CN1078893C - 聚－1－烯烃的制备方法 - Google Patents
聚－1－烯烃的制备方法Info
- Publication number
- CN1078893C CN1078893C CN94192743A CN94192743A CN1078893C CN 1078893 C CN1078893 C CN 1078893C CN 94192743 A CN94192743 A CN 94192743A CN 94192743 A CN94192743 A CN 94192743A CN 1078893 C CN1078893 C CN 1078893C
- Authority
- CN
- China
- Prior art keywords
- chromium
- cyclopentadienyl
- polymerization
- ethene
- alkene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims description 21
- 238000002360 preparation method Methods 0.000 title claims description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 5
- 125000000962 organic group Chemical group 0.000 claims abstract description 4
- 150000002739 metals Chemical class 0.000 claims abstract description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 13
- -1 hydrocarbyl lithium compound Chemical class 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 4
- 150000004678 hydrides Chemical class 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 125000002524 organometallic group Chemical group 0.000 claims description 3
- 238000012673 precipitation polymerization Methods 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 150000002902 organometallic compounds Chemical class 0.000 abstract description 7
- 229910052987 metal hydride Inorganic materials 0.000 abstract description 6
- 150000004681 metal hydrides Chemical class 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 239000011651 chromium Substances 0.000 description 21
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 18
- 229910052804 chromium Inorganic materials 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 229920000573 polyethylene Polymers 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 229960001866 silicon dioxide Drugs 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 229910000091 aluminium hydride Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- WVBBLFIICUWMEM-UHFFFAOYSA-N chromocene Chemical compound [Cr+2].C1=CC=[C-][CH]1.C1=CC=[C-][CH]1 WVBBLFIICUWMEM-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- AEVBUGHMKXBGBL-UHFFFAOYSA-N didecyl butanedioate Chemical compound CCCCCCCCCCOC(=O)CCC(=O)OCCCCCCCCCC AEVBUGHMKXBGBL-UHFFFAOYSA-N 0.000 description 1
- KWABLUYIOFEZOY-UHFFFAOYSA-N dioctyl butanedioate Chemical compound CCCCCCCCOC(=O)CCC(=O)OCCCCCCCC KWABLUYIOFEZOY-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000003454 indenyl group Chemical class C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/6392—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/63922—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/63925—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63908—Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63912—Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with an organoaluminium compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63916—Component covered by group C08F4/62 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Saccharide Compounds (AREA)
- Polymerization Catalysts (AREA)
Abstract
本发明涉及利用吸附在无机氧化物载体上的双(环戊二烯基)铬-Ⅱ化合物(Ⅰ)通过1-烯烃的聚合来制备聚1-烯烃的方法，在所述化合物中环戊二烯基环可带有惰性有机基团，其特征在于在Ⅰ至Ⅲ主族的金属的有机金属化合物或一种金属氢化物、尤其是正丁基锂的存在下进行该聚合反应。
Description
本发明涉及一种制备聚-1-烯烃的方法，尤其是涉及用吸附在无机氧化物载体上的双(环戊二烯基)铬-II化合物
通过1-烯烃的聚合来制备聚乙烯和乙烯与C3-C10-1-烯烃的共聚物的方法，在所述化合物中环戊二烯基环可带有惰性有机基团。
本发明还涉及按该方法获得的沉淀聚合物。
由US-A 3709853己知，用包括无机氧化物载体材料(尤其是二氧化硅)和双(环戊二烯基)铬-II(一般称为茂铬(chromocene))的载体催化剂通过乙烯或乙烯与C3-C10-1-烯烃的混合物的聚合来制各聚乙烯及乙烯与C3-C10-1-烯烃的共聚物。
由US-A 3879368还己知用硅烷或烷基硅烷预处理的这类催化剂。
此外，在DE-A 3634534中建议，用二氧化硅/三氧化铬-载体催化剂和烷基锂进行乙烯和乙烯与其它1-烯烃的聚合反应。
然而，这些方法中使用的催化剂的缺点是它使聚合物具有宽分子量分布(DE-A 3634534)或其产率相当低(US-A 3709853)，因此，它仅有条件地适合于大工业方法。
因此，发明了一种制备聚-1-烯烃的改进方法，该方法利用吸附在无机氧化物载体上的-双(环戊二烯基)-铬-II化合物
聚合1-烯烃来实施，在所述化合物中环戊二烯基环可带有惰性有机基团，其特征在于在I至III主族金属的有机金属化合物或这些金属的氢化物存在下进行该聚合反应。
作为聚合催化剂的活性组分首先考虑的是双(环戊二烯基)铬-II，此外还可是其衍生物，其中环戊二烯基基团可以带有C1-C5烷基和/或C5-C15芳基作为取代基团。另外，稠合的环戊二烯基如茚和芴也是适用的，它们同样可用上述基团取代。
金属氧化物如Si、Al或Zr的氧化物适于作为载体材料，其中优选二氧化硅或铝和硅的混合氧化物。例如在DE-A 3634534中记载了这类载体的制备。该载体应优选具有高内表面积，大约为50至1000m2/g，由此吸附的茂铬具有对烯烃尽可能高的接触面积。平均孔隙直径为1至100nm。特别优选的市售产品是例如Grace公司的硅胶332。
在载带茂铬之前必须活化载体材料，以便脱除吸附的水。因此将它在惰性气氛中加热到200至900℃大约1至30小时。
已述多种技术可使用活性组分加载载体。
因此，可通过升华进行干燥载体材料的加载，为此，在惰性气氛中混合茂铬和载体材料并接着减压到一定程度，使茂铬蒸发并吸附在载体材料上。
还可以下述方法制造载体催化剂：先将茂铬溶解在溶剂中，并让该溶液在载体材料上作用若干小时。适用的溶剂是烃类如戊烷、正己烷、环己烷、苯和二甲苯。溶剂用量应能够完全润湿载体材料。如果需要粉末状产物，则要从悬浮液中脱除溶剂。
载体催化剂中铬的量以载体材料为基准计一般为0.1～10％(重量)。
用本发明方法可生产的聚合物主要是聚乙烯以及乙烯与C3～C10、优选与C3～C5-1-烯烃的共聚物。此外，该方法还适合于定义的其它1-烯烃的共聚合。
以所用载体催化剂用量为基准计，1-烯烃的用量在100和10,000g/g之间，优选在1000和200,000g/g之间。
本发明方法的区别特征是在1-烯烃聚合时除茂铬载体催化剂外还使用金属氢化物或有机金属化合物，其中有机金属化合物的金属属于I至III主族。
有机金属化合物和金属氢化物含有I至III主族的金属。除用锂作为金属外，还可考虑钠、钾、铍、镁、钙、钡、硼和铝。
有机金属化合物中优选烷基金属和芳基金属。作为烃基可以考虑具有1至6个碳原子的脂族基团和具有6至15个碳原子的芳族基团。其中特别优选的是锂化合物，例如正丁基锂、仲丁基锂和苯基锂。
适用的金属氢化物是例如氢化钠和氢化钙，混合的氢化物如氢化钮铝和硼氢化钠以及硼氢化合物。
对于茂铬催化剂来说，本发明所用的有机金属化合物或金属氢化物的用量比例为每摩尔铬优选0.1至100、特别优选1至20当量金属。在总的聚合过程中通过相应地添加金属有机化合物或金属氢化物保持该比例关系是有利的。
对此，一般可采用例如在“Ullmanns Encyklopdie dertechnischen Chemie”，19卷，4版中所述的工艺技术。
优选在溶剂中进行沉淀聚合反应，其中单体而不是聚合物是可溶的。适宜的溶剂尤其是脂族烃，主要是C4～C10烷烃。
为了避免在反应器壁上形成敷层，一般使用抗静电剂。为此涉及到例如由水杨酸烷基酯铬盐、含磺基的丁二酸二辛酯或丁二酸二癸酯的钙盐和吖丙啶与不饱和羧酸的离子共聚物组成的混合物，如在DE-A 2302962中所述。
在沉淀聚合中，在正丁基锂存在下可得到细颗粒形式的聚合物，除去溶剂后出人意料地得到比按已知方法例如US-PS 3709853的方法得到的聚合物具有更高的堆积密度。该聚合物的优点是不用再造粒即可用于制造模制件。
本发明的方法总体上提供了特别高产率的优点，即，与目前所用催化剂相比较，生产一定量的聚合物需用更少量的催化剂。这可能是由于本发明所用的添加剂捕捉了活性氢或有氧化作用的杂质，并因此保护了敏感的催化剂。
实施例A.制造连续聚合用的载体催化剂
将100g上述载体材料悬浮于3.5g双(环戊二烯基)铬-II在500ml正庚烷中的溶液中。将该悬浮液搅拌8小时并接着直接使用。
按上述方法制造载有加倍量的双(环戊二烯基)铬-II的另一种载体催化剂，不同的是使用7.0g双(环戊二烯基)铬-II在500ml正庚烷中的溶液。B.制造用于非连续聚合用的载体催化剂
将15g硅胶(Grace公司的SG 332)悬浮在1.04g双(环戊二烯基)铬-II在200ml正庚烷中的溶液中，该硅胶已在800℃焙烧24小时，其粒度为20至45μm，比表面积为320m2/g，孔体积为1.75ccm/g。在室温搅拌2小时后，滤出载体材料，用正庚烷洗涤，并在室温下真空干燥成松散的粉末。
实施例1(本发明)连续聚合反应
在200升带封闭循环的环形反应器中以异丁烷作溶剂，在温度为88℃和4×103千帕(40巴压力)下使乙烯连续聚合，其中在整个实验期间保持乙烯浓度为18％(体积)。在反应器中还要各通入恒定量的15升/小时氢和0.14g/小时抗静电剂。向反应器中以恒量添加2.8g/小时载有1％(重量)铬的茂铬/SiO2载体催化剂(相当于0.5×10-3mol Cr/小时)和0.1g/小时正丁基锂(1.5×10-3mol/小时)，得到19kg/小时聚乙烯，相当于产率为每克催化剂生产6800g聚乙烯。所得聚乙烯的堆积密度为440g/l(按DIN 53 468测定)。
实施例IV/l(比较用)
该实验与实施例1的不同之处在于载有1％(重量)铬的茂铬/SiO2载体催化剂的添加量提高到5.6g/小时(相当于1.1×10-3mol Cr/小时)，但不加正丁基锂。获得14kg/小时聚乙烯，相当于产率为每克催化剂2500g聚乙烯。所得聚乙烯的堆积密度为360g/l(按DIN 53 468测定)。
实施例IV/2(比较用)
该实验与实施例1的不同之处在于添加含加倍量铬(2％(重量))的茂铬/SiO2载体催化剂和不加正丁基锂。获得23kg/小时聚乙烯，相当于产率为每克催化剂6600g聚乙烯。所得聚乙烯的堆积密度为375g/l(按DIN 53 468测定)。
实施例2-5非连续聚合反应(本发明)
在1升高压釜中在氩气氛下供入400ml用氩气清扫过的无水庚烷并混入一摩尔正丁基锂在庚烷中的溶液。此后在70℃用20千帕(0.2巴)氢和3×103千帕(30巴)乙烯将总压加压到3×103千帕(30巴)，并接着将100mg(3.8×10-3mmol Cr)茂铬/SiO2载体催化剂加到反应器中，接着立刻进行乙烯的聚合反应。在70℃恒温下保持3×103千帕(30巴)压力90分钟，之后通过高压釜的减压终止聚合反应并从生成的悬浮液中蒸出庚烷。
在实施例5至7中改变该实验，不同之处在于氢分压和丁基锂的量以及用三乙基铝(ATE)代替丁基锂(见表1)。
这些实施结果列在下表中。
实施例
2 3 4 5丁基锂[mg] 40 30 - -三乙基铝[ng] - - 30 30H2压力[千帕] 20 50 20 50产率1) 2.5 1.2 1.5 1.2堆积密度(g/l) 390 360 315 3001)kg聚合物/g催化剂
Claims (5)
1.一种聚1-烯烃的制备方法，该方法利用吸附在无机氧化物载体上的双(环戊二烯基)铬-II化合物通过1-烯烃的聚合来进行，在所述化合物中环戊二烯基环可带有惰性有机基团，其特征在于在I至III主族金属的金属有机化合物或这些金属的氢化物存在下进行该聚合反应，但金属氧化物载体不含磷酸盐，并且金属氧化物载体不用硅烷类进行处理。
2.根据权利要求1的方法，其特征在于用烃基锂化合物作为金属有机化合物。
3.根据权利要求2的方法，其特征在于用正丁基锂作为烃基锂化合物。
4.根据权利要求1至3中任一项的方法，其特征在于该方法用于乙烯或乙烯与一种或多种C3-C10-1-烯烃的混合物的聚合。
5.根据权利要求1至3中任一项的方法，其特征在于按沉淀聚合法进行聚合反应。
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| DE4323192A DE4323192A1 (de) | 1993-07-10 | 1993-07-10 | Verfahren zur Herstellung von Homo- und Copolymerisaten von Alk-1-enen |
| DEP4323192.6 | 1993-07-10 |
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| CN1078893C true CN1078893C (zh) | 2002-02-06 |
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| EP (1) | EP0708787B1 (zh) |
| JP (1) | JP3776929B2 (zh) |
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| CN (1) | CN1078893C (zh) |
| DE (2) | DE4323192A1 (zh) |
| ES (1) | ES2126765T3 (zh) |
| FI (1) | FI960098A (zh) |
| NO (1) | NO310364B1 (zh) |
| WO (1) | WO1995001999A1 (zh) |
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| NO960350A (no) † | 1996-01-26 | 1997-04-28 | Borealis As | Fremgangsmåte og katalysatorsystem for polymerisering av etylen, eventuelt sammen med <alfa>-olefiner, og fremstilt polymermateriale |
| DE19645939A1 (de) * | 1996-11-07 | 1998-05-14 | Buna Sow Leuna Olefinverb Gmbh | Verfahren zur Herstellung von ultrahochmolekularem Polyethylen und Methode zur Aktivierung des Katalysatorträgers |
| US6174953B1 (en) * | 1998-02-19 | 2001-01-16 | E. I. Du Pont De Nemours And Company | Low molecular weight (meth) acrylate copolymer emulsions |
| DE19833858C2 (de) | 1998-07-28 | 2000-06-08 | Elenac Gmbh | Geruchsarme Polyethylen-Blends |
| US6337297B1 (en) * | 1998-10-12 | 2002-01-08 | Tosoh Corporation | Catalyst for trimerization of ethylene and process for trimerizing ethylene using the catalyst |
| US6818585B2 (en) * | 1998-12-30 | 2004-11-16 | Univation Technologies, Llc | Catalyst compounds, catalyst systems thereof and their use in a polymerization process |
| DE60000318T2 (de) | 1999-04-01 | 2003-04-17 | Japan Polyolefins Co. Ltd., Tokio/Tokyo | Katalysator zur Herstellung von Ethylenpolymer und Verfahren zur Herstellung von Ethylenpolymer |
| GB0021301D0 (en) * | 2000-08-30 | 2000-10-18 | Borealis Tech Oy | Supported catalyst |
| DE10314369B4 (de) * | 2003-03-28 | 2005-08-25 | Otto-Von-Guericke-Universität Magdeburg | Polymerisationskatalysatoren auf Porenbetonbasis, Verfahren zu ihrer Herstellung und ihre Verwendung |
| KR101512548B1 (ko) | 2010-03-12 | 2015-04-15 | 오메로스 코포레이션 | Pde10 억제제 및 관련 조성물 및 방법 |
| NZ630810A (en) | 2014-04-28 | 2016-03-31 | Omeros Corp | Processes and intermediates for the preparation of a pde10 inhibitor |
| NZ716462A (en) | 2014-04-28 | 2017-11-24 | Omeros Corp | Optically active pde10 inhibitor |
| JP2018513153A (ja) | 2015-04-24 | 2018-05-24 | オメロス コーポレーション | Ｐｄｅ１０インヒビターならびに関連する組成物および方法 |
| WO2017079678A1 (en) | 2015-11-04 | 2017-05-11 | Omeros Corporation | Solid state forms of a pde10 inhibitor |
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| US3879368A (en) * | 1971-03-18 | 1975-04-22 | Union Carbide Corp | Catalyst modified with certain strong reducing agents and silane compounds and use in polymerization of olefins |
| EP0090374A1 (en) * | 1982-03-30 | 1983-10-05 | Phillips Petroleum Company | Catalyst system and process for producing a catalyst |
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| US3013002A (en) * | 1960-04-05 | 1961-12-12 | Hercules Powder Co Ltd | Polymerization of ethylene with dicyclopentadienyl chromium-metal alkylcatalysts |
| US3709853A (en) | 1971-04-29 | 1973-01-09 | Union Carbide Corp | Polymerization of ethylene using supported bis-(cyclopentadienyl)chromium(ii)catalysts |
| US3806500A (en) * | 1972-07-21 | 1974-04-23 | Union Carbide Corp | Polymerization with thermally aged catalyst |
| US4015059A (en) * | 1975-12-29 | 1977-03-29 | Union Carbide Corporation | Fused ring catalyst and ethylene polymerization process therewith |
| US4803253A (en) * | 1982-03-30 | 1989-02-07 | Phillips Petroleum Company | Ethylene polymer produced using a catalyst comprising a phosphate and with a bis-(cyclopentadienyl)chromium(II) compound |
| DE3634534A1 (de) | 1986-10-10 | 1988-04-14 | Basf Ag | Verfahren zum herstellen von homo- sowie copolymerisaten des ethens mittels eines chromtrioxid-katalysators |
| DE3635363A1 (de) | 1986-10-17 | 1988-04-21 | Basf Ag | Verfahren zur neutralisation von reaktionsgemischen, die durch beckmann'sche umlagerung von cyclohexanonoxim erhalten worden sind |
| GB8919925D0 (en) * | 1989-09-04 | 1989-10-18 | Bp Chem Int Ltd | Chromium-containing complex polymerisation catalyst |
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- 1994-06-23 ES ES94921621T patent/ES2126765T3/es not_active Expired - Lifetime
- 1994-06-23 DE DE59407708T patent/DE59407708D1/de not_active Expired - Fee Related
- 1994-06-23 KR KR1019960700197A patent/KR960703947A/ko not_active Application Discontinuation
- 1994-06-23 JP JP50379095A patent/JP3776929B2/ja not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3879368A (en) * | 1971-03-18 | 1975-04-22 | Union Carbide Corp | Catalyst modified with certain strong reducing agents and silane compounds and use in polymerization of olefins |
| EP0090374A1 (en) * | 1982-03-30 | 1983-10-05 | Phillips Petroleum Company | Catalyst system and process for producing a catalyst |
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| NO960089D0 (no) | 1996-01-09 |
| JPH08512339A (ja) | 1996-12-24 |
| FI960098A0 (fi) | 1996-01-09 |
| DE59407708D1 (de) | 1999-03-04 |
| JP3776929B2 (ja) | 2006-05-24 |
| FI960098A (fi) | 1996-01-09 |
| KR960703947A (ko) | 1996-08-31 |
| NO310364B1 (no) | 2001-06-25 |
| DE4323192A1 (de) | 1995-01-12 |
| WO1995001999A1 (de) | 1995-01-19 |
| ES2126765T3 (es) | 1999-04-01 |
| EP0708787A1 (de) | 1996-05-01 |
| CN1127002A (zh) | 1996-07-17 |
| NO960089L (no) | 1996-01-09 |
| EP0708787B1 (de) | 1999-01-20 |
| US6197901B1 (en) | 2001-03-06 |
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