NO770675L - PROCEDURES FOR PRODUCING A CATALYST. - Google Patents
PROCEDURES FOR PRODUCING A CATALYST.Info
- Publication number
- NO770675L NO770675L NO770675A NO770675A NO770675L NO 770675 L NO770675 L NO 770675L NO 770675 A NO770675 A NO 770675A NO 770675 A NO770675 A NO 770675A NO 770675 L NO770675 L NO 770675L
- Authority
- NO
- Norway
- Prior art keywords
- magnesium
- catalyst
- transition metal
- metal compound
- polymerization
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims description 43
- 238000000034 method Methods 0.000 title claims description 29
- 150000003623 transition metal compounds Chemical class 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 239000010936 titanium Substances 0.000 claims description 13
- 239000012876 carrier material Substances 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000003085 diluting agent Substances 0.000 claims description 8
- 159000000003 magnesium salts Chemical class 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 7
- 239000012190 activator Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 4
- 239000011654 magnesium acetate Substances 0.000 claims description 4
- 229940069446 magnesium acetate Drugs 0.000 claims description 4
- 235000011285 magnesium acetate Nutrition 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical group CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- UHNWOJJPXCYKCG-UHFFFAOYSA-L magnesium oxalate Chemical compound [Mg+2].[O-]C(=O)C([O-])=O UHNWOJJPXCYKCG-UHFFFAOYSA-L 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- PJJZFXPJNUVBMR-UHFFFAOYSA-L magnesium benzoate Chemical compound [Mg+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 PJJZFXPJNUVBMR-UHFFFAOYSA-L 0.000 claims description 2
- QUIOHQITLKCGNW-ODZAUARKSA-L magnesium;(z)-but-2-enedioate Chemical compound [Mg+2].[O-]C(=O)\C=C/C([O-])=O QUIOHQITLKCGNW-ODZAUARKSA-L 0.000 claims description 2
- GMDNUWQNDQDBNQ-UHFFFAOYSA-L magnesium;diformate Chemical group [Mg+2].[O-]C=O.[O-]C=O GMDNUWQNDQDBNQ-UHFFFAOYSA-L 0.000 claims description 2
- AICDYVDWYUUUGL-UHFFFAOYSA-L magnesium;propanedioate Chemical compound [Mg+2].[O-]C(=O)CC([O-])=O AICDYVDWYUUUGL-UHFFFAOYSA-L 0.000 claims description 2
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims 1
- 229920005862 polyol Polymers 0.000 claims 1
- 150000003077 polyols Chemical class 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- 229910052723 transition metal Inorganic materials 0.000 claims 1
- 150000003624 transition metals Chemical class 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 7
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001282 iso-butane Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- -1 alkyl aluminum halides Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
- B01J31/0212—Alkoxylates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
- B01J2231/12—Olefin polymerisation or copolymerisation
- B01J2231/122—Cationic (co)polymerisation, e.g. single-site or Ziegler-Natta type
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Description
Fremgangsmåte til fremstilling avMethod for the production of
en båret Ziegler-katalysator.a supported Ziegler catalyst.
Foreliggende oppfinnelse vedrører en fremgangsmåte til. fremstilling av en båret Ziegler-katalysator og bruken av katalysatoren ved polymerisasjon av olefiner. The present invention relates to another method. preparation of a supported Ziegler catalyst and the use of the catalyst in the polymerization of olefins.
Det har lenge vært kjent at olefiner slik som etylen kan polymeriseres ved å bringe dem i kontakt under polymerisasjonsbetingelser med en katalysator omfattende en overgangsmetall-forbindelse, f.eks. titantetraklorid og en ko-katalysator eller aktivator, f.eks. en organometallforbindelse slik som trietylaluminium. Katalysatorer av denne type kalles vanligvis Ziegler-katalysatorer og vil bli slik betegnet her. . Katalysatoren og ko-katalysatoren sammen vil bli betegnet som aktiverte Ziegler-katalysatorer. Det er også kjent å avsette slike katalysatorer på bærermaterialer slik som silisiumkarbid, kalsiumfosfat, magnesium- eller natriumkarbonat. It has long been known that olefins such as ethylene can be polymerized by contacting them under polymerization conditions with a catalyst comprising a transition metal compound, e.g. titanium tetrachloride and a co-catalyst or activator, e.g. an organometallic compound such as triethylaluminum. Catalysts of this type are usually called Ziegler catalysts and will be so designated here. . The catalyst and co-catalyst together will be referred to as activated Ziegler catalysts. It is also known to deposit such catalysts on support materials such as silicon carbide, calcium phosphate, magnesium or sodium carbonate.
Foreliggende oppfinnelse tilveiebringer en fremgangsmåte til. fremstilling av en båret Ziegler-katalysator omfattende dannelse av et bærermateriale ved oppvarming av magnesiumsaltet av en organisk karb.oksylsyre under slike betingelser at minst endel derav omdannes til magnesiumoksyd, og inkorporering av en overgangsmetall-forbindelse i det således dannede bærermateriale. The present invention provides another method. production of a supported Ziegler catalyst comprising forming a carrier material by heating the magnesium salt of an organic carboxylic acid under such conditions that at least part of it is converted to magnesium oxide, and incorporating a transition metal compound into the carrier material thus formed.
De benyttede magnesiumsalt kan være saltet av en mono- eller polykarboksylsyre, f.eks. magnesiumformiat, magnesiumacetat, magnesiumoksalat, magnesiummalonat eller magnesiummaleat, eller organiske syrer slik som magnesiumbenzoat. Saltet kan være vannfritt, hydratisert eller solvatisert. The magnesium salt used can be the salt of a mono- or polycarboxylic acid, e.g. magnesium formate, magnesium acetate, magnesium oxalate, magnesium malonate or magnesium maleate, or organic acids such as magnesium benzoate. The salt can be anhydrous, hydrated or solvated.
Oppvarmingen av. magnesiumsaltet må utføres under slike betingelser at minst endel, f.eks. 5 vekt-%, fortrinnsvis minst 50 vekt-#, og helst minst go vekt-% omdannes til magnesiumoksyd. Graden av omdannelse til magnesiumoksyd kan bestemmes på tilfredsstillende måte ved elementæranalyse eller ved.røntgen- strålediffraksjon. Temperaturen hvorved et magnesiumsalt av en organisk karboksylsyre begynner å dekomponere til magnesiumoksyd, vil naturligvis avhenge av det gitte salt og kan f.eks. være i området 300-700°C. Dekomponeringstemperaturen for et spesielt salt kan bestemmes ut fra forsøk. Oppvarmingen foretas, fortrinnsvis ved en temperatur som bare er marginalt over dekomponeringstemperaturen. for saltet, f.eks. mellom 5 og 100°C over dekomponeringstemperaturen. Oppvarmingen kan f.eks. utføres i vakuum, i en inert gass slik som vanndamp eller nitrogen eller i luft. Det er foretrukket å utføre oppvarmingen i luft. Om ønsket kan en gasstrøm, f.eks. vanndamp eller nitrogen, anvendes for å fluidisere det pulveriserte salt under oppvarmingen. The heating off. the magnesium salt must be carried out under such conditions that at least part, e.g. 5% by weight, preferably at least 50% by weight, and preferably at least 8% by weight is converted to magnesium oxide. The degree of conversion to magnesium oxide can be satisfactorily determined by elemental analysis or by X-ray diffraction. The temperature at which a magnesium salt of an organic carboxylic acid begins to decompose to magnesium oxide will naturally depend on the given salt and can e.g. be in the range 300-700°C. The decomposition temperature of a particular salt can be determined from experiments. The heating is carried out, preferably at a temperature which is only marginally above the decomposition temperature. for the salt, e.g. between 5 and 100°C above the decomposition temperature. The heating can e.g. carried out in vacuum, in an inert gas such as water vapor or nitrogen or in air. It is preferred to carry out the heating in air. If desired, a gas stream, e.g. water vapor or nitrogen, is used to fluidize the powdered salt during the heating.
Produktet fra oppvarmingen av mangesiumsaltet av karboksylsyren blir fortrinnsvis siktet før overgangsmetallforbindelsen inkorporeres deri. Hvis produktet fra oppvarmingen inneholder klumper, kan det f.eks. siktes for å utskille det produkt som har den ønskede partikkelstørrelsen og klumpene kan males og siktes 'på nytt. Det produkt som anvendes som bærermateriale har. fortrinnsvis en partikkelstørrelse i området l-500ym (midlere partikkeldiameter) og helst i området 50-250ym. The product of the heating of the manganese salt of the carboxylic acid is preferably sieved before the transition metal compound is incorporated therein. If the product from heating contains lumps, it can e.g. sieved to separate out the product which has the desired particle size and the lumps can be ground and sieved again. The product used as carrier material has preferably a particle size in the range 1-500 ym (mean particle diameter) and preferably in the range 50-250 ym.
Overgangsmetallforbindelsen som benyttes i foreliggende oppfinnelse kan være en hvilken som helst overgangsmetall-forbindelse egnet for fremstilling av Ziegler-katalysatorer. Foretrukne forbindelser er halogenidene, halogenalkoksydene og alkoksydene av metallene i gruppene IVa, Va og Via i det Periodiske System. Spesielt foretrukket er de forbindelser av titan som The transition metal compound used in the present invention can be any transition metal compound suitable for the production of Ziegler catalysts. Preferred compounds are the halides, halogenalkoxides and alkoxides of the metals in groups IVa, Va and Via of the Periodic Table. Particularly preferred are those compounds of titanium which
har den generelle formel Ti(OR) (Cl),. • hvor n er fra 0-4, inklusive, og R er en alkylgruppe som fortrinnsvis inneholder 1-6 karbonatomer, f.eks. titantetraklorid, titantetraetylat, titantetraisopropylat, Ti(0C2H^)^Cl, Ti(OiPr)2Cl2eller blandinger derav. has the general formula Ti(OR) (Cl),. • where n is from 0-4, inclusive, and R is an alkyl group which preferably contains 1-6 carbon atoms, e.g. titanium tetrachloride, titanium tetraethylate, titanium tetraisopropylate, Ti(OC2H^)^Cl, Ti(OiPr)2Cl2 or mixtures thereof.
Mengden av overgangsmetallforbindelse som benyttes er fortrinnsvis tilstrekkelig til å gi en konsentrasjon av The amount of transition metal compound used is preferably sufficient to give a concentration of
metall i katalysatoren i området 0,5-15 vekt-$, fortrinnsvis 1,5_9 vekt-%, basert på katalysatorens totalvekt. metal in the catalyst in the range of 0.5-15% by weight, preferably 1.5-9% by weight, based on the total weight of the catalyst.
Overgangsmetallforbindelsen kan inkorporeres i bærermaterialet under anvendelse av enhver passende teknikk. Bærermaterialet blir helst behandlet med overgangsmetallforbindelsen ved en temperatur i området fra -40 til 150°C, og fortrinnsvis mellom 20 og 100°C. Dette kan utføres, ved f.eks. blanding av bærermaterialet og overgangsmetallforbindelsen med eller uten et inert. fortynningsmiddel eller et oppløsningsmiddel . for overgangsmetallforbindelsen; eller dampen av en flyktig overgangsmetallforbindelse kan føres inn i et oppvarmet sjikt, f.eks. et fluidisert sjikt, av bærermaterialet. Det er fore trukket å oppvarme bærermaterialet og overgangsmetallforbindelsen sammen ved en temperatur i området- 70-100°C i§~5timer i nærvær av et inert. f ortynningsmiddel eller et oppløsningsmiddel. for overgangsmetallforbindelsen. Egnede inerte. fortynningsmidler (som i noen tilfeller også er oppløsnlngsmidler for overgangsmetallforbindelsen) er f.eks. mettede alifatiske hydrokarboner slik som petroleumeter, butan, pentan, heksan, heptan, metyl-cykloheksan og cykloheksan og aromatiske hydrokarboner slik som benzen, toluen og xylen. The transition metal compound can be incorporated into the support material using any suitable technique. The carrier material is preferably treated with the transition metal compound at a temperature in the range from -40 to 150°C, and preferably between 20 and 100°C. This can be done, e.g. mixture of the support material and the transition metal compound with or without an inert. diluent or a solvent. for the transition metal compound; or the vapor of a volatile transition metal compound can be introduced into a heated layer, e.g. a fluidized layer of the carrier material. It is fore drawn to heat the support material and the transition metal compound together at a temperature in the range- 70-100°C for §~5 hours in the presence of an inert. f diluent or a solvent. for the transition metal compound. Suitable inert. diluents (which in some cases are also solvents for the transition metal compound) are e.g. saturated aliphatic hydrocarbons such as petroleum ether, butane, pentane, hexane, heptane, methylcyclohexane and cyclohexane and aromatic hydrocarbons such as benzene, toluene and xylene.
Et eventuelt overskudd av overgangsmetallforbindelsen som forblir i katalysatoren etter inkorporeringstrinnet, Any excess of the transition metal compound remaining in the catalyst after the incorporation step,
blir fortrinnsvis fjernet fra katalysatoren f«eks. ved pppløsnings-middelvasking, destillasjon eller en annen egnet teknikk som ikke har noen skadelig innvirkning på- katalysatoren. Overfekudd titanforbindelser med formelen Ti(OR) n Cl4„ -n fj"ernes fortrinnsvis ved vasking av katalysatoren flere ganger med oppløsningsmidler slik som f.eks. de ovenfor angitte. is preferably removed from the catalyst, e.g. by pp solvent washing, distillation or any other suitable technique which has no harmful effect on the catalyst. Excess titanium compounds with the formula Ti(OR) n Cl4„ -n are preferably removed by washing the catalyst several times with solvents such as, for example, those indicated above.
Inkorporeringen av overgangsmetallforbindelsen The incorporation of the transition metal compound
utføres, fortrinnsvis i fravær av oksygen eller fuktighet.is carried out, preferably in the absence of oxygen or moisture.
Videre tilveiebringer oppfinnelsen en fremgangsmåte til polymerisasjon av 1-olefiner omfattende at monomeren under polymerisasjonsbetihgélser bringes i kontakt med den bårede Ziegler-katalysator ifølge oppfinnelsen i nærvær av en Ziegler-katalysator-aktivator. Furthermore, the invention provides a method for the polymerization of 1-olefins comprising bringing the monomer under polymerization conditions into contact with the supported Ziegler catalyst according to the invention in the presence of a Ziegler catalyst activator.
Foreliggende polymerisasjonsfremgangsmåte kan anvendes for polymerisasjon av 1-olefiner, f.eks. etylen eller propylen eller blandinger av olefiner, f.eks. etylen med andre 1-olefiner, f.eks. propylen, 1-buten, 1-penten, 1-heksen, 4-metylpenten-1, 1-3-butadien eller isopren. Fremgangsmåten er The present polymerization method can be used for the polymerization of 1-olefins, e.g. ethylene or propylene or mixtures of olefins, e.g. ethylene with other 1-olefins, e.g. propylene, 1-butene, 1-pentene, 1-hexene, 4-methylpentene-1, 1-3-butadiene or isoprene. The procedure is
.spesielt egnet for polymerisasjon av etylen eller kopolymerisa-sjon av etylen med opptil 40 vekt-% (basert på total monomer) .especially suitable for polymerization of ethylene or copolymerization of ethylene with up to 40% by weight (based on total monomer)
av komonomere, dvs. en eller flere andre 1-olefiner. of comonomers, i.e. one or more other 1-olefins.
Ziegler-katalysator-aktivatorer og de fremgangsmåter hvorved de anvendes, for å aktivere Ziegler-katalysatorer er velkjente. Eksempler på Ziegler-katalysator-aktivatorer er de organiske derivater eller hydrider av metaller i gruppene I, II, III og IV i det Periodiske System. Spesielt, foretrukket er trialkylaluminiumforbindelsene, f.eks. trietyl- eller tributylaluminium, eller alkylaluminiumhalogenider. Ziegler catalyst activators and the methods by which they are used to activate Ziegler catalysts are well known. Examples of Ziegler catalyst activators are the organic derivatives or hydrides of metals in groups I, II, III and IV of the Periodic Table. In particular, preferred are the trialkyl aluminum compounds, e.g. triethyl or tributyl aluminum, or alkyl aluminum halides.
Polymerisasjonsbetingelsene kan være i overens-stemmelse med kjent teknikk som anvendes, for Ziegler-polymerisasjon. Polymerisasjonen kan utføres i gassfasen eller i nærvær av et dispergeringsmedium hvori monomeren er oppløselig. Som flytende dispergeringsmedium kan anvendes et inert hydrokarbon som er væsk.eformig under polymerisasj onsbetingelsene, eller man kan anvende monomeren eller monomerene alene holdt i væskeformig til-stand under deres metningstrykk. Polymerisasjonen kan om ønsket, utføres i nærvær av hydrogengass eller et annet kjedeoverførings-middel for å variere molekylvekten til den fremstilte polymer. The polymerization conditions may be in accordance with known techniques used for Ziegler polymerization. The polymerization can be carried out in the gas phase or in the presence of a dispersion medium in which the monomer is soluble. An inert hydrocarbon which is liquid under the polymerization conditions can be used as a liquid dispersing medium, or the monomer or monomers alone kept in a liquid state under their saturation pressure can be used. The polymerization can, if desired, be carried out in the presence of hydrogen gas or another chain transfer agent to vary the molecular weight of the produced polymer.
Polymerisasjonen utføres fortrinnsvis under betingelser hvorved den aktiverte, bårede Ziegler-katalysator er suspendert i et. flytende fortynningsmiddel slik at polymeren dannes som faste partikler suspendert i det væskeformige fortynningsmiddel. Egnede, fortynningsmidler er f.eks. valgt fra parafiner og cykloparafiner med 3-30 karbonatomer pr. molekyl. Eksempler på fortynningsmidler er isopentan, isobutan og cykloheksan, idet isobutan foretrekkes. The polymerization is preferably carried out under conditions whereby the activated, supported Ziegler catalyst is suspended in a liquid diluent so that the polymer is formed as solid particles suspended in the liquid diluent. Suitable diluents are e.g. chosen from paraffins and cycloparaffins with 3-30 carbon atoms per molecule. Examples of diluents are isopentane, isobutane and cyclohexane, isobutane being preferred.
Polymerisasjonen kan utføres under kontinuerlige eller porsjonsvise betingelser. The polymerization can be carried out under continuous or batchwise conditions.
Metoder for innvinning av polyolefinproduktet er velkjente. Methods for recovering the polyolefin product are well known.
Polymerisasjonskatalysatoren som fremstilles ifølge foreliggende oppfinnelse kan anvendes for fremstilling av etylen-polymerer og kopolymerer med høy tetthet i høyt utbytte og med egenskaper som gjør den egnet for sprøytestøping. The polymerization catalyst produced according to the present invention can be used for the production of ethylene polymers and copolymers with high density in high yield and with properties that make it suitable for injection molding.
Oppfinnelsen illustreres ved følgende eksempler:The invention is illustrated by the following examples:
I eksemplene ble smelteindekset (MI^ -^g) og smelteindekset vedIn the examples, the melt index (MI^ -^g) and the melt index at
høy belastning (MI21 g) bestemt ifølge ASTM metode 1238 under anvendelse av belastninger på henholdsvis 2,16 kg og 21,6 kg; enhetene er gram pr. 10 minutter. "MIR" er smelteindeksforholdet<MI>21,6</MI>2,16- high load (MI21 g) determined according to ASTM method 1238 using loads of 2.16 kg and 21.6 kg respectively; the units are grams per 10 minutes. "MIR" is the melt index ratio<MI>21.6</MI>2.16-
Eksempel IAExample IA
80 g tørket magnesiumacetat ble anbragt i en ovn ved 200°C. Ovnen ble hurtig oppvarmet til 375°C og holdt ved denne temperatur i 20 timer. Ovnen ble spylt med nitrogen i de første 6 timer. 21,3 g grovt, blekgrått pulver ble oppnådd. Pulveret ble malt i en morter. Før bruk ble 10 g av bærermaterialet anbragt i en ovn ved 150°C under vakuum i 2 timer for å sikre tørrhet. Intet ytterligere vekttap ble observert. 57 ml isopropanol og 150 ml cykloheksan ble omrørt i en atmosfære av tørr nitrogen og 36,4 ml TiCl^ble langsomt tilsatt. Den resulterende gule oppløsning ble kokt under tilbakeløp i 2 timer. Oppløsningen fikk avkjøles til 55°C og 10 g av bærermaterialet, fremstilt som beskrevet ovenfor, ble 80 g of dried magnesium acetate was placed in an oven at 200°C. The oven was quickly heated to 375°C and held at this temperature for 20 hours. The oven was flushed with nitrogen for the first 6 hours. 21.3 g of coarse, pale gray powder was obtained. The powder was ground in a mortar. Before use, 10 g of the carrier material was placed in an oven at 150°C under vacuum for 2 hours to ensure dryness. No further weight loss was observed. 57 ml isopropanol and 150 ml cyclohexane were stirred in an atmosphere of dry nitrogen and 36.4 ml TiCl 2 was slowly added. The resulting yellow solution was refluxed for 2 hours. The solution was allowed to cool to 55°C and 10 g of the carrier material, prepared as described above, was
tilsatt. Blandingen ble kokt under tilbakeløp i 3 timer og katalysatoroppslemmingen ble vasket syv ganger med cykloheksan for å sikre at konsentrasjonen av titan i oppløsningsmidlet var mindre enn 1 g/l. Volumet ble øket til 500 ml med tørr cykloheksan og katalysatoren ble håndtert som en oppslemming med et faststoffinnhold på 51 mg/ml. Analyse av katalysatoren ga (vekt/vekt) - Ti 4,77%, Cl 34,26%." added. The mixture was refluxed for 3 hours and the catalyst slurry was washed seven times with cyclohexane to ensure that the concentration of titanium in the solvent was less than 1 g/l. The volume was made up to 500 ml with dry cyclohexane and the catalyst was handled as a slurry with a solids content of 51 mg/ml. Analysis of the catalyst gave (w/w) - Ti 4.77%, Cl 34.26%."
Eksempel IBExample IB
70 g tørket magnesiumacetat ble anbragt i en ovn ved- 200°C. Temperaturen ble hurtig hevet til 600°C. Det ble ikke benyttet noen gass-spyling. Denne temperatur ble holdt i 16 timer og 18,7 g grovt, grått pulver (i likhet med det som 70 g of dried magnesium acetate was placed in an oven at 200°C. The temperature was quickly raised to 600°C. No gas flushing was used. This temperature was maintained for 16 hours and 18.7 g of coarse, gray powder (similar to
ble dannet i eksempel 1), ble oppnådd. Dette ble malt i en morter og en katalysator ble. fremstilt som i eksempel IA. Faststoffinnholdet i denne katalysator var 60,5 mg/ml. Analyse av katalysatoren ga (vekt/vekt) - Ti 5*60%, Cl - 25.,<;>90%. was formed in Example 1), was obtained. This was ground in a mortar and a catalyst was. prepared as in example IA. The solids content of this catalyst was 60.5 mg/ml. Analysis of the catalyst gave (w/w) - Ti 5*60%, Cl - 25.,<;>90%.
Eksempel 2Example 2
80 g hydratisert magnesiumoksalat, Mg^O^. 2H20 ble anbragt i en ovn ved 125°C. Ovnen ble hurtig oppvarmet til 600°C og holdt ved denne temperatur i 17 timer. Ovnen ble spylt med nitrogen i de første 6 timene for å hindre farlig oppbygning av karbonmonooksyd. Vekten av det resulterende, fine hvite pulver var 20,5 g? Bærermaterialet ble fortørket og katalysatoren fremstilt som beskrevet i eksempel IA. Seks vaskinger var nødvendig for å fjerne frie Ti-salter. Faststoffinnholdet i katalysatoroppslemmingen var 79 mg/ml. Analyse av katalysatoren ga: Ti 4,86%, Cl 33,64%. 80 g of hydrated magnesium oxalate, Mg^O^. 2H 2 O was placed in an oven at 125°C. The oven was quickly heated to 600°C and held at this temperature for 17 hours. The oven was flushed with nitrogen for the first 6 hours to prevent a dangerous build-up of carbon monoxide. The weight of the resulting fine white powder was 20.5 g? The carrier material was pre-dried and the catalyst prepared as described in Example IA. Six washings were necessary to remove free Ti salts. The solids content of the catalyst slurry was 79 mg/ml. Analysis of the catalyst gave: Ti 4.86%, Cl 33.64%.
Polymerisas j onPolymerase ion
Polymerisasjoner ble utført under anvendelse av katalysatorene, fra eksempel 1 og 2 i en 2,31 rustfri stålautoklav med rører. Reaktoren ble spylt med nitrogen, oppvarmet til 70°C og deretter ble 2 ml av katalysatoren tilsatt med en sprøyte. Dette ble fulgt av trietylaluminium-ko-katalysator i 1 liter isobutan. Temperaturen ble hevet til 85°C. Det nødvendige trykk av hydrogen ble tilført fulgt av etylen for å bringe total-trykket i reaktorannholdet til 4l,4 bar. Etylen ble tilsatt kontinuerlig, for å opprettholde dette trykk under reaksjonen. Polymerisasjon og data for polymeregenskaper er angitt i neden-stående tabell. Polymerizations were carried out using the catalysts from Examples 1 and 2 in a 2.31 stainless steel stirred autoclave. The reactor was flushed with nitrogen, heated to 70°C and then 2 ml of the catalyst was added by syringe. This was followed by triethylaluminum co-catalyst in 1 liter of isobutane. The temperature was raised to 85°C. The required pressure of hydrogen was supplied followed by ethylene to bring the total pressure in the reactor vessel to 41.4 bar. The ethylene was added continuously, to maintain this pressure during the reaction. Polymerisation and data for polymer properties are given in the table below.
Claims (17)
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GB8031/76A GB1571491A (en) | 1976-03-01 | 1976-03-01 | Supported ziegler polymerization catalyst and components thereof |
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GB (1) | GB1571491A (en) |
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1977
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FR2342993A1 (en) | 1977-09-30 |
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