CA1069876A - Catalyst for alpha-olefin polymerization, method for its preparation and polymerization process employing such catalyst - Google Patents
Catalyst for alpha-olefin polymerization, method for its preparation and polymerization process employing such catalystInfo
- Publication number
- CA1069876A CA1069876A CA229,053A CA229053A CA1069876A CA 1069876 A CA1069876 A CA 1069876A CA 229053 A CA229053 A CA 229053A CA 1069876 A CA1069876 A CA 1069876A
- Authority
- CA
- Canada
- Prior art keywords
- carrier
- ranging
- polymerization
- alpha
- titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000004711 α-olefin Substances 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title 1
- 239000011777 magnesium Substances 0.000 claims abstract description 28
- 239000010936 titanium Substances 0.000 claims abstract description 23
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- -1 magnesium inorganic compound Chemical class 0.000 claims abstract description 12
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004411 aluminium Substances 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001399 aluminium compounds Chemical class 0.000 claims abstract description 6
- 101100058670 Aeromonas hydrophila subsp. hydrophila (strain ATCC 7966 / DSM 30187 / BCRC 13018 / CCUG 14551 / JCM 1027 / KCTC 2358 / NCIMB 9240 / NCTC 8049) bsr gene Proteins 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052681 coesite Inorganic materials 0.000 claims description 15
- 229910052906 cristobalite Inorganic materials 0.000 claims description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims description 15
- 229910052682 stishovite Inorganic materials 0.000 claims description 15
- 229910052905 tridymite Inorganic materials 0.000 claims description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 235000001055 magnesium Nutrition 0.000 claims 8
- 229940091250 magnesium supplement Drugs 0.000 claims 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 4
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 229910010066 TiC14 Inorganic materials 0.000 description 8
- 229940093470 ethylene Drugs 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000004913 activation Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 150000002681 magnesium compounds Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003348 petrochemical agent Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 101100198319 Colwellia psychrerythraea (strain 34H / ATCC BAA-681) rmf2 gene Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229940077746 antacid containing aluminium compound Drugs 0.000 description 1
- 239000008135 aqueous vehicle Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000004647 photon scanning tunneling microscopy Methods 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
The present invention relates to a catalytic system for the polymerization of alpha-olefins consisting of a) an aluminium compound chosen among those of formula AlR3 or AlRxY3-x, wherein R is a lower alkyl radical, Y is an halogen or hydrogen atom, and x is a number between 1 and 2, and b) a titanium compound finely dispersed on a carrier having a high surface area, which carrier has been previously treated with a magnesium inorganic compound of the formula MgX2.nH2O, wherein X represents a halide and n is a number ranging from 0 to 6, in which catalyst the amount of magnesium dispersed on the carrier is ranging from 0.1 to 10% by weight and the molar ratio of aluminium to titanium is ranging from 20 to 75. The invention also relates to a method for preparing this catalytic system which has a high activity and remains unimpaired in time.
The present invention relates to a catalytic system for the polymerization of alpha-olefins consisting of a) an aluminium compound chosen among those of formula AlR3 or AlRxY3-x, wherein R is a lower alkyl radical, Y is an halogen or hydrogen atom, and x is a number between 1 and 2, and b) a titanium compound finely dispersed on a carrier having a high surface area, which carrier has been previously treated with a magnesium inorganic compound of the formula MgX2.nH2O, wherein X represents a halide and n is a number ranging from 0 to 6, in which catalyst the amount of magnesium dispersed on the carrier is ranging from 0.1 to 10% by weight and the molar ratio of aluminium to titanium is ranging from 20 to 75. The invention also relates to a method for preparing this catalytic system which has a high activity and remains unimpaired in time.
Description
37~;
The present inventioll relates to a catalytic s~vstem useful for the po]ymerization of alpha-olefins, particularly ethylene, to a method for preparing the same and to a polymeriza-tio~ process employiny such a catalyst.
It is known that alpha-olefins may be polymerized by means of catalytic systems consisting of a combination ofa titanium compound and a metal organic aluminium compound.
Such catalytic systems however do not present a satisfactory activity.
The Applicants have -t~ought -that a satisfactory acti-vity could be obtained if the titanium compound of such catalytic systems is dispersed over a carrier having a high surface area.
The so obtained compound could be employed under the usual conditions, for polymerizing alpha-olefins at low pressure.
The Applicants have used silica, alumina or silica-alumina with a high surface area as catalyst carrier. It has been noted, however, that the catalyst activity of the titanium compound dispersed on such materials varies widely according to the chemical nature of the surface of the carriers. In particu-lar, some catalysts show such a low polymerization activity thatthey must be subjected to a specific treatment before being used, such as, for instance, with an organo-metallic compound of aluminium or magnesium, and more particularly with a metal alkyl chloride. Said compounds react with the surface hydroxyls of the carrier, thus preventing hydrolysis of the titanium compound that is dispersed. `~
Such a method of activation of the catalysts however entails some disadvantages deriving from the use of solutions of said aluminium and magnesium compounds, which are expensive and must be manipulated with great care. Furthermore, in the case of the magnesium alkyl-halides, they must be usually prepa-red in ether solvents, which present, in addition to their high costs, the considerable disadvantage that they must be prepared in a very pure state, and they are tied to the carrier ~L~698~
in an irreversible way, after the actiVatincJ trea-tment.
The present invention proposes a process ~or the polymeri~ation o~ alpha-olefins, by using a catal~tic system which has a high activity and remains unimpaired in time.
The catalytic system, according to the present invention, consists of two components, which are:
1) an aluminium compound chosen among those of formula AlR3 or AlRXY3_ , wherein R is a lower alkyl radical, Y is an halogen or hydrogen atom and x is a number between 1 an~ 2, and
The present inventioll relates to a catalytic s~vstem useful for the po]ymerization of alpha-olefins, particularly ethylene, to a method for preparing the same and to a polymeriza-tio~ process employiny such a catalyst.
It is known that alpha-olefins may be polymerized by means of catalytic systems consisting of a combination ofa titanium compound and a metal organic aluminium compound.
Such catalytic systems however do not present a satisfactory activity.
The Applicants have -t~ought -that a satisfactory acti-vity could be obtained if the titanium compound of such catalytic systems is dispersed over a carrier having a high surface area.
The so obtained compound could be employed under the usual conditions, for polymerizing alpha-olefins at low pressure.
The Applicants have used silica, alumina or silica-alumina with a high surface area as catalyst carrier. It has been noted, however, that the catalyst activity of the titanium compound dispersed on such materials varies widely according to the chemical nature of the surface of the carriers. In particu-lar, some catalysts show such a low polymerization activity thatthey must be subjected to a specific treatment before being used, such as, for instance, with an organo-metallic compound of aluminium or magnesium, and more particularly with a metal alkyl chloride. Said compounds react with the surface hydroxyls of the carrier, thus preventing hydrolysis of the titanium compound that is dispersed. `~
Such a method of activation of the catalysts however entails some disadvantages deriving from the use of solutions of said aluminium and magnesium compounds, which are expensive and must be manipulated with great care. Furthermore, in the case of the magnesium alkyl-halides, they must be usually prepa-red in ether solvents, which present, in addition to their high costs, the considerable disadvantage that they must be prepared in a very pure state, and they are tied to the carrier ~L~698~
in an irreversible way, after the actiVatincJ trea-tment.
The present invention proposes a process ~or the polymeri~ation o~ alpha-olefins, by using a catal~tic system which has a high activity and remains unimpaired in time.
The catalytic system, according to the present invention, consists of two components, which are:
1) an aluminium compound chosen among those of formula AlR3 or AlRXY3_ , wherein R is a lower alkyl radical, Y is an halogen or hydrogen atom and x is a number between 1 an~ 2, and
2) a titanium compound finely dispersecl over a carrier having a high surface area, which carrier has been previously treated with a magnesium inorganic compound of the formula:
~gX2.nH2O wherein X represents a halide and n a number ranging from 0 to 6, in which catalysts the amount of magnesium dispersed on the carrier is ranging from O.l to 10~ by weight and the molar ratio of aluminium to titanium is ranging from 20 to 75~
The magnesium inorganic compound which is a magnesium -halide, is dispersed over the carrier in a watery medium. After removing the water, the carrie~ is subsequently subjected to an activation treatment, by heating under vacuum at a temperature ranging between 200 and 250C. The obtained product is -then re-fluxed in liquid titanium tetrachloride, filtered, washed with a hydrocarbon solvent and finally dried under vacuum.
When compared to the known techniques for the treatment of a carrier with magnesium organic compound, the method accord- `
ing to the present invention presents the advantage that any easily available and water soluble magnesium compound, not neces-sarily pure, can be used without resorting to expensive and non removable solvent.
The catalytic system according to the invention shows a good response to hy~rogen (in particular to a Mg/q'i ratio between 0.5 and 2 on the carrier) and allows or the obtention 8~
o:E high yield of powder free, a~l(l polyetllylene with high bulk density (10% of the particles obt~ine~ have ~ diameter below 200 y).
The carriers that can be used according to the invention, can be chosen amon~ SiO2, SiO2/A12O3, A12O3, MgO, TiO2, Zro2 and the rare earths oxides, whereas the magnesium compound is chosen among the maynesium inorganic compounds of the formula MgX2 . n H2O, wherein X represents a halide and n is a number ranging from 0 to 6. The amount of magnesium dispersed on t~e carrier may vary between 0.1 and 10~ by weight and preferably between l and 5% by weight.
The polymerization reaction, when using the so obtained ca-talyst system, is carried out according to the usual method, at temperatures ranging from 0 to 200C and under pressures varying from 0.1 to 50 atmospheres.
When operating above the atmospheric pressure, the polymerization is carried out in a steel autoclave, provided with an anchor stirrer. The catalyst is introduced together with the solvent and the alkyl metal. The autoclave, which has a tempera-ture control set, is first pressurized with H2 at the polymeriza-tion temperature and afterwards with ethylene (or another olefin)at the required pressure ratio. The reaction is stopped by adding alcohol in the autoclave.
The present invention will be now better understood with particular reference to the following non-restrictive examples o~ polymerization wherein, in every case, khe polymeriza-tion reaction was carried out in the presence of 1 liter of n-hexane as solvent, 2 cm 3 of Al i-But3 as aluminium organic compound and a given amount of the hereinafter defined titanium compound dispersed on a carrier, in a pressure vessel at a temperature of ~5C.
10 y of SiO2, grade 56, produced by Davidson
~gX2.nH2O wherein X represents a halide and n a number ranging from 0 to 6, in which catalysts the amount of magnesium dispersed on the carrier is ranging from O.l to 10~ by weight and the molar ratio of aluminium to titanium is ranging from 20 to 75~
The magnesium inorganic compound which is a magnesium -halide, is dispersed over the carrier in a watery medium. After removing the water, the carrie~ is subsequently subjected to an activation treatment, by heating under vacuum at a temperature ranging between 200 and 250C. The obtained product is -then re-fluxed in liquid titanium tetrachloride, filtered, washed with a hydrocarbon solvent and finally dried under vacuum.
When compared to the known techniques for the treatment of a carrier with magnesium organic compound, the method accord- `
ing to the present invention presents the advantage that any easily available and water soluble magnesium compound, not neces-sarily pure, can be used without resorting to expensive and non removable solvent.
The catalytic system according to the invention shows a good response to hy~rogen (in particular to a Mg/q'i ratio between 0.5 and 2 on the carrier) and allows or the obtention 8~
o:E high yield of powder free, a~l(l polyetllylene with high bulk density (10% of the particles obt~ine~ have ~ diameter below 200 y).
The carriers that can be used according to the invention, can be chosen amon~ SiO2, SiO2/A12O3, A12O3, MgO, TiO2, Zro2 and the rare earths oxides, whereas the magnesium compound is chosen among the maynesium inorganic compounds of the formula MgX2 . n H2O, wherein X represents a halide and n is a number ranging from 0 to 6. The amount of magnesium dispersed on t~e carrier may vary between 0.1 and 10~ by weight and preferably between l and 5% by weight.
The polymerization reaction, when using the so obtained ca-talyst system, is carried out according to the usual method, at temperatures ranging from 0 to 200C and under pressures varying from 0.1 to 50 atmospheres.
When operating above the atmospheric pressure, the polymerization is carried out in a steel autoclave, provided with an anchor stirrer. The catalyst is introduced together with the solvent and the alkyl metal. The autoclave, which has a tempera-ture control set, is first pressurized with H2 at the polymeriza-tion temperature and afterwards with ethylene (or another olefin)at the required pressure ratio. The reaction is stopped by adding alcohol in the autoclave.
The present invention will be now better understood with particular reference to the following non-restrictive examples o~ polymerization wherein, in every case, khe polymeriza-tion reaction was carried out in the presence of 1 liter of n-hexane as solvent, 2 cm 3 of Al i-But3 as aluminium organic compound and a given amount of the hereinafter defined titanium compound dispersed on a carrier, in a pressure vessel at a temperature of ~5C.
10 y of SiO2, grade 56, produced by Davidson
- 3 -~ t7~
Petrochemicals, haviny a surEace area of 285 m /g, a diame-ter o pores of 168 A, and a volume oF pores o~ 1. 20 cm3/g, we~ 8U5-pended in a water solution (50 ml) of Mg C12 . 6 H2O (2,5 g).
The water was removed in a rotating evaporator and the product obtained, dried under vacuum Eor 4 hours at 170C, was refluxed in TiC14 (100 ml) for 4 hours. The product was filtered undex nitrogen on a sintered glass filter, washed on the filter with petroleum ether and dried under vacuum for 4 hours.
The product obtained had the following composition Ti= 4,72 Mg~ 2,12%
Cl-14,28%
251 mg of this product were used as dispersed titanium compound for the polymerization of ethylene (PH ~ 10 atm, PC2H4 After 2 hours, 116 g of polyethylene were obtained, with a MF2 16 1 015 a MF 1 6 of 39-56~ a RMF21 6/MF2.~6 Index according to the PSTM Ru'es). The so obta~ed polyethylene contained 98 ppm of Ti, had a bulk density of 0.295 g/cm , and showed less than 10~ of particles with a diameter of 200 ~.
10 g of the same type of SiO2 were refluxed after drying under vacuum for 4 hours at 175C, in liquid TiC14, without any pre-treatment.
The product after filtration, washing with hexane and drying, had the following composition Ti- 4.85%
Cl _7.98~
30A mg of this product, were used as dispersed titanium compound for the polymerization of ethylene under a pressure of 10 atm H2 and 10 atm C2H4. After 5 hours, 36 g of polymer were obtained having a MF2.16 of , a MF21.6 of 2-08, a MF2 16/~F2 16 o and containing 410 ppm of Ti.
E~AMPLE 2 312 mg of the same product prepared as described in the
Petrochemicals, haviny a surEace area of 285 m /g, a diame-ter o pores of 168 A, and a volume oF pores o~ 1. 20 cm3/g, we~ 8U5-pended in a water solution (50 ml) of Mg C12 . 6 H2O (2,5 g).
The water was removed in a rotating evaporator and the product obtained, dried under vacuum Eor 4 hours at 170C, was refluxed in TiC14 (100 ml) for 4 hours. The product was filtered undex nitrogen on a sintered glass filter, washed on the filter with petroleum ether and dried under vacuum for 4 hours.
The product obtained had the following composition Ti= 4,72 Mg~ 2,12%
Cl-14,28%
251 mg of this product were used as dispersed titanium compound for the polymerization of ethylene (PH ~ 10 atm, PC2H4 After 2 hours, 116 g of polyethylene were obtained, with a MF2 16 1 015 a MF 1 6 of 39-56~ a RMF21 6/MF2.~6 Index according to the PSTM Ru'es). The so obta~ed polyethylene contained 98 ppm of Ti, had a bulk density of 0.295 g/cm , and showed less than 10~ of particles with a diameter of 200 ~.
10 g of the same type of SiO2 were refluxed after drying under vacuum for 4 hours at 175C, in liquid TiC14, without any pre-treatment.
The product after filtration, washing with hexane and drying, had the following composition Ti- 4.85%
Cl _7.98~
30A mg of this product, were used as dispersed titanium compound for the polymerization of ethylene under a pressure of 10 atm H2 and 10 atm C2H4. After 5 hours, 36 g of polymer were obtained having a MF2.16 of , a MF21.6 of 2-08, a MF2 16/~F2 16 o and containing 410 ppm of Ti.
E~AMPLE 2 312 mg of the same product prepared as described in the
4 -` ~L0~98~i~6 previous example, were used for the polymerization of ethylene ith P ~ 15 km and P ~ 5 atm After 5 hours, 455 y of polymer were obtained, with a MF2 16 of 6-32, a MF21 6 of 230.1 MF21 6/MF2 16 f 36-4~ arld a Content of 27 ppm o~ Ti EX~MPI.E 3 10 g of SiO2 of the same type as used in example 1 were treated, in the same way as previously described, with 3~5 g of MgC12 . 6 H2O and activated under vacuum at 200c for 4 hours.
After refluxing in TiC14 (100 ml), this product was filtered and washed with benzene, according to the conventional procedures. The vacuum dried product had the following composition Ti -4.61 Mg- 2.84 Cl-16.18%
235 mg of this product yielded in a 5 hour polymerization test, H2 C2H4=lo atm, 427 g of polymer with a MF of 2.63, a MF21 6 of 91-50~ a RMF2 16 j MF 16 and a content of 25 ppm of Ti.
10 g of SiO2 of the same type as used in example 1 were impregnated by a treatment of the same type as previously described, with 10 g of MgC12 6 H2O.
After activation for 2 hours under vacuum at 200 C, the product was refluxed in TiC14, hot filtered, repeatedly washed with hexane, and finally dried under vacuum. When tested, this product had the following composition Ti- 15.08%
Mg ~ 3.95%
Cl =35.37%
205 mg of this product yielded, in a 2 hours polymerization reaction, 370 g of polymer having a MF2 16 of 2-41, a MF21 6 f . ~
.
MF21 6 / 2 16 f 42 4 and containing ~3 EXAMPhE S
10 g SiO2 (grade 951, supplied by Davidson Petrochemi-cals having a surface area of 600 m2/g, a diameter of pores of 67 ~, and a volume of pores of 1 cm3/g were trea'ed in a water solution of MgC12 . 6 H2O (2.2 g).
After a treatment similar to that described in example 1, the product, activated under vacuum at 200C for 4 hours and treated according to the normal procedures with TiC14 boiling for 4 hours, had the following composition Ti = 8.12%
Mg = 1.82~
Cl -13.83%
264 mg of this product were used for the polymerization of ethy-lene with PH _ 10 atm and PC ~1 -10 atm and a residence time of 2 hours. 120 g of polymer were obtained, having a MF2 16 f 2-40, a MF21 6 of 75.56, and a RMF of 30.8, and containing 178 ppm of Ti.
226 mg of the product prepared as described in example
After refluxing in TiC14 (100 ml), this product was filtered and washed with benzene, according to the conventional procedures. The vacuum dried product had the following composition Ti -4.61 Mg- 2.84 Cl-16.18%
235 mg of this product yielded in a 5 hour polymerization test, H2 C2H4=lo atm, 427 g of polymer with a MF of 2.63, a MF21 6 of 91-50~ a RMF2 16 j MF 16 and a content of 25 ppm of Ti.
10 g of SiO2 of the same type as used in example 1 were impregnated by a treatment of the same type as previously described, with 10 g of MgC12 6 H2O.
After activation for 2 hours under vacuum at 200 C, the product was refluxed in TiC14, hot filtered, repeatedly washed with hexane, and finally dried under vacuum. When tested, this product had the following composition Ti- 15.08%
Mg ~ 3.95%
Cl =35.37%
205 mg of this product yielded, in a 2 hours polymerization reaction, 370 g of polymer having a MF2 16 of 2-41, a MF21 6 f . ~
.
MF21 6 / 2 16 f 42 4 and containing ~3 EXAMPhE S
10 g SiO2 (grade 951, supplied by Davidson Petrochemi-cals having a surface area of 600 m2/g, a diameter of pores of 67 ~, and a volume of pores of 1 cm3/g were trea'ed in a water solution of MgC12 . 6 H2O (2.2 g).
After a treatment similar to that described in example 1, the product, activated under vacuum at 200C for 4 hours and treated according to the normal procedures with TiC14 boiling for 4 hours, had the following composition Ti = 8.12%
Mg = 1.82~
Cl -13.83%
264 mg of this product were used for the polymerization of ethy-lene with PH _ 10 atm and PC ~1 -10 atm and a residence time of 2 hours. 120 g of polymer were obtained, having a MF2 16 f 2-40, a MF21 6 of 75.56, and a RMF of 30.8, and containing 178 ppm of Ti.
226 mg of the product prepared as described in example
5, were used in a standard polymeri~ation, identical to that described in example 4, but with a residence time of 5 hours.
354 g of polymer were obtained, with a MF of 0.15, a MF21 6 21.6/MF2.16 of 37.5 and a Ti content of 52 ppm.
EXAMæLE 7 2 A]2O3 (SiO2 =87%, A12O3= 13%, surf~ce area =400 m2/g) were treated as described in example 1.
After activation at 200C under vacuurn, for 30', the product was refluxed in TiCl~ (100 ml). The produc-t obtained after washing and treatment as already described, had the ;~ 6 -10~ 6 following composi-tion Ti ~ 7.50 Mg = 1.10 Cl -19.70~
312 mg of this product were used for the polymerization of ethylene during 2 hours, with PH c 10 atm, PC H - 10 atm, 62 g of polymer was obtained, having a MF2 16 of 0.62, a MF21 6 of MF21 6/MF2.16 of 43.2 and con-taining 382 ppm of Ti 15 g of Sio2/A12O3, the same one as used in example 7 but dried for 20 hours at 450, were treated with 1 g of MgC12 anhydrous in 25 ml H2O.
The product obtained, previously dried on a rotating evaporator, was placed into an oven at 350 and treated for 6 hours with a slow stream of gaseous HCl.
The product obtained after the usual treatment with TiC14 (100 ml) at reflux, iltration and washing with benzene and drying under vacuum, had the following composition Ti ~ 3.8%
- Cl= 13.6 Mg = 0.15~
251 mg of this product were used for the polymerization of ethylene at PH ~ 5 atm, PC H ~ 10 atm. After 6 hours, 414 g of polymer were obtained, with a MF2 16 of -~, a MF21 6 of 4-54 and MF21 6/MF2 16 f 45-4 and a Ti content of 2 ppm.
10 g of SiO2/A12O3 of the same type as used in example 7, were treated with MgC12 . 6 ~l2O (1.6 y) in an aqueous vehicle. The water was removed firstly on a rotaring evaporator under vacuum at the room ternperature, and then hy azeotrope distillation with xylene.
-- 7 ~
:
. - : -. . :
The so obtained product was re1uxed in TiC14 (200 ml), filtered, washed and vacuum dried. At -the end of the above operations, i-t had the following composition Ti -- 8.5%
Mg = 1.1%
Cl -18.95~
155 mg of this product was used in a standard polymerization.
After 2 hours with PH _10 atm, PC2H4 were obtained, with a MF2 16 of 0 47~ a M~21 6 of 20-35 and a MF21.6/~F2.16 of 44.4 and a ~i content of 347 ppm.
62 mg of the product used in example 9 were used in a standard polymerization. After 6 hours with PH ~ 8 atm, PC H = 10 atm, 247 g of polymer were obtained, having a MF2 16 f 0 09 a MF of 5.56 and a RMF21 6/MF2 16 containing 22 ppm of Ti.
10 g of SiO2 . A12O3 of the same type as used in example 7, were treated with 2.5 g of MgC12 . 6 H2O according to the procedure described in example 8. The product had the following composition Ti ~ 8.41%
; Mg - 1.94%
Cl -23.62%
157 mg of this product were used in a standard polymerization After 2 hours with PH = 10 atm, PC H ~ 10 atm, 45 g of polymer were obtained, having a MF2 16 of 0.928, a MF21 6 of 39-35 and MF21 6/MF2 16 f 42-4~ and containing 294 ppm of Ti . , 10 y of SiO2 . A12O3 of the same type as used in example 7, were treated with MgC12 . 6 H2O (4 g) and finally with :
354 g of polymer were obtained, with a MF of 0.15, a MF21 6 21.6/MF2.16 of 37.5 and a Ti content of 52 ppm.
EXAMæLE 7 2 A]2O3 (SiO2 =87%, A12O3= 13%, surf~ce area =400 m2/g) were treated as described in example 1.
After activation at 200C under vacuurn, for 30', the product was refluxed in TiCl~ (100 ml). The produc-t obtained after washing and treatment as already described, had the ;~ 6 -10~ 6 following composi-tion Ti ~ 7.50 Mg = 1.10 Cl -19.70~
312 mg of this product were used for the polymerization of ethylene during 2 hours, with PH c 10 atm, PC H - 10 atm, 62 g of polymer was obtained, having a MF2 16 of 0.62, a MF21 6 of MF21 6/MF2.16 of 43.2 and con-taining 382 ppm of Ti 15 g of Sio2/A12O3, the same one as used in example 7 but dried for 20 hours at 450, were treated with 1 g of MgC12 anhydrous in 25 ml H2O.
The product obtained, previously dried on a rotating evaporator, was placed into an oven at 350 and treated for 6 hours with a slow stream of gaseous HCl.
The product obtained after the usual treatment with TiC14 (100 ml) at reflux, iltration and washing with benzene and drying under vacuum, had the following composition Ti ~ 3.8%
- Cl= 13.6 Mg = 0.15~
251 mg of this product were used for the polymerization of ethylene at PH ~ 5 atm, PC H ~ 10 atm. After 6 hours, 414 g of polymer were obtained, with a MF2 16 of -~, a MF21 6 of 4-54 and MF21 6/MF2 16 f 45-4 and a Ti content of 2 ppm.
10 g of SiO2/A12O3 of the same type as used in example 7, were treated with MgC12 . 6 ~l2O (1.6 y) in an aqueous vehicle. The water was removed firstly on a rotaring evaporator under vacuum at the room ternperature, and then hy azeotrope distillation with xylene.
-- 7 ~
:
. - : -. . :
The so obtained product was re1uxed in TiC14 (200 ml), filtered, washed and vacuum dried. At -the end of the above operations, i-t had the following composition Ti -- 8.5%
Mg = 1.1%
Cl -18.95~
155 mg of this product was used in a standard polymerization.
After 2 hours with PH _10 atm, PC2H4 were obtained, with a MF2 16 of 0 47~ a M~21 6 of 20-35 and a MF21.6/~F2.16 of 44.4 and a ~i content of 347 ppm.
62 mg of the product used in example 9 were used in a standard polymerization. After 6 hours with PH ~ 8 atm, PC H = 10 atm, 247 g of polymer were obtained, having a MF2 16 f 0 09 a MF of 5.56 and a RMF21 6/MF2 16 containing 22 ppm of Ti.
10 g of SiO2 . A12O3 of the same type as used in example 7, were treated with 2.5 g of MgC12 . 6 H2O according to the procedure described in example 8. The product had the following composition Ti ~ 8.41%
; Mg - 1.94%
Cl -23.62%
157 mg of this product were used in a standard polymerization After 2 hours with PH = 10 atm, PC H ~ 10 atm, 45 g of polymer were obtained, having a MF2 16 of 0.928, a MF21 6 of 39-35 and MF21 6/MF2 16 f 42-4~ and containing 294 ppm of Ti . , 10 y of SiO2 . A12O3 of the same type as used in example 7, were treated with MgC12 . 6 H2O (4 g) and finally with :
6~7~
TiC14 according to the procedure described in ex~mple 8.
The product had the following composition Ti = 8.59%
Mg = 2.85%
Cl -26.69~
250 mg of this product were used .in a standard polymerization, h PH2 10 atm, and PC H ~ 10 atm. After 2 hours, 106 g polymer were obtained, having a MF2 16 of 1-316~ a MF21 6 f MF21 6/MF 2 16 f 37-5 and containing 203 ppm in Ti .~ ~`' :
TiC14 according to the procedure described in ex~mple 8.
The product had the following composition Ti = 8.59%
Mg = 2.85%
Cl -26.69~
250 mg of this product were used .in a standard polymerization, h PH2 10 atm, and PC H ~ 10 atm. After 2 hours, 106 g polymer were obtained, having a MF2 16 of 1-316~ a MF21 6 f MF21 6/MF 2 16 f 37-5 and containing 203 ppm in Ti .~ ~`' :
Claims (9)
1. A catalytic system for the polymerization of alpha-olefins consisting of a) an aluminium compound chosen among those of formula AlR3 or AlRxY3-x, wherein R is a lower alkyl radical, Y is a halogen or hydrogen atom, and x is a number between 1 and 2, and b) a titanium compound finely dispersed on a carrier having a high surface area, which carrier has been previously treated with a magnesium inorganic compound of the formula:
MgX2.nH2O, wherein X represents a halide and n is a number ranging from O to 6, in which catalyst the amount of magnesium dispersed on the carrier is ranging from 0.1 to 10%
by weight and the molar ratio of aluminium to titanium is ranging from 20 to 75.
MgX2.nH2O, wherein X represents a halide and n is a number ranging from O to 6, in which catalyst the amount of magnesium dispersed on the carrier is ranging from 0.1 to 10%
by weight and the molar ratio of aluminium to titanium is ranging from 20 to 75.
2. A catalytic system for polymerization on of alpha-olefins according to claim 1, wherein the carrier having a high surface area is chosen among SiO2, SiO2.Al03, MgO, TiO2, ZrO2 and the oxides of rare earthes.
3. A catalytic system for the polymerization of alpha-olefins according to claim 1 or 2, wherein the amount of magne-sium on the carrier is ranging from 1 to 5% by weight.
4. A method for preparing a catalytic system for the polymerization of alpha-olefins consisting of a) an aluminium compound chosen among those of formula AlR3 or AlRxY3-x, wherein R is a lower alkyl radical, Y is a halogen or hydrogen atom, and x is a number between 1 and 2, and b) a titanium compound finely dispersed on a carrier having a high surface area which carrier has been previously treated with a magnesium inorganic compound of the formula: MgX2.nH2O wherein X repre-sents a halide and n a number ranging from 0 to 6, in which catalyst the amount of magnesium dispersed on the carrier is ranging from 0.1 to 10% by weight and the molar ratio of aluminium to titanium is ranging from 20 to 75, said method comprising the steps of first preparing the component b) by dispersing the magnesium inorganic compound on the carrier in the water removing the water heating the obtained product under vacuum at a temperature ranging between 200 and 250°C, refluxing said obtained product with liquid titanium tetrachlo-ride, and filtering and vacuum drying the so refluxed product, and thereafter adding the component a) to the component b).
5. A process for the polymerization of alpha-olefins, wherein the polymerization reaction is carried out in presence of a catalytic system consisting of a) an aluminium compound chose among those of formula AlR3 or AlRxY3-x where R is a lower alkyl radical, Y is a halogen or hydrogen atom and X is a number between 1 and 2, and b) a titanium compound finely dispersed on a carrier having a high surface area which carrier has been previously treated with a magnesium inorganic compound of the formula: MgX2.nH2O wherein X
represents a halide and n d number ranging from 0 to 6, in which catalyst the amount of magnesium dispersed on the carrier is ranging from 0.1 to 10% by weight and the molar ratio of aluminium to titanium is ranging from 20 to 75.
represents a halide and n d number ranging from 0 to 6, in which catalyst the amount of magnesium dispersed on the carrier is ranging from 0.1 to 10% by weight and the molar ratio of aluminium to titanium is ranging from 20 to 75.
6. A process for polymerization of alpha-olefins according to claim 5, wherein the carrier having a high surface area in chosen among SiO2, SiO2.Al2O3 MgO, TiO2, ZrO2, and the oxides of rare earthes.
7. A process for the polymerization of alpha-olefins according to claim 6, wherein the reaction is carried out in the presence of a hydrocarbon solvent.
8. A process for the polymerization of alpha-olefins according to claim 5, 6 or 7 wherein the reaction is carried out at a temperature ranging between 0 and 200°C and under a pressure ranging between 0.1 and 50 atm.
9. A process for the polymerization of alpha-olefins according to claim 5, 6 or 7, wherein the alpha-olefin is ethylene.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT23899/74A IT1014991B (en) | 1974-06-12 | 1974-06-12 | CATALYST FOR THE POLYMERIZATION OF ALPHA OLEFINE METHOD FOR ITS PREPARATION AND POLYMERIZATION PROCESS USING SAID CATALYST |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1069876A true CA1069876A (en) | 1980-01-15 |
Family
ID=11210741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA229,053A Expired CA1069876A (en) | 1974-06-12 | 1975-06-11 | Catalyst for alpha-olefin polymerization, method for its preparation and polymerization process employing such catalyst |
Country Status (19)
| Country | Link |
|---|---|
| JP (1) | JPS5111881A (en) |
| BE (1) | BE830112A (en) |
| CA (1) | CA1069876A (en) |
| CH (1) | CH620933A5 (en) |
| CS (1) | CS189708B2 (en) |
| DD (1) | DD119796A5 (en) |
| DE (1) | DE2526352A1 (en) |
| DK (1) | DK264375A (en) |
| FR (1) | FR2274631A1 (en) |
| GB (1) | GB1504417A (en) |
| HU (2) | HU173924B (en) |
| IL (1) | IL47461A (en) |
| IT (1) | IT1014991B (en) |
| LU (1) | LU72708A1 (en) |
| NL (1) | NL7507036A (en) |
| NO (1) | NO148851C (en) |
| SE (1) | SE7506765L (en) |
| YU (1) | YU142775A (en) |
| ZA (1) | ZA753470B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS591284B2 (en) * | 1975-06-24 | 1984-01-11 | 日石三菱株式会社 | Polyolefin Inno Seizouhouhou |
| DE2721094A1 (en) * | 1977-05-11 | 1978-11-23 | Basf Ag | Ziegler catalyst component contg. titanium - is prepd. by combining carrier, titanium tri:halide and magnesium cpd. in alcohol and mixing prod. with aluminium- or silicon cpd. |
| DE2721058C2 (en) * | 1977-05-11 | 1983-08-25 | Basf Ag, 6700 Ludwigshafen | Process for the preparation of homo- and copolymers of C? 2? - to C? 6? -? -Monoolefins |
| DE2721194C2 (en) * | 1977-05-11 | 1983-09-08 | Basf Ag, 6700 Ludwigshafen | Process for the preparation of homo- and copolymers of C? 2? - to C? 6? -? -Monoolefins |
| CA1219996A (en) * | 1982-11-10 | 1987-03-31 | Kazuo Matsuura | Process for preparing polyolefins |
| DE3823934C2 (en) * | 1987-07-31 | 2002-01-03 | Petroleo Brasileiro Sa | Process for producing an ethylene polymerization catalyst and ethylene polymerization process |
| FI89176C (en) * | 1989-03-20 | 1993-08-25 | Neste Oy | FOERFARANDE FOER FRAMSTAELLNING AV EN POLYMERISATIONSKATALYSATORKOMPONENT, EN MEDELST FOERFARANDET FRAMSTAELLD POLYMERISATIONSKATALYSATORKOMPONENT OCH DESS ANVAENDNING |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5040434B2 (en) * | 1971-12-14 | 1975-12-24 | ||
| JPS5248911B2 (en) * | 1974-05-13 | 1977-12-13 |
-
1974
- 1974-06-12 IT IT23899/74A patent/IT1014991B/en active
-
1975
- 1975-05-28 ZA ZA00753470A patent/ZA753470B/en unknown
- 1975-05-29 CS CS753788A patent/CS189708B2/en unknown
- 1975-06-03 YU YU01427/75A patent/YU142775A/en unknown
- 1975-06-04 CH CH719375A patent/CH620933A5/en not_active IP Right Cessation
- 1975-06-05 FR FR7517605A patent/FR2274631A1/en active Granted
- 1975-06-10 LU LU72708A patent/LU72708A1/xx unknown
- 1975-06-11 HU HU75SA3063A patent/HU173924B/en unknown
- 1975-06-11 NO NO752082A patent/NO148851C/en unknown
- 1975-06-11 CA CA229,053A patent/CA1069876A/en not_active Expired
- 1975-06-11 DK DK264375A patent/DK264375A/en not_active Application Discontinuation
- 1975-06-11 HU HU75SA00002800A patent/HU172079B/en unknown
- 1975-06-11 BE BE157227A patent/BE830112A/en not_active IP Right Cessation
- 1975-06-11 IL IL47461A patent/IL47461A/en unknown
- 1975-06-12 DD DD186600A patent/DD119796A5/xx unknown
- 1975-06-12 JP JP50070244A patent/JPS5111881A/en active Granted
- 1975-06-12 SE SE7506765A patent/SE7506765L/en unknown
- 1975-06-12 DE DE19752526352 patent/DE2526352A1/en active Pending
- 1975-06-12 NL NL7507036A patent/NL7507036A/en unknown
- 1975-06-12 GB GB2528175A patent/GB1504417A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| NO148851B (en) | 1983-09-19 |
| FR2274631B1 (en) | 1980-04-25 |
| YU142775A (en) | 1982-02-28 |
| DK264375A (en) | 1975-12-13 |
| IL47461A (en) | 1979-03-12 |
| NO752082L (en) | 1975-12-15 |
| DD119796A5 (en) | 1976-05-12 |
| BE830112A (en) | 1975-10-01 |
| LU72708A1 (en) | 1975-10-08 |
| JPS5111881A (en) | 1976-01-30 |
| HU172079B (en) | 1978-05-28 |
| IT1014991B (en) | 1977-04-30 |
| NL7507036A (en) | 1975-12-16 |
| CH620933A5 (en) | 1980-12-31 |
| IL47461A0 (en) | 1975-08-31 |
| SE7506765L (en) | 1975-12-15 |
| CS189708B2 (en) | 1979-04-30 |
| NO148851C (en) | 1984-01-04 |
| DE2526352A1 (en) | 1975-12-18 |
| ZA753470B (en) | 1976-05-26 |
| GB1504417A (en) | 1978-03-22 |
| FR2274631A1 (en) | 1976-01-09 |
| JPS5615644B2 (en) | 1981-04-11 |
| HU173924B (en) | 1979-09-28 |
| AU8170775A (en) | 1976-12-02 |
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