CN1031944C - High active catalyst for preparing full density polythene by gas phase method - Google Patents
High active catalyst for preparing full density polythene by gas phase method Download PDFInfo
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- CN1031944C CN1031944C CN92111570A CN92111570A CN1031944C CN 1031944 C CN1031944 C CN 1031944C CN 92111570 A CN92111570 A CN 92111570A CN 92111570 A CN92111570 A CN 92111570A CN 1031944 C CN1031944 C CN 1031944C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 19
- 229920000573 polyethylene Polymers 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000010936 titanium Substances 0.000 claims abstract description 26
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 150000002148 esters Chemical class 0.000 claims abstract description 12
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 150000002798 neodymium compounds Chemical class 0.000 claims abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 23
- 150000003609 titanium compounds Chemical class 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000005498 polishing Methods 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- 150000004820 halides Chemical class 0.000 claims description 8
- 125000003158 alcohol group Chemical group 0.000 claims description 7
- 229910003902 SiCl 4 Inorganic materials 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 5
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- FHUODBDRWMIBQP-UHFFFAOYSA-N Ethyl p-anisate Chemical compound CCOC(=O)C1=CC=C(OC)C=C1 FHUODBDRWMIBQP-UHFFFAOYSA-N 0.000 claims description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical group COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 238000012725 vapour phase polymerization Methods 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 229940095102 methyl benzoate Drugs 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 3
- 229930195733 hydrocarbon Natural products 0.000 claims 3
- 150000002430 hydrocarbons Chemical class 0.000 claims 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 18
- 238000012685 gas phase polymerization Methods 0.000 abstract description 12
- 238000009826 distribution Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 9
- 239000004698 Polyethylene Substances 0.000 abstract description 6
- 239000000428 dust Substances 0.000 abstract description 5
- 238000007334 copolymerization reaction Methods 0.000 abstract description 4
- 238000000227 grinding Methods 0.000 abstract description 4
- 239000005977 Ethylene Substances 0.000 abstract description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 abstract description 3
- -1 polyethylene Polymers 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 3
- 101100058670 Aeromonas hydrophila subsp. hydrophila (strain ATCC 7966 / DSM 30187 / BCRC 13018 / CCUG 14551 / JCM 1027 / KCTC 2358 / NCIMB 9240 / NCTC 8049) bsr gene Proteins 0.000 abstract 1
- 230000006583 body weight regulation Effects 0.000 abstract 1
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical compound C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 abstract 1
- 229910001629 magnesium chloride Inorganic materials 0.000 abstract 1
- 239000000178 monomer Substances 0.000 abstract 1
- 239000011592 zinc chloride Substances 0.000 abstract 1
- 235000005074 zinc chloride Nutrition 0.000 abstract 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- JHGDVEYCZZGUIW-UHFFFAOYSA-N ethene styrene Chemical compound C=C.C=C.C=CC1=CC=CC=C1 JHGDVEYCZZGUIW-UHFFFAOYSA-N 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229940073589 magnesium chloride anhydrous Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002901 organomagnesium compounds Chemical class 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing 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 present invention relates to a high activated catalyst for preparing full-density polyethylene by a gas phase method. The catalyst of the present invention uses titanium and neodymium compounds as main catalysts, uses MgCl2 and ZnCl2 as compound carriers, uses silicon compounds and ester as accelerants, and uses AlR3 as an auxiliary catalyst. The catalysts are prepared by a grinding method and a reaction method; firstly, basal body catalysts with activity are prepared by the grinding method; then, the basal body catalysts are processed by the reaction method; finally, the catalyst with favorable synthetic performance is obtained by prepolymerization. The catalyst of the present invention has high activity, favorable molecular weight regulation effect and stable polymerization reaction, and is capable of making the particle size distribution of polymerisates narrow and few dust particles. The present invention has favorable ethylene-styrene monomer copolymerization performance, and is used for ethylene gas phase polymerization fluidized beds.
Description
The present invention relates to a kind of high activated catalyst that is used for the gas-phase method total density polyvinyl preparation.
As everyone knows, halogen compound-supported in containing obtained highly active catalyzer on the various magnesium compound solid carriers by alkylaluminium cpd and a kind of titanium can be used for the polyreaction of ethene and alpha-olefin.Magnesium compound commonly used is a Magnesium Chloride Anhydrous, can use separately, also can and SiO
2Compound use, the preparation method can adopt common polishing, pickling process or reaction method.
This class catalyzer is used for the ethene gas-phase polymerization reaction, solid carrier and catalyst component and preparation method are to the over-all properties of catalyzer, as granules of catalyst form, size-grade distribution, polymerization activity, stable polymerization reaction control, copolyreaction performance and molecular weight product adjusting etc., have a significant impact.Because solvent is not adopted in the ethene gas-phase polymerization reaction, reaction heat spread out of certain limitation, the size-grade distribution of catalyzer, stable polymerization reaction control and the molecular weight of regulating product effectively for gas phase polymerization carry out smoothly, prevent to lump, make the product particle form that makes good, obtain the premium properties product important meaning arranged.So,, be the major issue that solution is thirsted in this field how obtaining to realize the above-mentioned over-all properties of catalyzer under the suitably high catalyst activity prerequisite.
The CNl037157A patent application discloses a kind of catalyzer for preparing gas-phase polyethylene, adopts organo-magnesium compound to prepare the MgCl of specific size distribution
2The dipping titanium compound, the catalyzer that makes has good particle form and size-grade distribution, and is active high; But catalyzer cost costliness, the active constituent of titanium compound mainly is distributed in MgCl
2The surface, stable polymerization reaction control has limitation.SiO is adopted in the introduction of US434988 patent
2Load MgCl
2Prepare the gas-phase polyethylene catalyzer with titanium compound, this patent is removed the SiO that needs the preparation specific standard
2Outward, the catalyst Ti compound activity component that makes is dispersed in SiO
2Pore surface makes the initial activity height of catalyzer and SiO
2The easy fragmentation of fragility makes and makes the product form, size-grade distribution is inhomogeneous.The CN87103866A patent application is also introduced and is adopted MgCl
2Be dissolved in the alcohol, adopt halogenating agent to prepare MgCl again
2, this method is except that a large amount of reagent of needs, and the catalyzer initial activity height, the molecule that make are many, are unfavorable for gas-phase fluidized-bed use.The catalyzer of above-mentioned prior art is used for the ethene gas-phase polymerization reaction, can only regulate molecular weight with hydrogen, regulates for molecular weight of product to have certain limitation, and is difficult to carry out ethene-styrene copolymerization.
The purpose of this invention is to provide a kind of high active catalyst for preparing full density polythene by gas phase, it has good adjusting molecular weight effect, stable polymerization reaction, and can make the polymerisate narrow particle size distribution, few dust particle, have good ethene-styrene copolymerized performance, thereby solve the existing problem of above-mentioned prior art.
Its component of catalyzer of the present invention comprises Primary Catalysts, complex carrier, promotor and promotor.With the titanium compound is Primary Catalysts, MgCl
2And ZnCl
2Form complex carrier; Silicon compound and ester are as promotor; AlR
3(aluminum alkyls) is promotor.In order to obtain good catalyzer over-all properties, catalyzer of the present invention adopts the preparation of grinding-reaction method, and method is as follows:
1, with MgCl
2, ZnCl
2, silicon compound, ester and Primary Catalysts component, adopt altogether polishing to make the active base catalyst of tool (1);
2, base catalyst (1) is dispersed in the varsol, with alcohol moiety dissolving and reaction treatment;
3, use AlR
3(or R
2Mg)-halide reagent handles above-mentioned catalyzer through pure processing reaction (1), obtains epigranular, catalyst solid component (2) (suspension) that component is adjustable;
4, adopt titanium compound-halide reagent to handle above-mentioned catalyzer (2), after filtration, wash catalyst solid component (3);
5, above-mentioned catalyzer (3) is added AlR
3(aluminum alkyls) carries out prepolymerization reaction, gained performed polymer and AlR
3Form high active catalyst for preparing full density polythene by gas phase of the present invention.
In the composition of base catalyst (1), be TiCl as the titanium compound of Primary Catalysts composition
4Or TiCl
4And Ti (OR )
4Mixture (Ti (OR ) wherein
4Content≤25% (mol ratio), R are propyl group or butyl).Also can in the Primary Catalysts composition, increase neodymium compound NdCl
3Or NdCl
33ROH (wherein ROH comprises methyl alcohol, ethanol, propyl alcohol or butanols) makes catalyzer have good ethene-styrene copolymerized performance.Silicon compound is R
*NSiCl
4-n(R
*For containing C
1～C
4Alkyl or C
6H
5Base, n are 0～4 number); Ester is methyl benzoate, ethyl benzoate or ethyl anisate.
Base catalyst (1) each component proportioning is: MgCl
2: ZnCl
2: TiCl
4(weight ratio)=1: (0.05～0.7): (0.2～0.8), all the other each components are with TiCl
4Mole number calculate, its proportioning (mol ratio) is:
TiCl
4 1
Ti(OR)
4 0～0.25
R
*nSiCl
4-n 0.20～0.90
Ester 0.1～1.0
Neodymium compound 0 or 0.02～0.30
Below the preparation method of high activated catalyst of the present invention is described further:
1, adopts polishing altogether, at N
2Protection prepares base catalyst (1) down.In the vibro-grinding cylinder, add anhydrous MgCl earlier
2, ZnCl
2(adding neodymium compound when needing again) ground 6～8 hours together, added ester, silicon compound then respectively and respectively ground 4～8 hours, added titanium compound again and ground 8～25 hours, and total milling time is no less than 35 hours, at N
2The protection bottom discharge gets Powdered active matrix catalyzer (1).
2, in reaction flask, add base catalyst (1), add alkane again, stir and slowly drip alcohol down, 0～100 ℃ of (40～80 ℃ commonly used) reaction 1～2 hour, base catalyst (1) is partly dissolved, and this moment, catalyzer did not have caking, stirred at normal temperatures 2～4 hours.
Used alkane can be hexane, heptane, octane or decane.Alcohol can be the various Fatty Alcohol(C12-C14 and C12-C18) that comprise 1～8 carbon atom, and consumption is MgCl
2: alcohol (mol ratio)=1: (0.1～3).The consumption of alkane is generally every gram base catalyst (1) 4～20ml.
3, above-mentioned in the catalyzer (1) that alcohol is handled, by alcohol: Al (mol ratio)=1: (0.1～1) adds AlR
3(or R '
2Mg)-and halide reagent, 0～100 ℃ of (commonly used 50～100 ℃) stirring reaction 2～6 hours, at room temperature obtain epigranular then, the controllable catalyzer of component (solid constituent (2) (suspension).
AlR
3In R comprise the alkyl that contains 2～8 carbon atoms.R '
2R ' among the Mg is C
2H
5, C
4H
9Or C
6H
5Group.Halide reagent comprises ZnCl
2, SiCl
4Or R "
nSiCl
4-n(R " is C
1～C
8Alkyl or C
6H
5Base, n are 1～3 number).AlR
3(or R '
2Mg)-consumption of halide reagent is alcohol: Al (mol ratio)=1: (0.1～1), Al: halide reagent (mol ratio)=1: (0.1～4).
4, slowly drip titanium compound-halide reagent to above-mentioned gained catalyzer (2), 20～120 ℃ of (60～120 ℃ commonly used) reactions 2～4 hours, filter, extremely there is not free titanium compound 5～6 times with the alkane washing, get catalyst suspension, after filtration, the dry catalyst solid component (3) that gets, can not filter yet, drying, directly use with suspension.
Titanium compound is TiCl
4, halide reagent is SiCl
4Consumption is a titanium compound: halogenation trial-production (mol ratio)=1: (0.1～4), titanium compound: alcohol (mol ratio)=(0.1～10): 1.
5, prepolymerization reaction: catalyst solid component (3) is dispersed in the alkane medium, adds AlR
3Under agitation lead to into ethene, carry out prepolymerization reaction under 20～60 ℃, the pre-polymerization multiple is 20～100g PE/g catalyzer, performed polymer drying, performed polymer, AlR
3Form catalyst prod of the present invention.
AlR
3Middle R is C
2～C
8Alkyl, pre-polymerization Al/Ti=(1～20)/1 (mol ratio), vapour phase polymerization Al/Ti=(5～200)/1 (mol ratio).
Catalyzer of the present invention adopts the good MgCl of composite performance
2And ZnCl
3As the carrier composite components, and the advantage of comprehensive polishing and reaction method, adopt polishing to prepare the active complex matrix catalyzer of tool (1) earlier, again with reagent such as alcohol through reaction modifying, remove molecule, make granules of catalyst even, short textureization; When further using AlR
3When-halide reagent is handled, make the titanium compound active constituent can load on complex carrier MgCl more evenly, effectively
2-ZnCl
2On; With a certain amount of titanium compound, silicon compound reaction dipping, activity of such catalysts component titanium content can be controlled again.Prepared catalyzer has high reactivity and good adjusting molecular weight effect, and polyreaction is more steady, particularly makes the polymerisate size-grade distribution more even, little particle dust; Introducing a spot of neodymium compound component in the composition makes catalyzer have good ethene-styrene copolymerized performance.So catalyzer of the present invention has good comprehensive performances, be suitable for the ethene gas-phase polymerization fluidized-bed and use.The present invention also has the few advantage of the preparation process three wastes.
Catalyzer of the present invention is used for normal pressure (pressure is 107.2KPa) ethene gas-phase polymerization, at 60～90 ℃, reacts 3 hours, and catalytic efficiency is 10～34Kg PE/gTi, and product does not have caking, seldom less than 200 purpose particulates.
Catalyzer of the present invention is used for the ethene fluidized bed gas-phase polymerization, when pressure is 1.2MPa, and H
2%=(5～40) %, Al/Ti=(60～150)/1, temperature is 90～105 ℃, reacts 3 hours; To the ethylene homo catalytic efficiency is 250～600KgpE/gTi, product MI
2.16Be 0.1～30; To ethene---butylene-1 gas-phase copolymerization, butene content are 10～15%, and catalytic efficiency is 200～400KgLLDPE/gTi, MI
2.16Be 0.1～30, product density is 0.9150～0.9300, and adjusting the butylene amount is 5～10%, and product density is 0.9300～0.9460.
The invention will be further described below by embodiment:
1, Preparation of Catalyst:
1-1 with anhydrous MgCl
240g, anhydrous ZnCl
210g, NdCl
33C
2H
5OH1.8g places the vibro-grinding cylinder of clean anaerobic, exclusion, at N
2Protection was ground 4 hours down, added 4 milliliters of (C
6H
5)
2SiCl
2Ground 4 hours, and added 4.4 milliliters of ethyl benzoates and ground 4 hours, add 1.5 milliliters of Ti (OBu)
4Ground 4 hours, and added 4.4ml TiCl
4Ground N 20 hours
2The protection bottom discharge gets base catalyst (1) 65g.
1-2 in reaction flask, adds 40 milliliters of heptane, base catalyst (1) 10g, and constantly stirring dripped the 3.5ml dehydrated alcohol down in 30 minutes, heat temperature raising to 60～70 ℃ reaction 2 hours, cooling, stirring 2 hours.
1-3 under agitation, drips in 30 minutes to contain 20%AlEt
3AlR
3-ZnCl
2Reagent l6.3ml (wherein Al/Zn (mol ratio)=3: 1) was warming up to 70～80 ℃ of stirring reactions 4 hours, was cooled to room temperature.Get catalyzer (2) suspension.
1-4 under agitation, drips 20% titanium compound (titaniferous mole number 6.25 * 10 in 30 minutes
-3)-SiCl
4(content is 6.5 * 10
-3) n-heptane solution.Be warming up to 80～90 ℃ of reactions 4 hours, filter, with 40 milliliters of hexane wash, filtration 5 times, add hexane 40ml, it is standby to get catalyzer (3) suspension.
2, prepolymerization reaction:
In the exsiccant reaction flask, use high-purity N
2After replacing 3 times, add the 60ml solvent by the 10g prepolymer product and calculate, add normal hexane, Al/Ti is 10/1 (mol ratio), adds aluminum alkyls, adds catalyzer (3) suspension again, under 10～30 ℃ of stirrings, leads to into ethene-H
2Gas (both volume ratios are 70: 30), the initial dividing potential drop of ethene is 133～266Pa, stirring velocity is 200～400 rev/mins; This moment, slow prepolymerization reaction took place in catalyzer, reacted 400～800 times of pre-polymerization multiples (for titanium) 3～7 hours.Pre-polymerization finishes, and uses N
2Displacement is taken out and is desolvated, and can be warming up to 60 ℃ (the highest be no more than 70 ℃) and obtain the exsiccant prepolymer, at N
2The protection lower seal is standby.
3, polyreaction:
The pressurization vapour phase polymerization adopts φ=100mm fluidized-bed reactor, when total pressure is 1.2MPa, and H
2% (V)=30%, Al/Ti=150/1, temperature is 90～100 ℃, reacts 3 hours, catalytic efficiency is 280KgPE/gTi, MI
2.16=6.2, corresponding without ZnCl
2Make the effective catalyst of carrier, catalytic efficiency 280KgPE/gTi, MI
2.16=2.5.The former is because of containing ZnCl in the catalyzer
2And improve the regulating effect of molecular weight greatly.Be used for ethene-butylene-1 copolymerization when total pressure be 1.2MPa, butene content is 13～15%, temperature is 85～95 ℃, catalytic efficiency is 250KgLLDPE/gTi, density is 0.9150g/cm
3
4, ethene atmospheric gas phase-polymerization:
In reaction flask, add the 1gPE powder as dispersion medium through 120 ℃ of dryings of vacuum 1～1.5 hour, N
2Replace 3 times, at N
2Add 20 milliliters of normal hexanes and Al/Ti (mol ratio) down and be 80 AlEt
3Under agitation add again the catalyzer (prepolymer) contain 0.5～1mg titanium stir made the catalyzer homodisperse in 5 minutes after, heating is taken out and is desolvated, to PE powder and catalyzer (prepolymer) fully after the flow dispersion, logical ethene is under the 107.2KPa at pressure, is warming up to 80～90 ℃ and carries out polyreaction.Write down per 5 minutes polyreaction consumption of ethylene, reacted stopped reaction 1.5～2.5 hours.The reaction product calculating catalytic efficiency of weighing is used standard sieve, and the weight granularity (%) that product is obtained in screening distributes, and the result is as shown in table 1.Obtain the ethene gas-phase polymerization polymerization kinetics curves according to reaction process reaction consumes ethene amount, the result as shown in Figure 1.
Table 1 is to adopt catalyzer of the present invention and prepared product size distribution of catalyzer that adopts the polishing preparation and catalytic efficiency contrast.From table, can find out that the product size distribution that makes with catalyzer of the present invention is narrow, mainly in 10～100 order scopes, (account for 92～96%), not have caking, few dust particle.And the prepared product of polishing catalyzer has the dust particle of small portion caking and more amount.The catalytic efficiency of catalyzer of the present invention is also much higher than polishing catalyzer.
Fig. 1 is the kinetic curve figure that catalyzer of the present invention and polishing catalyzer are used for the normal pressure ethene gas-phase polymerization.Wherein 1 is the curve of catalyzer of the present invention, and 2 is the curve of polishing catalyzer.Fig. 1 shows that catalyzer of the present invention is used for ethene gas-phase polymerization, and it is lower to have the initial reaction stage activity, and polymerization rate is advantage stably, and this has great importance on producing; The polishing catalyzer then exists initial reaction stage active high, and the polymerization rate decay is fast, the unmanageable shortcoming of polyreaction.
The different preparation method's catalyst performances of table 1 relatively
| Method for preparing catalyst | Bulk density | Caking | Product weight average distribution (%) | Catalytic efficiency | ||
| The 10-100 order | 100～200 orders | ＜200 orders | (gPE/gTi) | |||
| Polishing | 0.23 | 4.0% little caking | 74.8 | 14.2 | 7.0 | 13000 |
| The present invention 1 | 0.24 | There is not caking | 96.3 | 8.7 | 6 | 23000 |
| The present invention 2 | 0.25 | There is not caking | 92.0 | 8.0 | 0 | 23300 |
Claims (9)
1. gas-phase method total density polyvinyl catalyzer, its component comprises Primary Catalysts, complex carrier, promotor and promotor, it is characterized in that:
(1) with the titanium compound is Primary Catalysts, MgCl
2And ZnCl
2Be complex carrier, silicon compound and ester are promotor, AlR
3Be promotor;
(2) said catalyzer is to adopt following grinding-reaction method preparation:
1. with MgCl
2, ZnCl
2, silicon compound, ester and Primary Catalysts component, adopting altogether, polishing is prepared into the active base catalyst of tool (1);
2. base catalyst (1) is dispersed in the hydrocarbon solution, with alcohol moiety dissolving and reaction treatment;
3. use AlR
3Or R
2' Mg-halide reagent is handled the base catalyst (1) through pure processing reaction, obtains catalyst solid constituent (2) (suspension);
4. adopt titanium compound-halide reagent to handle catalyzer (2), after filtration, wash catalyst solid component (3);
5. catalyzer (3) is added AlR
3Carry out prepolymerization reaction, gained performed polymer and AlR
3Form catalyst prod of the present invention;
AlR in above-mentioned
3R be C
2～C
8Alkyl, R '
2The R ' of Mg is C
2H
5, C
4H
9Or C
8H
5Group.
2. according to the described catalyzer of claim 1, it is characterized in that the titanium compound as the Primary Catalysts composition is TiCl
4Or TiCl
4And Ti (OR )
4Mixture, R is propyl group or butyl.
3. according to claim 1 or 2 described catalyzer, it is characterized in that used silicon compound is Rn
*SiCl
4-n, R
*For containing C
1～C
4Alkyl or C
8H
5Base, n are O～4 numbers; Ester is methyl benzoate, ethyl benzoate or ethyl anisate.
4. according to the described catalyzer of claim 3, it is characterized in that base catalyst (1) each component proportioning is: MgCl
2: ZnCl
2: TiCl
4(weight ratio)=1: (O.05～0.7): (O.2～O.8), all the other each components are with TiCl
4Mole number calculate, its proportioning (mol ratio) is:
TiCl
4 1
Ti(OR)
4 0～0.25
R
*nSiCl
4-n 0.2～0.90
Ester 0.1～1.0
5. according to the described catalyzer of claim 1, it is characterized in that comprising the Fatty Alcohol(C12-C14 and C12-C18) that has 1～8 carbon atom that its consumption is MgCl in order to the alcohol of handling base catalyst (1)
2: alcohol (mol ratio)=1: (0.1～3).
6. according to the described catalyzer of claim 1, it is characterized in that used AlR
3Or R '
2Halide reagent in the Mg-halide reagent comprises ZnCl
2, SiCl
4Or R " nSiCl
4-n, R " is C
1～C
3Alkyl or C
6H
5Base, n are 1～3 number; AlR
3Or R '
2The consumption of Mg-halide reagent is alcohol: Al (mol ratio)=1: (O.1～1), Al: halide reagent (mol ratio)=1: (0.1～4).
7. according to the described catalyzer of claim 1, it is characterized in that the titanium compound in used titanium compound-halide reagent is TiCl
4, halide reagent is SiCl
4, consumption is a titanium compound: halide reagent (mol ratio)=1: (O.1～4), titanium compound: alcohol (mol ratio)=(0.1～10): 1.
8. according to the described catalyzer of claim 1, it is characterized in that catalyzer (3) adds AlR
3Pre-polymerization is to carry out in the hydrocarbon medium, and the pre-polymerization temperature is 20～60 ℃, and the pre-polymerization multiple is 20～100gPE/g catalyzer, pre-polymerization Al/Ti (mol ratio)=(1～20)/1, vapour phase polymerization Al/Ti (mol ratio)=(5～200)/1.
9. gas-phase method total density polyvinyl catalyzer, its component comprises Primary Catalysts, complex carrier, promotor and promotor, it is characterized in that:
(1) be Primary Catalysts with titanium compound and neodymium compound, MgCl
2And ZnCl
2Be complex carrier, silicon compound and ester are promotor, AlR
3Be promotor;
(2) said catalyzer is to adopt following grinding-reaction method preparation:
1. with MgCl
2, ZnCl
2, silicon compound, ester and Primary Catalysts component, adopt altogether polishing to make the active base catalyst of tool (1)
2. base catalyst (1) is dispersed in the hydrocarbon solution, with alcohol moiety dissolving and reaction treatment;
3. use AlR
3Or R '
2The base catalyst (1) that the Mg-halide reagent is handled through pure processing reaction obtains catalyst solid constituent (2) (suspension);
4. adopt titanium compound-halide reagent to handle catalyzer (2), after filtration, wash catalyst solid component (3);
5. catalyzer (3) is added AlR
3Carry out prepolymerization reaction, gained performed polymer and AlR
3Form catalyst prod of the present invention;
AlR in above-mentioned
3R be C
2～C
8Alkyl, R '
2The R ' of Mg is C
2H
5, C
4H
9Or C
6H
5Group.
10. according to the described catalyzer of claim 9, it is characterized in that the titanium compound as the Primary Catalysts composition is TiCl
4Or TiCl
4And Ti (OR )
4Mixture, R are propyl group or butyl; Neodymium compound is NdCl
3Or NdCl
33ROH, ROH comprise first, second, third, butanols; TiCl
4: neodymium compound (mol ratio)=1: (0.02～0.30).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92111570A CN1031944C (en) | 1992-10-09 | 1992-10-09 | High active catalyst for preparing full density polythene by gas phase method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92111570A CN1031944C (en) | 1992-10-09 | 1992-10-09 | High active catalyst for preparing full density polythene by gas phase method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1071934A CN1071934A (en) | 1993-05-12 |
| CN1031944C true CN1031944C (en) | 1996-06-05 |
Family
ID=4945411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92111570A Expired - Fee Related CN1031944C (en) | 1992-10-09 | 1992-10-09 | High active catalyst for preparing full density polythene by gas phase method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1031944C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042339C (en) * | 1994-01-08 | 1999-03-03 | 中山大学 | Ethene gas-phase homopolymerization and alpha-olefinic copolymerization composite catalyst |
| CN1054137C (en) * | 1997-07-18 | 2000-07-05 | 中山大学 | Ethylene gaseous phase polymerization multifunction catalyst and its preparation method |
-
1992
- 1992-10-09 CN CN92111570A patent/CN1031944C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1071934A (en) | 1993-05-12 |
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