CN101775086A - Preparation method for ethylene homopolymer and copolymer - Google Patents
Preparation method for ethylene homopolymer and copolymer Download PDFInfo
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- CN101775086A CN101775086A CN200910076325A CN200910076325A CN101775086A CN 101775086 A CN101775086 A CN 101775086A CN 200910076325 A CN200910076325 A CN 200910076325A CN 200910076325 A CN200910076325 A CN 200910076325A CN 101775086 A CN101775086 A CN 101775086A
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Abstract
The invention relates to a preparation method for ethylene homopolymers and copolymers. The preparation method adopts liquid phase polymerization or gas phase polymerization; the polymerization conditions are as follows: the reaction temperature is 80 DEG C, and the total reaction pressure is 0.73MPa; a ball-like particle ethylene polymer is prepared; magnesium chloride is dissolved in an isooctanol solvent at a dissolving temperature of 50 to 130 DEG C to obtain a liquid magnesium compound, and the liquid magnesium compound is interacted with triethyl phosphate to obtain a product; the product is contacted with titanium tetrachloride to be heated to 50 to 120 DEG C to precipitate solid as a catalyst; counted in per mole of magnesium chloride in the magnesium compound, the amount of a isooctanol compound is 0.1 to 10.0 mole, the amount of triethyl phosphate is 0.05 to 0.35 mole, and the amount of titanium tetrachloride is 30 to 40 mole; the catalyst is mixed with triethylaluminium or triisobutyl aluminium; and the molar ratio of aluminum to titanium is 20 to 200. The activity and the particle form of the catalyst are improved, so that the particle form of the polymer is improved, and the sensibility to hydrogen regulation is better.
Description
Technical field
The present invention relates to a kind ofly be used for that ethylene homo closes or preparation method that ethene and other alpha-olefin copolymers close.
Background technology
The preparation method of the efficient Ziegler-Natta catalyst of vinyl polymerization is well-known, mainly is by MgCl
2Or SiO
2The halogenide of the titanium of load is formed.Preparation of catalysts method as disclosed vinyl polymerization and copolymerization among the JP 4951378 is: magnesium dichloride through grinding and ethanol synthesis generate MgCl
26C
2H
5OH alcohol adduct slurries, again with aluminium diethyl monochloride generation esterification, last and TiCl
4Carry the titanium reaction, obtain MgCl
2Carrier loaded Titanium series catalyst.This method for preparing catalyst is simple, the reaction conditions gentleness, and activity is very high during the catalyst vinyl polymerization.But this preparation method exists the carrier magnesium chloride can not dissolve in mineral oil, the irregular platy shaped particle that produces when there be former grinding in magnesium chloride in the slurry reaction system, cause the solid catalyst particle form that obtains relatively poor, thickness is inhomogeneous, thereby polymer morphology is also bad, fine powder is more, easily produces static and easy blocking pipe.This catalyzer oligomer in the solvent when polymerization is more simultaneously, for aftertreatment has brought bigger trouble.
Patent CN1229092 discloses a kind of catalyst system that is used for vinyl polymerization and copolymerization, this catalyst system comprises: (1) contains the ingredient of solid catalyst of Ti, (2) alkylaluminium cpd, the ingredient of solid catalyst that wherein contains Ti is to be dissolved in organic epoxy compounds and organo phosphorous compounds forms homogeneous phase solution by magnesium halide, add Ethanol Treatment dissolved magnesium halide, this solution mixes with titanium tetrahalide then, in the presence of compounds such as precipitation agent such as organic acid anhydrides, organic acid, ether, ketone, separate out solids, obtain solid catalyst.When this catalyst system was used for vinyl polymerization, the resulting polymers fine powder content was more, catalyst activity is lower, hydrogen regulation performance is poor, was unsuitable for preparing bimodal polymers, was difficult to substitute existing high reactivity ethene slurry polymerization catalyzer.The bulk density of polymkeric substance is also a little less than the level that has catalyzer now simultaneously.
Patent CN1140722 discloses a kind of solid titanium catalyst component and preparation technology thereof, mainly adopts low-carbon alcohol to dissolve magnesium halide, and adds alkane diluent and silicane electron donor compound, with the halogenated titanium effect, separates out solid catalyst then.Although can make the ethene polymers with good particle performance when this catalyzer is used for vinyl polymerization, its catalytic activity and oligomer are still unsatisfactory.
Summary of the invention
The purpose of this invention is to provide a kind of is that the ethylene homo of catalyst component closes polymeric preparation method together with the solid titanium, can make vinyl polymerization have higher activity with this catalyst component, and make the ethene polymers that makes have class spheric particle form.
Present method adopts liquid polymerization or vapour phase polymerization; Polymerizing condition is: 80 ℃ of temperature of reaction, reaction stagnation pressure 0.73MPa; Make ethene polymers with spherical particle form; It is that their product contacts with titanium tetrachloride by the organo phosphorous compounds interaction of a kind of magnesium compound of liquid state and a kind of non-activity hydrogen, and the solid of separating out is a catalyzer;
Wherein said liquid magnesium compound is that magnesium chloride is dissolved in resulting product in the isooctyl alcohol solvent;
The organo phosphorous compounds of described non-activity hydrogen atom is selected triethyl phosphate for use;
In the every mole of magnesium chloride in the magnesium compound, the isooctyl alcohol compound amount is: 0.1～10.0 mole, the triethyl phosphate consumption is 0.05～0.35 mole, and the titanium tetrachloride consumption is 30～40 moles.
Catalyzer is joined trialkyl aluminium compound, and the mol ratio of aluminium and titanium is 20～200.
The preparation solid titanium catalyst:
Catalyst component of the present invention can adopt following method preparation:
(1) preparation liquid magnesium compound
Just magnesium chloride is dissolved in the isooctyl alcohol solvent, adds inert diluent in solvent system, forms homogeneous solution, 50～130 ℃ of solvent temperatures; In forming the process of solution or solution form the organo phosphorous compounds triethyl phosphate that the back adds the non-activity hydrogen atom.
(2) preparation solid titanium catalyst
Above-mentioned solution and titanium compound are carried out contact reacts, the organo phosphorous compounds triethyl phosphate of non-activity hydrogen atom also can add when the solution in (1) step and titanium compound carry out contact reacts, and mixture slowly is warming up to 50～120 ℃, particle is separated out and formed to solids gradually, after the reaction regular hour, remove unreacted reactant and solvent, and adopt the inert diluent washing, obtain catalyst component of the present invention.
Be equipped with triethyl aluminum or triisobutyl aluminium for well.Wherein the mol ratio of component aluminium and component titanium is 5～500, preferred 20～200.
Liquid polymerization can be adopted during polymerization, also vapour phase polymerization can be adopted.Liquid polymerization medium comprises: Trimethylmethane, hexane, heptane, hexanaphthene, petroleum naphtha, raffinate oil, inert solvent such as aliphatic saturated hydrocarbon such as hydrogenated gasoline, kerosene, benzene,toluene,xylene or aromatic hydrocarbon.Polymerizing condition is: 80 ℃ of temperature of reaction, reaction stagnation pressure 0.73MPa.
Therefore catalyzer of the present invention is easy to separate out class spheric granules of catalyst owing to adopt the organo phosphorous compounds of no reactive hydrogen to analyse agent for helping when Preparation of Catalyst.And in carrying the titanium process, do not need to use a large amount of titanium tetrachlorides to impel sedimentary separating out, also do not need repeatedly to use titanium tetrachloride to handle precipitation, so the add-on of titanium tetrachloride significantly reduce.The adding of organo phosphorous compounds simultaneously also helps to improve the improvement of the particle form of activity of such catalysts and catalyzer, thereby further improves the particle form of polymkeric substance.When this catalyzer is used for vinyl polymerization, show better hydrogen regulation sensitivity.
Embodiment
With embodiment the present invention is described below, but and unrestricted invention scope.
Embodiment 1
4.76 gram (50mmol) Magnesium Chloride Anhydrouss, 75 milliliters of decane and 16.3 gram (125mmol) isooctyl alcohol are heated to 130 ℃, make it to react 3 hours, obtain a kind of homogeneous phase solution.In this solution, add the triethyl phosphate of 15mmol and stir 2 hours so that triethyl phosphate is dissolved in this solution down at 50 ℃.Above-mentioned all homogeneous phase solutions that obtain are cooled to room temperature, in 1 hour, while stirring it are added drop-wise to then in the 150mL titanium tetrachloride that temperature remains 0 ℃.Mixture temperature was kept 1 hour down at 0 ℃, under agitation in 2 hours, temperature is carried to 120 ℃ then, and this temperature was kept 2 hours.After reaction in 2 hours finishes, the solid that generates is carried out heat filtering separate.With hexane and decane solid catalyst is carried out thorough washing respectively,, obtain a kind of solid titanium catalyst component after drying until in scavenging solution, can not detecting the titanium compound of separating out.
Vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, the triethyl aluminum 1.0mL that adds hexane 1L and concentration 1mol/L, the catalyzer that adds the above-mentioned preparation of accurate weighing with syringe, be warming up to 75 ℃, feed hydrogen and make the still internal pressure reach 0.28MPa, feed ethene again and make the interior stagnation pressure of still reach 0.73MPa (gauge pressure), polymerization is 2 hours under 80 ℃ of conditions, and polymerization result sees Table 1.
Embodiment 2
With embodiment 1, difference is that the add-on of triethyl phosphate is 20mmol.Polymerization result sees Table 1.
Embodiment 3
With embodiment 1, difference is that the add-on of triethyl phosphate is 10mmol.Polymerization result sees Table 1.
Embodiment 4 is with embodiment 1, and difference is that the add-on of decane is 50mL.Polymerization result sees Table 1.
Comparative Examples 1
With embodiment 1.Difference is that P contained compound changes tetraethoxysilane into, and vinyl polymerization the results are shown in Table 1.
Comparative Examples 2
With embodiment 1.The triethylenetetraminehexaacetic acid ester does not just phosphorate.Catalyzer is separated out difficult forming, and precipitation particles is superfine, is difficult to sedimentation, is taken away entirely during suction filtration, fails to form catalyzer.
Comparative Examples 3
The synthetic CN1229092 embodiment 1 described method of pressing of catalyzer prepares.
In the abundant metathetical reactor of high pure nitrogen, add the anhydrous MgCl of 0.042mol successively
2(about 4g), 60ml toluene, 0.032mol epoxy chloropropane, 0.022mol tributyl phosphate, 0.017mol ethanol, be warming up to 80 ℃ under stirring, and keep 15 minutes solids and dissolve fully, form homogeneous solution, add Tetra hydro Phthalic anhydride 0.0074mol then, kept again 1 hour, this solution is cooled to-25 ℃, again 0.5mol titanium tetrachloride (about 55ml) is splashed in it, slowly be warming up to 80 ℃ then, reacted 3 hours, use toluene and hexane wash 3 times after the filtration respectively, vacuum-drying obtains solid catalyst.The vinyl polymerization condition is with embodiment 1, and polymerization result sees Table 1.
Comparative Examples 4
The synthetic described method of JP49-51378 embodiment of pressing of catalyzer prepares.
In the abundant metathetical reactor of high pure nitrogen, add commercially available anhydrous MgCl
210mol is suspended in the 10L hexane, under the room temperature, splashes into 60mol ethanol, stirs 30 minutes.The temperature of maintenance system is no more than under 40 ℃ of conditions and splashes into the 31mol aluminium diethyl monochloride, stirs 30 minutes, adds 5molTiCl
4, system maintains 60 ℃, stirring reaction 6 hours.Through obtaining solid catalyst after filtration, the hexane wash.The vinyl polymerization condition is with embodiment 1, and polymerization result sees Table 1.
Table 1
Claims (1)
1. an ethylene homo closes polymeric preparation method together, it is characterized in that: adopt liquid polymerization or vapour phase polymerization; Polymerizing condition is: 80 ℃ of temperature of reaction, reaction stagnation pressure 0.73MPa; Make ethene polymers with spherical particle form; Catalyzer is: the liquid magnesium compound and the triethyl phosphate that magnesium chloride are dissolved in gained in the isooctyl alcohol solvent interact 50～130 ℃ of solvent temperatures; Interactional product contacts with titanium tetrachloride, is warming up to 50～120 ℃ of solids of separating out;
In the every mole of magnesium chloride in the magnesium compound, the isooctyl alcohol compound amount is: 0.1～10.0 mole, the triethyl phosphate consumption is 0.05～0.35 mole, and the titanium tetrachloride consumption is 30～40 moles;
Catalyzer is joined triethyl aluminum or triisobutyl aluminium; The mol ratio of aluminium and titanium is 20～200.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632759A (en) * | 2015-10-29 | 2017-05-10 | 中国石油化工股份有限公司 | Solid catalyst component for ethylene polymerization, preparation method and application thereof |
| CN107778392A (en) * | 2016-08-31 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of catalytic component for vinyl polymerization and preparation method thereof and catalyst |
| CN115975080A (en) * | 2021-10-14 | 2023-04-18 | 中国石油化工股份有限公司 | Magnesium-titanium-containing catalyst component for ethylene polymerization, catalyst and ethylene polymerization reaction method |
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| KR100476881B1 (en) * | 2000-12-29 | 2005-03-18 | 삼성토탈 주식회사 | A method for producing ethylene homo- and c0-polymer |
| KR100496776B1 (en) * | 2001-06-21 | 2005-06-22 | 삼성토탈 주식회사 | Catalyst for polymerization and copolymerization of ethylene |
| CN1955195B (en) * | 2005-10-26 | 2010-06-16 | 中国石油化工股份有限公司 | Catalyst, preparation method and application for olefin polymerization or copolymerization |
| CN101125898A (en) * | 2007-07-19 | 2008-02-20 | 中国科学院长春应用化学研究所 | Catalyst used for synthesizing polypropylene with wide molecular weight distribution |
| CN101215344B (en) * | 2008-01-14 | 2010-11-17 | 中国石油天然气股份有限公司大庆化工研究中心 | Olefin polymerization catalyst composition and preparing method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632759A (en) * | 2015-10-29 | 2017-05-10 | 中国石油化工股份有限公司 | Solid catalyst component for ethylene polymerization, preparation method and application thereof |
| CN107778392A (en) * | 2016-08-31 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of catalytic component for vinyl polymerization and preparation method thereof and catalyst |
| CN115975080A (en) * | 2021-10-14 | 2023-04-18 | 中国石油化工股份有限公司 | Magnesium-titanium-containing catalyst component for ethylene polymerization, catalyst and ethylene polymerization reaction method |
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