CN108219038A - The component and preparation method of alkoxyl magnesium particle - Google Patents
The component and preparation method of alkoxyl magnesium particle Download PDFInfo
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- CN108219038A CN108219038A CN201810018022.9A CN201810018022A CN108219038A CN 108219038 A CN108219038 A CN 108219038A CN 201810018022 A CN201810018022 A CN 201810018022A CN 108219038 A CN108219038 A CN 108219038A
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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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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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
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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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
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
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Abstract
The method that the present invention discloses a kind of component of spherical alkoxyl magnesium particle and prepares spherical alkoxyl magnesium particle.The present invention introduces a certain amount of acrylic polymer in alcohol or mixed alcohols compound, and metal magnesium powder haptoreaction, to prepare alkoxyl magnesium；Obtained alkoxyl magnesium particle shape is perfect, and sphericity is high, the bulk density higher of particle, particle uniform grading narrowly distributing.Meanwhile this alkoxyl magnesium particle can be used for preparing olefin polymerization catalysis.
Description
Technical field
The present invention relates to the preparation fields of alkoxyl magnesium, and in particular to a kind of component of spherical shape alkoxyl magnesium particle and use
The method that the component prepares spherical alkoxyl magnesium particle.
Background technology
It is well known that now with the development of economy, demand of the people to polyolefine material is higher and higher, poly- for producing
The Efficient polyolefin catalyst of olefin material is due to having good controllable particle shape and microstructure, in polyolefin catalyst
Field is widely used.What is wherein played a crucial role is exactly the composition and microstructure of carrier, the load that distinct methods obtain
Body just obtains different structure and the catalyst of performance accordingly.
The carrier using alkoxyl magnesium as high performance catalyst, alkoxyl magnesium carrier are disclosed in many patent documents
The catalyst of preparation has significantly higher active, good hydrogen response and excellent copolymerization performance.In recent years open
Technical literature report in have the various methods for preparing alkoxyl magnesium, mainly have following a few classes：One kind is Japanese Patent Laid-Open
Disclosed in 03-74341,04-368391 in the presence of iodine, magnesium metal is reacted with alcohol, obtains spherical or elliposoidal diethoxy
Base magnesium, however this method is difficult to control suitable reaction speed, obtained product can inevitably generate non-uniform bulky grain
Or fine powder, and general bulk density is relatively low；Another is that diethoxy magnesium alcohol is molten disclosed in the flat 6-8733 of open patent
The drying process with atomizing of liquid can prepare spheric granules, then also carry out decarboxylation processing, and the technique is cumbersome, somewhat expensive,
And obtained product is difficult thorough decarboxylation again, and product quality is difficult to meet downstream use；In addition, also one kind be magnesium metal with
Alcohol is obtained by the reaction alkoxyl magnesium, then controls granular size through mechanical lapping, this method there are the problem of be also obtained production
Composition granule size is uneven, seriously affects use.
Particle of uniform size, excellent particle shape should be the important goals for preparing alkoxyl magnesium particle, the present invention
Purpose seek to overcome some shortcomings in the prior art, the easier more practical preparation method of use obtains regular, tool
There is the spherical alkoxyl magnesium particulate matter of good form.
Invention content
For problems of the prior art, the purpose of the present invention is to provide a kind of groups of spherical alkoxyl magnesium particle
Part, the spherical alkoxyl magnesium particle shape prepared by the component is perfect, and sphericity is high, the bulk density higher of particle, accumulation
Density is greater than or equal to 0.30g/mL；Particle uniform grading narrowly distributing, particle diameter distribution are less than or equal to 1.2；Carrier can be used as
For preparing olefin polymerization catalysis.Another object of the present invention is to provide a kind of preparation side of spherical alkoxyl magnesium particle
Method.
To achieve the above object, the present invention uses following technical scheme：
A kind of component of spherical shape alkoxyl magnesium particle, the component include following component：Metal magnesium powder, alcohol or mixed alcohols
Compound, elemental iodine and acrylic polymer.
Further, the alcohol or mixed alcohols compound and the molar ratio of the metal magnesium powder are：2~40；The iodine list
Matter and the molar ratio of metal magnesium powder are：0.0001~0.2；The acrylic polymer adds in alcohol or mixed alcohols compound
Ratio is 0.001~500g/L.
Further, the alcohol or mixed alcohols compound such as general formula R1Shown in OH, R in formula1It is C1~C20Alkyl, can be with
It is saturations or undersaturated straight chain, branch or closed chain.
Further, the alcohol or mixed alcohols compound include but not limited to methanol, ethyl alcohol, isopropanol, n-butanol, just oneself
One or more mixtures in alcohol, isooctanol, benzyl alcohol, benzyl carbinol.
Further, the alcohol or mixed alcohols compound and the molar ratio of the metal magnesium powder are：4~30.
Further, the molar ratio of the elemental iodine and metal magnesium powder is：0.001~0.1.
Further, it is 0.01~200g/L that the acrylic polymer, which adds in alcohol or the ratio of mixed alcohols compound,.
A kind of method for preparing spherical alkoxyl magnesium particle, the method are：Under inert gas shielding, the propylene
Acids polymers are dissolved in the alcohol or mixed alcohols compound, then the elemental iodine is dissolved in alcohol or mixed alcohols compound
In, after adding in the metal magnesium powder, it is warming up to reflux temperature and maintains reaction, until no longer generating gas；To above-mentioned reaction
The solid product of generation is washed, is dried to obtain alkoxyl magnesium particle.
Further, the average grain diameter of spherical alkoxyl magnesium particle prepared by the method is 15-120 microns, particle diameter distribution
Span=(d90-d10)/d50 is less than or equal to 1.2.
Further, the bulk density of spherical alkoxyl magnesium particle prepared by the method is more than or equal to 0.30g/mL.
The present invention has following advantageous effects：
1st, reaction mass composition is simple, advantageously reduces production cost；
2nd, after introducing acrylic polymer, obtained alkoxyl magnesium particle bulky grain and fine powder is all less, particle diameter distribution
It is relatively narrow；
3rd, alkoxyl magnesium particle shape is perfect, particle good sphericity, and composition and architecture are used as olefin polymerization catalysis
Carrier.
Specific embodiment
In the following, embodiments of the present invention are described in further detail in conjunction with the embodiments.Following embodiment is used to illustrate
The present invention, but cannot be used for limiting the scope of the invention.
The present invention provides a kind of component of spherical alkoxyl magnesium particle, which includes following component：Metal magnesium powder, alcohol
Or mixed alcohols compound, elemental iodine and acrylic polymer；Wherein, alcohol or mixed alcohols compound and metal magnesium powder
Molar ratio is：When the addition of 2~40, preferably 4~30, alcohol or mixed alcohols compound is very few, the viscosity meeting of reaction system
It is quick to increase, it can not effectively uniformly disperse, the particle of generation is caused to be deteriorated, when the amount of alcohol or mixed alcohols compound is excessive, one
As the alkoxyl magnesium packing density of particle that generates it is relatively low, the intensity of particle is also poor, and the performance for being unfavorable for subsequent catalyst improves.
The molar ratio of elemental iodine and metal magnesium powder is：0.0001~0.2, preferably 0.001~0.1, to control suitable initial reaction
Rate.It is 0.001~500g/L that acrylic polymer, which adds in alcohol or the ratio of mixed alcohols compound, is preferably added ratio
It is 0.01~200g/L.
Prepared in the present invention in the method for alkoxyl magnesium particle does not have stringent limit to the metal magnesium powder grain shape used
System regulation, only requires its average particle size at 5~350 microns, preferably 20~200 microns of powder, to control the alkane of generation
The average particle size of oxygroup magnesium granules at 15~120 microns, while it is also ensured that particle reactivity than more uniform, alkoxyl magnesium
The particle shape of particle is also fairly perfect uniform.
Alcohol or mixed alcohols compound such as general formula R in the present invention1Shown in OH, R in formula1It is C1~C20Alkyl, can be full
And/or undersaturated straight chain, branch or closed chain；Alcohol or mixed alcohols compound include but not limited to methanol, ethyl alcohol, isopropanol,
One or more mixtures in n-butanol, n-hexyl alcohol, isooctanol, benzyl alcohol, benzyl carbinol；Preferably ethyl alcohol.In order to ensure
The function admirable of prepared alkoxyl magnesium, the fewer water content in alcohol the better, and general control is in 1000ppm hereinafter, it is preferred that control
System is in below 200ppm.
The addition sequence of reaction raw materials does not have stringent regulation in the method for the spherical alkoxyl magnesium particle of preparation of the present invention,
It can determine as needed, general first acrylic polymer to be dissolved in mixed alcohol, then elemental iodine is dissolved in alcohol, magnesium
After powder adds in, it is warming up to reflux temperature and maintains reaction.Magnesium powder disposably adds in, still in batches add in can, in batches plus
Reaction rate can preferably be controlled by entering, this reaction can be carried out at 0~100 degree, and in general temperature gets over high reaction rate
It is faster, react relatively good in reflux temperature than even more preferably controlling.Reaction generally requires 1 until no longer generating gas
~20 hours, preferably 2~10 hours.Solid product after reaction (can be contained with the mixed alcohol before reaction or common ethyl alcohol
Water is less than 200ppm) etc. wash several times, can also be washed with inert organic solvents such as hexane, toluene etc., then dry
Obtain alkoxyl magnesium particle.Whole process is completed under inert gas shielding, inert gas be helium, argon gas or nitrogen, this hair
It is preferable to use nitrogen in bright.
With reference to specific embodiment, the invention will be further described：
Embodiment 1
Reactor is sufficiently displaced from high pure nitrogen, sequentially adds 0.1 gram of Viscoplex1-156 (propylene under nitrogen protection
Acid ester polymer content 40-44%wt), 20 milliliters of absolute ethyl alcohols and 0.1 gram of iodine, heat up after stirring and dissolving, add in 80-150 mesh
1.0 grams and 10 milliliters absolute ethyl alcohols of magnesium powder, maintain back flow reaction, interval 20 minutes again add in 80-150 mesh magnesium powder 1.0
Gram and 10 milliliters of absolute ethyl alcohols, amount to points for 4 times and to add in 4.0 grams and 55 milliliters absolute ethyl alcohols of magnesium powder, reflux is maintained instead after adding material
It answers 4 hours, then is washed twice with absolute ethyl alcohol, the dosage of each absolute ethyl alcohol is 80 milliliters, then washed twice with hexane, every time
The dosage of hexane is 100 milliliters, dry that pale solid mobility powder, concrete outcome are shown in Table 1 after the completion of washing.
Embodiment 2
The embodiment is differed only in embodiment 1：By " 0.1 gram of Viscoplex 1-156 (acrylic acid in embodiment 1
Ester polymer content 40-44%wt) " it is adjusted to " 0.5 gram of Viscoplex 1-156 (acrylate polymer content 40-44%
wt)”。
Embodiment 3
The embodiment is differed only in embodiment 1：By " the 0.1 gram of iodine " in embodiment 1, it is adjusted to " 0.4 gram of iodine ".
Embodiment 4
The embodiment is differed only in embodiment 1：" 20 milliliters of absolute ethyl alcohols " in embodiment 1 is adjusted to " 50
Milliliter absolute ethyl alcohol ".
Embodiment 5
The embodiment is differed only in embodiment 1：By " 0.1 gram of Viscoplex 1-156 (acrylic acid in embodiment 1
Ester polymer content 40-44%wt) " it is adjusted to " 2.0 grams of Viscoplex 1-156 (acrylate polymer content 40-44%
wt)””。
Comparative example 1
Reactor is sufficiently displaced from high pure nitrogen, sequentially adds 15 milliliters of absolute ethyl alcohols and 0.15 gram under nitrogen protection
Iodine heats up after stirring and dissolving, adds in 1.0 grams and 10 milliliters absolute ethyl alcohols of magnesium powder of 80-150 mesh, maintains back flow reaction, is spaced 20
Minute adds in 1.0 grams and 10 milliliters absolute ethyl alcohols of magnesium powder of 80-150 mesh again, divides 4 times and amounts to 4.0 grams of addition magnesium powder and 55 millis
Absolute ethyl alcohol is risen, maintains back flow reaction 4 hours after adding material, then washed twice with absolute ethyl alcohol, the dosage of each absolute ethyl alcohol
It is 80 milliliters, then is washed twice with hexane, the dosage of each hexane is 100 milliliters, after the completion of washing, dry pale solid
Mobility powder, concrete outcome are shown in Table 1.
Embodiment 6
Alkoxyl magnesium particle prepared by the present invention can be used for synthesizing the catalyst component of olefinic polymerization：By High Purity Nitrogen
Gas is repeated in the reactor of displacement, is added in 50 milliliters of titanium tetrachloride, is cooled to 0 DEG C, adds in the alkoxyl magnesium obtained by embodiment 1
Then 5 grams of particle is to slowly warm up to 80 DEG C, add in 1.5 milliliters of DIBP (diisobutyl phthalate), be continuously heating to 110
And reaction 2 hours is maintained, then liquid pressure is filtered dry only, 50 milliliters of titanium tetrachlorides is added in again and is warming up to 110 and maintains reaction 2
Hour, then liquid pressure is filtered dry only, is repeated, the solid of gained is washed 3 times with 100 milliliters of 50 DEG C of hexanes, is finally done
It is dry to obtain solid catalyst powder.
Propylene polymerization：After reactor is sufficiently displaced from purging with high pure nitrogen, add in 1.5mmol triethyl aluminums and
The dimethoxydiphenylsilane of 0.1mmol adds above-mentioned catalyst 10mg, is added with stirring liquid propene 2.5L, hydrogen
1L (under standard state) is warming up to 70 DEG C and maintains reaction 1 hour, obtains 678 grams of polymer, polymer bulk density 0.44g/
Ml, the melt index of polymer is 3.95g/10min.
Table 1
As shown in table 1, relative to comparative example, alkoxyl magnesium particle shape prepared by embodiment 1-5 is good, and bulk density is high,
Distribution of particles is narrow.Meanwhile from the point of view of the result of embodiment 6, with the catalyst of the alkoxyl magnesium particle preparation, propylene polymerization activity
Height, bulk density is also higher, suitable for polyacrylic production.
Test method involved in the present invention is as follows：
1st, the granularity and distribution of carrier and catalyst：MASTERSIZE particles distribution instruments, n-hexane are measured as dispersant
0.02~2000 μm of range.Span=(D90-D10)/D50。
2nd, the measure of bulk density：DIN-53194.
3rd, particle sphericity is measured using Retsch companies of Germany CAMSIZER standard of instruments.
It is described above simply to illustrate that of the invention, it is understood that the invention is not limited in above example, meet
The various variants of inventive concept are within protection scope of the present invention.
Claims (10)
1. a kind of component of spherical shape alkoxyl magnesium particle, which is characterized in that the component includes following component：Metal magnesium powder, alcohol
Or mixed alcohols compound, elemental iodine and acrylic polymer.
2. the component of spherical shape alkoxyl magnesium particle according to claim 1, which is characterized in that the alcohol or mixed alcohols
Close object and the metal magnesium powder molar ratio be：2~40；The molar ratio of the elemental iodine and metal magnesium powder is：0.0001~
0.2；It is 0.001~500g/L that the acrylic polymer, which adds in alcohol or the ratio of mixed alcohols compound,.
3. the component of spherical shape alkoxyl magnesium particle according to claim 1, which is characterized in that the alcohol or mixed alcohols
Close object such as general formula R1Shown in OH, R in formula1It is C1~C20Alkyl, can be saturations or undersaturated straight chain, branch or closed chain.
4. the component of spherical shape alkoxyl magnesium particle according to claim 1, which is characterized in that the alcohol or mixed alcohols
Close object include but not limited to one kind in methanol, ethyl alcohol, isopropanol, n-butanol, n-hexyl alcohol, isooctanol, benzyl alcohol, benzyl carbinol or
A variety of mixtures.
5. the component of spherical shape alkoxyl magnesium particle according to claim 2, which is characterized in that the alcohol or mixed alcohols
Close object and the metal magnesium powder molar ratio be：4~30.
6. the component of spherical shape alkoxyl magnesium particle according to claim 2, which is characterized in that the elemental iodine and magnesium metal
The molar ratio of powder is：0.001~0.1.
7. the component of spherical shape alkoxyl magnesium particle according to claim 2, which is characterized in that the acrylic polymer
The ratio for adding in alcohol or mixed alcohols compound is 0.01~200g/L.
8. a kind of component using any spherical alkoxyl magnesium particles of claim 1-7 prepares spherical alkoxyl magnesium particle
Method, which is characterized in that the method is：Under inert gas shielding, the acrylic polymer is dissolved in described
In alcohol or mixed alcohols compound, then the elemental iodine is dissolved in alcohol or mixed alcohols compound, adds in the metal magnesium powder
Afterwards, it is warming up to reflux temperature and maintains reaction, until no longer generating gas；The solid product generated to above-mentioned reaction is washed
It washs, be dried to obtain alkoxyl magnesium particle.
9. the method according to claim 8 for preparing spherical alkoxyl magnesium particle, which is characterized in that prepared by the method
The average grain diameter of spherical alkoxyl magnesium particle is 15-120 microns, and particle diameter distribution Span=(d90-d10)/d50 is less than or equal to
1.2。
10. the method according to claim 8 for preparing spherical alkoxyl magnesium particle, which is characterized in that prepared by the method
The bulk density of spherical alkoxyl magnesium particle be more than or equal to 0.30g/mL.
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Cited By (2)
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| CN110483247A (en) * | 2019-07-16 | 2019-11-22 | 北京国达恒泰科贸有限责任公司 | Metal alkoxides powder and preparation method and application |
| CN110498871A (en) * | 2019-08-23 | 2019-11-26 | 上海化工研究院有限公司 | A kind of alkoxyl magnesium carrier granular and its application |
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