CA1059977A - Catalyst for the polymerization of alpha-olefins - Google Patents
Catalyst for the polymerization of alpha-olefinsInfo
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- CA1059977A CA1059977A CA223,243A CA223243A CA1059977A CA 1059977 A CA1059977 A CA 1059977A CA 223243 A CA223243 A CA 223243A CA 1059977 A CA1059977 A CA 1059977A
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- catalytic system
- carrier
- transition metal
- weight
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- 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
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
The polymerization of alpha-olefins is improved by carrying the polymerization reaction in the presence of a catalytic system consisting of (a) an aluminum compound represented by the formula AlR3 or AlRxY3-x in which R is an alkyl, aryl or cycloalkyl radical, Y is a halogen or hydrogen and x is a number between 1 and 2, and (b) the combination product of titanium trichloride and an isostructural chloride of another transition metal selected from the group consisting of V, Mn, Co and ??, this product being supported on a carrier having a high superficial area and selected from the oxides of elements belonging to Groups II to IV of the Periodic Table; the weight ratio between components (a) and (b) of the catalytic system ranges from 4 to 7?. The catalytic system of the invention has a high activity and does not require any preliminary treatment of the carrier.
The polymerization of alpha-olefins is improved by carrying the polymerization reaction in the presence of a catalytic system consisting of (a) an aluminum compound represented by the formula AlR3 or AlRxY3-x in which R is an alkyl, aryl or cycloalkyl radical, Y is a halogen or hydrogen and x is a number between 1 and 2, and (b) the combination product of titanium trichloride and an isostructural chloride of another transition metal selected from the group consisting of V, Mn, Co and ??, this product being supported on a carrier having a high superficial area and selected from the oxides of elements belonging to Groups II to IV of the Periodic Table; the weight ratio between components (a) and (b) of the catalytic system ranges from 4 to 7?. The catalytic system of the invention has a high activity and does not require any preliminary treatment of the carrier.
Description
lOS99~77 The present inventlon relatee to a proces~ for the polymerization Or alpha-olefins, particularly ethylene, b~
~eans Or a catalyst system constituted by an aluminium alkyl and the combination Or a tran6ition metal chloride and titanium trichloride finely dispersed on a material having a high superricial area; a further aspect Or the invention cQncerns the cataIytic system employed as ~ell as the method ror preparing 8uch a catalyst.
It 18 ~no~n that titaniu~ halides, ~hich are active rro~ a catalytic point Or vie~, are employed in the lo~ pressure polymerizatlon Or alpha-oleiin~. Theso are prepared by reducing titaniu~ tetrahalides ~ith alu~inium aIkyl or alkyl-halldo , co~pounds. Ihe rea¢tion i8 generally oarried out w der ~n i ~nert atmosphere and in the presen¢e of an inert sol~ent. The 1 catslyst thus obtained~ is then used togethor ~ith metal alkyl co~pounds ior the polymerization Or alpha-oleiins in suspe~slon ~ ln an organic solvent, under reasonable preasures of the monomer.
¦ ~o~ever~ the~e tltaniu~ halides are impure because of the presence Or alu~inium compounds and do not sho~ a very high ¢atal~tic activit~ 80 that the rinal polymer needs espensive shing operations in order to re~oie the catalytic r0~iduale.
~ ethods have been recentl~ proposed, according to ~h~ch the titanium h~lides are supported carried on inorganlc substances 80 as to obt~n pol~merization catal~sts having an ' i~proved errecti~eness. For instance, use may be made Or i,~ carrièrs such as ~agneslum oxide or hydroxide; howe~er~ it is to be ~oted that the catalytic activity o~ the titanium compound, , ~ .
oarried on tbese materials, highly varies according to the chemical nature oi the sur~ace thereor; therefore, such compounds ~0 must,in many case~, undergo trestments with Grignard reagents, aluminlu~ alkyl compounds or hydrogen, in order to improve their errectivene~s. ~ ' ~ .
-- 1 .
` ~ lOS997~
The subject invention proposes to provide an improved process for the polymerization of alpha-olefins, wherein use is made of a catalytic system which has a high activity and does not need any preliminary treatment of the carrier.
The catalytic system utili.zed, which constitutes a further aspect of the present invention, comprises the following two components:
a) an aluminum compound represented by the formula AlR3 or AlRXY3 x in which R is an alkyl, aryl or cycloalkyl radical, Y is a halogen or hydrogen, and x is a number between ~ 1 and 2;
; b) the combination product of titanium trichloride and an isostructural chloride of another transition metal selected from the group consisting of V, Mn, Co and Fe, the product being supported on a carrier having a high superficial area and selected from the oxides of elements belonging to Groups II to IV of the Periodic Table, the weight ratio between components (a) and (b) ranging from 4 to 78.
The component (b) of the catalytic system of the invention is very stable from a chemical point of view since the titanium trichloride and transition metal chloride are iso-structural; moreover, it contains titanium in its optimum valence : state, which provides for the best catalytic activity.
The component (b) is advantageously prepared by impregnating the carrier, previously dehydrated by a thermal treatment, with a low valence derivative of the other transition metal, preferably a transition metal derivative in the zero valence state such as a carbonyl metal derivative, dissolved in a hydrocarbon solvent, refluxing the impregnated carrier with titanium tetrachloride and, finally, removing excess of this latter from the carrier.
The zero val.ence transition metal derivative may contain ligands of a type different from the carbonyl one, for instance
~eans Or a catalyst system constituted by an aluminium alkyl and the combination Or a tran6ition metal chloride and titanium trichloride finely dispersed on a material having a high superricial area; a further aspect Or the invention cQncerns the cataIytic system employed as ~ell as the method ror preparing 8uch a catalyst.
It 18 ~no~n that titaniu~ halides, ~hich are active rro~ a catalytic point Or vie~, are employed in the lo~ pressure polymerizatlon Or alpha-oleiin~. Theso are prepared by reducing titaniu~ tetrahalides ~ith alu~inium aIkyl or alkyl-halldo , co~pounds. Ihe rea¢tion i8 generally oarried out w der ~n i ~nert atmosphere and in the presen¢e of an inert sol~ent. The 1 catslyst thus obtained~ is then used togethor ~ith metal alkyl co~pounds ior the polymerization Or alpha-oleiins in suspe~slon ~ ln an organic solvent, under reasonable preasures of the monomer.
¦ ~o~ever~ the~e tltaniu~ halides are impure because of the presence Or alu~inium compounds and do not sho~ a very high ¢atal~tic activit~ 80 that the rinal polymer needs espensive shing operations in order to re~oie the catalytic r0~iduale.
~ ethods have been recentl~ proposed, according to ~h~ch the titanium h~lides are supported carried on inorganlc substances 80 as to obt~n pol~merization catal~sts having an ' i~proved errecti~eness. For instance, use may be made Or i,~ carrièrs such as ~agneslum oxide or hydroxide; howe~er~ it is to be ~oted that the catalytic activity o~ the titanium compound, , ~ .
oarried on tbese materials, highly varies according to the chemical nature oi the sur~ace thereor; therefore, such compounds ~0 must,in many case~, undergo trestments with Grignard reagents, aluminlu~ alkyl compounds or hydrogen, in order to improve their errectivene~s. ~ ' ~ .
-- 1 .
` ~ lOS997~
The subject invention proposes to provide an improved process for the polymerization of alpha-olefins, wherein use is made of a catalytic system which has a high activity and does not need any preliminary treatment of the carrier.
The catalytic system utili.zed, which constitutes a further aspect of the present invention, comprises the following two components:
a) an aluminum compound represented by the formula AlR3 or AlRXY3 x in which R is an alkyl, aryl or cycloalkyl radical, Y is a halogen or hydrogen, and x is a number between ~ 1 and 2;
; b) the combination product of titanium trichloride and an isostructural chloride of another transition metal selected from the group consisting of V, Mn, Co and Fe, the product being supported on a carrier having a high superficial area and selected from the oxides of elements belonging to Groups II to IV of the Periodic Table, the weight ratio between components (a) and (b) ranging from 4 to 78.
The component (b) of the catalytic system of the invention is very stable from a chemical point of view since the titanium trichloride and transition metal chloride are iso-structural; moreover, it contains titanium in its optimum valence : state, which provides for the best catalytic activity.
The component (b) is advantageously prepared by impregnating the carrier, previously dehydrated by a thermal treatment, with a low valence derivative of the other transition metal, preferably a transition metal derivative in the zero valence state such as a carbonyl metal derivative, dissolved in a hydrocarbon solvent, refluxing the impregnated carrier with titanium tetrachloride and, finally, removing excess of this latter from the carrier.
The zero val.ence transition metal derivative may contain ligands of a type different from the carbonyl one, for instance
- 2 -`-`` lOS9977 .
allyl, cyclopentadienilic olefinic, nitrosyl groups, and the like.
During the process, volatile substances are developed and, in particular, carbon` monoxide in the case where use is made of carbonyl metal compounds; the oxidation of the metal and the simultaneous reduction of titanium tetrachloride to `
i trichloride occur according to the following reaction , M (CO)p + n TiC14 ) MCln.n TiC13+ p CO
wherein p represents the carbonyl number and n the valence state taken by the transition metal M during its oxidation by lo titanium tetrachloride.
The transition metal which is selected among V, Mn, Fe and Co is advantageously used in an amount ranging from 0.1 to 10%
by weight with respect to the weight of the carrier, preferably from 1 to 3% by weight.
The material employed as carrier is preferably selected ~ among silica, silica-alumina, ZnO2, MnO, TiO2 and CaO.
-~ As mentioned above, pretreatments are not necessary since the activity of the catalytic systems of the invention is high and homogeneous, even if the chemical nature of the carrier ; 20 undergoes changes; however, such carriers can also be subjected to pretreatments with Grignard reagents or aluminium alkyl-halides so as to further increase the performances thereof.
The activities observed in polymerization are anyhow higher than those obtained by means of carriers treated only with TiC14, the other conditions remaining the same.
The catalysts of the invention show a good behaviour in the presence of hydrogen and, in the case of the ethylene polymerization, give rise to a narrow molecular weight distri-bution.
The polymerization reaction is carried out according to known procedures, at temperatures comprised from 0 to 200C
and at pressures ranging from 0.1 to 50 atmospheres. It is performed in steel autoclave equipped with an anchor stirrer
allyl, cyclopentadienilic olefinic, nitrosyl groups, and the like.
During the process, volatile substances are developed and, in particular, carbon` monoxide in the case where use is made of carbonyl metal compounds; the oxidation of the metal and the simultaneous reduction of titanium tetrachloride to `
i trichloride occur according to the following reaction , M (CO)p + n TiC14 ) MCln.n TiC13+ p CO
wherein p represents the carbonyl number and n the valence state taken by the transition metal M during its oxidation by lo titanium tetrachloride.
The transition metal which is selected among V, Mn, Fe and Co is advantageously used in an amount ranging from 0.1 to 10%
by weight with respect to the weight of the carrier, preferably from 1 to 3% by weight.
The material employed as carrier is preferably selected ~ among silica, silica-alumina, ZnO2, MnO, TiO2 and CaO.
-~ As mentioned above, pretreatments are not necessary since the activity of the catalytic systems of the invention is high and homogeneous, even if the chemical nature of the carrier ; 20 undergoes changes; however, such carriers can also be subjected to pretreatments with Grignard reagents or aluminium alkyl-halides so as to further increase the performances thereof.
The activities observed in polymerization are anyhow higher than those obtained by means of carriers treated only with TiC14, the other conditions remaining the same.
The catalysts of the invention show a good behaviour in the presence of hydrogen and, in the case of the ethylene polymerization, give rise to a narrow molecular weight distri-bution.
The polymerization reaction is carried out according to known procedures, at temperatures comprised from 0 to 200C
and at pressures ranging from 0.1 to 50 atmospheres. It is performed in steel autoclave equipped with an anchor stirrer
- 3 -~` ~05997 7 when the operations are carried out at pressures higher than the atmospheric one. The catalyst is introduced together with the solvent and the metal alkyl compound.
The autoclave being thermostated at the polymerization temperature, H2 and then ethylene are introduced therein under pressure at the desired pressure ratio. The reaction is generally ~` stopped by adding alcohol into the autoclave.
With peculiar reference to the Examples hereinafter reported, the solvent, the organic metal compound (Al(-C4Hg)3 in concentration equal to 0.2~ by volume) and the transition element compound combination, previously prepared as specified in each example, are introduced into the autoclave, thermostated at 85C. The ethylene pressure was kept constant for the whole test which was carried out over six hours. The procedures described in the following examples will refer to these working conditions (standard polymerization). The polymers obtained are dried under vacuum up to a constant weight before evaluating the yields as polymer.
The examples which will now follow are given only to illustrate the subject invention which must not be considered as being limited thereto. In these examples, the designations "MF2 16" and "MF21 6" stand for the Melt Flow index under a charge of 2.16 kg and of 21.6 kg, respectively, according to ASTM-D 1236-65T.
100 g of "Low Alumina" SiO2/A12O3, SA = 400 m /g, were refluxed in boiling xylene in order to azeotropically remove water. The product, dried, filtered under nitrogen and washed with hexane, was added with 3 g of tetracarbonyl-vanadium cyclopentadienyl, V (CO)4 Cp, in 200 ml of hexane.This solvent was removed by means of a rotating evaporator and the yellow material obtained, which was air sensitive, was ~059~
refluxed~ after having been suspended in 200 ml of ~iC14~ over ~lx hours. During this time~ the material became dark violet. It ~as then filtered, repeatedly washed ~ith hexane and dried under ~acuum.
The analysis ~howed the following composition Ti 7.3%
V 0.40%
Cl 12.54%
240 mg of this ¢atalyst were ~mployed in the et~ylene polymerization at the partial pre~sure~ of H2- 13 atm; and C2H4= 8 atm.
500 g of polyethylene were obtained having MF21 6' 1 [ ~ 135C = 4.6 decaline d ~g and containing 36 ppm of Ti+ r, in which the ~i content was about 33 ppm.
EXAMP~E 2 The same SiO2- A1203 employed in example 1 was refluxed in ~ ~ thc same conditions with only titanium tetrachloride.
;~ ~fter the same treatment~ the ~hite material obta~ne~
hich ~a~ air sen~it~ve , ga~e the following anslysi~
Ti 4.10~
Cl 7.98%
224 mg of this cataly~t gave, in the ~ame polymerization co~ditions a~ describea in example 1, 60 g of polymer having ~F21 6=
135C = 6.6 dl/g and a Ti content equal to 150 ppm.
decaline 25 g of SiO2 ( > 9g%), SA = 400 m2/g, were dehgdrated~
through an azeotropic distillation with xylene, treated with 0.55 g V(CO)4 Cp in he~ane (50ml3 and then refluxed, after having re-~3D mo~ed the hydrocarbon solvent~ in liquid TiC14 (50ml)~ as described in example 1. ~he colour of the catalyst thus obtained was dar~
~iolet. The analy~is showed the following composition:
10599~7 Ti 4.65 V 0.40~
- C1 8.24%
105 mg of the cstalyst obtained were used in a standard polymerization at relative pregsures H2/C2H4 = 10/10 atm, 102 g of polyethylene were obtained having MF21 6 = 0 3 and Ti+V con-tent equal to 52 ppm, in which the Ti content Wa8 46 ppm.
85 g of SiO2/A1203 of the same type employed in examples 1 and 2 were dried in muffle at 400C over 24 hours and then impregnated with 4.0 g of E~ln2 (C0)10 in 200 ml of hexane.
- The solvent ~a9 removed by means of a rotating evaporation ~, and the orange-yellow solid obtained was refluxed in boiling Ti C14 over 6 hours.
1 The re~ulting violet material was filtered, washed with hexane and dried under vacuum; it showed the follo~ing analysis ~i 5.73%
~n 1.35%
. ., Cl 12.60%
169 mg of this product were employed in a standard polymeri-zation test at 13 atm. of H2 and 8 atm. of C2H4, and produced i 151 g of polyethylene having MF2 16 = 0-350, 21~21 6 = 15.684, MF21.6/~2.j6 = 44~ [ ~ = 3.3 dl/g and 79 ppm of Mn + Ti, in which the Ti oontent was 64 ppm.
416 mg of the product described in example 4 ~ere employed in a standard polymerization at relative pressures H2/C2H4 =
10/5 atm.3and produced 55 g of polyethyle1ne Ohaving ~F2 16 = 5.16, 21.6 1 .6, ~F21.6/ r.l~2,16 = 41~ ~1 Decaline = 1-6 dl~g and Ti + Mn content equal to 229 ppm in ~hich the Ti conten~
was 185 ppm.
, 260 mg of the product employed in example 4 were employed in a standard polymerization by replacing Al(i-C4Hg)3 with AlEt2Cl and working at relative pre~sures H2/C2H4 equal to 10/10 atm~h3~s.
120 g Qf polymer were obtain~e3d50hcaving MF2.16 135, 21.6 =8.727, MF2~ 6/MF2.16 = 64~ L~ decaline = 3.5 dl/g and a Ti + Mn content equal to 153 ppm, in which the Ti content ~as 124 ppm.
25 g of a finely powdered i`IgO, dried in muffle at 400C over one night, were reacted ~ith 1-5 g of Co2 (CO)g in 100 ml of hexa-ne. The solvent was then removed by means of a rotating evapora-tor and the residual was refluxed under nitrogen in TiC14 (100 ml~
over 8 hours.
A violet po~der ~as obtalned after hot filtration, wnich was repeatedly wa~hed with hexane and dried under vacuum; it sho~ed the following composition Ti 3.70%
Co 1.55%
Cl 31.15~
31 mg of the product thus obtained ~ere employed in a standard ~polymerization at 10 H2 atmospheres and 10 C2H4 atmospheres.
250 g of polyethylene were obtained having r~F2 16 = 0.869, ~;~ MF21.6 = 34.97~ MP21.6/M~2.16 = 40.2,~ d~x~ine = 1.92 dl/g and a ~; ~ Ti ~ Co content equal to 6.5 ppm, in which the ~i content ~as 4.6 ppm.
A ~ample of commercial MgO was hydrated in water at 80C for
The autoclave being thermostated at the polymerization temperature, H2 and then ethylene are introduced therein under pressure at the desired pressure ratio. The reaction is generally ~` stopped by adding alcohol into the autoclave.
With peculiar reference to the Examples hereinafter reported, the solvent, the organic metal compound (Al(-C4Hg)3 in concentration equal to 0.2~ by volume) and the transition element compound combination, previously prepared as specified in each example, are introduced into the autoclave, thermostated at 85C. The ethylene pressure was kept constant for the whole test which was carried out over six hours. The procedures described in the following examples will refer to these working conditions (standard polymerization). The polymers obtained are dried under vacuum up to a constant weight before evaluating the yields as polymer.
The examples which will now follow are given only to illustrate the subject invention which must not be considered as being limited thereto. In these examples, the designations "MF2 16" and "MF21 6" stand for the Melt Flow index under a charge of 2.16 kg and of 21.6 kg, respectively, according to ASTM-D 1236-65T.
100 g of "Low Alumina" SiO2/A12O3, SA = 400 m /g, were refluxed in boiling xylene in order to azeotropically remove water. The product, dried, filtered under nitrogen and washed with hexane, was added with 3 g of tetracarbonyl-vanadium cyclopentadienyl, V (CO)4 Cp, in 200 ml of hexane.This solvent was removed by means of a rotating evaporator and the yellow material obtained, which was air sensitive, was ~059~
refluxed~ after having been suspended in 200 ml of ~iC14~ over ~lx hours. During this time~ the material became dark violet. It ~as then filtered, repeatedly washed ~ith hexane and dried under ~acuum.
The analysis ~howed the following composition Ti 7.3%
V 0.40%
Cl 12.54%
240 mg of this ¢atalyst were ~mployed in the et~ylene polymerization at the partial pre~sure~ of H2- 13 atm; and C2H4= 8 atm.
500 g of polyethylene were obtained having MF21 6' 1 [ ~ 135C = 4.6 decaline d ~g and containing 36 ppm of Ti+ r, in which the ~i content was about 33 ppm.
EXAMP~E 2 The same SiO2- A1203 employed in example 1 was refluxed in ~ ~ thc same conditions with only titanium tetrachloride.
;~ ~fter the same treatment~ the ~hite material obta~ne~
hich ~a~ air sen~it~ve , ga~e the following anslysi~
Ti 4.10~
Cl 7.98%
224 mg of this cataly~t gave, in the ~ame polymerization co~ditions a~ describea in example 1, 60 g of polymer having ~F21 6=
135C = 6.6 dl/g and a Ti content equal to 150 ppm.
decaline 25 g of SiO2 ( > 9g%), SA = 400 m2/g, were dehgdrated~
through an azeotropic distillation with xylene, treated with 0.55 g V(CO)4 Cp in he~ane (50ml3 and then refluxed, after having re-~3D mo~ed the hydrocarbon solvent~ in liquid TiC14 (50ml)~ as described in example 1. ~he colour of the catalyst thus obtained was dar~
~iolet. The analy~is showed the following composition:
10599~7 Ti 4.65 V 0.40~
- C1 8.24%
105 mg of the cstalyst obtained were used in a standard polymerization at relative pregsures H2/C2H4 = 10/10 atm, 102 g of polyethylene were obtained having MF21 6 = 0 3 and Ti+V con-tent equal to 52 ppm, in which the Ti content Wa8 46 ppm.
85 g of SiO2/A1203 of the same type employed in examples 1 and 2 were dried in muffle at 400C over 24 hours and then impregnated with 4.0 g of E~ln2 (C0)10 in 200 ml of hexane.
- The solvent ~a9 removed by means of a rotating evaporation ~, and the orange-yellow solid obtained was refluxed in boiling Ti C14 over 6 hours.
1 The re~ulting violet material was filtered, washed with hexane and dried under vacuum; it showed the follo~ing analysis ~i 5.73%
~n 1.35%
. ., Cl 12.60%
169 mg of this product were employed in a standard polymeri-zation test at 13 atm. of H2 and 8 atm. of C2H4, and produced i 151 g of polyethylene having MF2 16 = 0-350, 21~21 6 = 15.684, MF21.6/~2.j6 = 44~ [ ~ = 3.3 dl/g and 79 ppm of Mn + Ti, in which the Ti oontent was 64 ppm.
416 mg of the product described in example 4 ~ere employed in a standard polymerization at relative pressures H2/C2H4 =
10/5 atm.3and produced 55 g of polyethyle1ne Ohaving ~F2 16 = 5.16, 21.6 1 .6, ~F21.6/ r.l~2,16 = 41~ ~1 Decaline = 1-6 dl~g and Ti + Mn content equal to 229 ppm in ~hich the Ti conten~
was 185 ppm.
, 260 mg of the product employed in example 4 were employed in a standard polymerization by replacing Al(i-C4Hg)3 with AlEt2Cl and working at relative pre~sures H2/C2H4 equal to 10/10 atm~h3~s.
120 g Qf polymer were obtain~e3d50hcaving MF2.16 135, 21.6 =8.727, MF2~ 6/MF2.16 = 64~ L~ decaline = 3.5 dl/g and a Ti + Mn content equal to 153 ppm, in which the Ti content ~as 124 ppm.
25 g of a finely powdered i`IgO, dried in muffle at 400C over one night, were reacted ~ith 1-5 g of Co2 (CO)g in 100 ml of hexa-ne. The solvent was then removed by means of a rotating evapora-tor and the residual was refluxed under nitrogen in TiC14 (100 ml~
over 8 hours.
A violet po~der ~as obtalned after hot filtration, wnich was repeatedly wa~hed with hexane and dried under vacuum; it sho~ed the following composition Ti 3.70%
Co 1.55%
Cl 31.15~
31 mg of the product thus obtained ~ere employed in a standard ~polymerization at 10 H2 atmospheres and 10 C2H4 atmospheres.
250 g of polyethylene were obtained having r~F2 16 = 0.869, ~;~ MF21.6 = 34.97~ MP21.6/M~2.16 = 40.2,~ d~x~ine = 1.92 dl/g and a ~; ~ Ti ~ Co content equal to 6.5 ppm, in which the ~i content ~as 4.6 ppm.
A ~ample of commercial MgO was hydrated in water at 80C for
4 hours and then dried in muffle at 400C in air for 24 hours.
20 mg of the MgO 90 treated were impregnated ~lith V(CO)4 Cp ~1.2 g) in hexane (100 ml) and the solvent was removed by means of a rotating evaporator. The dry residual was then refluxed in boi-- ` ~0599~7 .. . .
ling TiC14 (100 ml) over 4 hours. A violet product was obtained, which was filtered, washed and vaccum dried; it sho~ed the fol-lowing composition Ti 3~1%
V 0.58%
i Cl 35.23%
; .
20 mg of this catalyst were employed in a standard polymeri-zation at relative pressure~ H2/C2H4 = 10/10 atm. 235 g of polye-` thylene were obtained havi135Mc2.16 1. 3~ 21.6 - ~ 1.6/~F2.16 ' 40-8-t~ decaline = 1.90 dl/g and contai-ning 3.3 ppm of Ti + V, in which the Ti content was 2.8 ppm.
EX~MPIE 9 20g of MgO, treated according to the procedure of example 8, were refluxed in boilitng TiC14 (100 ml) over 4 hours.
A white solid was then filtered, which was wa~hed and vac-, . . .
, ~; ~ uum dried, it showed the following composition ~ ~ Ti 1.43%
: ! Cl 31.62%
42 mg of this catalyst were employed for the ~ake of compari-son, in a standard polymerization carried out as described in ex-nmple 8. 81 g of polyethylene were obtained having MF2 16 = 1.81, MF21.6 = 44~ MF21.6/MF2.16 = 36-3~ [~J decaline = 2.73 dl/g i.~
and a Ti content equal to 7.4 ppm.
EXA~PIE 10 25 g of SiO2, of the same type employed in example 3, were dehydrated b~ mean~ of an azeotropic distillation with xylene and reacted nith 2 ml of Al~tC12 in hexane (100 ml). The suspension was then added with V (CO)4 Cp (1.Og) and then the solvent was re-moved by means of a rotating evaporator. ~he re~ulting product was refluxed in boiling TiC14 over 6 hours. After filtration, washing with hexane and vacuum drying, the viol-t ob~ained product . - .
` lOS9977 had the following composition ~i 2.97%
V 0.86%
Al 1.90%
Cl 8.59%
192 mg o~ the catalyst thus obtained ~ere used in a standard polymerization at relative pressures H2/C~H4 e~ual to 10/10 atm.
96 g of polyethylene were obtained, having M~2 16=.335~MF21 6=
14.1,MF21.6/MF2.16=42.1[~]= 2.63 dl/g and ~i+V content equal to 80 ppm, in which the ~i content wa~ 60 ppm 25g of SiO2 = A1203 of the same type employed in e~ample 1, drled over one night in a stove at 200C, ~as treated ~ith an ether solution of chlorobutyl Grignard (10 ml, solution 1/1 ml) in 10 ml of exane. The solvent Wa9 evaporated by means of a ro-tating evaporator and then 1.2 g V (C0)4 Cp was sdded in 100 ml of hexane.
After the removal of the solvent, the dry product was re-fluxed in boiling ~iC14 over 6 hours. A violet solid ~as then flltered, washed and dried; it showed the following composition:
Ti 9,20%
V 0.74%
~g 1.07%
Cl 21.85%
212 mg of this product ~ere employed in a standard polyme-rization with 7.5 atm. of ethylene and lS H2 atm., and produced 325 g of polyethylene having M~2 16= 1.014, MF~l 6= 45~44~
MF21 6/MF2 16 = 45~44~L ~(~ = 2-0 dl/g and containing 65 ppm of Ti + V, in which the ~i content was 61 ppm.
, _ 9 _
20 mg of the MgO 90 treated were impregnated ~lith V(CO)4 Cp ~1.2 g) in hexane (100 ml) and the solvent was removed by means of a rotating evaporator. The dry residual was then refluxed in boi-- ` ~0599~7 .. . .
ling TiC14 (100 ml) over 4 hours. A violet product was obtained, which was filtered, washed and vaccum dried; it sho~ed the fol-lowing composition Ti 3~1%
V 0.58%
i Cl 35.23%
; .
20 mg of this catalyst were employed in a standard polymeri-zation at relative pressure~ H2/C2H4 = 10/10 atm. 235 g of polye-` thylene were obtained havi135Mc2.16 1. 3~ 21.6 - ~ 1.6/~F2.16 ' 40-8-t~ decaline = 1.90 dl/g and contai-ning 3.3 ppm of Ti + V, in which the Ti content was 2.8 ppm.
EX~MPIE 9 20g of MgO, treated according to the procedure of example 8, were refluxed in boilitng TiC14 (100 ml) over 4 hours.
A white solid was then filtered, which was wa~hed and vac-, . . .
, ~; ~ uum dried, it showed the following composition ~ ~ Ti 1.43%
: ! Cl 31.62%
42 mg of this catalyst were employed for the ~ake of compari-son, in a standard polymerization carried out as described in ex-nmple 8. 81 g of polyethylene were obtained having MF2 16 = 1.81, MF21.6 = 44~ MF21.6/MF2.16 = 36-3~ [~J decaline = 2.73 dl/g i.~
and a Ti content equal to 7.4 ppm.
EXA~PIE 10 25 g of SiO2, of the same type employed in example 3, were dehydrated b~ mean~ of an azeotropic distillation with xylene and reacted nith 2 ml of Al~tC12 in hexane (100 ml). The suspension was then added with V (CO)4 Cp (1.Og) and then the solvent was re-moved by means of a rotating evaporator. ~he re~ulting product was refluxed in boiling TiC14 over 6 hours. After filtration, washing with hexane and vacuum drying, the viol-t ob~ained product . - .
` lOS9977 had the following composition ~i 2.97%
V 0.86%
Al 1.90%
Cl 8.59%
192 mg o~ the catalyst thus obtained ~ere used in a standard polymerization at relative pressures H2/C~H4 e~ual to 10/10 atm.
96 g of polyethylene were obtained, having M~2 16=.335~MF21 6=
14.1,MF21.6/MF2.16=42.1[~]= 2.63 dl/g and ~i+V content equal to 80 ppm, in which the ~i content wa~ 60 ppm 25g of SiO2 = A1203 of the same type employed in e~ample 1, drled over one night in a stove at 200C, ~as treated ~ith an ether solution of chlorobutyl Grignard (10 ml, solution 1/1 ml) in 10 ml of exane. The solvent Wa9 evaporated by means of a ro-tating evaporator and then 1.2 g V (C0)4 Cp was sdded in 100 ml of hexane.
After the removal of the solvent, the dry product was re-fluxed in boiling ~iC14 over 6 hours. A violet solid ~as then flltered, washed and dried; it showed the following composition:
Ti 9,20%
V 0.74%
~g 1.07%
Cl 21.85%
212 mg of this product ~ere employed in a standard polyme-rization with 7.5 atm. of ethylene and lS H2 atm., and produced 325 g of polyethylene having M~2 16= 1.014, MF~l 6= 45~44~
MF21 6/MF2 16 = 45~44~L ~(~ = 2-0 dl/g and containing 65 ppm of Ti + V, in which the ~i content was 61 ppm.
, _ 9 _
Claims (15)
1. Process for the polymerization of alpha-olefins, characterized in that the polymerization reaction is carried out in the presence of a catalytic system consisting of (a) an aluminum compound represented by the formula AlR3 or AlRxY3-x in which R
is an alkyl, aryl or cycloalkyl radical, Y is a halogen or hydrogen and x is a number between 1 and 2, and (b) the combination product of titanium trichloride and an isostructural chloride of another transition metal selected from the group consisting of V, Mn, Co and Fe, said product being supported on a carrier having a high superficial area and selected from the oxides of elements belonging to Groups II to IV of the Periodic Table, the weight ratio between components (a) and (b) of the catalytic system ranging from 4 to 78.
is an alkyl, aryl or cycloalkyl radical, Y is a halogen or hydrogen and x is a number between 1 and 2, and (b) the combination product of titanium trichloride and an isostructural chloride of another transition metal selected from the group consisting of V, Mn, Co and Fe, said product being supported on a carrier having a high superficial area and selected from the oxides of elements belonging to Groups II to IV of the Periodic Table, the weight ratio between components (a) and (b) of the catalytic system ranging from 4 to 78.
2. Process according to claim 1, characterized in that the carrier is selected from the group consisting of SiO2, SiO2/Al2O3, ZnO2, MnO, TiO2 and CaO.
3. Process according to claim 1, characterized in that said other transition metal is present in an amount ranging from 0.1 to 10% by weight with respect to the weight of the carrier.
4. Process according to claim 3, characterized in that said amount is comprised between 1 and 3% by weight.
5. Process according to claim 1, characterized in that the olefin employed is ethylene.
6. Process according to claim 1, characterized in that the reaction is carried out in presence of a hydrocarbon solvent.
7. Process according to claim 1, characterized in that the reaction is carried out at a temperature of from 0 to 200°C, and at a pressure of from 0.1 to 50 atmospheres.
8. Process according to claim 8, characterized in that the temperature is comprised between 20 and 120°C.
9. Catalytic system for the polymerization of alpha-olefins, characterized in that it consists of the following two components:
a) an aluminum compound represented by the formula AlR3 or AlRxY3-x in which R is an alkyl, aryl or cycloalkyl radical, Y is a halogen or hydrogen, and x is a number between 1 and 2;
b) the combination product of titanium trichloride and an isostructural chloride of another transition metal selected from the group consisting of V, Mn, Co and Fe, said product being supported on a carrier having a high superficial area and selected from the oxides of elements belonging to Groups II to IV of the Periodic Table, the weight ratio between components (a) and (b) ranging from 4 to 78.
a) an aluminum compound represented by the formula AlR3 or AlRxY3-x in which R is an alkyl, aryl or cycloalkyl radical, Y is a halogen or hydrogen, and x is a number between 1 and 2;
b) the combination product of titanium trichloride and an isostructural chloride of another transition metal selected from the group consisting of V, Mn, Co and Fe, said product being supported on a carrier having a high superficial area and selected from the oxides of elements belonging to Groups II to IV of the Periodic Table, the weight ratio between components (a) and (b) ranging from 4 to 78.
10. Catalytic system according to claim 9, characterized in that the carrier is selected from the group consisting of SiO2, SiO2/Al2O3, ZnO2, MnO, TiO2 and CaO.
11. Catalytic system according to claim 9, characterized in that said other transition metal is present in an amount of from 0.1 to 10% by weight with respect to the weight of the carrier.
12. Catalytic system according to claim 11, characterized in that said amount is comprised between 1 and 3% by weight.
13. Catalytic system according to claim 9, characterized in that said component (b) is prepared by impregnating the carrier, previously dehydrated by a thermal treatment, with a low valence derivative of said other transition metal dissolved in a hydrocarbon solvent, refluxing the impregnated carrier with titanium tetrachloride and then removing excess titanium tetrachloride.
14. Catalytic system according to claim 13, characterized in that the transition metal derivative is a compound in the zero valence state, in free or complexed form.
15. Catalytic system according to claim 14, characterized in that the zero valence transition metal derivative is selected among carbonyl derivatives.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT49832/74A IT1013081B (en) | 1974-03-28 | 1974-03-28 | PROCEDURE FOR THE POLYMERIZATION OF ALPHA OLEFINE CATALYST USED IN THIS PROCEDURE AND ME TODO FOR ITS PREPARATION |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1059977A true CA1059977A (en) | 1979-08-07 |
Family
ID=11271666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA223,243A Expired CA1059977A (en) | 1974-03-28 | 1975-03-27 | Catalyst for the polymerization of alpha-olefins |
Country Status (18)
| Country | Link |
|---|---|
| JP (1) | JPS5237035B2 (en) |
| BE (1) | BE827259A (en) |
| CA (1) | CA1059977A (en) |
| CS (1) | CS195281B2 (en) |
| DD (1) | DD120449A5 (en) |
| DE (1) | DE2513927A1 (en) |
| DK (1) | DK144704C (en) |
| FR (1) | FR2265770A1 (en) |
| HU (1) | HU172294B (en) |
| IL (1) | IL47074A (en) |
| IT (1) | IT1013081B (en) |
| LU (1) | LU72137A1 (en) |
| NL (1) | NL164045C (en) |
| NO (1) | NO146867C (en) |
| SE (1) | SE425496B (en) |
| SU (1) | SU1072811A3 (en) |
| YU (1) | YU71775A (en) |
| ZA (1) | ZA751387B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1081277B (en) * | 1977-06-30 | 1985-05-16 | Snam Progetti | CHEMICAL COMPOSITIONS BASED ON TRIALHYGEN TITANIUM PROCEDURE FOR THEIR PREPARATION AND USE |
| JPS56159163U (en) * | 1980-04-28 | 1981-11-27 |
-
1974
- 1974-03-28 IT IT49832/74A patent/IT1013081B/en active
-
1975
- 1975-03-06 ZA ZA00751387A patent/ZA751387B/en unknown
- 1975-03-24 YU YU00717/75A patent/YU71775A/en unknown
- 1975-03-24 NO NO751002A patent/NO146867C/en unknown
- 1975-03-25 DK DK125775A patent/DK144704C/en not_active IP Right Cessation
- 1975-03-25 FR FR7509331A patent/FR2265770A1/en active Granted
- 1975-03-26 LU LU72137A patent/LU72137A1/xx unknown
- 1975-03-27 HU HU75SA00002769A patent/HU172294B/en unknown
- 1975-03-27 DD DD185083A patent/DD120449A5/xx unknown
- 1975-03-27 DE DE19752513927 patent/DE2513927A1/en not_active Withdrawn
- 1975-03-27 BE BE154833A patent/BE827259A/en not_active IP Right Cessation
- 1975-03-27 CA CA223,243A patent/CA1059977A/en not_active Expired
- 1975-03-27 SU SU752117218A patent/SU1072811A3/en active
- 1975-03-27 SE SE7503639A patent/SE425496B/en unknown
- 1975-03-28 NL NL7503801.A patent/NL164045C/en not_active IP Right Cessation
- 1975-03-28 CS CS752152A patent/CS195281B2/en unknown
- 1975-03-28 JP JP50037008A patent/JPS5237035B2/ja not_active Expired
- 1975-04-11 IL IL47074A patent/IL47074A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPS50130888A (en) | 1975-10-16 |
| IT1013081B (en) | 1977-03-30 |
| DK144704C (en) | 1982-10-11 |
| SU1072811A3 (en) | 1984-02-07 |
| BE827259A (en) | 1975-07-16 |
| NO146867C (en) | 1982-12-22 |
| DK125775A (en) | 1975-09-29 |
| IL47074A0 (en) | 1975-08-31 |
| LU72137A1 (en) | 1975-08-20 |
| FR2265770B1 (en) | 1980-04-11 |
| FR2265770A1 (en) | 1975-10-24 |
| ZA751387B (en) | 1976-04-28 |
| HU172294B (en) | 1978-07-28 |
| IL47074A (en) | 1980-01-31 |
| NL164045B (en) | 1980-06-16 |
| JPS5237035B2 (en) | 1977-09-20 |
| DE2513927A1 (en) | 1975-10-02 |
| DK144704B (en) | 1982-05-17 |
| NO146867B (en) | 1982-09-13 |
| SE425496B (en) | 1982-10-04 |
| NL164045C (en) | 1980-11-17 |
| NO751002L (en) | 1975-09-30 |
| YU71775A (en) | 1982-02-28 |
| CS195281B2 (en) | 1980-01-31 |
| DD120449A5 (en) | 1976-06-12 |
| SE7503639L (en) | 1975-09-29 |
| NL7503801A (en) | 1975-09-30 |
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