CA1122750A - Process for the production of polyolefins with a wide range of distribution in respect of molecular weights - Google Patents
Process for the production of polyolefins with a wide range of distribution in respect of molecular weightsInfo
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- CA1122750A CA1122750A CA336,078A CA336078A CA1122750A CA 1122750 A CA1122750 A CA 1122750A CA 336078 A CA336078 A CA 336078A CA 1122750 A CA1122750 A CA 1122750A
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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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
Abstract
Abstract of the Disclosure The invention concerns a process for the production of polyolefins with a wide range of distribution in respect of molecular weights. The process comprises polymerising ethylene, which is optionally accompanied by one or more other olefins, in contact with a catalytic system comprising:
a) a catalyst comprising a solid compound of titanium, magnesium and a halogen such as chlorine or bromine b) one or more organometallic compounds of a metal of groups II and III of the periodic table of elements c) one or more halogenated ethylenic hydrocarbons. The resulting polyolefins are particularly suitable for being shaped by means of extrusion-blowing.
a) a catalyst comprising a solid compound of titanium, magnesium and a halogen such as chlorine or bromine b) one or more organometallic compounds of a metal of groups II and III of the periodic table of elements c) one or more halogenated ethylenic hydrocarbons. The resulting polyolefins are particularly suitable for being shaped by means of extrusion-blowing.
Description
~ZZ7~ 01 The present invention concerns a process for the production of polyolefins by polymerisation of ethylene alone or accompanied by other olefins by means of highly active catalytic systems, resulting in the forma-tion of polymers with a wide range of distribution in respect of molecular weights.
It has already been proposed for ethylene to be polymerised within a liquid solvent, such as a saturated hydrocarbon, and in the presence of catalytic systems comprising a compound of titanium, generally titanium tetrachloride, an organoaluminium compound and a halogenated hydrocarbon, the effect of the latter compound being to maintain the catalytic system in the dissolved condition in the polymerisation solvent. Using this halogenated hydrocarbon makes it possible to produce polymers with molecular weights that are sufficiently low for it to be possible for the polymers subsequently to be shaped by injection or extrusion. In order to achieve a sufficient effect, it is however necessary to use relatively large amounts of halogenated hydro-carbon, but this entails the disadvantage of substantially reducing the level of activity of the catalytic system.
It has also been proposed for ethylene to be polymerised in the presence of ~alogen and a catalytic system comprising a compound of magnesium and titanium or a compound of magnesium and vanadium, an organoaluminium compound and a saturated chlorinated hydrocarbon. In order to produce poly-ethylenes which have a sufficient width of distribution in respect of molecular weights,it is necessary to use substantial proportions of saturated chlorinated hydrocarbon, but this considerably reduces the degree of activity of the catalytic system and results in the formation of polymers which have ~lZ2~7~ial poor rheological properties and which are accordingly difficult to put to use.
There has now been discovered a process for the polymerisation of ethylene, alone or accompanied by other olefinic monomers, by means of a highly active catalytic system which makes it possible to produce polymers which have a wide range of distribution in respect of molecular weights, and an elevated flow parameter. The width of distribution in respect of molecular weights, as referred to hereinbefore, is equal to the ratio of the mass average molecular weight Mw to the number average molecular weight Mn, these two values being generally measured by gel permeation.
The flow parameter n is equal to the ratio:
n = log (IF21 6 / IF5) log (21. 6js) wherein IF21 6 and IF5 represent the fluidity index of the polymer, as measured at a temperature of 190 C, under loads of 21.6 kg and 5 kg respect-ively.
The polymers produced in accordance with the present invention generally have a width of distribution in respect of molecular weightswhich is from 8 to 12, and a flow parameter which is from 1.9 to 2.5, which makes them particularly suitable for shaping by means of extrusian-blowing.
The subject of the present invention is a process for the polymer-isation of ethylene, which is optionally accompanied by one or more olefins having the formula ~H2 = CHA wherein A is an alkyl radical containing from 1 to 8 carbon atoms, in contact with a catalytic system comprising: a) a catalyst comprising a solid compound of titanium, magnesium and a halogen such as chlorine or bromine, b) one or more organometallic compounds of a ~1227~
metal of groups II and III of the periodic table, and c) one or more halogenated hydrocarbons, the process being characterised in that the halogenated hydrocarbon or hydrocarbons is or are selected from compounds having the formula:
Il 13 Cl = Cl wherein: Yl = F, Cl or Br Y2, Y3 = F, Cl, Br or CnH2n~l n being an integer of from 0 to 6 Y4 Cn 2n+1 n being an integer of from 0 to 6 and that the molar ratio of the halogenated hydrocarbon or hydrocarbons set forth in c) to the organometallic compounds set forth in b) is from 0.01 to 1 and preferably from 0.05 to 0.15.
In the foregoing formula, the number 'n' in the radical CnH2n+l is preferably 0 or 1; accordingly, the radical CnH2n~l preferably comprises a hydrogen atom or the radical CH3.
me halogenated hydrocarbon or hydrocarbons is or are advantageously selected from vinyl chloride, vinylidene chloride, 1,2-cis-trichloroethylene, 1~2-trans-trichloroethylene, l-chloropropene and 1,2-dichloropropene.
The catalyst may be produced by reaction at a temperature of from -20 to 150 C and preferably from 60 to 90 C, of one or more compounds of tetravalent titanium, having the formula TiXt4 n) (OR)n wherein X is a chlorine or bromine atom, R is an alkyl radical which may contain from 2 to 8 llZ2'75~
carbon atoms and n is an integer or a fraction which may be of any value from 0 to 4 and preferaby from 0 to 2, and an organomagnesium compound having the formula MgXR or the formula MgR2 wherein X and R are as defined above. The reaction between the tetravalent titanium compound or compounds and the organomagnesium compound is advantageously carried out in the presence of an aIkyl halide having the formula RX wherein R and X are as defined above, these various compounds being used in molar ratios such that:
either 0-1 < Tix(4 n) (R)n / RMgX - 0-5 and 1 ~ RX / RMgX ~ 2 or 0.1 ~ TiX(4 n) (OR)n/ MgR2 ~ 0 5 and 2 < RX / MgR2 < 4 If necessary, the organomagnesium compounds may be used in the form of complexes with electron-donor compounds such as ethers.
me catalyst may also be produced by reaction at a temperature of from -20 to 150 C and preferably from 60 to 90 C, of magnesium metal, one or more tetravalent titanium compounds and an alkyl halide, the latter compounds corresponding respectively to the formulae TiX(4 ) (OR)n and RX, as defined above. In this case, the reactants are preferably used in molar ratios such that:
0.1 ~ TiX(4 n) (R)n / Mg - 0-5 and 0.5 ~ RX / Mg < 10 or preferably, 1, RX / Mg ~ 2.
The organometallic compound or compounds of a metal of groups II
and III of the periodic table preferably comprise organoaluminium compounds having the mean formula AIR'XZ(3 ) wherein Rt represents an alkyl group containing from 1 to 16 carbon atoms and preferably from 2 to 12 carbon ~22'7~1D
atoms, Z is a hydrogen atom or a halogen such as chlorine or bromine and x is an integer or a fraction which can be of any value from 1 to 3. Prefer-ably, these compounds are selected from trialkylaluminiums having the formula AlR'3, wherein R' is an alkyl group as defined above.
These compounds are advantageously used in amounts such that the atomic ratio of metals of groups II and III of the co-catalysts to the titanium of the catalysts is from 0.5 to 50.
Polymerisation is generally carried out under a pressure of less than 40 bars and at a temperature of from 40 to 150 C. This operation may be performed by introducing the monomers comprising ethylene and possibly other olefins, into a liquid diluent such as a saturated aliphatic hydro-carbon or, in the absence of diluent~ by direct contact between the monomers in the gaseous condition and the constituents of the catalytic system. Poly-merisation is carried out in the presence of a chain-growth limiter, generally comprising hydrogen, whose proportion by volume with respect to the olefins introduced into the polymerisation medium is from 1 to 80 %, so as to produce a polymer having the desired fluidity number.
The constituents of the catalytic system may be used in different ways.
The catalyst may be introduced into the polymerisation reactor directly or in the form of a prepolymer produced by means of preliminary polymerisation of one or more olefins within an inert liquid such as an aliphatic hydrocarbon and in the presence of a solid compound of titanium, magnesium and a halogen, as defined in a) above.
llZ%750 The organometallic compound ~r compounds of a metal of groups II and III of the periodic table may also be introduced directly into the polymerisation reactor.
These compounds may also be used in the ~orm of a porous carrier which has previously been impregnated with such compounds, in this case, the porous carrier may be inert, organic or inorganic, or may comprise the prepolymer referred to in the preceding paragraph.
The halogenat-ed hydrocarbons may be introduced into the polymerisation reactor in mixture with the organo-metallic compolmds; they may also be introduced into the polymerisation reactor separately, in two or more batches, in the course of the polymerisati~ operation.
Exa~le A
____ ____ Preparation of a catalyst (catalyst A).
- The following are successively int-oduced at a temperature of 25C into a l litre glass balloon flas~
provided with a mechanical agitator and a heating and cooling means:
500 ml of n-heptane 9.7 g of magnesium in powder form (0.40 gram-atom) 1.2 g of odine.
While agitating the content of the balloon flask, the content is heated to a temperature of 80C and the following are introduced:
18.2 g of titanium tetrachloride (96 m. moles) and over a period of 3 hours, 74.5 g of ~-butyl chloride (o.805 mole).
The precipitate obtained is washed three times, with intermediate decantation, with 200 ml of n-heptane.
A~ter drying, the resulting catalyst A is analysed; it contains 9.1,b by weight of titanium.
Exa~le B
Preparation of a catalyst (catalyst B) Operation is as set forth in Example A above, except that the 18.2 g of titanium tetrachloride is replaced 5 by:
- 9.1 g of titanium tetrachloride (48 m. moles) and - 13.6~ g of tetrapropyltitanate (48 m. moles).
Catalyst B contains 8.1 g by weight of titanium.
Exam~le C
Preparation of a catalyst (catalyst C).
Firstly, n-butylmagnesiumchloride is prepared in a 1 litre balloon flask provided with a mechanical agitator, a reflux condenser and a means for heating or cooling the balloon flask by circulating a fluid in a ~b~x ~a~k3t.
15 ~ . The following are introduced into the balloon flask under a nitrogen atmosphere and at ambient temperature:
- 9.7 g (0.40 gram-atom) of magnesium in powder form - 500 ml of n-heptane _ 37 g (0.40 mole) of n-butyl chloride - an iodine crystal.
The reaction medium being heated to a temperature of 80C, the reaction begins and is maintained under these conditions- for a period of 2 hours. This results in a suspension of 0.40 mole of n-butylmagnesiumchloride in n-heptane.
Still under a nitrogen atmosphere, the n-butylmagnesium chloride suspension is heated to a temperature of 80C~
and a solution of 18.2g (96 m. moles) of titaniumtetrachloride 112Z~7~0 and 37.5 g (0.405 mole) of n-buty~chloride in 150 ml of n_heptane is progressively introduced over a period of
It has already been proposed for ethylene to be polymerised within a liquid solvent, such as a saturated hydrocarbon, and in the presence of catalytic systems comprising a compound of titanium, generally titanium tetrachloride, an organoaluminium compound and a halogenated hydrocarbon, the effect of the latter compound being to maintain the catalytic system in the dissolved condition in the polymerisation solvent. Using this halogenated hydrocarbon makes it possible to produce polymers with molecular weights that are sufficiently low for it to be possible for the polymers subsequently to be shaped by injection or extrusion. In order to achieve a sufficient effect, it is however necessary to use relatively large amounts of halogenated hydro-carbon, but this entails the disadvantage of substantially reducing the level of activity of the catalytic system.
It has also been proposed for ethylene to be polymerised in the presence of ~alogen and a catalytic system comprising a compound of magnesium and titanium or a compound of magnesium and vanadium, an organoaluminium compound and a saturated chlorinated hydrocarbon. In order to produce poly-ethylenes which have a sufficient width of distribution in respect of molecular weights,it is necessary to use substantial proportions of saturated chlorinated hydrocarbon, but this considerably reduces the degree of activity of the catalytic system and results in the formation of polymers which have ~lZ2~7~ial poor rheological properties and which are accordingly difficult to put to use.
There has now been discovered a process for the polymerisation of ethylene, alone or accompanied by other olefinic monomers, by means of a highly active catalytic system which makes it possible to produce polymers which have a wide range of distribution in respect of molecular weights, and an elevated flow parameter. The width of distribution in respect of molecular weights, as referred to hereinbefore, is equal to the ratio of the mass average molecular weight Mw to the number average molecular weight Mn, these two values being generally measured by gel permeation.
The flow parameter n is equal to the ratio:
n = log (IF21 6 / IF5) log (21. 6js) wherein IF21 6 and IF5 represent the fluidity index of the polymer, as measured at a temperature of 190 C, under loads of 21.6 kg and 5 kg respect-ively.
The polymers produced in accordance with the present invention generally have a width of distribution in respect of molecular weightswhich is from 8 to 12, and a flow parameter which is from 1.9 to 2.5, which makes them particularly suitable for shaping by means of extrusian-blowing.
The subject of the present invention is a process for the polymer-isation of ethylene, which is optionally accompanied by one or more olefins having the formula ~H2 = CHA wherein A is an alkyl radical containing from 1 to 8 carbon atoms, in contact with a catalytic system comprising: a) a catalyst comprising a solid compound of titanium, magnesium and a halogen such as chlorine or bromine, b) one or more organometallic compounds of a ~1227~
metal of groups II and III of the periodic table, and c) one or more halogenated hydrocarbons, the process being characterised in that the halogenated hydrocarbon or hydrocarbons is or are selected from compounds having the formula:
Il 13 Cl = Cl wherein: Yl = F, Cl or Br Y2, Y3 = F, Cl, Br or CnH2n~l n being an integer of from 0 to 6 Y4 Cn 2n+1 n being an integer of from 0 to 6 and that the molar ratio of the halogenated hydrocarbon or hydrocarbons set forth in c) to the organometallic compounds set forth in b) is from 0.01 to 1 and preferably from 0.05 to 0.15.
In the foregoing formula, the number 'n' in the radical CnH2n+l is preferably 0 or 1; accordingly, the radical CnH2n~l preferably comprises a hydrogen atom or the radical CH3.
me halogenated hydrocarbon or hydrocarbons is or are advantageously selected from vinyl chloride, vinylidene chloride, 1,2-cis-trichloroethylene, 1~2-trans-trichloroethylene, l-chloropropene and 1,2-dichloropropene.
The catalyst may be produced by reaction at a temperature of from -20 to 150 C and preferably from 60 to 90 C, of one or more compounds of tetravalent titanium, having the formula TiXt4 n) (OR)n wherein X is a chlorine or bromine atom, R is an alkyl radical which may contain from 2 to 8 llZ2'75~
carbon atoms and n is an integer or a fraction which may be of any value from 0 to 4 and preferaby from 0 to 2, and an organomagnesium compound having the formula MgXR or the formula MgR2 wherein X and R are as defined above. The reaction between the tetravalent titanium compound or compounds and the organomagnesium compound is advantageously carried out in the presence of an aIkyl halide having the formula RX wherein R and X are as defined above, these various compounds being used in molar ratios such that:
either 0-1 < Tix(4 n) (R)n / RMgX - 0-5 and 1 ~ RX / RMgX ~ 2 or 0.1 ~ TiX(4 n) (OR)n/ MgR2 ~ 0 5 and 2 < RX / MgR2 < 4 If necessary, the organomagnesium compounds may be used in the form of complexes with electron-donor compounds such as ethers.
me catalyst may also be produced by reaction at a temperature of from -20 to 150 C and preferably from 60 to 90 C, of magnesium metal, one or more tetravalent titanium compounds and an alkyl halide, the latter compounds corresponding respectively to the formulae TiX(4 ) (OR)n and RX, as defined above. In this case, the reactants are preferably used in molar ratios such that:
0.1 ~ TiX(4 n) (R)n / Mg - 0-5 and 0.5 ~ RX / Mg < 10 or preferably, 1, RX / Mg ~ 2.
The organometallic compound or compounds of a metal of groups II
and III of the periodic table preferably comprise organoaluminium compounds having the mean formula AIR'XZ(3 ) wherein Rt represents an alkyl group containing from 1 to 16 carbon atoms and preferably from 2 to 12 carbon ~22'7~1D
atoms, Z is a hydrogen atom or a halogen such as chlorine or bromine and x is an integer or a fraction which can be of any value from 1 to 3. Prefer-ably, these compounds are selected from trialkylaluminiums having the formula AlR'3, wherein R' is an alkyl group as defined above.
These compounds are advantageously used in amounts such that the atomic ratio of metals of groups II and III of the co-catalysts to the titanium of the catalysts is from 0.5 to 50.
Polymerisation is generally carried out under a pressure of less than 40 bars and at a temperature of from 40 to 150 C. This operation may be performed by introducing the monomers comprising ethylene and possibly other olefins, into a liquid diluent such as a saturated aliphatic hydro-carbon or, in the absence of diluent~ by direct contact between the monomers in the gaseous condition and the constituents of the catalytic system. Poly-merisation is carried out in the presence of a chain-growth limiter, generally comprising hydrogen, whose proportion by volume with respect to the olefins introduced into the polymerisation medium is from 1 to 80 %, so as to produce a polymer having the desired fluidity number.
The constituents of the catalytic system may be used in different ways.
The catalyst may be introduced into the polymerisation reactor directly or in the form of a prepolymer produced by means of preliminary polymerisation of one or more olefins within an inert liquid such as an aliphatic hydrocarbon and in the presence of a solid compound of titanium, magnesium and a halogen, as defined in a) above.
llZ%750 The organometallic compound ~r compounds of a metal of groups II and III of the periodic table may also be introduced directly into the polymerisation reactor.
These compounds may also be used in the ~orm of a porous carrier which has previously been impregnated with such compounds, in this case, the porous carrier may be inert, organic or inorganic, or may comprise the prepolymer referred to in the preceding paragraph.
The halogenat-ed hydrocarbons may be introduced into the polymerisation reactor in mixture with the organo-metallic compolmds; they may also be introduced into the polymerisation reactor separately, in two or more batches, in the course of the polymerisati~ operation.
Exa~le A
____ ____ Preparation of a catalyst (catalyst A).
- The following are successively int-oduced at a temperature of 25C into a l litre glass balloon flas~
provided with a mechanical agitator and a heating and cooling means:
500 ml of n-heptane 9.7 g of magnesium in powder form (0.40 gram-atom) 1.2 g of odine.
While agitating the content of the balloon flask, the content is heated to a temperature of 80C and the following are introduced:
18.2 g of titanium tetrachloride (96 m. moles) and over a period of 3 hours, 74.5 g of ~-butyl chloride (o.805 mole).
The precipitate obtained is washed three times, with intermediate decantation, with 200 ml of n-heptane.
A~ter drying, the resulting catalyst A is analysed; it contains 9.1,b by weight of titanium.
Exa~le B
Preparation of a catalyst (catalyst B) Operation is as set forth in Example A above, except that the 18.2 g of titanium tetrachloride is replaced 5 by:
- 9.1 g of titanium tetrachloride (48 m. moles) and - 13.6~ g of tetrapropyltitanate (48 m. moles).
Catalyst B contains 8.1 g by weight of titanium.
Exam~le C
Preparation of a catalyst (catalyst C).
Firstly, n-butylmagnesiumchloride is prepared in a 1 litre balloon flask provided with a mechanical agitator, a reflux condenser and a means for heating or cooling the balloon flask by circulating a fluid in a ~b~x ~a~k3t.
15 ~ . The following are introduced into the balloon flask under a nitrogen atmosphere and at ambient temperature:
- 9.7 g (0.40 gram-atom) of magnesium in powder form - 500 ml of n-heptane _ 37 g (0.40 mole) of n-butyl chloride - an iodine crystal.
The reaction medium being heated to a temperature of 80C, the reaction begins and is maintained under these conditions- for a period of 2 hours. This results in a suspension of 0.40 mole of n-butylmagnesiumchloride in n-heptane.
Still under a nitrogen atmosphere, the n-butylmagnesium chloride suspension is heated to a temperature of 80C~
and a solution of 18.2g (96 m. moles) of titaniumtetrachloride 112Z~7~0 and 37.5 g (0.405 mole) of n-buty~chloride in 150 ml of n_heptane is progressively introduced over a period of
2 hours, by means of a metering pump. When the operation of introducing these components has been concluded, the reaction medium is maintained at a temperature of 80C, with agitation, for 1 hour.
~ he resulting precipitate is washed several times with n-heptane. The dried catalyst C contains 9% by weight of titanium.
Pol~merisation ty~e Example This example sets forth the standard mode of operation used for testing catalytic systems.
1500 ml of n-heptane is introduced into a 3 litre stainless steel reactor provided ~ith an agitator and a heating and cooling means, which has been previously purged by means of a stream of nitrogen9 the 1500 ml of n-heptane then being heated to a temperature of 80C, fo~lowed then by the addition of the constituents of the catalytic system and then hydrogen at a relati~e pressure of from 1.5 to 2 bars. Ethylene is then introduced at a constant flow rate of 120 g/h. Except in Examples 23, 24 and 25 the halogenated hydrocarbon is introduced into the reactor in two equal portions, the first being introduced as soon as the ethylene is introduced and the second being introduced after a period of 2 hours 30 minutes.
After 6 hours of polymerisation, the polymer formed is isolated, weighed and analysed. The degree of activity of the catalyst is deduced from the weight of the polymer formed and is expressed in grams of polymer produced per grams of titanium of the catalyst ? per hour and per l~Z2~7~i~
bar of measured relative ethylene pressure. In addition, measurements are made, in accordance with standard ASTM D 1238, conditions P and F, in respect of the fluidity numbers of the polymer under loads of 5 kg and 21.6 kg, this making it possible to calculate the flow parameter n= log (IF21.6 /I 5) log (21.6/5) In addition, the weight-average molecular weight M and the number average molecular weight Mn of the resulting polymers are measured by gel permeation, from which the ratio M~ Mn is deduced.
Examples 1 to 18 In this series of examples, ethylene is polymerised in accordance with the standard mode of operation set forth in the above polymerisation type example, in the presence of an amount of catalyst A which corresponds to 0.375 milligram-atom of titanium and 3 m. moles of tri-n-octyl-aluminium.
me results obtained with various unsaturated hydrocarbons are set forth in Table 1, in relation to two comparative tests Cl and C2 which were carried out under the same conditions, but in the absence of any halogenated hydro-carbon.
It will be noted that the ethylenic halogenated hydrocarbons used, even in very small proportions, result in a very substantial increase in the flow parameter and the width of distribution in respect of the ratio MW/Mn.
_g _ ~22~7.SO
Exam~les 19 to 22 ____ _____________ Operation in this series of examples is as set forth in Example 1, while changing the nature of the organometallic compound used. The results which are set,forth in Table II shows the influence of the organo-metallic compounds on the fluidity numbe.s and the flow parameter.
Exam~les 23 to 25 This series of examples, the results of which are set forth in Table II, seeks to illustrate different modes of use of the halogenated hydrocarbons.
In Example 23~ operation is as in Example 2, except that the whole of the dichloroethylene is introduced into the reactor as soon as the ethylene is introduced.
In Example 24, operation is as in Example 2, except that the whole of the dichloroethylene is introduced into the reactor in the form of a mixture with tri-n-octylaluminium which has previously been maintained at a temperature of 80C for 1 hour, before addition of the catalyst.
In Example 25, operation is as in Example 2, except that the whole of the dichloroethylene is introduced into the reactor in the form of a mixture with three m. moles of tri-isobutylaluminium which has been previously maintained at a temperature of 80C for 1 hour, before addition of the catalyst.
Exa~Ie__C ,_C4_and C
These examples, the results of which are set forth in Table II, are comparative examples illustrating llse of ~12Z7S~) saturated halogenated hydrocarbons instead of the unsaturated - hydrocarbons of the invention. Operation is as in Example 2, with vinylidinechloride being replaced by 1,2-dichloro-ethane (Example C3), 1,2,2'-trichloroethane (Example C4) and 1,lt,2,2~-tetrachloroethane (Example C5) It will be observed that the catalytic activity on the one hand and the fluidity numbers of the polymer on the other hand are greatly reduced, in comparison with the results obtained in the preceding Examples.
.
Examples 26 to 28 and comparative Examples C6 to C8 _________________________________________________~
In Examples 26, 27 and 28, ethylene is polymerised in accordance with the standard mode of operation set forth in the polymerisation type example, in the presence of an amount of catalyst B which corresponds to 0.375 milligram-atom, 3 m. moles of an organoaluminium compound andvinylid~ne;chloride. The nature of the compounds used, the amounts thereof and the results obtained are set ~orth in Table III, in ~omparison with the results obtained in comparative tests C6, C7 and C8 which were carried out under the same conditions but without vinyiidenechloride.
It will be noted that the addition of vinylid~nechloride results in a substantial increase in the flow parameter, without causing a reduction in catalytic activity.
.
Example 29 and comparative Example Cg _____________________________________ In Example 29, ethylene is polymerised in accordance with the standard mode of operation set forth in the polymerisation type example, in thé presence of an amount of catalyst C which corresponds to 0.375 milligram-atom ~ 2 2~ S O
of titanium, 3 m. moles of tri-octylaluminium and 0.3 m.
mole o~ ~inylid~ne',chloride. The results ohtained in Example 29 are set forth in Table IV, in comparison with the results of a comparative test Cg which was carried out under the same conditions but in the absence of any halogenated hydrocarbon.
It will also be noted that in the presence of the catalyst C, the vinylidQne`chloride tends to increase in a very marked manner the flow parameter of the polyethylene produced.
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~ he resulting precipitate is washed several times with n-heptane. The dried catalyst C contains 9% by weight of titanium.
Pol~merisation ty~e Example This example sets forth the standard mode of operation used for testing catalytic systems.
1500 ml of n-heptane is introduced into a 3 litre stainless steel reactor provided ~ith an agitator and a heating and cooling means, which has been previously purged by means of a stream of nitrogen9 the 1500 ml of n-heptane then being heated to a temperature of 80C, fo~lowed then by the addition of the constituents of the catalytic system and then hydrogen at a relati~e pressure of from 1.5 to 2 bars. Ethylene is then introduced at a constant flow rate of 120 g/h. Except in Examples 23, 24 and 25 the halogenated hydrocarbon is introduced into the reactor in two equal portions, the first being introduced as soon as the ethylene is introduced and the second being introduced after a period of 2 hours 30 minutes.
After 6 hours of polymerisation, the polymer formed is isolated, weighed and analysed. The degree of activity of the catalyst is deduced from the weight of the polymer formed and is expressed in grams of polymer produced per grams of titanium of the catalyst ? per hour and per l~Z2~7~i~
bar of measured relative ethylene pressure. In addition, measurements are made, in accordance with standard ASTM D 1238, conditions P and F, in respect of the fluidity numbers of the polymer under loads of 5 kg and 21.6 kg, this making it possible to calculate the flow parameter n= log (IF21.6 /I 5) log (21.6/5) In addition, the weight-average molecular weight M and the number average molecular weight Mn of the resulting polymers are measured by gel permeation, from which the ratio M~ Mn is deduced.
Examples 1 to 18 In this series of examples, ethylene is polymerised in accordance with the standard mode of operation set forth in the above polymerisation type example, in the presence of an amount of catalyst A which corresponds to 0.375 milligram-atom of titanium and 3 m. moles of tri-n-octyl-aluminium.
me results obtained with various unsaturated hydrocarbons are set forth in Table 1, in relation to two comparative tests Cl and C2 which were carried out under the same conditions, but in the absence of any halogenated hydro-carbon.
It will be noted that the ethylenic halogenated hydrocarbons used, even in very small proportions, result in a very substantial increase in the flow parameter and the width of distribution in respect of the ratio MW/Mn.
_g _ ~22~7.SO
Exam~les 19 to 22 ____ _____________ Operation in this series of examples is as set forth in Example 1, while changing the nature of the organometallic compound used. The results which are set,forth in Table II shows the influence of the organo-metallic compounds on the fluidity numbe.s and the flow parameter.
Exam~les 23 to 25 This series of examples, the results of which are set forth in Table II, seeks to illustrate different modes of use of the halogenated hydrocarbons.
In Example 23~ operation is as in Example 2, except that the whole of the dichloroethylene is introduced into the reactor as soon as the ethylene is introduced.
In Example 24, operation is as in Example 2, except that the whole of the dichloroethylene is introduced into the reactor in the form of a mixture with tri-n-octylaluminium which has previously been maintained at a temperature of 80C for 1 hour, before addition of the catalyst.
In Example 25, operation is as in Example 2, except that the whole of the dichloroethylene is introduced into the reactor in the form of a mixture with three m. moles of tri-isobutylaluminium which has been previously maintained at a temperature of 80C for 1 hour, before addition of the catalyst.
Exa~Ie__C ,_C4_and C
These examples, the results of which are set forth in Table II, are comparative examples illustrating llse of ~12Z7S~) saturated halogenated hydrocarbons instead of the unsaturated - hydrocarbons of the invention. Operation is as in Example 2, with vinylidinechloride being replaced by 1,2-dichloro-ethane (Example C3), 1,2,2'-trichloroethane (Example C4) and 1,lt,2,2~-tetrachloroethane (Example C5) It will be observed that the catalytic activity on the one hand and the fluidity numbers of the polymer on the other hand are greatly reduced, in comparison with the results obtained in the preceding Examples.
.
Examples 26 to 28 and comparative Examples C6 to C8 _________________________________________________~
In Examples 26, 27 and 28, ethylene is polymerised in accordance with the standard mode of operation set forth in the polymerisation type example, in the presence of an amount of catalyst B which corresponds to 0.375 milligram-atom, 3 m. moles of an organoaluminium compound andvinylid~ne;chloride. The nature of the compounds used, the amounts thereof and the results obtained are set ~orth in Table III, in ~omparison with the results obtained in comparative tests C6, C7 and C8 which were carried out under the same conditions but without vinyiidenechloride.
It will be noted that the addition of vinylid~nechloride results in a substantial increase in the flow parameter, without causing a reduction in catalytic activity.
.
Example 29 and comparative Example Cg _____________________________________ In Example 29, ethylene is polymerised in accordance with the standard mode of operation set forth in the polymerisation type example, in thé presence of an amount of catalyst C which corresponds to 0.375 milligram-atom ~ 2 2~ S O
of titanium, 3 m. moles of tri-octylaluminium and 0.3 m.
mole o~ ~inylid~ne',chloride. The results ohtained in Example 29 are set forth in Table IV, in comparison with the results of a comparative test Cg which was carried out under the same conditions but in the absence of any halogenated hydrocarbon.
It will also be noted that in the presence of the catalyst C, the vinylidQne`chloride tends to increase in a very marked manner the flow parameter of the polyethylene produced.
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Claims (15)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the production of polyolefins with a wide range of distribution in respect of molecular masses, as characterised by its Mw/Mn ratio by polymerisation of ethylene, optionally accompanied by one or more olefins having the formula CH2 = CHA, wherein A is an alkyl radical containing from 1 to 8 carbon atoms, in contact with a catalytic system comprising:
a) a catalyst comprising a solid compound of titanium, magnesium and a halogen chosen from chlorine or bromine, b) one or more organometallic compounds of a metal of groups II
and III of the periodic table, and c) one or more halogenated hydrocarbons the process being char-acterised in that the halogenated hydrocarbon or hydrocarbons is or are selected from compounds having the formuia:
wherein: Yl = F, Cl or Br Y2, Y3 = F, Cl, Br or CnH2n+l, n being an integer of from 0 to 6 Y4 = CnH2n+l, n being an integer of from O to 6 and that the molar ratio of the halogenated hydrocarbon or hydrocarbons set forth in c) to the organometallic compounds set forth in b) is from 0.01 to 1.
a) a catalyst comprising a solid compound of titanium, magnesium and a halogen chosen from chlorine or bromine, b) one or more organometallic compounds of a metal of groups II
and III of the periodic table, and c) one or more halogenated hydrocarbons the process being char-acterised in that the halogenated hydrocarbon or hydrocarbons is or are selected from compounds having the formuia:
wherein: Yl = F, Cl or Br Y2, Y3 = F, Cl, Br or CnH2n+l, n being an integer of from 0 to 6 Y4 = CnH2n+l, n being an integer of from O to 6 and that the molar ratio of the halogenated hydrocarbon or hydrocarbons set forth in c) to the organometallic compounds set forth in b) is from 0.01 to 1.
2. A process as set forth in claim 1 wherein the molar ratio of the halogenated hydrocarbon or hydrocarbons to the organometallic compounds is from 0.05 to 0.15.
3. A process as set forth in claim 1 wherein the halogenated hydro-carbon or hydrocarbons is or are selected from compounds wherein the radical CnH2n+l comprises a hydrogen atom or the radical CH3.
4. A process as set forth in claim 1 wherein the halogenated hydrocarbon or hydrocarbons is or are selected from vinyl chloride, vinylidene chloride, 1,2-cis-trichloroethylene, 1,2-trans-trichloro-ethylene, l-chloropropene and 1,2-dichloropropene.
5. A process as set forth in claim 1 wherein the catalyst comprises a compound which is produced by reacting, at a tempera-ture of from -20°C to 150°C;
d) one or more compounds of tetravalent titanium having the formula TiX(4-n)(OR)n wherein X is a chlorine or bromine atom, R is an alkyl radical which can contain from 2 to 8 carbon atoms, and n is an integer or a fraction which can be of any value from 0 to 4 preferably from 0 to 2, e) an organomagnesium compound having the formula RMgX
wherein X and R are as defined above, and f) an alkyl halide having the formula RX wherein R and X are as defined above;
these various compounds being used in molar ratios such that:
0.1 < TiX(4-n)(OR)n/RMgX < 0-5 and 1 < RX / RMgX < 2.
d) one or more compounds of tetravalent titanium having the formula TiX(4-n)(OR)n wherein X is a chlorine or bromine atom, R is an alkyl radical which can contain from 2 to 8 carbon atoms, and n is an integer or a fraction which can be of any value from 0 to 4 preferably from 0 to 2, e) an organomagnesium compound having the formula RMgX
wherein X and R are as defined above, and f) an alkyl halide having the formula RX wherein R and X are as defined above;
these various compounds being used in molar ratios such that:
0.1 < TiX(4-n)(OR)n/RMgX < 0-5 and 1 < RX / RMgX < 2.
6. A process as set forth in claim 1 wherein the catalyst comprises a compound produced by reacting, at a temperature of from -20°C to 150°C.
g) one or more compounds of tetravalent titanium having the formula TiX(4-n)(OR)n wherein X is a chlorine or bromine atom, R is an alkyl radical which can contain from 2 to 8 carbon atoms and n is an integer or a fraction which can be of any value from 0 to 4 and pre:erably from 0.2, h) an organomagnesium compound having the formula MgR2 wherein R is as defined above, and i) an alkyl halide having the formula RX wherein R and X are as defined above, these various compounds being used in molar ratios such that:
0.1 < TiX(4-n)(OR)n / mgR2 < 0.5 and 2 < RX / MgR2 < 4.
g) one or more compounds of tetravalent titanium having the formula TiX(4-n)(OR)n wherein X is a chlorine or bromine atom, R is an alkyl radical which can contain from 2 to 8 carbon atoms and n is an integer or a fraction which can be of any value from 0 to 4 and pre:erably from 0.2, h) an organomagnesium compound having the formula MgR2 wherein R is as defined above, and i) an alkyl halide having the formula RX wherein R and X are as defined above, these various compounds being used in molar ratios such that:
0.1 < TiX(4-n)(OR)n / mgR2 < 0.5 and 2 < RX / MgR2 < 4.
7. A process as set forth in claim 5 or 6 wherein the reaction is carried out at a temperature of from 60°C to 90°C.
8. A process as set forth in claim 1 wherein the catalyst comprises a compound produced by reacting, at a temperature of from -20 to 150°C;
j) magnesium metal;
k) one or more compounds of tetravalent titanium having the formula TiX(4-n)(OR)n wherein X is a chlorine or bromine atom, R is an alkyl radical which can contain from 2 to 8 carbon atoms and n is an integer or a fraction which can be of any value from 0 to 4 and preferably from 0 to 2, and l) an alkyl halide having the formula RX wherein R and X are as defined above, these various compounds being used in molar ratios such that:
0.1 < TiX(4-n)(OR)n / Mg < 0.5 and 0.5 < RX / Mg < 10
j) magnesium metal;
k) one or more compounds of tetravalent titanium having the formula TiX(4-n)(OR)n wherein X is a chlorine or bromine atom, R is an alkyl radical which can contain from 2 to 8 carbon atoms and n is an integer or a fraction which can be of any value from 0 to 4 and preferably from 0 to 2, and l) an alkyl halide having the formula RX wherein R and X are as defined above, these various compounds being used in molar ratios such that:
0.1 < TiX(4-n)(OR)n / Mg < 0.5 and 0.5 < RX / Mg < 10
9. A process as set forth in claim 8 wherein the reaction is carried out at a temperature of from 60°C to 80°C.
10. A process as set forth in claim 1 wherein the catalyst is prepared from titanium tetrachloride as the tetravalent titanium compound.
11. A process as set forth in claim 1 wherein the catalyst is prepared jointly from titanium tetrachloride and tetrapropyltitanate as the tetravalent titanium compound.
12. A process as set forth in claim 1 wherein the organ-ometallic compound or compounds of a metal of groups II and III of the periodic table of elements comprise organo-aluminium compounds having the mean formula AlR'XA(3-x), wherein R' represents an alkyl group containing from 1 to 16 carbon atoms (and preferably from 2 to 12 carbon atoms), Z represents a hydrogen atom or a halogen chosen from chlorine or bromine and x is an integer or a fraction which can be of any value from 1 to 3.
13. A process as set forth in claim 1 or 12 wherein the organometallic compound or compounds of a metal of groups II and III of the periodic table comprise tri-alkylaluminium having the formula AlR'3 wherein R' represents an alkyl radical containing from 2 to 12 carbon atoms.
14. A process as set forth in claim 8 wherein the various compounds are used in molar ratios such that 0.1 < TiX(4-n)(OR)n/Mg < 0.5 and 1 < RX/Mg < 2.
15. Polymers and copolymers of ethylene which are prepared in accordance with the process of claim 1 and wherein the breadth of distribution in respect of molecular masses as expressed by the ratio Mw/Mn, is from 8 to 12 and the flow parameter as expressed by the ratio in which IF21.6 and IF5 represent the fluidity index of the polymer as measured at a temperature of 190°C under loads of 21.6 kg and 5 kg, is from 1.9 to 2.5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7827168 | 1978-09-22 | ||
| FR7827168A FR2436794A1 (en) | 1978-09-22 | 1978-09-22 | PROCESS FOR THE POLYMERIZATION OF ETHYLENE AND PRODUCTS THEREOF |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1122750A true CA1122750A (en) | 1982-04-27 |
Family
ID=9212909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA336,078A Expired CA1122750A (en) | 1978-09-22 | 1979-09-21 | Process for the production of polyolefins with a wide range of distribution in respect of molecular weights |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4355143A (en) |
| EP (1) | EP0009426B1 (en) |
| CA (1) | CA1122750A (en) |
| DE (1) | DE2966664D1 (en) |
| ES (1) | ES484368A1 (en) |
| FR (1) | FR2436794A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111019024A (en) * | 2019-11-28 | 2020-04-17 | 万华化学集团股份有限公司 | Catalyst for producing polyethylene with wide molecular weight distribution, preparation method and application thereof |
Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4593010A (en) * | 1983-08-31 | 1986-06-03 | Exxon Research & Engineering Co. | Polyethylene with broad molecular weight distribution |
| JPH07116253B2 (en) * | 1986-01-21 | 1995-12-13 | 東ソー株式会社 | Method for producing polyolefin |
| JPH06509840A (en) * | 1992-06-10 | 1994-11-02 | シェブロン リサーチ アンド テクノロジー カンパニー | Titanium magnesium catalyst precursor for olefin polymerization |
| FR2707651B1 (en) * | 1993-07-13 | 1995-08-25 | Bp Chemicals Snc | Process for increasing the activity of a Ziegler-Natta type catalyst. |
| FR2711656A1 (en) * | 1993-10-21 | 1995-05-05 | Bp Chemicals Snc | Process for the preparation of a catalyst for olefin polymerisation |
| KR100391694B1 (en) * | 1994-12-06 | 2004-03-06 | 비피 케미칼즈 리미티드 | Polymerization Method of Olefin Using Ziegler-Natta Catalyst |
| KR100334165B1 (en) * | 1998-04-17 | 2002-11-27 | 삼성종합화학주식회사 | A PRODUCTION METHOD OF A SUPPORTED CATALYST FOR ETHYLENE POLYMERIZATION AND ETHYLENE/α-OLEFIN COPOLYMERIZATION |
| KR100546499B1 (en) * | 1999-05-27 | 2006-01-26 | 삼성토탈 주식회사 | A catalyst for ethylene homo- and co-polymerization |
| KR100524293B1 (en) | 1999-05-27 | 2005-10-26 | 삼성토탈 주식회사 | A catalyst for ethylene homo- and co-polymerization |
| DE69920291T2 (en) | 1999-10-23 | 2005-02-17 | Samsung General Chemicals Co. Ltd., Seosan | IMPROVED CATALYST FOR OLEFINHOMO AND CO POLYMERIZATION |
| KR100361224B1 (en) | 1999-12-01 | 2002-11-29 | 삼성종합화학주식회사 | Method for preparing catalyst for ethylene homo- and co-polymerization |
| KR100351386B1 (en) | 2000-04-24 | 2002-09-05 | 삼성종합화학주식회사 | Catalyst for preparation of ultra high molecular weight polyethylene and preparation method of ultra high molecular weight polyethylene using the same |
| KR100353960B1 (en) | 2000-05-31 | 2002-09-27 | 삼성종합화학주식회사 | A method for producing ethylene homo- and co-polymer |
| KR100359932B1 (en) | 2000-06-15 | 2002-11-07 | 삼성종합화학주식회사 | A catalyst for ethylene homo- and copolymerization |
| KR100387734B1 (en) * | 2000-06-17 | 2003-06-18 | 삼성종합화학주식회사 | Catalyst and process for polymerization of olefin |
| KR100389477B1 (en) * | 2000-11-09 | 2003-06-27 | 삼성종합화학주식회사 | A method for producing ethylene homo- and co-polymer |
| KR100389476B1 (en) * | 2000-11-09 | 2003-06-27 | 삼성종합화학주식회사 | A method for producing ethylene homo- and co-polymer |
| KR100389475B1 (en) * | 2000-11-09 | 2003-06-27 | 삼성종합화학주식회사 | Preparation method of catalyst for ethylene polymeration or copolymeration |
| KR100389962B1 (en) * | 2000-11-10 | 2003-07-02 | 삼성종합화학주식회사 | Preparation method of catalyst for ethylene polymeration or copolymeration |
| KR100421551B1 (en) * | 2000-12-16 | 2004-03-09 | 삼성아토피나주식회사 | Catalyst obtained by prepolymerization of polyolefin and olefin polymerization method using the same |
| WO2002051882A1 (en) * | 2000-12-22 | 2002-07-04 | Samsung General Chemicals Co., Ltd. | Chelate catalyst for olefin polymerization and olefin polymerization method using the same |
| JP2004516379A (en) * | 2000-12-22 | 2004-06-03 | サムソン ジェネラル ケミカルズ カンパニー リミテッド | Polypropylene resin composition with improved surface hardness and scratch resistance |
| CN1247686C (en) * | 2000-12-22 | 2006-03-29 | 三星综合化学株式会社 | Polyolefine resin composition |
| JP3921448B2 (en) * | 2000-12-22 | 2007-05-30 | サムソン ジェネラル ケミカルズ カンパニー リミテッド | Flame retardant polypropylene resin composition |
| KR100421553B1 (en) | 2000-12-27 | 2004-03-09 | 삼성아토피나주식회사 | A polymerization method of alpha-olefins |
| KR100530794B1 (en) * | 2001-06-21 | 2005-11-23 | 삼성토탈 주식회사 | Catalyst for polymerization and copolymerization of ethylene |
| KR100496776B1 (en) * | 2001-06-21 | 2005-06-22 | 삼성토탈 주식회사 | Catalyst for polymerization and copolymerization of ethylene |
| KR100530795B1 (en) * | 2001-12-26 | 2005-11-23 | 삼성토탈 주식회사 | A method for ethylene homo- and copolymerization |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3029231A (en) * | 1956-10-17 | 1962-04-10 | Shell Oil Co | Process for polymerizing olefins |
| NL108637C (en) * | 1958-04-28 | |||
| US3101327A (en) * | 1958-10-08 | 1963-08-20 | Phillips Petroleum Co | Polymerization of 1-olefins in the presence of an allyl halide |
| BE585435A (en) * | 1959-12-03 | |||
| US3238146A (en) * | 1960-03-21 | 1966-03-01 | Shell Oil Co | Catalysts and their preparation |
| US4056668A (en) * | 1966-10-21 | 1977-11-01 | Solvay & Cie | Process for the polymerization and copolymerization of olefins with a solid support catalyst |
| CA920299A (en) * | 1968-08-01 | 1973-01-30 | Mitsui Petrochemical Industries | Process for the polymerization and/or copolymerization of olefins with use of ziegler-type catalytsts supported on carrier |
| GB1359547A (en) * | 1970-12-04 | 1974-07-10 | Naphtachimie Sa | Based catalysts |
| FR2099311A5 (en) * | 1971-06-30 | 1972-03-10 | Naphtachimie Sa | Olefins polymsn catalyst - consisting of organoaluminium cpd and component prepd by reacting magnesium, monohalohydrocarbon an |
| BE785673A (en) * | 1971-06-30 | 1973-01-02 | Naphtachimie Sa | POLYMERIZATION CATALYZERS OF OLEFINS PREPARED FROM DECOMPOSED ORGANOMAGNESIANS |
| GB1498852A (en) * | 1974-04-30 | 1978-01-25 | Asahi Chemical Ind | Catalyst and method for polymerizing ethylene and propylene |
| IT1037112B (en) * | 1975-03-28 | 1979-11-10 | Montedison Spa | CATALYSTS FOR THE POLYMERIZATION OF OLFINES |
| NL190723C (en) * | 1975-06-12 | 1994-07-18 | Montedison Spa | Process for preparing Ziegler catalysts for the polymerization of olefins. |
-
1978
- 1978-09-22 FR FR7827168A patent/FR2436794A1/en active Granted
-
1979
- 1979-08-28 EP EP79400589A patent/EP0009426B1/en not_active Expired
- 1979-08-28 DE DE7979400589T patent/DE2966664D1/en not_active Expired
- 1979-09-17 US US06/075,897 patent/US4355143A/en not_active Expired - Lifetime
- 1979-09-21 ES ES484368A patent/ES484368A1/en not_active Expired
- 1979-09-21 CA CA336,078A patent/CA1122750A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111019024A (en) * | 2019-11-28 | 2020-04-17 | 万华化学集团股份有限公司 | Catalyst for producing polyethylene with wide molecular weight distribution, preparation method and application thereof |
| CN111019024B (en) * | 2019-11-28 | 2022-09-20 | 万华化学集团股份有限公司 | Catalyst for producing polyethylene with wide molecular weight distribution, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0009426B1 (en) | 1984-02-15 |
| FR2436794B1 (en) | 1981-07-03 |
| FR2436794A1 (en) | 1980-04-18 |
| US4355143A (en) | 1982-10-19 |
| ES484368A1 (en) | 1980-05-16 |
| EP0009426A1 (en) | 1980-04-02 |
| DE2966664D1 (en) | 1984-03-22 |
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