CN101195666B - Supported catalyst for olefin polymerization and preparation method thereof - Google Patents
Supported catalyst for olefin polymerization and preparation method thereof Download PDFInfo
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- CN101195666B CN101195666B CN2006101648178A CN200610164817A CN101195666B CN 101195666 B CN101195666 B CN 101195666B CN 2006101648178 A CN2006101648178 A CN 2006101648178A CN 200610164817 A CN200610164817 A CN 200610164817A CN 101195666 B CN101195666 B CN 101195666B
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- Prior art keywords
- dicyclo
- methyl
- succinic acid
- succinate
- magnesium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title description 38
- 150000001336 alkenes Chemical class 0.000 title description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 239000001384 succinic acid Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 32
- 239000011777 magnesium Substances 0.000 claims description 30
- 229910052749 magnesium Inorganic materials 0.000 claims description 28
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 24
- LOLKAJARZKDJTD-UHFFFAOYSA-N 4-Ethoxy-4-oxobutanoic acid Chemical compound CCOC(=O)CCC(O)=O LOLKAJARZKDJTD-UHFFFAOYSA-N 0.000 claims description 22
- 239000010936 titanium Substances 0.000 claims description 16
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 150000004820 halides Chemical class 0.000 claims description 12
- WXUAQHNMJWJLTG-UHFFFAOYSA-N 2-methylbutanedioic acid Chemical compound OC(=O)C(C)CC(O)=O WXUAQHNMJWJLTG-UHFFFAOYSA-N 0.000 claims description 11
- 150000003608 titanium Chemical class 0.000 claims description 11
- -1 ester compounds Chemical class 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- FOSCDBCOYQJHPN-UHFFFAOYSA-M Cl[Mg] Chemical compound Cl[Mg] FOSCDBCOYQJHPN-UHFFFAOYSA-M 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019587 texture Nutrition 0.000 claims description 4
- WSNKEJIFARPOSQ-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-(1-benzothiophen-2-ylmethyl)benzamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)NCC2=CC3=C(S2)C=CC=C3)C=CC=1 WSNKEJIFARPOSQ-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 2
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 31
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 229920000098 polyolefin Polymers 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 125000005574 norbornylene group Chemical group 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 7
- 150000003900 succinic acid esters Chemical class 0.000 description 7
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 235000010210 aluminium Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- RALMAKOEVLJXQO-UHFFFAOYSA-N [Si].COC=1C(=C(C=CC1)C1=CC=CC=C1)OC Chemical compound [Si].COC=1C(=C(C=CC1)C1=CC=CC=C1)OC RALMAKOEVLJXQO-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 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 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- UIOXNNAWANDJCZ-UHFFFAOYSA-N 1,1-dimethoxypropane Chemical compound CCC(OC)OC UIOXNNAWANDJCZ-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 230000029305 taxis Effects 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- JDRMYOQETPMYQX-UHFFFAOYSA-N monomethyl succinate Chemical class COC(=O)CCC(O)=O JDRMYOQETPMYQX-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- XZKPFRIEWDWYDH-UHFFFAOYSA-N 1-(methoxymethyl)-9h-fluorene Chemical class C1C2=CC=CC=C2C2=C1C(COC)=CC=C2 XZKPFRIEWDWYDH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a supported catalyst for olefin polymers, which adopts a 1, 4-diester compound with a molecular framework containing two cyclic structures as an internal electron donor compound and has larger space volume, so that the obtained supported catalyst has high catalytic activity when catalyzing propylene polymerization, and can achieve higher stereoregularity by matching with a cocatalyst and an external electron donor.
Description
Technical field
The present invention relates to a kind of olefin polymer with loaded catalyst and preparation method thereof, be specifically related to propylene polymerization loading type ziegler-natta Catalysts and its preparation method.
Background technology
Vestolen PP 7052 is with fastest developing speed a kind of in the various polyolefine materials, and output worldwide is only second to Vilaterm.Natta invention TICl in 1954
3/ AIR
3Vestolen PP 7052 ziegler-natta (Z-N) catalyzer, but the catalyzer orientation property was low at that time, and activity is very low.To the middle and later periods sixties 20th century, through mechanical mill or chemical process some lewis alkali (being called internal electron donor) is sneaked in the titanous chloride crystal, catalyst surface area is increased considerably, the Vestolen PP 7052 degree of isotacticity that obtains also reaches 90～96%.People progressively find; The electron donor of introducing in the catalyzer has play a part crucial to the improvement of catalyst performance; Electron donor not only can improve activity of such catalysts and orientation property, the more important thing is the molecular structure that can change polymkeric substance, improves polyacrylic quality.So far, to the main energy of research of Vestolen PP 7052 Z-N catalyzer begun to forward to seek over-all properties better or have specific characteristics can electron donor.The renewal of electron donor compound is the principal element that promotes that catalyst updating is regenerated.
The catalystsystem that contains succinate class electron donor or two ethers internal electron donors is the novel Z-N catalystsystem that grew up in recent years.Wherein, the catalyzer that contains two ethers electron donors because of its need not to add possess high reactivity under the situation of external electron donor, and the Vestolen PP 7052 degree of isotacticity advantages of higher that make good to chain-transfer agent susceptibility, have wide prospect in industrial application.CN 1539857 describes contains 1 of quaternary ring texture, and the 3-diether has very high catalytic activity as the electron donor compound.But the Vestolen PP 7052 relative molecular mass narrow distribution that contains the catalystsystem preparation of two ethers electron donors.
The catalystsystem of succinate-containing class electron donor can be widened polyacrylic relative molecular mass and distribute, and succinate class electron donor structure is following:
Succinate class electron donor structural formula
At present, Basell company is with the industriallization of succinate class internal electron donor catalystsystem, and number of patents report (WO 00/63261, and WO 2004024785, and US 0050014631, CN 1313869A, CN 1398270, CN1681853 etc.) is also arranged both at home and abroad.WO 00/63261 has described with succinate with CN 1313869A or has replaced the catalyzer of succinate compounds as the preparation of internal electron donor component; Be used for alkene especially during propylene polymerization; Can access the polymkeric substance of high yield, and polymkeric substance has the very high isotactic index with the insoluble expression of YLENE.
US 0050014631 has described the succinate class catalyzer of loading type, compares with unsupported catalyst, has higher activity; Polymerisate has higher taxis.In a word, the prosposition on the succinate class electron donor compound molecule skeleton reported of existing patent is chiral carbon atom or the carbon atom that has different substituents.
Summary of the invention
The purpose of this invention is to provide a kind of loaded catalyst that comprises the ad hoc structure internal electron donor, this catalyzer is used for propylene polymerization and has high reactivity, and polymerisate has high taxis.Another object of the present invention provides this Preparation of catalysts method.
Loaded catalyst provided by the invention mainly is made up of magnesium halide alcohol adduct carrier, halogenated titanium and internal electron donor, it is characterized in that internal electron donor is to contain 1 of two ring texturees in the molecular skeleton, 4-two ester compounds, and its structural formula is:
Substituent R in the formula
1, R
2, R
3Can be identical or different, be selected from halogen atom, C
1～C
20The straight or branched alkyl; Substituent R
4, R
5Can be identical or different, be selected from C
1～C
20The straight or branched alkyl; The weight percent of each element and compound consists of in the catalyst component:
Internal electron donor compound 1-10%
Titanium 1-15%
Magnesium 10-25%
Halogen 40-60%
Above-mentioned internal electron donor compound adopts Actinochemical synthesis; Through norbornylene compounds and maleic anhydride effect; Obtain through the acid catalysis alcoholysis again, be specially: in dichloromethane solvent, add maleic anhydride and norbornylene or replace norbornylene; The mol ratio of maleic anhydride and norbornylene or replacement norbornylene is 1: (2～8), preferred 1: (2～4); Add UVNUL MS-40 again, the mol ratio of maleic anhydride and UVNUL MS-40 is 100: (1～10), preferred 100: (5～8), under agitation condition with UV-irradiation 6～48 hours, preferred 12～24 hours; Except that after desolvating, adding is pure accordingly with institute's synthesizing ester, and the mol ratio of alcohol and maleic anhydride is 100: (1～50), preferred 100: (10～30); Add sulfuric acid or p-methyl benzenesulfonic acid again, the acid that is added and the mol ratio of maleic anhydride are 1: (20～100), and preferred 1: (40～70), in 100 ℃ of reflux 2～48 hours, preferred 4～24 hours; Except that after washing, drying, distillation, obtaining again after desolvating.
Concrete internal electron donor can be selected from following arbitrary compound:
Dicyclo [2,2,1]-2,3-also-α, β-Succinic Acid methyl esters
Dicyclo [2,2,1]-2,3-also-α, β-ethyl succinate
Dicyclo [2,2,1]-2,3-also-α, β-Succinic Acid propyl ester
Dicyclo [2,2,1]-2,3-also-α, β-Succinic Acid isopropyl ester
Dicyclo [2,2,1]-2,3-also-α, β-Succinic Acid butyl ester
Dicyclo [2,2,1]-2,3-also-α, β-methyl-succinate
Dicyclo [2,2,1]-2,3-also-α, β-diethyl succinate
Dicyclo [2,2,1]-2,3-also-α, β-dipropyl succinate
Dicyclo [2,2,1]-2,3-also-α, β-diisopropyl ester amber acid
Dicyclo [2,2,1]-2,3-also-α, β-Tabutrex
Dicyclo [2,2,1]-5,6-dimethyl--2,3-also-α, β-Succinic Acid methyl esters
Dicyclo [2,2,1]-5,6-dimethyl--2,3-also-α, β-ethyl succinate
Dicyclo [2,2,1]-5,6-dimethyl--2,3-also-α, β-Succinic Acid propyl ester
Dicyclo [2,2,1]-5,6-dimethyl--2,3-also-α, β-Succinic Acid isopropyl ester
Dicyclo [2,2,1]-5,6-dimethyl--2,3-also-α, β-Succinic Acid butyl ester
Dicyclo [2,2,1]-5,6-dimethyl--2,3-also-α, β-methyl-succinate
Dicyclo [2,2,1]-5,6-dimethyl--2,3-also-α, β-diethyl succinate
Dicyclo [2,2,1]-5,6-dimethyl--2,3-also-α, β-dipropyl succinate
Dicyclo [2,2,1]-5,6-dimethyl--2,3-also-α, β-diisopropyl ester amber acid
Dicyclo [2,2,1]-5,6-dimethyl--2,3-also-α, β-Tabutrex
Dicyclo [2,2,1]-7-methyl-2,3-also-α, β-Succinic Acid methyl esters
Dicyclo [2,2,1]-7-methyl-2,3-also-α, β-ethyl succinate
Dicyclo [2,2,1]-7-methyl-2,3-also-α, β-Succinic Acid propyl ester
Dicyclo [2,2,1]-7-methyl-2,3-also-α, β-Succinic Acid isopropyl ester
Dicyclo [2,2,1]-7-methyl-2,3-also-α, β-Succinic Acid butyl ester
Dicyclo [2,2,1]-7-methyl-2,3-also-α, β-methyl-succinate
Dicyclo [2,2,1]-7-methyl-2,3-also-α, β-diethyl succinate
Dicyclo [2,2,1]-7-methyl-2,3-also-α, β-dipropyl succinate
Dicyclo [2,2,1]-7-methyl-2,3-also-α, β-diisopropyl ester amber acid
Dicyclo [2,2,1]-7-methyl-2,3-also-α, β-Tabutrex
Dicyclo [2,2,1]-7-chloro-2,3-also-α, β-Succinic Acid methyl esters
Dicyclo [2,2,1]-7-chloro-2,3-also-α, β-ethyl succinate
Dicyclo [2,2,1]-7-chloro-2,3-also-α, β-Succinic Acid propyl ester
Dicyclo [2,2,1]-7-chloro-2,3-also-α, β-Succinic Acid isopropyl ester
Dicyclo [2,2,1]-7-chloro-2,3-also-α, β-Succinic Acid butyl ester
Dicyclo [2,2,1]-7-chloro-2,3-also-α, β-methyl-succinate
Dicyclo [2,2,1]-7-chloro-2,3-also-α, β-diethyl succinate
Dicyclo [2,2,1]-7-chloro-2,3-also-α, β-dipropyl succinate
Dicyclo [2,2,1]-7-chloro-2,3-also-α, β-diisopropyl ester amber acid
Dicyclo [2,2,1]-7-chloro-2,3-also-α, β-Tabutrex
Described magnesium halide alcohol adduct size-grade distribution 50～250 μ m, its general formula are Mg (OR ') mX
(2-m)N (R
2OH), R ' is C in the formula
1～C
20Alkyl, aralkyl or aryl; X is a halogen; M is the integer of 0≤m＜2; N is the decimal or the integer of 0＜n＜5; R
2Be C
1～C
20Alkyl, aralkyl or aryl.Magnesium halide in the magnesium halide alcohol adduct is selected from wherein a kind of of magnesium chloride, magnesium bromide, chloro magnesium methylate or chloro magnesium ethylate, preferred magnesium chloride.Used alcohol is selected from wherein a kind of of methyl alcohol, ethanol, propyl alcohol or butanols, preferred alcohol.
After magnesium halide alcohol adduct adopts magnesium halide and alcohol to be total to heating for dissolving, high pressure ejection or high-speed stirring, the method that in heat-eliminating medium, is solidified into microsphere particle obtains, and concrete steps are referring to the associated description among the CN1110281A.
Catalyst component halogenated titanium general formula is Ti (OR)
nX
(4-n), R is C in the formula
1～C
20Alkyl, aryl or aralkyl; X is a halogen; N is the integer of 0≤n＜4.Specifically be selected from wherein a kind of of purity titanium tetraethoxide, four titanium butoxide, chloro tri-alkoxy titanium, dichloro dialkoxy titanium, trichlorine titan-alkoxide, titanium tetrachloride or titanium tetrabromide, preferred titanium tetrachloride.
The loaded catalyst detailed process that the present invention proposes comprises: (1) joins-50～20 ℃ with ball-type magnesium halide alcohol adduct particle; In the halogenated titanium liquid preferably-30～0 ℃; Reacted 10 minutes to 5 hours; Be preferably 1～4 hour, the mol ratio of magnesium and titanium is 1: 5～1: 100, is preferably 1: 10～1: 50; (2) be warming up to 0～80 ℃, be preferably 30～60 ℃, add the internal electron donor compound, the mol ratio of magnesium and internal electron donor compound is 2: 1～20: 1, is preferably 2: 1～12: 1; (3) be warming up to 100～150 ℃ again, be preferably 110～130 ℃, reacted 1～6 hour, be preferably 1～4 hour; (4) add halogenated titanium liquid with step (1) same amount after filtering again, in 110～130 ℃ of reactions 1～4 hour, be preferably 1～2 hour, through filtering, washing obtains after the drying again.
Above-mentioned loaded catalyst also need add a certain amount of promotor when the catalyzing propone polymerization.For obtaining better polymerization effect, the present invention recommends to add alkylaluminium cpd (helping catalyst component 1) and alkoxy silane compound (cocatalyst component 2) promotor.Wherein said alkylaluminium cpd general formula is AlR
nX
(3-n), R is C in the formula
1～C
20Alkyl, aryl or aralkyl; X is a halogen; N is the integer of 0≤n≤3.Specifically be selected from wherein a kind of of trimethylaluminium, triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride or a chloro-di-isobutyl aluminum, preferred triethyl aluminum or triisobutyl aluminium.Described alkoxy silane compound is selected from wherein a kind of of dimethoxy dimethyl-silicon, diethoxy dimethyl-silicon or dimethoxy phenylbenzene silicon, preferred dimethoxy phenylbenzene silicon.
The mol ratio of the aluminium in titanium during polymerization in the loaded catalyst and the cocatalyst component 1 is 1: 1～1: 2000, is preferably 1: 1～1: 500; The mol ratio of the silicon in titanium in the loaded catalyst and the cocatalyst component 2 is 1: 1～1: 50, is preferably 1: 1～1: 20.Polymerization temperature is 0～80 ℃, preferred 20～70 ℃.
Catalyst propylene polymerization provided by the invention can adopt the whole bag of tricks of the prior art, does not have special qualification.Only be example with the slurry polymerization here, the use that the brief description catalyzer is basic:, add the heptane of handling through anhydrous and oxygen-free through vacuum drying treatment and in nitrogen and the abundant metathetical reactor drum of propylene gas; Pressure is 1 normal atmosphere in the maintenance bottle; Add cocatalyst component 1 or add cocatalyst component 2 simultaneously by promptly deciding proportioning, stir after 5 minutes, add loaded catalyst; Polyreaction 1 hour; With acidifying ethanol termination reaction, suction filtration is also used washing with alcohol, and vacuum-drying gets polymkeric substance.
The present invention compared with prior art, adopting in the skeleton has 1 of two ring texturees, the 4-diester has bigger spatial volume as the internal electron donor compound, during with the loaded catalyst catalyzing propone polymerization of its preparation, has high catalytic activity.Cooperate the use of promotor and external electron donor, the product Vestolen PP 7052 can reach higher taxis.
Embodiment
Embodiment 1 dicyclo [2,2,1]-2,3-and α, β ethyl succinate synthetic
In the 150mL methylene dichloride, add the 1.17g maleic anhydride, the 5.00g norbornylene, the 0.58g UVNUL MS-40, under agitation condition with UV-irradiation 12 hours.Except that after desolvating, add 30mL ethanol, 3mL H
2SO
4, in 100 ℃ of reflux 4 hours.Except that after desolvating, with 3 * 50mL extracted with diethyl ether, saturated solution of sodium bicarbonate washing, anhydrous magnesium sulfate drying.After removing ether,, get 1.51g colourless liquid dicyclo [2,2,1]-2,3-and α, β ethyl succinate in 104 ℃ of (10mmHg) underpressure distillation.
Warp
1H NMR (CDCl
3, 300MHz) analytical results: δ 1.07 (m, 3H, CH
2); δ 1.30 (t, 3H, CH
3); δ 1.50 (m, 5H, CH
2, CH); δ 2.18 (d, 2H, CH); δ 3.38 (m, 2H, CH); δ 4.24 (q, 2H, CH
2).
Embodiment 2 dicyclos [2,2,1]-2,3-and α, β Succinic Acid methyl esters synthetic
Except that in synthetic, replacing the ethanol with methyl alcohol, all the other steps are with embodiment 1.Get 1.38g colourless liquid dicyclo [2,2,1]-2,3-and α, β Succinic Acid methyl esters in 102 ℃ (10mmHg).
Warp
1H NMR (CDCl
3, 300MHz) analytical results: δ 1.30-1.60 (m, 8H, 2CH, 6CH
2); δ 1.73 (q, 1H, CH); δ 2.04 (q, 1H, CH); δ 3.10 (t, 1H, CH); δ 3.67 (s, 3H, CH
3).
Embodiment 3 dicyclos [2,2,1]-2,3-and α, β diethyl succinate synthetic
In the 150mL methylene dichloride, add the 1.17g maleic anhydride, the 5.00g norbornylene, the 0.58g UVNUL MS-40, under agitation condition with UV-irradiation 12 hours.Remove desolvate after, add 30mL ethanol, 0.1 gram p-methyl benzenesulfonic acid was in 100 ℃ of reflux 48 hours.Except that after desolvating, with 3 * 50mL extracted with diethyl ether, saturated solution of sodium bicarbonate washing, anhydrous magnesium sulfate drying.Filter, remove ether, get the colourless thick dicyclo of 1.67g [2,2,1]-2,3-and α, β diethyl succinate.
Warp
1H NMR (CDCl
3, 300MHz) analytical results: δ 1.30-1.55 (m, 12H, 6CH
2, 6CH
3); δ 2.04 (m, 2H, CH); δ 3.14 (m, 2H, CH); δ 4.12 (m, 4H, CH
2).
Embodiment 4 dicyclos [2,2,1]-2,3-and α, β methyl-succinate synthetic
Except that in synthetic, replacing the ethanol with methyl alcohol, all the other steps are with embodiment 3.Get the 1.43 colourless thick dicyclos of gram [2,2,1]-2,3-and α, β methyl-succinate.Warp
1H NMR (CDCl
3, 300MHz) analytical results: δ 1.30-1.55 (m, 8H, 2CH, 6CH
2); δ 2.04 (m, 2H, CH); δ 3.14 (m, 2H, CH); δ 3.67 (s, 6H, CH
3).
Embodiment 5 dicyclos [2,2,1]-5,6-dimethyl--2,3-also-α, β-ethyl succinate synthetic
Remove norbornylene with 5, outside the 6-dimethyl-norbornylene 6.6g, all the other are with embodiment 1.Obtain 1.69g dicyclo [2,2,1]-5,6-dimethyl--2,3-also-α, β-ethyl succinate.
Embodiment 6 dicyclos [2,2,1]-7-methyl-2,3-also-α, β-ethyl succinate synthetic
Except that norbornylene with the 7-methyl norbornylene 5.9g, all the other are with embodiment 1.Obtain 1.62g dicyclo [2,2,1]-7-methyl-2,3-also-α, β-ethyl succinate
Embodiment 7 dicyclos [2,2,1]-7-chloro-2,3-also-α, β-ethyl succinate synthetic
Except that norbornylene with the 7-chlorine norbornylene 6.9g, all the other are with embodiment 1.Obtain 1.7g dicyclo [2,2,1]-7-chloro-2,3-also-α, β-ethyl succinate
Embodiment 8
The preparation of loaded catalyst: under the anhydrous and oxygen-free condition, (make by oneself, preparation process is with document CN1110281A, and mean particle size is 110 μ m, and specific surface is 150-230M with 5.0 gram microspheroidal magnesium chloride alcohol adduct particles
2/ g, alcohol is 2.85: 1 with the molar ratio of content of magnesium chloride, molecular formula: MgCl
22.85CH
3CH
2OH) join in 140 milliliters of titanium tetrachloride liquid of-20 ℃, react after 1 hour, be warming up to 60 ℃ gradually; Add 1.0 gram dicyclos [2,2,1]-2,3-also-α, β-Succinic Acid methyl esters (embodiment 2 makes) is warming up to 120 ℃ gradually, react filtration 2 hours; Add 140 milliliters of titanium tetrachlorides again, in 120 ℃ of reactions 1 hour and filtration.60 ℃ of washings 5 times, at room temperature use 30 milliliters of hexane wash once with 100 milliliters of hexanes, obtain magnesium chloride load type catalyzer after the vacuum-drying.Each components contents is in the catalyzer: titanium 4.20%, electron donor compound 5.16%, magnesium 13.21%, chlorine 50.97%.
Slurry polymerization: 250 milliliters through vacuum drying treatment and with nitrogen and the abundant metathetical reaction flask of propylene gas in; Add 100 milliliters of heptane of handling through anhydrous and oxygen-free; Pressure is 1 normal atmosphere in the maintenance bottle, and temperature is 50 ℃, adds 4 milliliters of triethyl aluminums; Stir after 5 minutes, add the above-mentioned loaded catalyst of 0.1g.The mol ratio of the aluminium in the loaded catalyst in titanium and the promotor is 1: 100.Polyreaction 1 hour, with acidifying ethanol termination reaction, suction filtration is also used washing with alcohol, and vacuum-drying gets polymkeric substance.
The polymerization relevant data is listed in table 1.
The comparative example 1
Propene polymerizing method just replaces dicyclo [2,2,1]-2 with diisobutyl phthalate with embodiment 8 in the catalyst cupport process, 3-also-α, β-Succinic Acid methyl esters.Test-results is as shown in table 1.
The comparative example 2
Propene polymerizing method is with embodiment 8, just in the catalyst cupport process with 1, two (the methoxymethyl)-tetramethylene of 1-(press the CN1539857A disclosed method synthesizes) replacement dicyclo [2,2,1]-2,3-also-α, β-Succinic Acid methyl esters.Warp
1H NMR (CDCl
3, 300MHz) analytical results: δ 1.88-1.96 (m, 6H, CH
2); δ 3.24 (d, 6H, CH
3); δ 3.29 (d, 4H, CH
2).Experimental result is as shown in table 1.
The comparative example 3
Propene polymerizing method is with embodiment 8, just in the catalyst cupport process with cis-1,2-dimethoxy methylcyclohexane (ACROS reagent company provides, and the preparation method is referring to JP10310605A) replacement dicyclo [2,2,1]-2,3-also-α, β-Succinic Acid methyl esters.Experimental result is as shown in table 1.
The comparative example 4
Propene polymerizing method is with embodiment 8, just in the catalyst cupport process with 9, two (methoxymethyl)-fluorenes (ACROS reagent company provides, and the preparation method is referring to CN1298887A) the replacement dicyclos of 9-[2,2,1]-2,3-also-α, β-Succinic Acid methyl esters.Experimental result is as shown in table 1.
Embodiment 9
The preparation of loaded catalyst: with embodiment 8.
Slurry polymerization: after adding the promotor triethyl aluminum, add dimethoxy phenylbenzene silicon, the mol ratio of silicon is 10: 1 in aluminium in the triethyl aluminum and the dimethoxy phenylbenzene silicon.All the other are with embodiment 8.
The polymerization relevant data is listed in table 1.
Embodiment 10
The preparation of loaded catalyst: remove the internal electron donor compound and adopt dicyclo [2,2,1]-2,3-also-α, outside β-ethyl succinate (embodiment 1 makes), all the other are with embodiment 8.The content of main ingredient is in the catalyzer: titanium 4.83%, electron donor compound 4.37%, magnesium 13.45%, chlorine 53.53%.
Slurry polymerization: with embodiment 8.
The polymerization relevant data is listed in table 1.
The comparative example 5
The Preparation of catalysts method is with embodiment 8, and propene polymerizing method just replaces dicyclo [2,2,1]-2 with diisobutyl phthalate with embodiment 9 in catalyst preparation process, 3-also-α, β-ethyl succinate.Test-results is as shown in table 1.
The comparative example 6
The Preparation of catalysts method is with embodiment 8, and propene polymerizing method is with embodiment 9, just in catalyst preparation process with 2,2-dimethyl--1; 3-Propanal dimethyl acetal (ACROS reagent company provides, and preparation is referring to CN1042547) replaces dicyclo [2,2; 1]-2,3-also-α, β-ethyl succinate.Experimental result is as shown in table 1.
The comparative example 7
The Preparation of catalysts method is with embodiment 8, and propene polymerizing method is with 2-sec.-propyl-2-isopentyl-1 in catalyst preparation process with embodiment 9; (ACROS reagent company provides the 3-Propanal dimethyl acetal; Preparation is referring to CN1042547) replacement dicyclo [2,2,1]-2; 3-also-α, β-ethyl succinate.Experimental result is as shown in table 1.
The comparative example 8
The Preparation of catalysts method is with embodiment 8, and propene polymerizing method is with 2-(2-chlorine n-propyl)-2-n-propyl-1 in catalyst preparation process with embodiment 9; (ACROS reagent company provides the 3-Propanal dimethyl acetal; Preparation is referring to EP0891988A2) replacement dicyclo [2,2,1]-2; 3-also-α, β-ethyl succinate.Experimental result is as shown in table 1.
The comparative example 9
The Preparation of catalysts method is with embodiment 8, and propene polymerizing method is with embodiment 9, just in catalyst preparation process with cis-1,2-two (methoxyl methyl)-hexanaphthene (ACROS reagent company provides, and prepares referring to JP10310605A).Experimental result is as shown in table 1.
Embodiment 11
The preparation of loaded catalyst: with embodiment 10.
Slurry polymerization: with embodiment 9.
The polymerization relevant data is listed in table 1.
Embodiment 12
The preparation of loaded catalyst: remove the internal electron donor compound and adopt dicyclo [2,2,1]-2,3-also-α, outside β-methyl-succinate, all the other are with embodiment 8.Each components contents is in the catalyzer: titanium 5.65%, electron donor compound 6.59%, magnesium 12.53%, chlorine 53.28%.
Slurry polymerization: with embodiment 8.
The polymerization relevant data is listed in table 1.
Embodiment 13
The preparation of loaded catalyst: with embodiment 12.
Slurry polymerization: with embodiment 9.
The polymerization relevant data is listed in table 1.
Embodiment 14
The preparation of loaded catalyst: remove the internal electron donor compound and adopt dicyclo [2,2,1]-2,3-also-α, outside β-diethyl succinate, all the other are with embodiment 8.Each components contents is in the catalyzer: titanium 4.24%, electron donor compound 4.76%, magnesium 12.96%, chlorine 50.28%.
Slurry polymerization: with embodiment 8.
The polymerization relevant data is listed in table 1.
Embodiment 15
The preparation of loaded catalyst: with embodiment 14.
Slurry polymerization: with embodiment 9.
The polymerization relevant data is listed in table 1.
Embodiment 16
Preparation of catalysts method and propene polymerizing method be with embodiment 8, just in catalyst preparation process with dicyclo [2,2,1]-5,6-dimethyl--2,3-also-α, β-ethyl succinate replacement dicyclo [2,2,1]-2,3-also-α, β-Succinic Acid methyl esters.Test-results is as shown in table 1.
Embodiment 17
Preparation of catalysts method and propene polymerizing method be with embodiment 8, just in catalyst preparation process with dicyclo [2,2,1]-7-methyl-2,3-also-α, β-Succinic Acid butyl ester replacement dicyclo [2,2,1]-2,3-also-α, β-Succinic Acid methyl esters.Test-results is as shown in table 1.
Embodiment 18
Preparation of catalysts method and propene polymerizing method be with embodiment 8, just in catalyst preparation process with dicyclo [2,2,1]-7-chloro-2,3-also-α, β-Succinic Acid isopropyl ester replacement dicyclo [2,2,1]-2,3-also-α, β-Succinic Acid methyl esters.Test-results is as shown in table 1.
The polymerizing condition of table 1 embodiment 8～18 and polymerization result
Claims (10)
1. a load type catalyst for olefinic polymerization mainly is made up of magnesium halide alcohol adduct carrier, halogenated titanium and internal electron donor, it is characterized in that internal electron donor is to contain 1 of two ring texturees in the molecular skeleton, 4-two ester compounds, and its structural formula is:
Substituent R in the formula
1, R
2, R
3Can be identical or different, be selected from halogen atom, C
1～C
20The straight or branched alkyl; Substituent R
4, R
5Can be identical or different, be selected from C
1～C
20The straight or branched alkyl; The weight percent of each element and compound consists of in the catalyst component:
Internal electron donor compound 1-10%
Titanium 1-15%
Magnesium 10-25%
Halogen 40-60%.
2. catalyzer according to claim 1 is characterized in that the internal electron donor in the catalyzer composition is selected from following arbitrary compound:
Dicyclo [2,2,1]-2,3-also-α, β-Succinic Acid methyl esters
Dicyclo [2,2,1]-2,3-also-α, β-ethyl succinate
Dicyclo [2,2,1]-2,3-also-α, β-Succinic Acid propyl ester
Dicyclo [2,2,1]-2,3-also-α, β-Succinic Acid isopropyl ester
Dicyclo [2,2,1]-2,3-also-α, β-Succinic Acid butyl ester
Dicyclo [2,2,1]-2,3-also-α, β-methyl-succinate
Dicyclo [2,2,1]-2,3-also-α, β-diethyl succinate
Dicyclo [2,2,1]-2,3-also-α, β-dipropyl succinate
Dicyclo [2,2,1]-2,3-also-α, β-diisopropyl ester amber acid
Dicyclo [2,2,1]-2,3-also-α, β-Tabutrex
Dicyclo [2,2,1]-5,6-dimethyl--2,3-also-α, β-Succinic Acid methyl esters
Dicyclo [2,2,1]-5,6-dimethyl--2,3-also-α, β-ethyl succinate
Dicyclo [2,2,1]-5,6-dimethyl--2,3-also-α, β-Succinic Acid propyl ester
Dicyclo [2,2,1]-5,6-dimethyl--2,3-also-α, β-Succinic Acid isopropyl ester
Dicyclo [2,2,1]-5,6-dimethyl--2,3-also-α, β-Succinic Acid butyl ester
Dicyclo [2,2,1]-5,6-dimethyl--2,3-also-α, β-methyl-succinate
Dicyclo [2,2,1]-5,6-dimethyl--2,3-also-α, β-diethyl succinate
Dicyclo [2,2,1]-5,6-dimethyl--2,3-also-α, β-dipropyl succinate
Dicyclo [2,2,1]-5,6-dimethyl--2,3-also-α, β-diisopropyl ester amber acid
Dicyclo [2,2,1]-5,6-dimethyl--2,3-also-α, β-Tabutrex
Dicyclo [2,2,1]-7-methyl-2,3-also-α, β-Succinic Acid methyl esters
Dicyclo [2,2,1]-7-methyl-2,3-also-α, β-ethyl succinate
Dicyclo [2,2,1]-7-methyl-2,3-also-α, β-Succinic Acid propyl ester
Dicyclo [2,2,1]-7-methyl-2,3-also-α, β-Succinic Acid isopropyl ester
Dicyclo [2,2,1]-7-methyl-2,3-also-α, β-Succinic Acid butyl ester
Dicyclo [2,2,1]-7-methyl-2,3-also-α, β-methyl-succinate
Dicyclo [2,2,1]-7-methyl-2,3-also-α, β-diethyl succinate
Dicyclo [2,2,1]-7-methyl-2,3-also-α, β-dipropyl succinate
Dicyclo [2,2,1]-7-methyl-2,3-also-α, β-diisopropyl ester amber acid
Dicyclo [2,2,1]-7-methyl-2,3-also-α, β-Tabutrex
Dicyclo [2,2,1]-7-chloro-2,3-also-α, β-Succinic Acid methyl esters
Dicyclo [2,2,1]-7-chloro-2,3-also-α, β-ethyl succinate
Dicyclo [2,2,1]-7-chloro-2,3-also-α, β-Succinic Acid propyl ester
Dicyclo [2,2,1]-7-chloro-2,3-also-α, β-Succinic Acid isopropyl ester
Dicyclo [2,2,1]-7-chloro-2,3-also-α, β-Succinic Acid butyl ester
Dicyclo [2,2,1]-7-chloro-2,3-also-α, β-methyl-succinate
Dicyclo [2,2,1]-7-chloro-2,3-also-α, β-diethyl succinate
Dicyclo [2,2,1]-7-chloro-2,3-also-α, β-dipropyl succinate
Dicyclo [2,2,1]-7-chloro-2,3-also-α, β-diisopropyl ester amber acid
Dicyclo [2,2,1]-7-chloro-2,3-also-α, β-Tabutrex.
3. catalyzer according to claim 1 is characterized in that the magnesium halide alcohol adduct general formula of catalyzer in forming is Mg (OR ') mX
(2-m)N (R
2OH), R ' is C in the formula
1～C
20Alkyl, aralkyl or aryl; X is a halogen; M is the integer of 0≤m＜2; N is the decimal or the integer of 0＜n＜5; R
2Alkyl, aralkyl or aryl for C1～C20.
4. catalyzer according to claim 3 is characterized in that size-grade distribution 50～250 μ m of the magnesium halide alcohol adduct of catalyzer in forming.
5. catalyzer according to claim 4 is characterized in that magnesium halide in the said magnesium halide alcohol adduct is selected from a kind of in magnesium chloride, magnesium bromide, chloro magnesium methylate or the chloro magnesium ethylate; Alcohol is selected from a kind of in methyl alcohol, ethanol, propyl alcohol or the butanols.
6. catalyzer according to claim 5 is characterized in that the magnesium halide in the said magnesium halide alcohol adduct is a magnesium chloride, and alcohol is ethanol.
7. catalyzer according to claim 1 is characterized in that the halogenated titanium general formula is Ti (OR)
nX
(4-n), R is C in the formula
1～C
20Alkyl, aryl or aralkyl; X is a halogen; N is the integer of 0≤n＜4.
8. catalyzer according to claim 7 is characterized in that halogenated titanium is a titanium tetrachloride.
9. method for preparing one of the said catalyzer of claim 1 to 8; It is characterized in that detailed process comprises: (1) joins ball-type magnesium halide alcohol adduct particle in-50～20 ℃ the halogenated titanium liquid; Reacted 10 minutes to 5 hours, the mol ratio of magnesium and titanium is 1: 5～1: 100; (2) be warming up to 0～80 ℃, add 1,4-diester class internal electron donor compound, the mol ratio of magnesium and internal electron donor compound is 2: 1～20: 1; (3) be warming up to 100～150 ℃ again, reacted 1～6 hour; (4) add halogenated titanium liquid with step (1) same amount after filtering again, in 110～130 ℃ of reactions 1～4 hour, through filtering, washing obtained loaded catalyst after the drying again.
10. according to the said method for preparing catalyzer of claim 9, it is characterized in that detailed process comprises: (1) joins ball-type magnesium halide alcohol adduct particle in-30～0 ℃ the halogenated titanium liquid, reacts 1～4 hour, and the mol ratio of magnesium and titanium is 1: 10～1: 50; (2) be warming up to 30～60 ℃, add 1,4-diester class internal electron donor compound, the mol ratio of magnesium and internal electron donor compound is 2: 1～12: 1; (3) be warming up to 110～130 ℃ again, reacted 1～4 hour; (4) add halogenated titanium liquid with step (1) same amount after filtering again, in 110～130 ℃ of reactions 1～2 hour, filter, washing obtains loaded catalyst after the drying.
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| CN102336852B (en) * | 2010-07-14 | 2014-04-02 | 中国石油天然气股份有限公司 | Preparation method of Ziegler-Natta catalyst |
| CN102464731A (en) * | 2010-11-04 | 2012-05-23 | 中国石油天然气股份有限公司 | Olefin polymerization catalyst and preparation method thereof |
| CN103665209B (en) * | 2012-09-18 | 2017-03-15 | 中国石油天然气股份有限公司 | Polypropylene catalyst and preparation method thereof |
| JP6829884B2 (en) * | 2017-05-29 | 2021-02-17 | 国立大学法人北陸先端科学技術大学院大学 | Ziegler-Natta catalyst with cyclobutane dicarboxylic acid esters as electron donors |
| CN110144022B (en) * | 2019-05-28 | 2020-02-21 | 国家能源集团宁夏煤业有限责任公司 | Industrial preparation method of Ziegler-Natta catalyst |
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| CN101195666A (en) | 2008-06-11 |
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