CN103214603A - Magnesium ethoxide/montmorillonite/titanium tetrachloride polyethylene catalyst and preparation and application thereof - Google Patents
Magnesium ethoxide/montmorillonite/titanium tetrachloride polyethylene catalyst and preparation and application thereof Download PDFInfo
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- CN103214603A CN103214603A CN2012100163989A CN201210016398A CN103214603A CN 103214603 A CN103214603 A CN 103214603A CN 2012100163989 A CN2012100163989 A CN 2012100163989A CN 201210016398 A CN201210016398 A CN 201210016398A CN 103214603 A CN103214603 A CN 103214603A
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- polynite
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- titanium tetrachloride
- magnesium ethylate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052901 montmorillonite Inorganic materials 0.000 title claims abstract description 47
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 title claims abstract description 37
- -1 polyethylene Polymers 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 19
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 19
- RVDLHGSZWAELAU-UHFFFAOYSA-N 5-tert-butylthiophene-2-carbonyl chloride Chemical compound CC(C)(C)C1=CC=C(C(Cl)=O)S1 RVDLHGSZWAELAU-UHFFFAOYSA-N 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 157
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 114
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 22
- 239000000725 suspension Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 claims description 70
- 238000003756 stirring Methods 0.000 claims description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 34
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 238000010792 warming Methods 0.000 claims description 17
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical group CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000012190 activator Substances 0.000 claims description 8
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- XZKPFRIEWDWYDH-UHFFFAOYSA-N 1-(methoxymethyl)-9h-fluorene Chemical class C1C2=CC=CC=C2C2=C1C(COC)=CC=C2 XZKPFRIEWDWYDH-UHFFFAOYSA-N 0.000 claims description 2
- HYCAYOQCLWBHIJ-UHFFFAOYSA-N 4-methoxy-4-(1-methoxyethyl)-2,6-dimethylheptane Chemical compound COC(C)C(CC(C)C)(CC(C)C)OC HYCAYOQCLWBHIJ-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000004437 phosphorous atom Chemical group 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 150000002681 magnesium compounds Chemical class 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- ZFAGXQVYYWOLNK-UHFFFAOYSA-N CCO[Mg] Chemical compound CCO[Mg] ZFAGXQVYYWOLNK-UHFFFAOYSA-N 0.000 abstract 1
- 230000003213 activating effect Effects 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 150000001924 cycloalkanes Chemical class 0.000 abstract 1
- 239000003085 diluting agent Substances 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 15
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 8
- VEZNCHDBSQWUHQ-UHFFFAOYSA-N chlorocyclopropane Chemical compound ClC1CC1 VEZNCHDBSQWUHQ-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 2
- NDTCXABJQNJPCF-UHFFFAOYSA-N chlorocyclopentane Chemical compound ClC1CCCC1 NDTCXABJQNJPCF-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to an ethoxy magnesium/montmorillonite/titanium tetrachloride polyethylene catalyst and a preparation method thereof, wherein the catalyst is prepared by the reaction of the following components: (1) montmorillonite; (2) a magnesium compound; (3) a fatty alcohol compound; (4) an internal electron donor; (5) a chlorinated cycloalkane; (6) titanium tetrachloride; calcining montmorillonite at high temperature to obtain a carrier; adding magnesium ethoxide into fatty alcohol by using decane as a diluent to form fatty alcohol suspension of magnesium ethoxide; adding the carrier into the suspension, and then adding an internal electron donor for reaction; dripping titanium tetrachloride at low temperature; the solid was washed with dry hexane; adding dry hexane and an activating agent into a reaction system for reaction; filtering and drying. The catalyst prepared by the method has the advantages of high catalytic activity, simple preparation method, good particle form, stable polymerization reaction and the like. The polymerization product has good barrier property, physical and mechanical properties and processability.
Description
Technical field
The present invention relates to a kind of magnesium ethylate/polynite/titanium tetrachloride polyethylene catalysts and preparation and application.
Background technology:
The catalyzer of preparation polyethylene/montmorillonite nanometer composite material normally carries out the preparation of montmorillonite carrier earlier at present, magnesium chloride is dissolved in the fat alcohol compound of 1-4 carbon, remove by filter unnecessary alcohol, montmorillonite carrier is joined in the magnesium chloride fatty alcohol solution again, add electron donor and titanium tetrachloride, make the polynite/TiCl 4 catalyst that satisfies different needs by kind and the add-on of adjusting electron donor.Catalyzer has catalytic activity height, advantage that hydrogen response is good, but exist the melt flowability of granules of catalyst poor morphology, polynite treatment process complexity, polymerisate poor, can not take into account the problems such as barrier property, physical and mechanical property and processing characteristics of polymerisate.
Patent CN1872908A, the catalyzer of CN1324886 has catalytic activity height, advantage that hydrogen response is good, use the polymerisate good mechanical properties of Preparation of Catalyst, but the melt flowability of polymerisate is poor, the processing and utilization difficulty of material can not be taken into account processing characteristics and physical and mechanical property.CN1510059A discloses a kind of synthetic method of montmorillonite carrier catalyzer, this catalyzer can be used for slurry polymerization or mass polymerization prepares polyethylene/montmorillonite nanometer composite material, but this method relates to complicated polynite treatment process, need expend a large amount of methylaluminoxane, thereby industrialization has little significance.
Summary of the invention:
The purpose of this invention is to provide a kind of magnesium ethylate/polynite/titanium tetrachloride polyethylene catalysts and preparation and application.At the weak point of present preparation polyethylene/montmorillonite nanometer composite material catalyzer, the composition and the Preparation of catalysts method of catalyst system are improved: (1) adopts chloro naphthenic hydrocarbon to make activator, has greatly improved the polymerization activity of catalyzer; (2) the granules of catalyst form is good, is the class sphere, and narrow diameter distribution, the fine powder of polymerisate are few; (3) method for preparing catalyst is simple, and the Preparation of Catalyst cost is low, helps carrying out suitability for industrialized production; (4) polymerisate has good barrier performance, physical and mechanical property and processing characteristics, has widened the Application Areas of polymerisate.
A kind of magnesium ethylate/polynite of the present invention/TiCl 4 catalyst and preparation and application, overcome the active shortcoming such as low of the treatment process complexity of polynite in the prior art, catalyst system, Ziegler-Natta catalyst is incorporated between cheating engaging layer, use internal electron donor as the catalyst form improving agent, improved the particle form of catalyzer; Use the chloro cycloalkane as catalyst activator, greatly improved the catalytic activity of catalyzer.
The catalyst system that the present invention proposes consists of: 1) clay of laminar silicate is specially the Na-polynite, Mg-polynite or Ca-polynite; 2) magnesium compound specifically is a magnesium ethylate; 3) fat alcohol compound can be the mixture of two kinds of alcohols; 4) internal electron donor contains the organic compound of oxygen, sulphur, nitrogen, silicon or a phosphorus atom at least; 5) catalyst activator, chloro naphthenic hydrocarbon C
nH
2n-1-Cl, 3≤n≤6; 6) titanium tetrachloride.
The preparation method of a kind of magnesium ethylate/polynite of the present invention/titanium tetrachloride polyethylene catalysts carries out according to following order:
(1) polynite was calcined 4-10 hour under 400-800 ℃ of high temperature, obtain montmorillonite carrier.
(2) use decane to make thinner, magnesium ethylate is joined in the Fatty Alcohol(C12-C14 and C12-C18), the mol ratio of Fatty Alcohol(C12-C14 and C12-C18) and magnesium ethylate is 2-5.
(3) according to the ratio of add-on 0.1-1g polynite/mmol magnesium ethylate, the montmorillonite carrier of handling in the step (1) is joined in the Fatty Alcohol(C12-C14 and C12-C18) suspension of magnesium ethylate, stirred 1 hour.
(4) according to the ratio of 1-5mmol internal electron donor/g polynite, add internal electron donor, stirring reaction 1 hour to reaction system.
(5) reaction system is cooled to-20-0 ℃, drips titanium tetrachloride in reaction system, titanium tetrachloride adds according to the mol ratio of [Ti]/[Mg]=1.5/1-10/1, and stirring reaction 2-4 hour, mixing speed 50-250r/min.
(6) reaction system slowly is warming up to 40-60 ℃.Solids is with dry hexane wash 3 times.
(7) ratio according to 5ml hexane/g polynite adds dry hexane in reaction system, according to the ratio adding catalyst activator of 0.01-10mmol activator/g polynite.Stirring reaction 1 hour, mixing speed 50-250r/min.
(8) reaction system is filtered, drying makes magnesium ethylate/polynite/TiCl 4 catalyst.
More than operation is all carried out under nitrogen protection.
The specific surface area 50-500m of used polynite
2/ g, the aperture is 50-500A, and pore volume is 1-500cc/g, and exchange capacity is 80-100meq/100g.
Fatty Alcohol(C12-C14 and C12-C18) is isooctyl alcohol, ethanol, propyl carbinol, methyl alcohol one or above-mentioned arbitrary combination.
Internal electron donor is dibutyl phthalate, ethyl acetate, tributyl phosphate, 2,2-dibutyl-1,3-Propanal dimethyl acetal, diisobutyl Propylene Glycol Dimethyl Ether or 9, two (methoxymethyl) fluorenes of 9-.
Described catalyzer can be used for preparing polyethylene/montmorillonite nanometer composite material, can be used for slurry polymerization processes and mass polymerization.
A kind of magnesium ethylate/polynite of the present invention/TiCl 4 catalyst and preparation method thereof has the catalyst activity height; The granules of catalyst form is good, is the class sphere, and narrow diameter distribution, the fine powder of polymerisate are few; The catalyzer hydrogen response is good, stable polymerization reaction, characteristics that the polymerisate bulk density is high; Catalyzer is suitable for the copolyreaction of ethene and propylene and other alpha-olefin, and copolymerization performance is good; Do not need to remove by filter superabundant fat alcohol in the catalyst preparation process or use chemical process to separate alcohol, simplified production technique; Can make it be applicable to the synthetic of different polyethylene/montmorillonite nanometer composite materials by selecting and using different Fatty Alcohol(C12-C14 and C12-C18) and composition thereof; Method for preparing catalyst is simple, and the Preparation of Catalyst cost is low, helps carrying out suitability for industrialized production.Polymerisate has good barrier performance, physical and mechanical property and processing characteristics.
Embodiment
Embodiment 1
Polynite was calcined 4 hours under 400 ℃ of high temperature, obtain montmorillonite carrier.Under nitrogen protection, use the 120ml decane to make thinner, the 4g magnesium ethylate is joined in the 14ml isooctyl alcohol.The 3.5g montmorillonite carrier is joined in the isooctyl alcohol suspension of magnesium ethylate, stirred 1 hour.In reaction system, add 1ml tributyl phosphate, stirring reaction 1 hour.Reaction system is cooled to-20 ℃, in reaction system, slowly drips 6ml titanium tetrachloride, stirring reaction 2 hours, mixing speed 50r/min.Reaction system slowly is warming up to 40 ℃.Solids is with dry hexane wash 3 times.In reaction system, add the dry hexane of 17.5ml, add chlorocyclohexane 1.1ml.Stirring reaction 1 hour, mixing speed 50r/min.Reaction system is filtered, and drying makes magnesium ethylate/polynite/TiCl 4 catalyst.
Embodiment 2
Polynite was calcined 4 hours under 500 ℃ of high temperature, obtain montmorillonite carrier.Under nitrogen protection, use the 120ml decane to make thinner, the 4g magnesium ethylate is joined in the 16.5ml isooctyl alcohol.The 7g montmorillonite carrier is joined in the isooctyl alcohol suspension of magnesium ethylate, stirred 1 hour.In reaction system, add 3.8ml tributyl phosphate, stirring reaction 1 hour.Reaction system is cooled to-15 ℃, in reaction system, slowly drips 7.7ml titanium tetrachloride, stirring reaction 2 hours, mixing speed 60r/min.Reaction system slowly is warming up to 40 ℃.Solids is with dry hexane wash 3 times.In reaction system, add the dry hexane of 35ml, add chlorocyclohexane 2.2ml.Stirring reaction 1 hour, mixing speed 60r/min.Reaction system is filtered, and drying makes magnesium ethylate/polynite/TiCl 4 catalyst.
Embodiment 3
Polynite was calcined 8 hours under 400 ℃ of high temperature, obtain montmorillonite carrier.Under nitrogen protection, use the 120ml decane to make thinner, the 4g magnesium ethylate is joined in the 22ml isooctyl alcohol.The 10.4g montmorillonite carrier is joined in the isooctyl alcohol suspension of magnesium ethylate, stirred 1 hour.In reaction system, add 8.5ml tributyl phosphate, stirring reaction 1 hour.Reaction system is cooled to-10 ℃, in reaction system, slowly drips 9.6ml titanium tetrachloride, stirring reaction 2 hours, mixing speed 80r/min.Reaction system slowly is warming up to 40 ℃.Solids is with dry hexane wash 3 times.In reaction system, add the dry hexane of 52ml, add chlorocyclohexane 3ml.Stirring reaction 1 hour, mixing speed 80r/min.Reaction system is filtered, and drying makes magnesium ethylate/polynite/TiCl 4 catalyst.
Embodiment 4
Polynite was calcined 4 hours under 800 ℃ of high temperature, obtain montmorillonite carrier.Under nitrogen protection, use the 120ml decane to make thinner, the 4g magnesium ethylate is joined in the 27ml isooctyl alcohol.The 14g montmorillonite carrier is joined in the isooctyl alcohol suspension of magnesium ethylate, stirred 1 hour.In reaction system, add 15ml tributyl phosphate, stirring reaction 1 hour.Reaction system is cooled to-10 ℃, in reaction system, slowly drips 15ml titanium tetrachloride, stirring reaction 2 hours, mixing speed 100r/min.Reaction system slowly is warming up to 40 ℃.Solids is with dry hexane wash 3 times.In reaction system, add the dry hexane of 70ml, add chlorocyclohexane 4ml.Stirring reaction 1 hour, mixing speed 100r/min.Reaction system is filtered, and drying makes magnesium ethylate/polynite/TiCl 4 catalyst.
Embodiment 5
Polynite was calcined 5 hours under 800 ℃ of high temperature, obtain montmorillonite carrier.Under nitrogen protection, use the 120ml decane to make thinner, the 4g magnesium ethylate is joined in the mixture of 16.4ml isooctyl alcohol and 10.1ml propyl carbinol.The 17g montmorillonite carrier is joined in the Fatty Alcohol(C12-C14 and C12-C18) suspension of magnesium ethylate, stirred 1 hour.In reaction system, add 5ml ethyl acetate, stirring reaction 1 hour.Reaction system is cooled to-12 ℃, in reaction system, slowly drips 9.6ml titanium tetrachloride, stirring reaction 2 hours, mixing speed 150r/min.Reaction system slowly is warming up to 40 ℃.Solids is with dry hexane wash 3 times.In reaction system, add the dry hexane of 85ml, add chlorocyclohexane 2ml.Stirring reaction 1 hour, mixing speed 150r/min.Reaction system is filtered, and drying makes magnesium ethylate/polynite/TiCl 4 catalyst.
Embodiment 6
Polynite was calcined 8 hours under 600 ℃ of high temperature, obtain montmorillonite carrier.Under nitrogen protection, use the 120ml decane to make thinner, the 4g magnesium ethylate is joined in the mixture of 9.1ml isooctyl alcohol and 12ml propyl carbinol.The 3.5g montmorillonite carrier is joined in the Fatty Alcohol(C12-C14 and C12-C18) suspension of magnesium ethylate, stirred 1 hour.In reaction system, add 1.7ml ethyl acetate, stirring reaction 1 hour.Reaction system is cooled to-5 ℃, in reaction system, slowly drips 13.5ml titanium tetrachloride, stirring reaction 2 hours, mixing speed 120r/min.Reaction system slowly is warming up to 40 ℃.Solids is with dry hexane wash 3 times.In reaction system, add the dry hexane of 10.5ml, add chlorocyclohexane 3.3ml.Stirring reaction 1 hour, mixing speed 120r/min.Reaction system is filtered, and drying makes magnesium ethylate/polynite/TiCl 4 catalyst.
Embodiment 7
Polynite was calcined 10 hours under 600 ℃ of high temperature, obtain montmorillonite carrier.Under nitrogen protection, use the 120ml decane to make thinner, the 4g magnesium ethylate is joined in the 20ml propyl carbinol.The 14g montmorillonite carrier is joined in the Fatty Alcohol(C12-C14 and C12-C18) suspension of magnesium ethylate, stirred 1 hour.In reaction system, add 2.7ml ethyl acetate, stirring reaction 1 hour.Reaction system is cooled to 0 ℃, in reaction system, slowly drips 19ml titanium tetrachloride, stirring reaction 2 hours, mixing speed 200r/min.Reaction system slowly is warming up to 40 ℃.Solids is with dry hexane wash 3 times.In reaction system, add the dry hexane of 70ml, add chlorocyclohexane 3ml.Stirring reaction 1 hour, mixing speed 200r/min.Reaction system is filtered, and drying makes magnesium ethylate/polynite/TiCl 4 catalyst.
Embodiment 8
Polynite was calcined 10 hours under 800 ℃ of high temperature, obtain montmorillonite carrier.Under nitrogen protection, use the 120ml decane to make thinner, the 4g magnesium ethylate is joined in the 20ml propyl carbinol.The 14g montmorillonite carrier is joined in the Fatty Alcohol(C12-C14 and C12-C18) suspension of magnesium ethylate, stirred 1 hour.In reaction system, add 2.7ml ethyl acetate, stirring reaction 1 hour.Reaction system is cooled to 0 ℃, in reaction system, slowly drips 19ml titanium tetrachloride, stirring reaction 2 hours, mixing speed 250r/min.Reaction system slowly is warming up to 40 ℃.Solids is with dry hexane wash 3 times.In reaction system, add the dry hexane of 70ml, add chloro cyclopropane 10.7ml.Stirring reaction 1 hour, mixing speed 250r/min.Reaction system is filtered, and drying makes magnesium ethylate/polynite/TiCl 4 catalyst.
Embodiment 9
Polynite was calcined 4 hours under 800 ℃ of high temperature, obtain montmorillonite carrier.Under nitrogen protection, use the 120ml decane to make thinner, the 4g magnesium ethylate is joined in the 6.4ml propyl carbinol.The 3.5g montmorillonite carrier is joined in the Fatty Alcohol(C12-C14 and C12-C18) suspension of magnesium ethylate, stirred 1 hour.In reaction system, add 0.34ml ethyl acetate, stirring reaction 1 hour.Reaction system is cooled to-10 ℃, slow Dropwise 5 .8ml titanium tetrachloride in reaction system, stirring reaction 2 hours, mixing speed 250r/min.Reaction system slowly is warming up to 40 ℃.Solids is with dry hexane wash 3 times.In reaction system, add the dry hexane of 10.5ml, add chloro cyclopropane 0.27ml.Stirring reaction 1 hour, mixing speed 250r/min.Reaction system is filtered, and drying makes magnesium ethylate/polynite/TiCl 4 catalyst.
Embodiment 10
Polynite was calcined 4 hours under 800 ℃ of high temperature, obtain montmorillonite carrier.Under nitrogen protection, use the 120ml decane to make thinner, the 4g magnesium ethylate is joined in the 16ml propyl carbinol.The 34g montmorillonite carrier is joined in the Fatty Alcohol(C12-C14 and C12-C18) suspension of magnesium ethylate, stirred 1 hour.In reaction system, add 16ml ethyl acetate, stirring reaction 1 hour.Reaction system is cooled to-10 ℃, in reaction system, slowly drips 38ml titanium tetrachloride, stirring reaction 2 hours, mixing speed 250r/min.Reaction system slowly is warming up to 40 ℃.Solids is with dry hexane wash 3 times.In reaction system, add the dry hexane of 170ml, add chloro cyclopropane 26ml.Stirring reaction 1 hour, mixing speed 250r/min.Reaction system is filtered, and drying makes magnesium ethylate/polynite/TiCl 4 catalyst.
Embodiment 11
Polynite was calcined 4 hours under 800 ℃ of high temperature, obtain montmorillonite carrier.Under nitrogen protection, use the 120ml decane to make thinner, the 4g magnesium ethylate is joined in the 11ml propyl carbinol.The 17g montmorillonite carrier is joined in the Fatty Alcohol(C12-C14 and C12-C18) suspension of magnesium ethylate, stirred 1 hour.In reaction system, add 4ml ethyl acetate, stirring reaction 1 hour.Reaction system is cooled to-10 ℃, in reaction system, slowly drips 19ml titanium tetrachloride, stirring reaction 2 hours, mixing speed 250r/min.Reaction system slowly is warming up to 40 ℃.Solids is with dry hexane wash 3 times.In reaction system, add the dry hexane of 85ml, add chloro cyclopropane 8ml.Stirring reaction 1 hour, mixing speed 250r/min.Reaction system is filtered, and drying makes magnesium ethylate/polynite/TiCl 4 catalyst.
Embodiment 12
Polynite was calcined 5 hours under 800 ℃ of high temperature, obtain montmorillonite carrier.Under nitrogen protection, use the 120ml decane to make thinner, the 4g magnesium ethylate is joined in the mixture of 13.6ml isooctyl alcohol and 8.0ml propyl carbinol.The 17g montmorillonite carrier is joined in the Fatty Alcohol(C12-C14 and C12-C18) suspension of magnesium ethylate, stirred 1 hour.In reaction system, add 2.5ml ethyl acetate and 6.9ml tributyl phosphate, stirring reaction 1 hour.Reaction system is cooled to-15 ℃, in reaction system, slowly drips 19ml titanium tetrachloride, stirring reaction 2 hours, mixing speed 150r/min.Reaction system slowly is warming up to 40 ℃.Solids is with dry hexane wash 3 times.In reaction system, add the dry hexane of 85ml, add chloro cyclopropane 4ml.Stirring reaction 1 hour, mixing speed 150r/min.Reaction system is filtered, and drying makes magnesium ethylate/polynite/TiCl 4 catalyst.
Embodiment 13
Polynite was calcined 5 hours under 800 ℃ of high temperature, obtain montmorillonite carrier.Under nitrogen protection, use the 120ml decane to make thinner, the 4g magnesium ethylate is joined in the mixture of 7ml ethanol and 7ml isooctyl alcohol.The 7g montmorillonite carrier is joined in the Fatty Alcohol(C12-C14 and C12-C18) suspension of magnesium ethylate, stirred 1 hour.In reaction system, add 1.4ml ethyl acetate and 3.7ml dibutyl phthalate, stirring reaction 1 hour.Reaction system is cooled to-15 ℃, in reaction system, slowly drips 19ml titanium tetrachloride, stirring reaction 2 hours, mixing speed 150r/min.Reaction system slowly is warming up to 40 ℃.Solids is with dry hexane wash 3 times.In reaction system, add the dry hexane of 35ml, add chlorocyclopentane 6ml.Stirring reaction 1 hour, mixing speed 150r/min.Reaction system is filtered, and drying makes magnesium ethylate/polynite/TiCl 4 catalyst.
Embodiment 14
Polynite was calcined 5 hours under 800 ℃ of high temperature, obtain montmorillonite carrier.Under nitrogen protection, use the 120ml decane to make thinner, the 4g magnesium ethylate is joined in the mixture of 5ml methyl alcohol and 6.8ml isooctyl alcohol.The 17g montmorillonite carrier is joined in the Fatty Alcohol(C12-C14 and C12-C18) suspension of magnesium ethylate, stirred 1 hour.In reaction system, add 9.1ml dibutyl phthalate, stirring reaction 1 hour.Reaction system is cooled to-20 ℃, in reaction system, slowly drips 9.6ml titanium tetrachloride, stirring reaction 2 hours, mixing speed 150r/min.Reaction system slowly is warming up to 40 ℃.Solids is with dry hexane wash 3 times.In reaction system, add the dry hexane of 85ml, add chlorocyclopentane 6ml.Stirring reaction 1 hour, mixing speed 150r/min.Reaction system is filtered, and drying makes magnesium ethylate/polynite/TiCl 4 catalyst.
Embodiment 15
Polynite was calcined 6 hours under 800 ℃ of high temperature, obtain montmorillonite carrier.Under nitrogen protection, use the 120ml decane to make thinner, the 4g magnesium ethylate is joined in the 20ml isooctyl alcohol.The 10g montmorillonite carrier is joined in the Fatty Alcohol(C12-C14 and C12-C18) suspension of magnesium ethylate, stirred 1 hour.In reaction system, add 2.7ml dibutyl phthalate and 2.7ml tributyl phosphate, stirring reaction 1 hour.Reaction system is cooled to-20 ℃, in reaction system, slowly drips 11ml titanium tetrachloride, stirring reaction 2 hours, mixing speed 150r/min.Reaction system slowly is warming up to 40 ℃.Solids is with dry hexane wash 3 times.In reaction system, add the dry hexane of 50ml, add chlorocyclohexane 2ml.Stirring reaction 1 hour, mixing speed 150r/min.Reaction system is filtered, and drying makes magnesium ethylate/polynite/TiCl 4 catalyst.
Claims (6)
1. the preparation method of magnesium ethylate/polynite/titanium tetrachloride polyethylene catalysts is characterized in that: the consisting of of catalyst system: 1) polynite is the Na-polynite, Mg-polynite or Ca-polynite; 2) magnesium ethylate; 3) mixture of one or both of fat alcohol compound; 4) internal electron donor is the organic compound that contains oxygen, sulphur, nitrogen, silicon or a phosphorus atom at least; 5) catalyst activator is a chloro naphthenic hydrocarbon, and structural formula is C
nH
2n-1-Cl, 3≤n≤6; 6) titanium tetrachloride;
Preparation of catalysts is carried out according to following order:
(1) polynite was calcined 4-10 hour under 400-800 ℃ of high temperature, obtain montmorillonite carrier;
(2) use decane to make thinner, magnesium ethylate is joined in the Fatty Alcohol(C12-C14 and C12-C18), the mol ratio of Fatty Alcohol(C12-C14 and C12-C18) and magnesium ethylate is 2-5;
(3) according to the ratio of add-on 0.1-1g polynite/mmol magnesium ethylate, the montmorillonite carrier of handling in the step (1) is joined in the Fatty Alcohol(C12-C14 and C12-C18) suspension of magnesium ethylate, stirred 1 hour;
(4) according to the ratio of 1-5mmol internal electron donor/g polynite, add internal electron donor, stirring reaction 1 hour to reaction system;
(5) reaction system is cooled to-20-0 ℃, drips titanium tetrachloride in reaction system, titanium tetrachloride adds according to the mol ratio of [Ti]/[Mg]=1.5/1-10/1, and stirring reaction 2-4 hour, mixing speed 50-250r/min;
(6) reaction system slowly is warming up to 40-60 ℃, solids is with dry hexane wash 3 times;
(7) ratio according to 5ml hexane/g polynite adds dry hexane in reaction system, according to the ratio adding catalyst activator of 0.01-10mmol activator/g polynite, stirring reaction 1 hour, mixing speed 50-250r/min;
(8) reaction system is filtered, drying makes magnesium ethylate/polynite/TiCl 4 catalyst;
More than operation is all carried out under nitrogen protection.
2. the preparation method of magnesium ethylate/polynite according to claim 1/titanium tetrachloride polyethylene catalysts is characterized in that: the specific surface area 50-500m of polynite
2/ g, the aperture is 50-500A, and pore volume is 1-500cc/g, and exchange capacity is 80-100meq/100g.
3. the preparation method of magnesium ethylate/polynite according to claim 1/titanium tetrachloride polyethylene catalysts is characterized in that: Fatty Alcohol(C12-C14 and C12-C18) is isooctyl alcohol, ethanol, propyl carbinol, methyl alcohol one or above-mentioned arbitrary combination.
4. the preparation method of magnesium ethylate/polynite according to claim 1/titanium tetrachloride polyethylene catalysts, it is characterized in that: internal electron donor is dibutyl phthalate, ethyl acetate, tributyl phosphate, 2,2-dibutyl-1,3-Propanal dimethyl acetal, diisobutyl Propylene Glycol Dimethyl Ether or 9, two (methoxymethyl) fluorenes of 9-.
5. magnesium ethylate/polynite/titanium tetrachloride polyethylene catalysts is characterized in that: preparation method's preparation of magnesium ethylate/polynite according to claim 1/titanium tetrachloride polyethylene catalysts.
6. the application of magnesium ethylate/polynite/titanium tetrachloride polyethylene catalysts is characterized in that: be used for slurry polymerization and bulk technique prepares polyethylene/montmorillonite nanometer composite material.
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| CN109694426A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of polypropylene and preparation method thereof |
| CN109819654A (en) * | 2016-10-03 | 2019-05-28 | 东邦钛株式会社 | Solid catalyst component for olefin polymerization, the manufacturing method of solid catalyst component for olefin polymerization, polymerization of olefines catalyst, the manufacturing method of olefin polymer, the manufacturing method of propylene series copolymer and propylene series copolymer |
| CN112898459A (en) * | 2019-12-03 | 2021-06-04 | 中国石油天然气股份有限公司 | Preparation method of spherical modified montmorillonite and preparation method of spherical polyolefin catalyst |
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| CN1872908A (en) * | 2005-05-31 | 2006-12-06 | 中国石油天然气股份有限公司 | Montmorillonite-titanium tetrachloride catalyst and preparation method of polyethylene/montmorillonite composite material thereof |
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| CN109819654A (en) * | 2016-10-03 | 2019-05-28 | 东邦钛株式会社 | Solid catalyst component for olefin polymerization, the manufacturing method of solid catalyst component for olefin polymerization, polymerization of olefines catalyst, the manufacturing method of olefin polymer, the manufacturing method of propylene series copolymer and propylene series copolymer |
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