CN105085738B - A kind of magnesium halide solution and preparation method thereof - Google Patents
A kind of magnesium halide solution and preparation method thereof Download PDFInfo
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- CN105085738B CN105085738B CN201410176196.XA CN201410176196A CN105085738B CN 105085738 B CN105085738 B CN 105085738B CN 201410176196 A CN201410176196 A CN 201410176196A CN 105085738 B CN105085738 B CN 105085738B
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Abstract
The present invention provides a kind of magnesium halide solution, and the magnesium halide solution is with anhydrous magnesium halide is dissolved in the mixed solvent comprising oxygen-containing organic titanic compound, organic nitrogen-containing heterocyclic compound, hydroxyl class compound and hydrocarbon compound and is formed；Wherein organic nitrogen-containing heterocyclic compound is 3~8 membered ring nitrogen-containing heterocycle compounds or with phenyl ring and is unified into the nitrogen-containing heterocycle compound of condensed ring.The present invention correspondingly provides the preparation method of the magnesium halide solution.Preparation method is simple by the present invention；The amorphous magnesium halide solution stability of gained is good, can be used for preparing olefinic polymerization and copolymerization catalyst.
Description
Technical field
The present invention relates to a kind of magnesium halide solutions and preparation method thereof.Gained magnesium halide solution stability is good, can be used for making
Standby olefinic polymerization and copolymerization catalyst.
Background technology
With the development of olefin polymetiation process, the catalyst to match with polymerization technique has also got significant progress,
Middle effective catalyst still occupies by its excellent polymerization and ripe application technology in polyolefin catalyst field
Consequence.Especially people increasingly pay close attention to the production development of new structure vistanex, to olefin polymerization catalysis
Comprehensive performance require also higher and higher, not only to adapt to process unit, but also adjustable to resin structure controllable.Through excessive
The exploratory development in year, shows that Mg-Ti systems effective catalyst is relatively suitble to this application.
The method that the preparation method of Mg-Ti systems effective catalyst mostly uses solution modeling at present, i.e., first make magnesium compound molten
In certain solvent, then reprecipitation be precipitated method.Such as day tekiaki 54-40293 propositions metatitanic acid liposoluble solution magnesium compound,
It proposes day tekiaki 56-811 and day tekiaki 58-83006 to dissolve magnesium compound with compounds such as alcohol, aldehyde, amine, carboxylic acids, day is special
Clear 58-19307 propositions organic phosphorus compound dissolving magnesium compound is opened, day tekiaki 58-183708 proposes organic epoxidation
The schemes such as object and organic phosphorus compound (phosphate compounds) mixed dissolution magnesium compound of conjunction.
Although above-mentioned magnesium compound dissolving method can also overcome the shortcomings that grinding method to a certain extent, but still have one
The magnesium that serial deficiency had much room for improvement as described in day tekiaki 54-40293, day tekiaki 58-19307, day tekiaki 58-183708
Catalyst is precipitated in compound solution, and activity is relatively low, and activity is decreased obviously when extending polymerization time, the accumulation of polymer
Density is relatively low.
The present inventor selects suitable magnesium halide dissolution system that can obtain good magnesium halide by testing discovery repeatedly
Solution；Its preparation condition is mild, and raw material is cheap and easy to get, and utilization rate of equipment and installations is high；And there is easy to operate, environmental-friendly advantage.
Invention content
Therefore, the present invention provides a kind of magnesium halide solution, and the magnesium halide solution is dissolved in anhydrous magnesium halide comprising oxygen-containing
Organic titanic compound, organic nitrogen-containing heterocyclic compound, hydroxyl class compound and hydrocarbon compound mixed solvent and formed；Its
Middle organic nitrogen-containing heterocyclic compound is 3~8 membered ring nitrogen-containing heterocycle compounds or with phenyl ring and is unified into the nitrogen heterocyclic ring chemical combination of condensed ring
Object.
The magnesium halide solution obtained in the present invention is amorphous magnesium halide form, that is to say, that magnesium halide solution of the invention
In do not contain crystalline state magnesium halide.In the present invention, Materials Absolute magnesium halide be crystalline state magnesium halide, can be α, β or
A variety of crystalline forms such as γ.In the present invention, the mixed solvent can also wrap other than above-mentioned essential four kinds of organic solvents
Containing other organic solvents, it is for example, selected from the organic solvent of the compounds such as esters, ketone and amine.These other organic solvents
Dosage is not premised on influencing the phase of final magnesium halide solution product.
Preferably, phosphate compounds are not included in the mixed solvent of the present invention.Under this preferable case, answer
, will not be in downstream product there are the residual of phosphorus when preparing downstream product with heretofore described magnesium halide solution, this is to being promoted
The product quality of downstream product is highly beneficial.Phosphate compounds in the present invention are, for example, that tributyl phosphate, tricresyl phosphate are different
Butyl ester, tricresyl phosphate propyl ester, triethyl phosphate or trimethyl phosphate.
Preferably, in the present invention, the magnesium halide solution be with anhydrous magnesium halide be dissolved in by oxygen-containing organic titanic compound,
Organic nitrogen-containing heterocyclic compound, hydroxyl class compound and hydrocarbon compound composition mixed solvent and formed.That is, excellent
The in the mixed solvent of anthology invention only includes above-mentioned essential four kinds of organic solvents.
Preferably, the general formula of the magnesium halide is MgX2, X is halogen in formula；The oxygen-containing organic titanic compound such as general formula
Ti(OR1)nX4-nIt is shown, R in formula1It is C1~C20Alkyl, can be saturations or undersaturated straight chain, branch or closed chain, 0<n
≤ 4, X are halogens.The hydroxyl class compound formula is HOR2, R in formula2It is C1~C20Alkyl, can be saturation or insatiable hunger
Straight chain, branch or the closed chain of sum；The hydrocarbon compound is C3~C100Aliphatic hydrocarbon or its halogenated hydrocarbons, or be aromatic series
Hydrocarbon or its halogenated hydrocarbons can be saturations or undersaturated straight chain, branch or closed chain；It is preferred that the hydrocarbon compound is C4~C20
Hydrocarbon compound.In a specific embodiment, the magnesium halide is magnesium chloride, magnesium bromide, magnesium iodide and its mixture；
The oxygen-containing organic titanic compound is metatitanic acid lipoid substance and its mixture, preferably tetraethyl titanate, tetraisopropyl titanate, titanium
Sour four butyl esters, four different monooctyl ester of metatitanic acid；The hydroxyl class compound be fatty alcohol, aromatic alcohol or phenols, preferably methanol, ethyl alcohol,
Isopropanol, n-butanol, n-hexyl alcohol, isooctanol, benzyl alcohol and benzyl carbinol；The hydrocarbon compound be selected from benzene,toluene,xylene,
Normal butane, iso-butane, isopentane, pentane, n-hexane, hexamethylene, heptane, octane, decane, 1,2- dichloroethanes, chlorobenzene and
Its mixture.
In the present invention, the preferably described organic nitrogen-containing heterocyclic compound be selected from pyrroles, thiazole, imidazoles, pyridine, pyrazine, pyrimidine,
It is one or more in pyridazine, indoles, quinoline, pyridine of talking endlessly.
In the present invention, it is preferred that in terms of every mole of magnesium halide, oxygen-containing organic titanic compound is 0.01~2.0 mole,
It is preferred that 0.1~1.5 mole；Organic nitrogen-containing heterocyclic compound be 0.01~10 mole, preferably 0.1~6.5 mole, hydroxyl class
It is 0.01~20 mole, preferably 0.1~15 mole to close object.Preferably, the molar concentration of magnesium halide is in magnesium halide solution
0.0001~20mol/L, more preferably 0.001~10mol/L.
The present invention also provides a kind of preparation methods of magnesium halide solution as described above, including first by anhydrous magnesium halide with it is described
Oxygen-containing organic titanic compound, organic nitrogen-containing heterocyclic compound and hydroxyl class compound are uniformly mixed, then by the transparent molten of gained
Liquid is mixed with the hydrocarbon compound, obtains the magnesium halide solution.Preferably, in the preparation method, mixing temperature
Selected from 0 DEG C~200 DEG C, preferably 20 DEG C~150 DEG C.
In preparing amorphous magnesium halide solution, magnesium compound, organic nitrogen-containing heterocyclic compound, oxygen-containing organic titanium chemical combination
The temperature that object, hydroxyl class compound and hydrocarbons contact with each other depends on the property of reactant, is typically chosen in relatively
It is dissolved at high temperature advantageously, preferably in the decomposition temperature of reactant hereinafter, temperature is normally no higher than 200 DEG C, one
As be not higher than 150 DEG C.The time of dissolving depends on the property and operating condition of reactant, and general selection of time is can obtain
Until fully transparent solution, required time is generally 10 minutes to 24 hours, preferably 2 to 16 hours.It can also add after dissolving
Enter diluent such as：Hexane, heptane, octane, benzene,toluene,xylene, 1,2- dichloroethanes, chlorobenzene and other hydro carbons or halogenated
Hydrocarbon compound is adjusted to a certain concentration and can place for a long time save backup.
Specific implementation mode
Example given below rather than is limited the invention in order to illustrate the present invention.
Embodiment 1
Prepare amorphous magnesium halide solution：4.75 grams of anhydrous magnesium chlorides are weighed, 17.6 milliliters of butyl titanates, 4.0 are added
Milliliter pyridine, 4.4 milliliters of absolute ethyl alcohols and 200 milliliters of toluene are kept stirring 6 hours at 60 DEG C and form clear solution.
Embodiment 2
" 200 milliliters of toluene " in amorphous magnesium halide solution preparation process in embodiment 1 is adjusted to " 50 milliliters oneself
Alkane ".Other conditions are the same as embodiment 1.
Embodiment 3
" 4.4 milliliters of absolute ethyl alcohols " in amorphous magnesium halide solution preparation process in embodiment 1 is adjusted to " 11.6 millis
Rise n-butanol ", other conditions are the same as embodiment 1.
Embodiment 4
" 4.0 milliliters of pyridines " in amorphous magnesium halide solution preparation process in embodiment 1 is adjusted to " 3.5 milli pyrroles
Cough up ", other conditions are the same as embodiment 1.
Embodiment 5
" 17.6 milliliters of butyl titanates " in amorphous magnesium halide solution preparation process in embodiment 1 is adjusted to " 9 millis
Rise tetraethyl titanate ", " 4.0 milliliters of pyridines " is adjusted to " 6.0 milliliters of pyridines ".Other conditions are the same as embodiment 1.
Claims (15)
1. a kind of magnesium halide solution, which is characterized in that the magnesium halide solution is first by anhydrous magnesium halide and oxygen-containing organic titanizing
Close object, organic nitrogen-containing heterocyclic compound and hydroxyl class compound are uniformly mixed, then by the clear solution and hydrocarbon of gained
Object is mixed and is formed；Wherein organic nitrogen-containing heterocyclic compound be 3 ~ 8 membered ring nitrogen-containing heterocycle compounds or with phenyl ring and be unified into condensed ring
Nitrogen-containing heterocycle compound, the magnesium halide solution be amorphous magnesium halide form.
2. magnesium halide solution according to claim 1, which is characterized in that the general formula of the magnesium halide is MgX2, X is in formula
Halogen；The oxygen-containing organic titanic compound such as general formula Ti (OR1)nX4-nIt is shown, R in formula1It is C1~C20Alkyl, can be saturation
Or undersaturated straight chain, branch or closed chain, 0<N≤4, X are halogens.
3. magnesium halide solution according to claim 1, which is characterized in that the hydroxyl class compound formula is HOR2, formula
Middle R2It is C1~C20Alkyl, can be saturations or undersaturated straight chain, branch or closed chain；The hydrocarbon compound is C3~
C100Aliphatic hydrocarbon or its halogenated hydrocarbons, or be aromatic hydrocarbon or its halogenated hydrocarbons, can be saturations or undersaturated straight chain, branch
Or closed chain.
4. magnesium halide solution according to claim 3, which is characterized in that the hydrocarbon compound is C4~C20Hydro carbons
Close object.
5. magnesium halide solution according to claim 1, which is characterized in that the magnesium halide is magnesium chloride, magnesium bromide, iodate
Magnesium and its mixture；The oxygen-containing organic titanic compound is metatitanic acid lipoid substance and its mixture；The hydroxyl class chemical combination
Object is fatty alcohol, aromatic alcohol or phenols；The hydrocarbon compound is selected from benzene,toluene,xylene, normal butane, iso-butane, isoamyl
Alkane, pentane, n-hexane, hexamethylene, heptane, octane, decane and its mixture.
6. magnesium halide solution according to claim 5, which is characterized in that the oxygen-containing organic titanic compound is selected from metatitanic acid four
Ethyl ester, four different monooctyl ester of tetraisopropyl titanate, butyl titanate and metatitanic acid；The hydroxyl class compound is selected from methanol, ethyl alcohol, different
Propyl alcohol, n-butanol, n-hexyl alcohol, isooctanol, benzyl alcohol and benzyl carbinol.
7. magnesium halide solution according to claim 1, which is characterized in that in terms of every mole of magnesium halide, oxygen-containing organic titanizing
It is 0.01~2.0 mole to close object；Organic nitrogen-containing heterocyclic compound is 0.01~10 mole, and hydroxyl class compound is 0.01~20
Mole.
8. magnesium halide solution according to claim 7, which is characterized in that in terms of every mole of magnesium halide, oxygen-containing organic titanizing
It is 0.1~1.5 mole to close object；Organic nitrogen-containing heterocyclic compound is 0.1~6.5 mole, and hydroxyl class compound is rubbed for 0.1~15
You.
9. the magnesium halide solution according to any one of claim 1 ~ 8, which is characterized in that magnesium halide in magnesium halide solution
Molar concentration be 0.0001~20mol/L.
10. magnesium halide solution according to claim 9, which is characterized in that the molar concentration of magnesium halide in magnesium halide solution
For 0.001~10mol/L.
11. the magnesium halide solution according to any one of claim 1 ~ 8, which is characterized in that the organic nitrogen-containing heterocycle
Compound is one or more in pyrroles, thiazole, imidazoles, pyridine, pyrazine, pyrimidine, pyridazine, indoles, quinoline, pyridine of talking endlessly.
12. a kind of preparation method of any one of such as claim 1 ~ 11 magnesium halide solution, which is characterized in that first by nothing
Water magnesium halide is uniformly mixed with the oxygen-containing organic titanic compound, organic nitrogen-containing heterocyclic compound and hydroxyl class compound, then
The clear solution of gained is mixed with the hydrocarbon compound, obtains the magnesium halide solution.
13. preparation method according to claim 12, which is characterized in that mixing temperature is selected from 0 DEG C ~ 200 DEG C；Incorporation time
Selected from 10 minutes ~ 24 hours.
14. preparation method according to claim 13, which is characterized in that mixing temperature is selected from 20 DEG C ~ 150 DEG C；When mixing
Between be selected from 2 ~ 16 hours.
15. a kind of such as the application of the magnesium halide solution in olefin polymerization of any one of claim 1 ~ 11.
Priority Applications (14)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410176196.XA CN105085738B (en) | 2014-04-29 | 2014-04-29 | A kind of magnesium halide solution and preparation method thereof |
| PCT/CN2015/077801 WO2015165402A1 (en) | 2014-04-29 | 2015-04-29 | Magnesium halide solution, and preparation method and application thereof |
| JP2016565275A JP6599895B2 (en) | 2014-04-29 | 2015-04-29 | Magnesium halide solution and its preparation and use |
| BR112016025378-7A BR112016025378B1 (en) | 2014-04-29 | 2015-04-29 | MAGNESIUM HALIDE SOLUTION, ITS METHOD OF PREPARATION AND USE |
| EP15785690.7A EP3138857A4 (en) | 2014-04-29 | 2015-04-29 | Magnesium halide solution, and preparation method and application thereof |
| SG11201609035PA SG11201609035PA (en) | 2014-04-29 | 2015-04-29 | Magnesium halide solution, and preparation method and application thereof |
| KR1020227004487A KR102444469B1 (en) | 2014-04-29 | 2015-04-29 | Magnesium halide solution, and preparation method and application thereof |
| US15/307,216 US10087264B2 (en) | 2014-04-29 | 2015-04-29 | Magnesium halide solution, preparing method and use thereof |
| RU2016146552A RU2688937C2 (en) | 2014-04-29 | 2015-04-29 | Magnesium halide solution and method for production thereof and use thereof |
| CA2947186A CA2947186C (en) | 2014-04-29 | 2015-04-29 | Magnesium halide solution, preparing method and use thereof |
| KR1020167033298A KR20170005030A (en) | 2014-04-29 | 2015-04-29 | Magnesium halide solution, and preparation method and application thereof |
| MYPI2016703973A MY183125A (en) | 2014-04-29 | 2015-04-29 | Magnesium halide solution, preparing method and use thereof |
| PH12016502155A PH12016502155B1 (en) | 2014-04-29 | 2016-10-28 | Magnesium halide solution, preparing method and use thereof |
| ZA2016/07704A ZA201607704B (en) | 2014-04-29 | 2016-11-08 | Magnesium halide solution, preparing method and use thereof |
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| CN101560273A (en) * | 2009-04-24 | 2009-10-21 | 营口市向阳催化剂有限责任公司 | Olefinic polymerization catalyst, preparation method and polymerization method |
| CN103665206A (en) * | 2013-12-10 | 2014-03-26 | 上海化工研究院 | Preparation method of multi-active-centre catalyst for olefin polymerization |
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| CA2201230A1 (en) * | 1996-04-01 | 1997-10-01 | Mitsui Petrochemical Industries, Ltd. | Process for preparing anhydrous magnesium halide solution and process for preparing solid titanium catalyst component for olefin polymerization |
| KR100389477B1 (en) * | 2000-11-09 | 2003-06-27 | 삼성종합화학주식회사 | A method for producing ethylene homo- and co-polymer |
| CN103509136B (en) * | 2012-06-19 | 2015-08-19 | 中国石油化工股份有限公司 | The preparation method of a kind of olefin polymerization catalyst components and corresponding catalyst |
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| CN101560273A (en) * | 2009-04-24 | 2009-10-21 | 营口市向阳催化剂有限责任公司 | Olefinic polymerization catalyst, preparation method and polymerization method |
| CN103665206A (en) * | 2013-12-10 | 2014-03-26 | 上海化工研究院 | Preparation method of multi-active-centre catalyst for olefin polymerization |
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