IL33680A - Catalysts for the polymerization of olefins - Google Patents
Catalysts for the polymerization of olefinsInfo
- Publication number
- IL33680A IL33680A IL33680A IL3368070A IL33680A IL 33680 A IL33680 A IL 33680A IL 33680 A IL33680 A IL 33680A IL 3368070 A IL3368070 A IL 3368070A IL 33680 A IL33680 A IL 33680A
- Authority
- IL
- Israel
- Prior art keywords
- catalyst
- titanium
- polymerization
- olefins
- catalyst according
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims description 28
- 238000006116 polymerization reaction Methods 0.000 title claims description 15
- 150000001336 alkenes Chemical class 0.000 title claims description 12
- 239000010936 titanium Substances 0.000 claims description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 24
- 229910052719 titanium Inorganic materials 0.000 claims description 24
- 239000011777 magnesium Substances 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 21
- 229910052749 magnesium Inorganic materials 0.000 claims description 19
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 18
- -1 magnesium halide Chemical class 0.000 claims description 16
- 150000003682 vanadium compounds Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 150000004678 hydrides Chemical class 0.000 claims description 3
- 150000002902 organometallic compounds Chemical class 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 229910000765 intermetallic Inorganic materials 0.000 claims 1
- 229920000098 polyolefin Polymers 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 14
- 239000005977 Ethylene Substances 0.000 description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- 229940091250 magnesium supplement Drugs 0.000 description 12
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 3
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 229910001623 magnesium bromide Inorganic materials 0.000 description 2
- 229960002337 magnesium chloride Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 101100219382 Caenorhabditis elegans cah-2 gene Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OPFTUNCRGUEPRZ-QLFBSQMISA-N Cyclohexane Natural products CC(=C)[C@@H]1CC[C@@](C)(C=C)[C@H](C(C)=C)C1 OPFTUNCRGUEPRZ-QLFBSQMISA-N 0.000 description 1
- NEAPKZHDYMQZCB-UHFFFAOYSA-N N-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]ethyl]-2-oxo-3H-1,3-benzoxazole-6-carboxamide Chemical compound C1CN(CCN1CCNC(=O)C2=CC3=C(C=C2)NC(=O)O3)C4=CN=C(N=C4)NC5CC6=CC=CC=C6C5 NEAPKZHDYMQZCB-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- RTQCAYKHUMWCEM-UHFFFAOYSA-N [Mg].ClO Chemical compound [Mg].ClO RTQCAYKHUMWCEM-UHFFFAOYSA-N 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- IQYKECCCHDLEPX-UHFFFAOYSA-N chloro hypochlorite;magnesium Chemical compound [Mg].ClOCl IQYKECCCHDLEPX-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- DARFZFVWKREYJJ-UHFFFAOYSA-L magnesium dichloride dihydrate Chemical compound O.O.[Mg+2].[Cl-].[Cl-] DARFZFVWKREYJJ-UHFFFAOYSA-L 0.000 description 1
- MJMDTFNVECGTEM-UHFFFAOYSA-L magnesium dichloride monohydrate Chemical compound O.[Mg+2].[Cl-].[Cl-] MJMDTFNVECGTEM-UHFFFAOYSA-L 0.000 description 1
- LGLXXNHIGIJYQQ-UHFFFAOYSA-L magnesium;dibromide;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Br-].[Br-] LGLXXNHIGIJYQQ-UHFFFAOYSA-L 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin 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
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
- C08F4/022—Magnesium halide as support anhydrous or hydrated or complexed by means of a Lewis base for Ziegler-type catalysts
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
Catalysts for the polymerization of olefins MONTECATINI EDISON S.p.A.
C: 31822 - 2 - 33680/2 The invention relates to the polymerisation of olefins and particularly to catalysts for the polymerization of ethylene or a mixture thereof with an -olefin and/or diolefln. The term α-olefin as Used herein excludes ethylene. More than one of each such class of co-monomers may of course be used.
The invention provides a catalyst for the polymerization of olefins which comprises a reaction product of a hydrated magnesium halide of the formula Mg£2 i nH20 Wherein X is a halogen atom (ether than fluorine) and n is a number -■©£ greater than C^wlth a halogen-containing titanium or vanadium compound under conditions such that the hydrated magnesium halide is transformed at least on the surface into an anhydrous magnesium halide, which product is activated with a hydride or organomatallic compound of a metal of Groups 1, ΪΪ or III of the Periodic System. Such catalysts have been found to show high activity.
Preferably the hydrated magnesium halide is a hydrated magnesium chloride or bromide containing from 1 to 6 and more preferably from 1 to 4 mols of water.
Examples of these halides are those of the formulae MgClg . 6H20^M 012 . 2H20»iOgCl2 . lHgO, MgBr . 6KgO and MgBr2 . H20. - 3 - 33680/2 The titanium or vanadium compounds suitable for the preparation of the catalysts include the normally liquid halogen containing titanium or vanadium compounds and also the normally solid halogen containing compounds which are soluble in solvents inert with respect to the magnesium halides. Representative examples are those of the formulae tflB 4, V014, V£ 4, 33il4{ Tl(0-1-0^)^01, $1(0-1-0^)2C12, ¾l(0-n-C4H9)2Cl2, ° ( alo-alcoholates) .
The preparation of the catalysts is preferably carried out by reacting the hydrated magnesium hallde i a stoichiometric excess of liquid or dissolved halogen containing titanium or vanadium compound preheated to its boiling temperature, and in general to a temperature greater than 100°0, and then removing the liquid phase. Another method comprises dissolving the titanium or vanadium compound in a solvent inert with respect to the hydrated magnesium hallde and/or the anhydrous hallde formed during the reaction and then reacting the hydrated magnesium hallde with the solution so obtained preheated at a temperature greater than 70 - 80°C and preferably than 100°0. In this case it is convenient to use the titanium or vanadium compound in an amount sufficient to react with the water contained in the hydrated magnesium hallde. - 4 - 33680/2 which remains on the support can vary from ver low values such as 0.01$ by weight to higher Values such as 20 ° or higher. It depends on the reaction conditions and on the percentage of water which is present in the hydrated magnesium halide. Preferably the conditions are such that the amount is from 0.1 to 10$ by weight expressed as titanium or vanadium tetrahalide.
Preferably the organometallic compound or hydride is of the formula A1(02H5)3, A1(02H5)2C1, AKiO^)^ Al(i04Hg)201, Al^H^Cl^ A1(C2H5)2H, Al(i04Hg)2Ii, LIB, CaH2, or¾tfg(C2H5)2. these the molar ratio between compoundsand the titanium or vanadium compound is not critical. For polymerizing ethylene the molar ratio Al/Ti is preferably from 50 to 1000.
Catalysts according to the invention are particularly useful for polymerizing ethylene or a mixture thereof with an a-olefin such as propylene or butene-1 and/or a diolefln, particularly with regard to the yield of polymer obtained.
They ca also be used in polymerizing a-olefins such as propylene or butene-1. The polymerization can be carried out in the liquid phase and in the presence or absence of an inert solvent or in the gaseous phase. The polymerization temperature may be from -80° to 200°P, preferably between 50° and 100°C, and the pressure atmospheric or elevated.
The molecular weight of the polymer may be regulated for example by carrying out the polymerization - 5 - 33680/2 in the presence of an alkyl halide, organometallic compound of cadmium or ¾inc, or hydrogen. Catalytic activity is only slightly influenced by the presence of the molecular weight regulators. For instance when polymerizing ethylene, it is possible to regulate the molecular weight of the polyethylene in a range of practically useful intrinsic viscosities (determined in tetralin at 135°C) from about 1.5 to 3*0 dl/g without a decrease in the polymer yield to a value below which it would be necessary to purify the polymer of catalyst residues.
The polyethylene obtained is a substantially linear and highly crystalline polymer, having a density of 0.96 g cc or more and having excellent workability, especially as far as injection moulding is concerned. The titanium content of polyethylene so prepared is generally lower than 20 parts by weight per million.
The following Examples illustrate the invention. Where not specifically indicated the percentages are by weight. The intrinsic viscosity of the polymers was measured in tetralin at 135°<3.
Example 2, Into a glass autoclave provided with a stirrer and fitted with a filter plate on the bottom there were introduced 300 cc of titanium tetrachloride. The temperature was brought up to 135°C. 70 g of magnesium chloride hexahydrate (MgCl2 . H20) free from magnesium oxychloride - 6 - 33680/2 were added. After one hour of reaction, the excess of titanium tetrachloride was removed by hot filtration.
The solid product left behind in the autoclave was repeatedly washed with boiling titanium tetrachloride and with cyclo-hexane at 80°C until the disappearance of the titanium tetrachloride from the wash liquid. The product was discharged from the autoclave and dried at 100°C under vacuum. Analysis of the dried product gave Ti - .28$, .01 = 52.7$.
X-ray analysis showed that no magnesium oxychlorlde was present and revealed the presenoe of anhydrous magnesium chloride. 50 mg of the product thus obtained were suspended in 30 cc of n-heptane and used to polymerize ethylene under the following conditions} into a stainless steel 1.8 litre autoclave purified with dry nitrogen, there were introduced 1000 cc of technical n-heptane and then 2 g of aluminium trl-iso-butyl . Thereupon the temperature was brought up to 75°C and 0.050 g of the catalyst suspended in 50 cc of n-heptane were added. Hydrogen was introduced until the pressure reached 3 atm. and then ethylene was added until the pressure increased to 10 atm. The temperature rose to about 85°C and was maintained at 80°G + 5 during the polymerization. The total pressure was kept constant by continuously feeding ethylene. After two hours the suspension wa discharged from the autoclave.
The polymer was separated b filtration and dried at 100°C under vacuum. There were obtained 355 g of polyethylene - 7 33680/2 having an intrinsic viscosity of 2.5 dl/g. The yield in polymer was 222,000 g/g of titanium.
The preparation of the catalyst of Example 1 was repeated with the variant however that the reaction took place at 100°C instead of 135 0. - Analysis of the product thus obtained gave: Ti - 5.045&, 01 * 52.5$. X-ray chloride and that no magnesium analysis showed the presence of m&ghesium/hydroxychloride (K (OH)CI) was formed. 0·059 g of the product was used to polymerize ethylene as in Example 1. There were obtained 334 g of polymer having an intrinsic viscosity of 2.7 dl/g.
The yield of polymer was 209,000 g/g titanium.
Example 3 75 g of magnesium chloride hexahydrate were dehydrated for 8 hours at 110°C in a nitrogen stream in such a way as to remove all the absorbed water and some of the water of crystallization. X-ray examination showed the presence of significant amounts of the monohydrate (MgCl2 · lHgO). 70 g of the product were reacted with titanium tetrachloride as in Example 1. The Analysis of the washed "and dried product gave a titanium content of 10.0$ and a chlorine content of 54.6 . On X-ray analysis magnesium hydroxy-chloride Mg(0H)Cl was not found to be present. 0.015 g of this product was used to polymerize ethylene as in Example 1. After 4 hours there were obtained 196 g of polymer with an intrinsic viscosity of 2.4 dl/g The yield in polymer was 151>000 g/g titanium. - 8 - 33680/2 Example 4 A catalyst prepared as in Example 1 was used in the polymerization of propylene carried out under the following conditions: 1800 cc of technical n-heptane, 4*7 g of aluminium diethyl monochloride 0.037 g of the catalyst were introduced into a 5 litre autoclave purified with dry nitrogen* 2.5 atin of propylene and 0.3 atm of hydrogen were introduced. The temperature was maintained at 70°C. The total pressure was kept constant during the polymerization by continuously feeding propylene* After 4 hours the reaction mixture was discharged from the autoclave. The polymer was separated by filtration and dried under vacuum at 100?C. There were obtained 200 g of partially crystalline polypropylene. The yield in V*. '!''·'■··■ polymer was 71»000 g/g titanium.
Example 5 7 g magnesium chloride hexahydrate were reacted with 50 cc of titanium tetrachloride as in Example 1* Analysis of the washed and dried product showed Tl = 4.55% and 01 = 6 .9 · X-ray analysis showed that the product was substantially anhydrous magnesium chloride* 0.034 g of this product was used to polymerize ethylene as in Example 1. After 6 hours there were obtained 284 g of polymer having intrinsic viscosity of 2.3 d /g. The yield in polymer was 248,000 g/g titanium. - 9 - 33680/2 Examle n 23 g of magnesium chloride dihydrate (MgCl2 . H20) were reacted with 400 cc of titanium tetrachloride as in Example 1* Analysis of the washed and dried product showed Ti = 3.75$ and 01 « 68.5$. X-ray analysis showed that the product Is substantiall anhydrous magnesium chloride. Ο.Ο425 g of this product were used to polymerize ethylene as in Example 1. After 4 hours there were obtained 452 g of polymer in a yield of 283,000 g/g titanium.
Example 7 Into the autoclave of Example 1 were Introduced 300 cc of titanium tetrachloride. Uhe temperature was brought up to 135°C. 70 g of magnesium bromide hexahydrate ( gBr2 . 6H20) were introduced. After 1 hour of heating the excess of titanium tetrachloride was removed by hot filtration. The solid product left behind in the autoclave was repeatedly washed with boiling titanium tetrachloride, and then with boiling cyclohexane until the total disappearance of the titanium tetrachloride., Analysis of the solid product dried under vacuum at 100°C showed TI » 4. 5$ and 01 and Br respectively * 53^ and 10.5$.
X-ray analysis of the product showed that it is formed of prevailing quantities of magnesium chloride. 0*041 of the product was used to polymerize ethylene as in Example 1.; After 3 hours there were obtained 545 g of polymer having an intrinsic viscosity of 2.3 dl/g. The polymer yield was 310,000 g/g titanium. - 10 - 33680/2 Example, 6 70 g of magnesium chloride monohydrate (MgCl2 , HgO) were reacted with 300 cc of titanium tetrachloride as in Example' 1. Analysis of the washed and dried product showed 3?i = 0.75S& and CI « 60.2$. X-ray analysis showed is that the product/substantially anhydrous magnesium chloride. Ho hydroxy-chloride was found. 0.031 g of this product was used to polymerize ethylene as in Example 1, After 4 hours there were obtained 159 g of polymer. ihe yield was 757»000 g/g titanium. - 11 - 33680/2
Claims (18)
1. A catalyst for the polymerization of olefins which comprises a reaction product of a hydrated magnesium halide of the formula KtgX2 . nH20 wherein X is a halogen atom (except fluorine) and n is a number greater than 0 with a halogen-containing titanium or vanadium compound under conditions such that the hydrated magnesium halide is transformed at least on the surface into an anhydrous magnesium halide, which product is activated with a hydride or organometallic compound of a metal of Groups I, II or III of the Periodic System.
2. A catalyst according to Claim 1 in which in the hydrated magnesium halide X is CI or Br and n is from 1 to 6.
3. A catalyst according to Claim 2 in which n is from 1 to 4.
4. A catalyst according to Claim 1 or Claim 2 in which the hydrated magnesium halide is of the formula MgCl2 . 6H20, gCl2 . 2H20, M Clg ... 1H20, KgBr ., 6H20 or M Br2 . H20.
5. A catalyst according to any of the preceding claims in which the halogen containing titanium or vanadium compound is a normally liquid compound. - 12 - 33680/2
6. A catalyst according to Claim 5 in which the titanium or vanadium compound is a tetrahalide or halo-alcoholate.
7. A catalyst according to any of Claims 1 to 4 in which the titanium or vanadium compound is a solid compound soluble in a solvent which is Inert with respect to the hydrated and/or anhydrous magnesium hallde.
8. A catalyst according to any of the preceding claims in which the amount of titanium or vanadium compound on the support expressed as tetrahalide is from 0.01 to 20$ by weight.
9. A catalyst for the polymerization of Olefins substantially as herein described.
10. A catalyst for the polymerization of olefins substantially as herein described in any of the Examples.
11. A method of preparing a Catalyst aeoordin to any of the precedin claims in which the hydrated magnesium hallde is reacted with a stoichiometric excess of the titanium or vanadium compound In a liquid phase preheated to its boiling temperature and then the liquid phase is removed from the reaction zone, and the reaction product is activated with the hydroxide of an organic metallic compound.
12. A method of preparing a catalyst for the polymerization of olefins substantially as herein described. - 13 - 33680/2
13. 15· A method of preparing a catalyst for the polymerization of olefins substantially as herein described in any of the Examples.
14. A catalyst prepared by a method according to any of Claims 11 to 13.
15. A process of polymerizing olefins which is carried out in the presence of a catalyst according to any of Claims 1 to 10 or 14.
16. A process of polymerizing olefins substantially as herein described.
17. · A process of polymerizing olefins substantially as herein described in any of the Examples.
18. An olefin polymer prepared by a process according to Claims 15 to 17. PC/rb
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT1136069 | 1969-01-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IL33680A0 IL33680A0 (en) | 1970-03-22 |
| IL33680A true IL33680A (en) | 1973-10-25 |
Family
ID=11135097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL33680A IL33680A (en) | 1969-01-10 | 1970-01-08 | Catalysts for the polymerization of olefins |
Country Status (19)
| Country | Link |
|---|---|
| JP (1) | JPS4819794B1 (en) |
| AT (1) | AT304867B (en) |
| BE (1) | BE744222A (en) |
| BR (1) | BR7015928D0 (en) |
| CA (1) | CA923106A (en) |
| CS (1) | CS149676B2 (en) |
| DE (1) | DE2000586C3 (en) |
| DK (1) | DK127542B (en) |
| EG (1) | EG10828A (en) |
| ES (1) | ES375278A1 (en) |
| FR (1) | FR2028106A1 (en) |
| GB (1) | GB1291552A (en) |
| IL (1) | IL33680A (en) |
| NL (1) | NL160280C (en) |
| PL (1) | PL80431B1 (en) |
| RO (1) | RO57664A (en) |
| SE (1) | SE366484B (en) |
| SU (1) | SU417928A3 (en) |
| YU (1) | YU34486B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| LU61899A1 (en) | 1970-10-20 | 1972-06-28 | ||
| LU61917A1 (en) * | 1970-10-23 | 1972-06-28 | ||
| NL170962C (en) * | 1971-04-06 | 1983-01-17 | Montedison Spa | PROCESS FOR PREPARING CATALYSTS FOR POLYMERIZING OLEGINS |
| IT969340B (en) * | 1972-09-13 | 1974-03-30 | Montedison Spa | CATALYSTS FOR POLYMERIZATION OF POLYMER OLEFINS IN SPHERICAL FORM |
| US3907759A (en) * | 1972-10-06 | 1975-09-23 | Nissan Chemical Ind Ltd | Catalyst for polymerization of olefins and process for polymerization of olefins with use of said catalyst |
| US4277370A (en) | 1979-02-15 | 1981-07-07 | Standard Oil Company (Indiana) | Alpha-olefin polymerization catalyst |
| CA1225080A (en) * | 1983-01-28 | 1987-08-04 | Gil R. Hawley | Polyolefin polymerization process and catalyst |
| US4503159A (en) * | 1983-08-19 | 1985-03-05 | Phillips Petroleum Company | Polyolefin polymerization process and catalyst |
| US4585749A (en) * | 1983-09-28 | 1986-04-29 | Phillips Petroleum Company | Process for the preparation of an olefin polymerization catalyst |
| US4520121A (en) * | 1983-10-28 | 1985-05-28 | Inkrott Kenneth E | Magnesium halide hydrates and polymerization catalysts prepared therefrom |
| TW248565B (en) | 1991-08-14 | 1995-06-01 | Mitsui Petroleum Chemicals Industry Co |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3238146A (en) * | 1960-03-21 | 1966-03-01 | Shell Oil Co | Catalysts and their preparation |
| FR85522E (en) * | 1964-03-03 | 1965-08-27 | Solvay | Process for the polymerization and copolymerization of olefins |
| NL135604C (en) * | 1965-06-25 | |||
| FR1516800A (en) * | 1966-10-21 | 1968-03-15 | Solvay | Process for the polymerization and copolymerization of olefins. |
| NL137364C (en) * | 1968-03-22 |
-
1970
- 1970-01-05 SE SE00070/70A patent/SE366484B/xx unknown
- 1970-01-07 NL NLAANVRAGE7000161,A patent/NL160280C/en not_active IP Right Cessation
- 1970-01-07 DK DK5070AA patent/DK127542B/en not_active IP Right Cessation
- 1970-01-08 GB GB916/70A patent/GB1291552A/en not_active Expired
- 1970-01-08 SU SU1395616A patent/SU417928A3/ru active
- 1970-01-08 IL IL33680A patent/IL33680A/en unknown
- 1970-01-08 DE DE2000586A patent/DE2000586C3/en not_active Expired
- 1970-01-08 PL PL1970138062A patent/PL80431B1/pl unknown
- 1970-01-08 CS CS70161A patent/CS149676B2/en unknown
- 1970-01-08 CA CA071729A patent/CA923106A/en not_active Expired
- 1970-01-08 YU YU28/70A patent/YU34486B/en unknown
- 1970-01-09 ES ES375278A patent/ES375278A1/en not_active Expired
- 1970-01-09 BR BR215928/70A patent/BR7015928D0/en unknown
- 1970-01-09 JP JP45002549A patent/JPS4819794B1/ja active Pending
- 1970-01-09 BE BE744222D patent/BE744222A/en not_active IP Right Cessation
- 1970-01-09 FR FR7000674A patent/FR2028106A1/fr active Pending
- 1970-01-09 AT AT16870A patent/AT304867B/en not_active IP Right Cessation
- 1970-01-09 RO RO62088A patent/RO57664A/ro unknown
-
1974
- 1974-09-15 EG EG386/74A patent/EG10828A/en active
Also Published As
| Publication number | Publication date |
|---|---|
| YU34486B (en) | 1979-09-10 |
| NL7000161A (en) | 1970-07-14 |
| DE2000586C3 (en) | 1983-11-10 |
| DE2000586A1 (en) | 1970-07-16 |
| CS149676B2 (en) | 1973-07-25 |
| DK127542B (en) | 1973-11-26 |
| GB1291552A (en) | 1972-10-04 |
| DE2000586B2 (en) | 1974-03-07 |
| RO57664A (en) | 1975-02-15 |
| SU417928A3 (en) | 1974-02-28 |
| BR7015928D0 (en) | 1973-04-05 |
| YU2870A (en) | 1979-02-28 |
| FR2028106A1 (en) | 1970-10-09 |
| BE744222A (en) | 1970-07-09 |
| EG10828A (en) | 1976-12-31 |
| PL80431B1 (en) | 1975-08-30 |
| CA923106A (en) | 1973-03-20 |
| NL160280B (en) | 1979-05-15 |
| NL160280C (en) | 1983-04-18 |
| IL33680A0 (en) | 1970-03-22 |
| ES375278A1 (en) | 1972-05-16 |
| JPS4819794B1 (en) | 1973-06-15 |
| SE366484B (en) | 1974-04-29 |
| AT304867B (en) | 1973-01-25 |
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