CA1207498A - Process for the preparation of a polyolefin, and a catalyst for this process - Google Patents
Process for the preparation of a polyolefin, and a catalyst for this processInfo
- Publication number
- CA1207498A CA1207498A CA000405526A CA405526A CA1207498A CA 1207498 A CA1207498 A CA 1207498A CA 000405526 A CA000405526 A CA 000405526A CA 405526 A CA405526 A CA 405526A CA 1207498 A CA1207498 A CA 1207498A
- Authority
- CA
- Canada
- Prior art keywords
- reaction
- temperature
- hydrocarbon
- titanium tetrachloride
- component
- 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
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims description 23
- 238000002360 preparation method Methods 0.000 title claims description 12
- 229920000098 polyolefin Polymers 0.000 title abstract description 5
- 239000011777 magnesium Substances 0.000 claims abstract description 62
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 38
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 21
- 239000011541 reaction mixture Substances 0.000 claims abstract description 14
- 150000001348 alkyl chlorides Chemical class 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 46
- -1 ethylene, propylene, 1-butene Chemical class 0.000 claims description 45
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 36
- 239000005977 Ethylene Substances 0.000 claims description 36
- 239000007787 solid Substances 0.000 claims description 34
- 239000007795 chemical reaction product Substances 0.000 claims description 21
- 229930195733 hydrocarbon Natural products 0.000 claims description 21
- 150000002430 hydrocarbons Chemical class 0.000 claims description 20
- 239000004215 Carbon black (E152) Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 230000000737 periodic effect Effects 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 150000002902 organometallic compounds Chemical class 0.000 claims description 6
- 239000002685 polymerization catalyst Substances 0.000 claims description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 14
- 235000001055 magnesium Nutrition 0.000 abstract 2
- 229940091250 magnesium supplement Drugs 0.000 abstract 2
- 239000004698 Polyethylene Substances 0.000 description 39
- 239000010936 titanium Substances 0.000 description 38
- 229920000573 polyethylene Polymers 0.000 description 35
- 239000000725 suspension Substances 0.000 description 24
- 239000000843 powder Substances 0.000 description 23
- 229910052782 aluminium Inorganic materials 0.000 description 21
- 239000002283 diesel fuel Substances 0.000 description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 17
- 229910052719 titanium Inorganic materials 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000000460 chlorine Substances 0.000 description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 239000007789 gas Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000010414 supernatant solution Substances 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000003682 vanadium compounds Chemical class 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 229910019438 Mg(OC2H5)2 Inorganic materials 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 229960003750 ethyl chloride Drugs 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- CMWCOKOTCLFJOP-UHFFFAOYSA-N titanium(3+) Chemical compound [Ti+3] CMWCOKOTCLFJOP-UHFFFAOYSA-N 0.000 description 2
- 101100058670 Aeromonas hydrophila subsp. hydrophila (strain ATCC 7966 / DSM 30187 / BCRC 13018 / CCUG 14551 / JCM 1027 / KCTC 2358 / NCIMB 9240 / NCTC 8049) bsr gene Proteins 0.000 description 1
- 241000861718 Chloris <Aves> Species 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 101000837192 Drosophila melanogaster Teneurin-m Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 241000286904 Leptothecata Species 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- SOGXWMAAMKKQCB-UHFFFAOYSA-M chloroalumane Chemical class Cl[AlH2] SOGXWMAAMKKQCB-UHFFFAOYSA-M 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- JCYWCSGERIELPG-UHFFFAOYSA-N imes Chemical class CC1=CC(C)=CC(C)=C1N1C=CN(C=2C(=CC(C)=CC=2C)C)[C]1 JCYWCSGERIELPG-UHFFFAOYSA-N 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- LMHHRCOWPQNFTF-UHFFFAOYSA-N s-propan-2-yl azepane-1-carbothioate Chemical compound CC(C)SC(=O)N1CCCCCC1 LMHHRCOWPQNFTF-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Abstract of the disclosure:
Polyolefins having a broad molecular weight dis-tribution are obtained in a very high yield even using, as the catalyst, a product from the reaction of a mag-nesium alcoholate with titanium tetrachloride, if the reaction between the magnesium alcoholate and the titanium tetrachloride is carried out at a relatively low tempera-ture and the reaction mixture is then heated to a fairly high temperature in order to split of alkyl chlorides.
Polyolefins having a broad molecular weight dis-tribution are obtained in a very high yield even using, as the catalyst, a product from the reaction of a mag-nesium alcoholate with titanium tetrachloride, if the reaction between the magnesium alcoholate and the titanium tetrachloride is carried out at a relatively low tempera-ture and the reaction mixture is then heated to a fairly high temperature in order to split of alkyl chlorides.
Description
¦ - 2 - HOE 81/F 146 Processes are known for the preparation of poly-olefins by means of catalysts which are formed by reacting magnesium alcoholates and/or complex ma~nesium alcoholates with transition metal halides. ~German Auslegeschriften 1,795,197 and 1,957,679 and German Offenlegungsschrift
2,0~0,566).
In one case9 a temperature range of O to 200C is recommended for the reaction of the magnesium compound and the chlorine-containing titanium compound, but the upper temperature limit should be so chosen that no decomposition products are formed. In addition to the high activity of the polymerization catalysts, it is mentioned as a special advantage that it is possible to prepare ethylene homo-polymers and ethylene/~-olefin copolymers which have a narrow molecular weight distribution (German Auslegeschriften : 15795,197 and 1,957,679~.
In another case, the reaction of the metal alco-holate with the transition metal compound is carried out in the presence or absence of an inert diluent at tempera-tures of 40 to 210C; the duration of the reaction is, in general, between 5 and 240 minutes (German Offenlegungs-schrift 2,000,566). An express warning is given against a longer reaction time, since it is alleged to cause an impairment Qf the properties of the catalyst. In this publication too9 it is mentioned as an advantage of the catalysts that they have a high activity and that it is possible to prepare polyolefinswhich have a narrow ~ . . ~. . .
1~3'74~3 _ 3 _ molecular wei~ht distribution. A cata]y.st which i5 obt~ined by reacting magnesium ethylate ~Jith van~ium tetrach~oride and which produces a polyethylene having a broad molecular weight distribution is described at the same time. However, vanadium compounds have the great disadvantage that, in cortrast with titanium compounds, they are extremely toxic.
Products containing vanadium compounds can, the~efore, only be employed to a limited extent. In addition, high costs are incurred in working up the catalyst mother liquors if vanadium compounds are employed in industrial polymerization processes.
The problem was therefore presented of finding polymerization catalysts based on a magnesium alcoholate, by means of which polyolefins having a broad molecular weight distribution can be prepared in a high yield.
It has now been found that polyolefins having a broad molecular weight distribution can be obtained in a - very high yield~even using the products of the reaction of magnesium alcoholates with titanium tetrachloride, if the reaction between the magnesium alcoholate and the titanium tetrachloride is carried out at a relatively low temperature and the reaction mixture is then subjected to a heat treatment at a fairly high temperature in order to split off alkyl chlorides.
The invention relates therefore to a process for the polymerization of a 1-olefin of the formula R4CH=CH2 in which R4 denotes hydrogen or an alkyl radical having 1 to 10 carbon atoms, in the presence of a catalyst com-posed o~ the product from the reaction of a magnesium alcoholate with titanium tetrachloride (component A) and an organometallic compound of Groups I to III of the periodic system (component B), which comprises carrying out the polymerization in the presence of a catalyst in which the component A has been prepared by a procedure in which, in a first reaction stage, a magnesium alco~olate }~s been reacted with titanium tetrachloride in a hydrocarbon at a temperature of 50 to 100C, the reaction mixture formed is subjected, in a second reaction stage, to a heat treat-10 ment at a temperature of 110 to 200C, until no further ~ alkyl chloride is split off, and the sclid is then freed j from soluble reaction products by washing several times t with a hydrocarbon.
. . ~ -- --- -- -- . .
The invention also relates, however, to the cata~
lyst used for this process and to its preparation.
~ A magnesium alcoholate iis used for the preparation ¦ of the component A. This magnesium alcoholate can be a "simple" magnesium alcoholate of the formula Mg(OR)2 in which R denotes identical or dif~erent alkyl radicals having l to 6 carbon atoms. Examples are Mg(OC2H5)2,
In one case9 a temperature range of O to 200C is recommended for the reaction of the magnesium compound and the chlorine-containing titanium compound, but the upper temperature limit should be so chosen that no decomposition products are formed. In addition to the high activity of the polymerization catalysts, it is mentioned as a special advantage that it is possible to prepare ethylene homo-polymers and ethylene/~-olefin copolymers which have a narrow molecular weight distribution (German Auslegeschriften : 15795,197 and 1,957,679~.
In another case, the reaction of the metal alco-holate with the transition metal compound is carried out in the presence or absence of an inert diluent at tempera-tures of 40 to 210C; the duration of the reaction is, in general, between 5 and 240 minutes (German Offenlegungs-schrift 2,000,566). An express warning is given against a longer reaction time, since it is alleged to cause an impairment Qf the properties of the catalyst. In this publication too9 it is mentioned as an advantage of the catalysts that they have a high activity and that it is possible to prepare polyolefinswhich have a narrow ~ . . ~. . .
1~3'74~3 _ 3 _ molecular wei~ht distribution. A cata]y.st which i5 obt~ined by reacting magnesium ethylate ~Jith van~ium tetrach~oride and which produces a polyethylene having a broad molecular weight distribution is described at the same time. However, vanadium compounds have the great disadvantage that, in cortrast with titanium compounds, they are extremely toxic.
Products containing vanadium compounds can, the~efore, only be employed to a limited extent. In addition, high costs are incurred in working up the catalyst mother liquors if vanadium compounds are employed in industrial polymerization processes.
The problem was therefore presented of finding polymerization catalysts based on a magnesium alcoholate, by means of which polyolefins having a broad molecular weight distribution can be prepared in a high yield.
It has now been found that polyolefins having a broad molecular weight distribution can be obtained in a - very high yield~even using the products of the reaction of magnesium alcoholates with titanium tetrachloride, if the reaction between the magnesium alcoholate and the titanium tetrachloride is carried out at a relatively low temperature and the reaction mixture is then subjected to a heat treatment at a fairly high temperature in order to split off alkyl chlorides.
The invention relates therefore to a process for the polymerization of a 1-olefin of the formula R4CH=CH2 in which R4 denotes hydrogen or an alkyl radical having 1 to 10 carbon atoms, in the presence of a catalyst com-posed o~ the product from the reaction of a magnesium alcoholate with titanium tetrachloride (component A) and an organometallic compound of Groups I to III of the periodic system (component B), which comprises carrying out the polymerization in the presence of a catalyst in which the component A has been prepared by a procedure in which, in a first reaction stage, a magnesium alco~olate }~s been reacted with titanium tetrachloride in a hydrocarbon at a temperature of 50 to 100C, the reaction mixture formed is subjected, in a second reaction stage, to a heat treat-10 ment at a temperature of 110 to 200C, until no further ~ alkyl chloride is split off, and the sclid is then freed j from soluble reaction products by washing several times t with a hydrocarbon.
. . ~ -- --- -- -- . .
The invention also relates, however, to the cata~
lyst used for this process and to its preparation.
~ A magnesium alcoholate iis used for the preparation ¦ of the component A. This magnesium alcoholate can be a "simple" magnesium alcoholate of the formula Mg(OR)2 in which R denotes identical or dif~erent alkyl radicals having l to 6 carbon atoms. Examples are Mg(OC2H5)2,
3 7 ~ 3 7)2' Mg(nC4Hg)2- Mg(OC~3)(0C2H ) and Mg(OC2H5)(0nC3H73. It is also possible to use a "simple"
magnesium alcoholate o~ the formula Mg(OR)nX~ in which X
is halogen- (~4)1/2~ OH~ (C3)1/2' (P4)1/3 i 25 the meaning mentioned above and n + m is 2.
It is also possible, h~ever, to em?loy a "complex" magnesium alcoholate. me tenm "complex" magnesium alcoholate describes a magnesium alcoholate which, as well as magnesium, contains at least one meta] o~ the 1st to 4th main group of the ~2~'7gL98 .
periodic system. The following are examples of a complex t . magnesium alcoholate of this type: ~Mg(OiC3H7)4~Li2;
¦ 2 3 7~8]Mg; [SitOC2H5~63Mg; [Mg(OC H ) ]Na;
~Al2(0iC~Hg)~Mg; and [Al2(0~secC4Hg)6(0C2H5)2~Mg. The complex magnesium alcoholates (alkoxo salts~ are pr~epared by known methods (literature references: Meerwein; Ann.
455 (1927), page 234 and 476 (1929), page 113, Houben~
Weyl, Methoden der organischen Chemie ~"Methods of organic chemistry"], volume 6/2, page 30). The following examples of the preparation of the complex magnesium alcoholate may be mentioned: -1 1. Two metal alcoholates are allowed to act on one another in a suitable solvent, for example 2Al(OR~3 ~ Mg(OR)2 ~ fAl2~0R)B]Mg 2. Magnesium is dissolved in an alcoholic solution of a metal alcoholate 1 2LiOR + Mg ~ 2 ROH ~ lMg(OR)4]Li2 ~ ~2 3. Two metals are dissolved in alcohol simultaneously B ROH + Mg + 2 Al ~ lAl2(OR)~]Mg ~ 4 H2 The simple magnesium alcoholates, in particular Mg(OC2H5)2, Mg~OnC3H7)2 an~d M~(OiC3H7)2 are ~referably used. The magnesium alcoholate is employed in a - pure form or fixed on a support.
The preparation of the component A is effected in b 25 two reaction stages at different temperatures.
In the first reaction stage? the magnesium alco-holate is reacted with titanium tetrachloride ~t a tempera-ture of 50 to 100C, preferably 60 to 90C, in the presence of an inert hydrQcarbon and while stirring. 1 to 5 moles 0'74~3 of titanium te~rachloride are employed for 1 mole of mag-¦ nesium alcoholate, preferably 1.4 to 3.5 moles o~ titanium tetrachloride for 1 mole of magnesium alcoholate.
A suitable inert hydrocarbon is an aliphatic or 5 cycloaliphatic hydrocarbon, such as butane, pentane, hexane, heptane, isooctane, cyclohexane or methylcyclohexane, and an aromatic hydrocarbon, such as toluene or xylene; it is also possible to ~se a hydrogenated diesel oil or gasoline fraction which has been carefully freed from oxygen, sulfur 10 compounds and moisture.
i~
The reaction time in the ~irst stage is 0.5 to 8 hours, preferably 2 to 6 hours.
A substantial replacement of the alkoxy groups of the magnesium alcoholate by the chlorine atoms of the 15 titanium tetraGhloride takes place in the first reaction ~tage. The reastion product obtained in this stage is a I solid which is insoluble in hydrocarbons and contains ¦ magnesium and titanium, and tltanium compounds wh~ch are soluble in hydrocarbon5 and contain chlorine and alkoxy 20 groups.
In the second reaction stage, the resulting reaction mixture is subjected to a heat treatment at a temperature ! of 110 to 200C, preferably 110 to 160C9 while stirring.
During this heat treatment, the titanium content of the 25 hydrocarbon-insoluble solid increases greatly and alkyl chlorides are split off. It is assumed that the soluble titanium alkoxychloridesare converted, by the splitting off of alkyl chlorides,into condensed titanates which are insoluble in hydrocarbons and which are precipitated ~g l Z(~749B
¦ on the solid. The heat treatment is carried out until no further alkyl chloridesare split off. As a rule, a re-action time of 1~ to 100 hours is required for this.
All the soluble reaction products are then removed by washing several times with a hydrocarbon, and a solid which is insoluble in the hydrocarbon and which contains magnesium and titanium, i5 obtained; this will be desig-; nated component A.
The polymerization ca~alyst to be used in accordance with the invention is prepared by bringing into contactwith one another the component A and an organometallic com-pound of Groups I to III of the periodic system ~component It is preferable to use organoaluminum compounds as the component B. Suitable organoaluminum compounds are organoaluminum compounds containing chlorine9 the dialkyl-I aluminum monochlorides of the formula R2AlCl or the alkyl-aluminum sesquichlorides of the formula R3Al2C13 in which R~ can be identical or different alkyl radicals having I to 16 carbon atoms. The following may be mentioned as examples: (C2H~)2AlCl, (iC4Hg)2AlCl and (C2H533Al2Cl3.
It is particularly preferable to employ chlorine~
free compounds as the organoaluminum compounds. Compounds suitable for this purpose are, firstly, the products from the reaction of aluminum trialkyls or aluminum dialkyl~
hydrides with hydrocarbon radicals having 1 to 6 carbon atoms, preferably the reaction of Al(iC4Hg)3 or Al(iC4Hg)~H
with diolefins containing 4 to 20 carbon atoms, preferably isoprene. Aluminum isoprenyl may be mentioned as an ~ 374~8 ëxarnple.
¦ Secon~ly 9 chlorine-free organoaluminum compounds of this type are aluminum trialkyls AlR3 or aluminum di-alkylhydrides of the formula AlR2H in which R3 denotes identical or different alkyl radicals having 1 to 16 carbon atoms. Examples are Al(C2H5)3, Al(C2H5)2H, Al(C H ~3, Al(C3H7)2H9 Al(iC4Hg)3, 4 9 2 Al(C H 7)3, Al~C12~25)3~ Al(C2H5)(C12 2S)2 Al(iC4Hg)(C12H25)2 It is also possible to employ mixtures of organo-metallic compounds of -C-roups I to III of the periodic system, particularly mixtures of different organoaluminum compounds. The following mixtures may be mentioned as exa~ples: Al~C2H5)3 and Al(iC4H9~3, Al(C2H5)2Cl and Al(C H 7)3, Al(C2H5)3 and Al(C8H17)3, 4 9 2 ~l(C8H17)3, Al(iC~Hg)3 and Al(C8H17)3, Al(C2H5)3 and Al(C H 5)3, Al(iC4Hg)3 and Al(C12H25)3, 2 5 3 16H33)3~ Al(C3H7)3 and Al(Cl~H37)2(iC4H9) or Al(C2H5)3 and aluminum isoprenyl (the reaction product of isoprene with Al(iC4Hg)3 or Al(iC4Hg)2H~.
The component A and the component B can be mixed in a stirred kettle at a temperature of -30C to 150C, preferably -10 to 120C, before the polymerization. It is also possible to combine the two components directly in the polymerization kettle at a polymerization temperature of 20 to 200C. The addition of the component B c~n, how-ever9 also be effected in two stages by pre-activating the component A with part of the component B at a temperature of -30C to 150UC before the polymeriz~tion reaction, and ;,~
~L~07~'~8 adding the remainder of the component B in the polymer-ization reactor at a temperature of 20 to 200C.
The polymerization catalyst to be used in accord-~nce with the invention is employed for the polymerization of 1-olefins of the formula R CH=CH2 in which R4 denotes hydrogen or an alkyl radical having 1 to 10 carbon atoms, for example ethylene, propylene, l-butene, 1-hexene9 4-methyl-l-pentene or 1-octeneO It is preferable to poly-imerize ethylene on its own or in the form of a mixture ~10 containing at 7east 70% by weight of ethylene and not more ¦than 30~ by weight of another l-olefin of the above formula.
¦In particular9 ethylene is polymerized on its own, or a mix-ture containing at least ~P/Oby weight of e~hylene and not more than l~/o by weight of another 1-olefin of the above fon~a is polymerized.
j 15 The polymerization is carried out in a known manner in solution, in suspension or in the gas phase, continuously ¦ or discontinuously, in a single stage or in several stages and at a tempe~ature of 20 to 200C, preferably 50 to 150C.
The press~re is 0~5 to 50 bar. Polymerization within t~e pressure range li20 f~l5 to 30 bar, which is of partic~ar interest in industry,is preferred. ,-In this polymerization, the component A is used in a concentration, calculated as titanium, of 0.0001 to 1, pre~erably 0.001 to 0.5, mmole of Ti per liter of dispersion medium or per liter of reactor volume. me organometallic compound is used in a concentration of 0.1 to 5 mmoles, preferably 0.5 to 4 mmoles, per liter of dispersion medium or per liter of reactor volume. In prin-ciple, however, higher concentrations are also possible.
Suspension polymeriæation is carried cut in an inert dispersion medium which is customary for the Ziegler ~L~07~
low-pressure process, for example in an aliphatic or cyclo-aliphatic hydrocarbon; butane, pentane, hexane, heptane, i~ooctane, cyclohexane or methylcyclohexane may be mentioned as examples of such a hydrocarbon. It is also possible to use a gasoline or hydrogenated diesel oil fraction which has been carefully freed from oxygen, sulfur compounds and moisture. The molecular weight of the polymer is regulated in a known manner; it is preferable to use hydro-gen for this purpose.
As a result of the high activity of the c~talyst to be used, the process according to the invention produces ~ polymers havin~ a very low content of titanium and halogen I and, therefore, extremely good values in the test for color stability and corrosion. It also makes it possible to prepare polymers having a very broad molecular weight distribution; the Mw/Mn values of the polymers are over 10.
A further decisive advantage of the process accord-ing to the invention can be seen in the fact that it makes it possible to prepare polymers having molecular weights which differ very greatly, merely by varying the eoncen-tration of hydrogen. For example~ polymers having molecular weights above 2 million are formed in a polymerization in the absence of hydrogen, and polymers having molecular weights in the region of 30,000 are formed at hydrogen contents of 70% by volume in the gas space.
The polymers can be fabricated at high throughput rates by the extrusion and blow-extrusion process to give hollow articles, tubes, cables and films which have smooth ,~,;,~
.
~Z0749~
t surfaces.
: By virtue of a special structural composition, the hollow articles and bottles produced from the polyolefins obtained in accordance with the invention are distinguished 5 by a considerable lack of sensitivity to stress crackingO
Furthermore 9 the process according to the invention makes it possible to prepare, by suspension and gas phase polymerization, free-flowing polymer powders having high bulk densities, so that they can ~e processed further ! 10 directly to give shaped articles without a granulation I stage.
¦ EXAMPL~S
, In the examples which follow, a hydrogenated diesel oil fraction having a boiling range of 130 to 170C is used ~or the preparation of ~he catalyst and for the polymerization.
The titanium content of the cataiysts is determined colorimetrically (literature reference: GØ Mùller~
Prakti~um der quantitativen chemischen Analyse ["Practical manual of quantitative chemioal analysis"], 4th edition (1957), page 243)~ ~
The melt index MFI is determined as specified in DIN 53,735 (E).
The Mw/Mn values are determined from the fraction-ation data of a gel permeation chromatograph at 130C,using 1,2,4-trichlorobenzene as the solvent and eXtraction medium.
The intrinsic viscosity is determined as specified in DIN 53,728, sheet 4, using an Ubbelohde viscometer~
~ 2~791~
with decahydronaphthalene as the solvent.
¦ The density is determined as specified in DIN
53,47g and the bulk density as specified in DIN 53,468.
Example 1 a) Preparation of the component A
114.3 g of magnesium ethylate were-dispersed, under a blanket of N2, in 1.5 l of a diesel oil fraction in a3 lfour-necked flask equipped with a dropping funrlel, KPG stirrer, a reflux conden~er and a thermometer. 332 g of titanium tetrachloride were added dropwise at 90C to ¦ this dispersion in the course of 2 hours. The mixture was then warmed to 130C and was stirred at this temperature for ~0 hours. A gentle stream of N2 was passed over the reaction mixture during the whole reaction time in order to expel gaseous reaction products, and this stream was then passed through a cold trap cooled with methanol/solid carbon dioxide. The evolution of gaseous reaction products was complete after 60 hours. 116 g of a water-white liquid o~ the following composition: Cl = 55% by weight, C =
37% by weight and H = 8% by weight were collected in the cold trap. This was ethyl chlori~e, The reaction product was then washed with the diesel oil fraction mentioned above, until the supernatant solution no longer contained any titanium.
~5 After drying, the solid (component A) had the following analytical composition:
Ti 25.4% by weight Mg 9.5% by weight Cl 50.2% by weight .~ .
12~
The Cl : Ti atomic ratio was 2.67.
¦ b) Pre-activation of the component A
19 g of the component A were made up to 190 ml with diesel oil, and 100 ml of an aluminum triisobutyl 5 solution containing 1 mole of Al(iC4Hg)3 per 1 l of sol-ution were added at 20C, while stirring. 45% by weight of the tetravalent titaniumwere reduced to titanium-(III) by this means.
c) Polymerization of ethylene in suspension I 10 100 l of diesel oil 7 30 mmoles of aluminum tri-¦ isobutyl and 8.7 ml of the dispersion described under b) were charged to a 150 l kettle. 5 kg per hour of ethylene and sufficient H2 to give an H2 content of 55% by ~olume in the gas space were then passecl in, at a polymerization temperature of 8SC. After 6 hours the polymerization . was terminated at a pressure of 25.3 bar, by releasing the pressure. The suspension was filtered and the poly-ethylene powder was dried by passing hot nitrogen over r it.
28.7 kg of polyethylene were obtained. This corresponds to a catalyst activity of 50.4 kg of polyethylene/g of catalyst solid (component A) or 9.5 kg of polyethylene/mmole of Ti. The polyethylene powder had an MFI 190/5 of 0.54 gJ10 minutes. The breadth of molec-L 25 ular weight distribution Mw/Mn was 22 and the MFI 190/15J
MFI 190/5 was 11.5. The density of the powder was 0.955 g/
cm3 and its bulk density was 0.49 g/cm3.
, ~, 12'~3'7~9~
; Example 2 Polymerization of ethylene in suspension 100 mmoles of aluminum triisobutyl and 2.2 ml of the dispersion described in Example lb) were charged to the kettle under the same conditions as those described ln Example lc). 5 kg per hour of ethylene were then passed in at a polymerization temperature of 75C. After 6 hours the polymerization was terminated at a pressure of 24.8 bar, by releasing the pressure. The suspension was filtered and the polyethylene powder was dried by passing hot nitrogen over it. 27.9 kg of polyethylene were obtained.
This corresponds to a catalyst activity of 194 kg of polyethylene/g of catalyst solid or 36.5 kg of poly-ethylene/mmole of Ti. The polyethylene powder had an intrinsic viscosity of 2~400 ml~g; this corresponds to a molecular weight of 2 million. Its bulk density was 0.45 g/cm3.
Example 3 Polymerization of ethylene in suspension 100 mmoles of aluminum triisobutyl and 29 ml of the dispersion described in Example lb) were charged to the kettle under the same conditions as those described in Example lo). 4 kg per hour of ethylene and sufficient H2 to give an H2 content of 75% by volurne in the gas space were then passed in at a polymerization temperature of 85C. After 6 hours the polymerization was terminated at a pressure of 25.6 bar, by releasing the pressure.
The suspension was filtered and the polyethylene powder was dried by passing hot nitrogen over it. 23.6 kg of : , :~2~7~9l5~
polyethylene were isolated. This corresponds to a catalyst yield of 12.4 kg of polyethylene/g of catalyst solid or 2.3 kg of polyethylene/mmole of Ti. The poly-ethylene had an MFI 190/5 of 105 g/10 minutes, an intrinsic viscosity of 110 ml/g, a density o~ 0.965 g/cm3 and a bulk density of 0.50 g/cm3 . The breadth of molecular weight distribution Mw/Mn was 25.
Example 4 Copolymerization of ethYlene and l-decene in suspension 750 ml of hexane, 5 mmoles of aluminum isoprenyl and 2.9 mg of the component A obtained in accordance with Example lb~ were charged to a 1.5 l steel autoclave. H2 was then injected at 8 bar, and ethylene at 14 bar~ at a polymerization temperature of 85~C. The ethylene was subsequently metered in at such a rate that a total pressure of 22 bar was maintain~d. 20 ml per hour of 1-decene were metered in at the same time. The experiment was discontinued after 6 hours. The copolymer was isolated by filtration and dried in a vacuum drying cabinet. 156 g of copolymer were obtained. This corresponds to a ! catalyst yield of 53.8 kg of polymer/g of catalyst solid or 10.1 kg of polymer/mmole of Ti. The ethylene/1-decene ~ copolymer had a melt index MFI 190/5 o* 0.68g/10 minutes ¦ and a density of 0.950 g/cm3 1 25 Example 5 Copolymeri~ation of ethylene and 1-hexene in suspension 360 l of hexane, 360 mmoles of aluminum isoprenyl and 58 ml of the dispersion described in Example lb) were initially taken in a 500 l kettle. 17 kg/hour of ethylene, ` ''~ .
7~
2 ~/hour of 1-hexene and sufficient H2 to set up an H2 con-tent of 45% by volume in the gas space were then passed in at a polymerization temperature of 85C.
After 6 hours the polymerization pressure had risen to 8.2 bar, and the polymerization was discontinued by releasin~ the pressure. The polymer powder was iso-lated by filtration and was dried with hot nitrogen.
100.4 kg of polymer were obtained. This corresponds to a catalyst yield of 26.4 kg of polymer/g of cata-lyst solid or 5.0 kg of polymer/mmole of Ti.
The ethylene/1-hexene copolymer had a melt index MFI 190/5 of 0.9 g/10 minutes, an MFI 190/15/MFI 190/5 ratio of 9.8, a density of 0.942 g/cm3 and a bulk density of 0.42 g/cm3.
Bottles were produced from the powder on a blow-molding apparatus for bottles (extruder screw: D = 60 mm).
A very high output, 62 kgJhour, was obtained at a screw speed of 40 r.p.m. The bottles had a very smooth surface and had a very high resistance to stress cracking, over 1,000 hours, in the Bell stress cracking test.
Example _ Copolymeri ation of ethylene and 1-butene in suspension 720 mmoles of aluminum triisobutyl and 58 ml of the dispersion described in Example lb) were charged under the same conditions as those described in Example 5. 17 kg per hour of ethylene and 4 l per hour of 1-butene were added at 65C. Sufficient H~ was passed in to give a concentration of 40% by volume of the latter in the gas space. After 6 hours the polymerization was discontinued .~ , , 3 ` ~2~
~ at a final pressure of 6.7 bar, by releasing the pressure.
f The suspension was cooled to room temperature and the solid was isolated by filtration and dried with hot 108.4 kg of product having an MFI 190/5 of 1.8 g/
10 minutes, an MFI 190/15/MFI 190/5 of 10.4, a density of 0.920 g¦cm3 and a bulk density of 0.30 g/cm3 were obtained. This corresponds to a ca~talyst yield of 28.S kg-of copolymer/g of c~talyst solid or 5.4 kg of copolymer/mmole of Ti.
. ~
Polymerization of ethylene in the gas phase 500 g of polyethylene powder (M~I 190/5 = 1.5 g/
10 minutes; bulk density = 0.45 g/cm3) were initially ¦ 15 taken in a 20 l horizontal reactor equipped with a stirrer operating close to the wall. The reactor was freed from ¦ air by being evacuated several t;imes and flushed for ¦ several hours with ethylene and was then warmed to 80C.
50 mmoles of aluminum triisobutyl and 94.3 mg of the cata-lyst component A prepared in accordance with Example la) were added to the reactor.
400 g/hour of ethylene and sufficienk hydrogen to ! keep the proportion of hydrogen in the gas space at 30%
¦ by volume during the polymerization were passed in. The pressure rose to 15 bar during the reaction time.
After 12.5 hours the polymerization was discontinued.
5.4 kg of polyethylene having an MFI 190/5 value of 0.6 g/
10 minutes were obtained. This corresponds to a catalyst yield of 52 kg of polyethylene/g of catalyst solid ~, .
~20~8 or 9.8 kg of polyethylenetmmole of Ti.
I Comparison Example A
¦ a) ~paration of the component A
114.3 g of magnesium ethylate were dispersed, under a blanket of N2, in 1.5 l of a diesel oil fraction in a 3 l four-necked flask equipped with a dropping funnel, - a KPG stirrer, a reflux condenser and a thermometer. 332 g of titanium tetrachloride were added dropwise at 90C to this dispersion in the course of 2 hours. The reaction j 10 product was then washed with the diesel oil fraction until ¦ the supernatant solution no longer contained any titanium.
After drying, the solid (component A) had the following ¦ analytical composition:
; . Ti 4. 9% by weight Mg 19.8% by weight ! Cl 61.3% by weight.
b) Pre-activation of the component A
98 g of the component A were suspended in sufficient diesel oil to give a volume of suspension of 190 ml, and 100 ml of an aluminum triisobutyl solution containing 1 mole of Al(iC4Hg)3 per 1 l were added at 20~C, while stirring9 52% by weight of the tetravalent titanium were reduced to titanium-(III) by this means.
c~ Pol~merization of ethylene in suspension 100 l of hexane, 30 mmoles of aluminum triisobutyl and 14.5 ml of the suspension described under ~) were charged to a 150 l kettle. 5 kgthour of ethylene and sufficient H2 to set up a hydrogen content of 30% by vol--ume in the gas ~pace were then passed in at 85C. After ::~2~[~7~9~3 6 hours the polymerization was discontinued at a pressure of 4.6 bar, by releasing the pressure. 29~6 kg of poly-ethylene were obtained~ This corresponds to a catalyst yield of 6.1 kg/g of catalyst solid or 5.9 kg of polyethylene/mmole of Ti.
The product had an MFI 190/5 value of 1.6 g/10 minutes, an MFI 190/15/MFI 190/S value of 5.2, a density of 0.956 g/cm3 and a bulk density of 0.42 g/cm3. The . product had a narrow molecular weight distribution:
I 10 Mw/Mn = 4.70 An output of 43 kg/hour was obtained at a screw speed of 40 r.p.m. when processing the powder on the blow~molding apparatus for hollow articles also used in Exa~le 5. The bottles had a rough surface, since melt fracture occurred when they were processed. The resistance to stress cracking of the bottles in the Bell test was 68 I hours.
! d) Polymerization of ethylene in suspension 100 l of diesel oil, 30 mmoles of aluminum tri-isobutyl and 8.7 ml of the dispersion described under b)were charged to a 150 l kettle. 5 kg per hour of ethylene and sufficient H2 to give an H2 content of 55% by volume in the gas space were then passed in at a polymerization temperature of 85C. After 6 hours -the polymerization was terminated at a pressure of 20.4 bar, by releasing the pressure. The suspension was filtered and the po]y~
ethylene powder was dried by passing hot nitrogen over it.
28.2 kg of polyethylene were obtained. This corresponds to a catalyst activity of 9.6 kg of 9~.
polyethylene/g of catalyst solid or 9.4 kg of polyethylene/
mmole of Ti. The polymer powder had an MFI 190/5 o~ 28 g/
10 minutes. The breadth of molecular weight distribution Mw/Mn was 4.6 and the MFI 190/15/MFI 190/5 was 5.4. The density of the powder was 0.960 g/cm3 and its bulk density was 0.41 g/cm3.
Example 8 I a) Preparation of the component A
114.3 g of magnesium ethylate were dispersed, under a blanket of N2, in 1.5 l of a diesel oil ~raction in a 3 l four-necked flask equipped with a dropping funnel, a KPG stirrer~ a reflux condenser and a thermometer.
569 g of titanium tetrachloride were added dropwise at 90C to this dispersion in the course of 2 hours. The mixture was then warmed to 130C and stirred at this temperature for 60 hours. A gentle stream of N2 was passed over the reaction mixture during the whole reaction time in order to expel gaseous reaction products, and this stream was then passed through a cold trap cooled with methanol/solid carbon dioxide~ The evolution of gaseous reaction products was complete after 60 hours.
107 g of a water-white liquid oi` the following composition:
Cl = 5S% by weight, C = 37% by weight and H = 8% by weight were collected in the cold trap. This was ethyl chloride.
The reaction product was then washed with the diesel oil fraction until the supernatant solution no longer con-tained any titanium.
After drying, the solid ~component A) had the following analytical composition:
~ 2 0 7 ~ ~
¦ Ti 24. 7% by weight Mg 9.7% by weight ¦ Cl 51.2% by weight.
The Cl : Ti atomic ratio was 2.80.
b) Pre-activation of the component A
19.4 g of component A were made up to 190 ml with diesel oil, and 100 ml of an aluminum triisobutyl solution containing 1 mole of Al(iC4Hg~3 per 1 1 were added at 20C, while stirring. 47% by weight of the tetravalent titanium were reduced to titanium~(III) by this means.
c) Polymerization of ethylene in suspension 100 l of diesel oil, 25 mmoles of aluminum tri-! isobutyl and 8.0 ml of the dispersion described under b) were charged to a 150 l kettle. 5 kg per hour of ethylene and sufficient ~2 to give an H2 content of 55% by volume in the gas space were then passed in at a polymerization temperature of 85C. A~ter 6 hours the polymerization was terminated at a pressure of 22.4 bar, by releasing the pressure. The suspension was filtered and the polyethylene powder was dried by passing hot nitrogen over it.
27.S kg of polyethylene were obtained. This corresponds to a catalyst activity of 51.4 kg of polyethylene/g of catalyst solid or 10 kg of polyethylene/
mmole of Ti. The polyethylene powder had an MFI 190/5 of 0.94 g/10 minutes. The breadth of molecular weight distribution Mw/Mn was 26 and the MFI 190/15/MFI 190/5 was 11.9. The density of the powder was 0.956 g/cm3 and its ~ulk density was 0.47 g/cm3.
:~Z~ L9~
Example 9 .
a) Preparation of the component A
142.3 g of magnesium isopropylate were dispersed7 under a blanket of N2, in 1.0 l of a diesel oil fraction ; 5 in a 3 l four~necked flask equipped with a dropping funnel, a KPG stirrer, a reflux condenser and a thermometer. 285 g of titanium tetrachloride were added dropwise at 75C to this dispersion in the course o~ 4 hours. The mixture was then warmed to 110C and w~s stirred at this tempera-ture for 45 hours. A gentle stream of N2 was passed over the reaction mixture during the whole reaction time in order to expel gaseous reaction products, and this stream was then passed through a &old trap cooled with methanol/
solid carbon dioxide. The evolution of gaseous reaction products was complete after 60 hours. 156 g of a water-white liquid of the following composition: Cl = 45% by weight, C = 46% by weight and H = 8.9% by weight were collected in the cold trap. Thira was isopropyl chloride.
The reaction product was then washed with the diesel oil fraction mentioned above, until the supernatant solution no longer contained any titanium.
After drying, the solid ~component A) contained the following:
Ti 26.6% by weight Mg 9.0/0 by weight Cl 52.5% by weight.
The Cl : Ti atomic ratio was 2.67.
~2C)7~
b) Polymerization of ethylene in suspension 100 l of diesel oil, 100 mmoles of aluminum iso-prenyl and 900 mg of the catalyst solid described under a) were charged to a 150 l kettle. 5 kg per hour of ethylene and sufficient H2 to give an H2 content of 55%
by volume i~ the gas space were then passed in at a poly-merization temperature of 85C. After 6 hours the poly-merization was terminated at a pressure of 23.8 bar, by ~ releasing the pressure. The suspension was filtered and ¦ 10 the polyethylene powder was dried by passing hot nitrogen over it.
¦ 29.1 kg of polyethylene were obtained. This ¦ corresponds to a catalyst activity of 32.3 kg of polyethylene/g of catalyst solid or 5.8 kg of polyethylene/
! 15 mmole of Ti. The polyethylene powder had an MFI 190/5 of 0.36 g/10 minutes. The ~readth of molecular weight distribution ~ Mw/Mn was 28 and the MFI 190/15/MFI 190/5 was 12.7. The ! density of the powder was 0.954 g/cm3 and its bulk density was 0.39 g/cm3 .
Exarnple 10 a) Preparation of the component A
j 250~3 g of Na2[Mg(0C2Hs)43(H. Meerwein and T.
~ersin, Liebigs Annalen der Chemie 476, 113 [1929]) were dispersed, under a blanket of N2, in 2 0 l of a diesel oil fraction in a 3 l four-necked flask equipped with a dropping funnel, a KPG stirrer9 a reflux condenser and a thermometer. 759 g of titanium tetrachloride were added dropwise at 80C to this dispersion in the course of 4 hours. The mixture was then warmed to 145C and stirred 9~3~1 at this temperature for 45 hours. A gentle stream of N2 was passed over the reaction mixture during the whole reaction time in order to expel gaseous reaction products, and this stream was then passed through a cold trap cooled with methanol/solid carbon dioxide. The evolution of gaseous reaction products was complete after 60 hours.
118 g of a water-white liquid of the following composition:
Cl = 55% by weight, C = 37% by weight and H = 8% by weight were collected in the cold trap. This was ethyl chloride.
The reaction product was then washed with the diesel oil fraction mentioned above until the supernatant solution no longer contained any titanium.
After drying, the solid (component A) had the following analytical composition:
Ti 16.9% by weight : Mg 6.~% by weight Cl 52.9% by weight b)Polymerization of ethylene in suspension 100 1 of diesel oil, 30 mmoles of aluminum tri-isobutyl and 1,417 mg of ~he catalyst solid described under a) were charged to a 150 l kettle. 5 kg per hour of ethylene and sufficient H2 to give an H2 content of 65% by volume in the gas space were then passed in at a polymerization temperature of 85C. After 6 hours the polymerization was terminated at a pressure of 21.7 bar, by releasing the pressure. The suspension was filtered and the polyethylene powder was dried by passing hot nitrogen over ito 28.2 kg of polyethylene were obtained. This .
~2~7491~
~ - 25 ¦ oorresponds to a catalyst activity of l9o9 kg of polyethylene/g of catalyst solid or 701 kg of polyethylene/
mmole of Ti. The polyethylene powder had an MFI 190/5 of 3.2 g/10 minutes. The breadth of molecular weight distribution Mw/Mn was 21 and the MFI 190/15/MFI 190/5 . was 10.5. The density of the powder was 0.955 g/cm3 and its bulk density was 0-49 e/cm3.
.
' "
magnesium alcoholate o~ the formula Mg(OR)nX~ in which X
is halogen- (~4)1/2~ OH~ (C3)1/2' (P4)1/3 i 25 the meaning mentioned above and n + m is 2.
It is also possible, h~ever, to em?loy a "complex" magnesium alcoholate. me tenm "complex" magnesium alcoholate describes a magnesium alcoholate which, as well as magnesium, contains at least one meta] o~ the 1st to 4th main group of the ~2~'7gL98 .
periodic system. The following are examples of a complex t . magnesium alcoholate of this type: ~Mg(OiC3H7)4~Li2;
¦ 2 3 7~8]Mg; [SitOC2H5~63Mg; [Mg(OC H ) ]Na;
~Al2(0iC~Hg)~Mg; and [Al2(0~secC4Hg)6(0C2H5)2~Mg. The complex magnesium alcoholates (alkoxo salts~ are pr~epared by known methods (literature references: Meerwein; Ann.
455 (1927), page 234 and 476 (1929), page 113, Houben~
Weyl, Methoden der organischen Chemie ~"Methods of organic chemistry"], volume 6/2, page 30). The following examples of the preparation of the complex magnesium alcoholate may be mentioned: -1 1. Two metal alcoholates are allowed to act on one another in a suitable solvent, for example 2Al(OR~3 ~ Mg(OR)2 ~ fAl2~0R)B]Mg 2. Magnesium is dissolved in an alcoholic solution of a metal alcoholate 1 2LiOR + Mg ~ 2 ROH ~ lMg(OR)4]Li2 ~ ~2 3. Two metals are dissolved in alcohol simultaneously B ROH + Mg + 2 Al ~ lAl2(OR)~]Mg ~ 4 H2 The simple magnesium alcoholates, in particular Mg(OC2H5)2, Mg~OnC3H7)2 an~d M~(OiC3H7)2 are ~referably used. The magnesium alcoholate is employed in a - pure form or fixed on a support.
The preparation of the component A is effected in b 25 two reaction stages at different temperatures.
In the first reaction stage? the magnesium alco-holate is reacted with titanium tetrachloride ~t a tempera-ture of 50 to 100C, preferably 60 to 90C, in the presence of an inert hydrQcarbon and while stirring. 1 to 5 moles 0'74~3 of titanium te~rachloride are employed for 1 mole of mag-¦ nesium alcoholate, preferably 1.4 to 3.5 moles o~ titanium tetrachloride for 1 mole of magnesium alcoholate.
A suitable inert hydrocarbon is an aliphatic or 5 cycloaliphatic hydrocarbon, such as butane, pentane, hexane, heptane, isooctane, cyclohexane or methylcyclohexane, and an aromatic hydrocarbon, such as toluene or xylene; it is also possible to ~se a hydrogenated diesel oil or gasoline fraction which has been carefully freed from oxygen, sulfur 10 compounds and moisture.
i~
The reaction time in the ~irst stage is 0.5 to 8 hours, preferably 2 to 6 hours.
A substantial replacement of the alkoxy groups of the magnesium alcoholate by the chlorine atoms of the 15 titanium tetraGhloride takes place in the first reaction ~tage. The reastion product obtained in this stage is a I solid which is insoluble in hydrocarbons and contains ¦ magnesium and titanium, and tltanium compounds wh~ch are soluble in hydrocarbon5 and contain chlorine and alkoxy 20 groups.
In the second reaction stage, the resulting reaction mixture is subjected to a heat treatment at a temperature ! of 110 to 200C, preferably 110 to 160C9 while stirring.
During this heat treatment, the titanium content of the 25 hydrocarbon-insoluble solid increases greatly and alkyl chlorides are split off. It is assumed that the soluble titanium alkoxychloridesare converted, by the splitting off of alkyl chlorides,into condensed titanates which are insoluble in hydrocarbons and which are precipitated ~g l Z(~749B
¦ on the solid. The heat treatment is carried out until no further alkyl chloridesare split off. As a rule, a re-action time of 1~ to 100 hours is required for this.
All the soluble reaction products are then removed by washing several times with a hydrocarbon, and a solid which is insoluble in the hydrocarbon and which contains magnesium and titanium, i5 obtained; this will be desig-; nated component A.
The polymerization ca~alyst to be used in accordance with the invention is prepared by bringing into contactwith one another the component A and an organometallic com-pound of Groups I to III of the periodic system ~component It is preferable to use organoaluminum compounds as the component B. Suitable organoaluminum compounds are organoaluminum compounds containing chlorine9 the dialkyl-I aluminum monochlorides of the formula R2AlCl or the alkyl-aluminum sesquichlorides of the formula R3Al2C13 in which R~ can be identical or different alkyl radicals having I to 16 carbon atoms. The following may be mentioned as examples: (C2H~)2AlCl, (iC4Hg)2AlCl and (C2H533Al2Cl3.
It is particularly preferable to employ chlorine~
free compounds as the organoaluminum compounds. Compounds suitable for this purpose are, firstly, the products from the reaction of aluminum trialkyls or aluminum dialkyl~
hydrides with hydrocarbon radicals having 1 to 6 carbon atoms, preferably the reaction of Al(iC4Hg)3 or Al(iC4Hg)~H
with diolefins containing 4 to 20 carbon atoms, preferably isoprene. Aluminum isoprenyl may be mentioned as an ~ 374~8 ëxarnple.
¦ Secon~ly 9 chlorine-free organoaluminum compounds of this type are aluminum trialkyls AlR3 or aluminum di-alkylhydrides of the formula AlR2H in which R3 denotes identical or different alkyl radicals having 1 to 16 carbon atoms. Examples are Al(C2H5)3, Al(C2H5)2H, Al(C H ~3, Al(C3H7)2H9 Al(iC4Hg)3, 4 9 2 Al(C H 7)3, Al~C12~25)3~ Al(C2H5)(C12 2S)2 Al(iC4Hg)(C12H25)2 It is also possible to employ mixtures of organo-metallic compounds of -C-roups I to III of the periodic system, particularly mixtures of different organoaluminum compounds. The following mixtures may be mentioned as exa~ples: Al~C2H5)3 and Al(iC4H9~3, Al(C2H5)2Cl and Al(C H 7)3, Al(C2H5)3 and Al(C8H17)3, 4 9 2 ~l(C8H17)3, Al(iC~Hg)3 and Al(C8H17)3, Al(C2H5)3 and Al(C H 5)3, Al(iC4Hg)3 and Al(C12H25)3, 2 5 3 16H33)3~ Al(C3H7)3 and Al(Cl~H37)2(iC4H9) or Al(C2H5)3 and aluminum isoprenyl (the reaction product of isoprene with Al(iC4Hg)3 or Al(iC4Hg)2H~.
The component A and the component B can be mixed in a stirred kettle at a temperature of -30C to 150C, preferably -10 to 120C, before the polymerization. It is also possible to combine the two components directly in the polymerization kettle at a polymerization temperature of 20 to 200C. The addition of the component B c~n, how-ever9 also be effected in two stages by pre-activating the component A with part of the component B at a temperature of -30C to 150UC before the polymeriz~tion reaction, and ;,~
~L~07~'~8 adding the remainder of the component B in the polymer-ization reactor at a temperature of 20 to 200C.
The polymerization catalyst to be used in accord-~nce with the invention is employed for the polymerization of 1-olefins of the formula R CH=CH2 in which R4 denotes hydrogen or an alkyl radical having 1 to 10 carbon atoms, for example ethylene, propylene, l-butene, 1-hexene9 4-methyl-l-pentene or 1-octeneO It is preferable to poly-imerize ethylene on its own or in the form of a mixture ~10 containing at 7east 70% by weight of ethylene and not more ¦than 30~ by weight of another l-olefin of the above formula.
¦In particular9 ethylene is polymerized on its own, or a mix-ture containing at least ~P/Oby weight of e~hylene and not more than l~/o by weight of another 1-olefin of the above fon~a is polymerized.
j 15 The polymerization is carried out in a known manner in solution, in suspension or in the gas phase, continuously ¦ or discontinuously, in a single stage or in several stages and at a tempe~ature of 20 to 200C, preferably 50 to 150C.
The press~re is 0~5 to 50 bar. Polymerization within t~e pressure range li20 f~l5 to 30 bar, which is of partic~ar interest in industry,is preferred. ,-In this polymerization, the component A is used in a concentration, calculated as titanium, of 0.0001 to 1, pre~erably 0.001 to 0.5, mmole of Ti per liter of dispersion medium or per liter of reactor volume. me organometallic compound is used in a concentration of 0.1 to 5 mmoles, preferably 0.5 to 4 mmoles, per liter of dispersion medium or per liter of reactor volume. In prin-ciple, however, higher concentrations are also possible.
Suspension polymeriæation is carried cut in an inert dispersion medium which is customary for the Ziegler ~L~07~
low-pressure process, for example in an aliphatic or cyclo-aliphatic hydrocarbon; butane, pentane, hexane, heptane, i~ooctane, cyclohexane or methylcyclohexane may be mentioned as examples of such a hydrocarbon. It is also possible to use a gasoline or hydrogenated diesel oil fraction which has been carefully freed from oxygen, sulfur compounds and moisture. The molecular weight of the polymer is regulated in a known manner; it is preferable to use hydro-gen for this purpose.
As a result of the high activity of the c~talyst to be used, the process according to the invention produces ~ polymers havin~ a very low content of titanium and halogen I and, therefore, extremely good values in the test for color stability and corrosion. It also makes it possible to prepare polymers having a very broad molecular weight distribution; the Mw/Mn values of the polymers are over 10.
A further decisive advantage of the process accord-ing to the invention can be seen in the fact that it makes it possible to prepare polymers having molecular weights which differ very greatly, merely by varying the eoncen-tration of hydrogen. For example~ polymers having molecular weights above 2 million are formed in a polymerization in the absence of hydrogen, and polymers having molecular weights in the region of 30,000 are formed at hydrogen contents of 70% by volume in the gas space.
The polymers can be fabricated at high throughput rates by the extrusion and blow-extrusion process to give hollow articles, tubes, cables and films which have smooth ,~,;,~
.
~Z0749~
t surfaces.
: By virtue of a special structural composition, the hollow articles and bottles produced from the polyolefins obtained in accordance with the invention are distinguished 5 by a considerable lack of sensitivity to stress crackingO
Furthermore 9 the process according to the invention makes it possible to prepare, by suspension and gas phase polymerization, free-flowing polymer powders having high bulk densities, so that they can ~e processed further ! 10 directly to give shaped articles without a granulation I stage.
¦ EXAMPL~S
, In the examples which follow, a hydrogenated diesel oil fraction having a boiling range of 130 to 170C is used ~or the preparation of ~he catalyst and for the polymerization.
The titanium content of the cataiysts is determined colorimetrically (literature reference: GØ Mùller~
Prakti~um der quantitativen chemischen Analyse ["Practical manual of quantitative chemioal analysis"], 4th edition (1957), page 243)~ ~
The melt index MFI is determined as specified in DIN 53,735 (E).
The Mw/Mn values are determined from the fraction-ation data of a gel permeation chromatograph at 130C,using 1,2,4-trichlorobenzene as the solvent and eXtraction medium.
The intrinsic viscosity is determined as specified in DIN 53,728, sheet 4, using an Ubbelohde viscometer~
~ 2~791~
with decahydronaphthalene as the solvent.
¦ The density is determined as specified in DIN
53,47g and the bulk density as specified in DIN 53,468.
Example 1 a) Preparation of the component A
114.3 g of magnesium ethylate were-dispersed, under a blanket of N2, in 1.5 l of a diesel oil fraction in a3 lfour-necked flask equipped with a dropping funrlel, KPG stirrer, a reflux conden~er and a thermometer. 332 g of titanium tetrachloride were added dropwise at 90C to ¦ this dispersion in the course of 2 hours. The mixture was then warmed to 130C and was stirred at this temperature for ~0 hours. A gentle stream of N2 was passed over the reaction mixture during the whole reaction time in order to expel gaseous reaction products, and this stream was then passed through a cold trap cooled with methanol/solid carbon dioxide. The evolution of gaseous reaction products was complete after 60 hours. 116 g of a water-white liquid o~ the following composition: Cl = 55% by weight, C =
37% by weight and H = 8% by weight were collected in the cold trap. This was ethyl chlori~e, The reaction product was then washed with the diesel oil fraction mentioned above, until the supernatant solution no longer contained any titanium.
~5 After drying, the solid (component A) had the following analytical composition:
Ti 25.4% by weight Mg 9.5% by weight Cl 50.2% by weight .~ .
12~
The Cl : Ti atomic ratio was 2.67.
¦ b) Pre-activation of the component A
19 g of the component A were made up to 190 ml with diesel oil, and 100 ml of an aluminum triisobutyl 5 solution containing 1 mole of Al(iC4Hg)3 per 1 l of sol-ution were added at 20C, while stirring. 45% by weight of the tetravalent titaniumwere reduced to titanium-(III) by this means.
c) Polymerization of ethylene in suspension I 10 100 l of diesel oil 7 30 mmoles of aluminum tri-¦ isobutyl and 8.7 ml of the dispersion described under b) were charged to a 150 l kettle. 5 kg per hour of ethylene and sufficient H2 to give an H2 content of 55% by ~olume in the gas space were then passecl in, at a polymerization temperature of 8SC. After 6 hours the polymerization . was terminated at a pressure of 25.3 bar, by releasing the pressure. The suspension was filtered and the poly-ethylene powder was dried by passing hot nitrogen over r it.
28.7 kg of polyethylene were obtained. This corresponds to a catalyst activity of 50.4 kg of polyethylene/g of catalyst solid (component A) or 9.5 kg of polyethylene/mmole of Ti. The polyethylene powder had an MFI 190/5 of 0.54 gJ10 minutes. The breadth of molec-L 25 ular weight distribution Mw/Mn was 22 and the MFI 190/15J
MFI 190/5 was 11.5. The density of the powder was 0.955 g/
cm3 and its bulk density was 0.49 g/cm3.
, ~, 12'~3'7~9~
; Example 2 Polymerization of ethylene in suspension 100 mmoles of aluminum triisobutyl and 2.2 ml of the dispersion described in Example lb) were charged to the kettle under the same conditions as those described ln Example lc). 5 kg per hour of ethylene were then passed in at a polymerization temperature of 75C. After 6 hours the polymerization was terminated at a pressure of 24.8 bar, by releasing the pressure. The suspension was filtered and the polyethylene powder was dried by passing hot nitrogen over it. 27.9 kg of polyethylene were obtained.
This corresponds to a catalyst activity of 194 kg of polyethylene/g of catalyst solid or 36.5 kg of poly-ethylene/mmole of Ti. The polyethylene powder had an intrinsic viscosity of 2~400 ml~g; this corresponds to a molecular weight of 2 million. Its bulk density was 0.45 g/cm3.
Example 3 Polymerization of ethylene in suspension 100 mmoles of aluminum triisobutyl and 29 ml of the dispersion described in Example lb) were charged to the kettle under the same conditions as those described in Example lo). 4 kg per hour of ethylene and sufficient H2 to give an H2 content of 75% by volurne in the gas space were then passed in at a polymerization temperature of 85C. After 6 hours the polymerization was terminated at a pressure of 25.6 bar, by releasing the pressure.
The suspension was filtered and the polyethylene powder was dried by passing hot nitrogen over it. 23.6 kg of : , :~2~7~9l5~
polyethylene were isolated. This corresponds to a catalyst yield of 12.4 kg of polyethylene/g of catalyst solid or 2.3 kg of polyethylene/mmole of Ti. The poly-ethylene had an MFI 190/5 of 105 g/10 minutes, an intrinsic viscosity of 110 ml/g, a density o~ 0.965 g/cm3 and a bulk density of 0.50 g/cm3 . The breadth of molecular weight distribution Mw/Mn was 25.
Example 4 Copolymerization of ethYlene and l-decene in suspension 750 ml of hexane, 5 mmoles of aluminum isoprenyl and 2.9 mg of the component A obtained in accordance with Example lb~ were charged to a 1.5 l steel autoclave. H2 was then injected at 8 bar, and ethylene at 14 bar~ at a polymerization temperature of 85~C. The ethylene was subsequently metered in at such a rate that a total pressure of 22 bar was maintain~d. 20 ml per hour of 1-decene were metered in at the same time. The experiment was discontinued after 6 hours. The copolymer was isolated by filtration and dried in a vacuum drying cabinet. 156 g of copolymer were obtained. This corresponds to a ! catalyst yield of 53.8 kg of polymer/g of catalyst solid or 10.1 kg of polymer/mmole of Ti. The ethylene/1-decene ~ copolymer had a melt index MFI 190/5 o* 0.68g/10 minutes ¦ and a density of 0.950 g/cm3 1 25 Example 5 Copolymeri~ation of ethylene and 1-hexene in suspension 360 l of hexane, 360 mmoles of aluminum isoprenyl and 58 ml of the dispersion described in Example lb) were initially taken in a 500 l kettle. 17 kg/hour of ethylene, ` ''~ .
7~
2 ~/hour of 1-hexene and sufficient H2 to set up an H2 con-tent of 45% by volume in the gas space were then passed in at a polymerization temperature of 85C.
After 6 hours the polymerization pressure had risen to 8.2 bar, and the polymerization was discontinued by releasin~ the pressure. The polymer powder was iso-lated by filtration and was dried with hot nitrogen.
100.4 kg of polymer were obtained. This corresponds to a catalyst yield of 26.4 kg of polymer/g of cata-lyst solid or 5.0 kg of polymer/mmole of Ti.
The ethylene/1-hexene copolymer had a melt index MFI 190/5 of 0.9 g/10 minutes, an MFI 190/15/MFI 190/5 ratio of 9.8, a density of 0.942 g/cm3 and a bulk density of 0.42 g/cm3.
Bottles were produced from the powder on a blow-molding apparatus for bottles (extruder screw: D = 60 mm).
A very high output, 62 kgJhour, was obtained at a screw speed of 40 r.p.m. The bottles had a very smooth surface and had a very high resistance to stress cracking, over 1,000 hours, in the Bell stress cracking test.
Example _ Copolymeri ation of ethylene and 1-butene in suspension 720 mmoles of aluminum triisobutyl and 58 ml of the dispersion described in Example lb) were charged under the same conditions as those described in Example 5. 17 kg per hour of ethylene and 4 l per hour of 1-butene were added at 65C. Sufficient H~ was passed in to give a concentration of 40% by volume of the latter in the gas space. After 6 hours the polymerization was discontinued .~ , , 3 ` ~2~
~ at a final pressure of 6.7 bar, by releasing the pressure.
f The suspension was cooled to room temperature and the solid was isolated by filtration and dried with hot 108.4 kg of product having an MFI 190/5 of 1.8 g/
10 minutes, an MFI 190/15/MFI 190/5 of 10.4, a density of 0.920 g¦cm3 and a bulk density of 0.30 g/cm3 were obtained. This corresponds to a ca~talyst yield of 28.S kg-of copolymer/g of c~talyst solid or 5.4 kg of copolymer/mmole of Ti.
. ~
Polymerization of ethylene in the gas phase 500 g of polyethylene powder (M~I 190/5 = 1.5 g/
10 minutes; bulk density = 0.45 g/cm3) were initially ¦ 15 taken in a 20 l horizontal reactor equipped with a stirrer operating close to the wall. The reactor was freed from ¦ air by being evacuated several t;imes and flushed for ¦ several hours with ethylene and was then warmed to 80C.
50 mmoles of aluminum triisobutyl and 94.3 mg of the cata-lyst component A prepared in accordance with Example la) were added to the reactor.
400 g/hour of ethylene and sufficienk hydrogen to ! keep the proportion of hydrogen in the gas space at 30%
¦ by volume during the polymerization were passed in. The pressure rose to 15 bar during the reaction time.
After 12.5 hours the polymerization was discontinued.
5.4 kg of polyethylene having an MFI 190/5 value of 0.6 g/
10 minutes were obtained. This corresponds to a catalyst yield of 52 kg of polyethylene/g of catalyst solid ~, .
~20~8 or 9.8 kg of polyethylenetmmole of Ti.
I Comparison Example A
¦ a) ~paration of the component A
114.3 g of magnesium ethylate were dispersed, under a blanket of N2, in 1.5 l of a diesel oil fraction in a 3 l four-necked flask equipped with a dropping funnel, - a KPG stirrer, a reflux condenser and a thermometer. 332 g of titanium tetrachloride were added dropwise at 90C to this dispersion in the course of 2 hours. The reaction j 10 product was then washed with the diesel oil fraction until ¦ the supernatant solution no longer contained any titanium.
After drying, the solid (component A) had the following ¦ analytical composition:
; . Ti 4. 9% by weight Mg 19.8% by weight ! Cl 61.3% by weight.
b) Pre-activation of the component A
98 g of the component A were suspended in sufficient diesel oil to give a volume of suspension of 190 ml, and 100 ml of an aluminum triisobutyl solution containing 1 mole of Al(iC4Hg)3 per 1 l were added at 20~C, while stirring9 52% by weight of the tetravalent titanium were reduced to titanium-(III) by this means.
c~ Pol~merization of ethylene in suspension 100 l of hexane, 30 mmoles of aluminum triisobutyl and 14.5 ml of the suspension described under ~) were charged to a 150 l kettle. 5 kgthour of ethylene and sufficient H2 to set up a hydrogen content of 30% by vol--ume in the gas ~pace were then passed in at 85C. After ::~2~[~7~9~3 6 hours the polymerization was discontinued at a pressure of 4.6 bar, by releasing the pressure. 29~6 kg of poly-ethylene were obtained~ This corresponds to a catalyst yield of 6.1 kg/g of catalyst solid or 5.9 kg of polyethylene/mmole of Ti.
The product had an MFI 190/5 value of 1.6 g/10 minutes, an MFI 190/15/MFI 190/S value of 5.2, a density of 0.956 g/cm3 and a bulk density of 0.42 g/cm3. The . product had a narrow molecular weight distribution:
I 10 Mw/Mn = 4.70 An output of 43 kg/hour was obtained at a screw speed of 40 r.p.m. when processing the powder on the blow~molding apparatus for hollow articles also used in Exa~le 5. The bottles had a rough surface, since melt fracture occurred when they were processed. The resistance to stress cracking of the bottles in the Bell test was 68 I hours.
! d) Polymerization of ethylene in suspension 100 l of diesel oil, 30 mmoles of aluminum tri-isobutyl and 8.7 ml of the dispersion described under b)were charged to a 150 l kettle. 5 kg per hour of ethylene and sufficient H2 to give an H2 content of 55% by volume in the gas space were then passed in at a polymerization temperature of 85C. After 6 hours -the polymerization was terminated at a pressure of 20.4 bar, by releasing the pressure. The suspension was filtered and the po]y~
ethylene powder was dried by passing hot nitrogen over it.
28.2 kg of polyethylene were obtained. This corresponds to a catalyst activity of 9.6 kg of 9~.
polyethylene/g of catalyst solid or 9.4 kg of polyethylene/
mmole of Ti. The polymer powder had an MFI 190/5 o~ 28 g/
10 minutes. The breadth of molecular weight distribution Mw/Mn was 4.6 and the MFI 190/15/MFI 190/5 was 5.4. The density of the powder was 0.960 g/cm3 and its bulk density was 0.41 g/cm3.
Example 8 I a) Preparation of the component A
114.3 g of magnesium ethylate were dispersed, under a blanket of N2, in 1.5 l of a diesel oil ~raction in a 3 l four-necked flask equipped with a dropping funnel, a KPG stirrer~ a reflux condenser and a thermometer.
569 g of titanium tetrachloride were added dropwise at 90C to this dispersion in the course of 2 hours. The mixture was then warmed to 130C and stirred at this temperature for 60 hours. A gentle stream of N2 was passed over the reaction mixture during the whole reaction time in order to expel gaseous reaction products, and this stream was then passed through a cold trap cooled with methanol/solid carbon dioxide~ The evolution of gaseous reaction products was complete after 60 hours.
107 g of a water-white liquid oi` the following composition:
Cl = 5S% by weight, C = 37% by weight and H = 8% by weight were collected in the cold trap. This was ethyl chloride.
The reaction product was then washed with the diesel oil fraction until the supernatant solution no longer con-tained any titanium.
After drying, the solid ~component A) had the following analytical composition:
~ 2 0 7 ~ ~
¦ Ti 24. 7% by weight Mg 9.7% by weight ¦ Cl 51.2% by weight.
The Cl : Ti atomic ratio was 2.80.
b) Pre-activation of the component A
19.4 g of component A were made up to 190 ml with diesel oil, and 100 ml of an aluminum triisobutyl solution containing 1 mole of Al(iC4Hg~3 per 1 1 were added at 20C, while stirring. 47% by weight of the tetravalent titanium were reduced to titanium~(III) by this means.
c) Polymerization of ethylene in suspension 100 l of diesel oil, 25 mmoles of aluminum tri-! isobutyl and 8.0 ml of the dispersion described under b) were charged to a 150 l kettle. 5 kg per hour of ethylene and sufficient ~2 to give an H2 content of 55% by volume in the gas space were then passed in at a polymerization temperature of 85C. A~ter 6 hours the polymerization was terminated at a pressure of 22.4 bar, by releasing the pressure. The suspension was filtered and the polyethylene powder was dried by passing hot nitrogen over it.
27.S kg of polyethylene were obtained. This corresponds to a catalyst activity of 51.4 kg of polyethylene/g of catalyst solid or 10 kg of polyethylene/
mmole of Ti. The polyethylene powder had an MFI 190/5 of 0.94 g/10 minutes. The breadth of molecular weight distribution Mw/Mn was 26 and the MFI 190/15/MFI 190/5 was 11.9. The density of the powder was 0.956 g/cm3 and its ~ulk density was 0.47 g/cm3.
:~Z~ L9~
Example 9 .
a) Preparation of the component A
142.3 g of magnesium isopropylate were dispersed7 under a blanket of N2, in 1.0 l of a diesel oil fraction ; 5 in a 3 l four~necked flask equipped with a dropping funnel, a KPG stirrer, a reflux condenser and a thermometer. 285 g of titanium tetrachloride were added dropwise at 75C to this dispersion in the course o~ 4 hours. The mixture was then warmed to 110C and w~s stirred at this tempera-ture for 45 hours. A gentle stream of N2 was passed over the reaction mixture during the whole reaction time in order to expel gaseous reaction products, and this stream was then passed through a &old trap cooled with methanol/
solid carbon dioxide. The evolution of gaseous reaction products was complete after 60 hours. 156 g of a water-white liquid of the following composition: Cl = 45% by weight, C = 46% by weight and H = 8.9% by weight were collected in the cold trap. Thira was isopropyl chloride.
The reaction product was then washed with the diesel oil fraction mentioned above, until the supernatant solution no longer contained any titanium.
After drying, the solid ~component A) contained the following:
Ti 26.6% by weight Mg 9.0/0 by weight Cl 52.5% by weight.
The Cl : Ti atomic ratio was 2.67.
~2C)7~
b) Polymerization of ethylene in suspension 100 l of diesel oil, 100 mmoles of aluminum iso-prenyl and 900 mg of the catalyst solid described under a) were charged to a 150 l kettle. 5 kg per hour of ethylene and sufficient H2 to give an H2 content of 55%
by volume i~ the gas space were then passed in at a poly-merization temperature of 85C. After 6 hours the poly-merization was terminated at a pressure of 23.8 bar, by ~ releasing the pressure. The suspension was filtered and ¦ 10 the polyethylene powder was dried by passing hot nitrogen over it.
¦ 29.1 kg of polyethylene were obtained. This ¦ corresponds to a catalyst activity of 32.3 kg of polyethylene/g of catalyst solid or 5.8 kg of polyethylene/
! 15 mmole of Ti. The polyethylene powder had an MFI 190/5 of 0.36 g/10 minutes. The ~readth of molecular weight distribution ~ Mw/Mn was 28 and the MFI 190/15/MFI 190/5 was 12.7. The ! density of the powder was 0.954 g/cm3 and its bulk density was 0.39 g/cm3 .
Exarnple 10 a) Preparation of the component A
j 250~3 g of Na2[Mg(0C2Hs)43(H. Meerwein and T.
~ersin, Liebigs Annalen der Chemie 476, 113 [1929]) were dispersed, under a blanket of N2, in 2 0 l of a diesel oil fraction in a 3 l four-necked flask equipped with a dropping funnel, a KPG stirrer9 a reflux condenser and a thermometer. 759 g of titanium tetrachloride were added dropwise at 80C to this dispersion in the course of 4 hours. The mixture was then warmed to 145C and stirred 9~3~1 at this temperature for 45 hours. A gentle stream of N2 was passed over the reaction mixture during the whole reaction time in order to expel gaseous reaction products, and this stream was then passed through a cold trap cooled with methanol/solid carbon dioxide. The evolution of gaseous reaction products was complete after 60 hours.
118 g of a water-white liquid of the following composition:
Cl = 55% by weight, C = 37% by weight and H = 8% by weight were collected in the cold trap. This was ethyl chloride.
The reaction product was then washed with the diesel oil fraction mentioned above until the supernatant solution no longer contained any titanium.
After drying, the solid (component A) had the following analytical composition:
Ti 16.9% by weight : Mg 6.~% by weight Cl 52.9% by weight b)Polymerization of ethylene in suspension 100 1 of diesel oil, 30 mmoles of aluminum tri-isobutyl and 1,417 mg of ~he catalyst solid described under a) were charged to a 150 l kettle. 5 kg per hour of ethylene and sufficient H2 to give an H2 content of 65% by volume in the gas space were then passed in at a polymerization temperature of 85C. After 6 hours the polymerization was terminated at a pressure of 21.7 bar, by releasing the pressure. The suspension was filtered and the polyethylene powder was dried by passing hot nitrogen over ito 28.2 kg of polyethylene were obtained. This .
~2~7491~
~ - 25 ¦ oorresponds to a catalyst activity of l9o9 kg of polyethylene/g of catalyst solid or 701 kg of polyethylene/
mmole of Ti. The polyethylene powder had an MFI 190/5 of 3.2 g/10 minutes. The breadth of molecular weight distribution Mw/Mn was 21 and the MFI 190/15/MFI 190/5 . was 10.5. The density of the powder was 0.955 g/cm3 and its bulk density was 0-49 e/cm3.
.
' "
Claims (10)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the polymerization of at least one 1-olefin of the formula R4CH=CH2 wherein R4 denotes hydrogen or an alkyl radical having 1 to 10 carbon atoms, in the presence of a catalyst composed of (A) the product from the reaction of a magnesium alcoholate with titanium tetrachloride and (B) an organometallic compound of Groups I to III of the periodic system wherein component A has been prepared by reacting, in a first reaction stage, a magnesium alcoholate with titanium tetrachloride in a hydrocarbon at a temperature of 50 to 100°C, subjecting the reaction mixture formed to a heat treatment at a temperature of 110 to 200°C until no further alkyl chloride is split off, and freeing the solid from soluble reaction products by washing several times with a hydrocarbon.
2. A process as claimed in claim 1 in which component A is prepared by reacting, in the first reaction stage,a magnesium alcoholate of the formula Mg(OR)2 wherein R denotes identical or different alkyl radicals having 1 to 6 carbon atoms, with titanium tetrachloride in a hydrocarbon at a temperature of 50 to 100°C, subjecting, in a second reaction stage, the reaction mixture which has been formed to a heat treatment at a temperature of 110 to 200°C until no further alkyl chloride is split off, and then freeing the solid from soluble reaction products by washing it several times with a hydrocarbon.
3. A process as claimed in claim 1 in which component A is prepared by reacting, in the first reaction stage a complex magnesium alcoholate which, as well as magnesium, contains at least one metal of the 1st to 4th main group of the periodic system, with titanium tetrachloride in a hydrocabon at a tempera-ture of 50 to 100°C, subjecting, in a second reaction stage, the reaction mixture which has been formed to a heat treatment at a temperature of 110 to 200°C until no further alkyl chloride is split off, and then freeing the solid from soluble reaction products by washing it several times with a hydrocarbon.
4. A process as claimed in claim 1, claim 2 or claim 3 in which the 1-olefin is selected from the group of ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene.
5. A process as claimed in claim 1, claim 2 or claim 3 in which the 1-olefin is ethylene.
6. A process as claimed in claim 1, claim 2 or claim 3 in which the 1-olefin is a mixture of at least 70% by weight of ethylene and not more than 30% by weight of another 1-olefin of the above formula.
7. A process as claimed in claim 1, claim 2 or claim 3 in which the polymerization is carried out at a temperature of from 20 to 200°C at a pressure of 0.5 to 50 bar.
8. A process for the preparation of a polymerization catalyst composed of (A) the product from the reaction of a magnesium alcoholate with titanium tetrachloride and (B) an organometallic compound of Groups I to III of the periodic system in which component A is prepared by reacting, in a first reaction stage, a magnesium alcoholate with titanium tetrachloride in an inert hydrocarbon at a temperature of 50 to 100°C, subjecting, in a second reaction stage, the reaction mixture which has been formed to a heat treatment at a temperature of 110 to 200°C
until no further alkyl chloride is split off, and then freeing the solid from soluble reaction products by washing it several times with a hydrocarbon.
until no further alkyl chloride is split off, and then freeing the solid from soluble reaction products by washing it several times with a hydrocarbon.
9. A process as claimed in claim 8 in which component A is prepared by reacting, in the first reaction stage, a magnesium alcoholate of the formula Mg(OR)2 wherein R denotes identical or different alkyl radicals having 1 to 6 carbon atoms, with titanium tetrachloride in an inert hydrocarbon at a temperature of 50 to 110°C, subjecting, in a second reaction stage, the reaction mixture which has been formed to a heat treatment at a temperature of 110 to 200°C until no further alkyl chloride is split off, and then freeing the solid from soluble reaction products by washing it several times with a hydrocarbon.
10. A process as claimed in claim 8 in which component A is prepared by reacting, in the first reaction stage, a complex magnesium alcoholate which, as well as magnesium, contains at least one metal of the 1st to 4th main group of the periodic system, with titanium tetrachloride in a hydrocarbon at a tempera-ture of 50 to 100°C, subjecting, in a second reaction stage, the reaction mixture which has been formed to a heat treatment at a temperature of 110 to 200°C until no further alkyl chloride is split off, and then freeing the solid from soluble reaction products by washing it several times with a hydrocarbon.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3124223.5 | 1981-06-20 | ||
| DE19813124223 DE3124223A1 (en) | 1981-06-20 | 1981-06-20 | "METHOD FOR PRODUCING A POLYOLEFIN AND CATALYST THEREFOR" |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1207498A true CA1207498A (en) | 1986-07-08 |
Family
ID=6134984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000405526A Expired CA1207498A (en) | 1981-06-20 | 1982-06-18 | Process for the preparation of a polyolefin, and a catalyst for this process |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US4447587A (en) |
| EP (1) | EP0068257B1 (en) |
| JP (1) | JPS582306A (en) |
| AR (1) | AR244715A1 (en) |
| AU (1) | AU550824B2 (en) |
| BR (1) | BR8203592A (en) |
| CA (1) | CA1207498A (en) |
| DE (2) | DE3124223A1 (en) |
| ES (1) | ES8304163A1 (en) |
| IN (1) | IN157122B (en) |
| ZA (1) | ZA824319B (en) |
Families Citing this family (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6131401A (en) * | 1984-07-24 | 1986-02-13 | Ube Ind Ltd | Process for polymerizing ethylene |
| DE3538099A1 (en) * | 1985-10-26 | 1987-04-30 | Ruhrchemie Ag | METHOD FOR HOMO AND MIXED POLYMERIZATION OF OLEFINS |
| US4698323A (en) * | 1986-09-29 | 1987-10-06 | Stauffer Chemical Company | Transition metal catalyst component containing magnesium alkoxy alkoxides |
| DE3918646A1 (en) * | 1989-06-08 | 1990-12-13 | Hoechst Ag | PROCESS FOR PREPARING A POLY-L-OLEFIN |
| US5286694A (en) * | 1991-12-11 | 1994-02-15 | Phillips Petroleum Company | Lanthanide halide catalyst, method of producing the catalyst, and polymerization process employing the catalyst |
| DE19945980A1 (en) | 1999-09-24 | 2001-03-29 | Elenac Gmbh | Polyethylene molding compound with improved ESCR stiffness ratio and swelling rate, process for its production and hollow bodies made from it |
| DE10122111B4 (en) * | 2001-05-08 | 2007-03-01 | Ticona Gmbh | Process for the preparation of olefin polymers, as well as selected catalysts |
| WO2004056921A1 (en) | 2002-12-19 | 2004-07-08 | Basell Polyolefine Gmbh | Polyethylene blow molding composition for producing small containers |
| ES2268493T3 (en) * | 2002-12-24 | 2007-03-16 | Basell Polyolefine Gmbh | COMPOSITION OF POLYETHYLENE FOR THE PRODUCTION OF DRILLS OF THE L-RING TYPE. |
| KR20050088304A (en) * | 2002-12-24 | 2005-09-05 | 바젤 폴리올레핀 게엠베하 | Polyethylene blow moulding composition for producing jerry cans |
| PL377195A1 (en) * | 2002-12-24 | 2006-01-23 | Basell Polyolefine Gmbh | Polyethylene blow molding composition for producing large containers |
| CN100349413C (en) * | 2004-11-15 | 2007-11-14 | 华为技术有限公司 | Service calling method in intelligent network |
| DE102004055588A1 (en) * | 2004-11-18 | 2006-05-24 | Basell Polyolefine Gmbh | Polyethylene molded mass, useful for preparing protective coating for steel tubes, comprises low molecular ethylene homopolymers, high molecular copolymers of ethylene and other 4-8C olefin and of ultrahigh molecular ethylene copolymer |
| DE102004055587A1 (en) | 2004-11-18 | 2006-05-24 | Basell Polyolefine Gmbh | Polyethylene molded mass, useful for the external covering of electro cables, comprises low molecular ethylene homopolymers, high molecular copolymers of ethylene and other 4-8C olefin and of ultrahigh molecular ethylene copolymer |
| DE102005007186A1 (en) * | 2005-02-16 | 2006-08-31 | Basell Polyolefine Gmbh | Preparation of olefin polymer, i.e. ethylene polymer, for production of e.g. films, by (co)polymerization of ethylene in the presence of catalyst comprising reaction product of magnesium alkoxide with tetravalent transition metal compound |
| DE102005009916A1 (en) * | 2005-03-01 | 2006-09-07 | Basell Polyolefine Gmbh | Polyethylene molding compound for producing blown films with improved mechanical properties |
| DE102005009896A1 (en) | 2005-03-01 | 2006-09-07 | Basell Polyolefine Gmbh | Polyethylene molding compound for producing blown films with improved mechanical properties |
| DE102005009895A1 (en) * | 2005-03-01 | 2006-09-07 | Basell Polyolefine Gmbh | Polyethylene molding compound for producing blown films with improved mechanical properties |
| DE102005030941A1 (en) * | 2005-06-30 | 2007-01-11 | Basell Polyolefine Gmbh | Polyethylene molding compound for the production of injection-molded finished parts |
| DE102005040390A1 (en) * | 2005-08-25 | 2007-03-01 | Basell Polyolefine Gmbh | Multi-modal polyethylene moulding material for production of pipes, e.g. water pipes, comprises low-mol. wt. ethylene homopolymer, high-mol. wt. ethylene copolymer and ultrahigh-mol. wt. ethylene copolymer |
| CN101273445B (en) * | 2005-09-28 | 2012-07-25 | 大见忠弘 | Atmosphere controlled joint device, method and electronic device |
| KR101769163B1 (en) | 2009-06-03 | 2017-08-17 | 바젤 폴리올레핀 게엠베하 | Polyethylene composition and finished products made thereof |
| ES2421297T3 (en) | 2009-06-30 | 2013-08-30 | Basell Polyolefine Gmbh | Composition for polyethylene molding |
| CN102482371A (en) | 2009-08-06 | 2012-05-30 | 巴塞尔聚烯烃股份有限公司 | Catalyst component for the polymerization of olefins |
| BR112012009515A2 (en) * | 2009-10-22 | 2017-02-21 | Basell Polyolefine Gmbh | "catalytic components for the polymerization of olefins and catalysts obtained therefrom" |
| ES2556349T3 (en) | 2009-12-23 | 2016-01-15 | Basell Poliolefine Italia S.R.L. | Catalyst components for the polymerization of olefins and catalysts obtained from them |
| JP5695869B2 (en) * | 2010-09-28 | 2015-04-08 | 日本ポリエチレン株式会社 | Ziegler-Natta catalyst reforming method, modified Ziegler-Natta catalyst, olefin polymerization method using the same, and obtained olefin polymer |
| US11214633B2 (en) | 2019-09-10 | 2022-01-04 | Braskem America, Inc. | Ziegler-Natta catalyst systems and methods of controlling particle size |
| WO2022161402A1 (en) * | 2021-02-01 | 2022-08-04 | 中国石油化工股份有限公司 | Ethylene polymer and preparation method therefor |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3644318A (en) * | 1968-08-21 | 1972-02-22 | Hoechst Ag | Process for the polymerization of olefins |
| GB1275641A (en) * | 1969-01-06 | 1972-05-24 | Solvay | Catalysts for the polymerisation and copolymerisation of olefins |
| DE2830929A1 (en) * | 1978-07-14 | 1980-01-24 | Basf Ag | METHOD FOR PRODUCING A TITANIUM COMPONENT FOR POLYMERIZATION CATALYSTS OF THE ZIEGLER NATTA TYPE |
| JPS57158204A (en) * | 1981-03-25 | 1982-09-30 | Mitsui Petrochem Ind Ltd | Modification of titanium catalytic component and modified titanium catalytic component |
-
1981
- 1981-06-20 DE DE19813124223 patent/DE3124223A1/en not_active Withdrawn
-
1982
- 1982-06-14 US US06/388,023 patent/US4447587A/en not_active Expired - Lifetime
- 1982-06-14 ES ES513076A patent/ES8304163A1/en not_active Expired
- 1982-06-14 EP EP82105165A patent/EP0068257B1/en not_active Expired
- 1982-06-14 DE DE8282105165T patent/DE3263246D1/en not_active Expired
- 1982-06-14 IN IN682/CAL/82A patent/IN157122B/en unknown
- 1982-06-18 BR BR8203592A patent/BR8203592A/en not_active IP Right Cessation
- 1982-06-18 AU AU84993/82A patent/AU550824B2/en not_active Ceased
- 1982-06-18 CA CA000405526A patent/CA1207498A/en not_active Expired
- 1982-06-18 JP JP57104073A patent/JPS582306A/en active Granted
- 1982-06-18 AR AR82289719A patent/AR244715A1/en active
- 1982-06-18 ZA ZA824319A patent/ZA824319B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE3124223A1 (en) | 1982-12-30 |
| IN157122B (en) | 1986-01-18 |
| ZA824319B (en) | 1983-04-27 |
| EP0068257A1 (en) | 1983-01-05 |
| US4447587A (en) | 1984-05-08 |
| EP0068257B1 (en) | 1985-04-24 |
| AU550824B2 (en) | 1986-04-10 |
| AR244715A1 (en) | 1993-11-30 |
| BR8203592A (en) | 1983-06-14 |
| JPS582306A (en) | 1983-01-07 |
| ES513076A0 (en) | 1983-03-01 |
| AU8499382A (en) | 1983-01-06 |
| ES8304163A1 (en) | 1983-03-01 |
| JPH0415806B2 (en) | 1992-03-19 |
| DE3263246D1 (en) | 1985-05-30 |
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| MKEX | Expiry |