CA1087153A - Process for the preparation of a catalyst - Google Patents
Process for the preparation of a catalystInfo
- Publication number
- CA1087153A CA1087153A CA266,614A CA266614A CA1087153A CA 1087153 A CA1087153 A CA 1087153A CA 266614 A CA266614 A CA 266614A CA 1087153 A CA1087153 A CA 1087153A
- Authority
- CA
- Canada
- Prior art keywords
- titanium
- compound
- catalyst
- magnesium
- carrier
- 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
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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
Abstract
Abstract of the disclosure:
A process for preparing a catalyst for the polymerization of 1-olefins and a process for preparing polyolefins using said catalyst. The catalyst is prepared by reacting a carrier comprising a silicon dioxide, an aluminum oxide, or mixture thereof, having a content of hydroxyl groups with a magnesium compound of the formula RMgX wherein R is a hydrocarbon radical having 1 to 20 carbon atoms and X is chlorine, bromine or iodine, the reaction product is reacted with a halogen-containing titanium compound, and the resultant product is subsequently reacted with an organo-metallic compound.
A process for preparing a catalyst for the polymerization of 1-olefins and a process for preparing polyolefins using said catalyst. The catalyst is prepared by reacting a carrier comprising a silicon dioxide, an aluminum oxide, or mixture thereof, having a content of hydroxyl groups with a magnesium compound of the formula RMgX wherein R is a hydrocarbon radical having 1 to 20 carbon atoms and X is chlorine, bromine or iodine, the reaction product is reacted with a halogen-containing titanium compound, and the resultant product is subsequently reacted with an organo-metallic compound.
Description
-`` 1087~53 The present invention relates to the preparation of a cata-lyst for the polymerization of ethylene and higher 1-olefins.
A process for the preparation of a catalyst for use in the polymerization of olefins has been described, in which organic alkali metal compounds are allowed to act on the hydroxyl groups of finely dispersed metal oxides, for example silicon dioxide, and the reaction product is reacted subsequently with a metal halide selected from group VII a of the Periodic system, espe-cially manganese hexachloride (cf. US Patent 3,205,177). The solid obtained gives a catalyst suitable for use in the olefin polymerization when being combined with a metallo-organic com-pound selected from on~ of groups I-to III of the periodic system. These catalysts, however, have a low activity and produce only ~.4 kg of polyethylene per gram of manganese in 3 ~5 hours at a polymerization temperature of 95 C and under an ethylene pressure of 98 atmospheres.
A further process comprises impregnating a solid carrier, for example calcium carbonate, with an aluminum-organic compound and treating it subsequently with an excess of titanium tetrà-chloride, whereby reduced titanium trichloride forms a sediment on the carrier (cf. British Patent No. 927,969). Thereafter, the excess of titanium tetrachlorid must be removed. The poly-merization activity of the catalysts thus obtained, however, is likewi$e so low that the residual catalyst must be removed from the polyolefin produced.
Furthermore, thera are known catalysts to be used in the polymerization of olefins, which are obtained by treating an oxide, hydroxide, carbonate or sulfate of magnesium or calcium 29 with an aluminum-organic compound and by subseauently reacting ~0~153 the compound obtained with a mixture of halides of titanium and vanadium (cf. German Auslegeschrift No. 2,140,326~. In the pre-paration of these catalysts the aluminum-organic compound and the transition metal compound of titanium and vanadium are used in an amount such that the separation of an excess of these compounds may be dispensed with, but on the other hand, active `
catalysts for the polyolefin polymerization cannot be obtained when using as transition metal compounds singly titanium com-pounds. A catalyst, for examplej which had been prepared by reacting magnesium oxide with aluminum triethyl and by subse-quently treating the product obtained with titanium tetrachloride yielded per hour only 19.5 g of polyethylene per ~ gram of ti-tanium under an ethylene pressure of 39 atmospheres. A secondary treatment of the polyethylene obtained was necessary for remov-ing the residual catalyst because of the discoloration of poly-ethylene.
Finally process for the preparation of supported catalysts has been disclosed, in which an excess of a metallo-organic magne-sium or aluminum compound is allowed to act on silicon dioxide, ; 20 aluminum oxide or a mixture consisting of silicon dioxide and aluminum oxide having superficial hydroxyl groups and the re-action product is reac~ed,after the excess of said organo-metallic compound has been removed by washing, with an excess of a halogen compound of a transition metal selected from one of groups IVa, Va or VIa of the periodical system, and the ex-cess of the transition metal compound is removed by washing with a $olvent. By washing out the metallo-organic compounds of magnesium or aluminum and the transition metals there are formed ~9 highly diluted solutions, which must be decomposed subsequently.
:' , ~ ': . ' . ' .. , . ~ .
- '10~7153 As a consquence thereof, undesired waste products are obtained, which charge the waste water (cf. German Offenlegungsschrift No.
A process for the preparation of a catalyst for use in the polymerization of olefins has been described, in which organic alkali metal compounds are allowed to act on the hydroxyl groups of finely dispersed metal oxides, for example silicon dioxide, and the reaction product is reacted subsequently with a metal halide selected from group VII a of the Periodic system, espe-cially manganese hexachloride (cf. US Patent 3,205,177). The solid obtained gives a catalyst suitable for use in the olefin polymerization when being combined with a metallo-organic com-pound selected from on~ of groups I-to III of the periodic system. These catalysts, however, have a low activity and produce only ~.4 kg of polyethylene per gram of manganese in 3 ~5 hours at a polymerization temperature of 95 C and under an ethylene pressure of 98 atmospheres.
A further process comprises impregnating a solid carrier, for example calcium carbonate, with an aluminum-organic compound and treating it subsequently with an excess of titanium tetrà-chloride, whereby reduced titanium trichloride forms a sediment on the carrier (cf. British Patent No. 927,969). Thereafter, the excess of titanium tetrachlorid must be removed. The poly-merization activity of the catalysts thus obtained, however, is likewi$e so low that the residual catalyst must be removed from the polyolefin produced.
Furthermore, thera are known catalysts to be used in the polymerization of olefins, which are obtained by treating an oxide, hydroxide, carbonate or sulfate of magnesium or calcium 29 with an aluminum-organic compound and by subseauently reacting ~0~153 the compound obtained with a mixture of halides of titanium and vanadium (cf. German Auslegeschrift No. 2,140,326~. In the pre-paration of these catalysts the aluminum-organic compound and the transition metal compound of titanium and vanadium are used in an amount such that the separation of an excess of these compounds may be dispensed with, but on the other hand, active `
catalysts for the polyolefin polymerization cannot be obtained when using as transition metal compounds singly titanium com-pounds. A catalyst, for examplej which had been prepared by reacting magnesium oxide with aluminum triethyl and by subse-quently treating the product obtained with titanium tetrachloride yielded per hour only 19.5 g of polyethylene per ~ gram of ti-tanium under an ethylene pressure of 39 atmospheres. A secondary treatment of the polyethylene obtained was necessary for remov-ing the residual catalyst because of the discoloration of poly-ethylene.
Finally process for the preparation of supported catalysts has been disclosed, in which an excess of a metallo-organic magne-sium or aluminum compound is allowed to act on silicon dioxide, ; 20 aluminum oxide or a mixture consisting of silicon dioxide and aluminum oxide having superficial hydroxyl groups and the re-action product is reac~ed,after the excess of said organo-metallic compound has been removed by washing, with an excess of a halogen compound of a transition metal selected from one of groups IVa, Va or VIa of the periodical system, and the ex-cess of the transition metal compound is removed by washing with a $olvent. By washing out the metallo-organic compounds of magnesium or aluminum and the transition metals there are formed ~9 highly diluted solutions, which must be decomposed subsequently.
:' , ~ ': . ' . ' .. , . ~ .
- '10~7153 As a consquence thereof, undesired waste products are obtained, which charge the waste water (cf. German Offenlegungsschrift No.
2,l09,273).
It has now been found that a catalyst suitable for use in the polymerization of 1-olefins can be obtained by starting from the reaction product of a metal oxide with a Grignard com-pound as a carrier and a soluble titanium compound, which ca-talyst gives high yields and allows a good control of the mole-cular weight by means of hydrogen without making a separa-tion Of the excess of metallo-organic compounds and/or of ti-tanium compounds from the carrier necessary.
The present invention consequently provides a process for the preparation of a catalyst by reacting the reaction product of silicon dioxide and/or aluminum oxide and 1. a halogen-containing magnesium-organic compound and 2. a halogen compound of a transition metal ~omponent A) with a metaIlo-organic com7ound (component B), which comprises reacti.ng a silicon dioxide and/or aluminum oxide having a hydroxyl groups content of from 0.5 to 50 mmols/g first with a magnesium compound of the formula RMgX, in which R is a hydrocarbon radical having from 1 to 20 carbon atoms and X ts chlorine, bromine or iodine, in the presence of a diluent,.
in an amount of from 0.05 to 1 mol of magnesium compound per mol of hydroxyl~roups of the carrier and reacting thereafter the solid reaction product in suspension with a halogen-contain-ing titanium (IVl compound of the formula Tixn(oR~l4 n~ in which n is an integer of from 1 to 4, X is chlorine or bromine and R is a hydrocarbon radical having of from 1 to 12 carbon 2~ atoms, in an amount of from 0.01 to 1 mol of titanium compound = 1~)87153 per mol of hydroxyl groups of the carrier, to obtain the compo-nent A.
Suitable carriers are porous oxides or mixed oxides of sili-con and/or aluminum having a specific surface of from 50 to 1000 m2/g, preferably from 100 to 800, especially from 150 to 650 and a pore volume in the range of from 0.2 to 2 ml/g, pre-ferably of from 0.4 to 2, especially of from 0.6 to 1.7 ml/g.
The particle size is in the range of from 1 to 500 ~m, preferably from ~0 to 200 ~m, especially of from 20 to ~00 ~m. The number ~0 of hydroxyl groups depends on the specific surface and the tem- -perature of the preliminary treatment and is in the range of from 0.5 to 50 mmols, preferably of from 1 to 20, especially of from ~.5 to ~0, hydroxyl groups per gram of carrier, A num-ber of these oxides is prepared especially for ~eing used as a ~5 carrier of supported catalysts e They are commercial products.
Prior to the reaction of the hydroxyl groups of the carrier with the halogen-containing magnesium-organic compounds the ab-sorbed water must be removed by drying at a temperature of from ~20 to 800 C, preferably of from 200 to 500 C. The number of -hydroxyl groups (mmol of hydroxyl groups per gram of carrier~
may be modified by said treatment at high temperature, whereby - it is reduced with an increasing temperature.
After drying the carrier is kept under an inert gas atmos-phere, for example of nitrogen or argon, with the exclusion of air or water.
Suitable halogen--ontaining magnesium -organic compounds are compounds of the formula RMgX, in which R is a hydrocar~on radical having from ~ to 2~, preferably from 2 to ~0 carbon 29 atoms and X is c~lorine, bromine or iodine. These compounds are -:
. ~ . : .:, - : . : ~
-- , ~ ~ , : . . ..
:
110~7iS3 known as Grignard compounds and may be prepared, for example by reaction of metallic magnesium with a halogenhydrocarbon having from 1 to 20, preferably from 2 to 10 carbon atoms, for example an alkyl, cycloalkyl or arylhalide, in the presence of a nucleo-philic solvent, for example an ether (cf. Organikum, VEB DeutscherVerlag der Wissenschaften, Berlin, 1964, page 466). These com-pounds may also be prepared in a hydrocarbon in the absence of an ether. Preferred magnesium compounds are ethyl magnesium chloride, n-propyl magnesium chloride, i-propyl magnesium iodide, n-butyl magnesium chloride, t-butyl magnesium chloride, phenyl magnesium bromide. n-Propyl magnesium chloride and n-butyl mag-nesium chloride are used particularly preferably.
The Grignard compound reacts in known manner with the hy-s droxyl groups placed at the surface of the carrier at a tempera-~5 ture below 100 C while splitting off hydrocarbon , with the addi-tion of -MgX to the oxygen of the hydroxyl group according to the following equation:
_ o --O
-o-Si-oH + RMgX -O-Si-O-MgX + R-H
: . --O --O
~onsequently one mol of magnesium alkyl chlor~de is chemi-cally bound per mole of hydroxyl groups of the carrier. The number of hydroxyl groups of the carrier may, consequently, be determined by volumetric or chromatographic analysis of the ; hydrocarbon formed or by retitration of the excess of Grignard compound.
29 The reaction of the solid carrier with the Grignard com-~OE 75/F 298 i3 pound may be carried out in the following way: The solid carrier is suspended in an inert diluent, the dissolved Grignard compound is added at a temperature of from -20 to 150 C, preferably of from 0 to 120 C, especially of from 20 to 100 C and allowed to act on the suspension for a period of from 0.5 to 20, pre-ferably from 0.5 to 10, especially from 0.5 to 2 hours.. The pro-portion of Grignard compound and solid carrier is chosen such that from 0.05 to 1, preferably from 0.1 to 0.95 mol of alkyl magnesium halide are used per mole of hydroxyl groups of the carrier. The magnesium compound is applied on the carrier quan-titatively in said process. The reaction is completed when no more magnesium can be detected in the S~Pernatant solution after the solid carrier has settled.
Suitable diluents are all solvents inert with regard to Grignard compounds, for example saturatéd hydrocarbons or ethers, for example pentane, hexane, heptane, diethyl ether, tetrahydro-furane, or mixtures of both types of compounds.
After completion of the above reaction the diluent is sepa-rated by filtration and drying or directly by distillation, at 2Q a temperature of from 50 to 200 C, if it contains an ether.
~he separation of the diluent is necessary for removing the ether, which has been used for the preparation of the Grignard compound and formed a ~complex w~th said com~
pound, owin~ to the fact that the ether also reacts with the titanium compound while forming a complex ~nd disactivates the catalyst .
The separated diluent may be reused after having been re-covered.
29 The solid carrier impregnated with the Grignard compound .
~087~S3 is thereafter suspended again in an inert dispersing agent, pre-ferably in an inert hydrocarbon. A dispersing agent convention-ally used for the polymerization under low pressure according to Ziegler is chosen preferably.
When there had not been used an ether for the preparation of the Grignard compound, but a saturated hydrocarbon, the di-luent need not be separated and the titanium(IV) compound may be directly added to the reaction mixture.
Suitable inert dispersing agents are aliphatic or cycloali-phatic hydrocarbons, for example pentane, hexane, heptane, cyclo-hexane, methylcyclohex~ne as well as aromatic hydrocarbons, for example benzene, toluene, xylene, furthermore benzine or Diesel oil fractions, which have been carefully liberated from oxygen, sulfur compounds and moisture,may be used.
To the suspension obtained there is added subse~uently a halogen-containing titanium(IV) compound, at a temperature of from 20 to 140 C, preferably of from 30 to 130 C,especially of from 40 to 120 C and the mixture is stirred at this tempera-ture until a titanium compound can be detected no longer in the suernatant solution, generally within a period of from 2 to 20 hour$.
The halogen-containing titanium(IV~ compound is a compound of the formula TiX (OR~4 n' wherein n is an integer of from 1 to 4 and X is chlorine or bromine and R1 is a hydrocarbon radi-cal, preferably an alkyl, aryl or aralkyl radical having from 1 to ~2, preferably from 1 to 8 carbon atoms, especially a straight chain or branched alkyl radical having from 1 to 8 carbon atoms, for example TiCl4, Ticl3(o-n-c3H7?~ TiCl2(O-n-C3R7~2, 23 3 7)3' TiCl2(O-i-C3H7)2, TiCl3(O-i-c3H
~:" 1087153
It has now been found that a catalyst suitable for use in the polymerization of 1-olefins can be obtained by starting from the reaction product of a metal oxide with a Grignard com-pound as a carrier and a soluble titanium compound, which ca-talyst gives high yields and allows a good control of the mole-cular weight by means of hydrogen without making a separa-tion Of the excess of metallo-organic compounds and/or of ti-tanium compounds from the carrier necessary.
The present invention consequently provides a process for the preparation of a catalyst by reacting the reaction product of silicon dioxide and/or aluminum oxide and 1. a halogen-containing magnesium-organic compound and 2. a halogen compound of a transition metal ~omponent A) with a metaIlo-organic com7ound (component B), which comprises reacti.ng a silicon dioxide and/or aluminum oxide having a hydroxyl groups content of from 0.5 to 50 mmols/g first with a magnesium compound of the formula RMgX, in which R is a hydrocarbon radical having from 1 to 20 carbon atoms and X ts chlorine, bromine or iodine, in the presence of a diluent,.
in an amount of from 0.05 to 1 mol of magnesium compound per mol of hydroxyl~roups of the carrier and reacting thereafter the solid reaction product in suspension with a halogen-contain-ing titanium (IVl compound of the formula Tixn(oR~l4 n~ in which n is an integer of from 1 to 4, X is chlorine or bromine and R is a hydrocarbon radical having of from 1 to 12 carbon 2~ atoms, in an amount of from 0.01 to 1 mol of titanium compound = 1~)87153 per mol of hydroxyl groups of the carrier, to obtain the compo-nent A.
Suitable carriers are porous oxides or mixed oxides of sili-con and/or aluminum having a specific surface of from 50 to 1000 m2/g, preferably from 100 to 800, especially from 150 to 650 and a pore volume in the range of from 0.2 to 2 ml/g, pre-ferably of from 0.4 to 2, especially of from 0.6 to 1.7 ml/g.
The particle size is in the range of from 1 to 500 ~m, preferably from ~0 to 200 ~m, especially of from 20 to ~00 ~m. The number ~0 of hydroxyl groups depends on the specific surface and the tem- -perature of the preliminary treatment and is in the range of from 0.5 to 50 mmols, preferably of from 1 to 20, especially of from ~.5 to ~0, hydroxyl groups per gram of carrier, A num-ber of these oxides is prepared especially for ~eing used as a ~5 carrier of supported catalysts e They are commercial products.
Prior to the reaction of the hydroxyl groups of the carrier with the halogen-containing magnesium-organic compounds the ab-sorbed water must be removed by drying at a temperature of from ~20 to 800 C, preferably of from 200 to 500 C. The number of -hydroxyl groups (mmol of hydroxyl groups per gram of carrier~
may be modified by said treatment at high temperature, whereby - it is reduced with an increasing temperature.
After drying the carrier is kept under an inert gas atmos-phere, for example of nitrogen or argon, with the exclusion of air or water.
Suitable halogen--ontaining magnesium -organic compounds are compounds of the formula RMgX, in which R is a hydrocar~on radical having from ~ to 2~, preferably from 2 to ~0 carbon 29 atoms and X is c~lorine, bromine or iodine. These compounds are -:
. ~ . : .:, - : . : ~
-- , ~ ~ , : . . ..
:
110~7iS3 known as Grignard compounds and may be prepared, for example by reaction of metallic magnesium with a halogenhydrocarbon having from 1 to 20, preferably from 2 to 10 carbon atoms, for example an alkyl, cycloalkyl or arylhalide, in the presence of a nucleo-philic solvent, for example an ether (cf. Organikum, VEB DeutscherVerlag der Wissenschaften, Berlin, 1964, page 466). These com-pounds may also be prepared in a hydrocarbon in the absence of an ether. Preferred magnesium compounds are ethyl magnesium chloride, n-propyl magnesium chloride, i-propyl magnesium iodide, n-butyl magnesium chloride, t-butyl magnesium chloride, phenyl magnesium bromide. n-Propyl magnesium chloride and n-butyl mag-nesium chloride are used particularly preferably.
The Grignard compound reacts in known manner with the hy-s droxyl groups placed at the surface of the carrier at a tempera-~5 ture below 100 C while splitting off hydrocarbon , with the addi-tion of -MgX to the oxygen of the hydroxyl group according to the following equation:
_ o --O
-o-Si-oH + RMgX -O-Si-O-MgX + R-H
: . --O --O
~onsequently one mol of magnesium alkyl chlor~de is chemi-cally bound per mole of hydroxyl groups of the carrier. The number of hydroxyl groups of the carrier may, consequently, be determined by volumetric or chromatographic analysis of the ; hydrocarbon formed or by retitration of the excess of Grignard compound.
29 The reaction of the solid carrier with the Grignard com-~OE 75/F 298 i3 pound may be carried out in the following way: The solid carrier is suspended in an inert diluent, the dissolved Grignard compound is added at a temperature of from -20 to 150 C, preferably of from 0 to 120 C, especially of from 20 to 100 C and allowed to act on the suspension for a period of from 0.5 to 20, pre-ferably from 0.5 to 10, especially from 0.5 to 2 hours.. The pro-portion of Grignard compound and solid carrier is chosen such that from 0.05 to 1, preferably from 0.1 to 0.95 mol of alkyl magnesium halide are used per mole of hydroxyl groups of the carrier. The magnesium compound is applied on the carrier quan-titatively in said process. The reaction is completed when no more magnesium can be detected in the S~Pernatant solution after the solid carrier has settled.
Suitable diluents are all solvents inert with regard to Grignard compounds, for example saturatéd hydrocarbons or ethers, for example pentane, hexane, heptane, diethyl ether, tetrahydro-furane, or mixtures of both types of compounds.
After completion of the above reaction the diluent is sepa-rated by filtration and drying or directly by distillation, at 2Q a temperature of from 50 to 200 C, if it contains an ether.
~he separation of the diluent is necessary for removing the ether, which has been used for the preparation of the Grignard compound and formed a ~complex w~th said com~
pound, owin~ to the fact that the ether also reacts with the titanium compound while forming a complex ~nd disactivates the catalyst .
The separated diluent may be reused after having been re-covered.
29 The solid carrier impregnated with the Grignard compound .
~087~S3 is thereafter suspended again in an inert dispersing agent, pre-ferably in an inert hydrocarbon. A dispersing agent convention-ally used for the polymerization under low pressure according to Ziegler is chosen preferably.
When there had not been used an ether for the preparation of the Grignard compound, but a saturated hydrocarbon, the di-luent need not be separated and the titanium(IV) compound may be directly added to the reaction mixture.
Suitable inert dispersing agents are aliphatic or cycloali-phatic hydrocarbons, for example pentane, hexane, heptane, cyclo-hexane, methylcyclohex~ne as well as aromatic hydrocarbons, for example benzene, toluene, xylene, furthermore benzine or Diesel oil fractions, which have been carefully liberated from oxygen, sulfur compounds and moisture,may be used.
To the suspension obtained there is added subse~uently a halogen-containing titanium(IV) compound, at a temperature of from 20 to 140 C, preferably of from 30 to 130 C,especially of from 40 to 120 C and the mixture is stirred at this tempera-ture until a titanium compound can be detected no longer in the suernatant solution, generally within a period of from 2 to 20 hour$.
The halogen-containing titanium(IV~ compound is a compound of the formula TiX (OR~4 n' wherein n is an integer of from 1 to 4 and X is chlorine or bromine and R1 is a hydrocarbon radi-cal, preferably an alkyl, aryl or aralkyl radical having from 1 to ~2, preferably from 1 to 8 carbon atoms, especially a straight chain or branched alkyl radical having from 1 to 8 carbon atoms, for example TiCl4, Ticl3(o-n-c3H7?~ TiCl2(O-n-C3R7~2, 23 3 7)3' TiCl2(O-i-C3H7)2, TiCl3(O-i-c3H
~:" 1087153
3 2C6H5), TiC12(O-CH2C6H5)2, TiC13(0-i-C H ) and Ticl2(o-i-c4H9)2 Titanium tetrachloride, TiC12(0-i-C3H7)2 and TiC13 (0-i-C3H7) are used preferably.
The proportion between titanium compound and solid carrier is chosen such that of from 0.01 to 1, preferably o from 0.05 to 1, especially of from 0.1 to 1 mol of titanium compound are used per 1 mole of hydroxyl groups of the solid carrier.
The proportion of Grignard compound and titanium compound is chosen such that the atomar ratio between magnesium and titanium in the catalyst component A is in the range of from 0.01 to 10, preferably of from 0.05 to 5, especially of from 0.1 to 2~
The catalyst component A thus obtained is used either directly in the form of the suspension or after removal of the diluent and drying, Suitable compounds for the component B are organic compounds of the metals selected from groups IA, IIA and IIIA of the periodic system. Aluminum-organic compounds are preferably used as component B, Suitable aluminium-organic compounds are the reaction products of aluminum-trialkyls or aluminum dialkyl hydrides, containing alkyl radicals having from 1 to 16 carbon atoms, with dienes having from 4 to 20 carbon atoms. The reaction products of aluminum trialkyls or aluminum-dialkyl hydrides, the alkyl radicals of which have from 4 to 8 carbon atoms, for example phellandrene or a diene of the formula _ g _ .
~87153 CH2 C ~ (CH2 ) a ~ C = CH2 - 9a -7~3 wherein R2 is hydrogen, an alkyl radical, an alkylene radical having a non terminal double bond or a mononuclear ar~ radical and a is 0 or 1, are u,ed preferably. There may be mentioned, by way of example, 1,4-butadiene, isoprene, 2-phenyl butadiene, 1,4-pentadiene, 1,3-pentadiene and myrcene. The reaction pro-ducts of Al(i-C4Hg)3 or Al(i-C4H9)2H with isoprene are used preferably. They comprise, for example, compounds of the formula ~Z - Al - R4 - ~Y7n ~ Z
wherein Y means the groups -Al-, -Al- or -Al / A1-, R
Z is hydrogen, the isobutyl group, the dihydroisoprenyl group ~5 or an oligomer of this group, R3 is the isobutyl radical, R4 is the tetrahydroisoprenylene radical and n is an integer of from 1 to 20, and compounds of the formula r Al - R4 - ~Y7 - R4 w~erein Y, R3 and R4 and n are defined as above. The ratio be-tween C5 and C4 radicals in the reaction products of Al(i-C4Hg)3 or Al(i-C4Hg~2H with isoprene may generally be in the range of from 0.25 to 10, preferably 1 to 4. A compound of this type being commercially available under the name "aluminum isoprenyl"
is used particularly preferably.
Further suitable compounds for component B are chlorine-containing aluminum-organic compounds, for example dialkyl alu-2~ minum monochlorides of the formula R52AlCl or alkyl aluminum ses-~ ~O --1' .
qui-chlorides of the formula R53Al2Cl3, wherein R5 is a hydro-carbon radical having from 1 to 16 carbon atoms, preferably an alkyl radical having from 1 to 16, especially from 2 to 12 car-bon atoms. There may be mentioned, by way of example (C2H5)2AlCl, (i-C4H9~2AlCl~ (C2H5)3A 2 3 Especially suitable compounds for the component B are alu-minum trialkyles of the formula AlR53 or aluminum dialkyl hydri-des of the formula AlR52H, wherein R5 is a hydrocarbon radical having from 1 to 16 carbon atoms, preferably an alkyl radical having from 1 to 16, especially from 2 to 4 carbon atoms, for example Al(C2H5)3, Al(C2H5)2~ Al(C3H7)2H~ ( 4 9 3 Al(i-C4H9)2H-The conversion of the titanium(IV~ compound of component A
into the polymerization active compound ha~ing a lower valency is advantageously performed during the polymerization by the metallo-organic compound (component B) at a temperature of from 20 to ~50 C, preferably of from 60 to 140 C~
Component A may also be treated with a metallo-organic com-pound prior to polymerizing and be used subsequently in the poly-merization at a temperature of from -30 to 150a C, preferably of from 0 to ~00 C, with a molar ratio between metallo-organic compound and titanium compound of from 0.2:1 to 3:1, preferably from 0.5 1~to 2 1. If a chlor;ne-containing metallo-organic compound is used it is advisable to wash the reaction product obtained with fresh dispersing agent. Therea$ter it is activa-ted with a further metallo-organic compound at a temperature o$
from 20 to 150 C.
When usingAthe catalyst according to the invention at least 29 one 1-olefin of the formula R6-CH--CH2, wherein R6 is hydrogen - ~1 -.
or a straight chain or branched alkyl radical having from 1 to 10, preferably from 1 to 8 carbon atoms, is polymerized. Examples of such olefins are ethylene, propylene, butene-1, hexene-1,
The proportion between titanium compound and solid carrier is chosen such that of from 0.01 to 1, preferably o from 0.05 to 1, especially of from 0.1 to 1 mol of titanium compound are used per 1 mole of hydroxyl groups of the solid carrier.
The proportion of Grignard compound and titanium compound is chosen such that the atomar ratio between magnesium and titanium in the catalyst component A is in the range of from 0.01 to 10, preferably of from 0.05 to 5, especially of from 0.1 to 2~
The catalyst component A thus obtained is used either directly in the form of the suspension or after removal of the diluent and drying, Suitable compounds for the component B are organic compounds of the metals selected from groups IA, IIA and IIIA of the periodic system. Aluminum-organic compounds are preferably used as component B, Suitable aluminium-organic compounds are the reaction products of aluminum-trialkyls or aluminum dialkyl hydrides, containing alkyl radicals having from 1 to 16 carbon atoms, with dienes having from 4 to 20 carbon atoms. The reaction products of aluminum trialkyls or aluminum-dialkyl hydrides, the alkyl radicals of which have from 4 to 8 carbon atoms, for example phellandrene or a diene of the formula _ g _ .
~87153 CH2 C ~ (CH2 ) a ~ C = CH2 - 9a -7~3 wherein R2 is hydrogen, an alkyl radical, an alkylene radical having a non terminal double bond or a mononuclear ar~ radical and a is 0 or 1, are u,ed preferably. There may be mentioned, by way of example, 1,4-butadiene, isoprene, 2-phenyl butadiene, 1,4-pentadiene, 1,3-pentadiene and myrcene. The reaction pro-ducts of Al(i-C4Hg)3 or Al(i-C4H9)2H with isoprene are used preferably. They comprise, for example, compounds of the formula ~Z - Al - R4 - ~Y7n ~ Z
wherein Y means the groups -Al-, -Al- or -Al / A1-, R
Z is hydrogen, the isobutyl group, the dihydroisoprenyl group ~5 or an oligomer of this group, R3 is the isobutyl radical, R4 is the tetrahydroisoprenylene radical and n is an integer of from 1 to 20, and compounds of the formula r Al - R4 - ~Y7 - R4 w~erein Y, R3 and R4 and n are defined as above. The ratio be-tween C5 and C4 radicals in the reaction products of Al(i-C4Hg)3 or Al(i-C4Hg~2H with isoprene may generally be in the range of from 0.25 to 10, preferably 1 to 4. A compound of this type being commercially available under the name "aluminum isoprenyl"
is used particularly preferably.
Further suitable compounds for component B are chlorine-containing aluminum-organic compounds, for example dialkyl alu-2~ minum monochlorides of the formula R52AlCl or alkyl aluminum ses-~ ~O --1' .
qui-chlorides of the formula R53Al2Cl3, wherein R5 is a hydro-carbon radical having from 1 to 16 carbon atoms, preferably an alkyl radical having from 1 to 16, especially from 2 to 12 car-bon atoms. There may be mentioned, by way of example (C2H5)2AlCl, (i-C4H9~2AlCl~ (C2H5)3A 2 3 Especially suitable compounds for the component B are alu-minum trialkyles of the formula AlR53 or aluminum dialkyl hydri-des of the formula AlR52H, wherein R5 is a hydrocarbon radical having from 1 to 16 carbon atoms, preferably an alkyl radical having from 1 to 16, especially from 2 to 4 carbon atoms, for example Al(C2H5)3, Al(C2H5)2~ Al(C3H7)2H~ ( 4 9 3 Al(i-C4H9)2H-The conversion of the titanium(IV~ compound of component A
into the polymerization active compound ha~ing a lower valency is advantageously performed during the polymerization by the metallo-organic compound (component B) at a temperature of from 20 to ~50 C, preferably of from 60 to 140 C~
Component A may also be treated with a metallo-organic com-pound prior to polymerizing and be used subsequently in the poly-merization at a temperature of from -30 to 150a C, preferably of from 0 to ~00 C, with a molar ratio between metallo-organic compound and titanium compound of from 0.2:1 to 3:1, preferably from 0.5 1~to 2 1. If a chlor;ne-containing metallo-organic compound is used it is advisable to wash the reaction product obtained with fresh dispersing agent. Therea$ter it is activa-ted with a further metallo-organic compound at a temperature o$
from 20 to 150 C.
When usingAthe catalyst according to the invention at least 29 one 1-olefin of the formula R6-CH--CH2, wherein R6 is hydrogen - ~1 -.
or a straight chain or branched alkyl radical having from 1 to 10, preferably from 1 to 8 carbon atoms, is polymerized. Examples of such olefins are ethylene, propylene, butene-1, hexene-1,
4-methyl-pentene-1, octene-1. ~thylene is preferably polymeriz-ed alone or as a mixture consisting of at least 70 ~ by weightof ethylene and at most 30 % by weight of a further 1-olefin of the above formula . Ethylene is especially polymerized either alone or as a mixture of at least 92 % by weight of ethy-lene and at most 8 ~ by weight of a further 1-olefin of the above formula.
The molecular weight of the polymer is controlled in known manner, preferably by using hydrogen.
The po~ymerization may be carried out in solution, in sus-pension or in the gaseous phase, continuously or discontinuously, at a temperature of from 20 to 150 C, preferably of from 60 to 140~ C, under a pressure of from 0.5 to 50 bars. It is carried out preferably under the technically interesting pressure in the range of from 1 to 40 bars.
Thereby the titanium compound is used in a concentration of 2Q from 0.005 to 1.5 preferably of from 0.05 to 1 mmol per liter of dispersing agent or reactor volume. The metallo-organic com-pound is used in a con~entration of from 0.5 to 10 mmols, pre-ferably of from 2 to 6 mmols per liter of dispersing agent or reactor volume. Higher concentrations are also possible princi-pally.
~e polymerization in suspens;i~on or solution is carried out in a conventional inert solvent for low pressure processes accord-ing to Zieglerrwhich have been described above.
24 The process according to the invention has the advantage that ' . .
.
8~S3 excessive metal compounds must no be removed from the catalyst component A by washing,owing to the fact that both the halo-gen-containing magnesium-organic compound used and the halogen-containing titanium(IV) compound react completely with the carrier. Consequently, no washing]iquids are formed, from which the metal compouns must be separated prior to the secon-dary treatment. As a consequence thereof there are formed no metal-containing waste water or slurries. During the polymeri-zation of ethylene and higher 1-olefins the catalyst according to the invention gives high catalyst yields already under low pressure, for example of from 1 to 7 bars, such that the mag-nesium/titanium and aluminum compound may completely remain in the polymer; a dïscoloration of the polyolefin or corrosion - phenomena on the processing machines do not occur. Thus expen-sive operations such as a decomposition of the catalyst and a removal of the catalyst may be dispensed with. Carrying out the ~ polymerization under a higher pressure permits to use a still ; smaller quantity of catalyst, as the catalyst yield is highly im-proved with an increasing polymerization pressure.
The catalyst according to the invention is especially sui-table for the polymerization of ethylene in the gaseous phase in a fluidized bed. The use of oxide carriers having a particle size of more than 30 ~m, which may be obtained, for example by separating fine particles by sieving, prevents that finely di-vided catalysts or polymer parts are carried out of the fluidiz-ed bed and form deposits in exterior zones of the reactor.
The catalyst according to the invention permits to prepare a polymer, the powder in bulk of which has a high air permeabi-2~ lity and thus the powder may directly be used in the processing - ~3 -:, .
by injection molding or extrusion without previous granulation.
A good air permeability of the powder in bulk in the extruder, feeding zone prevents an incorporation of air into the molten polymer, which would cause a formation of bubbles in the finish-ed part.
The porous silicon dioxide having superficial OH group is designed as "silicic acid" in the examples.
For determinating the number of hydrox~ groups of the carrier 10.0 g of the dried silicic ~cid are reacted under an argon atmosphere while refluxing and stirring with a solution of 500 mmols of n-propyl magnesium chloride in 500 ml of diethyl ether, for a period of 4 hours. After settling of the silicic acid magnesium is retitrated in the supernatant solution by way of complexometry.
The titanium content of component A is determined colorimetri-cally by using hydrogen peroxide (cf. G.O. M~ller, Praktikum der quantitativen chemischen Analyse, 4th edition, (1957~, page 243~.
For the polymerization in suspension there is used a hy-drated Diesel o~l fraction having a boiling range of from 140 to 200 C.
The melt index of the polymer is determined according to DIN (--German Industrial Standard) 53,735, at 190 C, by using a load of 5 kg for i5 and of 15 kg for i15.
The reduced specific viscosity (RSV~ is determined with a solution of decahydronaphthalene at ~35 C at a concentration of g/l.
The bulk density is determined by weighing 100 cm3 of poly-2~ ethylene powder.
- ~4 -. .' . ,: : , : ..
.
- . -,. ' ' ' .
The air permeability is determined in the following manner: 100 cm3 of polyethylene powder are placed in a graduated cylinder, which has an inner diamter of 3 cm and a fritted glass bottom and air is suctioned through the powder at a rate of flow of 4 l/h; the pressure decrease occuring in the powder in bulk is determined. The air per-; meability is then determined in the following manner:
air permeability(L) = height of the packageXflow velocity diameter of the cylinder X pressure loss.
In the present invention L is 0.023/~ p - 1, whereby ~ p are millimeters of the water column and 1 mm water column corresponds to the pressure loss of the glas frit. The di-mension of L is tcm3 sec/g).
; ~5 All solvents are dist;lled under an inert gas atmosphere having a purity of at least 99.995 % in a circulation appa-ratus while passing over benzophenone potassium and are with-drawn under an inert gas atmosphere. The preparation of the catalyst and the polymerization of ethylene are carried out ; 2Q under an argon atmosphere or under an atmosphere of purified nitrogen while carfully excluding air and humidity.
The following examples ~llustrate the invention:
; E X A M P L E 1:
A silicic acid having a specif~c surface of about 300 m2/g, a pore volume of ~.65 cm3/g, and an average particle size of 70 ~m is dri-ed for 6 hcurs ~n a fluidized bed at 460 C under an argon atmosphere and kept under an argon atmosphere. The number of hydroxyl groups is 1.7 mmols of hydroxy groups per 29 1 g of si~ic~c acid.
:: . . :
- : :
: :
: . : :
. .
~ lS3 HOE 75/F 298 107 g of this silicic acid are suspended in 500 ml of n-heptane under an argon atmosphere, 343 ml of a solution of 172 mmols of n-propyl magnesium chloride (1.6 mmols of magnesium per 1 g of silicic acid) in diethyl ether are added and the mix-ture is heated for 4 hours to 50 C. The solvent is withdrawn thereafter in a rotary evaporator and the solid product is dried for 2 hours at 120 C under 0.5 torr. Thereafter the . solid product is suspended in 500 ml of n-heptane under an argon atmosphere, 20.3 g of titanium tetrachloride (1.0 mmol of tita-nium per 1 g of silicic acid~ are added and the mixture is stir-red for 7 hours at 90 C. Heptane is thereafter withdrawn at 120 C in the rotary evaporator under atmospheric pressure. 128 g of a flowable powder is obtained.
The titanium analysis reveals 39.8 mg of titanium per 1 g of the component A. The atomar ratio of magnesium/titanium is 1.6:~.
500 ml of Diesel oil are given into a 1 liter autoclave provided with a flatblade agitator, the air is displaced by eva-cuating and introducin3 nitrogen under pressure three times and the autoclave ~s heated to 85 C. 1.14 g of aluminum triethyl and Q.~2 g of the catalyst component A are added. Hydrogen is then introduced until a pressure of 2 bars is attained and ethy-lene in an amount sufficient to maintain a total pressure of
The molecular weight of the polymer is controlled in known manner, preferably by using hydrogen.
The po~ymerization may be carried out in solution, in sus-pension or in the gaseous phase, continuously or discontinuously, at a temperature of from 20 to 150 C, preferably of from 60 to 140~ C, under a pressure of from 0.5 to 50 bars. It is carried out preferably under the technically interesting pressure in the range of from 1 to 40 bars.
Thereby the titanium compound is used in a concentration of 2Q from 0.005 to 1.5 preferably of from 0.05 to 1 mmol per liter of dispersing agent or reactor volume. The metallo-organic com-pound is used in a con~entration of from 0.5 to 10 mmols, pre-ferably of from 2 to 6 mmols per liter of dispersing agent or reactor volume. Higher concentrations are also possible princi-pally.
~e polymerization in suspens;i~on or solution is carried out in a conventional inert solvent for low pressure processes accord-ing to Zieglerrwhich have been described above.
24 The process according to the invention has the advantage that ' . .
.
8~S3 excessive metal compounds must no be removed from the catalyst component A by washing,owing to the fact that both the halo-gen-containing magnesium-organic compound used and the halogen-containing titanium(IV) compound react completely with the carrier. Consequently, no washing]iquids are formed, from which the metal compouns must be separated prior to the secon-dary treatment. As a consequence thereof there are formed no metal-containing waste water or slurries. During the polymeri-zation of ethylene and higher 1-olefins the catalyst according to the invention gives high catalyst yields already under low pressure, for example of from 1 to 7 bars, such that the mag-nesium/titanium and aluminum compound may completely remain in the polymer; a dïscoloration of the polyolefin or corrosion - phenomena on the processing machines do not occur. Thus expen-sive operations such as a decomposition of the catalyst and a removal of the catalyst may be dispensed with. Carrying out the ~ polymerization under a higher pressure permits to use a still ; smaller quantity of catalyst, as the catalyst yield is highly im-proved with an increasing polymerization pressure.
The catalyst according to the invention is especially sui-table for the polymerization of ethylene in the gaseous phase in a fluidized bed. The use of oxide carriers having a particle size of more than 30 ~m, which may be obtained, for example by separating fine particles by sieving, prevents that finely di-vided catalysts or polymer parts are carried out of the fluidiz-ed bed and form deposits in exterior zones of the reactor.
The catalyst according to the invention permits to prepare a polymer, the powder in bulk of which has a high air permeabi-2~ lity and thus the powder may directly be used in the processing - ~3 -:, .
by injection molding or extrusion without previous granulation.
A good air permeability of the powder in bulk in the extruder, feeding zone prevents an incorporation of air into the molten polymer, which would cause a formation of bubbles in the finish-ed part.
The porous silicon dioxide having superficial OH group is designed as "silicic acid" in the examples.
For determinating the number of hydrox~ groups of the carrier 10.0 g of the dried silicic ~cid are reacted under an argon atmosphere while refluxing and stirring with a solution of 500 mmols of n-propyl magnesium chloride in 500 ml of diethyl ether, for a period of 4 hours. After settling of the silicic acid magnesium is retitrated in the supernatant solution by way of complexometry.
The titanium content of component A is determined colorimetri-cally by using hydrogen peroxide (cf. G.O. M~ller, Praktikum der quantitativen chemischen Analyse, 4th edition, (1957~, page 243~.
For the polymerization in suspension there is used a hy-drated Diesel o~l fraction having a boiling range of from 140 to 200 C.
The melt index of the polymer is determined according to DIN (--German Industrial Standard) 53,735, at 190 C, by using a load of 5 kg for i5 and of 15 kg for i15.
The reduced specific viscosity (RSV~ is determined with a solution of decahydronaphthalene at ~35 C at a concentration of g/l.
The bulk density is determined by weighing 100 cm3 of poly-2~ ethylene powder.
- ~4 -. .' . ,: : , : ..
.
- . -,. ' ' ' .
The air permeability is determined in the following manner: 100 cm3 of polyethylene powder are placed in a graduated cylinder, which has an inner diamter of 3 cm and a fritted glass bottom and air is suctioned through the powder at a rate of flow of 4 l/h; the pressure decrease occuring in the powder in bulk is determined. The air per-; meability is then determined in the following manner:
air permeability(L) = height of the packageXflow velocity diameter of the cylinder X pressure loss.
In the present invention L is 0.023/~ p - 1, whereby ~ p are millimeters of the water column and 1 mm water column corresponds to the pressure loss of the glas frit. The di-mension of L is tcm3 sec/g).
; ~5 All solvents are dist;lled under an inert gas atmosphere having a purity of at least 99.995 % in a circulation appa-ratus while passing over benzophenone potassium and are with-drawn under an inert gas atmosphere. The preparation of the catalyst and the polymerization of ethylene are carried out ; 2Q under an argon atmosphere or under an atmosphere of purified nitrogen while carfully excluding air and humidity.
The following examples ~llustrate the invention:
; E X A M P L E 1:
A silicic acid having a specif~c surface of about 300 m2/g, a pore volume of ~.65 cm3/g, and an average particle size of 70 ~m is dri-ed for 6 hcurs ~n a fluidized bed at 460 C under an argon atmosphere and kept under an argon atmosphere. The number of hydroxyl groups is 1.7 mmols of hydroxy groups per 29 1 g of si~ic~c acid.
:: . . :
- : :
: :
: . : :
. .
~ lS3 HOE 75/F 298 107 g of this silicic acid are suspended in 500 ml of n-heptane under an argon atmosphere, 343 ml of a solution of 172 mmols of n-propyl magnesium chloride (1.6 mmols of magnesium per 1 g of silicic acid) in diethyl ether are added and the mix-ture is heated for 4 hours to 50 C. The solvent is withdrawn thereafter in a rotary evaporator and the solid product is dried for 2 hours at 120 C under 0.5 torr. Thereafter the . solid product is suspended in 500 ml of n-heptane under an argon atmosphere, 20.3 g of titanium tetrachloride (1.0 mmol of tita-nium per 1 g of silicic acid~ are added and the mixture is stir-red for 7 hours at 90 C. Heptane is thereafter withdrawn at 120 C in the rotary evaporator under atmospheric pressure. 128 g of a flowable powder is obtained.
The titanium analysis reveals 39.8 mg of titanium per 1 g of the component A. The atomar ratio of magnesium/titanium is 1.6:~.
500 ml of Diesel oil are given into a 1 liter autoclave provided with a flatblade agitator, the air is displaced by eva-cuating and introducin3 nitrogen under pressure three times and the autoclave ~s heated to 85 C. 1.14 g of aluminum triethyl and Q.~2 g of the catalyst component A are added. Hydrogen is then introduced until a pressure of 2 bars is attained and ethy-lene in an amount sufficient to maintain a total pressure of
5.9 bars. After 2 hours of polymerization at 85 C the poly-et~ylene powder is separated from the dispersing agent by filtra-tion and dried for 15 hours at 95 C in vacuo. 115 g of poly-ethylene are obtained having an i5 value of 9.3 and a bulk den-s~ty of 330 g/l.
29 The yield of polyethylene was 24,000 g per 1 g of titanium .
- ~08~7i53 or 958 g per 1 g of the catalyst component A.
E X A M P_L E 2:
Ethylene is polymerized in the presence of 0.22 g of the catalyst component A described in Example 1 under the same condi-tions as in Example 1,but by using instead of aluminum triethyle 1.98 g of aluminum triisobutyle. After 2 hours there are obtain-ed 145 g of polyethylene having a melt index i5 of 7.9 and a bulk density of 350 g/l. The RSV value is 1.84 g dl/g. There are obtained per 1 gram of titanium 16 600 g of polyethylene and per gram of the catalyst component A, 659 g.
E X A M P ~ E 3:
Polymerization of ethylene in the gaseous phase .. _, . . . . . .. .
2 kg of polyethylene (i5=10.8, buIk desnsity 4~0 g/I) are introduced in-to a lying 80 liter rea^tor provided with a scraping stirrer.
~5 The reactor is liberated from air by evacuating several times and by flushing for several hours with an ethylene-hydrogen mix-ture and is heated thereafter to 90 C. 17.1 g of aluminum tri-ethyl and 2.4~ g of the catalyst component A prepared according to Example 1 are added. 2 kg of ethylene/hour and hydrogen are introduced for a period of 6 hours until the hydrogen portion is 20 ~ by volume. The polymerization temperature ;s 95 C.
The pressure mounts to ~0.7 bars in the course of the reaction.
There are obtained ~4 kg of polyethylene having a melt index i5 o~ 0.95 and a bulk density of 435 g/l. A sieve analysis reveals a fine portion of 0.2 % by weight below 100 ~m and 0 % by weight below 5Q ~m. ~25,000 g of polyethylene per gram of titanium and 5,80~ g of polyethylene per gram of the catalyst component A are obtained.
- ~7 -: ' ' , ' , ' ,:
' , ' . '' ,' . ~ ' ~ , :
: . ' , , ~ ~ ' ' ' . ' ~ ' ' , , .
,' '' ' ,' ' ' . :
. . : ' ' ' . , : .
.
.
: ' ' . , ' :.
.
, COMPARATIVE EXAMPLE A:
; The examples demonstratesthat the catalyst activity is not ~i improved when using an excess of titanium tetrachloride under the conditions indicated in Example 1, while washing several times the excess of titanium component.
10.0 g of the silicic acid treated previously with the Grignard compound according to Example 1-- are suspended in 50 ml of n-heptane and heated with 12.0 g of titanium tetrachloride (6.3 mmols per gram of silicic acid) for a period of ; hours at 90 C while stirring under an argon atmosphere. The insoluble solid matter is washed eight times by decanting and stirring with each 80 ml of n-hep-tane until 10 ml of the supernatant solution contains less than 0.001 mmol of titanium compound. Heptane is then withdrawn in the rotary evaporator at 120 C. There are obtained 9.7 g of a flowable powder, which contains 40.1 mg of titanium per gram.
Ethylene is polymerized with 0.12 g of the powder obtained under the same conditions as in Example 1. There are obtained 80 g of polyethylene having a melt index i5 of 5.7 and a bulk density of 295 g/l. There are obtained 16,600 g of polyethy-lene per gram of titanium and 666 g per gram of the catalyst com-ponent A.
COMPARATIVE EXAMPLE B:
The example demonstrates that the activity of the catalyst is not improved when using an excess of the Grignard and tita-nium compound during the catalyst preparation and when remov-ing the excess of magnesium and titanium compounds by washing several timesO
29 6.6 g of the dried silicic acid according to Example 1 are .
. . .: . .
.
1~87153 suspended in 25 ml of n- heptane, 66 ml of a solution of 33 mmols of n-propyl magnesium chloride (5 mmols per 1 gram of sili-cic acid) in diethyl ether are added and the mixture is refluxed for 4 hours. The insoluble solid matter is washed three times with each 80 ml of diethyl ether and two times with each 80 ml of n-heptane, by decan~ing and stirring until no more magnesium can be detected in the separated solution. The solvent is then removed in the rotary evaporator under 1 torr at 150 C.
The pulverulent solid is suspended in 50 ml of n-heptane, mixed with 7.9 g of titanium tetrachloride (6.3 mmols per 1 gram of silicic acid~ and stirred for 7 hours at 90 C. The in-soluble solid is then washed five times with each time 80 ml of n-heptane by decanting and stirring, until less than 0.001 mmol of titanium compound are contained in the supernatant solu-tion. Heptane is then withdrawn at 120 C in the rotary eva-porator. There are obtained 5.8 g of a flowable powder, which contain 27.6 mg of titanium per gram. The atomar ratio between magnesium and titanium is 2.6:1.
Under the same conditions as in Example 1 ethylene is poly-merized while using 0.31 g of the catalyst component A. There are obtained 166 g of polyethylene having a melt index i5 of 4.0 and i15 of 2~.6. The bulk density is 310 g/l. Per gram of ti-tanium there are obtained 19, 400 g of polyethylene and per gram ; of the catalyst component A 535 g.
E X A M P L E 4:
7.2 g of the silicic acid dried according to Example 1, ~hich has been reacted with n-propyl magnesium chloride, are suspended i,n 5Q ml of n-heptane. 1.73 g of titanium tetra- -29 chloride (1.27 mmols per ~ g of silicic acid) are added and the _ ~9 _ . . : .
. . , : . :
reaction mixture is heated for 7 hours at 90 C while stirring.
Heptane is withdrawn in the rotary evaporator and the residue is dried for 2 hours at 120 C under atmospheric pressure and for 0.5 hour at 80 C under 0.5 torr. 8.3 g of catalyst component A are obtained. The titanium analysis reveals 45.8 ml mg of titanium per 1 g of the component A. The magnesium/titanium atomar ratio is 1.3:1.
500 ml of Diesel oil are introduced into a 1 liter autoclave provided with a flat blade agitator, the air is displaced by evacuating and introducing nitrogen under pressure several times and the contents of the autoclave are heated to 85 C; 10 mmols of a solution a aluminum isoprenyl (reaction product of isoprene and aluminum triisobutyl having an aluminum content of 15 to 16 %
by weight and a C5/C4 ratio of 2.5:1 after hydrolysis~are added.
~5 0.25 g of catalyst comp~nent A are then added. Hydrogen is in-troduced until a pressure of 2 bars is attained and ethylene is added in an amount sufficient to maintain a total pressure of 5.9 bars, After 2 hours the polyethylene powder is separated from the dispersing agent by filtration and dried for 15 hours at 95 C in vacuo~ There are obtained 237 g of polyethylene having a melt index ~5 of 5.2 and i~5 of 28.~ The RSV ~alue is ~.8 dl/g.
The bulk density is 360 g/l, the air permeabi~ty 0.0058 cm3- sec/g.
The sieve analysis reveals a portion of fine particles having a ; diameter of less than ~00 ~m of 0.5 % by weight. There are ob-tained 20,700 g of polyethylene per gram of titanium and 948 g per gram of the catalyst cor,lponent A.
E X A M P L E 5:
Polymerization of ethylene in the gaseous phase.
29 Ethylene ~s polymerized in the gaseous phase in the presence - ~0 -:. . :,. ~ .
~. . ., . -- . ~ ~ ' ~7~53 HOE 75/F 298 of 2.Q9 g of the catalyst component A prepared according to Example 4 under the conditions of Example 3. After 6 hours the pressure set up is 9.8 ~ars. There are obtained 14,000 g of polyethylene having a melt index i5 of 0.78 and a bulk density of 395 g/l. The portion of fine particles having a diameter below 100 ~m is 0.4 % by weight. There are obtained 125,000 g of polyethylene per gram of titanium and 6.698 g of polyethy-lene per gram of the catalyst component A.
E X A M P L E 6:
8.6 g of the dried silicic acid according to Example 1 are suspended in 50 ml of ~iethyl ether, 13.7 ml of a solution of
29 The yield of polyethylene was 24,000 g per 1 g of titanium .
- ~08~7i53 or 958 g per 1 g of the catalyst component A.
E X A M P_L E 2:
Ethylene is polymerized in the presence of 0.22 g of the catalyst component A described in Example 1 under the same condi-tions as in Example 1,but by using instead of aluminum triethyle 1.98 g of aluminum triisobutyle. After 2 hours there are obtain-ed 145 g of polyethylene having a melt index i5 of 7.9 and a bulk density of 350 g/l. The RSV value is 1.84 g dl/g. There are obtained per 1 gram of titanium 16 600 g of polyethylene and per gram of the catalyst component A, 659 g.
E X A M P ~ E 3:
Polymerization of ethylene in the gaseous phase .. _, . . . . . .. .
2 kg of polyethylene (i5=10.8, buIk desnsity 4~0 g/I) are introduced in-to a lying 80 liter rea^tor provided with a scraping stirrer.
~5 The reactor is liberated from air by evacuating several times and by flushing for several hours with an ethylene-hydrogen mix-ture and is heated thereafter to 90 C. 17.1 g of aluminum tri-ethyl and 2.4~ g of the catalyst component A prepared according to Example 1 are added. 2 kg of ethylene/hour and hydrogen are introduced for a period of 6 hours until the hydrogen portion is 20 ~ by volume. The polymerization temperature ;s 95 C.
The pressure mounts to ~0.7 bars in the course of the reaction.
There are obtained ~4 kg of polyethylene having a melt index i5 o~ 0.95 and a bulk density of 435 g/l. A sieve analysis reveals a fine portion of 0.2 % by weight below 100 ~m and 0 % by weight below 5Q ~m. ~25,000 g of polyethylene per gram of titanium and 5,80~ g of polyethylene per gram of the catalyst component A are obtained.
- ~7 -: ' ' , ' , ' ,:
' , ' . '' ,' . ~ ' ~ , :
: . ' , , ~ ~ ' ' ' . ' ~ ' ' , , .
,' '' ' ,' ' ' . :
. . : ' ' ' . , : .
.
.
: ' ' . , ' :.
.
, COMPARATIVE EXAMPLE A:
; The examples demonstratesthat the catalyst activity is not ~i improved when using an excess of titanium tetrachloride under the conditions indicated in Example 1, while washing several times the excess of titanium component.
10.0 g of the silicic acid treated previously with the Grignard compound according to Example 1-- are suspended in 50 ml of n-heptane and heated with 12.0 g of titanium tetrachloride (6.3 mmols per gram of silicic acid) for a period of ; hours at 90 C while stirring under an argon atmosphere. The insoluble solid matter is washed eight times by decanting and stirring with each 80 ml of n-hep-tane until 10 ml of the supernatant solution contains less than 0.001 mmol of titanium compound. Heptane is then withdrawn in the rotary evaporator at 120 C. There are obtained 9.7 g of a flowable powder, which contains 40.1 mg of titanium per gram.
Ethylene is polymerized with 0.12 g of the powder obtained under the same conditions as in Example 1. There are obtained 80 g of polyethylene having a melt index i5 of 5.7 and a bulk density of 295 g/l. There are obtained 16,600 g of polyethy-lene per gram of titanium and 666 g per gram of the catalyst com-ponent A.
COMPARATIVE EXAMPLE B:
The example demonstrates that the activity of the catalyst is not improved when using an excess of the Grignard and tita-nium compound during the catalyst preparation and when remov-ing the excess of magnesium and titanium compounds by washing several timesO
29 6.6 g of the dried silicic acid according to Example 1 are .
. . .: . .
.
1~87153 suspended in 25 ml of n- heptane, 66 ml of a solution of 33 mmols of n-propyl magnesium chloride (5 mmols per 1 gram of sili-cic acid) in diethyl ether are added and the mixture is refluxed for 4 hours. The insoluble solid matter is washed three times with each 80 ml of diethyl ether and two times with each 80 ml of n-heptane, by decan~ing and stirring until no more magnesium can be detected in the separated solution. The solvent is then removed in the rotary evaporator under 1 torr at 150 C.
The pulverulent solid is suspended in 50 ml of n-heptane, mixed with 7.9 g of titanium tetrachloride (6.3 mmols per 1 gram of silicic acid~ and stirred for 7 hours at 90 C. The in-soluble solid is then washed five times with each time 80 ml of n-heptane by decanting and stirring, until less than 0.001 mmol of titanium compound are contained in the supernatant solu-tion. Heptane is then withdrawn at 120 C in the rotary eva-porator. There are obtained 5.8 g of a flowable powder, which contain 27.6 mg of titanium per gram. The atomar ratio between magnesium and titanium is 2.6:1.
Under the same conditions as in Example 1 ethylene is poly-merized while using 0.31 g of the catalyst component A. There are obtained 166 g of polyethylene having a melt index i5 of 4.0 and i15 of 2~.6. The bulk density is 310 g/l. Per gram of ti-tanium there are obtained 19, 400 g of polyethylene and per gram ; of the catalyst component A 535 g.
E X A M P L E 4:
7.2 g of the silicic acid dried according to Example 1, ~hich has been reacted with n-propyl magnesium chloride, are suspended i,n 5Q ml of n-heptane. 1.73 g of titanium tetra- -29 chloride (1.27 mmols per ~ g of silicic acid) are added and the _ ~9 _ . . : .
. . , : . :
reaction mixture is heated for 7 hours at 90 C while stirring.
Heptane is withdrawn in the rotary evaporator and the residue is dried for 2 hours at 120 C under atmospheric pressure and for 0.5 hour at 80 C under 0.5 torr. 8.3 g of catalyst component A are obtained. The titanium analysis reveals 45.8 ml mg of titanium per 1 g of the component A. The magnesium/titanium atomar ratio is 1.3:1.
500 ml of Diesel oil are introduced into a 1 liter autoclave provided with a flat blade agitator, the air is displaced by evacuating and introducing nitrogen under pressure several times and the contents of the autoclave are heated to 85 C; 10 mmols of a solution a aluminum isoprenyl (reaction product of isoprene and aluminum triisobutyl having an aluminum content of 15 to 16 %
by weight and a C5/C4 ratio of 2.5:1 after hydrolysis~are added.
~5 0.25 g of catalyst comp~nent A are then added. Hydrogen is in-troduced until a pressure of 2 bars is attained and ethylene is added in an amount sufficient to maintain a total pressure of 5.9 bars, After 2 hours the polyethylene powder is separated from the dispersing agent by filtration and dried for 15 hours at 95 C in vacuo~ There are obtained 237 g of polyethylene having a melt index ~5 of 5.2 and i~5 of 28.~ The RSV ~alue is ~.8 dl/g.
The bulk density is 360 g/l, the air permeabi~ty 0.0058 cm3- sec/g.
The sieve analysis reveals a portion of fine particles having a ; diameter of less than ~00 ~m of 0.5 % by weight. There are ob-tained 20,700 g of polyethylene per gram of titanium and 948 g per gram of the catalyst cor,lponent A.
E X A M P L E 5:
Polymerization of ethylene in the gaseous phase.
29 Ethylene ~s polymerized in the gaseous phase in the presence - ~0 -:. . :,. ~ .
~. . ., . -- . ~ ~ ' ~7~53 HOE 75/F 298 of 2.Q9 g of the catalyst component A prepared according to Example 4 under the conditions of Example 3. After 6 hours the pressure set up is 9.8 ~ars. There are obtained 14,000 g of polyethylene having a melt index i5 of 0.78 and a bulk density of 395 g/l. The portion of fine particles having a diameter below 100 ~m is 0.4 % by weight. There are obtained 125,000 g of polyethylene per gram of titanium and 6.698 g of polyethy-lene per gram of the catalyst component A.
E X A M P L E 6:
8.6 g of the dried silicic acid according to Example 1 are suspended in 50 ml of ~iethyl ether, 13.7 ml of a solution of
6.8 mmols (0.79 mmol per 1 gram of silicic acid) of n-propyl magnesium chloride in diethyl ether are added and the mixture is refluxed for 3 hours. The solvent is withdrawn in the ro-tary evaporator and the residue is dried for 2 hours at 150 C
under 1.5 torrs. The dried free flowing powder is suspended in 50 ml of n-heptane, mixed with 1.65 g of titanium tetrachloride (~.0 mmol per 1 gram of silicic acid~ and heated for 7 hours at 90 C while stirring. The solvent is then withdrawn at 120 C
23 in the rotary evaporator and the residue is dried for 0.5 hour at 80 C under ~ torr. 9.6 g of the free flowing catalyst com-ponent A is obtained, which contains 40.1 mg of titanium per gram.
The atomar ratio of magnesium~titanium is 0.8;~.
Ethylene is polym3rized under the conditions of Example 1 in the presence of 0.37 g of the component A. 215 g of poly-ethylene are obtained having a melt index i5 of ~.7 and i~5 of 9~5e The buik density is 348 g/l. Per gram of titanium there 29 are obtained ~4,500 g, per gram of the component A, 581 g of ' '. ,' ' . ' : ' " ~ . '.
: ''' , ~ ~ ' ' -,, . - .
' 1~7153 polyethylene.
_ X A M P L E 7:
Into a 1 liter autoclave made from stainless steel there are introduced 500 ml of Diesel oil, the air is displaced by eva-cuating and by introducing nitrogen under pressure three times.
Thereafter the autoclave is heated to 85 C. 1.14 g of aluminum triethyl and 0.12 g of the catalyst component A prepared accord-ing to Example 6 are a~ded. Hydrogen is introduced until a pressure of 5 bars is attained and ethylene is introduced in an amount sufficient to maintain a total pressure of 16.7 bars.
After 2 hours of polymerization at 85 C the polyethylene powder is separated by filtration from the dispersing agent and dried for 15 hours at 95 C in vacuo. 203 g of polyethylene are ob-tained having a melt index i5 of 1.1 and a bukl density of 430 g/l. The a~r permeability of the polyethylene powder is 0.012 cm3 sec/g. The sieve analysis reveals a portion of fine par-ticles having a diameter below 100 ~m of less than 0.1 ~ by weight. Per gram of titanium there are obtained 42,200 g of polyethylene, per gram of the catalyst component A, 1,692 g.
E X A M P L E 3.
.
The catalyst is prepared in analogous manner to Example 6, but by reacting 7.9 g of the dried silicic acid with 6.3 ml of a solution of 3.2 mmols of n-propyl magnesium chloride (0.4 mmols per 1 gram of silicic acid~ in diethyl ether. There-after the product obtained is reacted with 1.5 g of titaniumtetrachloride (1.0 mmol per 1 gram of silicic acid~. There are obtained 9.0 g of a flowable catalyst component A which contains 39.9 my of titanium per gram. The atomar ratio of magnesium/ti-29 tanium is 0.41:l.
--` 16)B~1~3 Ethylen is polymerized in the presence of 0.44 g of the powder obtained under the same conditions as in Example 1. There are obtained 182 g of polyethylene powder having a melt index i5 of 1.7 and i15 of 12.9. The bulk density is 285 g/l. Per gram of titanium there obtained 10,400 g of polyethylene, per gram of the catalyst component A, 414 g.
E X A M P L E 9:
Ethylene is polymerized under the same conditions as in Example 2 in the presence of 0.54 g of the catalyst component A
~0 prepared according to Example 8. There are obtained 193 g of polyethylene having a melt index iS of 0 44 and i15 of 3.6. The RSV value is 2.88 gl/g, the bulk density about 305 g/l. Per gram of titanium there are obtained 9,000 g of polyethylene, per gram of the component A, 357 g.
COMPA~ATIVE EXAMPLE C:
The Example demons~ates that the catalystsobtained are not very active, when using a silicic acid~ch has no~t ~een treat~
ed preliminary with the Grignard compound. Moreover the sen-sitivity to hydrogen of the catalyst is so low that the poly-ethylene formed has such a high molecular weight that it is unsuitable for processing by injection molding or extrusion.
8.7 g of the dried silicic acid according to Example 1 are suspended in 50 ml of n-heptane and 1.65 g of titanium tetra-chloride (1 mmol per 1 g of silicic acid) are added. The mix-ture is heated at 90 C while stirring under an argon atmos-phere, for a period of 7 hours. Heptane is then withdrawn in a rotary evaporator at 120 C and the residue is dried for 0.5 hour at 80 C under 2 torrs. 9.3 g of a powder having a ti-~9 tan~um content of 47.4 mg per gram are obtained. Ethylene is - ': . ' . ' ' ~ ' .:
:, . ~, :
.
HOE ?5/F 298 ~71S3 polymerized in the presence of 1.05 g of the powder obtained under the same conditions as in Example 2. There are obtained 84 g of polyethylene having a bulk density of 378 g/l. A melt index i5 or i15 cannot be measured. The RSV is 14.5 dl/g. There are ob-tained 1,700 g of polyethylene per gram of titanium and 80 g per gram of the catalyst component A.
COM2ARATIVE EXAMPLE D:
Comparative Example C is repeated by suspending 10.1 g of the dried si~cic acid according to Example 1 in 86 g (50 ml) of ~ titanium tetrachloride (44.8 mmols per 1 gram of silicic acid) and by stirring the suspension for 4 hours at 120 C in an argon stream to remove hydrogen chloride. The product obtained is wash-ed seven times'with each time 80 ml of n-hexane until 10 ml of the supernatant solution contain less than 0.001 mmol of titanium compound. At the end the solvent is distilled off at 10Q C under , atmospheric pressure and the resi,due is dried for 0.5 hour at 80 C and under a pressure of 0.5 torr. ~0.8 g of a free flowing powder are obtained having a titanium content of 35.5 mg per gram.
Ethylene ,is polymerized in the presence of 1.45 g of the 2Q po,wder obtained under the conditi`ons descr~-bed in Example 2.
There are obta~ned 130 g of polyethylene having a bulk density of 394 g/l. A melt index i5 or i~5 cann~t be measured. The X$V is 17,2 dl/g. There are obtained 2,500 g of polyethylene per gram of titanium and 90 g per gram of the catalyst component A.
COMPARATIVE EXAMPLE E;
Comparative Example C i$ repeated by suspending 9.8 g of ~' the dri,ed silicic acid according to Example 1in 50 ml of n-hep-tane, adding ~8.6 g (10immols per 1 gram of silicic acid) of ti-29 tanium tetrachloride and stirring the mixture for 7 hours at 90 C, ~. . ~ . . .
.: ~ . . . .
~ 371S3 The product obtained is washed five times with each time 80 ml of heptane until 10 ml of the supernatant solution contains less than 0.001 mmol of titanium compounds. At the end heptane is withdrawn in the rotary evaporator at 120 C and the residue is dried for 0.5 hour at 80 C under a pressure of 0.7 torr. 10.2 g of a free flowing powder are obtained having a titanium content of 37.7 mg per gram.
Ethylene is polymerized under the conditions of Example 2 in the presence of 1.21 g of said powder. There are obtained 118 g of polyethylene having a bulk density of 292 dlJg. A melt index i5 and i15 cannot be measured. The RSV is 12.2 dl/g. Per gram of titanium there are obtained 2,600 g, per gram of the catalyst component A 98 g, of polyethylene.
E X A M P L E 10:
~5 8.2 g of the dried silicic acid, which has been reacted with n-propyl magnesium c~loride according to Example 1 are sus-pended in 70 ml of n- heptane and 1.60 g (1.O mmol per 1 g of silicic acid~ of TiCl3(OiC3H7) are added. The mixture is stirred for 6 hours at 90 C. The solvent is withdrawn in the rotary eva-por~tor at 120 C and the residue is dried for 0.5 hour at 80 C
under 2 torrs. 9.26 g of a free flowlng powder are obtained hav-ing a titanium content of 39.4 mg per gram. Ethylene is poly-merized under the conditions described in Example 2 in the pre-sence of 0.44 g of the powder obtained. There are obtained 145 g o~ polyethylene having a melt index i5 of 0.50 and a bulk density of 380 g/l. Per gram of titanium there are obtained 8,400 g of polyethylene, per gram of the catalyst component A, 330 g.
E X A M P L E ~1 .
29 Ethylene is polymerized under the conditions described in Ex-.
'' ': ' - ' . , ~ ~. :
:, . ' ~: :.:: , . - -. :
- . . - - : :
^ HOE 75/F 298 ~.~B7153 ample 4 in the presence of 0.62 g of the catalyst component A
prepared according to Example 10. There are obtained 186 g of polyethylene having a melt index i5 of 0.70, i15 of 4.57 and a bulk density of 367 g/l. Per gram of titanium there are obtain-ed 7,600 g of polyethylene, per gram of component A, 300 g.
E X A M P L ~_ 12:
Polymerization of ethylene in the gaseous phase.
Ethylene is polymerized under the conditions of Example 3 in the presence of 2.4 g of the catalyst component A prepared according to Example 10. After 6 hours the pressure is 20.7 bars. There are obtained 14 kg of polyethylene having a melt index i5 of 0.33 and a bulk density of 465 g/l. The polyethy-lene powder has a portion of fine particles having a diameter ; of less than 100 ~ of 0.1 % by weight. Per gram of titanium there are obtained 127,000 g, per gram of the catalyst component A 5,833 g of polyethylene.
E X A M P L E 13:
110 g of the dried silicic acid which has been reacted with n-propyl magnesium chloride according to Example 1 are sus-2Q pended in 700 ml of n-heptane and 26 g (1 mmol of titanium per 1 gram of si~cic acid charged with magnesium~ of TiCl2(OiC3H7~ -are added. The mixture is stirred for 6 hours at 90 C. The solvent is withdrawn in the rotary evaporator at 120 C and the residue is dried for 2 hours at 80 C under 1 torr. There are obtained 124 g of a dry free flowing powder having a tita-nium content of 39.1 mg per gram.
Ethylene is polymerized under the conditions of Example 2 in the presence of 0.35 g of the powder obtained. There are ob-29 tained 130 g of polyethylene having a melt index i5 of 2.1 ~ O~S3 HOE 75/F 298 i15 of 15.8 and a bulk density of 390 g/l. The density is 0.960 g/cm3. Per gram of titanium there are obtained 9,500 g of polyethylene, per gram of the component A 371 g, of polyethy-lene.
_X A M P L E 14:
Copolymerization of ethylene and butene-1 100 liters of Diesel oil are placed in a 100 liter vessel, the contents of the vessel are heated to 85 C and the air is displaced by flushing with nitrogen. 45.6 g of aluminum tri-ethyl and 12.25 g of the catalyst component A prepared accord-ing to Example 13 are added. 5 kg of ethylene are introduced for a period of 6 hours and a quantity of h~d~o~en such that the hydrogen part in t~e gaseous phase is 15 % by volume. Bu-tene-l is moreover introduced at a rate of 50 g/h. The pressure mounts to 5.2 bars in the course of the polymerization. The suspension is separated from the dispersing agent by a pressure filter and the polymer is dried in a fluidized bed dryer. There are obtained 28.5 ~g of polyethylene having a RSV of 2.8 dl/g and a density of 0.946 g/cm3. The bulk density is 450 g/l. Per gram of titanium there are obtained 59,500 g of copolymer based on ethylene and butene-1, per gram of the catalyst component A, 2,326 gram of copolymer.
E X A M P L E 15:
Ethylene is polymerized under the conditions of Example 4 in the presence of 0.56 g of the catalyst component A prepared according to Example 13. There are obtained 135 g of polyethy-lene having a melt index i5 of 2.3 and a bulk density of 345 g/l~ -Per gram of titanium there are obtained 6,200 g, per gram of 29 the component A 241 g, of polyethylene.
-' ': . - : : ~ ,' .
~87~S3 HOE 75/F 298 E X A M P L E 16:
6.2 g of the dried silicic acid according to Example 1 are suspended in 50 ml of a solution of 9.1 mmols of t-butyl mag-nesium chloride (1.47 mmols per 1 gram Df silicic acid) in di-ethyl ether and refluxed for one hour while stirring. The sol-vent is withdrawn in a rotary evaporator and the residue is dried for 2 ~ours at 120 C under 0.3 torr. The dried solid is suspended in 50 ml of n-heptane, 1.17 g (1 mmol of titanium per ~ gram of silicic acid) of titanium-tetrachloride are added ~0 and the mixture is stirred for 6 hours at 90 C. Heptane is withdrawn in a rotary evaporator and the solid is dried for 2 hours at ~20 C under atmospheric pressure and for 0.5 hour at 80 C under a pressure of 0.4 torr. There are obtained 7.7 g of a dry free flowing powder having a titanium content of 38.5 mg per gram. The atomar ratio of magnesium and titanium is 1.5~
Ethylene is polymerized under the conditions of Example 2 in the presence of 0.42 g of the powder prepared. There are obtained 2~2 g of polyethylene having a melt index i5 of 0.26 2Q and i~5 of 1.7. The bulk density is 364 gtl. Per gram of ti-tanium there are obtained ~,300 g of polyethylene, per gram of the component A, 504 ~ of polyethylene.
E X A M P L E ~7:
A porous silicic acid having a specific surface of about 300 m2/g, a pore volume of 1.65 cm3~g and an average particle size of 50 ~m is dried for 4 hours in a flu~dized bed In an argon flow-, at 350 C and thereafter allowed to stand under an argon atmosp~ere. The silicic acid contains thereafter 1.9 29 mmols of hydroxyl groups per gram.
': ~
~ 7iS3 HOE 75/F 298 ~ , 9.94 g of the silicic acid obtained are suspended in 30 ml of diethyl ether. 49 ml of a solution of 18.2 mmols (1.83 mmols of magnesium per 1 g of silicic acid) of phenyl magnesium bromide in diethyl ether are added and the mixture is heated while re-fluxing. The solvent is withdrawn in the rotary evaporator and the solid matter is dried for 2 hours at 120 C under 0.3 torr.
The pretreated silicic acid is suspended in 50 ml of n-heptane and 1.89 g of titanium tetrachloride (1.0 mmol per 1 g of sili-cic aci~ are added. The mixture is stirred for 4 hours at 90 C, the solvent is withdrawn and the residue is dried for one hour at 80 C under 0.8 torr. There are obtained 12.6 g of a flow-able powder having a titanium content of 36.8 mg per gram. The atomar ratio of magnesium/titanium is 1.8:1.
Ethylene is polymerized under the conditions of Example 2 in the presence of 0.45 g of the powder prepared. There are ob-tained 175 g of polyethylene having a melt index i5 of 1.73 and i15 of 12.6. The bulk density is 335 g/l, the air permeability of the powder 0.0058 cm3 sec/g. Per gram of titanium there are obtained ~0,600 g of polyethylene, per gram of the component A, 390 g of polyethylene.
E X A M P L E 18:
Ethylene is polymerized under the conditions of Example 4 by means of a . 48 g of the catalyst component A prepared accord-ing to Example 17. There are obtained 224 g of polyethylene having a melt index i5 of 2.1 and i~5 of 12.9. The bulk densi-ty is 340 g/l, the air permeability of the powder 0.077 cm3-sec/g.
Per gram of titanium there are obtained 12,700 g, per gram of ^1 the component A, 467 g, of polyethylene.
:~
~OE 75/F 298 ~7~S3 ~ ., E X A M P L E 19:
A porous aluminum silicate (85.7 % of SiO2 and 14.2 % of Al2O3) having a specific surface of about 550 m2/g,a pore volume of 0.71 cm3/g and an average particle size of 135 ~m is dried in a fluidized bed in an argon flow for 4 hours, at 460 C and kept under an argon atmosphere. Thereafter it contains 3.0 mmols of hydroxyl groups per gram.
600 g of the silicate obtained are suspended in 3 liters of diethyl ether, 1.3 liters of a solution of 1.79 mols (2.98 mmols per 1 g of silicate) of n-Pro~yl magnesium chloride in diethyl ether are added and the mixture is refluxed for one hour while stirring. After settling of the solid matter no magnesium can be detected in the supernatant solution. The solvent is with-drawn in the rotary evaporator and the residue is dried for 2 hours at 120 C under 0.5 torr. The carrier pretreated is sus-pended in 5 liters of cyclohexane, 182 g of titanium tetrachlo-ride (~.6 mmols of titanium per 1 g of silicic acid~ are added in 2 hours and the mixture is stirred for 6 hours at 100 C.
The solvent is withdrawn at 120 C and the residue is dried $or one ~our at 90 C under a pressure of 0.5 torr. There are o~tained 880 g of a flowable powder having a titanium content of 5~.2 mg per gram. The atomar ratio between magnesium and titanium is 1~86:1.
Ethylene is polymerized under the conditions of Example 2 in the presence of 0.23 g of said catalyst component A. There are obtained 169 g of polyethylene having a melt index i5 of 0.85 and a bulk density of 315 g/l. Per gram of titanium there are obtained 14,400 g, per gram of the component A, 735 g, of 29 polyethylene.
E X_A M P L E 20:
Polymerization of ethylene in the gaseous phase 2 kg of polyethylene (i5=10.8,bulk density 410 g/l) are plac-ed in a lying 80 liter reactor, which is provided with a scrapina stirrer. The reactor is liberated from air by evacuating several times and by flusing for several hours with an ethylene/hydrogen mixture and heated thereafter to 90 C. 17.1 g aluminum tri-ethyl and 2.8 g of the catalyst component A prepared according to Example 19 are there~fter placed in the reactor. Ethylene is introduced into the reactor at a rate of 2 kg/hour for a period of 6 hours and hydrogen, until the hydrogen portion is 20 % by volume. The polymerization temperature is 105 C. The pressure mounts in the course of the polymeri~tion to 9,8 bars. 14 kg of polyethylene are obtainedhaving a melt index i5 of 0.98 and a bulk density of 415 g/l. Per gram of titanium there are ob-tained 83,700 g fpO~hy~ene, per gram of the component A, 5,000 g of polyethylene.
- : . .
.: , . . :
:
under 1.5 torrs. The dried free flowing powder is suspended in 50 ml of n-heptane, mixed with 1.65 g of titanium tetrachloride (~.0 mmol per 1 gram of silicic acid~ and heated for 7 hours at 90 C while stirring. The solvent is then withdrawn at 120 C
23 in the rotary evaporator and the residue is dried for 0.5 hour at 80 C under ~ torr. 9.6 g of the free flowing catalyst com-ponent A is obtained, which contains 40.1 mg of titanium per gram.
The atomar ratio of magnesium~titanium is 0.8;~.
Ethylene is polym3rized under the conditions of Example 1 in the presence of 0.37 g of the component A. 215 g of poly-ethylene are obtained having a melt index i5 of ~.7 and i~5 of 9~5e The buik density is 348 g/l. Per gram of titanium there 29 are obtained ~4,500 g, per gram of the component A, 581 g of ' '. ,' ' . ' : ' " ~ . '.
: ''' , ~ ~ ' ' -,, . - .
' 1~7153 polyethylene.
_ X A M P L E 7:
Into a 1 liter autoclave made from stainless steel there are introduced 500 ml of Diesel oil, the air is displaced by eva-cuating and by introducing nitrogen under pressure three times.
Thereafter the autoclave is heated to 85 C. 1.14 g of aluminum triethyl and 0.12 g of the catalyst component A prepared accord-ing to Example 6 are a~ded. Hydrogen is introduced until a pressure of 5 bars is attained and ethylene is introduced in an amount sufficient to maintain a total pressure of 16.7 bars.
After 2 hours of polymerization at 85 C the polyethylene powder is separated by filtration from the dispersing agent and dried for 15 hours at 95 C in vacuo. 203 g of polyethylene are ob-tained having a melt index i5 of 1.1 and a bukl density of 430 g/l. The a~r permeability of the polyethylene powder is 0.012 cm3 sec/g. The sieve analysis reveals a portion of fine par-ticles having a diameter below 100 ~m of less than 0.1 ~ by weight. Per gram of titanium there are obtained 42,200 g of polyethylene, per gram of the catalyst component A, 1,692 g.
E X A M P L E 3.
.
The catalyst is prepared in analogous manner to Example 6, but by reacting 7.9 g of the dried silicic acid with 6.3 ml of a solution of 3.2 mmols of n-propyl magnesium chloride (0.4 mmols per 1 gram of silicic acid~ in diethyl ether. There-after the product obtained is reacted with 1.5 g of titaniumtetrachloride (1.0 mmol per 1 gram of silicic acid~. There are obtained 9.0 g of a flowable catalyst component A which contains 39.9 my of titanium per gram. The atomar ratio of magnesium/ti-29 tanium is 0.41:l.
--` 16)B~1~3 Ethylen is polymerized in the presence of 0.44 g of the powder obtained under the same conditions as in Example 1. There are obtained 182 g of polyethylene powder having a melt index i5 of 1.7 and i15 of 12.9. The bulk density is 285 g/l. Per gram of titanium there obtained 10,400 g of polyethylene, per gram of the catalyst component A, 414 g.
E X A M P L E 9:
Ethylene is polymerized under the same conditions as in Example 2 in the presence of 0.54 g of the catalyst component A
~0 prepared according to Example 8. There are obtained 193 g of polyethylene having a melt index iS of 0 44 and i15 of 3.6. The RSV value is 2.88 gl/g, the bulk density about 305 g/l. Per gram of titanium there are obtained 9,000 g of polyethylene, per gram of the component A, 357 g.
COMPA~ATIVE EXAMPLE C:
The Example demons~ates that the catalystsobtained are not very active, when using a silicic acid~ch has no~t ~een treat~
ed preliminary with the Grignard compound. Moreover the sen-sitivity to hydrogen of the catalyst is so low that the poly-ethylene formed has such a high molecular weight that it is unsuitable for processing by injection molding or extrusion.
8.7 g of the dried silicic acid according to Example 1 are suspended in 50 ml of n-heptane and 1.65 g of titanium tetra-chloride (1 mmol per 1 g of silicic acid) are added. The mix-ture is heated at 90 C while stirring under an argon atmos-phere, for a period of 7 hours. Heptane is then withdrawn in a rotary evaporator at 120 C and the residue is dried for 0.5 hour at 80 C under 2 torrs. 9.3 g of a powder having a ti-~9 tan~um content of 47.4 mg per gram are obtained. Ethylene is - ': . ' . ' ' ~ ' .:
:, . ~, :
.
HOE ?5/F 298 ~71S3 polymerized in the presence of 1.05 g of the powder obtained under the same conditions as in Example 2. There are obtained 84 g of polyethylene having a bulk density of 378 g/l. A melt index i5 or i15 cannot be measured. The RSV is 14.5 dl/g. There are ob-tained 1,700 g of polyethylene per gram of titanium and 80 g per gram of the catalyst component A.
COM2ARATIVE EXAMPLE D:
Comparative Example C is repeated by suspending 10.1 g of the dried si~cic acid according to Example 1 in 86 g (50 ml) of ~ titanium tetrachloride (44.8 mmols per 1 gram of silicic acid) and by stirring the suspension for 4 hours at 120 C in an argon stream to remove hydrogen chloride. The product obtained is wash-ed seven times'with each time 80 ml of n-hexane until 10 ml of the supernatant solution contain less than 0.001 mmol of titanium compound. At the end the solvent is distilled off at 10Q C under , atmospheric pressure and the resi,due is dried for 0.5 hour at 80 C and under a pressure of 0.5 torr. ~0.8 g of a free flowing powder are obtained having a titanium content of 35.5 mg per gram.
Ethylene ,is polymerized in the presence of 1.45 g of the 2Q po,wder obtained under the conditi`ons descr~-bed in Example 2.
There are obta~ned 130 g of polyethylene having a bulk density of 394 g/l. A melt index i5 or i~5 cann~t be measured. The X$V is 17,2 dl/g. There are obtained 2,500 g of polyethylene per gram of titanium and 90 g per gram of the catalyst component A.
COMPARATIVE EXAMPLE E;
Comparative Example C i$ repeated by suspending 9.8 g of ~' the dri,ed silicic acid according to Example 1in 50 ml of n-hep-tane, adding ~8.6 g (10immols per 1 gram of silicic acid) of ti-29 tanium tetrachloride and stirring the mixture for 7 hours at 90 C, ~. . ~ . . .
.: ~ . . . .
~ 371S3 The product obtained is washed five times with each time 80 ml of heptane until 10 ml of the supernatant solution contains less than 0.001 mmol of titanium compounds. At the end heptane is withdrawn in the rotary evaporator at 120 C and the residue is dried for 0.5 hour at 80 C under a pressure of 0.7 torr. 10.2 g of a free flowing powder are obtained having a titanium content of 37.7 mg per gram.
Ethylene is polymerized under the conditions of Example 2 in the presence of 1.21 g of said powder. There are obtained 118 g of polyethylene having a bulk density of 292 dlJg. A melt index i5 and i15 cannot be measured. The RSV is 12.2 dl/g. Per gram of titanium there are obtained 2,600 g, per gram of the catalyst component A 98 g, of polyethylene.
E X A M P L E 10:
~5 8.2 g of the dried silicic acid, which has been reacted with n-propyl magnesium c~loride according to Example 1 are sus-pended in 70 ml of n- heptane and 1.60 g (1.O mmol per 1 g of silicic acid~ of TiCl3(OiC3H7) are added. The mixture is stirred for 6 hours at 90 C. The solvent is withdrawn in the rotary eva-por~tor at 120 C and the residue is dried for 0.5 hour at 80 C
under 2 torrs. 9.26 g of a free flowlng powder are obtained hav-ing a titanium content of 39.4 mg per gram. Ethylene is poly-merized under the conditions described in Example 2 in the pre-sence of 0.44 g of the powder obtained. There are obtained 145 g o~ polyethylene having a melt index i5 of 0.50 and a bulk density of 380 g/l. Per gram of titanium there are obtained 8,400 g of polyethylene, per gram of the catalyst component A, 330 g.
E X A M P L E ~1 .
29 Ethylene is polymerized under the conditions described in Ex-.
'' ': ' - ' . , ~ ~. :
:, . ' ~: :.:: , . - -. :
- . . - - : :
^ HOE 75/F 298 ~.~B7153 ample 4 in the presence of 0.62 g of the catalyst component A
prepared according to Example 10. There are obtained 186 g of polyethylene having a melt index i5 of 0.70, i15 of 4.57 and a bulk density of 367 g/l. Per gram of titanium there are obtain-ed 7,600 g of polyethylene, per gram of component A, 300 g.
E X A M P L ~_ 12:
Polymerization of ethylene in the gaseous phase.
Ethylene is polymerized under the conditions of Example 3 in the presence of 2.4 g of the catalyst component A prepared according to Example 10. After 6 hours the pressure is 20.7 bars. There are obtained 14 kg of polyethylene having a melt index i5 of 0.33 and a bulk density of 465 g/l. The polyethy-lene powder has a portion of fine particles having a diameter ; of less than 100 ~ of 0.1 % by weight. Per gram of titanium there are obtained 127,000 g, per gram of the catalyst component A 5,833 g of polyethylene.
E X A M P L E 13:
110 g of the dried silicic acid which has been reacted with n-propyl magnesium chloride according to Example 1 are sus-2Q pended in 700 ml of n-heptane and 26 g (1 mmol of titanium per 1 gram of si~cic acid charged with magnesium~ of TiCl2(OiC3H7~ -are added. The mixture is stirred for 6 hours at 90 C. The solvent is withdrawn in the rotary evaporator at 120 C and the residue is dried for 2 hours at 80 C under 1 torr. There are obtained 124 g of a dry free flowing powder having a tita-nium content of 39.1 mg per gram.
Ethylene is polymerized under the conditions of Example 2 in the presence of 0.35 g of the powder obtained. There are ob-29 tained 130 g of polyethylene having a melt index i5 of 2.1 ~ O~S3 HOE 75/F 298 i15 of 15.8 and a bulk density of 390 g/l. The density is 0.960 g/cm3. Per gram of titanium there are obtained 9,500 g of polyethylene, per gram of the component A 371 g, of polyethy-lene.
_X A M P L E 14:
Copolymerization of ethylene and butene-1 100 liters of Diesel oil are placed in a 100 liter vessel, the contents of the vessel are heated to 85 C and the air is displaced by flushing with nitrogen. 45.6 g of aluminum tri-ethyl and 12.25 g of the catalyst component A prepared accord-ing to Example 13 are added. 5 kg of ethylene are introduced for a period of 6 hours and a quantity of h~d~o~en such that the hydrogen part in t~e gaseous phase is 15 % by volume. Bu-tene-l is moreover introduced at a rate of 50 g/h. The pressure mounts to 5.2 bars in the course of the polymerization. The suspension is separated from the dispersing agent by a pressure filter and the polymer is dried in a fluidized bed dryer. There are obtained 28.5 ~g of polyethylene having a RSV of 2.8 dl/g and a density of 0.946 g/cm3. The bulk density is 450 g/l. Per gram of titanium there are obtained 59,500 g of copolymer based on ethylene and butene-1, per gram of the catalyst component A, 2,326 gram of copolymer.
E X A M P L E 15:
Ethylene is polymerized under the conditions of Example 4 in the presence of 0.56 g of the catalyst component A prepared according to Example 13. There are obtained 135 g of polyethy-lene having a melt index i5 of 2.3 and a bulk density of 345 g/l~ -Per gram of titanium there are obtained 6,200 g, per gram of 29 the component A 241 g, of polyethylene.
-' ': . - : : ~ ,' .
~87~S3 HOE 75/F 298 E X A M P L E 16:
6.2 g of the dried silicic acid according to Example 1 are suspended in 50 ml of a solution of 9.1 mmols of t-butyl mag-nesium chloride (1.47 mmols per 1 gram Df silicic acid) in di-ethyl ether and refluxed for one hour while stirring. The sol-vent is withdrawn in a rotary evaporator and the residue is dried for 2 ~ours at 120 C under 0.3 torr. The dried solid is suspended in 50 ml of n-heptane, 1.17 g (1 mmol of titanium per ~ gram of silicic acid) of titanium-tetrachloride are added ~0 and the mixture is stirred for 6 hours at 90 C. Heptane is withdrawn in a rotary evaporator and the solid is dried for 2 hours at ~20 C under atmospheric pressure and for 0.5 hour at 80 C under a pressure of 0.4 torr. There are obtained 7.7 g of a dry free flowing powder having a titanium content of 38.5 mg per gram. The atomar ratio of magnesium and titanium is 1.5~
Ethylene is polymerized under the conditions of Example 2 in the presence of 0.42 g of the powder prepared. There are obtained 2~2 g of polyethylene having a melt index i5 of 0.26 2Q and i~5 of 1.7. The bulk density is 364 gtl. Per gram of ti-tanium there are obtained ~,300 g of polyethylene, per gram of the component A, 504 ~ of polyethylene.
E X A M P L E ~7:
A porous silicic acid having a specific surface of about 300 m2/g, a pore volume of 1.65 cm3~g and an average particle size of 50 ~m is dried for 4 hours in a flu~dized bed In an argon flow-, at 350 C and thereafter allowed to stand under an argon atmosp~ere. The silicic acid contains thereafter 1.9 29 mmols of hydroxyl groups per gram.
': ~
~ 7iS3 HOE 75/F 298 ~ , 9.94 g of the silicic acid obtained are suspended in 30 ml of diethyl ether. 49 ml of a solution of 18.2 mmols (1.83 mmols of magnesium per 1 g of silicic acid) of phenyl magnesium bromide in diethyl ether are added and the mixture is heated while re-fluxing. The solvent is withdrawn in the rotary evaporator and the solid matter is dried for 2 hours at 120 C under 0.3 torr.
The pretreated silicic acid is suspended in 50 ml of n-heptane and 1.89 g of titanium tetrachloride (1.0 mmol per 1 g of sili-cic aci~ are added. The mixture is stirred for 4 hours at 90 C, the solvent is withdrawn and the residue is dried for one hour at 80 C under 0.8 torr. There are obtained 12.6 g of a flow-able powder having a titanium content of 36.8 mg per gram. The atomar ratio of magnesium/titanium is 1.8:1.
Ethylene is polymerized under the conditions of Example 2 in the presence of 0.45 g of the powder prepared. There are ob-tained 175 g of polyethylene having a melt index i5 of 1.73 and i15 of 12.6. The bulk density is 335 g/l, the air permeability of the powder 0.0058 cm3 sec/g. Per gram of titanium there are obtained ~0,600 g of polyethylene, per gram of the component A, 390 g of polyethylene.
E X A M P L E 18:
Ethylene is polymerized under the conditions of Example 4 by means of a . 48 g of the catalyst component A prepared accord-ing to Example 17. There are obtained 224 g of polyethylene having a melt index i5 of 2.1 and i~5 of 12.9. The bulk densi-ty is 340 g/l, the air permeability of the powder 0.077 cm3-sec/g.
Per gram of titanium there are obtained 12,700 g, per gram of ^1 the component A, 467 g, of polyethylene.
:~
~OE 75/F 298 ~7~S3 ~ ., E X A M P L E 19:
A porous aluminum silicate (85.7 % of SiO2 and 14.2 % of Al2O3) having a specific surface of about 550 m2/g,a pore volume of 0.71 cm3/g and an average particle size of 135 ~m is dried in a fluidized bed in an argon flow for 4 hours, at 460 C and kept under an argon atmosphere. Thereafter it contains 3.0 mmols of hydroxyl groups per gram.
600 g of the silicate obtained are suspended in 3 liters of diethyl ether, 1.3 liters of a solution of 1.79 mols (2.98 mmols per 1 g of silicate) of n-Pro~yl magnesium chloride in diethyl ether are added and the mixture is refluxed for one hour while stirring. After settling of the solid matter no magnesium can be detected in the supernatant solution. The solvent is with-drawn in the rotary evaporator and the residue is dried for 2 hours at 120 C under 0.5 torr. The carrier pretreated is sus-pended in 5 liters of cyclohexane, 182 g of titanium tetrachlo-ride (~.6 mmols of titanium per 1 g of silicic acid~ are added in 2 hours and the mixture is stirred for 6 hours at 100 C.
The solvent is withdrawn at 120 C and the residue is dried $or one ~our at 90 C under a pressure of 0.5 torr. There are o~tained 880 g of a flowable powder having a titanium content of 5~.2 mg per gram. The atomar ratio between magnesium and titanium is 1~86:1.
Ethylene is polymerized under the conditions of Example 2 in the presence of 0.23 g of said catalyst component A. There are obtained 169 g of polyethylene having a melt index i5 of 0.85 and a bulk density of 315 g/l. Per gram of titanium there are obtained 14,400 g, per gram of the component A, 735 g, of 29 polyethylene.
E X_A M P L E 20:
Polymerization of ethylene in the gaseous phase 2 kg of polyethylene (i5=10.8,bulk density 410 g/l) are plac-ed in a lying 80 liter reactor, which is provided with a scrapina stirrer. The reactor is liberated from air by evacuating several times and by flusing for several hours with an ethylene/hydrogen mixture and heated thereafter to 90 C. 17.1 g aluminum tri-ethyl and 2.8 g of the catalyst component A prepared according to Example 19 are there~fter placed in the reactor. Ethylene is introduced into the reactor at a rate of 2 kg/hour for a period of 6 hours and hydrogen, until the hydrogen portion is 20 % by volume. The polymerization temperature is 105 C. The pressure mounts in the course of the polymeri~tion to 9,8 bars. 14 kg of polyethylene are obtainedhaving a melt index i5 of 0.98 and a bulk density of 415 g/l. Per gram of titanium there are ob-tained 83,700 g fpO~hy~ene, per gram of the component A, 5,000 g of polyethylene.
- : . .
.: , . . :
:
Claims (15)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of a catalyst in which a carrier comprising a silicon dioxide, an aluminum oxide or a mixture thereof, having a content of hydroxyl groups of 0.5 to 50 mmols/g is reacted in the presence of a diluent first with a magnesium compound of the formula RMgX, wherein R is a hydrocarbon radical having from 1 to 20 carbon atoms and X is chlorine, bromine or iodine, in an amount of from 0.05 to 1 mol of magnesium compound per mol of hydroxyl groups of the carrier and the solid reaction product is reacted in suspension with a halogen-containing titanium (IV) compound of the formula TiXn(OR1)4-n, wherein n is an integer of from 1 to 4 and X is chlorine or bromine and R1 is a hydrocarbon radical having from 1 to 12 carbon atoms, in an amount of from 0.01 to 1 mol of titanium compound per mole of hydroxyl groups of the carrier, and the resultant product is subsequently reacted with an organic compound of a metal selected from groups IA, IIA or IIIA of the periodic system.
2. A process as claimed in claim 1 in which the carrier has a specific surface of from 50 to 1000m2/g, a pore volume in the range of from 0.2 to 2 ml/g and a particle size of from 1 to 500 µm.
3. A process as claimed in claim 1 in which the content of hydroxyl groups is in the range of from 1 to 20 mmols.
4. A process as claimed in claim 1 in which the compound of the formula RMgX is selected from the group of ethyl magnesium chloride, n-propyl magnesium chloride, i-propyl magnesium iodide, n-butyl magnesium chloride, t-butyl magnesium chloride and phenyl magnesium bromide.
5. A process as claimed in claim 1 in which the reaction product is reacted with the titanium compound at a temperature of from 20 to 140°C.
6. A process as claimed in claim 1 in which the titanium compound is selected from the group of titanium tetrachloride, TiCl2(O-i-C3H7)2 and TiCl3(O-i-C3H7).
7. A process as claimed in claim 1 in which the metal organic compound is an aluminum organic compound.
8. A process as claimed in claim 1 in which the metal organic compound is selected from the group of reaction products of aluminum trialkyls or aluminum dialkyl hydrides, the alkyl groups having from 1 to 16 carbon atoms, with dienes having from 4 to 20 carbon atoms.
9. A catalyst, whenever obtained according to a process as claimed in claim 1, claim 2 or claim 3.
10. A catalyst, whenever obtained according to a process as claimed in claim 4, claim 5 or claim 6.
11. A catalyst, whenever obtained according to a process as claimed in claim 7 or claim 8.
12. A process for the preparation of a polyolefin in which at least one 1-olefin of the formula R6-CH=CH2, wherein R6 is hydrogen or a straight chain or branched alkyl radical having from 1 to 10 carbon atoms, is polymerized in the presence of a catalyst, the catalyst having been obtained by a process in which a carrier comprising a silicon dioxide, an aluminum oxide or a mixture thereof, having a content of hydroxyl groups of from 0.5 to 50 mmols/g, is reacted in the presence of a diluent first with a magnesium compound of the formula RMgX, wherein R is a hydrocarbon radical having from 1 to 20 carbon atoms and X is chlorine, bromine or iodine, in an amount of from 0.05 to 1 mol of magnesium compound per mol of hydroxyl groups of the carrier and the solid reaction product is reacted in suspension with a halogen-containing titanium (IV) compound of the formula TiXn(OR1)4-n, wherein n is an integer of from 1 to 4 and X is chlorine or bromine and R1 is a hydrocarbon radical having from 1 to 12 carbon atoms, in an amount of from 0.01 to 1 mol of titanium compound per mol of hydroxyl groups of the carrier, and the resultant product is subsequently reacted with an organic compound of a metal selected from groups IA, IIA or IIIA of the period system.
13. A process as claimed in claim 12 in which the 1-olefin is selected from the group of ethylene, propylene, butene-1, hexene-1,4-methyl-pentene-1 and octene-1.
14. A process as claimed in claim 12 in which the 1-olefin comprises a mixture of at least 70% by weight of ethylene with at most 30% by weight of another olefin of the formula R6-CH=CH2 wherein R6 is as defined in claim 12.
15. A process as claimed in claim 12, claim 13 or claim 14 in which the reaction is carried out at a temperature of from 20 to 150°C and at a pressure of from 0.5 to 50 bars.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19752553179 DE2553179A1 (en) | 1975-11-27 | 1975-11-27 | METHOD OF MANUFACTURING A CATALYST |
| DEP2553179.7 | 1975-11-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1087153A true CA1087153A (en) | 1980-10-07 |
Family
ID=5962717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA266,614A Expired CA1087153A (en) | 1975-11-27 | 1976-11-26 | Process for the preparation of a catalyst |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US4148754A (en) |
| JP (1) | JPS5265791A (en) |
| AU (1) | AU503330B2 (en) |
| BE (1) | BE848870A (en) |
| BR (1) | BR7607894A (en) |
| CA (1) | CA1087153A (en) |
| DE (1) | DE2553179A1 (en) |
| DK (1) | DK534676A (en) |
| ES (1) | ES453524A1 (en) |
| FR (1) | FR2333001A1 (en) |
| GB (1) | GB1552700A (en) |
| IN (1) | IN145227B (en) |
| LU (1) | LU76264A1 (en) |
| NL (1) | NL7612983A (en) |
| ZA (1) | ZA767073B (en) |
Families Citing this family (79)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55135105A (en) * | 1979-04-10 | 1980-10-21 | Mitsui Petrochem Ind Ltd | Titanium catalyst component for olefin polymerization |
| US4383096A (en) * | 1979-08-01 | 1983-05-10 | Chemplex Company | Method of polymerizing 1-olefins |
| US4405495A (en) | 1980-06-30 | 1983-09-20 | Union Carbide Corporation | Catalyst impregnated on fine silica, process for preparing, and use for ethylene polymerization |
| DE3100736A1 (en) | 1981-01-13 | 1982-08-26 | Ruhrchemie Ag, 4200 Oberhausen | METHOD FOR PRODUCING CARRIER CATALYSTS FOR THE POLYMERIZATION OF (ALPHA) -OLEFINES |
| US4359403A (en) * | 1981-04-13 | 1982-11-16 | Chemplex Company | Polymerization catalyst and method |
| NL8103704A (en) * | 1981-08-06 | 1983-03-01 | Stamicarbon | PROCESS FOR PREPARING A CATALYST COMPONENT AND POLYMERIZATION OF 1-OLEGINS THEREOF |
| US4605638A (en) * | 1981-12-04 | 1986-08-12 | Mobil Oil Corporation | Highly active catalyst composition for polymerizing alpha-olefins |
| AU564992B2 (en) * | 1981-12-04 | 1987-09-03 | Mobil Oil Corp. | Olefin polymerisation catalyst |
| US5025072A (en) * | 1981-12-04 | 1991-06-18 | Mobil Oil Corporation | Highly active catalyst composition for polymerizing alpha-olefins |
| US4481301A (en) * | 1981-12-04 | 1984-11-06 | Mobil Oil Corporation | Highly active catalyst composition for polymerizing alpha-olefins |
| DE3223331A1 (en) * | 1982-06-23 | 1983-12-29 | Ruhrchemie Ag, 4200 Oberhausen | METHOD FOR PRODUCING A SUPPORT CATALYST FOR THE (CO) POLYMERIZATION OF (ALPHA) -OLEFINES |
| US4434242A (en) | 1982-11-24 | 1984-02-28 | Cities Service Co. | Polymerization catalyst |
| US4435520A (en) | 1982-11-24 | 1984-03-06 | Cities Service Co. | Catalyst composition |
| US4435519A (en) | 1982-11-24 | 1984-03-06 | Cities Service Co. | Novel catalyst composition |
| US4435518A (en) | 1982-11-24 | 1984-03-06 | Cities Service Co. | Polymerization catalyst |
| US4707530A (en) * | 1983-01-31 | 1987-11-17 | Exxon Research & Engineering Co. | Polymerization catalyst |
| US4477639A (en) * | 1983-05-27 | 1984-10-16 | Shell Oil Company | Olefin polymerization catalyst component and composition and method of preparation |
| US4593009A (en) * | 1984-04-04 | 1986-06-03 | Mobil Oil Corporation | Catalyst composition for polymerizing alpha-olefins |
| US4672096A (en) * | 1984-04-04 | 1987-06-09 | Mobil Oil Corporation | Catalyst composition for polymerizing alpha-olefins |
| US4618662A (en) * | 1984-04-23 | 1986-10-21 | Mobil Oil Corporation | Catalyst composition for polymerizing alpha-olefins |
| US4568658A (en) * | 1984-09-05 | 1986-02-04 | Mobil Oil Corporation | Catalyst composition for polymerizing alpha-olefins at low reactants partial pressures |
| US4675369A (en) * | 1984-09-05 | 1987-06-23 | Mobil Oil Corporation | Catalyst composition for polymerizing alpha-olefins at low reactants partial pressures |
| US4560733A (en) * | 1984-10-01 | 1985-12-24 | Phillips Petroleum Company | Polymerization and catalyst |
| US4562169A (en) * | 1984-10-04 | 1985-12-31 | Mobil Oil Corporation | Alpha-olefins polymerization catalyst of high productivity |
| US4634752A (en) * | 1984-10-04 | 1987-01-06 | Mobil Oil Corporation | Process for preparing alpha-olefin polymers |
| US4613712A (en) * | 1984-12-31 | 1986-09-23 | Mobil Oil Corporation | Alpha-olefin polymers as lubricant viscosity properties improvers |
| US4668650A (en) * | 1986-01-03 | 1987-05-26 | Mobil Oil Corporation | Catalyst composition for polymerizing alpha-olefin polymers of relatively narrow molecular weight distribution |
| US4876321A (en) * | 1986-01-03 | 1989-10-24 | Mobil Oil Corporation | Preparation of alpha-olefin polymers of relatively narrow molecular weight distribution |
| US4677087A (en) * | 1986-01-03 | 1987-06-30 | Mobil Oil Corporation | Catalyst composition for polymerizing alpha-olefin polymers of relatively narrow molecular weight distribution |
| US5055533A (en) * | 1986-01-24 | 1991-10-08 | Mobil Oil Corporation | Process for polymerizing alpha-olefins with trimethylaluminum-activated catalyst |
| US4732882A (en) * | 1986-01-24 | 1988-03-22 | Mobil Oil Corporation | Catalyst composition for polymerizing alpha-olefins |
| USRE33683E (en) * | 1986-01-24 | 1991-09-03 | Mobil Oil Corporation | Catalyst composition for polymerizing alpha-olefins |
| US4888318A (en) * | 1986-01-24 | 1989-12-19 | Mobil Oil Corporation | Catalyst composition for polymerizing alpha-olefins |
| US4849389A (en) * | 1988-01-14 | 1989-07-18 | Mobil Oil Corporation | Catalyst composition for polymerizing alpha-olefin polymers of narrow molecular weight distribution |
| US4954470A (en) * | 1988-01-14 | 1990-09-04 | Mobil Oil Corporation | Chlorinated alcohol-containing catalyst composition for polymerizing alpha-olefins |
| US5093443A (en) * | 1988-01-14 | 1992-03-03 | Mobil Oil Corporation | Alpha-olefins polymerization with chlorinated alcohol-containing catalyst composition |
| US4833111A (en) * | 1988-01-14 | 1989-05-23 | Mobil Oil Corporation | Catalyst composition for polymerizing alpha-olefin polymers of narrow molecular weight distribution |
| US6248702B1 (en) | 1990-01-16 | 2001-06-19 | Mobil Oil Corporation | Dispersant and dispersant viscosity index improvers from selectively hydrogenated aryl-substituted olefin containing diene copolymers |
| US5231151A (en) * | 1991-01-18 | 1993-07-27 | The Dow Chemical Company | Silica supported transition metal catalyst |
| US6172173B1 (en) | 1991-01-18 | 2001-01-09 | The Dow Chemical Company | Silica supported transition metal catalyst |
| US6747113B1 (en) | 1991-01-18 | 2004-06-08 | The Dow Chemical Company | Silica supported transition metal catalyst |
| US5693583A (en) * | 1991-06-10 | 1997-12-02 | Mobil Oil Corporation | High activity polyethylene catalysts which produce bimodal or trimodal product molecular weight distributions |
| US5246900A (en) * | 1991-08-23 | 1993-09-21 | Phillips Petroleum Company | Olefin polymerization catalysts and processes of making the same |
| US5470812A (en) * | 1991-11-06 | 1995-11-28 | Mobil Oil Corporation | High activity polyethylene catalysts prepared with alkoxysilane reagents |
| US5336652A (en) * | 1991-11-06 | 1994-08-09 | Mobil Oil Corporation | High activity polyethylene catalysts prepared with alkoxysilane reagents |
| US5514634A (en) * | 1991-11-06 | 1996-05-07 | Mobil Oil Corporation | High activity polyethylene catalysts |
| US5939348A (en) * | 1991-11-06 | 1999-08-17 | Mobil Oil Corporation | Catalyst for the manufacture of polythylene with a narrow molecular weight distribution |
| US5210167A (en) * | 1991-11-25 | 1993-05-11 | Mobil Oil Corporation | LLDPE films with improved optical properties |
| US5461017A (en) * | 1991-12-13 | 1995-10-24 | Mobil Oil Corporation | Olefin polymerization catalysts |
| US5362824A (en) * | 1991-12-13 | 1994-11-08 | Mobil Oil Corporation | Olefin polymerization catalysts |
| US5583083A (en) * | 1991-12-31 | 1996-12-10 | Neste Oy | Procatalyst composition for homo- and copolymerization of alpha olefins, its preparation and its use |
| US5416051A (en) * | 1992-03-24 | 1995-05-16 | Exxon Research & Engineering Co. | Pillared metakandite clay compositions as sorbents, catalysts and ceramic and refractory precursors |
| US5260245A (en) * | 1992-10-19 | 1993-11-09 | Mobil Oil Corporation | High activity polyethylene catalysts |
| US5258345A (en) * | 1992-11-20 | 1993-11-02 | Mobil Oil Corporation | High-activity polyethylene catalysts |
| US5330951A (en) * | 1992-12-09 | 1994-07-19 | Mobil Oil Corporation | Catalyst composition for polymerizing alpha-olefin |
| JP3670010B2 (en) * | 1993-11-18 | 2005-07-13 | モービル・オイル・コーポレーション | Method for producing catalyst composition |
| CN1117500A (en) | 1994-08-08 | 1996-02-28 | 菲利浦石油公司 | Catalyst and polymerization of olefins |
| US5661097A (en) * | 1994-08-12 | 1997-08-26 | The Dow Chemical Company | Supported olefin polymerization catalyst |
| US6191239B1 (en) | 1998-02-18 | 2001-02-20 | Eastman Chemical Company | Process for producing polyethylene |
| US6534613B2 (en) | 1998-02-18 | 2003-03-18 | Eastman Chemical Company | Process for producing polyethylene |
| US6228957B1 (en) | 1998-02-18 | 2001-05-08 | Eastman Chemical Company | Process for producing polyethlene |
| US6271321B1 (en) | 1998-02-18 | 2001-08-07 | Eastman Chemical Company | Process for producing polyethylene |
| US6319881B1 (en) | 1998-06-23 | 2001-11-20 | Exxonmobil Oil Corporation | Haze free oil additive compositions containing dispersants from selectively hydrogenated diene copolymers |
| US6215033B1 (en) | 1998-12-11 | 2001-04-10 | Mobil Oil Corporation | Dispersants and dispersant viscosity index improvers from selectively hydrogenated polymers: blends with lower molecular weight components |
| US6291613B1 (en) | 1998-10-27 | 2001-09-18 | Eastman Chemical Company | Process for the polymerization of olefins |
| ATE528328T1 (en) | 1998-10-27 | 2011-10-15 | Westlake Longview Corp | METHOD FOR POLYMERIZING OLEFINS; POLYETHYLENE, AND FILMS, AND ITEMS MADE THEREFROM |
| US6300432B1 (en) | 1999-03-30 | 2001-10-09 | Eastman Chemical Company | Process for producing polyolefins |
| MXPA01009833A (en) | 1999-03-30 | 2002-11-04 | Eastman Chem Co | Process for producing polyolefins. |
| US6191238B1 (en) | 1999-08-31 | 2001-02-20 | Eastman Chemical Company | Process for producing polyolefins |
| BRPI0107604B1 (en) | 2000-01-12 | 2015-03-31 | Westlake Longview Corp | Solid procatalyst, catalyst system, and process for polymerizing at least one or more olefins |
| US6465383B2 (en) | 2000-01-12 | 2002-10-15 | Eastman Chemical Company | Procatalysts, catalyst systems, and use in olefin polymerization |
| US6696380B2 (en) | 2000-01-12 | 2004-02-24 | Darryl Stephen Williams | Procatalysts, catalyst systems, and use in olefin polymerization |
| US6677266B1 (en) | 2002-07-09 | 2004-01-13 | Eastman Chemical Company | Process for preparing a vanadium/titanium catalyst and use in olefin polymerization |
| CN1213081C (en) * | 2002-10-16 | 2005-08-03 | 中国石油化工股份有限公司 | Catalyst component for ethene polymerization, preparing method and catalyst thereof |
| US7307036B2 (en) * | 2004-07-22 | 2007-12-11 | Formosa Plastics Corporation U.S.A. | Highly active alpha-olefin polymerization catalyst |
| US9068025B2 (en) | 2010-08-19 | 2015-06-30 | China Petroleum & Chemical Corporation | Catalyst component for polymerization of olefin and preparation method |
| CN104159933B (en) | 2012-03-05 | 2017-09-12 | 尤尼威蒂恩技术有限责任公司 | The manufacture method of carbon monoxide-olefin polymeric and the polymeric articles by its production |
| CN104277146B (en) * | 2013-07-01 | 2016-08-17 | 中国石油化工股份有限公司 | Catalyst component, its preparation method and application for olefinic polymerization |
| WO2018064048A1 (en) | 2016-09-27 | 2018-04-05 | Univation Technologies, Llc | Method for long chain branching control in polyethylene production |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3202645A (en) * | 1964-12-16 | 1965-08-24 | Cabot Corp | Surface treated inorganic solid polymerization catalyst and method of polymerization therewith |
| FR2082153A5 (en) * | 1970-03-05 | 1971-12-10 | Solvay | ADVANCED CATALYSTS AND PROCESS FOR THE POLYMERIZATION AND COPOLYMERIZATION OF OLEFINS |
-
1975
- 1975-11-27 DE DE19752553179 patent/DE2553179A1/en not_active Withdrawn
-
1976
- 1976-11-20 ES ES453524A patent/ES453524A1/en not_active Expired
- 1976-11-22 NL NL7612983A patent/NL7612983A/en not_active Application Discontinuation
- 1976-11-23 US US05/744,310 patent/US4148754A/en not_active Expired - Lifetime
- 1976-11-25 JP JP51140833A patent/JPS5265791A/en active Pending
- 1976-11-25 BR BR7607894A patent/BR7607894A/en unknown
- 1976-11-25 IN IN2108/CAL/76A patent/IN145227B/en unknown
- 1976-11-25 LU LU76264A patent/LU76264A1/xx unknown
- 1976-11-26 GB GB49431/76A patent/GB1552700A/en not_active Expired
- 1976-11-26 DK DK534676A patent/DK534676A/en unknown
- 1976-11-26 CA CA266,614A patent/CA1087153A/en not_active Expired
- 1976-11-26 AU AU20032/76A patent/AU503330B2/en not_active Expired
- 1976-11-26 ZA ZA767073A patent/ZA767073B/en unknown
- 1976-11-29 FR FR7635886A patent/FR2333001A1/en active Granted
- 1976-11-29 BE BE172808A patent/BE848870A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR2333001B1 (en) | 1982-10-01 |
| DE2553179A1 (en) | 1977-06-08 |
| FR2333001A1 (en) | 1977-06-24 |
| US4148754A (en) | 1979-04-10 |
| DK534676A (en) | 1977-05-28 |
| BE848870A (en) | 1977-05-31 |
| IN145227B (en) | 1978-09-16 |
| ZA767073B (en) | 1977-11-30 |
| NL7612983A (en) | 1977-06-01 |
| GB1552700A (en) | 1979-09-19 |
| JPS5265791A (en) | 1977-05-31 |
| BR7607894A (en) | 1977-11-08 |
| AU2003276A (en) | 1978-06-01 |
| ES453524A1 (en) | 1978-03-01 |
| AU503330B2 (en) | 1979-08-30 |
| LU76264A1 (en) | 1977-06-07 |
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