxyl magnesium carrier for olefin polymerization catalysis according to claim 1, it is characterised in that described magnesium metal, alcohol and inert organic solvents are 50～100 minutes add continuously or 2～8 times be added separately to the addition manner of reaction system.
4. the preparation method of the alkoxyl magnesium carrier for olefin polymerization catalysis according to claim 1, it is characterised in that described halogenating agent is iodine, carbon tetrachloride, magnesium iodide, magnesium chloride or Alkoxymagnesium halides.
5. the preparation method of the alkoxyl magnesium carrier for olefin polymerization catalysis according to claim 1, it is characterised in that described inertia alkane organic solvent is at least one in the group of the free hexane of choosing, heptane, octane, decane.
6. the preparation method of the alkoxyl magnesium carrier for olefin polymerization catalysis according to claim 1, it is characterised in that described alcohol is at least one in the unitary aliphatic alcohol of C2～C10 or the unitary aromatic alcohols of C2～C10.
7. the preparation method of the alkoxyl magnesium carrier for olefin polymerization catalysis according to claim 6, it is characterised in that described alcohol is at least one in the group selecting free methanol, ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, n-amyl alcohol, isoamyl alcohol, hexanol, isohexyl alcohol, n-heptanol, iso-heptanol, n-octyl alcohol, isooctanol, n-nonyl alcohol, isononyl alcohol, Decanol, isodecanol, phenol, benzyl alcohol, phenethanol, phenylpropanol to form.
8. the preparation method of the alkoxyl magnesium carrier for olefin polymerization catalysis according to claim 2, it is characterized in that in 1 mole metal magnesium, total consumption of described alcohol is 5～20 moles, total consumption of described halogenating agent is 0.0025～0.01 mole, and total consumption of described inert organic solvents is 2～20 moles.
9., for the alkoxyl magnesium carrier of olefin polymerization catalysis, it is that the preparation method of the alkoxyl magnesium carrier for olefin polymerization catalysis described in any one of claim 1～8 prepares.
10. the alkoxyl magnesium carrier for olefin polymerization catalysis according to claim 9, it is characterised in that the bulk density of described alkoxyl carrier is more than or equal to 0.33g/cm3。
11. the alkoxyl magnesium carrier for olefin polymerization catalysis according to claim 9, it is characterised in that the mean diameter D50 of described alkoxyl magnesium carrier is 10～15 μm.
12. the alkoxyl magnesium carrier for olefin polymerization catalysis according to claim 9, it is characterised in that particle size distribution Span=(the D90-D10)/D50 of described alkoxyl magnesium carrier is less than or equal to 1.5.
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| CN107936154A (en) * | 2017-12-01 | 2018-04-20 | 中国石油天然气股份有限公司 | A kind of alkoxyl magnesium catalyst carrier and its preparation method and application |
| CN108102014A (en) * | 2018-01-09 | 2018-06-01 | 为信（深圳）材料科技有限公司 | A kind of component and preparation method of spherical shape alkoxyl magnesium particle |
| CN108219038A (en) * | 2018-01-09 | 2018-06-29 | 为信（深圳）材料科技有限公司 | The component and preparation method of alkoxyl magnesium particle |
| CN108341899A (en) * | 2017-01-22 | 2018-07-31 | 任丘市利和科技发展有限公司 | A kind of catalytic component, preparation method and applications being used for vinyl polymerization or combined polymerization based on alkoxyl magnesium carrier |
| CN114456281A (en) * | 2020-10-22 | 2022-05-10 | 中国石油化工股份有限公司 | Alkoxy magnesium carrier, Ziegler-Natta catalyst, catalyst for olefin polymerization, preparation method and application thereof |
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| CN108341899A (en) * | 2017-01-22 | 2018-07-31 | 任丘市利和科技发展有限公司 | A kind of catalytic component, preparation method and applications being used for vinyl polymerization or combined polymerization based on alkoxyl magnesium carrier |
| CN107936154A (en) * | 2017-12-01 | 2018-04-20 | 中国石油天然气股份有限公司 | A kind of alkoxyl magnesium catalyst carrier and its preparation method and application |
| US11084890B2 (en) | 2017-12-01 | 2021-08-10 | Petrochina Company Ltd. | Magnesium alkoxide catalyst support and the preparation method and use thereof |
| CN108102014A (en) * | 2018-01-09 | 2018-06-01 | 为信（深圳）材料科技有限公司 | A kind of component and preparation method of spherical shape alkoxyl magnesium particle |
| CN108219038A (en) * | 2018-01-09 | 2018-06-29 | 为信（深圳）材料科技有限公司 | The component and preparation method of alkoxyl magnesium particle |
| CN114456281A (en) * | 2020-10-22 | 2022-05-10 | 中国石油化工股份有限公司 | Alkoxy magnesium carrier, Ziegler-Natta catalyst, catalyst for olefin polymerization, preparation method and application thereof |
| CN114456281B (en) * | 2020-10-22 | 2024-03-26 | 中国石油化工股份有限公司 | Alkoxy magnesium carrier, ziegler-Natta catalyst, catalyst for olefin polymerization, preparation method and application thereof |
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|---|---|
| CN105777951B (en) | 2018-10-16 |
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