CN100491418C - Preparing method of catalyst for slurry polymerization of ethylene - Google Patents
Preparing method of catalyst for slurry polymerization of ethylene Download PDFInfo
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- CN100491418C CN100491418C CNB2005101319689A CN200510131968A CN100491418C CN 100491418 C CN100491418 C CN 100491418C CN B2005101319689 A CNB2005101319689 A CN B2005101319689A CN 200510131968 A CN200510131968 A CN 200510131968A CN 100491418 C CN100491418 C CN 100491418C
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- magnesium chloride
- catalyst
- ethylene
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- organic solvent
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Abstract
The present invention is preparation process of Ziegler-Natta catalyst for slurry polymerization of ethylene. The preparation process includes the following steps: high temperature reaction of organic alcohol and magnesium chloride in inert dispersant and adding special organic modifier to obtain homogeneous magnesium chloride solution; further dispersing in organic solvent at low temperature; and final reaction with titanium tetrachloride solution to obtain the catalyst on magnesium chloride carrier. The Ziegler-Natta catalyst is used together with organoaluminium cocatalyst for homopolymerization of ethylene and the copolymerization of ethylene and alpha-olefin, has high polymerization activity, high hydrogen sensitivity and excellent copolymerization performance, and is superior to traditional catalyst for slurry polymerization of ethylene.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst for ethylene thick liquid polymerizing, particularly relate to a kind of preparation method who can be used for the ziegler natta catalyst of ethylene thick liquid polymerizing.
Background technology
Metallocene type catalyzer is the core of conventional polyolefins catalyst technology.Metallocene type catalyzer generally is to be carrier loaded titanium active constituent with magnesium chloride, forms in conjunction with complexings such as various electron donors, organo-aluminium compounds simultaneously.For example: JP 80151010, the JP 8086804 disclosed catalyzer that are used for ethylene thick liquid polymerizing technology, being about to magnesium chloride dissolves with a large amount of alcohol, separate alcohol by pyrolysis alcohol or chemistry magnesium chloride is separated out again, again the titanium component is stated from the magnesium chloride, form the active centre.
Traditional metallocene type catalyzer generally all adopts this technological line, has the characteristics such as catalyst prod polymerization activity height that technology is simple, obtain.But in this catalyst preparation process, generally select low-carbon alcohol for use, be subjected to the restriction of boiling point etc., the reaction of itself and magnesium chloride can only be carried out at low temperatures, the lattice damage of magnesium chloride is not thorough, therefore the magnesium chloride crystalline is separated out the granules of catalyst size distribution broad that obtains again in subsequent technique, according to " print effect ", also just cause polymer particle size to distribute and do not concentrate, fine powder content is higher; The not enough homogeneous in while gained granules of catalyst titanium active centre, oligopolymer growing amount height when being used for the ethene slurry polymerization, is unfavorable for the expansion of the production load of device at the production cycle of having reduced device like this.
Summary of the invention
At the problems referred to above, the present invention carries out technological innovation to the catalyzer synthesis route, at first prepare homogeneous phase solution with higher alcohols and multiple organic modifiers and magnesium chloride, then again in organic solvent magnesium chloride obtain the further degree of depth and disperse, in titanium tetrachloride solution, separate out again at last, simultaneously, load titanium active constituent obtains solid catalyst.Bigger advantage when being used for ethylene thick liquid polymerizing, the catalyzer that makes is arranged aspect polymerization.
To describe preparation method below in detail according to a kind of catalyst for ethylene thick liquid polymerizing of the present invention:
Step a. is pyroreaction in the inertia dispersion agent with higher alcohols and magnesium chloride, makes the magnesium chloride homogeneous phase solution through adding organic modifiers; It is in 6～12 the monohydroxy-alcohol one or more that described higher alcohols are selected from carbon atom number, is the disposable adding of 2.0～4.0:1 by the magnesium alkoxide mol ratio; The inertia dispersion agent is selected from C
5～C
15Alkane or C
6～C
8Aromatic hydrocarbons; Organic modifiers is silicoorganic compound and acid anhydrides, two kinds of organic modifiers by with the disposable adding of mol ratio 0.04～0.5:1 of magnesium chloride, the preferred 0.1～0.2:1 of the mol ratio of organic modifiers and magnesium, most preferably 0.15:1.90～170 ℃ of temperature of reaction, 0.5～5 hour reaction times, preferred 1～4 hour.
Wherein, silicoorganic compound are selected from: tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, methyltrimethoxy silane, ethyl trimethoxy silane, ethyl triethoxysilane, cyclopentyl Trimethoxy silane, cyclohexyl trimethoxy silane, cyclohexyl methyl dimethoxy silane or dimethoxydiphenylsilane; Preferred tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane or four butoxy silanes; Tetraethoxysilane most preferably.
Acid anhydrides is selected from: diacetyl oxide, Tetra hydro Phthalic anhydride, maleic anhydride or benzoyl oxide.Preferred diacetyl oxide or Tetra hydro Phthalic anhydride; Tetra hydro Phthalic anhydride most preferably.
Step b. gained magnesium chloride solution further disperses with organic solvent at a certain temperature again; Described organic solvent is selected from: monochlorethane, a chloropropane, a chlorobutane, a chloropentane, methylene dichloride, ethylene dichloride, 1, in 3-propylene dichloride, 1,4-dichlorobutane, a chlorine hexanaphthene, dichloro hexanaphthene, mono chloro benzene, dichlorobenzene, the trichloromethane one or more; A preferred chlorobutane, ethylene dichloride, trichloromethane or methylene dichloride; Methylene dichloride most preferably.0-50 ℃ of this process reaction temperature, 0.5～5 hour reaction times.Step c and titanium tetrachloride solution react, and titanium tetrachloride are cooled to-30～-15 ℃, add through the further dispersive magnesium chloride of step b homogeneous phase solution, and obtaining with the magnesium chloride is the solid of carrier; 90-170 ℃ of this process reaction temperature, 0.5～5 hour reaction times.
Steps d. after the inert solvent washing, the preferred inertia alkane of inert solvent, more preferably hexane or heptane obtain catalyst prod through nitrogen drying,
When the resulting catalyzer of the present invention is used for ethylene thick liquid polymerizing, need to cooperate the adding activator to carry out ethylene polymerization.The activator of selecting for use is an aluminum alkyls, is preferably triethyl aluminum or triisobutyl aluminium or the mixture of the two, and its consumption is advisable with aluminium/titanium mol ratio 20～400:1.
The invention provides a kind of method for preparing catalyst that can be used for ethylene thick liquid polymerizing technology.The present invention carries out technological innovation to the catalyzer synthesis route, at first prepares the magnesium chloride homogeneous phase solution with higher alcohols and properties-correcting agent, then further disperses in organic solvent again, and last and titanium tetrachloride reaction obtains solid catalyst.Its feature of the catalyzer that makes is as follows: the granules of catalyst form be class sphere, titanium content more than 6.2 (wt%), particle diameter between 10-20 μ m, particle size distribution is concentrated, fine polymer powder content is few.
The polymerization catalyst evaluation result that following table makes for this method.From the result, the polymerization catalyst excellent performance is especially more having remarkable advantages with respect to traditional ethylene thick liquid polymerizing catalyzer aspect bulk density and the size-grade distribution.
Annotate: slurry polymerization, 80 ℃, 2.0hr, H
2/ C
2=0.28MPa/0.45MPa
A: this catalyzer; B: traditional ethylene thick liquid polymerizing catalyzer
Embodiment
Embodiment 1
(Preparation of catalysts)
Under nitrogen protection, open and stir, in reactor, add 38ml decane, 35ml isooctyl alcohol, 2.4ml tetraethoxysilane, 7g magnesium chloride, 1.6g Tetra hydro Phthalic anhydride successively, slowly be warming up to 130 ℃, isothermal reaction obtained the magnesium chloride homogeneous phase solution in 2 hours.Then stirring is kept in cooling naturally.
In the magnesium chloride homogeneous phase solution that obtains, add the 10ml methylene dichloride, then stirred 1 hour at 20 ℃.
The 160ml titanium tetrachloride is joined in the catalyzer synthesis reactor, be cooled to-22 ℃, will slowly add, in 3 hours, slowly be warming up to 115 ℃, constant temperature 2 hours through the magnesium chloride solution of further processing.
After constant temperature finishes, the filtrate press filtration in the reactor in returnable bottle, is used the interior solid of hexane wash reactor four times, each hexane consumption 100ml; After the hot nitrogen drying obtains catalyzer dry powder.Ti in the ingredient of solid catalyst (weight) 6.85%.
[polymerization]
Nitrogen pump drainage three times of 2L stainless steel autoclave are pressed into the 0.5L hexane then in polymeric kettle, add certain density triethyl aluminum hexane solution.Open stirring then and add a certain amount of catalyzer, add the 1L hexane at last.Begin to heat up, and feed a certain amount of hydrogen and ethene, hydrogen alkene compares 0.28/0.45Mpa.By the add-on of solenoid control ethene, it is constant that the stagnation pressure of reaction system is kept, and by temperature controller controlled chilling discharge, makes to be aggregated in 80 ℃ of reactions two hours down, closes ethene then, stopped reaction.Cooling also bleeds off the still internal pressure, takes out polymerisate and suction filtration drying.The dry good product of weighing calculates catalyst activity, in gPE/gcat. measure bulk density and size-grade distribution simultaneously.Polymerization catalyst the results are shown in Table 1.
Embodiment 2
Prepare catalyst component with the method identical, but when the preparation catalyst component, isooctyl alcohol changes the isohexyl alcohol of equimolar amount into embodiment 1.Temperature of reaction changes 110 ℃ into by 130 ℃.Ti in the ingredient of solid catalyst that obtains (weight) 6.59%.Carry out polymerization with catalyst component with embodiment 1 identical method.Its polymerization result is listed in table 1.
Embodiment 3
Prepare catalyst component with the method identical, but when the preparation catalyst component, the isooctyl alcohol consumption changes 47ml into embodiment 1.Reaction times changed 1 hour into by 2 hours.Ti in the ingredient of solid catalyst that obtains (weight) 6.53%.Carry out polymerization with catalyst component with embodiment 1 identical method.Its polymerization result is listed in table 1.
Embodiment 4
Prepare catalyst component with the method identical, but when the preparation catalyst component, tetraethoxysilane changes the ethyl triethoxysilane of equimolar amount into embodiment 1.Ti in the ingredient of solid catalyst that obtains (weight) 6.27%.Carry out polymerization with catalyst component with embodiment 1 identical method.Its polymerization result is listed in table 1.
Embodiment 5
Prepare catalyst component with the method identical with embodiment 1, but when the preparation catalyst component, the tetraethoxysilane consumption reduces by half, the Tetra hydro Phthalic anhydride amount doubles.Ti in the ingredient of solid catalyst that obtains (weight) 5.36%.Carry out polymerization with catalyst component with embodiment 1 identical method.Its polymerization result is listed in table 1.
Embodiment 6
Prepare catalyst component with the method identical, but when the preparation catalyst component, Tetra hydro Phthalic anhydride changes diacetyl oxide into embodiment 1; Organic solvent changes ethylene dichloride into by methylene dichloride, and churning time changed 2 hours into by 1 hour simultaneously.Ti in the ingredient of solid catalyst that obtains (weight) 6.61%.Carry out polymerization with catalyst component with embodiment 1 identical method.Its polymerization result is listed in table 1.
Embodiment 7
Prepare catalyst component with the method identical with embodiment 1, but when the preparation catalyst component, the organic solvent dichloromethane consumption increases and is twice.Ti in the ingredient of solid catalyst that obtains (weight) 6.78%.Carry out polymerization with catalyst component with embodiment 1 identical method.Its polymerization result is listed in table 1.
Embodiment 8
Prepare catalyst component with the method identical with embodiment 1, but when the preparation catalyst component, the titanium tetrachloride solution consumption increases to 240ml by 160ml, temperature of reaction drops to 90 ℃ by 115 ℃ simultaneously.Ti in the ingredient of solid catalyst that obtains (weight) 6.48%.Carry out polymerization with catalyst component with embodiment 1 identical method.Its polymerization result is listed in table 1.
Embodiment 9
Prepare catalyst component with the method identical, but when the preparation catalyst component, washing composition changes heptane into by hexane with embodiment 1.Ti in the ingredient of solid catalyst that obtains (weight) 6.18%.Carry out polymerization with catalyst component with embodiment 1 identical method.Its polymerization result is listed in table 1.
Table one
Claims (9)
1. the preparation method of a catalyst for ethylene thick liquid polymerizing, this method comprises:
A. with higher alcohols and magnesium chloride, by the magnesium alkoxide mol ratio is in the disposable adding inertia of the 2.0～4.0:1 dispersion agent, pyroreaction, through adding two kinds of organic modifiers: silicoorganic compound and acid anhydrides, make the magnesium chloride homogeneous phase solution, two kinds of organic modifiers sums by with the mol ratio 0.04～0.5:1 of magnesium, disposable adding; 90～170 ℃ of this process reaction temperature, 0.5～5 hour reaction times;
Wherein, higher alcohols are one or more in the monohydroxy-alcohol of carbon atom number 6～12;
The inertia dispersion agent is selected from C
5～C
15Alkane or C
6～C
8Aromatic hydrocarbons;
Silicoorganic compound are; Tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, methyltrimethoxy silane, ethyl trimethoxy silane or ethyl triethoxysilane; Acid anhydrides is: diacetyl oxide or Tetra hydro Phthalic anhydride;
B. the magnesium chloride homogeneous phase solution that makes with the further dispersion steps a of organic solvent at low temperatures; 0～50 ℃ of this process reaction temperature, 0.5～5 hour reaction times;
Wherein, organic solvent is selected from: monochlorethane, a chloropropane, a chlorobutane, a chloropentane, methylene dichloride, ethylene dichloride, 1, in 3-propylene dichloride, 1,4-dichlorobutane, a chlorine hexanaphthene, dichloro hexanaphthene, mono chloro benzene, dichlorobenzene, the trichloromethane one or more;
C. react with titanium tetrachloride solution, titanium tetrachloride is cooled to-30～-15 ℃, add the magnesium chloride homogeneous phase solution after step b further disperses, 90～170 ℃ of temperature of reaction, in 0.5～5 hour reaction times, obtaining with the magnesium chloride is the solid of carrier;
D. after inert solvent washs, nitrogen drying obtains catalyst prod.
2. according to the process of claim 1 wherein, the mol ratio of two kinds of organic modifiers sums and magnesium chloride is 0.1～0.2:1 among the step a; Reaction times is 1～4 hour.
3. according to the process of claim 1 wherein, the mol ratio of two kinds of organic modifiers sums and magnesium chloride is 0.15:1 among the step a.
4. according to the process of claim 1 wherein, silicoorganic compound are selected among the step a: tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane or four butoxy silanes.
5. according to the process of claim 1 wherein, silicoorganic compound are tetraethoxysilane among the step a; Acid anhydrides is a Tetra hydro Phthalic anhydride.
6. according to the process of claim 1 wherein, step b organic solvent is selected from: a chlorobutane, ethylene dichloride, trichloromethane or methylene dichloride.
7. according to the process of claim 1 wherein, step b organic solvent is a methylene dichloride.
8. according to the process of claim 1 wherein, in the steps d, inert solvent is an inertia alkane.
9. according to the process of claim 1 wherein, in the steps d, inert solvent is selected from: hexane or heptane.
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| CN100491418C true CN100491418C (en) | 2009-05-27 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102432706B (en) * | 2011-09-15 | 2014-04-02 | 中国石油天然气股份有限公司 | Composite magnesium chloride spherical carrier, preparation and application |
| CN104017114B (en) * | 2014-06-25 | 2016-03-16 | 营口市向阳催化剂有限责任公司 | The ziegler natta catalyst of a kind of modified spherical magnesium halide carrier and preparation thereof |
| CN106632765B (en) * | 2015-10-29 | 2019-06-28 | 中国石油化工股份有限公司 | A kind of preparation method of the polyethylene powder for 3D printing |
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Non-Patent Citations (2)
| Title |
|---|
| 用调节剂改善聚丙烯高效催化剂性能的研究. 张文平等.现代化工，第23卷. 2003 |
| 用调节剂改善聚丙烯高效催化剂性能的研究. 张文平等.现代化工，第23卷. 2003 * |
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Granted publication date: 20090527 Termination date: 20100122 |