CN116003656A - External electron donor composition, ziegler-Natta catalyst composition and propylene polymerization process - Google Patents
External electron donor composition, ziegler-Natta catalyst composition and propylene polymerization process Download PDFInfo
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- CN116003656A CN116003656A CN202211711360.3A CN202211711360A CN116003656A CN 116003656 A CN116003656 A CN 116003656A CN 202211711360 A CN202211711360 A CN 202211711360A CN 116003656 A CN116003656 A CN 116003656A
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- silane
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- 239000000203 mixture Substances 0.000 title claims abstract description 164
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 130
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 120
- 239000011954 Ziegler–Natta catalyst Substances 0.000 title claims abstract description 85
- 239000003054 catalyst Substances 0.000 claims abstract description 102
- -1 halogenated ether compound Chemical class 0.000 claims abstract description 57
- 239000004743 Polypropylene Substances 0.000 claims abstract description 24
- 229920001155 polypropylene Polymers 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 229910000077 silane Inorganic materials 0.000 claims abstract description 6
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 40
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 27
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 21
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 21
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 20
- ZFAGXQVYYWOLNK-UHFFFAOYSA-N CCO[Mg] Chemical compound CCO[Mg] ZFAGXQVYYWOLNK-UHFFFAOYSA-N 0.000 claims description 16
- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 16
- QCFYJCYNJLBDRT-UHFFFAOYSA-N Bis(2-chloro-1-methylethyl)ether Chemical compound ClCC(C)OC(C)CCl QCFYJCYNJLBDRT-UHFFFAOYSA-N 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005054 agglomeration Methods 0.000 claims description 6
- 230000002776 aggregation Effects 0.000 claims description 6
- OJMVRGXLTANFRG-UHFFFAOYSA-N 1-(2-chloroethoxy)butane Chemical compound CCCCOCCCl OJMVRGXLTANFRG-UHFFFAOYSA-N 0.000 claims description 5
- BHDSGQOSIWVMJW-UHFFFAOYSA-N 1-(2-chloroethoxy)propane Chemical compound CCCOCCCl BHDSGQOSIWVMJW-UHFFFAOYSA-N 0.000 claims description 5
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 claims description 5
- OXEJPGWJAKMECQ-UHFFFAOYSA-N 2-bromo-1-(2-bromo-3-methylbutoxy)-3-methylbutane Chemical compound C(C)(C)C(COCC(C(C)C)Br)Br OXEJPGWJAKMECQ-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 4
- CVDGHGWEHQIJTE-UHFFFAOYSA-N bromo(bromomethoxy)methane Chemical compound BrCOCBr CVDGHGWEHQIJTE-UHFFFAOYSA-N 0.000 claims description 4
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 claims description 4
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229920005555 halobutyl Polymers 0.000 claims description 3
- 125000004968 halobutyl group Chemical group 0.000 claims description 3
- 125000004969 haloethyl group Chemical group 0.000 claims description 3
- 125000004970 halomethyl group Chemical group 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- HSCLUIKEZDGKBP-UHFFFAOYSA-N 2,3-di(propan-2-yl)butanedioic acid Chemical compound CC(C)C(C(O)=O)C(C(C)C)C(O)=O HSCLUIKEZDGKBP-UHFFFAOYSA-N 0.000 claims description 2
- ULUNQYODBKLBOE-UHFFFAOYSA-N 2-(1h-pyrrol-2-yl)-1h-pyrrole Chemical compound C1=CNC(C=2NC=CC=2)=C1 ULUNQYODBKLBOE-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 2
- QEPVYYOIYSITJK-UHFFFAOYSA-N cyclohexyl-ethyl-dimethoxysilane Chemical compound CC[Si](OC)(OC)C1CCCCC1 QEPVYYOIYSITJK-UHFFFAOYSA-N 0.000 claims description 2
- YRMPTIHEUZLTDO-UHFFFAOYSA-N cyclopentyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCC1 YRMPTIHEUZLTDO-UHFFFAOYSA-N 0.000 claims description 2
- YPENMAABQGWRBR-UHFFFAOYSA-N dibutyl(dimethoxy)silane Chemical compound CCCC[Si](OC)(OC)CCCC YPENMAABQGWRBR-UHFFFAOYSA-N 0.000 claims description 2
- ZVMRWPHIZSSUKP-UHFFFAOYSA-N dicyclohexyl(dimethoxy)silane Chemical compound C1CCCCC1[Si](OC)(OC)C1CCCCC1 ZVMRWPHIZSSUKP-UHFFFAOYSA-N 0.000 claims description 2
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 claims description 2
- NQSVPQIOJRYMGQ-UHFFFAOYSA-N diethyl 2-methyl-2-propan-2-ylpropanedioate Chemical compound CCOC(=O)C(C)(C(C)C)C(=O)OCC NQSVPQIOJRYMGQ-UHFFFAOYSA-N 0.000 claims description 2
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 2
- JVUVKQDVTIIMOD-UHFFFAOYSA-N dimethoxy(dipropyl)silane Chemical compound CCC[Si](OC)(OC)CCC JVUVKQDVTIIMOD-UHFFFAOYSA-N 0.000 claims description 2
- NHYFIJRXGOQNFS-UHFFFAOYSA-N dimethoxy-bis(2-methylpropyl)silane Chemical compound CC(C)C[Si](OC)(CC(C)C)OC NHYFIJRXGOQNFS-UHFFFAOYSA-N 0.000 claims description 2
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 claims description 2
- OANIYCQMEVXZCJ-UHFFFAOYSA-N ditert-butyl(dimethoxy)silane Chemical compound CO[Si](OC)(C(C)(C)C)C(C)(C)C OANIYCQMEVXZCJ-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- BJDLPDPRMYAOCM-UHFFFAOYSA-N triethoxy(propan-2-yl)silane Chemical compound CCO[Si](OCC)(OCC)C(C)C BJDLPDPRMYAOCM-UHFFFAOYSA-N 0.000 claims description 2
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- LGROXJWYRXANBB-UHFFFAOYSA-N trimethoxy(propan-2-yl)silane Chemical compound CO[Si](OC)(OC)C(C)C LGROXJWYRXANBB-UHFFFAOYSA-N 0.000 claims description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 2
- 230000037048 polymerization activity Effects 0.000 abstract description 9
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 34
- 239000002245 particle Substances 0.000 description 14
- 239000010936 titanium Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000003068 static effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- SXQXMKMHOFIAHT-UHFFFAOYSA-N 1,1-dichloro-2-(2,2-dichloroethoxy)ethane Chemical group ClC(Cl)COCC(Cl)Cl SXQXMKMHOFIAHT-UHFFFAOYSA-N 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- CIACLSGBPZWWNK-UHFFFAOYSA-N 2-(chloromethoxy)-2-methylpropane Chemical compound CC(C)(C)OCCl CIACLSGBPZWWNK-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003701 inert diluent Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- JAMFGQBENKSWOF-UHFFFAOYSA-N bromo(methoxy)methane Chemical compound COCBr JAMFGQBENKSWOF-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 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 application relates to the field of propylene polymerization catalysis, and in particular to an external electron donor composition, a ziegler-natta catalyst composition and a propylene polymerization method. The external electron donor composition comprises halogenated ether compound shown in formula I and C 1 ～C 10 The alkoxy silane compound forms a composition according to the mole ratio of 1:99-99:1, so that the formed Ziegler-Natta catalyst composition can be applied to propylene polymerization, and not only can the stereospecificity of the catalyst and the isotacticity of polypropylene be greatly improved, but also the polymerization activity and the hydrogen sensitivity of the catalyst can be improved.
Description
Technical Field
The present application relates to the field of propylene polymerization catalysis, and in particular to an external electron donor composition, a ziegler-natta catalyst composition and a propylene polymerization method.
Background
Currently, the catalysts used in commercial polypropylene units are mainly MgCl 2 The supported Ziegler-Natta catalyst has diester internal electron donor, and has high activity and stereoregularity. The main function of the external electron donor is to adjust the isotacticity of polypropylene, and in addition, the addition of the external electron donor also has a certain influence on the performances of the catalyst, such as hydrogen sensitivity, catalyst activity and the like. In the prior art, in addition to the catalyst and the cocatalyst aluminum alkyl, an appropriate amount of external electron donor is usually added in the production process to realize balance between polymerization activity and polypropylene isotacticity. To date, it has been difficult for industry to increase the polymerization activity of olefins, especially propylene, by changing the composition of the external electron donor, by simply adding a small amount of a silane compound for production.
The prior art shows that the addition of the external electron donor mainly improves the isotacticity (namely the stereospecificity of the catalyst) of the polypropylene, but has limited improvement on the activity and hydrogen sensitivity of the catalyst.
Disclosure of Invention
The inventor of the application finds that the composition of the alkoxy silane and the halogenated ether compound is used as an external electron donor, so that the stereospecificity of the catalyst and the isotacticity of polypropylene can be greatly improved, and the polymerization activity and the hydrogen sensitivity of the catalyst can be improved. Therefore, the embodiment of the application at least discloses the following technical scheme:
in a first aspect, embodiments of the present application disclose an external electron donor composition of a ziegler-natta catalyst for propylene polymerization, comprising a first external electron donor and a second external electron donor, wherein the molar ratio of the first external electron donor to the second external electron donor is 1:99-99:1; wherein,,
the first external electron donor is a halogenated ether compound with a-C-O-C-ether functional group, and the second external electron donor is a C1-C10 alkoxy silane compound;
the first external electron donor is selected from compounds shown in a formula I;
in formula I, at least one R is independently selected from the group consisting of halomethyl, haloethyl, halopropyl, haloisopropyl, halobutyl, haloisobutyl, halosec-butyl, and halotert-butyl.
In a second aspect, embodiments herein disclose a Ziegler-Natta catalyst composition for propylene polymerization comprising:
a carrier selected from magnesium chloride and/or magnesium ethoxide;
a first catalyst selected from titanium tetrachloride and/or titanium trichloride;
the internal electron donor is a mixture of 1, 3-diether and aromatic acid ester;
the second catalyst is aluminum alkyl;
the external electron donor composition of the first aspect;
in the Ziegler-Natta catalyst composition for propylene polymerization, the molar ratio of aluminum to titanium element is 10-1200, and the molar ratio of silicon to titanium element is 2-50.
In a third aspect, embodiments herein disclose a process for polymerizing propylene in the presence of hydrogen, using the Ziegler-Natta catalyst composition of the second aspect to catalyze the polymerization of propylene.
Specific technical effects of the external electron donor composition, the Ziegler-Natta catalyst composition and the propylene polymerization method provided in the examples of the present application will be described in detail in the examples.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application will be further described in detail with reference to examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application. Reagents not specifically and individually described in this application are all conventional reagents and are commercially available; methods which are not specifically described in detail are all routine experimental methods and are known from the prior art.
It should be noted that, the terms "first," "second," and the like in the description and the claims of the present application are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order, and are not intended to limit the essential characteristics thereof. It is to be understood that the data so used may be interchanged where appropriate such that embodiments of the present application described herein may be implemented in sequences other than those described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
In one embodiment of the present application, there is provided an external electron donor composition of a Ziegler-Natta catalyst for propylene polymerization, comprising a first external electron donor and a second external electron donor, wherein the molar ratio of the first external electron donor to the second external electron donor is 1:99-99:1; wherein,,
the first external electron donor is a halogenated ether compound with a-C-O-C-ether functional group, and the second external electron donor is a C1-C10 alkoxy silane compound;
the first external electron donor is selected from compounds shown in a formula I;
in formula I, at least one R is independently selected from the group consisting of halomethyl, haloethyl, halopropyl, haloisopropyl, halobutyl, haloisobutyl, halosec-butyl, and halotert-butyl.
Wherein halogen such as fluorine, chlorine, bromine or iodine, the number of atoms of the "halo" is 1 to 2.
In some embodiments, the first external electron donor is selected from one of bromomethyl ether, 2-bromoethyl methyl ether, isopropyl-2-bromoethyl ether, 2-dichloroethyl ether, 2-chloroethyl propyl ether, dichloroisopropyl ether, 2-chloroethyl n-butyl ether, or tert-butyl chloromethyl ether.
In some embodiments, the second external electron donor is selected from the group consisting of cyclohexylmethyldimethoxy silane, dicyclopentyl dimethoxy silane, diisobutyldimethoxy silane, diisopropyldimethoxy silane, dicyclohexyldimethoxy silane, di-tert-butyldimethoxy silane, ethylcyclohexyldimethoxy silane, diphenyldimethoxy silane, di-n-propyldimethoxy silane, di-n-butyldimethoxy silane, cyclopentyltrimethoxy silane, n-propyltrimethoxy silane, isopropyltrimethoxy silane, n-propyltriethoxy silane, isopropyltriethoxy silane, tetraethoxy silane, tetramethoxy silane, cyclopentylpyrrole dimethoxy silane, dipyrrole dimethoxy silane, or bisperhydroisoquinoline dimethoxy silane.
In the present application, when the first external electron donor or the second external electron donor is used as the external electron donor to construct the catalytic system to catalyze and synthesize polypropylene, the obtained polypropylene has lower prescribed properties than the case of combining the first external electron donor and the second external electron donor. And when the second external electron donor is independently used as the external electron donor in the propylene polymerization reaction process, the polymerization reaction is easy to generate larger static fluctuation, at least polymer agglomeration is generated, or the polymerization reaction temperature is too high, so that the reaction is not controlled. In view of this, this application adopts first external electron donor and second external electron donor combination, can directional control catalyst activity, easily to reaction temperature control to the polymer that makes obtains has higher equi-prescription nature. And moreover, by adopting the combination of the first external electron donor and the second external electron donor, the electrostatic fluctuation of the reaction can be reduced, the reaction is more stable, the reaction can be controlled at a lower temperature, the energy is saved, and the production rate and the utilization efficiency of the catalyst can be improved.
In addition, the applicant has surprisingly found that when the molar ratio of the first external electron donor to the second external electron donor is between 35:65 and 65:35, it is more advantageous to improve the regulation properties of the obtained polypropylene and the like, and to prevent the polymerization temperature fluctuation and the static fluctuation, improve the control over the reaction process, and provide the production rate and the utilization efficiency of the catalyst.
In one embodiment, a Ziegler-Natta catalyst composition for propylene polymerization is provided comprising:
a carrier selected from magnesium chloride and/or magnesium ethoxide;
a first catalyst selected from titanium tetrachloride and/or titanium trichloride;
an internal electron donor selected from the group consisting of diisobutyl phthalate, di-n-butyl 2-isopropyl malonate, diethyl 2-methyl-2-isopropyl malonate, diisobutyl diisopropyl succinate, 2, 3-diisopropyl succinic acid and mixtures thereof;
the second catalyst is aluminum alkyl;
the external electron donor composition as provided in the above embodiment;
in the Ziegler-Natta catalyst composition for propylene polymerization, the molar ratio of aluminum to titanium element is 10-1200, and the molar ratio of silicon to titanium element is 2-50.
In some embodiments, the carrier comprises magnesium chloride and magnesium ethoxide in a molar ratio of 1:99 to 99:1; the first catalyst comprises titanium tetrachloride and titanium trichloride, and the molar ratio of the titanium tetrachloride to the titanium trichloride is 1:99-99:1; the alkyl aluminum is selected from one or two of triethyl aluminum and triisobutyl aluminum.
In one embodiment, a process for polymerizing propylene is provided for catalyzing the polymerization of propylene in the presence of hydrogen using the Ziegler-Natta catalyst composition provided in the previous embodiment.
In some embodiments, the polymerization process of propylene comprises:
adding propylene monomer, the carrier, the first catalyst, the internal electron donor, the second catalyst and the external electron donor composition into a reaction system respectively or simultaneously in the presence of hydrogen; and
and extracting polypropylene from the reaction system.
In some embodiments, the second external electron donor is added at the beginning of the reaction, and the first external electron donor is present at the time of: polymer agglomeration occurs during the polymerization reaction and/or the polymerization temperature is too high during the polymerization reaction; is added in the case of (2). In some embodiments, the second external electron donor is added at the beginning of the reaction, and the first external electron donor is added to the reaction system in batch form. Thus, the static fluctuation and the temperature fluctuation of the reaction can be reduced, the polymerization reaction is stable and is convenient to control, meanwhile, the agglomeration of the polymer can be reduced, and the reaction efficiency and the catalyst utilization rate are improved.
In some embodiments, the carrier, the first catalyst, and the internal electron donor are first processed to prepare a solid component, and the solid component, the second catalyst, the first external electron donor, and the second external electron donor are individually packaged, stored, and shipped, respectively; and
the solid component, the second catalyst, the first external electron donor and the second external electron donor are used in a polymerization reaction by being individually packaged.
The present application is further described below in connection with the examples. It should be noted that the following examples should not be construed as limiting the scope of the present application, and any modifications made thereto do not depart from the spirit of the present application.
Example 1
The present embodiment provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, comprising: the first external electron donor is bromomethyl ether, the second external electron donor is cyclohexylmethyl dimethoxy silane, and the external electron donor composition comprises 35mol percent of bromomethyl ether and 65mol percent of cyclohexylmethyl dimethoxy silane.
The embodiment provides a Ziegler-Natta catalyst composition for propylene polymerization, which comprises a carrier, a first catalyst, an internal electron donor, a second catalyst and an external electron donor composition, wherein the carrier is a composition of 5mol% of magnesium chloride and 95mol% of ethoxymagnesium, the first catalyst is titanium tetrachloride and 75mol% of titanium trichloride in a mole ratio, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
A process for preparing a ziegler-natta catalyst composition for propylene polymerization:
1) Adding a first catalyst to the carrier under nitrogen protection conditions at-40 ℃;
2) Gradually heating to 50 ℃, adding an internal electron donor, then heating to 100 ℃, preserving heat for 1h, continuously heating to 150 ℃, stirring for 1h, and separating out solid particles;
3) The filtered solid particles are repeatedly and alternately washed by adopting a first catalyst and an inert diluent, and dried to obtain a solid component;
4) And 3) packaging, storing and transporting the solid component, the second catalyst, the first external electron donor and the second external electron donor obtained in the step 3) independently. During propylene polymerization, the Ziegler-Natta catalyst composition for propylene polymerization is formed by combining.
Propylene polymerization:
the 5L autoclave was heated and evacuated, air and water were removed, replaced with nitrogen, and repeated three times, and the solid fraction (20 mg MgCl) was first prepared in the above-mentioned proportions 2 Ti content of 3.38% of the load), secondThe catalyst (n (Al)/n (Ti) = 1011.2) and the second external electron donor ((n (Si)/n (Ti) =28.7) were all added while 50% by weight of the first external electron donor described in the above examples was added, then hydrogen (n (H2)/n (C3) =6.47 mmol/mol was introduced first, and propylene was introduced again to make the total pressure in the reactor 0.35MPa.
Example 2
The present embodiment provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, comprising: the first external electron donor is 2-bromoethyl methyl ether, the second external electron donor is cyclohexylmethyl dimethoxy silane, and the external electron donor composition comprises 35mol percent of 2-bromoethyl methyl ether and 65mol percent of cyclohexylmethyl dimethoxy silane.
The present example provides a Ziegler-Natta catalyst composition for propylene polymerization comprising a support, a first catalyst, an internal electron donor, a second catalyst and an external electron donor composition. Wherein the carrier is a composition of 5mol percent magnesium chloride and 95mol percent ethoxymagnesium, the first catalyst is titanium tetrachloride and titanium trichloride with the mol percent of 25mol percent and 75mol percent, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization were the same as in example 1.
Example 3
The present embodiment provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, comprising: the first external electron donor is isopropyl-2-bromoethyl ether, the second external electron donor is cyclohexylmethyl dimethoxy silane, and the external electron donor composition comprises 35mol percent of isopropyl-2-bromoethyl ether and 65mol percent of cyclohexylmethyl dimethoxy silane.
The present example provides a Ziegler-Natta catalyst composition for propylene polymerization comprising a support, a first catalyst, an internal electron donor, a second catalyst and an external electron donor composition. Wherein the carrier is a composition of 5mol percent magnesium chloride and 95mol percent ethoxymagnesium, the first catalyst is titanium tetrachloride and titanium trichloride with the mol percent of 25mol percent and 75mol percent, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization were the same as in example 1.
Example 4
The present embodiment provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, comprising: the first external electron donor is 2, 2-dichloroethyl ether, the second external electron donor is cyclohexylmethyldimethoxy silane, and the external electron donor composition comprises 35mol percent of 2, 2-dichloroethyl ether and 65mol percent of cyclohexylmethyldimethoxy silane.
The present example provides a Ziegler-Natta catalyst composition for propylene polymerization comprising a support, a first catalyst, an internal electron donor, a second catalyst and an external electron donor composition. Wherein the carrier is a composition of 5mol percent magnesium chloride and 95mol percent ethoxymagnesium, the first catalyst is titanium tetrachloride and titanium trichloride with the mol percent of 25mol percent and 75mol percent, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization were the same as in example 1.
Example 5
The present embodiment provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, comprising: the first external electron donor is 2-chloroethyl propyl ether, the second external electron donor is cyclohexylmethyl dimethoxy silane, and the external electron donor composition comprises 35mol percent of 2-chloroethyl propyl ether and 65mol percent of cyclohexylmethyl dimethoxy silane.
The present example provides a Ziegler-Natta catalyst composition for propylene polymerization comprising a support, a first catalyst, an internal electron donor, a second catalyst and an external electron donor composition. Wherein the carrier is a composition of 5mol percent magnesium chloride and 95mol percent ethoxymagnesium, the first catalyst is titanium tetrachloride and titanium trichloride with the mol percent of 25mol percent and 75mol percent, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization were the same as in example 1.
Example 6
The present embodiment provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, comprising: the first external electron donor is dichloroisopropyl ether, the second external electron donor is cyclohexylmethyl dimethoxy silane, and the external electron donor composition comprises 35mol percent of dichloroisopropyl ether and 65mol percent of cyclohexylmethyl dimethoxy silane.
The present example provides a Ziegler-Natta catalyst composition for propylene polymerization comprising a support, a first catalyst, an internal electron donor, a second catalyst and an external electron donor composition. Wherein the carrier is a composition of 5mol percent magnesium chloride and 95mol percent ethoxymagnesium, the first catalyst is titanium tetrachloride and titanium trichloride with the mol percent of 25mol percent and 75mol percent, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization were the same as in example 1.
Example 7
The present embodiment provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, comprising: the first external electron donor is 2-chloroethyl n-butyl ether, the second external electron donor is cyclohexylmethyl dimethoxy silane, and the external electron donor composition comprises 35mol percent of 2-chloroethyl n-butyl ether and 65mol percent of cyclohexylmethyl dimethoxy silane.
The present example provides a Ziegler-Natta catalyst composition for propylene polymerization comprising a support, a first catalyst, an internal electron donor, a second catalyst and an external electron donor composition. Wherein the carrier is a composition of 5mol percent magnesium chloride and 95mol percent ethoxymagnesium, the first catalyst is titanium tetrachloride and titanium trichloride with the mol percent of 25mol percent and 75mol percent, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization were the same as in example 1.
Example 8
The present embodiment provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, comprising: the first external electron donor is tert-butyl chloromethyl ether, the second external electron donor is cyclohexylmethyl dimethoxy silane, and the external electron donor composition comprises 35mol percent of tert-butyl chloromethyl ether and 65mol percent of cyclohexylmethyl dimethoxy silane.
The present example provides a Ziegler-Natta catalyst composition for propylene polymerization comprising a support, a first catalyst, an internal electron donor, a second catalyst and an external electron donor composition. Wherein the carrier is a composition of 5mol percent magnesium chloride and 95mol percent ethoxymagnesium, the first catalyst is titanium tetrachloride and titanium trichloride with the mol percent of 25mol percent and 75mol percent, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization were the same as in example 1.
Example 9
The present embodiment provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, comprising: the first external electron donor is dichloroisopropyl ether, the second external electron donor is cyclohexylmethyl dimethoxy silane, and the external electron donor composition comprises 55mol percent of dichloroisopropyl ether and 45mol percent of cyclohexylmethyl dimethoxy silane.
The present example provides a Ziegler-Natta catalyst composition for propylene polymerization comprising a support, a first catalyst, an internal electron donor, a second catalyst and an external electron donor composition. Wherein the carrier is a composition of 5mol percent magnesium chloride and 95mol percent ethoxymagnesium, the first catalyst is titanium tetrachloride and titanium trichloride with the mol percent of 25mol percent and 75mol percent, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization were the same as in example 1.
Example 10
The present embodiment provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, comprising: the first external electron donor is dichloroisopropyl ether, the second external electron donor is cyclohexylmethyl dimethoxy silane, and the external electron donor composition comprises 65mol percent of dichloroisopropyl ether and 35mol percent of cyclohexylmethyl dimethoxy silane.
The present example provides a Ziegler-Natta catalyst composition for propylene polymerization comprising a support, a first catalyst, an internal electron donor, a second catalyst and an external electron donor composition. Wherein the carrier is a composition of 5mol percent magnesium chloride and 95mol percent ethoxymagnesium, the first catalyst is titanium tetrachloride and titanium trichloride with the mol percent of 25mol percent and 75mol percent, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization were the same as in example 1.
Example 11
The present embodiment provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, comprising: the first external electron donor is dichloroisopropyl ether, the second external electron donor is cyclohexylmethyl dimethoxy silane, and the external electron donor composition comprises 65mol percent of dichloroisopropyl ether and 35mol percent of cyclohexylmethyl dimethoxy silane.
The present example provides a Ziegler-Natta catalyst composition for propylene polymerization comprising a support, a first catalyst, an internal electron donor, a second catalyst and an external electron donor composition. Wherein the carrier is a composition of 5mol percent magnesium chloride and 95mol percent ethoxymagnesium, the first catalyst is titanium tetrachloride and titanium trichloride with the mol percent of 25mol percent and 75mol percent, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization were the same as in example 1. Wherein the addition amount of the second external electron donor is n (Si)/n (Ti) =10.
Example 12
The present embodiment provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, comprising: the first external electron donor is dichloroisopropyl ether, the second external electron donor is cyclohexylmethyl dimethoxy silane, and the external electron donor composition comprises 65mol percent of dichloroisopropyl ether and 35mol percent of cyclohexylmethyl dimethoxy silane.
The present example provides a Ziegler-Natta catalyst composition for propylene polymerization comprising a support, a first catalyst, an internal electron donor, a second catalyst and an external electron donor composition. Wherein the carrier is a composition of 5mol percent magnesium chloride and 95mol percent ethoxymagnesium, the first catalyst is titanium tetrachloride and titanium trichloride with the mol percent of 25mol percent and 75mol percent, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization were the same as in example 1. Wherein the addition amount of the second external electron donor is n (Si)/n (Ti) =50.
Example 13
The present embodiment provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, comprising: the first external electron donor is dichloroisopropyl ether and 2, 2-dichloroethyl ether, the second external electron donor is cyclohexylmethyl dimethoxy silane, and the external electron donor composition comprises 45mol percent of dichloroisopropyl ether, 20mol percent of 2, 2-dichloroethyl ether and 35mol percent of cyclohexylmethyl dimethoxy silane.
The present example provides a Ziegler-Natta catalyst composition for propylene polymerization comprising a support, a first catalyst, an internal electron donor, a second catalyst and an external electron donor composition. Wherein the carrier is a composition of 5mol percent magnesium chloride and 95mol percent ethoxymagnesium, the first catalyst is titanium tetrachloride and titanium trichloride with the mol percent of 25mol percent and 75mol percent, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization were the same as in example 1.
Comparative example 1
This comparative example provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, said external electron donor composition comprising only bromomethyl methyl ether.
This comparative example provides a ziegler-natta catalyst composition for propylene polymerization comprising a support, a first catalyst, an internal electron donor, a second catalyst, and an external electron donor composition. Wherein the carrier is a composition of 5mol percent magnesium chloride and 95mol percent ethoxymagnesium, the first catalyst is titanium tetrachloride and titanium trichloride with the mol percent of 25mol percent and 75mol percent, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
A process for preparing a ziegler-natta catalyst composition for propylene polymerization:
1) Adding a first catalyst to the carrier under nitrogen protection conditions at-40 ℃;
2) Gradually heating to 50 ℃, adding an internal electron donor, then heating to 100 ℃, preserving heat for 1h, continuously heating to 150 ℃, stirring for 1h, and separating out solid particles;
3) The filtered solid particles are repeatedly and alternately washed by adopting a first catalyst and an inert diluent, and dried to obtain a solid component;
4) And (3) packaging the solid component obtained in the step (3), the second catalyst and the external electron donor respectively and independently, storing and transporting. During propylene polymerization, the Ziegler-Natta catalyst composition for propylene polymerization is formed by combining.
Propylene polymerization:
the 5L autoclave was heated and evacuated, air and water were removed, replaced with nitrogen, and repeated three times, and the solid fraction (20 mg MgCl) was first prepared in the above-mentioned proportions 2 Ti with 3.38% of load), a second catalyst (n (Al)/n (Ti) = 1011.2), an external electron donor ((n (-O-)/n (Ti) =28.7, i.e. the mole ratio of ether bond to titanium is 28.7) are all added, then hydrogen (n (H2)/n (C3) =6.47 mmol/mol) is firstly introduced, then propylene is introduced to make the total pressure in the reactor reach 0.35MPa, the reactor is closed, the reactor temperature is raised to 70 ℃ for 2 hours, unreacted propylene is discharged, polypropylene particles are obtained, and the performance of the catalyst and the particle size distribution result of the obtained polypropylene are shown in table 1 and table 2.
Comparative example 2
This comparative example provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, said external electron donor composition comprising only 2-bromoethyl methyl ether.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization comparative example 1.
Comparative example 3
This comparative example provides an external electron donor composition for a Ziegler-Natta catalyst for propylene polymerization, comprising only isopropyl-2-bromoethyl ether.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization comparative example 1.
Comparative example 4
This comparative example provides an external electron donor composition for a Ziegler-Natta catalyst for propylene polymerization comprising only 2, 2-dichloroethyl ether.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization comparative example 1.
Comparative example 5
This comparative example provides an external electron donor composition for a Ziegler-Natta catalyst for propylene polymerization comprising only 2-chloroethyl propyl ether.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization comparative example 1.
Comparative example 6
This comparative example provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, said external electron donor composition comprising only dichloroisopropyl ether.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization comparative example 1.
Comparative example 7
This comparative example provides an external electron donor composition for a Ziegler-Natta catalyst for propylene polymerization comprising only 2-chloroethyl n-butyl ether.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization comparative example 1.
Comparative example 8
This comparative example provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization comprising only t-butyl chloromethyl ether.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization comparative example 1.
Comparative example 9
This comparative example provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization comprising only cyclohexylmethyldimethoxysilane.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization comparative example 1.
Table 1 shows the properties of the Ziegler-Natta catalyst compositions for propylene polymerization provided in examples 1 to 12 and comparative examples 1 to 9, respectively, wherein:
the polymerization activity in KgPP/(gCat.h) was calculated as follows:
polymerization Activity = yield of polymer (Kg/h)/catalyst (Cat. G)
The melt index (MFR) of the polypropylene was determined according to test Standard ASTM D1238, test conditions being 2.16Kg,230℃and melt index in g/10min.
Degree of isotacticity: according to GB/T2546.1-2006 using n-heptane extraction method determination, using a Soxhlet extractor, about 2g polypropylene sample in the Soxhlet extractor, boiling heptane extraction for 6 hours, residual polypropylene drying to constant weight, residual polypropylene and first polypropylene ratio is equal to the degree of isotacticity.
The electrostatic fluctuation is detected by adopting an electrostatic probe connected to the reaction kettle and an electrostatic detector connected with the electrostatic probe, and the method is concretely referred to the "Unipol polypropylene process reactor electrostatic fluctuation analysis and treatment [ J ] plastics industry, volume 50, 3 rd phase".
The temperature fluctuation detection is carried out by adopting a temperature probe connected to the reaction kettle and a temperature detector connected with the temperature probe.
As can be seen from Table 1, the activity of the catalyst in the examples of the present application was higher than that of the comparative example, the static fluctuation value DeltaV in the reaction vessel was less than 20V, the temperature fluctuation value DeltaT was less than 5℃and, as a result, the reaction vessel was free of PP sticking material.
Table 1 shows that each of comparative examples 1 to 9 uses either the first external donor or the second external donor alone as the external donor in the Ziegler-Natta catalyst composition for propylene polymerization, so that the isotacticity and melt index of the produced polypropylene are relatively low, as compared with example 6; particularly, the static fluctuation value and the temperature fluctuation value in the reaction kettle are increased, and meanwhile, polymer agglomeration exists in the reaction kettle, so that the extraction of reactants is inconvenient.
As can be seen from table 1, the catalyst composition according to example 13 was used to prepare polypropylene having high isotacticity and melt index, and had high polymerization activity, and the effect of suppressing static electricity was most remarkable, and the reaction temperature was stable and the reaction process was stable.
TABLE 1 physical Properties of Ziegler-Natta catalyst compositions for propylene polymerization
Further, the relative molecular mass of the Polymer and its distribution index were measured by using a gel permeation chromatograph PL-GPC220 of Polymer lab, UK, 1,2, 4-trichlorobenzene as a solvent, a flow rate of 1.0mL/min, a mass concentration of 1mg/mL, and polystyrene as a standard. The fractions of the polymer particles were sieved with a standard sieve, then weighed separately and the mass fractions of the fractions were calculated to obtain the particle size distribution. Bulk density was measured by reference to ASTM D1895-1969.
As shown in Table 2, the polymer bulk densities provided in examples 1 to 13 of the present application were all higher than those in comparative examples 1 to 9, and the weight average molecular weights were also higher than those in comparative examples 1 to 9, indicating that propylene polymerization using the Ziegler-Natta catalyst compositions provided in examples 1 to 13, respectively, could give polypropylene of a higher weight average molecular weight. And the molecular weight distribution index was lower than that of comparative examples 1 to 9, indicating that the polypropylene particles prepared in examples 1 to 13 were more concentrated in molecular weight and more concentrated in particle size, since the polymer particles exceeding 75 μm were also more than those of comparative examples 1 to 9.
In addition, as can be seen from tables 1 and 2, the catalyst composition provided in example 13 was used to obtain polypropylene having high isotacticity and melt index, high polymerization activity, most remarkable static suppression effect, and stable reaction temperature, compared with other examples, so that the polymer particles prepared were larger in molecular weight, more concentrated in molecular weight distribution, more regular in polymer particles, and higher in product quality.
TABLE 2 Polymer Properties
Comprehensive analysis shows that the embodiment 1-13 adopts the combination of the first external electron donor and the second external electron donor as the external electron donor in the Ziegler-Natta catalyst composition for olefin polymerization, has high polymerization activity, stable polymerization process, difficult electrostatic fluctuation generation, difficult agglomeration and difficult wall hanging of a polymerization product, ensures long-term stable operation of polymerization production, and has the advantages of less polymer fine powder, moderate stacking density and reasonable particle size distribution. The catalyst system has wide application range and is suitable for propylene polymerization in various processes.
The foregoing is merely a preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the technical scope of the present application should be covered by the scope of the present application.
Claims (10)
1. An external electron donor composition of a Ziegler-Natta catalyst for propylene polymerization, which is characterized by comprising a first external electron donor and a second external electron donor, wherein the molar ratio of the first external electron donor to the second external electron donor is 1:99-99:1; wherein,,
the first external electron donor is a halogenated ether compound with a-C-O-C-ether functional group, and the second external electron donor is a C1-C10 alkoxy silane compound;
the first external electron donor is selected from compounds shown in a formula I;
in formula I, at least one R is independently selected from the group consisting of halomethyl, haloethyl, halopropyl, haloisopropyl, halobutyl, haloisobutyl, halosec-butyl, and halotert-butyl.
2. The external electron donor composition according to claim 1, wherein the first external electron donor is selected from at least one of bromomethyl ether, 2-bromoethyl methyl ether, isopropyl-2-bromoethyl ether, 2-dichloroethyl ether, 2-chloroethyl propyl ether, dichloroisopropyl ether, 2-chloroethyl n-butyl ether, or t-butylchloromethyl ether.
3. The external electron donor composition according to claim 1, wherein the second external electron donor is selected from at least one of cyclohexylmethyldimethoxy silane, dicyclopentyl dimethoxy silane, diisobutyldimethoxy silane, diisopropyldimethoxy silane, dicyclohexyldimethoxy silane, di-tert-butyldimethoxy silane, ethylcyclohexyldimethoxy silane, diphenyldimethoxy silane, di-n-propyldimethoxy silane, di-n-butyldimethoxy silane, cyclopentyltrimethoxy silane, n-propyltrimethoxy silane, isopropyltrimethoxy silane, n-propyltriethoxy silane, isopropyltriethoxy silane, tetraethoxy silane, tetramethoxy silane, cyclopentylpyrrole dimethoxy silane, dipyrrole dimethoxy silane, or bisperhydroisoquinoline dimethoxy silane.
4. The external electron donor composition of claim 1, wherein the molar ratio of the first external electron donor to the second external electron donor is from 35:65 to 65:35.
5. A ziegler-natta catalyst composition for propylene polymerization comprising:
a carrier selected from magnesium chloride and/or magnesium ethoxide;
a first catalyst selected from titanium tetrachloride and/or titanium trichloride;
an internal electron donor selected from the group consisting of diisobutyl phthalate, di-n-butyl 2-isopropyl malonate, diethyl 2-methyl-2-isopropyl malonate, diisobutyl diisopropyl succinate, 2, 3-diisopropyl succinic acid and mixtures thereof;
the second catalyst is aluminum alkyl;
the external electron donor composition according to any one of claims 1 to 4;
in the Ziegler-Natta catalyst composition for propylene polymerization, the molar ratio of aluminum to titanium element is 10-1200, and the molar ratio of silicon to titanium element is 2-50.
6. The Ziegler-Natta catalyst composition according to claim 5, wherein,
the carrier comprises magnesium chloride and ethoxymagnesium, and the molar ratio of the magnesium chloride to the ethoxymagnesium is 1:99-99:1;
the first catalyst comprises titanium tetrachloride and titanium trichloride, and the molar ratio of the titanium tetrachloride to the titanium trichloride is 1:99-99:1;
the alkyl aluminum is selected from one or two of triethyl aluminum and triisobutyl aluminum.
7. A process for the polymerization of propylene, characterized in that propylene is catalyzed by a ziegler-natta catalyst composition according to claim 5 or 6 in the presence of hydrogen.
8. The polymerization process of claim 7, comprising:
adding propylene monomer, the carrier, the first catalyst, the internal electron donor, the second catalyst and the external electron donor composition into a reaction system respectively or simultaneously in the presence of hydrogen; and
and extracting polypropylene from the reaction system.
9. The polymerization process according to claim 7, wherein the second external electron donor is added at the beginning of the reaction, and the first external electron donor is added in the presence of "polymer agglomeration during the polymerization and/or too high a polymerization temperature during the polymerization"; or alternatively
The second external electron donor is added at the beginning of the reaction, and the first external electron donor is added to the reaction system in a batch form.
10. The polymerization process of claim 7, wherein the support, the first catalyst, the internal electron donor are first processed to prepare a solid component, and the solid component, the second catalyst, the first external electron donor, and the second external electron donor are individually packaged, stored, and shipped, respectively; and
the solid component, the second catalyst, the first external electron donor and the second external electron donor are used in a polymerization reaction by being individually packaged.
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