CN102321206B - Ethylene polymerization catalyst, preparation and application thereof - Google Patents
Ethylene polymerization catalyst, preparation and application thereof Download PDFInfo
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- CN102321206B CN102321206B CN2011101709469A CN201110170946A CN102321206B CN 102321206 B CN102321206 B CN 102321206B CN 2011101709469 A CN2011101709469 A CN 2011101709469A CN 201110170946 A CN201110170946 A CN 201110170946A CN 102321206 B CN102321206 B CN 102321206B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000005977 Ethylene Substances 0.000 title claims abstract description 8
- 239000002685 polymerization catalyst Substances 0.000 title abstract description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 239000000725 suspension Substances 0.000 claims abstract description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 53
- 239000000243 solution Substances 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical class [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical class Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 235000011147 magnesium chloride Nutrition 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000010926 purge Methods 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 32
- 150000001875 compounds Chemical class 0.000 abstract description 22
- 238000009826 distribution Methods 0.000 abstract description 22
- 238000006116 polymerization reaction Methods 0.000 abstract description 16
- 239000002002 slurry Substances 0.000 abstract description 7
- 239000002244 precipitate Substances 0.000 abstract 1
- -1 polyethylene Polymers 0.000 description 19
- 239000000460 chlorine Substances 0.000 description 15
- 239000004698 Polyethylene Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 229920000573 polyethylene Polymers 0.000 description 13
- 229910052801 chlorine Inorganic materials 0.000 description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- SXSVTGQIXJXKJR-UHFFFAOYSA-N [Mg].[Ti] Chemical compound [Mg].[Ti] SXSVTGQIXJXKJR-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000012216 screening Methods 0.000 description 7
- 150000003609 titanium compounds Chemical class 0.000 description 7
- 150000002681 magnesium compounds Chemical class 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 229910052622 kaolinite Inorganic materials 0.000 description 3
- 230000035800 maturation Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000003701 inert diluent Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000011218 segmentation Effects 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- RYZZHQUICKTJHD-UHFFFAOYSA-N C(C)[Ti](OC)(OC)CC Chemical compound C(C)[Ti](OC)(OC)CC RYZZHQUICKTJHD-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- JWGATVZPLATOHU-UHFFFAOYSA-K aluminum trichlorophosphane trichloride Chemical compound [Al+3].[Cl-].[Cl-].[Cl-].ClP(Cl)Cl JWGATVZPLATOHU-UHFFFAOYSA-K 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical class CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- HFTSQAKJLBPKBD-UHFFFAOYSA-N magnesium;butan-1-olate Chemical compound [Mg+2].CCCC[O-].CCCC[O-] HFTSQAKJLBPKBD-UHFFFAOYSA-N 0.000 description 1
- WNJYXPXGUGOGBO-UHFFFAOYSA-N magnesium;propan-1-olate Chemical compound CCCO[Mg]OCCC WNJYXPXGUGOGBO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- 150000002901 organomagnesium compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical class ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- 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
- C08F10/02—Ethene
-
- 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
- C08F110/02—Ethene
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to an ethylene polymerization catalyst and preparation and application thereof; mg (OR) of the general formula (I)1)nCl2-nA compound and a Ti (OR) of the formula (II)2)nCl4-nReacting to form a transparent solution; the clear solution is brought into contact with M of the formula (III)3)nCl4-nReacting the compounds to form a precipitate to obtain a catalyst suspension; the compound of the general formula (II) is controlled to be 0.01-10 mol, and the compound of the general formula (III) is controlled to be 0.01-20 mol per mol of the compound of the general formula (I); the catalyst of the present invention has excellent particle shape and narrow particle size distribution, and is suitable for slurry polymerization of ethylene, especially for slurry polymerization in double reactors.
Description
Technical field
The present invention relates to a kind of ethylene rolymerization catalyst of the good particle form for vinyl polymerization or copolymerization, and the preparation method of this catalyzer and purposes.
Background technology
After the seventies, high-efficiency polyethylene catalyst was succeeded in developing, great change had occured in world's polyethylene industry.Over nearly more than 20 years, follow the development of ethene polymerization process, the catalyzer that matches with polymerization technique has also been got significant progress, wherein effective catalyst relies on its good polymerization and ripe utilisation technology still to occupy an important position in the polyethylene catalysts field, still has in recent years a large amount of patented technologies to occur.In the patented technology of these applications, the research core is nothing more than the hydrogen response of the particle form of the polymerization activity that is catalyzer, catalyzer and size distribution, catalyzer and copolymerization performance etc.And in the slurry polymerization processes of ethene, except requiring catalyzer should have the higher catalytic activity, polyvinyl size and size distribution that control is produced are very important.At vinyl polymerization, particularly in the slurry polymerization process of ethene, be easy to produce fine polymer powder, this fine powder easily produces static, easily lumps, and causes the obstruction of equipment pipe.And the effective means of the control size of polymkeric substance and size distribution is particle diameter and the size distribution of control catalyzer.
In the prior art, in order to obtain having the catalyzer of single-size diameter and better particle form, people adopt two following class methods to come Kaolinite Preparation of Catalyst usually.
The first is the magnesium compounds such as magnesium chloride to be dissolved in obtain homogeneous solution in some solvent, and then with this solution and titanium compound and randomly electron donor mix, method by precipitation obtains containing the solids of magnesium, titanium and optional electron donor, and obtains granules of catalyst after this solids processed with excessive liquid titanium compound.Such as disclosed among Chinese patent CN1099041A, the CN1229092 etc.The shortcoming of this traditional method is that particle diameter and the size distribution of granules of catalyst controlled by precipitation process fully, and this is the recrystallization process of magnesium carrier composition, and its stable control ratio is difficulty.
For example, in patent CN1229092, take magnesium chloride as carrier, titanium tetrachloride is active ingredient, and the preparation method of catalyzer is as follows: first with MgCl
2Be dissolved in the solvent system, form homogeneous transparent solution, then the precipitation additive phthalic anhydride exist and low temperature under with TiCl
4Reaction is separated out solid catalyst by slow intensification.When the catalyst component that makes was used for vinyl polymerization, although the particle form of polymkeric substance is better, the fine polymer powder that catalyzer prepares in industrial production was still more, and hydrogen response and the catalytic activity of catalyzer are also unsatisfactory simultaneously.Simultaneously, when synthetic this catalyzer, need adopt the organism such as phthalic anhydride to promote separating out of precipitation as precipitation additive, and need to add a large amount of titanium tetrachlorides.Therefore not only the existence of acid anhydrides produces adverse influence to catalyzer, and the use of simultaneously a large amount of titanium tetrachlorides also can cause a large amount of wastes and pollution.
The second is to prepare first the carrier with good particle form, then carries titanium, and reaction prepares highly active polyolefin catalyst.Chinese patent CN85105150 for example, the patents such as CN101300278.
Chinese patent CN85105150 at first adopts magnesium halide and titan-alkoxide reaction, then generate the solid magnesium-containing carrier with better particle form with the aluminum alkyls reaction, this carrier and titanium tetrachloride reaction obtain solid catalyst at last, and the polyethylene polymer of this catalyzer preparation has high, the active high of tap density.But magnesium halide and titan-alkoxide reaction product fail to form solution in the preparation process of this catalyzer when reacting with aluminum alkyls, and the magnesium-containing carrier particle form that obtains is not ideal enough, and the polymkeric substance segmentation content of preparation is still more.
Therefore, being starved of provides a kind of catalyzer that is applicable to the slurry polymerization processes of ethene, and catalytic activity is high, particle diameter is even, narrow diameter distribution, and the polymkeric substance of its preparation has the advantages such as uniform particles, narrow diameter distribution, segmentation content are few.
Summary of the invention
The purpose of this invention is to provide and a kind ofly close or the catalyst component of ethene and other a-alpha-olefinic copolymerization and preparation method thereof for ethylene homo, comprising: a kind of magnesium compound, a kind of liquid state contain oxygen titanium compound and at least a chlorine-containing compound.
Described magnesium compound such as general formula (I) Mg (OR
1)
nCl
2-nShown in, R in the formula
1C
2～C
20Alkyl, can be saturated or undersaturated straight chain, side chain or closed chain, 0≤n≤2, concrete compound such as MgCl
2, Mg (OEt) Cl, Mg (OEt)
2And the alkoxyl magnesium compound of long-chain, the organo-magnesium compound that uses in the reaction is preferably diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium, two octyloxy magnesium etc.
Described liquid state contains oxygen titanium compound such as general formula (II) Ti (OR
2)
nCl
4-nShown in, R in the formula
2C
2～C
20Alkyl, can be saturated or undersaturated straight chain, side chain or closed chain, tetravalent titanium compound is preferably used in 0≤n≤4, because they are in a liquid state usually at normal temperatures, and also fine with the consistency of some solvents under normal conditions.The compound of n=4 and their mixture in the titanium compound preferred formula of specifically using in the reaction, such as purity titanium tetraethoxide, four titanium butoxide, the tetramethoxy titanium, dimethoxy diethyl titanium, four hexyloxy titaniums, four the last of the ten Heavenly stems oxygen base titanium, benzyloxy-4 titanium, four phenoxide titaniums etc., preferred purity titanium tetraethoxide wherein
Described chlorine-containing compound such as general formula (III) M (OR
3)
nCl
4-nShown in, M is metal or non-metallic element in the formula, R
3C
2～C
20Alkyl, can be saturated or undersaturated straight chain, side chain or closed chain, 0≤n≤4.The example of chlorine-containing compound comprises: silicon tetrachloride, titanium tetrachloride, zirconium tetrachloride, boron trichloride, phosphorus trichloride aluminum chloride etc., wherein preferred silicon tetrachloride.
Catalyst component of the present invention preferably adopts the following step to be prepared:
(1) general formula (I) compound and general formula (II) compound react the formation clear solution at a certain temperature.
The compound of the clear solution that (2) step (1) is obtained and general formula (III) compound forms precipitation, obtains catalyst suspension.
In the preparation process of catalyst component of the present invention, ratio between the each component is, in every mole of general formula (I) compound, general formula (II) compound is controlled at 0.01～10 mole, preferred 0.05～5 mole, general formula (III) compound is controlled at 0.01～20 mole, preferred 0.2～12 mole.
In the first step of Kaolinite Preparation of Catalyst, the temperature that magnesium compound and titanium compound are in contact with one another depends on the character of reactant, be typically chosen in dissolve under the relatively high temperature comparatively favourable, preferably below the decomposition temperature of reactant, temperature is generally 120～200 ℃, is generally 120～150 ℃.The time of dissolving is depended on character and the operational condition of reactant, and general selection of time be with till can obtaining fully transparent solution, and required time is generally at 10 minutes to 20 hours, preferred 4 to 10 hours.After magnesium compound and titanium compound dissolving, the magnesium titanium complex solution that forms can mix with inert diluent use, inert diluent is selected from aliphatic hydrocarbon usually, for example Trimethylmethane, pentane, hexane, heptane or hexanaphthene and composition thereof, and general hexane is proper inert solvent.
In the second step of Kaolinite Preparation of Catalyst, the mixing temperature of magnesium titanium complex solution and chlorine-containing compound generally will be lower than the decomposition temperature of material, for simplicity, general select-10～150 ℃ between, between preferred-10～50 ℃.The mixing time of magnesium titanium complex solution and chlorine-containing compound is general selects 0.5 minute to 5 hours, preferred 30 minutes to 1 hour.
The second step of catalyzer preparation also can be described as settling step, finishes the chlorination reaction of magnesium titanium complex in this step, and namely the chlorine element replaces the alkoxyl group in magnesium compound and the titanium compound, thereby makes liquid title complex Precipitation from solution.The contact method of magnesium titanium complex solution and chlorine-containing compound can adopt any known suitable method to carry out, can adopt magnesium titanium complex solution progressively is added drop-wise to mode in the chlorine-containing compound solution, also can adopt chlorine-containing compound solution progressively is added drop-wise to mode in the magnesium titanium complex solution.Rate of addition is selected to be as the criterion with the local superheating that does not induce reaction usually, usually stirs steadily carrying out of being beneficial to react in the dropping process.In this precipitin reaction step, temperature can be controlled between-10～150 ℃, preferably between-10～50 ℃.The reaction times of settling step should be long enough to obtain completely precipitation, and the reaction times can be lasted 1 minute to 10 hours, preferred 0.5～5 hour.
Experiment is found, after settling step, reacting at a certain temperature for some time, to carry out maturation process more favourable to the grain type of catalyzer, it can make the size distribution narrow of catalyzer, also can improve simultaneously the intensity of catalyst particle, thereby reduce the particle fragmentation phenomenon of catalyzer in the catalyzed ethylene polymerization process.The temperature of maturation process generally is equal to or higher than the temperature of precipitin reaction, and the time of slaking reaction can be controlled at 0.5～15 hour, preferred 1～5 hour.
After carrying out maturation process, generally to wash, in order to remove the by product that forms in excessive reactant and the preparation process, any inert solvent all can be used for this washing step, such as selecting Trimethylmethane, pentane, hexane, heptane or hexanaphthene and composition thereof etc., usually select hexane to be the inert solvent of washing in the experiment.After washing, catalyst suspension can be by carrying out drying with nitrogen purging, to obtain catalyst fines under heating state.
The invention still further relates to a kind of catalyzer for vinyl polymerization or copolymerization, it contains above-mentioned catalyst component of the present invention and the reaction product of alkylaluminium cpd, and wherein the general formula of used alkylaluminium cpd is AlR " '
3, R " ' be identical or not identical C
1-8Alkyl, wherein one or two alkyl can be replaced by chlorine, can select one or more aluminum alkyls mix to use, preferred AlEt
3, Al (iso-Bu)
3, Al (n-C
6H
13)
3, Al (n-C
8H
17)
3, AlEt
2Cl etc.
The catalyzer that the present invention relates to is applicable to the equal polymerization of various ethene or the copolymerization of ethene and other alpha-olefins, and wherein alpha-olefin adopts a kind of in propylene, butylene, amylene, hexene, octene, the 4-methylpentene-1.
The characteristics of catalyzer maximum of the present invention are exactly to have good particle form and very narrow size-grade distribution, are highly suitable for the slurry polymerization processes of ethene, are particularly suitable for the double-reactor slurry polymerization processes.
Embodiment
The median size of catalyzer and the test of size-grade distribution thereof
Catalyst sample is dispersed in the hexane, adopts the size distribution curve of Malversizer laser particle size analyzer specimen, wherein
The median size of catalyzer provides with D (50)
The size-grade distribution Span=of catalyzer (D (90)-D (10))/D (50)
D in the formula (50) be in the size distribution curve of Malversizer laser particle size analyzer test all 50% of particles diameter be lower than the diameter value of this value; D (10) is the diameter value that 10% diameter of whole particles is lower than this value; D (90) is the diameter value that 90% diameter of whole particles is lower than this value.Polymerization catalyst performance evaluation
1L hexane, 1mmol triethyl aluminum and a certain amount of catalyzer are joined in the 2L stainless steel stirring tank, then temperature is brought up to 90 ℃, then the hydrogen of disposable adding 0.4MPa maintain 1.0MPa with ethene with the total pressure of system and carry out polyreaction, reacts after 2 hours, stop to add ethene, cooling, pressure release, polyethylene powder is weighed, calculate the activity of catalyzer, and the polyethylene powder that obtains is sieved.
Embodiment 1:
(1) takes by weighing 10.2 gram magnesium chlorides, add 78 milliliters of tetrabutyl titanates, until the formation clear solution is down to room temperature with solution temperature, add 200 milliliters of dry hexane diluted for use 140 ℃ of stirring and dissolving.
(2) get the solution that 20 milliliter of (1) step obtains, this solution slowly is added drop-wise at normal temperatures in the mixed solution of 30 milliliters of hexanes and 20 milliliters of silicon tetrachlorides, after being added dropwise to complete, bathed 45 ℃ of stirring reactions of temperature 1 hour, bathe 65 ℃ of stirring reactions of temperature 2 hours, and obtained catalyst suspension.
(3) the catalyst suspension temperature is down to room temperature, leaves standstill, sedimentation, with hexane washing three times, the consumption of hexane is 50 milliliters at every turn, after washing is finished, in the situation that bathe 65 ℃ of temperature, purges drying with high pure nitrogen, gets the solids flowability powder.
The median size of catalyzer (D (50)): 22 microns, particle diameter distribution width Span:0.6, the activity of catalyzer and the screening result of polyethylene powder are as shown in table 1.
Embodiment 2
20 milliliters of silicon tetrachlorides in the catalyst preparation step (2) are adjusted into 20 milliliters of titanium tetrachlorides, and other conditions are with embodiment 1.
The median size of catalyzer (D (50)): 16 microns, particle diameter distribution width Span:1.5, the activity of catalyzer and the screening result of polyethylene powder are as shown in table 1.
Embodiment 3
The hexane that uses in embodiment 1 catalyst preparation step is adjusted into toluene with volume, but still uses the hexane with volume during catalyst detergent.
The median size of catalyzer (D (50)): 12 microns, particle diameter distribution width Span:0.6, the activity of catalyzer and the screening result of polyethylene powder are as shown in table 1.
Embodiment 4
20 milliliters of silicon tetrachlorides in the catalyst preparation step (2) are adjusted into 20 milliliters of boron trichlorides, and other conditions are with embodiment 1.
The median size of catalyzer (D (50)): 25 microns, particle diameter distribution width Span:1.2, the activity of catalyzer and the screening result of polyethylene powder are as shown in table 1.
Embodiment 5
20 milliliters of silicon tetrachlorides in the catalyst preparation step (2) are adjusted into 20 milliliters of phosphorus trichlorides, and other conditions are with embodiment 1.
The median size of catalyzer (D (50)): 20 microns, particle diameter distribution width Span:0.8, the activity of catalyzer and the screening result of polyethylene powder are as shown in table 1
Comparative Examples 1
(1) takes by weighing 114 gram diethoxy magnesium, add 340 milliliters of tetrabutyl titanates, until the formation clear solution is down to room temperature with solution temperature, add 400 milliliters of dry hexane diluted for use 140 ℃ of stirring and dissolving.
(2) get the solution that 9 milliliter of (1) step obtains, slowly drip the hexane solution (3M) of 15 milliliters of ethyl aluminum dichlorides with drop-burette, after being added dropwise to complete, 60 ℃ of stirring reactions obtained catalyst suspension in 4 hours.
(3) the catalyst suspension temperature is down to room temperature, leaves standstill, sedimentation, with hexane washing three times, the consumption of hexane is 50 milliliters at every turn, after washing is finished, in the situation that bathe 65 ℃ of temperature, purges drying with high pure nitrogen, gets the mobile powder of brown solid.
The median size of catalyzer (D (50)): 30 microns, particle diameter distribution width Span:2.0, the activity of catalyzer and the screening result of polyethylene powder are as shown in table 1
Comparative Examples 2
The synthetic CN85105150 embodiment 1 described method of pressing of catalyst component prepares.
The median size of catalyzer (D (50)): 8.2 microns, particle diameter distribution width Span:1.2, the activity of catalyzer and the screening result of polyethylene powder are as shown in table 1
Catalyzer particle shape of the present invention is regular, the particle size homogeneous, and macroparticle and small-particle are few.Can find out from the aggregated data of table 1, under same polymerizing condition, the size distribution of catalyzer resulting polymers of the present invention is narrower, crosses thick or meticulous particle in the polymkeric substance all less.
Table 1
Claims (1)
1. the preparation method of an ethylene rolymerization catalyst is characterized in that:
(1) takes by weighing 10.2 gram magnesium chlorides, add 78 milliliters of tetrabutyl titanates, until the formation clear solution is down to room temperature with solution temperature, add 200 milliliters of dry toluene diluted for use 140 ℃ of stirring and dissolving;
(2) get the solution that 20 milliliter of (1) step obtains, this solution slowly is added drop-wise at normal temperatures in the mixed solution of 30 milliliters of toluene and 20 milliliters of silicon tetrachlorides, after being added dropwise to complete, bathed 45 ℃ of stirring reactions of temperature 1 hour, bathe 65 ℃ of stirring reactions of temperature 2 hours, and obtained catalyst suspension;
(3) the catalyst suspension temperature is down to room temperature, leaves standstill, sedimentation, with hexane washing three times, the consumption of hexane is 50 milliliters at every turn, after washing is finished, in the situation that bathe 65 ℃ of temperature, purges drying with high pure nitrogen, gets the solids flowability powder.
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| JP5670753B2 (en) * | 2008-03-14 | 2015-02-18 | サウディ ベーシック インダストリーズ コーポレイション | Catalyst system and process for producing polyethylene in the presence of this catalyst system |
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